Negative photosensitive resin composition, cured film, display device provided with cured film, and method for manufacturing the same

Abstract

The present invention provides a negative photosensitive resin composition which is high in sensitivity, excellent in half-tone characteristics, capable of obtaining a pattern shape with low taper, and alkali developable. A negative photosensitive resin composition comprising at least (A1) a resin containing a weak acid group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin, the (A1) resin containing a weak acid group having an acid dissociation constant in dimethyl sulfoxide in the range of 13.0 to 23.0, and the (A2) resin containing an unsaturated group having an ethylenic unsaturated double bond group.

Description

[0001] This application is a divisional application of the application with the application number 201780016752.9, the application date of 17 March 2017, and the title "Negative photosensitive resin composition, cured film, display device provided with the cured film, and manufacturing method thereof". TECHNICAL FIELD

[0002] The present application relates to a negative photosensitive resin composition, and a cured film, a display device, and a manufacturing method of the display device using the same. BACKGROUND

[0003] In recent years, in display devices having a thin display such as a smartphone, a tablet, and a television, products using an organic electroluminescence (hereinafter referred to as "EL") display have been developed in large quantities.

[0004] For an organic EL display, a transparent electrode such as indium tin oxide (hereinafter referred to as "ITO") is generally provided on the light-extraction side of a light-emitting element, and a metal electrode such as an alloy of magnesium and silver is provided on the non-light-extraction side of the light-emitting element. In addition, in order to partition the pixels of the light-emitting element, an insulating layer called a pixel partition layer is formed between the layers of the transparent electrode and the metal electrode. After the pixel partition layer is formed, a light-emitting material is deposited using vapor deposition through a vapor deposition mask in a region corresponding to a pixel region, which is a region in which the transparent electrode or the metal electrode as a substrate is exposed by the opening of the pixel partition layer, thereby forming a light-emitting layer. The transparent electrode and the metal electrode are generally deposited by sputtering, and in order to prevent the deposited transparent electrode or metal electrode from being broken, the pixel partition layer is required to have a low-tapered pattern shape.

[0005] An organic EL display is a self-emitting element that emits light using energy generated by the recombination of electrons injected from a cathode and holes injected from an anode. Therefore, when a substance that hinders the movement of electrons or holes, or a substance that forms an energy level that hinders the recombination of electrons and holes, etc. are present, the light-emitting efficiency of the light-emitting element is reduced, or the light-emitting material is deactivated, etc., which leads to a decrease in the lifetime of the light-emitting element. Since the pixel partition layer is formed adjacent to the light-emitting element, outgassing and the outflow of ionic components from the pixel partition layer can be one of the causes of the decrease in the lifetime of the organic EL display. Therefore, the pixel partition layer is required to have high heat resistance. As a technique for forming a pixel partition layer having high heat resistance and a low-tapered pattern shape in cross section, a positive photosensitive resin composition using a polyimide is known (for example, see Patent Literature 1). In order to impart positive photosensitivity, it is necessary to contain a naphthoquinonediazide compound, but this compound contained in the pixel partition layer is decomposed by the action of light and / or heat to generate outgassing, which is a major cause of the decrease in the lifetime of the light-emitting element.

[0006] In the manufacture of panels of organic EL displays, a large-area glass substrate is generally used, thereby achieving an improvement in production efficiency (a plurality of panels are formed from one glass substrate, etc.). As a method for further improving production efficiency, from the viewpoint of shortening process time, the shortening of takt time at the time of patterning exposure due to a reduction in exposure amount at the time of patterning exposure can be cited. Therefore, a photosensitive resin composition for forming a pixel partition layer is required to have high sensitivity for enabling the formation of a pattern with a small exposure amount.

[0007] In addition, when forming a light-emitting layer, evaporation is performed with an evaporation mask in contact with the pixel partition layer, but when the contact area of the pixel partition layer with the evaporation mask is large, this becomes a major cause of a reduction in the yield of panels (due to the generation of particles). In addition, the pixel partition layer is damaged due to deposits of the evaporation mask, moisture intrudes, thereby becoming a major cause of the deterioration of light-emitting elements. Therefore, in order to reduce the contact area of the pixel partition layer, a method in which the pixel partition layer is formed in two layers and the size width of the second layer is reduced can be cited, but the process becomes complicated, and therefore there is a problem of becoming a major cause of an increase in process time or a reduction in the yield of panels. As a method for solving these problems, a method in which a halftone photomask is used as a photomask to form a pattern can be cited (for example, see Patent Document 2). This is a method in which a pixel partition layer having a step-shaped form is formed in such a manner that the film formation is one layer, thereby reducing the contact area with the evaporation mask without increasing the process time. However, in order to form a pixel partition layer having a step-shaped form, it is necessary to use a positive photosensitive resin composition containing a naphthoquinonediazide compound, and similarly there is a problem of becoming a major cause of the aforementioned outgassing.

[0008] As a technique for forming a pixel partition layer using a resin composition not containing a naphthoquinonediazide compound, a negative photosensitive resin composition used in a color filter of a liquid crystal display can be cited (for example, see Patent Document 3). However, in general, an acrylic resin is used as the negative photosensitive resin composition, and the heat resistance is poor, and the reliability of a light-emitting element is reduced. From the viewpoint of the photosensitive mechanism, it is known that a negative photosensitive is more advantageous than a positive photosensitive in essence when the photosensitive resin composition is made high-sensitivity. Therefore, in the case of aiming at high-sensitivity, a negative photosensitive resin composition is generally used. However, for the photosensitive mechanism of the negative type, since the photocuring is performed from the surface of the film, a rectangular or an inverted taper-shaped pattern shape is easily formed, and the photocuring is insufficient in a region where the exposure amount is small, and thus, a case where the pattern is not left after alkali development is the majority. Therefore, for the negative photosensitive resin composition, even if a half-tone photomask is used, it is difficult to form a pixel partition layer having a step-shaped pattern shape in which a sufficient film thickness difference exists between a thick film portion and a thin film portion. In addition, as a method for making the negative photosensitive resin composition high-sensitivity, the ratio of a compound having a plurality of ethylenic unsaturated double bond groups in the molecule can be increased, but this becomes a main cause of making the cross-sectional pattern shape rectangular or inverted taper-shaped. Therefore, a negative photosensitive resin composition in which the sensitivity is high, the characteristics of being able to form a pattern having a step-shaped pattern shape by a one-process using a half-tone photomask (hereinafter referred to as "half-tone characteristics") are excellent, and a low-tapered pattern shape can be obtained is being sought.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Patent Application Laid-Open (JP-A) No. 2002-091343

[0012] Patent Document 2: Japanese Patent Application Laid-Open (JP-A) No. 2005-322564

[0013] Patent Document 3: Japanese Patent Application Laid-Open (JP-A) No. 2015-093986 SUMMARY

[0014] PROBLEMS TO BE SOLVED BY THE INVENTION

[0015] However, in terms of a material for forming a pixel partition layer having a step-shaped pattern shape of an organic EL display, the characteristics of the conventionally known photosensitive resin compositions are all insufficient. Specifically, the sensitivity, the half-tone characteristics, or the pattern shape are all insufficient.

[0016] Therefore, an object of the present application is to provide a negative photosensitive resin composition in which the sensitivity is high, the half-tone characteristics are excellent, a low-tapered pattern shape can be obtained, and alkali development can be performed.

[0017] Further, as another problem, with the conventional negative photosensitive resin composition, it is difficult to form a pixel partition layer having a step-shaped form, and thus there is a case where the reliability of a light emitting element is reduced due to contact of an evaporation mask with the pixel partition layer.

[0018] Therefore, an object of the present application is to provide an organic EL display having a pixel partition layer having a step-shaped form in which there is a sufficient difference in film thickness between a thick film portion and a thin film portion, and excellent reliability of a light emitting element.

[0019] Further, as another problem, when a pixel partition layer having a step-shaped form is formed using a negative photosensitive resin composition, there is a case where complicated processes need to be performed.

[0020] Therefore, an object of the present application is to provide a method of forming a pattern having a step-shaped form by a one-process using a half-tone photomask, and a manufacturing method of an organic EL display using the same.

[0021] Means for solving the problem

[0022] The negative photosensitive resin composition of the present application contains at least (A1) a resin containing a weak acidic group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin, the (A1) resin containing a weak acidic group has an acidic group having an acid dissociation constant in dimethyl sulfoxide in the range of 13.0 to 23.0, and the (A2) resin containing an unsaturated group has an ethylenic unsaturated double bond group.

[0023] Specifically, the present application includes the following modes.

[0024] 1. A negative photosensitive resin composition containing at least (A1) a resin containing a weak acidic group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin,

[0025] the (A1) resin containing a weak acidic group has an acidic group having an acid dissociation constant in dimethyl sulfoxide in the range of 13.0 to 23.0,

[0026] the (A2) resin containing an unsaturated group has an ethylenic unsaturated double bond group.

[0027] 2. The negative photosensitive resin composition according to item 1, wherein the (A1) resin containing a weak acidic group has an acidic group selected from one or more of a phenolic hydroxyl group, a silanol group, a hydroxyimide group, and a hydroxyamide group.

[0028] 3. The negative photosensitive resin composition according to item 1 or 2, further containing (B) a radical polymerizable compound and (C) a photosensitizer.

[0029] 4. The negative photosensitive resin composition according to any one of items 1 to 3, wherein

[0030] The (Al) weak-acid-group-containing resin does not have an ethylenically unsaturated double bond group,

[0031] The (Al) weak-acid-group-containing resin is contained in the (A) alkali-soluble resin at a content ratio in the range of 30 to 99 mass%.

[0032] 5. The negative photosensitive resin composition according to item 4, wherein the (Al) weak-acid-group-containing resin is contained in the (A) alkali-soluble resin at a content ratio in the range of 70 to 97 mass%.

[0033] 6. The negative photosensitive resin composition according to any one of items 1 to 5, wherein the acid equivalent of the (Al) weak-acid-group-containing resin is in the range of 200 to 1,200 g / mol.

[0034] 7. The negative photosensitive resin composition according to any one of items 1 to 6, wherein the double bond equivalent of the (A2) unsaturated-group-containing resin is in the range of 250 to 5,000 g / mol.

[0035] 8. The negative photosensitive resin composition according to any one of items 1 to 7, further comprising (D) a colorant.

[0036] 9. The negative photosensitive resin composition according to any one of items 1 to 8, wherein the (Al) weak-acid-group-containing resin comprises one or more selected from the group consisting of (Ala-l) a polyimide, (Ala-2) a polyimide precursor, (Ala-3) a carboxylic acid-modified polysiloxane, (Ala-4) a carboxylic acid-modified Novolac resin, (Ala-5) a carboxylic acid-modified polyhydroxystyrene, (Alb-l) a polybenzoxazole, (Alb-2) a polybenzoxazole precursor, (Alb-3) a polysiloxane, (Alb-4) a Novolac resin, and (Alb-5) a polyhydroxystyrene.

[0037] 10. The negative photosensitive resin composition according to any one of claims 1 to 9, wherein the (A2) resin containing an unsaturated group contains one or more selected from the group consisting of (A2a-1) a polyimide containing an unsaturated group, (A2a-2) a polyimide precursor containing an unsaturated group, (A2a-3) a carboxylic acid-modified polysiloxane containing an unsaturated group, (A2b-1) a polybenzoxazole containing an unsaturated group, (A2b-2) a polybenzoxazole precursor containing an unsaturated group, (A2b-3) a polysiloxane containing an unsaturated group, (A2c-1) an aromatic resin containing a polycyclic side chain, (A2c-2) an acrylic resin, and (A2c-3) a carboxylic acid-modified epoxy resin.

[0038] 11. A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 10.

[0039] 12. The cured film according to claim 11, wherein the optical density per 1 μm of film thickness is in the range of 0.3 to 5.0.

[0040] 13. A display device comprising the cured film according to claim 11 or 12.

[0041] 14. The display device according to claim 13, wherein the cured film is a cured pattern having a step-shaped form.

[0042] 15. The display device according to claim 14, wherein the taper angle of the inclined side in the cross section of the cured pattern having a step-shaped form is in the range of 1 to 60°.

[0043] 16. The display device according to claim 14 or 15, wherein

[0044] the film thickness of the thick film portion in the step-shaped form of the cured pattern is set to (T FT ) μm, and the film thickness of the thin film portion is set to (T HT ) μm,

[0045] the film thickness difference (ΔT FT-HT ) μm between (T FT ) and (T HT ) is in the range of 0.5 to 10.0 μm.

[0046] 17. The display device according to claim 16, wherein (T FT ) and (T HT ) also satisfy the relationships represented by general formulas (α) to (γ),

[0047] 2.0 ≤ (T FT ) ≤ 10 (α)

[0048] 0.10 ≤ (T HT)≤7.5 (β)

[0049] 0.10×(T FT )≤(T HT )≤0.75×(T FT ) (γ)。

[0050] 18. The display device according to item 16, wherein the (T FT ) and (T HT ) also satisfy the relationships represented by general formulae (δ) to (ζ),

[0051] 3.0≤(T FT )≤9.0 (δ)

[0052] 0.20≤(T HT )≤7.0 (ε)

[0053] 0.20×(T FT )≤(T HT )≤0.70×(T FT ) (ζ).

[0054] 19. The display device according to any one of items 15 to 18, which has a display portion in the form of a curved surface having a radius of curvature in the range of 0.1 to 10 mm.

[0055] 20. The display device according to any one of items 13 to 19, which is an organic EL display or a liquid crystal display.

[0056] 21. A method for producing a display device, comprising the following steps:

[0057] (1) forming a coating film of the negative photosensitive resin composition according to any one of items 1 to 10 on a substrate;

[0058] (2) irradiating the resin composition with active photochemical rays through a photomask;

[0059] (3) forming a pattern of the resin composition having a step-shaped form by development using an alkaline solution; and

[0060] (4) obtaining a cured pattern of the resin composition having a step-shaped form by heating the pattern,

[0061] the photomask is a photomask having a pattern comprising a light-transmitting portion and a light-blocking portion, and the photomask has a semi-light-transmitting portion between the light-transmitting portion and the light-blocking portion, the semi-light-transmitting portion having a transmittance lower than that of the light-transmitting portion and higher than that of the light-blocking portion.

[0062] Effects of the Invention

[0063] According to the present application, a negative photosensitive resin composition having high sensitivity, excellent half-tone characteristics, capable of obtaining a pattern shape with low taper, and capable of being subjected to alkali development can be provided. In addition, by using the negative photosensitive resin composition, a cured film having a step shape with sufficient film thickness difference between a thick film portion and a thin film portion can be formed, and thus the reliability of a light emitting element can be improved. Furthermore, according to the above resin composition, a pattern having a step shape can be formed by a one-step process using a half-tone photomask, and thus the process time can be shortened. BRIEF DESCRIPTION OF DRAWINGS

[0064] [ Figure 1 ] Figure 1 (1) to (7) are process diagrams showing an example of a schematic cross-sectional view in a manufacturing process of an organic EL display using a cured film of the negative photosensitive resin composition of the present application.

[0065] [ Figure 2 ] Figure 2 (1) to (12) are process diagrams showing an example of a schematic cross-sectional view in a manufacturing process of a liquid crystal display using a cured film of the negative photosensitive resin composition of the present application.

[0066] [ Figure 3 ] Figure 3 (1) to (10) are process diagrams showing an example of a schematic cross-sectional view in a manufacturing process of a flexible organic EL display using a cured film of the negative photosensitive resin composition of the present application.

[0067] [ Figure 4 ] Figure 4 is a cross-sectional view showing an example of a cross section of a cured pattern having a step shape.

[0068] [ Figure 5 ] Figure 5 (1) to (4) are schematic diagrams showing an example of an organic EL display device used in a light emitting property evaluation.

[0069] [ Figure 6 ] Figure 6 is a cross-sectional view showing an example of an organic EL display not having a polarizing layer. DETAILED DESCRIPTION

[0070] The negative photosensitive resin composition of the present application contains at least (Al) a resin containing a weak acid group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin, the (Al) resin containing a weak acid group has an acid group having an acid dissociation constant in dimethyl sulfoxide in the range of 13.0 to 23.0, and the (A2) resin containing an unsaturated group has an ethylenic unsaturated double bond group.

[0071] <(A1) Resin Containing Weak Acidic Group and (A2) Resin Containing Unsaturated Group>

[0072] The negative photosensitive resin composition of the present application contains at least (A1) a resin containing a weak acidic group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin.

[0073] The so-called (A1) resin containing a weak acidic group refers to an alkali-soluble resin having an acidic group with an acid dissociation constant (hereinafter referred to as "pK a " ) in the range of 13.0 to 23.0 in dimethyl sulfoxide as an alkali-soluble group.

[0074] By containing (A1) a resin containing a weak acidic group, the half-tone characteristic can be improved. It is presumed that the reason is that the above resin having a weak acidic group has moderate solubility in an alkali developing solution, whereby the difference in the dissolution rate in the alkali developing solution between the cured portion and the half-tone exposed portion at the time of exposure can be moderated. That is, it is considered that the reason is that at the time of alkali development, the difference in the film loss of the half-tone exposed portion where the curing is not completed can be adjusted, whereby a gradient of the film loss is generated between the cured portion and the half-tone exposed portion, and a step-shaped form is easily formed.

[0075] The acidic group having a pK a in the range of 13.0 to 23.0 in dimethyl sulfoxide is, for example, an acidic group having an acidity lower than that of a carboxyl group as a Brønsted acid.

[0076] As an index of the acidity as a Brønsted acid equivalent to that of a carboxyl group, as a compound having a carboxyl group and the pK a of the compound in dimethyl sulfoxide, for example, acetic acid (pK a = 12.3) or benzoic acid (pK a = 11.1) can be mentioned.

[0077] The acidic group having a pK a in the range of 13.0 to 23.0 in dimethyl sulfoxide showing a weak acidity is, for example, a phenolic hydroxyl group, a silanol group, a hydroxyimide group, a hydroxyamide group, a mercapto group, or a methylene group having two or more carbonyl groups or ester groups bonded thereto, and from the viewpoints of the pattern processing property using an alkali developing solution and the availability of the compound, a phenolic hydroxyl group, a silanol group, a hydroxyimide group or a hydroxyamide group is preferred, and a phenolic hydroxyl group or a silanol group is more preferred. That is, (A1) the resin containing a weak acidic group preferably has one or more acidic groups selected from a phenolic hydroxyl group, a silanol group, a hydroxyimide group and a hydroxyamide group, and more preferably has a phenolic hydroxyl group and / or a silanol group.

[0078] Regarding indicators of weak acidity, the compounds possessing acidic groups exhibiting weak acidity and their pK values ​​in dimethyl sulfoxide are considered. a For example, phenol (pK) can be cited. a =18.0), benzohydroxyoxime acid (pK a =13.7), n-Butyl mercaptan (pK) a =17.0), acetylacetone (pK) a =13.3), Ethyl acetoacetate (pK) a =14.2) or diethyl malonate (pK a =15.7).

[0079] (A1) The pK of the alkali-soluble groups in dimethyl sulfoxide in resins containing weakly acidic groups. a The pK value is 13.0 or higher, preferably 13.5 or higher, more preferably 14.0 or higher, even more preferably 14.5 or higher, and especially preferably 15.0 or higher. a Within the aforementioned range, halftone characteristics can be improved. On the other hand, pK a The pK value is 23.0 or less, preferably 22.5 or less, more preferably 22.0 or less, even more preferably 21.5 or less, and especially preferably 21.0 or less. a Within the above range, the resolution after development can be improved.

[0080] As a resin containing weakly acidic groups (A1), it is preferable to lack olefinic unsaturated double bond groups. The absence of olefinic unsaturated double bond groups improves halftone properties. This is presumably because, in exposure using a halftone photomask, a gradual difference in the degree of UV curing occurs between the cured section and the halftone exposed section, resulting in a gradient of film loss during alkaline development.

[0081] As a resin containing a weakly acidic group (A1), it preferably contains one or more selected from (A1a-1) polyimide, (A1a-2) polyimide precursor, (A1a-3) carboxylic acid modified polysiloxane, (A1a-4) carboxylic acid modified Novolac resin, (A1a-5) carboxylic acid modified polyhydroxystyrene, (A1b-1) polybenzoxazole, (A1b-2) polybenzoxazole precursor, (A1b-3) polysiloxane, (A1b-4) Novolac resin, and (A1b-5) polyhydroxystyrene. More preferably, it contains one or more selected from (A1a-1) polyimide, (A1a-2) polyimide precursor, (A1a-3) carboxylic acid modified polysiloxane, (A1b-1) polybenzoxazole, (A1b-2) polybenzoxazole precursor, and (A1b-3) polysiloxane.

[0082] The negative photosensitive resin composition of the present application further contains (A2) a resin containing an unsaturated group as the (A) alkali-soluble resin.

[0083] The (A2) resin containing an unsaturated group is an alkali-soluble resin having an ethylenically unsaturated double bond group as a radical polymerizable group. Further, it is preferable to have one or more selected from a phenolic hydroxyl group, a silanol group, a hydroxyimide group, a hydroxyamide group, a carboxyl group, and a carboxylic anhydride group as an alkali-soluble group.

[0084] By containing the (A2) resin containing an unsaturated group, the sensitivity at the time of exposure can be improved. It is presumed that the reason for this is that, by the above resin having an ethylenically unsaturated double bond group, the UV curing at the time of exposure is promoted, and the curing of the exposed portion is easily performed.

[0085] As the (A2) resin containing an unsaturated group, it is preferable to have one or more selected from a phenolic hydroxyl group, a silanol group, a hydroxyimide group, and a hydroxyamide group as an alkali-soluble group. By having these alkali-soluble groups, the half-tone characteristics can be improved. It is presumed that the reason for this is that the solubility in an alkali developer can be adjusted, and thus the difference in the dissolution speed in the alkali developer between the cured portion at the time of exposure and the half-tone exposed portion can be moderated.

[0086] As the (A2) resin containing an unsaturated group, it is also preferable to have a carboxyl group and / or a carboxylic anhydride group as an alkali-soluble group. By having these alkali-soluble groups, the resolution after development can be improved. It is presumed that the reason for this is that, by the above acidic group, the solubility in an alkali developer can be improved, and thus the generation of residue at the time of alkali development can be suppressed.

[0087] As the resin containing an unsaturated group of (A2), one or more selected from the group consisting of (A2a-1) a polyimide containing an unsaturated group, (A2a-2) a polyimide precursor containing an unsaturated group, (A2a-3) a carboxylic acid-modified polysiloxane containing an unsaturated group, (A2b-1) a polybenzoxazole containing an unsaturated group, (A2b-2) a polybenzoxazole precursor containing an unsaturated group, (A2b-3) a polysiloxane containing an unsaturated group, (A2c-1) an aromatic resin containing a polycyclic side chain, (A2c-2) an acrylic resin, and (A2c-3) a carboxylic acid-modified epoxy resin is preferable. More preferably, one or more selected from the group consisting of (A2a-1) a polyimide containing an unsaturated group, (A2a-2) a polyimide precursor containing an unsaturated group, (A2a-3) a carboxylic acid-modified polysiloxane containing an unsaturated group, (A2b-1) a polybenzoxazole containing an unsaturated group, (A2b-2) a polybenzoxazole precursor containing an unsaturated group, (A2b-3) a polysiloxane containing an unsaturated group, (A2c-1) an aromatic resin containing a polycyclic side chain, and (A2c-3) a carboxylic acid-modified epoxy resin is preferable. Further preferably, one or more selected from the group consisting of (A2a-1) a polyimide containing an unsaturated group, (A2a-2) a polyimide precursor containing an unsaturated group, (A2a-3) a carboxylic acid-modified polysiloxane containing an unsaturated group, (A2b-1) a polybenzoxazole containing an unsaturated group, (A2b-2) a polybenzoxazole precursor containing an unsaturated group, and (A2b-3) a polysiloxane containing an unsaturated group is preferable.

[0088] As the resin containing a weakly acidic group of (A1), the content ratio of a structural unit having one or more selected from the group consisting of phenolic hydroxyl group, silanol group, hydroxyimide group, and hydroxyamide group is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, and further preferably 30 to 100 mol% of the total structural units. When the content ratio is within the above range, the half-tone characteristics and the resolution after development can be improved.

[0089] As the acid equivalent of the resin containing a weakly acidic group of (A1), 200 g / mol or more is preferable, 220 g / mol or more is more preferable, 280 g / mol or more is further preferable, and 310 g / mol or more is particularly preferable. When the acid equivalent is within the above range, the film damage at the time of alkali development can be suppressed. On the other hand, as the acid equivalent of the resin containing a weakly acidic group of (A1), 1,200 g / mol or less is preferable, 1,100 g / mol or less is more preferable, 1,000 g / mol or less is further preferable, and 800 g / mol or less is particularly preferable. When the acid equivalent is within the above range, the half-tone characteristics and the resolution after development can be improved.

[0090] In addition, the acid equivalent is preferably one derived from one or more selected from the group consisting of phenolic hydroxyl groups, silanol groups, hydroxyimide groups, and hydroxyamide groups from the viewpoint of improving halftone characteristics.

[0091] The acid equivalent of the resin containing an unsaturated group (A2) is preferably 200 g / mol or more, more preferably 220 g / mol or more, further preferably 280 g / mol or more, and particularly preferably 310 g / mol or more. When the acid equivalent is within the above range, film damage at the time of alkali development can be suppressed. On the other hand, the acid equivalent of the resin containing an unsaturated group (A2) is preferably 1,200 g / mol or less, more preferably 1,100 g / mol or less, further preferably 1,000 g / mol or less, and particularly preferably 800 g / mol or less. When the acid equivalent is within the above range, halftone characteristics and resolution after development can be improved.

[0092] In addition, the acid equivalent is preferably one derived from one or more selected from the group consisting of phenolic hydroxyl groups, silanol groups, hydroxyimide groups, and hydroxyamide groups from the viewpoint of improving halftone characteristics. On the other hand, the acid equivalent is also preferably one derived from carboxyl groups and / or carboxylic anhydride groups from the viewpoint of improving resolution after development.

[0093] The acid equivalent referred to herein is the mass of the resin per 1 mol of acid groups, and is expressed in g / mol. The number of acid groups in the resin can be calculated from the value of the acid equivalent. The acid equivalent can be calculated from the acid value.

[0094] The acid value referred to herein is the mass of potassium hydroxide that reacts with 1 g of the resin, and is expressed in mgKOH / g. The acid value can be calculated by titration of 1 g of the resin with an aqueous potassium hydroxide solution.

[0095] The double bond equivalent of the resin containing an unsaturated group (A2) is preferably 250 g / mol or more, more preferably 300 g / mol or more, and further preferably 350 g / mol or more. When the double bond equivalent is within the above range, halftone characteristics and adhesion to a base substrate can be improved. On the other hand, the double bond equivalent of the resin containing an unsaturated group (A2) is preferably 5,000 g / mol or less, more preferably 2,000 g / mol or less, and further preferably 1,500 g / mol or less. When the double bond equivalent is within the above range, sensitivity at the time of exposure can be improved.

[0096] The double bond equivalent referred to herein is the mass of the resin per 1 mol of ethylenically unsaturated double bond groups, and is expressed in g / mol. The number of ethylenically unsaturated double bond groups in the resin can be calculated from the value of the double bond equivalent. The double bond equivalent can be calculated from the iodine value.

[0097] The iodine value referred to herein is a value obtained by converting the amount of halogen that reacts with 100 g of resin into the mass of iodine, and is expressed in gI / 100 g. It can be obtained by reacting 100 g of resin with iodine monochloride, then capturing the unreacted iodine with an aqueous potassium iodide solution, and titrating the unreacted iodine with an aqueous sodium thiosulfate solution.

[0098] In the negative photosensitive resin composition of the present application, the content ratio of the (Al) resin containing a weak acid group in the (A) alkali-soluble resin is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, further more preferably 70% by mass or more, and particularly preferably 80% by mass or more. When the content ratio is within the above range, the half-tone characteristic can be improved. On the other hand, the content ratio of the (Al) resin containing a weak acid group is preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less, and particularly preferably 95% by mass or less. When the content ratio is within the above range, the sensitivity at the time of exposure and the resolution after development can be improved.

[0099] In the negative photosensitive resin composition of the present application, the content ratio of the (A2) resin containing an unsaturated group in the (A) alkali-soluble resin is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. When the content ratio is within the above range, the sensitivity at the time of exposure and the resolution after development can be improved. On the other hand, the content ratio of the (A2) resin containing an unsaturated group is preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further more preferably 30% by mass or less, and particularly preferably 20% by mass or less. When the content ratio is within the above range, the half-tone characteristic can be improved.

[0100] By making the content ratios of the (Al) resin containing a weak acid group and the (A2) resin containing an unsaturated group in the negative photosensitive resin composition of the present application within the above ranges, the sensitivity at the time of exposure and the half-tone characteristic can be improved. Therefore, a high sensitivity can be maintained, and a cured film having a step-shaped form in which there is a sufficient difference in film thickness between a thick film portion and a thin film portion can be formed by a one-step process using a half-tone photomask. Therefore, the cured film obtained from the negative photosensitive resin composition of the present application is suitable for an insulating layer or the like requiring a step-shaped form, such as a pixel partition layer of an organic EL display.

[0101] <(Ala) Resin Containing Two Acid Groups>

[0102] As the (Al) resin containing a weak acid group, a (Ala) resin containing two acid groups is preferably included.

[0103] The so-called (Ala) resin containing two kinds of acidic groups refers to an alkali-soluble resin having an acidic group showing weak acidity, i.e., one or more selected from a phenolic hydroxyl group, a silanol group, a hydroxyimide group, and a hydroxyamide group, and another acidic group different in acidity as an alkali-soluble group.

[0104] As the other acidic group different in acidity, for example, a carboxyl group, a carboxylic anhydride group, or a sulfonic acid group can be given, and from the viewpoint of improving the resolution after development, a carboxyl group or a carboxylic anhydride group is preferred.

[0105] By including the (Ala) resin containing two kinds of acidic groups, not only the halftone characteristics can be improved, but also the resolution after development can be improved. It is presumed that the reason is that the solubility in the alkali developer can be improved by the other acidic group different in acidity, whereby the generation of residue at the time of alkali development can be suppressed.

[0106] As the (Ala) resin containing two kinds of acidic groups, one or more selected from (Ala-1) polyimide, (Ala-2) polyimide precursor, (Ala-3) carboxylic acid-modified polysiloxane, (Ala-4) carboxylic acid-modified Novolac resin, and (Ala-5) carboxylic acid-modified polyhydroxystyrene described later is preferred.

[0107] <(Alb) second resin containing a weakly acidic group>

[0108] As the (Al) resin containing a weakly acidic group, it is preferred to include the (Alb) second resin containing a weakly acidic group.

[0109] The so-called (Alb) second resin containing a weakly acidic group refers to an alkali-soluble resin having an acidic group showing weak acidity, i.e., one or more selected from a phenolic hydroxyl group, a silanol group, a hydroxyimide group, and a hydroxyamide group, as an alkali-soluble group, and refers to a resin different from the above (Ala) resin containing two kinds of acidic groups.

[0110] By including the (Alb) second resin containing a weakly acidic group, the halftone characteristics can be improved.

[0111] Further, as the (Al) resin containing a weakly acidic group, it is more preferred to include the (Ala) resin containing two kinds of acidic groups and the (Alb) second resin containing a weakly acidic group.

[0112] By including the (Ala) resin containing two kinds of acidic groups and the (Alb) second resin containing a weakly acidic group, the halftone characteristics can be further improved. It is presumed that the reason is that by increasing the content ratio of the acidic group showing weak acidity, the solubility in the alkali developer can be adjusted, and the difference in the dissolution speed in the alkali developer between the cured portion at the time of exposure and the halftone-exposed portion can be moderated.

[0113] In the negative photosensitive resin composition of the present application, the content ratio of the (Ala) resin containing two kinds of acidic groups in the (Al) resin containing a weakly acidic group is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by mass or more. When the content ratio is within the above range, not only the half-tone characteristic can be improved, but also the resolution after development can be improved. On the other hand, the content ratio of the (Ala) resin containing two kinds of acidic groups is preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less, and particularly preferably 95% by mass or less. When the content ratio is within the above range, the half-tone characteristic can be improved.

[0114] In the negative photosensitive resin composition of the present application, the content ratio of the (Alb) second resin containing a weakly acidic group in the (Al) resin containing a weakly acidic group is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. When the content ratio is within the above range, the half-tone characteristic can be improved. On the other hand, the content ratio of the (Alb) second resin containing a weakly acidic group is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 20% by mass or less. When the content ratio is within the above range, not only the half-tone characteristic can be improved, but also the resolution after development can be improved.

[0115] As the (Alb) second resin containing a weakly acidic group, one or more selected from the group consisting of (Alb-1) polybenzoxazole, (Alb-2) polybenzoxazole precursor, (Alb-3) polysiloxane, (Alb-4) Novolac resin, and (Alb-5) polyhydroxystyrene described later are preferable.

[0116] <(A2a) Resin Containing Two Kinds of Acidic Groups and Unsaturated Group>

[0117] As the (A2) resin containing an unsaturated group, it is preferable to contain the (A2a) resin containing two kinds of acidic groups and an unsaturated group.

[0118] The (A2a) resin containing two kinds of acidic groups and an unsaturated group is a base-soluble resin having an ethylenically unsaturated double bond group as a radical-polymerizable group and having an acidic group showing weak acidity, i.e., one or more selected from the group consisting of phenolic hydroxyl group, silanol group, hydroxyimide group, and hydroxyamide group, and other acidic groups different in acidity as a base-soluble group.

[0119] As other acid groups different in acidity, for example, a carboxyl group, a carboxylic anhydride group, or a sulfonic acid group can be mentioned, and from the viewpoint of improving the resolution after development, a carboxyl group or a carboxylic anhydride group is preferred.

[0120] By including (A2a) a resin containing two acid groups and an unsaturated group, it is possible to improve not only the sensitivity at the time of exposure but also the half-tone characteristics and the resolution after development.

[0121] As (A2a) a resin containing two acid groups and an unsaturated group, it is preferred to contain one or more selected from the group consisting of (A2a-1) a polyimide containing an unsaturated group, (A2a-2) a polyimide precursor containing an unsaturated group, and (A2a-3) a carboxylic acid-modified polysiloxane containing an unsaturated group, which will be described later.

[0122] <(A2b) a resin containing a weak acid group and an unsaturated group>

[0123] As (A2) a resin containing an unsaturated group, it is preferred to include (A2b) a resin containing a weak acid group and an unsaturated group.

[0124] (A2b) a resin containing a weak acid group and an unsaturated group" means an alkali-soluble resin having an ethylenically unsaturated double bond group as a radically polymerizable group, and having an acid group showing weak acidity, i.e., one or more selected from the group consisting of a phenolic hydroxyl group, a silanol group, a hydroxyimide group, and a hydroxyamide group, as an alkali-soluble group. Note that (A2b) a resin containing a weak acid group and an unsaturated group" means a resin different from (A2a) a resin containing two acid groups and an unsaturated group" described above.

[0125] By including (A2b) a resin containing a weak acid group and an unsaturated group, it is possible to improve not only the sensitivity at the time of exposure but also the half-tone characteristics.

[0126] As (A2b) a resin containing a weak acid group and an unsaturated group, it is preferred to contain one or more selected from the group consisting of (A2b-1) a polybenzoxazole containing an unsaturated group, (A2b-2) a polybenzoxazole precursor containing an unsaturated group, and (A2b-3) a polysiloxane containing an unsaturated group, which will be described later.

[0127] <(A2c) a resin containing an acid group and an unsaturated group>

[0128] As (A2) a resin containing an unsaturated group, it is preferred to include (A2c) a resin containing an acid group and an unsaturated group.

[0129] The so-called (A2c) resin containing an acidic group and an unsaturated group refers to an alkali-soluble resin having an ethylenically unsaturated double bond group as a radically polymerizable group and having a carboxyl group and / or a carboxylic anhydride group as an alkali-soluble group.

[0130] By including the (A2c) resin containing an acidic group and an unsaturated group, not only the sensitivity at the time of exposure can be improved, but also the resolution after development can be improved.

[0131] As the (A2c) resin containing an acidic group and an unsaturated group, one or more selected from the group consisting of the (A2c-1) aromatic resin containing a polycyclic side chain, the (A2c-2) acrylic resin, and the (A2c-3) carboxylic acid-modified epoxy resin described later is preferable.

[0132] <Polymide and Polymide Precursor>

[0133] In the negative photosensitive resin composition of the present application, the so-called (A1a-1) polyimide refers to a general polyimide described below.

[0134] In the negative photosensitive resin composition of the present application, the so-called (A1a-2) polyimide precursor refers to a general polyimide precursor described below.

[0135] As the (A1a-2) polyimide precursor, for example, a product obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride or tetracarboxylic diester dichloride, etc. with a diamine, a corresponding diisocyanate compound or trimethylsilylated diamine, etc. can be given, which has a tetracarboxylic acid and / or derivative residue thereof, and a diamine and / or derivative residue thereof. As the (A1a-2) polyimide precursor, for example, a polyamic acid, a polyamic acid ester, a polyamic acid amide, or a polyisoimide can be given.

[0136] As the (A1a-1) polyimide, for example, a product obtained by dehydration ring closure of the above polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide by heating or a reaction using an acid or a base, etc. can be given, which has a tetracarboxylic acid and / or derivative residue thereof, and a diamine and / or derivative residue thereof.

[0137] (A1a-2) is a resin whose heat resistance is improved after dehydration and ring closure, and thus is suitable for use in cases where it is desired to simultaneously achieve the properties of the precursor structure before dehydration and ring closure and the heat resistance of the cured film, and the like.

[0138] In addition, (A1a-1) polyimide and (A1a-2) polyimide precursor have imide bonds and / or amide bonds as polar bonds. Therefore, in particular, in cases where (D1) pigment is contained as (D) colorant described later, these polar bonds strongly interact with (D1) pigment, and thus it is possible to improve the dispersion stability of (D1) pigment.

[0139] (A1a-1) polyimide and (A1a-2) polyimide precursor used in the present application have phenolic hydroxyl groups and carboxyl groups as alkali-soluble groups. By having phenolic hydroxyl groups, it is possible to improve the half-tone characteristics. By having carboxyl groups, it is possible to improve not only the half-tone characteristics but also the resolution after development. In addition to phenolic hydroxyl groups, it is also possible to further have one or more weakly acidic groups selected from silanol groups, hydroxyimide groups, and hydroxyamide groups.

[0140] (A2a-1) polyimide containing an unsaturated group and (A2a-2) polyimide precursor containing an unsaturated group used in the present application have an ethylenically unsaturated double bond group as a radical polymerizable group. By having an ethylenically unsaturated double bond group, it is possible to improve the sensitivity at the time of exposure. As (A2a-1) polyimide containing an unsaturated group and (A2a-2) polyimide precursor containing an unsaturated group, it is preferable to use a product obtained by reacting a part of the phenolic hydroxyl groups and / or carboxyl groups of (A1a-1) polyimide and (A1a-2) polyimide precursor with a compound having an ethylenically unsaturated double bond group. By the above reaction, it is possible to introduce an ethylenically unsaturated double bond group in the side chain of the resin.

[0141] As the polyimide used in the present application, it is preferable to contain a structural unit represented by General Formula (1) from the viewpoint of improving the heat resistance of the cured film.

[0142] [Chemical Formula 1]

[0143]

[0144] (In General Formula (1), R1 represents a 4- to 10-valent tetracarboxylic acid and / or derivative residue thereof, R 2 represents a 2- to 10-valent diamine and / or derivative residue thereof. R 3 and R 4 each independently represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by General Formula (5) or General Formula (6). p represents an integer of 0 to 6, and q represents an integer of 0 to 8.

[0145] R in General Formula (1) 1 represents a tetracarboxylic acid and / or derivative residue thereof, R 2 represents a diamine and / or derivative residue thereof. As the tetracarboxylic acid derivative, a tetracarboxylic dianhydride, a tetracarboxylic acid dichloride, or a tetracarboxylic acid active diester can be mentioned. As the diamine derivative, a diisocyanate compound or a trimethylsilylated diamine can be mentioned.

[0146] R in General Formula (1) 1 represents a 4- to 10-valent tetracarboxylic acid and / or derivative residue thereof, R 2 represents a 2- to 10-valent diamine and / or derivative residue thereof. R 3 and R 4 each independently represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by General Formula (5) or General Formula (6). p represents an integer of 0 to 6, and q represents an integer of 0 to 8. R in General Formula (1) as the tetracarboxylic acid and / or derivative residue thereof 1 is preferably a 4- to 10-valent organic group having one or more kinds selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms, and more preferably a 4- to 10-valent organic group having one or more kinds selected from the group consisting of an aliphatic structure having 4 to 15 carbon atoms, an alicyclic structure having 4 to 15 carbon atoms, and an aromatic structure having 6 to 25 carbon atoms. In addition, R as the diamine and / or derivative residue thereof 2 is preferably a 2- to 10-valent organic group having one or more kinds selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms, and more preferably a 2- to 10-valent organic group having one or more kinds selected from the group consisting of an aliphatic structure having 4 to 15 carbon atoms, an alicyclic structure having 4 to 15 carbon atoms, and an aromatic structure having 6 to 25 carbon atoms. q is preferably 1 to 8. The above-mentioned aliphatic structure, alicyclic structure, and aromatic structure can have a hetero atom, and can be any of an unsubstituted form or a substituted form.

[0147] [Chemical Formula 2]

[0148]

[0149] R in General Formulae (5) and (6)19 ~R 21 each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. In General Formulae (5) and (6), R 19 ~R 21 each independently preferably represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The above-mentioned alkyl group, acyl group, and aryl group can be any of unsubstituted forms or substituted forms.

[0150] As the (Ala-l) polyimide, it is preferable to contain a structural unit represented by General Formula (1) as a main component, and in the polyimide, the content ratio of the structural unit represented by General Formula (1) among the structural units derived from all carboxylic acids and derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the content ratio is in the above-mentioned range, the heat resistance of the cured film can be improved.

[0151] As the (Ala-2) polyimide precursor used in the present application, it is preferable to contain a structural unit represented by General Formula (3) from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development.

[0152] [Chemical Formula 3]

[0153]

[0154] (In General Formula (3), R 9 represents a 4- to 10-valent tetracarboxylic acid and / or a derivative thereof residue, R 10 represents a 2- to 10-valent diamine and / or a derivative thereof residue. R 11 represents a substituent represented by the above General Formula (5) or General Formula (6), R 12 represents a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group, R 13 represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above General Formula (5) or General Formula (6). t represents an integer of 2 to 8, u represents an integer of 0 to 6, and v represents an integer of 0 to 8, 2≤t+u≤8.)

[0155] In General Formula (3), R 9 represents a tetracarboxylic acid and / or a derivative thereof residue, R 10 represents a diamine and / or a derivative thereof residue. As the tetracarboxylic acid derivative, a tetracarboxylic dianhydride, a tetracarboxylic acid dichloride, or a tetracarboxylic acid active diester can be mentioned. As the diamine derivative, a diisocyanate compound or a trimethylsilylated diamine can be mentioned.

[0156] In General Formula (3), R 9represents a 4- to 10-valent residue of a tetracarboxylic acid and / or a derivative thereof, R 10 represents a 2- to 10-valent residue of a diamine and / or a derivative thereof, R 11 represents a substituent represented by the above general formula (5) or general formula (6), R 12 represents a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group, R 13 represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6). t represents an integer of 2 to 8, u represents an integer of 0 to 6, and v represents an integer of 0 to 8, 2 ≤ t + u ≤ 8. In general formula (3), R 9 is preferably a 4- to 10-valent organic group having one or more kinds selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms, and is more preferably a 4- to 10-valent organic group having one or more kinds selected from the group consisting of an aliphatic structure having 4 to 15 carbon atoms, an alicyclic structure having 4 to 15 carbon atoms, and an aromatic structure having 6 to 25 carbon atoms. In addition, R 10 is preferably a 2- to 10-valent organic group having one or more kinds selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms, and is more preferably a 2- to 10-valent organic group having one or more kinds selected from the group consisting of an aliphatic structure having 4 to 15 carbon atoms, an alicyclic structure having 4 to 15 carbon atoms, and an aromatic structure having 6 to 25 carbon atoms. v is preferably 1 to 8. The above aliphatic structure, alicyclic structure, and aromatic structure can have a hetero atom, and can be any of unsubstituted or substituted.

[0157] As the (Ala-2) polyimide precursor, it is preferable to contain a structural unit represented by general formula (3) as a main component. In the polyimide precursor, the content ratio of the structural unit represented by general formula (3) in the structural units derived from all carboxylic acids and derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the content ratio is in the above range, the resolution can be improved.

[0158] <Polybenzoxazole and polybenzoxazole precursor>

[0159] In the negative photosensitive resin composition of the present application, the so-called (Alb-1) polybenzoxazole refers to the general polybenzoxazole described below.

[0160] In the negative photosensitive resin composition of the present application, the so-called (Alb-2) polybenzoxazole precursor refers to the general polybenzoxazole precursor described below.

[0161] As the (Alb-2) polybenzoxazole precursor, for example, a product obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, or a dicarboxylic acid active diester, etc. with a bisamino phenol compound as a diamine, etc. can be mentioned, which has a dicarboxylic acid and / or a derivative residue thereof, and a bisamino phenol compound and / or a derivative residue thereof. As the (Alb-2) polybenzoxazole precursor, for example, a polyhydroxy amide can be mentioned.

[0162] As the (Alb-l) polybenzoxazole, for example, a product obtained by dehydrating and ring-closing a dicarboxylic acid with a bisamino phenol compound as a diamine by a reaction using polyphosphoric acid, a product obtained by dehydrating and ring-closing the above polyhydroxy amide by heating or a reaction using a phosphoric acid anhydride, a base, or a carbodiimide compound, etc. can be mentioned; which has a dicarboxylic acid and / or a derivative residue thereof, and a bisamino phenol compound and / or a derivative residue thereof.

[0163] The (Alb-2) polybenzoxazole precursor is a thermosetting resin, and by thermally curing it at a high temperature, dehydrating and ring-closing is performed, thereby forming a benzoxazole ring having high heat resistance and rigidity, and a (Alb-l) polybenzoxazole is obtained. Therefore, by making the resin composition contain the (Alb-l) polybenzoxazole having the benzoxazole ring having high heat resistance and rigidity, the heat resistance of the obtained cured film can be significantly improved. Therefore, it is suitable for a case where the cured film is used for a use requiring high heat resistance, etc. In addition, the (Alb-2) polybenzoxazole precursor is a resin whose heat resistance is improved after dehydrating and ring-closing, and therefore it is suitable for a case where it is used in a use where it is desired to simultaneously achieve the properties of the precursor structure before dehydrating and ring-closing and the heat resistance of the cured film, etc.

[0164] In addition, the (Alb-l) polybenzoxazole and the (Alb-2) polybenzoxazole precursor have an oxazole bond and / or an amide bond as a polar bond. Therefore, especially in a case where the (Dl) pigment is contained as the (D) colorant described later, these polar bonds strongly interact with the (Dl) pigment, and therefore the dispersion stability of the (Dl) pigment can be improved.

[0165] The (Alb-l) polybenzoxazole and the (Alb-2) polybenzoxazole precursor used in the present application have a phenolic hydroxyl group as a base-soluble group. By having a phenolic hydroxyl group, the half-tone properties can be improved. In addition to the phenolic hydroxyl group, one or more weakly acidic groups selected from a silanol group, a hydroxy imide group, and a hydroxy amide group can be present.

[0166] The (A2b-1) unsaturated group-containing polybenzoxazole and the (A2b-2) unsaturated group-containing polybenzoxazole precursor used in the present application have an ethylenically unsaturated double bond group as a radical polymerizable group. By having an ethylenically unsaturated double bond group, sensitivity at the time of exposure can be improved. As the (A2b-1) unsaturated group-containing polybenzoxazole and the (A2b-2) unsaturated group-containing polybenzoxazole precursor, a product obtained by reacting a part of the phenolic hydroxyl group and / or the carboxyl group of the (Alb-1) polybenzoxazole and the (Alb-2) polybenzoxazole precursor with a compound having an ethylenically unsaturated double bond group is preferable. By the above reaction, an ethylenically unsaturated double bond group can be introduced into the side chain of the resin.

[0167] From the viewpoint of improving the heat resistance of the cured film, the (Alb-1) polybenzoxazole used in the present application preferably contains a structural unit represented by General Formula (2).

[0168] [Chemical Formula 4]

[0169]

[0170] (In General Formula (2), R 5 represents a 2- to 10-valent dicarboxylic acid and / or a derivative residue thereof, R 6 represents a 4- to 10-valent bisphenolic compound having an aromatic structure and / or a derivative residue thereof. R 7 and R 8 each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above General Formula (5) or the above General Formula (6). r represents an integer of 0 to 8, and s represents an integer of 0 to 6.)

[0171] In General Formula (2), R 5 represents a dicarboxylic acid and / or a derivative residue thereof, R 6 represents a bisphenolic compound and / or a derivative residue thereof. As the dicarboxylic acid derivative, a dicarboxylic anhydride, a dicarboxylic acid chloride, a dicarboxylic acid active ester, a tricarboxylic anhydride, a tricarboxylic acid chloride, a tricarboxylic acid active ester, or a dicarboxylic compound can be mentioned.

[0172] In General Formula (2), R 5 represents a 2- to 10-valent dicarboxylic acid and / or a derivative residue thereof, R 6 represents a 4- to 10-valent bisphenolic compound having an aromatic structure and / or a derivative residue thereof. R 7 and R 8 each independently represent a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above General Formula (5) or the above General Formula (6). r represents an integer of 0 to 8, and s represents an integer of 0 to 6. In General Formula (2), R 5The 2- to 10-valent organic group preferably has one or more of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms, and more preferably has one or more of an aliphatic structure having 4 to 15 carbon atoms, an alicyclic structure having 4 to 15 carbon atoms, and an aromatic structure having 6 to 25 carbon atoms. In addition, R 6 The 4- to 10-valent organic group preferably has an aromatic structure having 6 to 30 carbon atoms, and more preferably has an aromatic structure having 6 to 25 carbon atoms. s is preferably 1 to 8. The above-mentioned aliphatic structure, alicyclic structure, and aromatic structure can have a hetero atom, and can be any of unsubstituted or substituted.

[0173] As the (Alb-1) polybenzoxazole, it is preferable to contain a structural unit represented by General Formula (2) as a main component. In the polybenzoxazole, the content ratio of the structural unit represented by General Formula (2) among the structural units derived from all amines and derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the content ratio is in the above-mentioned range, the heat resistance of the cured film can be improved.

[0174] As the (Alb-2) polybenzoxazole precursor used in the present application, it is preferable to contain a structural unit represented by General Formula (4) from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development.

[0175] [Chemical Formula 5]

[0176]

[0177] (In General Formula (4), R 14 represents a 2- to 10-valent dicarboxylic acid and / or a derivative residue thereof, R 15 represents a 4- to 10-valent bisaminophenol compound having an aromatic structure and / or a derivative residue thereof. R 16 represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above General Formula (5) or General Formula (6), R 17 represents a phenolic hydroxyl group, R 18 represents a sulfonic acid group, a mercapto group, or a substituent represented by the above General Formula (5) or General Formula (6). w represents an integer of 0 to 8, x represents an integer of 2 to 8, y represents an integer of 0 to 6, and 2 ≤ x + y ≤ 8.

[0178] R 14 represents a dicarboxylic acid and / or a derivative residue thereof, R 15represents a residue of a diamino phenol compound and / or a derivative thereof. As a dicarboxylic acid derivative, a dicarboxylic anhydride, a dicarboxylic acid chloride, a dicarboxylic acid active ester, a tricarboxylic anhydride, a tricarboxylic acid chloride, a tricarboxylic acid active ester, a dicarboxylic compound can be mentioned.

[0179] In General Formula (4), R 14 represents a residue of a 2- to 10-valent dicarboxylic acid and / or a derivative thereof, R 15 represents a residue of a 4- to 10-valent diamino phenol compound having an aromatic structure and / or a derivative thereof. R 16 represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by General Formula (5) or General Formula (6) above, R 17 represents a phenolic hydroxyl group, R 18 represents a sulfonic acid group, a mercapto group, or a substituent represented by General Formula (5) or General Formula (6) above. w represents an integer of 0 to 8, x represents an integer of 2 to 8, and y represents an integer of 0 to 6, with 2 ≤ x + y ≤ 8. In General Formula (4), R 14 is preferably a 2- to 10-valent organic group having one or more kinds of structures selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms, and more preferably a 2- to 10-valent organic group having one or more kinds of structures selected from the group consisting of an aliphatic structure having 4 to 15 carbon atoms, an alicyclic structure having 4 to 15 carbon atoms, and an aromatic structure having 6 to 25 carbon atoms. In addition, R 15 is preferably a 4- to 10-valent organic group having an aromatic structure having 6 to 30 carbon atoms, and more preferably a 4- to 10-valent organic group having an aromatic structure having 6 to 25 carbon atoms. The aliphatic structure, the alicyclic structure, and the aromatic structure described above can have a hetero atom, and can be any of an unsubstituted form or a substituted form.

[0180] As the (Alb-2) polybenzoxazole precursor, it is preferable to contain a structural unit represented by General Formula (4) as a main component. In the polybenzoxazole precursor, the content ratio of the structural unit represented by General Formula (4) among the structural units derived from all amines and derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the content ratio is in the above range, the resolution can be improved.

[0181] <Quaternary carboxylic acid, tricarboxylic acid, and dicarboxylic acid and derivatives thereof>

[0182] The (Ala-l) polyimide and / or (Ala-2) polyimide precursor can contain the following tetra carboxylic acid and / or derivatives thereof. As the tetra carboxylic acid, for example, an aromatic tetra carboxylic acid, an alicyclic tetra carboxylic acid, or an aliphatic tetra carboxylic acid can be given. These tetra carboxylic acids can have a hetero atom other than an oxygen atom in addition to the oxygen atom of the carboxyl group.

[0183] As the aromatic tetra carboxylic acid and derivatives thereof, for example, 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 2,3,5,6-pyridinetetracarboxylic acid or 3,4,9,10-perylenetetracarboxylic acid, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3,4-dicarboxybenzamide), and the like compounds of the following structure, or their tetra carboxylic dianhydride, tetra carboxylic acid dichloride, or tetra carboxylic acid active diester can be given.

[0184] [Chemical Formula 6]

[0185]

[0186] In the compound of the above structure, Y 66 represents a direct bond, an oxygen atom, or an alkylene chain having 1 to 4 carbon atoms. Y 66 In the case where Y 66 is an alkylene chain having 1 to 4 carbon atoms, R 230 and R 231 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 8 fluorine atoms. R 232 and R 233 each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group. a and b each independently represent an integer of 0 to 4. The above alkylene chain, alkyl group can be any of unsubstituted or substituted.

[0187] As alicyclic tetracarboxylic acids and derivatives thereof, for example, dicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, or 2,3,4,5-tetrahydrofurantetracarboxylic acid, or tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid active diesters thereof can be mentioned.

[0188] As aliphatic tetracarboxylic acids and derivatives thereof, for example, butane-1,2,3,4-tetracarboxylic acid, or tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid active diesters thereof can be mentioned.

[0189] As dicarboxylic acids and derivatives thereof in (Alb-1) polybenzoxazoles and (Alb-2) polybenzoxazole precursors, tricarboxylic acids and / or derivatives thereof can be used.

[0190] As dicarboxylic acids and tricarboxylic acids, for example, aromatic dicarboxylic acids, aromatic tricarboxylic acids, alicyclic dicarboxylic acids, alicyclic tricarboxylic acids, aliphatic dicarboxylic acids, or aliphatic tricarboxylic acids can be mentioned. These dicarboxylic acids and tricarboxylic acids can have heteroatoms other than oxygen atoms in addition to oxygen atoms of carboxyl groups.

[0191] As aromatic dicarboxylic acids and derivatives thereof, for example, phthalic acid, isophthalic acid, terephthalic acid, 4,4'-dicarboxybiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-dicarboxybiphenyl, 4,4'-benzophenonedicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(3-carboxyphenyl)hexafluoropropane, or 4,4'-dicarboxy diphenyl ether, or dicarboxylic anhydrides, dicarboxylic acid chlorides, active esters of dicarboxylic acids, or dicarboxylic compounds thereof can be mentioned.

[0192] As aromatic tricarboxylic acids and derivatives thereof, for example, 1,2,4-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, 2,4,5-benzophenone tricarboxylic acid, 2,4,4'-biphenyl tricarboxylic acid, or 3,3',4'-tricarboxy diphenyl ether, or tricarboxylic anhydrides, tricarboxylic acid chlorides, active esters of tricarboxylic acids, or dicarboxylic monocarboxylic acids thereof can be mentioned.

[0193] As alicyclic dicarboxylic acids and derivatives thereof, for example, 1,4-cyclohexanedicarboxylic acid or 1,2-cyclohexanedicarboxylic acid, or dicarboxylic anhydrides, dicarboxylic acid chlorides, active esters of dicarboxylic acids, or dicarboxylic compounds thereof can be mentioned.

[0194] As alicyclic tricarboxylic acids and derivatives thereof, for example, 1,2,4-cyclohexanetricarboxylic acid or 1,3,5-cyclohexanetricarboxylic acid, or tricarboxylic anhydrides, tricarboxylic acid chlorides, active esters of tricarboxylic acids, or dicarboxylic monocarboxylic acids thereof can be mentioned.

[0195] As the aliphatic dicarboxylic acid and derivatives thereof, for example, hexane-1, 6-dicarboxylic acid or succinic acid, or a dicarboxylic anhydride, a dicarboxylic acid chloride, a dicarboxylic acid active ester, or a dicarboxylic compound thereof can be mentioned.

[0196] As the aliphatic tricarboxylic acid and derivatives thereof, for example, hexane-1, 3, 6-tricarboxylic acid or propane-1, 2, 3-tricarboxylic acid, or a tricarboxylic anhydride, a tricarboxylic acid chloride, a tricarboxylic acid active ester, or a dicarboxylic monocarboxylic acid thereof can be mentioned.

[0197] <Di-amine and derivatives thereof>

[0198] As the di-amine and derivatives thereof, for example, an aromatic di-amine, a bis-amino phenol compound, an alicyclic di-amine, an alicyclic di-hydroxy di-amine, an aliphatic di-amine, or an aliphatic di-hydroxy di-amine can be mentioned. These di-amines and derivatives thereof can have hetero atoms other than the nitrogen atom and the oxygen atom possessed by the amino group and derivatives thereof.

[0199] As the aromatic diamine and bisamino phenol compounds and their derivatives, for example, there can be mentioned m-phenylenediamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-diaminobiphenyl, bis(4-aminophenoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,3'-diamino-4,4'-biphenol, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis(3-amino-4-hydroxyphenyl)methane, 1,1-bis(3-amino-4-hydroxyphenyl)ethane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, bis[4-(4-aminophenoxy)phenyl] ether, bis(3-amino-4-hydroxyphenyl) ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, or dimercaptobenzene diamine, N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3-aminobenzamide), and the like compounds of the following structures or their diisocyanate compounds or trimethylsilylated diamines.

[0200] [Chemical Formula 7]

[0201]

[0202] In the compounds of the above structures, Y 67 and Y 68 each independently represent a direct bond, an oxygen atom, or an alkylene chain having 1 to 4 carbon atoms. Y 67 and Y 68 are a direct bond or an oxygen atom, a, b, c, and d are 0. Y 67 and Y 68 are an alkylene chain having 1 to 4 carbon atoms, R 234 to R 237each independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 8 fluorine atoms and having 1 to 4 carbon atoms. R 238 ~R 250 each independently represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group. a, b, c, and d each independently represent an integer of 0 to 4. The above-mentioned alkylene chain, alkyl group can be any of unsubstituted or substituted.

[0203] As the alicyclic diamine and alicyclic dihydroxydiamine and derivatives thereof, for example, a compound obtained by substituting a part of hydrogen atoms of the aromatic ring of the above-mentioned aromatic diamine and bisamino phenol compound with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, or a halogen atom, 1,2-cyclohexane diamine, 1,4-cyclohexane diamine, bis(4-aminocyclohexyl)methane, 3,6-dihydroxy-1,2-cyclohexane diamine, 2,5-dihydroxy-1,4-cyclohexane diamine, or bis(3-hydroxy-4-aminocyclohexyl)methane, or a diisocyanate compound or trimethylsilylated diamine thereof can be given.

[0204] As the aliphatic diamine and aliphatic dihydroxydiamine and derivatives thereof, for example, 1,6-hexanediamine or 2,5-dihydroxy-1,6-hexanediamine, or a diisocyanate compound or trimethylsilylated diamine thereof can be given.

[0205] <Structural Unit Having Fluorine Atom>

[0206] One or more selected from (Ala-1) polyimide, (Alb-1) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor preferably contain a structural unit having a fluorine atom. By causing one or more selected from polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor to contain a structural unit having a fluorine atom, the transparency is improved, and the sensitivity at the time of exposure can be improved. In addition, water repellency can be imparted to the film surface, and the penetration from the film surface at the time of alkali development can be suppressed. Here, the exposure refers to irradiation of active actinic rays (radiation), and for example, irradiation of visible light, ultraviolet rays, electron beams, or X-rays, or the like can be given. From the viewpoint that a light source is usually used, a super-high-pressure mercury lamp light source capable of irradiating, for example, visible light, ultraviolet rays is preferred, and irradiation of j line (wavelength 313 nm), i line (wavelength 365 nm), h line (wavelength 405 nm), or g line (wavelength 436 nm) is more preferred. Hereinafter, the exposure refers to irradiation of active actinic rays (radiation).

[0207] Further, in the case of using (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, or (Alb-2) polybenzoxazole precursor, in general, it is necessary to use N-methyl-2-pyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, or γ-butyrolactone, or the like, which is a high-polar solvent, as a solvent for dissolving these resins. However, in particular, in the case of containing (Dl) pigment as (D) colorant described later, these high-polar solvents strongly interact with (Dl) pigment, and thus there is a case where the effect of improving dispersion stability by (Al) resin containing a weakly acidic group, (A2) resin containing an unsaturated group, or (E) dispersant described later is insufficient.

[0208] By containing one or more kinds selected from (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor, which contain a structural unit having a fluorine atom, it is possible to improve the solubility in a solvent. Thus, it is possible to reduce the content of the aforementioned high-polar solvent, or it is possible to dissolve these resins without using a high-polar solvent, and it is possible to improve the dispersion stability of (Dl) pigment.

[0209] As the structural unit having a fluorine atom contained in (Ala-l) polyimide and / or (Ala-2) polyimide precursor, a structural unit derived from a tetracarboxylic acid having a fluorine atom and / or a derivative thereof, or a structural unit derived from a diamine having a fluorine atom and / or a derivative thereof can be mentioned.

[0210] As the structural unit having a fluorine atom contained in (Alb-l) polybenzoxazole and / or (Alb-2) polybenzoxazole precursor, a structural unit derived from a dicarboxylic acid having a fluorine atom and / or a derivative thereof, or a structural unit derived from a bisaminophenol compound having a fluorine atom and / or a derivative thereof can be mentioned.

[0211] As the tetracarboxylic acid having a fluorine atom and derivatives thereof, for example, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, or N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3,4-dicarboxybenzamide), or a tetracarboxylic dianhydride, tetracarboxylic acid dichloride, or tetracarboxylic acid active diester thereof can be mentioned.

[0212] As the dicarboxylic acid having a fluorine atom and derivatives thereof, for example, 2,2'-bis(trifluoromethyl)-4,4'-dicarboxybiphenyl, 2,2-bis(4-carboxyphenyl)hexafluoropropane, or 2,2-bis(3-carboxyphenyl)hexafluoropropane, or a dicarboxylic anhydride, dicarboxylic acid chloride, dicarboxylic acid active ester, or dimethyl compound thereof can be mentioned.

[0213] As the diamine or bisamino phenol compound having a fluorine atom and their derivatives, for example, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis(4- aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, or N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3- aminobenzamide) or their diisocyanate compounds or trimethylsilylated diamines can be mentioned.

[0214] In the one or more resins selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor, the contained ratio of the structural unit from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tetracarboxylic acid derivative having a fluorine atom, dicarboxylic acid having a fluorine atom, and dicarboxylic acid derivative having a fluorine atom, in the structural units from all carboxylic acids and their derivatives, is preferably in the range of 30 to 100 mol%, more preferably in the range of 50 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the contained ratio is in the above range, the sensitivity at the time of exposure can be improved.

[0215] In the one or more resins selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor, the contained ratio of the structural unit from one or more selected from the group consisting of diamine having a fluorine atom, diamine derivative having a fluorine atom, bisamino phenol compound having a fluorine atom, and bisamino phenol compound derivative having a fluorine atom, in the structural units from all amines and their derivatives, is preferably in the range of 30 to 100 mol%, more preferably in the range of 50 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the contained ratio is in the above range, the sensitivity at the time of exposure can be improved.

[0216] <Structural unit from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tetracarboxylic acid derivative having a fluorine atom, dicarboxylic acid having a fluorine atom, and dicarboxylic acid derivative having a fluorine atom>

[0217] In the (Ala-l) polyimide and / or (Ala-2) polyimide precursor, it is preferable to contain the structural unit represented by General Formula (16) and / or the structural unit represented by General Formula (17) as the structural unit from tetracarboxylic acid having a fluorine atom and its derivatives.

[0218] In the (Ala-l) polyimide and / or (Ala-2) polyimide precursor, it is more preferable that R 1 or R 9contains a structural unit represented by General Formula (16) and / or a structural unit represented by General Formula (17).

[0219] [Chemical Formula 8]

[0220]

[0221] In General Formulas (16) and (17), R 40 , R 41 , R 44 , and R 45 each independently represent a substituent represented by the above General Formula (5) or the above General Formula (6), R 42 , R 43 , R 46 , and R 47 each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group. X 9 ~ X 12 each independently represent a direct bond, an oxygen atom, or a bond represented by General Formula (20). X 9 ~ X 12 In the case of a direct bond, Y 9 ~ Y 12 each independently represent a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. X 9 ~ X 12 In the case of an oxygen atom or a bond represented by General Formula (20), Y 9 ~ Y 12 each independently represent an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. a to d each independently represent an integer of 0 to 4, e to h each independently represent an integer of 0 to 3, 0 ≤ a + c ≤ 4, 0 ≤ b + d ≤ 4, 0 ≤ e + g ≤ 3, and 0 ≤ f + h ≤ 3. In General Formulas (16) and (17), R 42 , R 43 , R 46 , and R 47 each independently are preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group. Y 9 ~ Y 12 each independently are preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. The above alkyl group, cycloalkyl group, aryl group, alkylene chain, cycloalkylene chain, and arylene chain can be any of unsubstituted forms or substituted forms.

[0222] [Chemical Formula 9]

[0223]

[0224] In General Formula (20), R 38 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. In General Formula (20), R 38 is preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The alkyl group, the acyl group, and the aryl group described above can be any of unsubstituted forms or substituted forms.

[0225] In the (Alb-l) polybenzoxazole and / or the (Alb-2) polybenzoxazole precursor, it is preferable to contain a structural unit represented by General Formula (18) and / or a structural unit represented by General Formula (19) as a structural unit derived from a dicarboxylic acid having a fluorine atom and derivatives thereof.

[0226] In the (Alb-l) polybenzoxazole and / or the (Alb-2) polybenzoxazole precursor, it is more preferable that R 5 of General Formula (2) and / or R 14 of General Formula (4).

[0227] [Chemical Formula 10]

[0228]

[0229] In General Formulae (18) and (19), R 48 , R 49 , R 52 , and R 53 each independently represent a substituent represented by the above General Formula (5) or the above General Formula (6), R 50 , R 51 , R 54 , and R 55 each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group. X 13 , X 16 each independently represent a direct bond, an oxygen atom, or a bond represented by the above General Formula (20). X 13 , X 16 In the case where Y 13 , Y 16 each independently represent a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. X 13 , X 16Y represents an oxygen atom or a bond represented by the above general formula (20), and 13 ~Y 16 each independently represents an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. Each of a to d independently represents an integer of 0 to 4, each of e to h independently represents an integer of 0 to 3, 0 ≤ a + c ≤ 4, 0 ≤ b + d ≤ 4, 0 ≤ e + g ≤ 3, and 0 ≤ f + h ≤ 3. In general formulae (18) and (19), R 50 , R 51 , R 54 , and R 55 each independently preferably is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group. Y 13 ~Y 16 each independently preferably is a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. The above-mentioned alkyl group, cycloalkyl group, aryl group, alkylene chain, cycloalkylene chain, and arylene chain can be any of unsubstituted forms or substituted forms.

[0230] <Structural unit derived from one or more selected from the group consisting of a diamine having a fluorine atom, a diamine derivative having a fluorine atom, a bisaminophenol compound having a fluorine atom, and a bisaminophenol compound derivative having a fluorine atom>

[0231] In the (Ala-l) polyimide and / or (Ala-2) polyimide precursor, it is preferable to contain a structural unit represented by general formula (12) and / or a structural unit represented by general formula (13) as the structural unit derived from a diamine having a fluorine atom and a derivative thereof.

[0232] In the (Ala-l) polyimide and / or (Ala-2) polyimide precursor, it is more preferable that R 2 or R 10 of general formula (3) contain a structural unit represented by general formula (12) and / or a structural unit represented by general formula (13).

[0233] [Chemical Formula 11]

[0234]

[0235] In general formulae (12) and (13), R 30 ~R 33 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a sulfonic acid group, a carboxyl group, or a mercapto group. X 1 ~X 4Each independently represents a direct bond, an oxygen atom, or a bond represented by the above general formula (20). X 1 ~ X 4 In the case of a direct bond, Y 1 ~ Y 4 Each independently represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. X 1 ~ X 4 In the case of an oxygen atom or a bond represented by the above general formula (20), Y 1 ~ Y 4 Each independently represents an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. a to d and α to δ each independently represent an integer of 0 to 4, e to h each independently represent an integer of 0 to 3, 0 ≤ a + c ≤ 4, 0 ≤ b + d ≤ 4, 0 ≤ e + g ≤ 3, and 0 ≤ f + h ≤ 3. Y 1 ~ Y 4 In the case of a direct bond, α to δ are 0. In general formulae (12) and (13), R 30 ~ R 33 Each independently is preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, a sulfonic acid group, a carboxyl group, or a mercapto group. Y 1 ~ Y 4 Each independently is preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. a and b each independently are preferably 1 to 4. e and f each independently are preferably 1 to 3. The above alkyl group, cycloalkyl group, aryl group, alkylene chain, cycloalkylene chain, and arylene chain can be any of unsubstituted or substituted ones.

[0236] In the (Alb-l) polybenzoxazole and / or (Alb-2) polybenzoxazole precursor, it is preferable to contain a structural unit represented by general formula (14) and / or a structural unit represented by general formula (15) as a structural unit derived from a bisamino phenol compound having a fluorine atom and derivatives thereof.

[0237] In the (Alb-l) polybenzoxazole and / or (Alb-2) polybenzoxazole precursor, it is more preferable that R 6 or R 15 of general formula (4) contain a structural unit represented by general formula (14) and / or a structural unit represented by general formula (15).

[0238] [Chemical Formula 12]

[0239]

[0240] In General Formulae (14) and (15), R 34 ~R 37 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a sulfonic acid group, a carboxyl group, or a mercapto group. X 5 ~X 8 each independently represents a direct bond, an oxygen atom, or a bond represented by the above General Formula (20). X 5 ~X 8 In the case of a direct bond, Y 5 ~Y 8 each independently represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. X 5 ~X 8 In the case of an oxygen atom or a bond represented by the above General Formula (20), Y 5 ~Y 8 each independently represents an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. a to d and ε to θ each independently represent an integer of 0 to 4, e to h each independently represent an integer of 0 to 3, 0 ≤ a + c ≤ 4, 0 ≤ b + d ≤ 4, 0 ≤ e + g ≤ 3, and 0 ≤ f + h ≤ 3. Y 5 ~Y 8 In the case of a direct bond, ε to θ are 0. In General Formulae (14) and (15), R 34 ~R 37 each independently preferably is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, a sulfonic acid group, a carboxyl group, or a mercapto group. Y 5 ~Y 8 each independently preferably is a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. a and b each independently preferably are 1 to 4. e and f each independently preferably are 1 to 3. The above alkyl group, cycloalkyl group, aryl group, alkylene chain, cycloalkylene chain, and arylene chain can be any of unsubstituted forms or substituted forms.

[0241] <Structural units from aromatic, alicyclic, and aliphatic carboxylic acids and derivatives thereof>

[0242] (A1a-1) polyimide and / or (A1a-2) polyimide precursor preferably contains a structural unit derived from an aromatic tetracarboxylic acid and / or a derivative thereof. By making (A1a-1) polyimide and / or (A1a-2) polyimide precursor contain a structural unit derived from an aromatic carboxylic acid and / or a derivative thereof, it is possible to utilize the heat resistance of the aromatic group to improve the heat resistance of the cured film. As the aromatic carboxylic acid and the derivative thereof, an aromatic tetracarboxylic acid and / or a derivative thereof is preferable.

[0243] In (A1a-1) polyimide, the content ratio of the structural unit derived from an aromatic tetracarboxylic acid and / or a derivative thereof in the structural units derived from all carboxylic acids and derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the content ratio is in the above range, it is possible to improve the heat resistance of the cured film.

[0244] In (A1a-2) polyimide precursor, the content ratio of the structural unit derived from an aromatic tetracarboxylic acid and / or a derivative thereof in the structural units derived from all carboxylic acids and derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the content ratio is in the above range, it is possible to improve the heat resistance of the cured film.

[0245] (A1a-1) polyimide and / or (A1a-2) polyimide precursor can contain a structural unit derived from an alicyclic carboxylic acid or an aliphatic carboxylic acid and / or a derivative thereof. As the alicyclic carboxylic acid or the aliphatic carboxylic acid and the derivative thereof, an alicyclic tetracarboxylic acid or an aliphatic tetracarboxylic acid and / or a derivative thereof is preferable.

[0246] (A1b-1) polybenzoxazole and / or (A1b-2) polybenzoxazole precursor preferably contains a structural unit derived from an aromatic carboxylic acid and / or a derivative thereof. By making (A1b-1) polybenzoxazole and / or (A1b-2) polybenzoxazole precursor contain a structural unit derived from an aromatic carboxylic acid and / or a derivative thereof, it is possible to utilize the heat resistance of the aromatic group to improve the heat resistance of the cured film. As the aromatic carboxylic acid and the derivative thereof, an aromatic dicarboxylic acid or an aromatic tricarboxylic acid and / or a derivative thereof is preferable, and more preferably an aromatic dicarboxylic acid and / or a derivative thereof.

[0247] In (A1b-1) polybenzoxazole, the content ratio of the structural unit derived from an aromatic carboxylic acid and / or a derivative thereof in the structural units derived from all carboxylic acids and derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the content ratio is in the above range, it is possible to improve the heat resistance of the cured film.

[0248] (A1b-2) In the polybenzoxazole precursor, the contained ratio of the structural units derived from the aromatic carboxylic acid and / or the derivative thereof among the structural units derived from all the carboxylic acids and the derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the contained ratio is in the above range, the heat resistance of the cured film can be improved.

[0249] (A1b-1) The polybenzoxazole and / or (A1b-2) the polybenzoxazole precursor can contain a structural unit derived from an alicyclic carboxylic acid or an aliphatic carboxylic acid and / or a derivative thereof. As the alicyclic carboxylic acid or the aliphatic carboxylic acid and the derivative thereof, an alicyclic dicarboxylic acid, an aliphatic dicarboxylic acid, an alicyclic tricarboxylic acid or an aliphatic tricarboxylic acid, and / or a derivative thereof is preferable, and an alicyclic dicarboxylic acid or an aliphatic dicarboxylic acid and / or a derivative thereof is more preferable.

[0250] <Structural units derived from aromatic, alicyclic and aliphatic amines and derivatives thereof>

[0251] One or more selected from the group consisting of (A1a-1) the polyimide, (A1b-1) the polybenzoxazole, (A1a-2) the polyimide precursor and (A1b-2) the polybenzoxazole precursor preferably contains a structural unit derived from an aromatic amine and / or a derivative thereof. By causing one or more selected from the group consisting of (A1a-1) the polyimide, (A1b-1) the polybenzoxazole, (A1a-2) the polyimide precursor and (A1b-2) the polybenzoxazole precursor to contain a structural unit derived from an aromatic amine and / or a derivative thereof, the heat resistance of the cured film can be improved using the heat resistance of the aromatic group. As the aromatic amine and the derivative thereof, an aromatic diamine, a bisamino phenol compound, an aromatic triamine or a triamino phenol compound, and / or a derivative thereof is preferable, and an aromatic diamine or a bisamino phenol compound and / or a derivative thereof is more preferable.

[0252] In the resin of one or more selected from the group consisting of (A1a-1) the polyimide, (A1b-1) the polybenzoxazole, (A1a-2) the polyimide precursor and (A1b-2) the polybenzoxazole precursor, the contained ratio of the structural units derived from the aromatic amine and / or the derivative thereof among the structural units derived from all the amines and the derivatives thereof is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the contained ratio is in the above range, the heat resistance of the cured film can be improved.

[0253] One or more selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor can contain a structural unit derived from alicyclic amine or aliphatic amine and / or a derivative thereof. As the alicyclic amine or aliphatic amine and the derivative thereof, an alicyclic diamine, alicyclic dihydroxydiamine, aliphatic diamine, or aliphatic dihydroxydiamine and / or a derivative thereof is preferable.

[0254] <Structural unit derived from diamine having silyl or siloxane bond and derivative thereof>

[0255] One or more selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor preferably contains a structural unit derived from diamine having silyl or siloxane bond and / or a derivative thereof. By containing a structural unit derived from diamine having silyl or siloxane bond and / or a derivative thereof in one or more selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor, the adhesion to the base substrate and the chemical resistance of the cured film can be improved due to the increased interaction at the interface between the cured film of the resin composition and the base substrate.

[0256] As the diamine having silyl or siloxane bond and the derivative thereof, 1,3-bis(3- aminopropyl)tetramethyldisiloxane or 1,9-bis(4-aminophenyl)octamethylpentasiloxane, for example, can be given.

[0257] In the resin of one or more selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor, the content ratio of the structural unit derived from diamine having silyl or siloxane bond and / or a derivative thereof in the structural units derived from all amines and derivatives thereof is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and further preferably 1 mol% or more. When the content ratio is within the above range, the adhesion to the base substrate and the chemical resistance of the cured film can be improved. On the other hand, the content ratio of the structural unit derived from diamine having silyl or siloxane bond and / or a derivative thereof is preferably 30 mol% or less, more preferably 20 mol% or less, and further preferably 10 mol% or less. When the content ratio is within the above range, the heat resistance of the cured film can be improved.

[0258] <Structural unit derived from amine having oxyalkylene structure and derivative thereof>

[0259] It is preferable that one or more selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor contain a structural unit derived from an amine having an oxyalkylene structure and / or a derivative thereof. By causing one or more selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor to contain a structural unit derived from an amine having an oxyalkylene structure and / or a derivative thereof, it is possible to obtain a pattern shape with low taper, and it is possible to improve the mechanical properties of the cured film.

[0260] As the amine having an oxyalkylene structure and the derivative thereof, it is preferable that a diamine having an oxyalkylene structure or a triamine having an oxyalkylene structure and / or a derivative thereof be used.

[0261] It is preferable that one or more selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor contain a structural unit represented by General Formula (21) as a structural unit derived from a diamine having an oxyalkylene structure and a derivative thereof.

[0262] In (Ala-l) polyimide and / or (Ala-2) polyimide precursor, it is more preferable that R 2 or R 10 contains a structural unit represented by General Formula (21) below.

[0263] [Chemical Formula 13]

[0264]

[0265] In General Formula (21), X 65 represents a direct bond or an alkylene chain having 1 to 10 carbon atoms. R 138 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a and b each independently represent an integer of 1 to 10. In General Formula (21), X 65 represents a direct bond or an alkylene chain having 1 to 6 carbon atoms. R 138 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms. a preferably represents an integer of 1 to 6. The above-described alkylene chain, alkyl group, cycloalkyl group, and aryl group can be any of unsubstituted forms or substituted forms.

[0266] As the triamine having an oxyalkylene structure and the derivative thereof, it is preferable that a compound represented by General Formula (22) below be used.

[0267] [Chemical Formula 14]

[0268]

[0269] In General Formula (22), X 66 ~ X 68 each independently represents a direct bond or an alkylene chain having 1 to 10 carbon atoms, Y 65 represents methine, an alkane-1, 1, 1-triyl group having 1 to 10 carbon atoms, a cycloalkane triyl group having 4 to 10 carbon atoms, or an arene triyl group having 6 to 15 carbon atoms. R 139 ~ R 147 each independently represents hydrogen or an alkyl group having 1 to 10 carbon atoms. c, d, e, f, g, and h each independently represents an integer of 1 to 10. In General Formula (22), X 66 ~ X 68 each independently preferably represents a direct bond or an alkylene chain having 1 to 6 carbon atoms. In addition, Y 65 preferably represents methine, an alkane-1, 1, 1-triyl group having 1 to 6 carbon atoms, a cycloalkane triyl group having 4 to 7 carbon atoms, or an arene triyl group having 6 to 10 carbon atoms. In addition, R 139 ~ R 147 each independently preferably represents hydrogen or an alkyl group having 1 to 6 carbon atoms. In addition, c, d, and e each independently preferably represents an integer of 1 to 6. The above alkyl group, alkylene chain, alkane-1, 1, 1-triyl group, cycloalkane triyl group, or arene triyl group can be any of unsubstituted or substituted.

[0270] As diamines having an oxyalkylene structure and derivatives thereof, for example, "JEFFAMINE" (registered trademark) D-230, JEFFAMINE D-400, JEFFAMINE D-2000, JEFFAMINE D-4000, JEFFAMINE HK-511, JEFFAMINE ED-600, JEFFAMINE ED-900, JEFFAMINE ED-2003, JEFFAMINE EDR-148, JEFFAMINE EDR-176, JEFFAMINE SD-231, JEFFAMINE SD-401, JEFFAMINE SD-2001, JEFFAMINE THF-100, JEFFAMINE THF-140, JEFFAMINE THF-170, JEFFAMINE XTJ-582, JEFFAMINE XTJ-578, JEFFAMINE XTJ-542, JEFFAMINE XTJ-548, or JEFFAMINE XTJ-559, or "ELASTAMINE" (registered trademark) RP-405, ELASTAMINE RP-409, ELASTAMINE RP-2005, ELASTAMINE RP-2009, ELASTAMINE RT-1000, ELASTAMINE RE-600, ELASTAMINE RE-900, ELASTAMINE RE-2000, ELASTAMINE HE-150, ELASTAMINE HE-180, ELASTAMINE HE-1700, ELASTAMINE HT-1700, ELASTAMINE RE1-1000, ELASTAMINE RE1-2005, ELASTAMINE RE1-2007, ELASTAMINE RP3-400, or ELASTAMINE RP3-5000 (all of which are manufactured by HUNTSMAN Corporation) can be given.

[0271] As triamines having an oxyalkylene structure and derivatives thereof, for example, "JEFFAMINE" (registered trademark) T-403, JEFFAMINE T-3000, JEFFAMINE T-5000, or JEFFAMINE ST-404 (all of which are manufactured by HUNTSMAN Corporation) can be given.

[0272] The content ratio of the structural unit derived from the amine having an oxyalkylene structure and / or its derivative is preferably 1 mol% or more, more preferably 5 mol% or more, and further preferably 10 mol% or more, in the total structural units derived from the amine and its derivative, in the resin selected from one or more of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor. When the content ratio is within the above range, a pattern shape with low taper can be obtained, and the mechanical properties of the cured film can be improved. On the other hand, the content ratio of the structural unit derived from the amine having an oxyalkylene structure and / or its derivative is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. When the content ratio is within the above range, the heat resistance of the cured film can be improved.

[0273] <End-capping agent>

[0274] The terminal of the resin selected from one or more of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor can be capped with an end-capping agent such as a monoamine, a dicarboxylic anhydride, a monocarboxylic acid, a monocarboxylic acid chloride, or a monocarboxylic acid active ester. By capping the terminal of the resin with the end-capping agent, the storage stability of the coating liquid containing the resin composition selected from one or more of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor can be improved.

[0275] As the monoamine used as the end-capping agent, for example, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminophenylthiol, 3-aminophenylthiol, or 4-aminophenylthiol can be given.

[0276] As the dicarboxylic anhydride used as the end-capping agent, for example, phthalic anhydride, maleic anhydride, succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, cyclohexane dicarboxylic anhydride, or 3-hydroxyphthalic anhydride can be given.

[0277] As the monocarboxylic acid and the monocarboxylic acid chloride used as the end-capping agent, for example, benzoic acid, 3-carboxyphenol, 4-carboxyphenol, 3-carboxyphenylthiol, 4-carboxyphenylthiol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid or 4-carboxybenzenesulfonic acid, a monocarboxylic acid chloride thereof, or a monocarboxylic acid chloride of terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene or 2,6-dicarboxynaphthalene can be exemplified.

[0278] As the monocarboxylic acid active ester used as the end-capping agent, for example, a monocarboxylic acid active ester compound obtained by the reaction of the above-mentioned acid chloride with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxylic acid imide can be exemplified.

[0279] Among the one or more resins selected from (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor and (Alb-2) polybenzoxazole precursor, the contained ratio of the structural unit from the end-capping agent in the structural units from all the amines, all the carboxylic acids and their derivatives is preferably 1 mol% or more, more preferably 3 mol% or more, and further preferably 5 mol% or more. When the contained ratio is within the above-mentioned range, the storage stability of the coating solution of the resin composition can be improved. On the other hand, the contained ratio of the structural unit from the end-capping agent is preferably 30 mol% or less, more preferably 25 mol% or less, and further preferably 20 mol% or less. When the contained ratio is within the above-mentioned range, the resolution after development can be improved.

[0280] The contained ratio of the structural unit from various carboxylic acids or amines and their derivatives in (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor or (Alb-2) polybenzoxazole precursor can be combined 1 H-NMR, 13 C-NMR, 15 N-NMR, IR, TOF-MS, elemental analysis and ash determination, etc.

[0281] <Introduction of an ethylenically unsaturated double bond group>

[0282] (A2) The resin containing an unsaturated group has an ethylenically unsaturated double bond group. As the polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor, it is also preferable to be a product obtained by introducing an ethylenically unsaturated double bond group in the side chain of the resin by a reaction of introducing an ethylenically unsaturated double bond group.

[0283] As the (A2a-1) unsaturated group-containing polyimide, (A2a-2) unsaturated group-containing polyimide precursor, (A2b-1) unsaturated group-containing polybenzoxazole, or (A2b-2) unsaturated group-containing polybenzoxazole precursor used in the present application, preferably is a product obtained by reacting a part of the phenolic hydroxyl group and / or carboxyl group of the (Ala-1) polyimide, (Ala-2) polyimide precursor, (Alb-1) polybenzoxazole, or (Alb-2) polybenzoxazole precursor with a compound having an ethylenically unsaturated double bond group. By the above reaction, an ethylenically unsaturated double bond group can be introduced into the side chain of the resin.

[0284] As the compound having an ethylenically unsaturated double bond group, from the viewpoint of reactivity, preferably is an electrophilic compound having an ethylenically unsaturated double bond group.

[0285] As the electrophilic compound, for example, an isocyanate compound, an isothiocyanate compound, an epoxy compound, an aldehyde compound, a thioaldehyde compound, a ketone compound, a thioketone compound, an acetate compound, a carboxylic acid chloride, a carboxylic anhydride, a carboxylic acid active ester compound, a carboxylic acid compound, a haloalkyl compound, an azidoalkyl compound, a triflate alkyl compound, a mesylate alkyl compound, a tosylate alkyl compound, or a cyanated alkyl compound can be mentioned, from the viewpoints of reactivity and compound availability, preferably an isocyanate compound, an epoxy compound, an aldehyde compound, a ketone compound, or a carboxylic anhydride, more preferably an isocyanate compound or an epoxy compound.

[0286] As the isocyanate compound having an ethylenically unsaturated double bond group, preferably is a compound represented by the following general formula (23) or a compound represented by the following general formula (24).

[0287] [Chemical Formula 15]

[0288]

[0289] In the general formula (23), X 17 represents an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. R 56 ~R 58 each independently represents hydrogen or an alkyl group having 1 to 10 carbon atoms. In the general formula (23), X 17 represents an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. R 56 ~R 58 each independently preferably represents hydrogen or an alkyl group having 1 to 6 carbon atoms. In the general formula (24), X 18 and X 19R represents an alkylene chain with 1 to 10 carbon atoms, a cycloalkylene chain with 4 to 10 carbon atoms, or an arylene chain with 6 to 15 carbon atoms. 59 ~R 65 Each of these can independently represent either hydrogen or an alkyl group having 1 to 10 carbon atoms. In general formula (24), X 18 and X 19 Preferably, it is an alkylene chain with 1 to 6 carbon atoms, a cycloalkylene chain with 4 to 7 carbon atoms, or an arylene chain with 6 to 10 carbon atoms. 59 ~R 65 Each is preferably an alkyl group having 1 to 6 carbon atoms. The alkylene chain, cycloalkylene chain, aryl chain, and alkyl group described above can be any of the unsubstituted or substituted forms.

[0290] As an epoxy compound having an olefinic unsaturated double bond group, the compound represented by general formula (25) is preferred.

[0291] [Chemical Formula 16]

[0292]

[0293] In general formula (25), X 20 R represents an alkylene chain with 1 to 10 carbon atoms, a cycloalkylene chain with 4 to 10 carbon atoms, or an arylene chain with 6 to 15 carbon atoms. 66 ~R 68 Each of these can independently represent either hydrogen or an alkyl group having 1 to 10 carbon atoms. In general formula (25), X 20 Preferably, it is an alkylene chain with 1 to 6 carbon atoms, a cycloalkylene chain with 4 to 7 carbon atoms, or an arylene chain with 6 to 10 carbon atoms. 66 ~R 68 Each is preferably an alkyl group having 1 to 6 carbon atoms. The alkylene chain, cycloalkylene chain, aryl chain, and alkyl group described above can be any of the unsubstituted or substituted forms.

[0294] Examples of isocyanate compounds having olefinic unsaturated double bond groups include (meth)acryloyloxymethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, 4-(meth)acryloyloxyn-butyl isocyanate, 4-(meth)acryloyloxycyclohexyl isocyanate, 4-(meth)acryloyloxyphenyl isocyanate, or 1,1-bis((meth)acryloyloxymethyl)ethyl isocyanate.

[0295] As the epoxy compound having an ethylenically unsaturated double bond group, for example, (meth)glycidyl acrylate, (meth)glycidyl (a-ethyl) acrylate, (meth)glycidyl (3,4-epoxy) n-butyl acrylate, (meth)glycidyl (3,4-epoxy) heptyl acrylate, 2-vinyl glycidyl acetate, 2-vinyl cyclohexane glycidyl ether, 2-vinyl benzyl glycidyl ether, or 2,3-bis(epoxypropoxy methyl) styrene can be given.

[0296] As the aldehyde compound having an ethylenically unsaturated double bond group, for example, propenal, trans-crotonaldehyde, cis-crotonaldehyde, trans-cinnamaldehyde, or cis-cinnamaldehyde can be given.

[0297] As the ketone compound having an ethylenically unsaturated double bond group, for example, methyl vinyl ketone, crotyl methyl ketone, cinnamyl methyl ketone, 2-cyclopenten-1-one, 2-cyclohexen-1-one, or 2-(2-acetyloxy acetyloxy) ethyl (meth)acrylate can be given.

[0298] As the carboxylic acid anhydride having an ethylenically unsaturated double bond group, for example, (meth)acrylic anhydride, itaconic anhydride, maleic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, or 3-methyl-1,2,3,6-tetrahydrophthalic anhydride can be given.

[0299] As the conditions of the reaction for introducing the ethylenically unsaturated double bond group, for example, the inside of the reaction vessel is sufficiently subjected to nitrogen substitution under air or by bubbling, reduced pressure degassing, or the like, and then (A1a-1) polyimide, (A1a-2) polyimide precursor, (A1b-1) polybenzoxazole, or (A1b-2) polybenzoxazole precursor, and a compound having an ethylenically unsaturated double bond group are added in a reaction solvent, and allowed to react at 20 to 110°C for 30 to 500 minutes. In addition, a polymerization inhibitor such as a phenol compound, an acid catalyst, or a base catalyst can be used as necessary.

[0300] As the acid catalyst, for example, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, or a polycarboxylic acid or an anhydride thereof, or an ion exchange resin can be given. As the base catalyst, for example, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, diethylamine, triethanolamine, diethanolamine, N,N-dimethyl-4-aminopyridine, sodium hydroxide, potassium hydroxide, or an ion exchange resin can be given.

[0301] <Physical properties of polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor>

[0302] The number of repetitions n of the structural unit in the resin selected from one or more of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor is preferably 5 or more, more preferably 10 or more, and further preferably 15 or more. When the number of repetitions n is within the above range, the resolution after development can be improved. On the other hand, the number of repetitions n is preferably 1,000 or less, more preferably 500 or less, and further preferably 100 or less. When the number of repetitions n is within the above range, the leveling property at the time of coating and the pattern processing property using an alkali developer can be improved.

[0303] The weight average molecular weight (hereinafter referred to as "Mw") of the resin selected from one or more of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor is preferably 1,000 or more, more preferably 3,000 or more, and further preferably 5,000 or more, as measured by gel permeation chromatography (hereinafter referred to as "GPC") and calculated as polystyrene. When the Mw is within the above range, the resolution after development can be improved. On the other hand, the Mw is preferably 500,000 or less, more preferably 300,000 or less, and further preferably 100,000 or less. When the Mw is within the above range, the leveling property at the time of coating and the pattern processing property using an alkali developer can be improved.

[0304] In addition, the number average molecular weight (hereinafter referred to as "Mn") is preferably 1,000 or more, more preferably 3,000 or more, and further preferably 5,000 or more. When the Mn is within the above range, the resolution after development can be improved. On the other hand, the Mn is preferably 500,000 or less, more preferably 300,000 or less, and further preferably 100,000 or less. When the Mn is within the above range, the leveling property at the time of coating and the pattern processing property using an alkali developer can be improved.

[0305] The Mw and Mn of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, or (Alb-2) polybenzoxazole precursor can be easily measured as a value calculated as polystyrene by GPC, light scattering method, or X-ray small angle scattering method. When the number of repetitions n of the structural unit in (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, or (Alb-2) polybenzoxazole precursor is calculated as n = Mw / M, where the molecular weight of the structural unit is M and the weight average molecular weight of the resin is Mw.

[0306] The alkali dissolution rate of one or more selected from (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor is preferably 50 nm / min or more, more preferably 70 nm / min or more, and further preferably 100 nm / min or more. When the alkali dissolution rate is within the above range, the resolution after development can be improved. On the other hand, the alkali dissolution rate is preferably 12,000 nm / min or less, more preferably 10,000 nm / min or less, and further preferably 8,000 nm / min or less. When the alkali dissolution rate is within the above range, the film damage during alkali development can be suppressed.

[0307] The alkali dissolution rate herein refers to the decrease in film thickness after development for 60 seconds in a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 23 ± 1°C, rinsing with water for 30 seconds, after coating a solution obtained by dissolving a resin in γ-butyrolactone on a Si wafer, and prebaking the prebaked film at 120°C for 4 minutes to form a prebaked film having a film thickness of 10 μm ± 0.5 μm.

[0308] <Method for synthesizing polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor>

[0309] (Ala-l) polyimide or (Ala-2) polyimide precursor can be synthesized by known methods. For example, the following methods can be mentioned: a method in which tetracarboxylic dianhydride is reacted with a diamine (a part of which is replaced with a monoamine as an end-capping agent) in a polar solvent such as N-methyl-2-pyrrolidone at 80 to 200°C; or a method in which tetracarboxylic dianhydride (a part of which is replaced with a dicarboxylic anhydride, a monocarboxylic acid, a monocarboxylic acid chloride, or a monocarboxylic acid active ester as an end-capping agent) is reacted with a diamine in a polar solvent such as N-methyl-2-pyrrolidone at 80 to 200°C; and the like.

[0310] (Alb-l) polybenzoxazole or (Alb-2) polybenzoxazole precursor can be synthesized by known methods. For example, the following methods can be mentioned: a method in which active diester of dicarboxylic acid is reacted with a bisaminophenol compound (a part of which is replaced with a monoamine as an end-capping agent) in a polar solvent such as N-methyl-2-pyrrolidone at 80 to 250°C; or a method in which active diester of dicarboxylic acid (a part of which is replaced with a dicarboxylic anhydride, a monocarboxylic acid, a monocarboxylic acid chloride, or a monocarboxylic acid active ester as an end-capping agent) is reacted with a bisaminophenol compound in a polar solvent such as N-methyl-2-pyrrolidone at 80 to 250°C; and the like.

[0311] As for one or more selected from the group consisting of (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, and (Alb-2) polybenzoxazole precursor, it is preferable to perform reprecipitation in a poor solvent for one or more selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor after the completion of the polymerization reaction, and then perform washing and drying. By performing the reprecipitation treatment, low molecular weight components and the like can be removed, and thus the mechanical properties of the cured film are greatly improved.

[0312] A specific method for synthesizing (Ala-l) polyimide, (Alb-l) polybenzoxazole, (Ala-2) polyimide precursor, or (Alb-2) polybenzoxazole precursor will be described. First, a diamine compound or a bisamino phenol compound is dissolved in a reaction solvent, and substantially equimolar amounts of a carboxylic anhydride compound are slowly added to the solution. The mixed solution is stirred using a mechanical stirrer at a temperature of preferably 0 to 200°C, more preferably 40 to 150°C, for preferably 0.5 to 50 hours, more preferably 2 to 24 hours. In the case of using a capping agent, after the addition of the carboxylic anhydride compound, the solution is stirred at the prescribed temperature for the prescribed time, and then the capping agent is slowly added and stirred.

[0313] The reaction solvent used in the polymerization reaction can be any solvent that can dissolve the diamine compound or the bisamino phenol compound and the carboxylic anhydride compound as raw materials, and is preferably a polar solvent. As the reaction solvent, for example, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, or N-methyl-2-pyrrolidone; cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-hexalactone, ε-hexalactone, or α-methyl-γ-butyrolactone; carbonates such as ethylene carbonate or propylene carbonate; ethylene glycols such as triethylene glycol; phenols such as m-cresol or p-cresol; or other solvents such as acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, or dimethyl sulfoxide can be used. In the case where the total amount of the diamine compound or the bisamino phenol compound and the carboxylic anhydride compound is 100 parts by mass, the amount of the reaction solvent is preferably 100 to 1900 parts by mass, more preferably 150 to 950 parts by mass.

[0314] The imide ring closure rate (imidization rate) of (Ala-l) polyimide or (Ala-2) polyimide precursor can be easily determined, for example, as follows. First, the infrared absorption spectrum of the resin is measured, and the presence of the absorption peak of the imide bond from the polyimide structure (1780 cm -1 nearby, 1377 cm -1 nearby) is confirmed. Next, the resin is heat cured at 350°C for 1 hour, and the infrared absorption spectrum is measured. The imide ring closure rate (imidization rate) is determined from the change in the absorption peak of the imide bond (1780 cm -1 nearby or 1377 cm -1The content of the imide bond in the resin before heat curing is calculated by comparing the peak intensities near 1574 cm"1or 1557 cm"1, and thus the imidization rate can be obtained.

[0315] The oxazole ring ring-closing rate (oxazole rate) of (Alb-l) polybenzoxazole or (Alb-2) polybenzoxazole precursor can be easily obtained using, for example, the following method. First, the infrared absorption spectrum of the resin is measured, and the presence of the absorption peak of the oxazole bond from the polybenzoxazole structure (1574 cm"1or 1557 cm"1) is confirmed. Next, the resin is heat cured at 350°C for 1 hour, and the infrared absorption spectrum is measured. The oxazole rate is obtained by comparing the peak intensities near 1574 cm"1or 1557 cm"1before and after heat curing. -1 nearby, 1557 cm -1 nearby). -1 Next, the resin is heat cured at 350°C for 1 hour, and the infrared absorption spectrum is measured. The oxazole rate is obtained by comparing the peak intensities near 1574 cm"1or 1557 cm"1before and after heat curing. -1

[0316] <Polysiloxane>

[0317] In the negative photosensitive resin composition of the present application, (Alb-3) polysiloxane can be contained as the (Al) resin containing a weakly acidic group. The (Alb-3) polysiloxane means a general polysiloxane described below.

[0318] As the (Alb-3) polysiloxane used in the present application, for example, a polysiloxane obtained by hydrolysis and dehydration condensation of one or more selected from a trifunctional organosilane, a tetrafunctional organosilane, a bifunctional organosilane, and a monofunctional organosilane can be given.

[0319] The (Alb-3) polysiloxane is a thermosetting resin, and by heat curing at a high temperature, dehydration condensation is performed, and thus a siloxane bond (Si-O) having high heat resistance can be formed. Therefore, by containing a polysiloxane having a siloxane bond having high heat resistance in the resin composition, the heat resistance of the obtained cured film can be improved. Further, since it is a resin in which the heat resistance is improved after dehydration condensation, it is suitable for use in applications in which it is desired to simultaneously achieve the properties before dehydration condensation and the heat resistance of the cured film, and the like.

[0320] The (Alb-3) polysiloxane used in the present application has a silanol group as the alkali-soluble group. By having a silanol group, the half-tone characteristics can be improved. In addition to the silanol group, one or more weakly acidic groups selected from a phenolic hydroxyl group, a hydroxyimide group, and a hydroxyamide group can be present.

[0321] The (A2b-3) polysiloxane containing an unsaturated group used in the present application has an ethylenic unsaturated double bond group as the radical polymerizable group. By having an ethylenic unsaturated double bond group, the sensitivity at the time of exposure can be improved. ​

[0322] The (A1a-3) carboxylic acid-modified polysiloxane used in this invention, in addition to having silanol groups as alkali-soluble groups, also has carboxyl groups and / or carboxylic anhydride groups as alkali-soluble groups. The presence of carboxyl groups and / or carboxylic anhydride groups improves halftone characteristics and resolution after development.

[0323] The (A2a-3) carboxylic acid-modified polysiloxane containing unsaturated groups used in this invention, in addition to silanol groups, also has carboxyl groups and / or carboxylic anhydride groups as alkali-soluble groups. The presence of carboxyl groups and / or carboxylic anhydride groups improves halftone characteristics and post-development resolution. Furthermore, the presence of olefinic unsaturated double bonds serves as a free radical polymerization group. The presence of olefinic unsaturated double bonds enhances sensitivity during exposure.

[0324] Furthermore, polysiloxanes possess silanol groups as reactive groups. Therefore, especially when (D1) pigment is included as the (D) colorant described later, the silanol groups can interact with and / or bond to the surface of the (D1) pigment, and can also interact with and / or bond to the surface-modifying groups of the (D1) pigment. Thus, the dispersion stability of the (D1) pigment can be improved.

[0325] <Trifunctional organosilane units, tetrafunctional organosilane units, difunctional organosilane units, and monofunctional organosilane units>

[0326] As the (A1b-3) polysiloxane used in this invention, from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development, it is preferable to contain trifunctional organosilane units and / or tetrafunctional organosilane units. As a trifunctional organosilane, organosilane units represented by general formula (7) are preferred. As a tetrafunctional organosilane unit, organosilane units represented by general formula (8) are preferred.

[0327] The (A1b-3) polysiloxane used in this invention may contain a bifunctional organosilane unit from the viewpoint of reducing the taper of the pattern shape and improving the mechanical properties of the cured film. As a bifunctional organosilane, the organosilane unit represented by general formula (9) is preferred.

[0328] The (A1b-3) polysiloxane used in this invention may contain a monofunctional organosilane unit from the viewpoint of improving the storage stability of the coating solution of the resin composition. As a monofunctional organosilane unit, an organosilane unit represented by general formula (10) is preferred.

[0329] [Chemical Formula 17]

[0330]

[0331] In general formulas (7) to (10), R 22 ~R27 each independently represents hydrogen, alkyl, cycloalkyl, alkenyl or aryl. In general formulae (7) to (10), R 22 ~R 27 each independently is preferably hydrogen, alkyl having 1 to 10 carbon atoms, cycloalkyl having 4 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms or aryl having 6 to 15 carbon atoms, more preferably hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 4 to 7 carbon atoms, alkenyl having 2 to 8 carbon atoms or aryl having 6 to 10 carbon atoms. The above-mentioned alkyl, cycloalkyl, alkenyl and aryl can have a hetero atom, and can be any of unsubstituted or substituted.

[0332] As R 22 ~R 27 of general formulae (7) to (10), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl or n-decyl can be mentioned. Further, as a substituent thereof, for example, a halogen atom, an epoxy group, a glycidyl group, an oxetanyl group, an amino group, a mercapto group or an isocyanate group can be mentioned. When the alkyl group is a substituted one, as R 22 ~R 27 , for example, trifluoromethyl, 3,3,3-trifluoropropyl, 3-epoxypropyloxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-[(3-ethyl-3-oxetanyl)methoxy]propyl, 3-aminopropyl, 3-mercaptopropyl, 3-isocyanatepropyl or a substituent of the following structure can be mentioned.

[0333] [Chemical Formula 18]

[0334]

[0335] As R 22 ~R 27 of general formulae (7) to (10), for example, cyclopentyl or cyclohexyl can be mentioned. Further, as a substituent thereof, for example, a halogen atom, an epoxy group, a glycidyl group, an oxetanyl group, an amino group, a mercapto group or an isocyanate group can be mentioned.

[0336] As R 22 ~R 27 of general formulae (7) to (10), for example, ethenyl, allyl, 3-(meth)acryloyloxypropyl or 2-(meth)acryloyloxyethyl can be mentioned.

[0337] As R 22 ~R 27R1is an aromatic group and a substituted body thereof, for example, phenyl, 4-methylphenyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 1-naphthyl, 2-naphthyl, 4-styryl, 2-phenylethyl, 1-(4-hydroxyphenyl)ethyl, 2-(4-hydroxyphenyl)ethyl, or 4-hydroxy-5-(4-hydroxyphenylcarbonyloxy)pentyl.

[0338] As the organosilane having the organosilane unit represented by General Formula (7), for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-hexyltrimethoxysilane, n-decyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-[(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-(4-aminophenyl)propyltrimethoxysilane, 1-[4-(3-trimethoxysilylpropyl)phenyl]urea, 1-(3-trimethoxysilylpropyl)urea, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1,3,5-tris(3-trimethoxysilylpropyl)isocyanuric acid, N-tert-butyl-2-(3-trimethoxysilylpropyl)succinimide, or N-tert-butyl-2-(3-triethoxysilylpropyl)succinimide, and the like trifunctional organosilane.

[0339] The contained ratio of the organosilane unit represented by General Formula (7) in the (A1b-3) polysiloxane is preferably in the range of 50 to 100 mol%, more preferably in the range of 60 to 100 mol%, and further preferably in the range of 70 to 100 mol% in terms of Si atom mole ratio. When the contained ratio is in the above range, the heat resistance of the cured film can be improved.

[0340] As the organosilane having the organosilane unit represented by General Formula (8), for example, tetrafunctional organosilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n- propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, or tetraacetyloxysilane; methyl silicate 51 (manufactured by Fusso Chemical Industry Co., Ltd.), M Silicate 51 (manufactured by Tama Chemical Industry Co., Ltd.), Silicate 40 or Silicate 45 (both manufactured by Tama Chemical Industry Co., Ltd.), or silicate compounds such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, or ethyl silicate 48 (all manufactured by COLCOAT Co., Ltd.) can be mentioned. From the viewpoint of improving the heat resistance of the cured film and improving the resolution after development, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, methyl silicate 51 (manufactured by Fusso Chemical Industry Co., Ltd.), M Silicate 51 (manufactured by Tama Chemical Industry Co., Ltd.), or methyl silicate 51 (manufactured by COLCOAT Co., Ltd.) are preferred.

[0341] The content ratio of the organosilane unit represented by General Formula (8) in the (A1b-3) polysiloxane is preferably in the range of 0 to 40 mol%, more preferably in the range of 0 to 30 mol%, and further preferably in the range of 0 to 20 mol% in terms of Si atom mole ratio. When the content ratio is in the above range, the heat resistance of the cured film and the resolution after development can be improved.

[0342] As the organosilane having an organosilane unit represented by General Formula (9), for example, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 3-isocyanatopropylmethyldiethoxysilane and the like bifunctional organosilane, 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-dimethoxydisiloxane, or 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane or DMS-S12, DMS-S15, PDS-1615, or PDS-9931 (all of which are manufactured by Gelest) and the like bifunctional organosilane oligomer can be given. From the viewpoint of low tapering of the pattern shape and improvement of the mechanical properties of the cured film, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,1,3,3-tetramethyl-1,3-dimethoxydisiloxane, 1,1,3,3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraethyl-1,3-dimethoxydisiloxane, or 1,1,3,3-tetraethyl-1,3-diethoxydisiloxane are preferred.

[0343] The contained ratio of the organosilane unit represented by General Formula (9) in the (A1b-3) polysiloxane is preferably in the range of 0 to 60 mol%, more preferably in the range of 0 to 50 mol%, and further preferably in the range of 0 to 40 mol% in terms of Si atom mole ratio. When the contained ratio is in the above range, the heat resistance of the cured film and the resolution after development can be improved.

[0344] As the organosilane having an organosilane unit represented by General Formula (10), for example, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, tri-n-propyltrimethoxysilane, tri-n-propyltriethoxysilane, tri-n-butytrimethoxysilane, tri-n-butytriethoxysilane, (3-glycidoxypropyl)dimethylmethoxysilane, or (3-glycidoxypropyl)dimethylethoxysilane and the like monofunctional organosilane can be given.

[0345] The contained ratio of the organosilane unit represented by General Formula (10) in the (Alb-3) polysiloxane is preferably in the range of 0 to 20 mol%, more preferably in the range of 0 to 10 mol%, and further preferably in the range of 0 to 5 mol% in terms of Si atom mole ratio. When the contained ratio is in the above range, the heat resistance of the cured film can be improved.

[0346] As the (Alb-3) polysiloxane used in the present application, a polysiloxane obtained by hydrolyzing and dehydration condensing one or more selected from the group consisting of an organosilane represented by General Formula (7a), an organosilane represented by General Formula (8a), an organosilane represented by General Formula (9a), and an organosilane represented by General Formula (10a) is preferable.

[0347] [Chemical Formula 19]

[0348]

[0349] In General Formulas (7a) to (10a), R 22 ~R 27 each independently represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, R 150 ~R 159 each independently represents hydrogen, an alkyl group, an acyl group, or an aryl group. In General Formulas (7a) to (10a), R 22 ~R 27 each independently is preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and more preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. In addition, R 150 ~R 159 each independently is preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and more preferably hydrogen, an alkyl group having 1 to 4 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The above alkyl group, cycloalkyl group, alkenyl group, aryl group, and acyl group can have a hetero atom, and can be any of an unsubstituted form or a substituted form.

[0350] In the (Alb-3) polysiloxane, the organosilane unit represented by General Formula (7), the organosilane unit represented by General Formula (8), the organosilane unit represented by General Formula (9), and the organosilane unit represented by General Formula (10) can be any of a regular arrangement or an irregular arrangement. As the regular arrangement, for example, there can be mentioned alternating copolymerization, periodic copolymerization, block copolymerization, graft copolymerization, or the like. As the irregular arrangement, for example, there can be mentioned random copolymerization or the like.

[0351] Further, in the (Alb-3) polysiloxane, the organosilane unit represented by General Formula (7), the organosilane unit represented by General Formula (8), the organosilane unit represented by General Formula (9), and the organosilane unit represented by General Formula (10) can be any of two-dimensional arrangement or three-dimensional arrangement. As the two-dimensional arrangement, for example, a straight chain can be given. As the three-dimensional arrangement, for example, a ladder shape, a cage shape, or a mesh shape, or the like can be given.

[0352] <Organosilane unit having a fluorine atom>

[0353] As the polysiloxane used in the present application, a polysiloxane containing an organosilane unit having a fluorine atom is preferable. Such a polysiloxane is preferably a substance obtained using an organosilane having a fluorine atom as the organosilane unit represented by General Formula (7), General Formula (9), or General Formula (10). By containing an organosilane unit having a fluorine atom in the polysiloxane, the transparency is improved, and the sensitivity at the time of exposure can be improved. Further, water repellency can be imparted to the film surface, and the penetration from the film surface at the time of alkali development can be suppressed.

[0354] The polysiloxane preferably contains an organosilane unit selected from one or more of General Formula (11a), General Formula (11b), and General Formula (11c) as the organosilane unit having a fluorine atom.

[0355] [Chemical Formula 20]

[0356]

[0357] In General Formula (11a) to (11c), Rf 1 ~Rf 3 Each independently represents an alkyl group having 1 to 20 fluorine atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 28 and R 29 Each independently represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. W represents an integer of 1 to 2, x represents an integer of 0 to 1, and w + x = 2. Y represents an integer of 1 to 3, z represents an integer of 0 to 2, and y + z = 3. In General Formula (11a) to (11c), Rf 1 ~Rf 3 Each independently is preferably an alkyl group having 1 to 12 fluorine atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Further, R 28 and R 29Each of R1to R4is independently preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, more preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The above alkyl group, cycloalkyl group, alkenyl group, and aryl group can have a hetero atom, and can be any of unsubstituted or substituted.

[0358] As the organosilane having a fluorine atom represented by General Formula (11a), General Formula (11b), or General Formula (11c), for example, there can be mentioned trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, trifluoromethoxypropyltrimethoxysilane, trifluoromethoxypropyltriethoxysilane, 3,3,3-trifluoropropoxypropyltrimethoxysilane, 3,3,3-trifluoropropoxypropyltriethoxysilane, 1,2,3,4,5-pentafluorophenyltrimethoxysilane, or 3-(1,2,3,4,5-pentafluorophenyl)propyltrimethoxysilane, and the like trifunctional organosilane; 3,3,3-trifluoropropylmethyldimethoxysilane, 3,3,3-trifluoropropylmethyldimethoxysilane, or trifluoromethoxypropylmethyldimethoxysilane, and the like bifunctional organosilane; 3,3,3-trifluoropropyldimethylmethoxysilane, 3,3,3-trifluoropropyldimethylmethoxysilane, or trifluoromethyldimethylmethoxysilane, and the like monofunctional organosilane, or FS1265-300CS, FS1265-1000CS, or FS1265-10000CS (all of which are manufactured by Dow Corning Toray Co., Ltd.), and the like bifunctional organosilane oligomer.

[0359] The content ratio of the organosilane unit having a fluorine atom in the polysiloxane is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more in terms of Si atom mole ratio. When the content ratio is within the above range, the sensitivity at the time of exposure can be improved. On the other hand, the content ratio of the organosilane unit having a fluorine atom is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. When the content ratio is within the above range, the mechanical properties of the cured film can be improved. In particular, the Si atom mole ratio of the organosilane unit represented by General Formula (7), General Formula (9), or General Formula (10) and having a fluorine atom is preferably within the above range.

[0360] <Organosilane unit having an aromatic group>

[0361] As the polysiloxane used in the present application, it is preferable to contain an organosilane unit having an aromatic group. Such a polysiloxane is preferably a substance obtained using an organosilane having an aromatic group as an organosilane unit represented by General Formula (7), General Formula (9) or General Formula (10). By making the polysiloxane contain an organosilane unit having an aromatic group, it is possible to improve the heat resistance of the cured film by the heat resistance of the aromatic group.

[0362] Further, especially when containing (D1) pigment as (D) colorant described later, by making the polysiloxane contain an organosilane unit having an aromatic group, it is possible to improve the dispersion stability of (D1) pigment using the steric hindrance of the aromatic group. Furthermore, when (D1) pigment is (D1-2) organic pigment, since the aromatic group in the polysiloxane interacts with the aromatic group of (D1-2) organic pigment, it is possible to improve the dispersion stability of (D1-2) organic pigment.

[0363] As the organosilane having an organosilane unit represented by General Formula (7), General Formula (9) or General Formula (10) and having an aromatic group, for example, there can be mentioned a trifunctional organosilane such as phenyltrimethoxysilane, phenyltriethoxysilane, 4-methylphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-tert-butylphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 4-styryltrimethoxysilane, 2-phenylethyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 1-(4-hydroxyphenyl)ethyltrimethoxysilane, 2-(4-hydroxyphenyl)ethyltrimethoxysilane or 4-hydroxy-5-(4-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, or a bifunctional organosilane such as diphenyldimethoxysilane or diphenyldiethoxysilane. From the viewpoint of improving the heat resistance of the cured film, it is preferable to be phenyltrimethoxysilane, 4-methylphenyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 4-styryltrimethoxysilane, 2-phenylethyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, diphenyldimethoxysilane or diphenyldiethoxysilane, more preferable to be phenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, diphenyldimethoxysilane or diphenyldiethoxysilane, and further preferable to be 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, diphenyldimethoxysilane or diphenyldiethoxysilane.

[0364] The content ratio of the organosilane unit having an aromatic group in the polysiloxane is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more, in terms of Si atom mole ratio. When the content ratio is within the above range, the heat resistance of the cured film can be improved. On the other hand, the content ratio of the organosilane unit having an aromatic group is preferably 80 mol% or less, more preferably 75 mol% or less, and further preferably 70 mol% or less. When the content ratio is within the above range, the pattern processing property with an alkaline developer can be improved. In particular, the Si atom mole ratio of the organosilane unit represented by General Formula (7), General Formula (9), or General Formula (10) and having an aromatic group is preferably within the above range.

[0365] Among the organosilanes represented by General Formula (7), General Formula (9), or General Formula (10) and having an aromatic group, from the viewpoint of improving the pattern processing property with an alkaline developer and improving the resolution after development, phenyltrimethoxysilane, 4-tolyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 4-styryltrimethoxysilane, 2-phenylethyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, diphenyldimethoxysilane, or diphenyldiethoxysilane is preferred, phenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, diphenyldimethoxysilane, or diphenyldiethoxysilane is more preferred, and 1-naphthyltrimethoxysilane or 2-naphthyltrimethoxysilane is further preferred.

[0366] <Organosilane unit having an ethylenically unsaturated double bond group>

[0367] As the polysiloxane, a product obtained by introducing an ethylenically unsaturated double bond group into the side chain of the resin by means of an organosilane unit having an ethylenically unsaturated double bond group is also preferred.

[0368] As the polysiloxane used in the present application, an organosilane unit having an ethylenically unsaturated double bond group is preferably contained. Such a polysiloxane is preferably a substance obtained by using an organosilane having an ethylenically unsaturated double bond group as the organosilane having an organosilane unit represented by General Formula (7), General Formula (9), or General Formula (10). By containing an organosilane unit having an ethylenically unsaturated double bond group in the polysiloxane, the UV curing at the time of exposure can be promoted, and the sensitivity can be improved.

[0369] As the organosilane having an organosilane unit represented by General Formula (7), General Formula (9), or General Formula (10) and having an ethylenically unsaturated double bond group, for example, mention can be made of vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, or 4-phenylstyryltrimethoxysilane, and the like trifunctional organosilane or bifunctional organosilane such as methylvinyl dimethoxysilane or divinyl diethoxysilane. From the viewpoint of improving sensitivity at the time of exposure, it is preferable to be vinyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, or 4-phenylstyryltrimethoxysilane.

[0370] As the (A2b-3) unsaturated group-containing polysiloxane and the (A2a-3) carboxylic acid-modified unsaturated group-containing polysiloxane used in the present application, it is preferable to be a polysiloxane obtained by hydrolyzing and dehydration condensing an organosilane having an ethylenically unsaturated double bond group and other organosilanes. By the above reaction, it is possible to introduce an ethylenically unsaturated double bond group in the side chain of the resin.

[0371] <Organosilane unit having an acidic group>

[0372] As the polysiloxane, it is also preferable to be a product obtained by introducing an acidic group in the side chain of the resin by an organosilane unit having an acidic group.

[0373] As the polysiloxane used in the present application, it is preferable to contain an organosilane unit having an acidic group. Such a polysiloxane is preferably a substance obtained using an organosilane having an acidic group as an organosilane having an organosilane unit represented by General Formula (7), General Formula (9), or General Formula (10). By making the polysiloxane contain an organosilane unit having an acidic group, it is possible to improve the pattern processing property with an alkaline developer and the resolution after development.

[0374] As the acidic group, a group showing acidity with a pH of less than 6 is preferred. As the group showing acidity with a pH of less than 6, for example, a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a phenolic hydroxyl group, a hydroxyimide group, or a hydroxyamide group can be given. From the viewpoint of improving the pattern processing properties using an alkaline developer and improving the resolution after development, a carboxyl group, a carboxylic anhydride group, a phenolic hydroxyl group, or a hydroxyimide group is preferred, and a carboxyl group or a carboxylic anhydride group is more preferred. On the other hand, from the viewpoint of improving the halftone characteristic, a phenolic hydroxyl group, a hydroxyimide group, or a hydroxyamide group is preferred.

[0375] As the organosilane having an organosilane unit represented by General Formula (7), General Formula (9), or General Formula (10) and having an acidic group, for example, a trifunctional organosilane such as 2-(3-trimethoxysilylpropyl)-4-(N-tert-butyl)amino-4-oxobutanoic acid, 3-(3-trimethoxysilylpropyl)-4-(N-tert-butyl)amino-4-oxobutanoic acid, 3-trimethoxysilylpropyl succinic acid, 3-triethoxysilylpropyl succinic acid, 3-trimethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 5-trimethoxysilylpentanoic acid, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 4-(3-trimethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, 4-(3-trimethoxysilylpropyl)phthalic anhydride, 4-hydroxyphenyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 1-(4-hydroxyphenyl)ethyltrimethoxysilane, 2-(4-hydroxyphenyl)ethyltrimethoxysilane, or 4-hydroxy-5-(4-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane, a bifunctional organosilane such as 3-methyldimethoxysilylpropyl succinic acid, 3-methyldimethoxysilylpropionic acid, or 3-methyldimethoxysilylpropyl succinic anhydride, or a monofunctional organosilane such as 3-dimethylmethoxysilylpropyl succinic acid, 3-dimethylmethoxysilylpropionic acid, or 3-dimethylmethoxysilylpropyl succinic anhydride can be given. From the viewpoint of improving the pattern processing properties using an alkaline developer and improving the resolution after development, a trifunctional organosilane such as 2-(3-trimethoxysilylpropyl)-4-(N-tert-butyl)amino-4-oxobutanoic acid, 3-(3-trimethoxysilylpropyl)-4-(N-tert-butyl)amino-4-oxobutanoic acid, 3-trimethoxysilylpropyl succinic acid, 3-triethoxysilylpropyl succinic acid, 3-trimethoxysilylpropionic acid, 4-trimethoxysilylbutyric acid, 5-trimethoxysilylpentanoic acid, 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylpropyl succinic anhydride, 4-(3-trimethoxysilylpropyl)cyclohexane-1,2-dicarboxylic anhydride, or 4-(3-trimethoxysilylpropyl)phthalic anhydride is preferred.

[0376] As the (Ala-3) carboxylic acid-modified polysiloxane and the (A2a-3) carboxylic acid-modified polysiloxane having an unsaturated group used in the present application, a polysiloxane obtained by hydrolyzing and dehydration condensing an organosilane having a carboxyl group and / or a carboxylic anhydride group and other organosilanes is preferred. By the above reaction, a carboxyl group and / or a carboxylic anhydride group can be introduced into the side chain of the resin.

[0377] The content ratio of each organosilane unit in the polysiloxane can be combined 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis, ash measurement, and the like.

[0378] <Physical properties of the polysiloxane>

[0379] As the Mw of the polysiloxane used in the present application, it is preferably 500 or more, more preferably 700 or more, and further preferably 1,000 or more, as measured by GPC and converted to polystyrene. When the Mw is within the above range, the resolution after development can be improved. On the other hand, as the Mw, it is preferably 100,000 or less, more preferably 50,000 or less, and further preferably 20,000 or less. When the Mw is within the above range, the leveling property at the time of coating and the pattern processing property with an alkaline developer can be improved.

[0380] <Method for synthesizing the polysiloxane>

[0381] The polysiloxane can be synthesized by a known method. For example, a method in which an organosilane is hydrolyzed and dehydration condensed in a reaction solvent can be mentioned. As the method in which an organosilane is hydrolyzed and dehydration condensed, for example, a method in which a reaction solvent and water are added to a mixture containing an organosilane, and a catalyst is added as necessary, and heated and stirred at 50 to 150°C, preferably 90 to 130°C, for about 0.5 to 100 hours can be mentioned. Note that in the heating and stirring, the hydrolysis by-products (alcohols such as methanol), the condensation by-products (water) can be removed by distillation as necessary.

[0382] <Polycyclic side chain-containing aromatic resin>

[0383] In the negative photosensitive resin composition of the present application, a (A2c-1) polycyclic side chain-containing aromatic resin can be included as the (A2) unsaturated group-containing resin. The (A2c-1) polycyclic side chain-containing aromatic resin means a polycyclic side chain-containing aromatic resin described below.

[0384] As the aromatic resin containing a polycyclic side chain (A2c-1) used in the present application, for example, (I) an aromatic resin containing a polycyclic side chain obtained by reacting a phenol compound, a carboxylic anhydride and an epoxy compound; (II) an aromatic resin containing a polycyclic side chain obtained by reacting an epoxy compound, a carboxylic acid compound and an epoxy compound; or (III) an aromatic resin containing a polycyclic side chain obtained by reacting an epoxy compound, a carboxylic acid compound and a carboxylic anhydride can be given.

[0385] The aromatic resin containing a polycyclic side chain (A2c-1) is a thermosetting resin having a structure in which a main chain is connected to a bulky side chain through one atom, and has a cyclic structure such as a fluorene ring having high heat resistance and rigidity as the bulky side chain. Therefore, by containing the aromatic resin containing a polycyclic side chain having a cyclic structure such as a fluorene ring having high heat resistance and rigidity in the resin composition, the heat resistance of the obtained cured film can be improved. Therefore, it is suitable for the case where the cured film is used for a use requiring heat resistance and the like.

[0386] The aromatic resin containing a polycyclic side chain (A2c-1) used in the present application has an ethylenic unsaturated double bond group. The aromatic resin containing a polycyclic side chain (A2c-1) is a resin in which the ethylenic unsaturated double bond group can be easily introduced to the side chain branched from the main chain of the resin. By having the ethylenic unsaturated double bond group, the aromatic resin containing a polycyclic side chain is a photocurable resin, and by UV-curing at the time of exposure, a three-dimensional crosslinked structure of carbon-carbon bonds can be formed. Therefore, by containing the aromatic resin containing a polycyclic side chain having an ethylenic unsaturated double bond group in the side chain in the resin composition, the sensitivity at the time of exposure can be improved. In addition, in the three-dimensional crosslinked structure formed, an alicyclic structure or an aliphatic structure is the main component, so the softening point of the resin can be inhibited from being high, a low taper pattern shape can be obtained, and the mechanical properties of the obtained cured film can be improved. Therefore, it is suitable for the case where the cured film is used for a use requiring mechanical properties and the like.

[0387] The aromatic resin containing a polycyclic side chain (A2c-1) used in the present application has a carboxyl group and / or a carboxylic anhydride group as an alkali-soluble group. By having a carboxyl group and / or a carboxylic anhydride group, the resolution after development can be improved.

[0388] As the (A2c-1) aromatic resin containing polycyclic side chains used in this invention, from the viewpoint of improving the heat resistance of the cured film, it is preferable to contain one or more structural units selected from the structural units represented by general formula (47), general formula (48), general formula (49), and general formula (50). Furthermore, the (A2c-1) aromatic resin containing polycyclic side chains used in this invention has olefinic unsaturated double bond groups. From the viewpoint of improving the sensitivity during exposure and improving the mechanical properties of the cured film, it is preferable to have olefinic unsaturated double bond groups at any one of the main chain, side chains, and ends.

[0389] [Chemical Formula 21]

[0390]

[0391] In general formulas (47) to (50), X 69 X 70 X 72 X 73 X 75 X 76 X 78 and X 79 Each can be used independently to represent a monocyclic or fused polycyclic hydrocarbon ring. 71 X 74 X 77 and X 80 Each of these independently represents a divalent to decavalent organic group of a carboxylic acid and / or its derivative residue. W 1 ~W 4 Each can be used independently to represent an organic group having two or more aromatic groups. R 130 ~R 137 Each independently represents either hydrogen or an alkyl group having 1 to 6 carbon atoms, R 170 ~R 175 R 177 and R 178 Each can independently represent hydrogen or an organic group having an alkene-type unsaturated double bond. R 176 Represents an alkyl group with 1 to 10 hydrogen or carbon atoms. a, b, c, d, e, f, g, and h each independently represent an integer from 0 to 10, and α, β, γ, and δ each independently represent an integer of 0 or 1. In general formulas (47) to (50), X 69 X 70 X 72 X 73 X 75 X 76 X 78 and X 79Each independently is preferably a monocyclic or condensed polycyclic hydrocarbon ring having 6 to 15 carbon atoms and 4 to 10 valences, and more preferably a monocyclic or condensed polycyclic hydrocarbon ring having 6 to 10 carbon atoms and 4 to 10 valences. In addition, X 71 , X 74 , X 77 , and X 80 Each independently is preferably a 2 to 10 valence organic group having a carboxylic acid and / or derivative residue of one or more selected from aliphatic structure having 2 to 20 carbon atoms, alicyclic structure having 4 to 20 carbon atoms, and aromatic structure having 6 to 30 carbon atoms, and more preferably a 4 to 10 valence organic group having a carboxylic acid and / or derivative residue of one or more selected from aliphatic structure having 4 to 15 carbon atoms, alicyclic structure having 4 to 15 carbon atoms, and aromatic structure having 6 to 25 carbon atoms. In addition, W 1 to W 4 Each independently is preferably a substituent represented by any one of General Formulae (51) to (56). In addition, R 130 to R 137 Each independently is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms, R 170 to R 175 , R 177 , and R 178 Each independently is preferably a substituent represented by General Formula (57). In addition, R 176 is preferably hydrogen or an alkyl group having 1 to 6 carbon atoms. The above-mentioned alkyl chain, aliphatic structure, alicyclic structure, aromatic structure, monocyclic or condensed polycyclic aromatic hydrocarbon ring, and organic group having an ethylenically unsaturated double bond group can have a heteroatom, and can be any of unsubstituted or substituted.

[0392] [Chemical Formula 22]

[0393]

[0394] In General Formulae (51) to (56), R 179 to R 182 , R 185 , and R 188 Each independently represents an alkyl group having 1 to 10 carbon atoms. R 183 , R 184 , R 186 , R 187 , R 189 , R 191 , and R 193 to R 196 Each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 190 , and R 192each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and at least one of R 190 and R 192 forms a ring. As the ring formed by R 190 and R 192 , for example, a benzene ring or a cyclohexane ring can be given. At least one of R 183 and R 184 is an aryl group having 6 to 15 carbon atoms. At least one of R 186 and R 187 is an aryl group having 6 to 15 carbon atoms. At least one of R 189 and R 190 is an aryl group having 6 to 15 carbon atoms, and at least one of R 191 and R 192 is an aryl group having 6 to 15 carbon atoms, and at least one of R 190 and R 192 forms a ring. At least one of R 193 and R 194 is an aryl group having 6 to 15 carbon atoms, and at least one of R 195 and R 196 is an aryl group having 6 to 15 carbon atoms. i, j, k, 1, m, and n each independently represents an integer of 0 to 4. In General Formulae (51) to (56), R 179 to R 182 , R 185 , and R 188 each independently preferably is an alkyl group having 1 to 6 carbon atoms. In addition, R 183 , R 184 , R 186 , R 187 , R 189 , R 191 , and R 193 to R 196 each independently preferably is hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms. R 190 and R 192 each independently preferably is hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and the ring formed by R 190 and R 192 is preferably a benzene ring. The above alkyl group, cycloalkyl group, and aryl group can be any of unsubstituted ones or substituted ones.

[0395] [Chemical Formula 23]

[0396]

[0397] In General Formula (57), X81 represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms, X 82 represents a direct bond or an arylene chain having 6 to 15 carbon atoms. R 197 represents a vinyl group, an aryl group, or a (meth)acryl group. In General Formula (57), X 81 preferably represents a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. In addition, X 82 preferably represents a direct bond or an arylene chain having 6 to 10 carbon atoms. The above-described alkylene chain, cycloalkylene chain, arylene, vinyl group, aryl group, and (meth)acryl group can be any of unsubstituted or substituted ones.

[0398] <Method for synthesizing aromatic resin containing polycyclic side chain>

[0399] As the (A2c-1) aromatic resin containing a polycyclic side chain used in the present application, preferably, a (A2c-1) aromatic resin containing a polycyclic side chain obtained by using any one or more of the following (I) to (IV) as a synthesis method.

[0400] As the (A2c-1) aromatic resin containing a polycyclic side chain used in the present application, preferably, a (A2c-1) aromatic resin containing a polycyclic side chain obtained by using any one or more of the following (I) to (IV) as a synthesis method.

[0401] As the aromatic resin containing a polycyclic side chain of (II), there can be mentioned an aromatic resin containing a polycyclic side chain obtained by reacting a polyfunctional active carboxylic acid derivative (one or more selected from the group consisting of tetracarboxylic dianhydride, dicarboxylic acid dichloride and dicarboxylic acid active diester) with a resin obtained by ring-opening addition reaction of a compound represented by General Formula (58) having a hydroxyl group and two or more aromatic groups in the molecule with an unsaturated compound represented by General Formula (60) having an ethylenic unsaturated double bond group and an epoxy group. As the polyfunctional active carboxylic acid derivative, tetracarboxylic dianhydride is preferred. In addition to the polyfunctional active carboxylic acid derivative, as a capping agent, tricarboxylic anhydride, dicarboxylic anhydride, moncarboxylic acid chloride or moncarboxylic acid active ester can be used as a reaction component

[0402] As the aromatic resin containing a polycyclic side chain of (III), there can be mentioned an aromatic resin containing a polycyclic side chain obtained by ring-opening addition reaction of an unsaturated compound represented by General Formula (60) having an ethylenic unsaturated double bond group and an epoxy group with a resin obtained by ring-opening addition reaction of a compound represented by General Formula (59) having an epoxy group and two or more aromatic groups in the molecule with a polyfunctional carboxylic acid (one or more selected from the group consisting of tetracarboxylic acid, tricarboxylic acid and dicarboxylic acid). As the polyfunctional carboxylic acid, tetracarboxylic acid or tricarboxylic acid is preferred. In addition to the polyfunctional carboxylic acid, as a capping agent, moncarboxylic acid can be used as a reaction component.

[0403] As the aromatic resin containing a polycyclic side chain of (IV), there can be mentioned an aromatic resin containing a polycyclic side chain obtained by reacting a polyfunctional active carboxylic acid derivative (one or more selected from the group consisting of tetracarboxylic dianhydride, dicarboxylic acid dichloride and dicarboxylic acid active diester) with a resin obtained by ring-opening addition reaction of a compound represented by General Formula (59) having an epoxy group and two or more aromatic groups in the molecule with an unsaturated carboxylic acid having an ethylenic unsaturated double bond group. As the polyfunctional active carboxylic acid derivative, tetracarboxylic dianhydride is preferred. In addition to the polyfunctional active carboxylic acid derivative, as a capping agent, tricarboxylic anhydride, dicarboxylic anhydride, moncarboxylic acid chloride or moncarboxylic acid active ester can be used as a reaction component.

[0404] [Chemical Formula 24]

[0405]

[0406] In General Formulas (58) and (59), X 83 ~ X 86 each independently represents a monocyclic or condensed polycyclic aromatic hydrocarbon ring, W 5 and W 6 each independently represents an organic group having two or more aromatic groups. R 160 ~ R 163each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms. o, p, q, and r each independently represent an integer of 0 to 10. In General Formulae (58) and (59), X 83 ~ X 86 each independently is preferably a monocyclic or condensed polycyclic aromatic hydrocarbon ring having 6 to 15 carbon atoms and 4 to 10 valences, and more preferably a monocyclic or condensed polycyclic aromatic hydrocarbon ring having 6 to 10 carbon atoms and 4 to 10 valences. In addition, W 5 and W 6 each independently is preferably a substituent represented by any one of General Formulae (51) to (56) described above. In addition, R 160 ~ R 163 each independently is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms. The monocyclic or condensed polycyclic aromatic hydrocarbon ring described above can have a hetero atom, and can be any of an unsubstituted form or a substituted form.

[0407] [Chemical Formula 25]

[0408]

[0409] In General Formula (60), X 87 represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms. X 87 In the case where X is a direct bond or an arylene chain having 6 to 15 carbon atoms, X 88 represents a direct bond. X 87 In the case where X is an alkylene chain having 1 to 10 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms, X 88 represents a direct bond or an arylene chain having 6 to 15 carbon atoms. R 198 represents a vinyl group, an aryl group, or a (meth)acrylic acid-based group. In General Formula (60), X 87 is preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. In addition, X 88 is preferably a direct bond or an arylene chain having 6 to 10 carbon atoms. The alkylene chain, the cycloalkylene chain, the arylene group, the vinyl group, the aryl group, and the (meth)acrylic acid-based group described above can have a hetero atom, and can be any of an unsubstituted form or a substituted form.

[0410] Examples of compounds represented by general formula (58) that have a hydroxyl group and two or more aromatic groups within the molecule include 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-hydroxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1,1-diphenylmethane, 1,1-bis(4-hydroxyphenyl)-3-phenyl-2,3-dihydroindene, 1,1-bis(4-hydroxyphenyl)-1,3-diphenylpropane, 1,1-bis(4-hydroxyphenyl)-2,4-diphenylcyclopentane, 2,2-bis(4-hydroxyphenyl)-2,3-dihydroindene, or 3,3-bis(4-hydroxyphenyl)-2,5-diphenylpentane.

[0411] Examples of compounds having an epoxy group and having two or more aromatic groups in the molecule, represented by general formula (59), include 9,9-bis[4-(2-epoxypropoxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-epoxypropoxypropoxy)phenyl]fluorene, 9,9-bis[4-(2-epoxypropoxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-epoxypropoxyethoxy)-3,5-dimethylphenyl]fluorene, 9,9-bis(4-epoxypropoxyphenyl)fluorene, 9,9-bis(4-epoxypropoxy-3-methylphenyl)fluorene, and 9,9-bis(4-epoxypropoxy-3-methylphenyl)fluorene. - fluorene (4-epoxypropoxyphenyl)-1,1-diphenylmethane, 1,1-bis(4-epoxypropoxyphenyl)-3-phenyl-2,3-dihydroindene, 1,1-bis(4-epoxypropoxyphenyl)-1,3-diphenylpropane, 1,1-bis(4-epoxypropoxyphenyl)-2,4-diphenylcyclopentane, 2,2-bis(4-epoxypropoxyphenyl)-2,3-dihydroindene or 3,3-bis(4-epoxypropoxyphenyl)-2,5-diphenylpentane or "OGSOL" (registered trademark) PG, OGSOL PG-100, OGSOL EG, OGSOL EG-200, OGSOL EG-210 (all manufactured by Osaka GasChemicals Co., Ltd.).

[0412] As the unsaturated compound having an ethylenically unsaturated double bond group and an epoxy group represented by General Formula (60), for example, there can be mentioned glycidyl (meth) acrylate, (α-ethyl) glycidyl (meth) acrylate, (α-n-propyl) glycidyl (meth) acrylate, (3,4-epoxy) heptyl (meth) acrylate, 2-vinyl glycidyl acetate, 4-vinyl cyclohexanecarboxylic acid glycidyl ester, 4-vinylbenzoic acid glycidyl ester, allyl glycidyl ether, vinyl glycidyl ether, 4-vinylbenzyl glycidyl ether, α-methyl-4-vinylbenzyl glycidyl ether, 2,4-bis(epoxypropoxy methyl) styrene, or 2,4,6-tris(epoxypropoxy methyl) styrene.

[0413] As the unsaturated carboxylic acid having an ethylenically unsaturated double bond group, for example, there can be mentioned (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, succinic acid mono (2-propenoyloxyethyl ester), phthalic acid mono (2-propenoyloxyethyl ester), tetrahydrophthalic acid mono (2-propenoyloxyethyl ester), 2-vinyl acetic acid, 2-vinyl cyclohexanecarboxylic acid, 3-vinyl cyclohexanecarboxylic acid, 4-vinyl cyclohexanecarboxylic acid, 2-vinyl benzoic acid, 3-vinyl benzoic acid, 4-vinyl benzoic acid, (meth) acrylic acid 4-hydroxyphenyl ester, or (meth) acrylic acid 2-hydroxyphenyl ester.

[0414] As the tetracarboxylic acid, tetracarboxylic dianhydride, tricarboxylic acid, tricarboxylic anhydride, dicarboxylic acid, dicarboxylic anhydride, dicarboxylic acid diacyl chloride, dicarboxylic acid active diester, monocarboxylic acid, monocarboxylic acid acid chloride, or monocarboxylic acid active ester, there can be mentioned a compound contained in the above-mentioned tetracarboxylic acid and / or derivative thereof, tricarboxylic acid and / or derivative thereof, dicarboxylic acid and / or derivative thereof, monocarboxylic acid, monocarboxylic acid acid chloride, or monocarboxylic acid active ester.

[0415] As the catalyst used in the ring-opening addition reaction of the compound represented by General Formula (59) having an epoxy group and two or more aromatic groups in the molecule, the unsaturated compound represented by General Formula (60) having an ethylenically unsaturated double bond group and an epoxy group, or the unsaturated carboxylic acid having an ethylenically unsaturated double bond group, for example, there can be mentioned an amine-based catalyst such as triethylamine, dimethyl aniline, tetramethyl ethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, dimethyl benzyl amine, or tri-n-octyl 7 amine, a quaternary ammonium salt such as tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium fluoride, or alkyl urea such as tetramethyl urea, alkyl guanidine such as tetramethyl guanidine, a tin-based catalyst such as bis (2-ethyl hexanoate) tin (II) or di-n-butyl tin (IV) dilaurate, a titanium-based catalyst such as tetra (2-ethyl hexanoate) titanium (IV), a phosphorus-based catalyst such as triphenyl phosphine or triphenyl phosphine oxide, a chromium-based catalyst such as tris (acetylacetone) chromium (III), chromium (III) chloride, chromium (III) octanoate, or chromium (III) naphthenate, or a cobalt-based catalyst such as cobalt (II) octanoate.

[0416] <structural units derived from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tetracarboxylic dianhydride having a fluorine atom, tricarboxylic acid having a fluorine atom, and dicarboxylic acid having a fluorine atom>

[0417] As the aromatic resin having a polycyclic side chain used in the present application, (A2c-1) preferably contains structural units derived from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tetracarboxylic dianhydride having a fluorine atom, tricarboxylic acid having a fluorine atom, and dicarboxylic acid having a fluorine atom. By making the aromatic resin having a polycyclic side chain of (A2c-1) contain structural units derived from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tetracarboxylic dianhydride having a fluorine atom, tricarboxylic acid having a fluorine atom, and dicarboxylic acid having a fluorine atom, the transparency is improved, and the sensitivity at the time of exposure can be improved. In addition, water repellency can be imparted to the film surface, and penetration from the film surface at the time of alkali development can be suppressed.

[0418] As the tetracarboxylic acid having a fluorine atom, tetracarboxylic dianhydride having a fluorine atom, tricarboxylic acid having a fluorine atom, or dicarboxylic acid having a fluorine atom, a compound contained in the above-mentioned tetracarboxylic acid having a fluorine atom, tetracarboxylic acid derivative having a fluorine atom, dicarboxylic acid having a fluorine atom, or dicarboxylic acid derivative having a fluorine atom can be mentioned.

[0419] In the aromatic resin having a polycyclic side chain of (A2c-1), the contained ratio of structural units derived from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tetracarboxylic dianhydride having a fluorine atom, tricarboxylic acid having a fluorine atom, and dicarboxylic acid having a fluorine atom, among structural units derived from all tetracarboxylic acids and all dicarboxylic acids and their derivatives, is preferably in the range of 30 to 100 mol%, more preferably in the range of 50 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the contained ratio is in the above-mentioned range, the sensitivity at the time of exposure can be improved.

[0420] <structural units derived from one or more selected from the group consisting of tetracarboxylic acid having an aromatic group, tetracarboxylic dianhydride having an aromatic group, tricarboxylic acid having an aromatic group, and dicarboxylic acid having an aromatic group>

[0421] As the aromatic resin having a polycyclic side chain used in the present application, (A2c-1) preferably contains structural units derived from one or more selected from the group consisting of tetracarboxylic acid having an aromatic group, tetracarboxylic dianhydride having an aromatic group, tricarboxylic acid having an aromatic group, and dicarboxylic acid having an aromatic group. By making the aromatic resin having a polycyclic side chain of (A2c-1) contain structural units derived from one or more selected from the group consisting of tetracarboxylic acid having an aromatic group, tetracarboxylic dianhydride having an aromatic group, tricarboxylic acid having an aromatic group, and dicarboxylic acid having an aromatic group, the heat resistance of the cured film can be improved by the heat resistance of the aromatic group.

[0422] In addition, particularly when the (D1) pigment is contained as the (D) colorant described later, by causing the aromatic resin containing a polycyclic side chain to contain a structural unit derived from a copolymerization component having an aromatic group, it is possible to improve the dispersion stability of the (D1) pigment using the steric hindrance of the aromatic group. Furthermore, when the (D1) pigment is a (D1-2) organic pigment, since the aromatic group in the aromatic resin containing a polycyclic side chain interacts with the aromatic group of the (D1-2) organic pigment, it is possible to improve the dispersion stability of the (D1-2) organic pigment.

[0423] As the tetracarboxylic acid having an aromatic group, tetracarboxylic dianhydride having an aromatic group, tricarboxylic acid having an aromatic group, or dicarboxylic acid having an aromatic group, a compound contained in the above-described aromatic tetracarboxylic acid and / or derivative thereof, aromatic tricarboxylic acid and / or derivative thereof, or aromatic dicarboxylic acid and / or derivative thereof can be mentioned.

[0424] In the (A2c-1) aromatic resin containing a polycyclic side chain, the contained ratio of the structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having an aromatic group, tetracarboxylic dianhydride having an aromatic group, tricarboxylic acid having an aromatic group, and dicarboxylic acid having an aromatic group, among the structural units derived from all tetracarboxylic acids and all dicarboxylic acids and their derivatives, is preferably in the range of 10 to 100 mol%, more preferably in the range of 20 to 100 mol%, and further preferably in the range of 30 to 100 mol%. When the contained ratio is in the above-described range, it is possible to improve the heat resistance of the cured film.

[0425] <Structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having an alicyclic group, tetracarboxylic dianhydride having an alicyclic group, tricarboxylic acid having an alicyclic group, and dicarboxylic acid having an alicyclic group>

[0426] As the (A2c-1) aromatic resin containing a polycyclic side chain used in the present application, it is preferable to contain a structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having an alicyclic group, tetracarboxylic dianhydride having an alicyclic group, tricarboxylic acid having an alicyclic group, and dicarboxylic acid having an alicyclic group. By causing the (A2c-1) aromatic resin containing a polycyclic side chain to contain a structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having an alicyclic group, tetracarboxylic dianhydride having an alicyclic group, tricarboxylic acid having an alicyclic group, and dicarboxylic acid having an alicyclic group, it is possible to improve the heat resistance and transparency of the cured film by the heat resistance and transparency of the alicyclic group.

[0427] As the tetra carboxylic acid having an alicyclic group, the tetra carboxylic dianhydride having an alicyclic group, the tri carboxylic acid having an alicyclic group, or the di carboxylic acid having an alicyclic group, a compound contained in the above-described alicyclic tetra carboxylic acid and / or a derivative thereof, the alicyclic tri carboxylic acid and / or a derivative thereof, or the alicyclic di carboxylic acid and / or a derivative thereof can be exemplified.

[0428] In the aromatic resin containing a polycyclic side chain of (A2c-1), the contained ratio of the structural unit from one or more selected from the group consisting of the tetra carboxylic acid having an alicyclic group, the tetra carboxylic dianhydride having an alicyclic group, the tri carboxylic acid having an alicyclic group, and the di carboxylic acid having an alicyclic group among the structural units from all of the tetra carboxylic acid and all of the di carboxylic acid and their derivatives is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. When the contained ratio is within the above-described range, the heat resistance and the transparency of the cured film can be improved. On the other hand, the contained ratio is preferably 90 mol% or less, more preferably 85 mol% or less, and further preferably 75 mol% or less. When the contained ratio is within the above-described range, the mechanical properties of the cured film can be improved.

[0429] <Acidic group from tetra carboxylic acid, tetra carboxylic dianhydride, tri carboxylic acid, tri carboxylic anhydride, or di carboxylic dianhydride>

[0430] As the aromatic resin containing a polycyclic side chain used in the present application of (A2c-1), the structural unit from the tetra carboxylic acid, the tetra carboxylic dianhydride, the tri carboxylic acid, the tri carboxylic anhydride, or the di carboxylic dianhydride is contained, and it is preferable that the aromatic resin containing a polycyclic side chain of (A2c-1) has an acidic group. By making the aromatic resin containing a polycyclic side chain have an acidic group, the pattern processing property with an alkaline developer and the resolution after development can be improved.

[0431] As the acidic group, a group showing an acidity of pH less than 6 is preferable. As the group showing an acidity of pH less than 6, for example, a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a phenolic hydroxyl group, or a hydroxyimide group can be exemplified. From the viewpoint of improving the pattern processing property with an alkaline developer and improving the resolution after development, a carboxyl group, a carboxylic anhydride group, or a phenolic hydroxyl group is preferable, and a carboxyl group or a carboxylic anhydride group is more preferable.

[0432] As the tetra carboxylic acid, the tetra carboxylic dianhydride, the tri carboxylic acid, the tri carboxylic anhydride, or the di carboxylic dianhydride, the aforementioned compound can be exemplified.

[0433] The contained ratio of the structural unit from each monomer component in the aromatic resin containing a polycyclic side chain can be combined 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis, and ash measurement, etc. are used.

[0434] <Properties of aromatic resin containing polycyclic side chain>

[0435] As the Mw of the (A2c-1) aromatic resin containing polycyclic side chain used in the present application, it is preferably 500 or more, more preferably 1,000 or more, and further preferably 1,500 or more, as measured by GPC and calculated as polystyrene. When the Mw is within the above range, the resolution after development can be improved. On the other hand, as the Mw, it is preferably 100,000 or less, more preferably 50,000 or less, and further preferably 20,000 or less. When the Mw is within the above range, the planarity at the time of coating and the pattern processing properties with an alkaline developer can be improved.

[0436] <Acrylic resin>

[0437] As the (A2) resin containing an unsaturated group in the negative photosensitive resin composition of the present application, (A2c-2) acrylic resin can be contained. The (A2c-2) acrylic resin refers to a general acrylic resin described below.

[0438] As the (A2c-2) acrylic resin used in the present application, for example, an acrylic resin obtained by radical copolymerization of one or more copolymer components selected from the group consisting of a copolymer component having an acid group, a copolymer component from a (meth)acrylate, and other copolymer components can be mentioned.

[0439] The (A2c-2) acrylic resin used in the present application has an ethylenic unsaturated double bond group. The acrylic resin is a resin in which the ethylenic unsaturated double bond group can be easily introduced into a side chain branched from the main chain of the resin. The acrylic resin having an ethylenic unsaturated double bond group is a photocurable resin, and by UV curing at the time of exposure, a three-dimensional crosslinked structure of carbon-carbon bonds is formed. Therefore, by containing in the resin composition an acrylic resin having an ethylenic unsaturated double bond group in the side chain, the sensitivity at the time of exposure can be improved. In addition, in the three-dimensional crosslinked structure formed, an alicyclic structure or an aliphatic structure is the main component, so the softening point of the resin can be inhibited from being high, a low taper pattern shape can be obtained, and the mechanical properties of the obtained cured film can be improved. Therefore, it is suitable for cases where the cured film is used for uses requiring mechanical properties, and the like.

[0440] As the (A2c-2) acrylic resin used in the present application, from the viewpoint of improving the sensitivity at the time of exposure and improving the mechanical properties of the cured film, it is preferable to contain a structural unit represented by General Formula (61) and / or a structural unit represented by General Formula (62).

[0441] [Chemical Formula 26]

[0442]

[0443] In General Formulae (61) and (62), Rd 1 and Rd 2 each independently represents an alkyl group having an ethylenically unsaturated double bond group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 15 carbon atoms, or an aryl group with 6 to 15 carbon atoms. R 200 ~R 205 each independently represents hydrogen, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. X 90 and X 91 each independently represents a direct bond, an alkylene chain with 1 to 10 carbon atoms, a cycloalkylene chain with 4 to 10 carbon atoms, or an arylene chain with 6 to 15 carbon atoms. In General Formulae (61) and (62), Rd 1 and Rd 2 each independently is preferably an alkyl group having an ethylenically unsaturated double bond group with 1 to 6 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms. In addition, R 200 ~R 205 each independently is preferably hydrogen, an alkyl group with 1 to 6 carbon atoms, a cycloalkyl group with 4 to 7 carbon atoms, or an aryl group with 6 to 10 carbon atoms. In addition, X 90 and X 91 each independently is preferably a direct bond, an alkylene chain with 1 to 6 carbon atoms, a cycloalkylene chain with 4 to 7 carbon atoms, or an arylene chain with 6 to 10 carbon atoms. The above-mentioned alkyl group, cycloalkyl group, aryl group, alkylene chain, cycloalkylene chain, and arylene chain can have a heteroatom, and can be any of an unsubstituted form or a substituted form.

[0444] As the (A2c-2) acrylic acid resin used in the present application, it is preferable that a copolymerization component having an acid group or another copolymerization component is subjected to radical copolymerization to obtain the (A2c-2) acrylic acid resin. As the other copolymerization component, it is preferable that a copolymerization component having an aromatic group or a copolymerization component having an alicyclic group.

[0445] <Structure Unit from Copolymerization Component Having Acidic Group>

[0446] As the (A2c-2) acrylic acid resin used in the present application, it is preferable that a structure unit from a copolymerization component having an acid group is contained, and it is preferable that the acrylic acid resin has an acid group. By making the acrylic acid resin have an acid group, it is possible to improve the pattern processing property using an alkaline developer and the resolution after development.

[0447] As the acidic group, a group showing acidity with a pH of less than 6 is preferred. As the group showing acidity with a pH of less than 6, for example, a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a phenolic hydroxyl group, or a hydroxyimide group can be given. From the viewpoint of improving the pattern processing properties using an alkaline developer and improving the resolution after development, a carboxyl group, a carboxylic anhydride group, or a phenolic hydroxyl group is preferred, and a carboxyl group or a carboxylic anhydride group is more preferred.

[0448] As the copolymer component having an acidic group, for example, (meth)acrylic acid, (meth)acrylic anhydride, itaconic acid, itaconic anhydride, maleic acid, fumaric acid, succinic acid mono(2-acryloyloxyethyl ester), phthalic acid mono(2-acryloyloxyethyl ester), tetrahydrophthalic acid mono(2-acryloyloxyethyl ester), 2-vinylacetic acid, 2-vinylcyclohexanecarboxylic acid, 3-vinylcyclohexanecarboxylic acid, 4-vinylcyclohexanecarboxylic acid, 2-vinylbenzoic acid, 3-vinylbenzoic acid, 4-vinylbenzoic acid, (meth)acrylic acid 4-hydroxyphenyl ester, or (meth)acrylic acid 2-hydroxyphenyl ester can be given. From the viewpoint of improving the pattern processing properties using an alkaline developer and improving the resolution after development, (meth)acrylic acid, (meth)acrylic anhydride, itaconic acid, itaconic anhydride, maleic acid, fumaric acid, succinic acid mono(2-acryloyloxyethyl ester), phthalic acid mono(2-acryloyloxyethyl ester), or tetrahydrophthalic acid mono(2-acryloyloxyethyl ester) is preferred, and (meth)acrylic acid, (meth)acrylic anhydride, itaconic acid, itaconic anhydride, maleic acid, fumaric acid, and succinic acid mono(2-acryloyloxyethyl ester) is more preferred.

[0449] As the acid equivalent of the (A2c-2) acrylic acid resin used in the present application, 280 g / mol or more, more preferably 300 g / mol or more, and further preferably 400 g / mol or more is preferred. When the acid equivalent is 280 g / mol or more, film damage at the time of alkali development can be suppressed. On the other hand, as the acid equivalent, 1,400 g / mol or less, more preferably 1,100 g / mol or less, and further preferably 950 g / mol or less is preferred. When the acid equivalent is 1,400 g / mol or less, the pattern processing properties using an alkaline developer and the resolution after development can be improved. In addition, from the viewpoint of improving the pattern processing properties using an alkaline developer and improving the resolution after development, the acid equivalent is more preferably a carboxylic acid equivalent.

[0450] As the (A2c-2) acrylic resin used in the present application, when the acrylic resin has a carboxyl group, an acrylic resin having no epoxy group is preferred. If the acrylic resin has both a carboxyl group and an epoxy group, the carboxyl group and the epoxy group can possibly react in the preservation of the coating liquid of the resin composition. Thus, it becomes a cause of lowering the preservation stability of the coating liquid of the resin composition. As the acrylic resin having no epoxy group, an acrylic resin obtained by free radical copolymerization of a copolymerization component having a carboxyl group or a carboxylic anhydride group and another copolymerization component having no epoxy group is preferred.

[0451] <Structural unit from copolymerization component having aromatic group>

[0452] As the (A2c-2) acrylic resin used in the present application, it is preferred to contain a structural unit from a copolymerization component having an aromatic group. By containing a structural unit from a copolymerization component having an aromatic group in the acrylic resin, it is possible to improve the heat resistance of the cured film by the heat resistance of the aromatic group.

[0453] Further, especially when containing the (D1) pigment as the (D) colorant to be described later, by containing a structural unit from a copolymerization component having an aromatic group in the acrylic resin, it is possible to improve the dispersion stability of the (D1) pigment by the steric hindrance of the aromatic group. Furthermore, when the (D1) pigment is the (D1-2) organic pigment, since the aromatic group in the acrylic resin interacts with the aromatic group of the (D1-2) organic pigment, it is possible to improve the dispersion stability of the (D1-2) organic pigment.

[0454] As the copolymerization component having an aromatic group, for example, mono(2-acryloyloxyethyl) phthalate, 4-hydroxyphenyl (meth)acrylate, 2-hydroxyphenyl (meth)acrylate, phenyl (meth)acrylate, 4-methylphenyl (meth)acrylate, 4-phenylstyryl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 4-biphenyl (meth)acrylate, benzyl (meth)acrylate, phenylethyl (meth)acrylate, styrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, or α-methylstyrene can be given. From the viewpoint of improving the heat resistance of the cured film, mono(2-acryloyloxyethyl) phthalate, 4-hydroxyphenyl (meth)acrylate, 2-hydroxyphenyl (meth)acrylate, phenyl (meth)acrylate, 4-methylphenyl (meth)acrylate, 4-phenylstyryl (meth)acrylate, 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, 4-biphenyl (meth)acrylate, styrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, or α-methylstyrene are preferred, and 1-naphthyl (meth)acrylate, 2-naphthyl (meth)acrylate, styrene are more preferred.

[0455] The content ratio of the structural unit derived from the copolymerization component having an aromatic group in the acrylic resin is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more, in the total structural units derived from the copolymerization components. When the content ratio is within the above range, the heat resistance of the cured film can be improved. On the other hand, the content ratio of the structural unit derived from the copolymerization component having an aromatic group is preferably 80 mol% or less, more preferably 75 mol% or less, and further preferably 70 mol% or less. When the content ratio is within the above range, the sensitivity at the time of exposure can be improved.

[0456] <Structural unit derived from copolymerization component having alicyclic group>

[0457] As the (A2c-2) acrylic resin used in the present application, it is preferable to contain a structural unit derived from a copolymerization component having an alicyclic group. By containing a structural unit derived from a copolymerization component having an alicyclic group in the acrylic resin, the heat resistance and transparency of the cured film can be improved by the heat resistance and transparency of the alicyclic group.

[0458] As the copolymerization component having an alicyclic group, for example, mon(2-acryloyloxyethyl) tetrahydrophthalate, (meth)acrylic acid cyclopentyl ester, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid cyclohexenyl ester, (meth)acrylic acid (4-methoxy)cyclohexyl ester, (meth)acrylic acid (2-isopropyl oxycarbonyl)ethyl ester, (meth)acrylic acid (2-cyclopentyloxycarbonyl)ethyl ester, (meth)acrylic acid (2-cyclohexyloxycarbonyl)ethyl ester, (meth)acrylic acid (2-cyclohexenyl oxycarbonyl)ethyl ester, (meth)acrylic acid [2-(4-methoxycyclohexyl)oxycarbonyl]ethyl ester, 2-norbornene (meth)acrylic acid, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetracyclodecane (meth)acrylate, dicyclopentene (meth)acrylate, adamantane (meth)acrylate, adamantylmethyl (meth)acrylate, or [(1-methyl)adamantyl] (meth)acrylate can be given. From the viewpoint of improving the heat resistance and transparency of the cured film, (meth)acrylic acid 2-norbornyl ester, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetracyclodecane (meth)acrylate, dicyclopentene (meth)acrylate, adamantane (meth)acrylate, adamantylmethyl (meth)acrylate, or [(1-methyl)adamantyl] (meth)acrylate is preferable.

[0459] The content ratio of the structural unit derived from the copolymerization component having an alicyclic group in the acrylic resin is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more, in the structural units derived from all the copolymerization components. When the content ratio is within the above range, the heat resistance and the transparency of the cured film can be improved. On the other hand, the content ratio of the structural unit derived from the copolymerization component having an alicyclic group is preferably 90 mol% or less, more preferably 85 mol% or less, and further preferably 75 mol% or less. When the content ratio is within the above range, the mechanical properties of the cured film can be improved.

[0460] <Structural unit derived from copolymerization component having fluorine atom>

[0461] As the (A2c-2) acrylic resin used in the present application, it is preferable to contain a structural unit derived from a copolymerization component having a fluorine atom. By containing a structural unit derived from a copolymerization component having a fluorine atom in the acrylic resin, the transparency is improved, and the sensitivity at the time of exposure can be improved. In addition, water repellency can be imparted to the film surface, and the penetration from the film surface at the time of alkali development can be suppressed.

[0462] As the copolymerization component having a fluorine atom, for example, (meth)acrylic acid trifluoromethyl ester, (meth)acrylic acid (2,2,2-trifluoro)ethyl ester, (meth)acrylic acid (3,3,3-trifluoro)propyl ester, (meth)acrylic acid trifluoromethoxypropyl ester, (meth)acrylic acid (6,6,6,5,5,4,4,3,3-nonafluoro) n-hexyl ester, (meth)acrylic acid (1,2,3,4,5-pentafluoro) phenyl ester, or (meth)acrylic acid 3-(1,2,3,4,5-pentafluorophenyl) propyl ester can be given.

[0463] The content ratio of the structural unit derived from the copolymerization component having a fluorine atom in the acrylic resin is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more, in the structural units derived from all the copolymerization components. When the content ratio is within the above range, the sensitivity at the time of exposure can be improved. On the other hand, the content ratio of the structural unit derived from the copolymerization component having a fluorine atom is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. When the content ratio is within the above range, the mechanical properties of the cured film can be improved.

[0464] As the (A2c-2) acrylic resin used in the present application, it is preferable to contain a structural unit derived from a copolymerization component having a fluorine atom. By containing a structural unit derived from a copolymerization component having a fluorine atom in the acrylic resin, the transparency is improved, and the sensitivity at the time of exposure can be improved. In addition, water repellency can be imparted to the film surface, and the penetration from the film surface at the time of alkali development can be suppressed.

[0465] As the catalyst used in the ring-opening addition reaction of the unsaturated compound having an ethylenically unsaturated double bond group and an epoxy group represented by General Formula (60), for example, amine-based catalysts such as triethylamine, dimethyl aniline, tetramethylethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol, dimethylbenzylamine, or tri-n-octylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium fluoride, or alkyl ureas such as tetramethylurea, alkyl guanidines such as tetramethylguanidine, tin-based catalysts such as bis(2-ethylhexanoate)tin(II) or di-n-butyltin dilaurate, titanium-based catalysts such as tetra(2-ethylhexanoate)titanium(IV), phosphorus-based catalysts such as triphenylphosphine or triphenylphosphine oxide, chromium-based catalysts such as tris(acetylacetone)chromium(III), chromium(III) chloride, chromium(III) octoate, or chromium(III) naphthenate, or cobalt-based catalysts such as cobalt(II) octoate can be given.

[0466] The content ratio of the structural units from the various copolymer components in the acrylic resin can be combined 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis, and ash determination, etc.

[0467] <Physical properties of the acrylic resin>

[0468] As the double bond equivalent of the (A2-3) acrylic resin used in the present application, 150 g / mol or more, more preferably 200 g / mol or more, and further preferably 250 g / mol or more is preferable. When the double bond equivalent is 150 g / mol or more, the adhesion to the base substrate can be improved. On the other hand, as the double bond equivalent, 10,000 g / mol or less, more preferably 5,000 g / mol or less, and further preferably 2,000 g / mol or less is preferable. When the double bond equivalent is 10,000 g / mol or less, the sensitivity at the time of exposure can be improved.

[0469] As the Mw of the acrylic resin used in the present application, 1,000 or more, more preferably 3,000 or more, and further preferably 5,000 or more is preferable as measured by GPC and converted to polystyrene. When the Mw is within the above range, the resolution after development can be improved. On the other hand, as the Mw, 100,000 or less, more preferably 70,000 or less, and further preferably 50,000 or less is preferable. When the Mw is within the above range, the leveling at the time of coating and the patterning properties using an alkaline developer can be improved.

[0470] (A2c-2) The acrylic resin can be synthesized by a known method. For example, a method in which the copolymerization components are subjected to radical copolymerization in the presence of a radical polymerization initiator under air or under nitrogen can be mentioned. As the method for radical copolymerization, for example, a method in which the copolymerization components and the radical polymerization initiator are added to a reaction solvent after sufficiently performing nitrogen substitution in the reaction vessel under air or by bubbling, reduced pressure degassing, or the like, and then the reaction is performed at 60 to 110°C for 30 to 500 minutes can be mentioned. In addition, a chain transfer agent such as a mercaptan compound and / or a polymerization inhibitor such as a phenol compound can be used as necessary.

[0471] <carboxylic acid-modified epoxy resin>

[0472] The negative photosensitive resin composition of the present application can contain a (A2c-3) carboxylic acid-modified epoxy resin as the (A2) resin containing an unsaturated group. The (A2c-3) carboxylic acid-modified epoxy resin means a generally known carboxylic acid-modified epoxy resin described below.

[0473] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, for example, (I) a carboxylic acid-modified epoxy resin obtained by reacting a phenol compound, a carboxylic anhydride, and an epoxy compound; (II) a carboxylic acid-modified epoxy resin obtained by reacting an alcohol compound, a carboxylic anhydride, and an epoxy compound; (III) a carboxylic acid-modified epoxy resin obtained by reacting an epoxy compound, a carboxylic acid compound, and an epoxy compound; or (IV) a carboxylic acid-modified epoxy resin obtained by reacting an epoxy compound, a carboxylic acid compound, and a carboxylic anhydride can be mentioned.

[0474] The (A2c-3) carboxylic acid-modified epoxy resin is a thermosetting resin having a high-heat-resistant aromatic cyclic structure in the epoxy resin skeleton of the main chain. Therefore, by containing the carboxylic acid-modified epoxy resin in the resin composition, the heat resistance of the obtained cured film can be improved. Therefore, it is suitable for the case where the cured film is used for a use requiring heat resistance or the like.

[0475] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, an epoxy resin having an ethylenically unsaturated double bond group is preferable. The (A2c-3) carboxylic acid-modified epoxy resin is a resin which can easily introduce an ethylenically unsaturated double bond group into a side chain branched from the main chain of the resin. By having an ethylenically unsaturated double bond group, the carboxylic acid-modified epoxy resin is a photocurable resin, and a three-dimensional crosslinked structure in which carbon-carbon bonds are formed by UV curing at the time of exposure is formed. Therefore, by containing in the resin composition a carboxylic acid-modified epoxy resin having an ethylenically unsaturated double bond group in a side chain, it is possible to improve the sensitivity at the time of exposure. In addition, since the three-dimensional crosslinked structure formed has alicyclic structures or aliphatic structures as main components, it is possible to suppress the increase in the softening point of the resin, to obtain a low-tapered pattern shape, and to improve the mechanical properties of the obtained cured film. Therefore, it is suitable for cases where the cured film is used for applications requiring mechanical properties, and the like.

[0476] The (A2c-3) carboxylic acid-modified epoxy resin used in the present application has a carboxyl group and / or a carboxylic anhydride group as an alkali-soluble group. By having a carboxyl group and / or a carboxylic anhydride group, it is possible to improve the resolution after development.

[0477] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, from the viewpoint of improving the heat resistance of the cured film, it is preferable to contain one or more selected from the group consisting of a structural unit represented by General Formula (26), a structural unit represented by General Formula (27), a structural unit represented by General Formula (28), a structural unit represented by General Formula (29), a structural unit represented by General Formula (32), a structural unit represented by General Formula (33), and a structural unit represented by General Formula (34). In addition, the (A2c-3) carboxylic acid-modified epoxy resin used in the present application has an ethylenically unsaturated double bond group, and from the viewpoint of improving the sensitivity at the time of exposure and improving the mechanical properties of the cured film, it is preferable to have an ethylenically unsaturated double bond group at any one or more of the main chain, the side chain, and the terminal end.

[0478] [Chemical Formula 27]

[0479]

[0480] In General Formulas (26) to (29), X 21 ~ X 24 Each independently represents an aliphatic structure having 1 to 6 carbon atoms. Z 21 represents a condensed polycyclic aromatic hydrocarbon ring having 10 to 15 carbon atoms and 4 to 10 valences. R 71 ~ R 75 Each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R 76 and R 77 Each independently represents an alkyl group having 1 to 10 carbon atoms, R78 ~R 82 each independently represents a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R 83 ~R 88 each independently represents a substituent represented by General Formula (30). a, b, c, d, and e each independently represent an integer of 0 to 10, f represents an integer of 0 to 8, g represents an integer of 0 to 6, h, i, j, and k each independently represent an integer of 0 to 3, and 1 represents an integer of 0 to 4. In General Formulae (26) to (29), X 21 ~X 24 each independently preferably is an aliphatic structure having 1 to 4 carbon atoms. R 71 ~R 75 each independently preferably is an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, R 76 and R 77 each independently preferably is an alkyl group having 1 to 6 carbon atoms, R 78 ~R 82 each independently preferably is a halogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The above-mentioned alkyl group, cycloalkyl group, aryl group, aliphatic structure, and fused polycyclic aromatic hydrocarbon ring can have a hetero atom, and can be any of an unsubstituted form or a substituted form.

[0481] [Chemical Formula 28]

[0482]

[0483] In General Formula (30), X 25 represents an alkylene chain having 1 to 6 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms. R 89 ~R 91 each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 92 represents hydrogen or a substituent represented by General Formula (31). In General Formula (30), X 25 preferably is an alkylene chain having 1 to 4 carbon atoms or a cycloalkylene chain having 4 to 7 carbon atoms. R 89 and R 90 each independently preferably is hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably is hydrogen. R 91 preferably is hydrogen or an alkyl group having 1 to 4 carbon atoms, and more preferably is hydrogen or a methyl group. In General Formula (31), X 26 represents an alkylene chain having 1 to 6 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms. In General Formula (31), X 26An alkylene chain having 1 to 4 carbon atoms or a cycloalkylene chain having 4 to 7 carbon atoms is preferable. The alkylene chain, cycloalkylene chain, alkyl group and aryl group described above can be any of unsubstituted or substituted ones.

[0484] [Chemical Formula 29]

[0485]

[0486] In General Formulas (32) to (34), X 27 ~X 31 Each independently represents an aliphatic structure having 1 to 6 carbon atoms, X 32 and X 33 Each independently represents an alkylene chain having 1 to 6 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms. R 93 ~R 97 Each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R 98 ~R 104 Each independently represents halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, R 105 represents hydrogen or an alkyl group having 1 to 6 carbon atoms, R 106 and R 107 Each independently represents a substituent represented by General Formula (30), R 108 represents hydrogen, a substituent represented by General Formula (30) or a substituent represented by General Formula (31). m, n, o, p and q each independently represent an integer of 0 to 10, and r, s, t, u, v, w and x each independently represent an integer of 0 to 3. In General Formulas (32) to (34), X 27 ~X 31 Each independently preferably represents an aliphatic structure having 1 to 4 carbon atoms, X 32 and X 33 Each independently preferably represents an alkylene chain having 1 to 4 carbon atoms or a cycloalkylene chain having 4 to 7 carbon atoms. R 93 ~R 97 Each independently preferably represents an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 98 ~R 104 Each independently preferably represents halogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms or an aryl group having 6 to 10 carbon atoms, R 105 represents hydrogen or an alkyl group having 1 to 4 carbon atoms. The alkylene chain, cycloalkylene chain, alkyl group, cycloalkyl group, aryl group and aliphatic structure described above can have a hetero atom, and can be any of unsubstituted or substituted ones.

[0487] In the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, as the (A2c-3) carboxylic acid-modified epoxy resin having a structural unit represented by General Formula (34), a (A2c-3) carboxylic acid-modified epoxy resin having a substituent represented by General Formula (35) and / or a substituent represented by General Formula (36) at the terminal is preferred.

[0488] [Chemical Formula 30]

[0489]

[0490] In General Formula (35), R 109 represents a substituent represented by General Formula (30). In General Formula (36), X 34 represents an aliphatic structure having 1 to 6 carbon atoms. R 110 represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R 111 and R 112 each independently represent a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 113 represents a substituent represented by General Formula (30). α represents an integer of 0 to 10. β and γ represent integers of 0 to 4. In General Formula (36), X 34 is preferably an aliphatic structure having 1 to 4 carbon atoms. R 110 is preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, R 111 and R 112 each independently are preferably a halogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0491] <Method for synthesizing carboxylic acid-modified epoxy resin>

[0492] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, a (A2c-3) carboxylic acid-modified epoxy resin obtained by using any one or more of the following (I) to (IV) as a method for synthesis is preferred.

[0493] As the carboxylic acid-modified epoxy resin of (I), a carboxylic acid-modified epoxy resin obtained by subjecting an unsaturated compound represented by General Formula (60) having an ethylenically unsaturated double bond group and an epoxy group to ring-opening addition reaction with a resin obtained by reacting a compound having an aromatic group and having a phenolic hydroxyl group and / or a hydroxyl group with an active carboxylic acid derivative (one or more selected from the group consisting of tricarboxylic anhydride, tricarboxylic acid chloride, tricarboxylic acid active ester, dicarboxylic anhydride, dicarboxylic acid chloride, and dicarboxylic acid active ester) can be given. As the active carboxylic acid derivative, tricarboxylic anhydride or dicarboxylic anhydride is preferred.

[0494] As the carboxylic acid-modified epoxy resin of (II), a carboxylic acid-modified epoxy resin obtained by reacting an active carboxylic acid derivative (one or more selected from the group consisting of tricarboxylic anhydride, tricarboxylic acid chloride, tricarboxylic acid active ester, dicarboxylic anhydride, dicarboxylic acid chloride and dicarboxylic acid active ester) with a resin obtained by ring-opening addition reaction of a compound having an aromatic group and having a phenolic hydroxyl group and / or a hydroxyl group with an unsaturated compound having an ethylenic unsaturated double bond group and an epoxy group represented by general formula (60). As the active carboxylic acid derivative, tricarboxylic anhydride or dicarboxylic anhydride is preferable.

[0495] As the carboxylic acid-modified epoxy resin of (III), a carboxylic acid-modified epoxy resin obtained by ring-opening addition reaction of an unsaturated compound having an ethylenic unsaturated double bond group and an epoxy group represented by general formula (60) with a resin obtained by ring-opening addition reaction of a compound having an aromatic group and an epoxy group with a polyfunctional carboxylic acid (one or more selected from the group consisting of tetracarboxylic acid, tricarboxylic acid and dicarboxylic acid).

[0496] As the carboxylic acid-modified epoxy resin of (IV), a carboxylic acid-modified epoxy resin obtained by reacting an active carboxylic acid derivative (one or more selected from the group consisting of tricarboxylic anhydride, tricarboxylic acid chloride, tricarboxylic acid active ester, dicarboxylic anhydride, dicarboxylic acid chloride and dicarboxylic acid active ester) with a resin obtained by ring-opening addition reaction of a compound having an aromatic group and an epoxy group with an unsaturated carboxylic acid having an ethylenic unsaturated double bond group. As the active carboxylic acid derivative, tricarboxylic anhydride or dicarboxylic anhydride is preferable.

[0497] As the unsaturated compound having an ethylenic unsaturated double bond group and an epoxy group represented by general formula (60), as described above, for example, glycidyl (meth)acrylate, (α-ethyl)glycidyl (meth)acrylate, (α-n-propyl)glycidyl (meth)acrylate or (3,4-epoxy)heptyl (meth)acrylate, etc. can be mentioned.

[0498] As the unsaturated carboxylic acid having an ethylenic unsaturated double bond group, as described above, for example, (meth)acrylic acid, itaconic acid, maleic acid, fumaric acid or succinic acid mono(2-acryloyloxyethyl ester), etc. can be mentioned.

[0499] As the tetracarboxylic acid, tricarboxylic acid, tricarboxylic anhydride, tricarboxylic acid chloride, tricarboxylic acid active ester, dicarboxylic acid, dicarboxylic anhydride, dicarboxylic acid chloride or dicarboxylic acid active ester, a compound included in the aforementioned tetracarboxylic acid, tricarboxylic acid and / or derivative thereof, dicarboxylic acid and / or derivative thereof can be mentioned.

[0500] As the catalyst used in the ring-opening addition reaction of an unsaturated carboxylic acid having an ethylenically unsaturated double bond group, an unsaturated compound represented by General Formula (60) having an ethylenically unsaturated double bond group and an epoxy group, or an epoxy resin having an aromatic group and an epoxy group, for example, an amine-based catalyst, a quaternary ammonium salt, an alkyl urea, an alkyl guanidine, a tin-based catalyst, a titanium-based catalyst, a phosphorus-based catalyst, a chromium-based catalyst, or a cobalt-based catalyst can be cited, as described above.

[0501] <Structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tricarboxylic acid having a fluorine atom, tricarboxylic acid anhydride having a fluorine atom, dicarboxylic acid having a fluorine atom, and dicarboxylic acid anhydride having a fluorine atom>

[0502] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, it is preferable to contain a structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tricarboxylic acid having a fluorine atom, tricarboxylic acid anhydride having a fluorine atom, dicarboxylic acid having a fluorine atom, and dicarboxylic acid anhydride having a fluorine atom. By containing a structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tricarboxylic acid having a fluorine atom, tricarboxylic acid anhydride having a fluorine atom, dicarboxylic acid having a fluorine atom, and dicarboxylic acid anhydride having a fluorine atom in the (A2c-3) carboxylic acid-modified epoxy resin, transparency is improved, and sensitivity at the time of exposure can be improved. In addition, water repellency can be imparted to the film surface, and penetration from the film surface at the time of alkali development can be suppressed.

[0503] As the tetracarboxylic acid having a fluorine atom, the tricarboxylic acid having a fluorine atom, the tricarboxylic acid anhydride having a fluorine atom, the dicarboxylic acid having a fluorine atom, or the dicarboxylic acid anhydride having a fluorine atom, a compound included in the aforementioned tetracarboxylic acid having a fluorine atom and / or a derivative thereof, the tricarboxylic acid having a fluorine atom and / or a derivative thereof, the dicarboxylic acid having a fluorine atom and / or a derivative thereof can be cited.

[0504] In the (A2c-3) carboxylic acid-modified epoxy resin, the content ratio of the structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having a fluorine atom, tricarboxylic acid having a fluorine atom, tricarboxylic acid anhydride having a fluorine atom, dicarboxylic acid having a fluorine atom, and dicarboxylic acid anhydride having a fluorine atom, among the structural units derived from all of the tetracarboxylic acid and all of the dicarboxylic acid and their derivatives, is preferably in the range of 30 to 100 mol%, more preferably in the range of 50 to 100 mol%, and further preferably in the range of 70 to 100 mol%. When the content ratio is in the above range, sensitivity at the time of exposure can be improved.

[0505] <Structural unit derived from one or more selected from the group consisting of tetracarboxylic acid having an aromatic group, tricarboxylic acid having an aromatic group, tricarboxylic acid anhydride having an aromatic group, dicarboxylic acid having an aromatic group, and dicarboxylic acid anhydride having an aromatic group>

[0506] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, it is preferable to contain a structural unit derived from one or more selected from the group consisting of a tetracarboxylic acid having an aromatic group, a tricarboxylic acid having an aromatic group, a tricarboxylic anhydride having an aromatic group, a dicarboxylic acid having an aromatic group, and a dicarboxylic anhydride having an aromatic group. By making the (A2c-3) carboxylic acid-modified epoxy resin contain a structural unit derived from one or more selected from the group consisting of a tetracarboxylic acid having an aromatic group, a tricarboxylic acid having an aromatic group, a tricarboxylic anhydride having an aromatic group, a dicarboxylic acid having an aromatic group, and a dicarboxylic anhydride having an aromatic group, it is possible to improve the heat resistance of the cured film by the heat resistance of the aromatic group.

[0507] Further, especially in the case of containing the (D1) pigment as the (D) colorant described later, by making the (A2c-3) carboxylic acid-modified epoxy resin contain a structural unit derived from a copolymerization component having an aromatic group, it is possible to improve the dispersion stability of the (D1) pigment by the steric hindrance of the aromatic group. Furthermore, when the (D1) pigment is a (D1-2) organic pigment, since the aromatic group in the (A2c-3) carboxylic acid-modified epoxy resin interacts with the aromatic group of the (D1-2) organic pigment, it is possible to improve the dispersion stability of the (D1-2) organic pigment.

[0508] As the tetracarboxylic acid having an aromatic group, the tricarboxylic acid having an aromatic group, the tricarboxylic anhydride having an aromatic group, the dicarboxylic acid having an aromatic group, or the dicarboxylic anhydride having an aromatic group, a compound included in the aforementioned aromatic tetracarboxylic acid and / or a derivative thereof, aromatic tricarboxylic acid and / or a derivative thereof, aromatic dicarboxylic acid and / or a derivative thereof can be mentioned.

[0509] In the (A2c-3) carboxylic acid-modified epoxy resin, the content ratio of the structural unit derived from one or more selected from the group consisting of a tetracarboxylic acid having an aromatic group, a tricarboxylic acid having an aromatic group, a tricarboxylic anhydride having an aromatic group, a dicarboxylic acid having an aromatic group, and a dicarboxylic anhydride having an aromatic group, among the structural units derived from all tetracarboxylic acids and all dicarboxylic acids and their derivatives, is preferably in the range of 10 to 100 mol%, more preferably in the range of 20 to 100 mol%, and further preferably in the range of 30 to 100 mol%. When the content ratio is in the above range, it is possible to improve the heat resistance of the cured film.

[0510] <Structural unit derived from one or more selected from the group consisting of a tetracarboxylic acid having an alicyclic group, a tricarboxylic acid having an alicyclic group, a tricarboxylic anhydride having an alicyclic group, a dicarboxylic acid having an alicyclic group, and a dicarboxylic anhydride having an alicyclic group>

[0511] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, it is preferable to contain a structural unit derived from one or more selected from the group consisting of a tetra-carboxylic acid having an alicyclic group, a tri-carboxylic acid having an alicyclic group, a tri-carboxylic anhydride having an alicyclic group, a di-carboxylic acid having an alicyclic group, and a di-carboxylic anhydride having an alicyclic group. By making the (A2c-3) carboxylic acid-modified epoxy resin contain a structural unit derived from one or more selected from the group consisting of a tetra-carboxylic acid having an alicyclic group, a tri-carboxylic acid having an alicyclic group, a tri-carboxylic anhydride having an alicyclic group, a di-carboxylic acid having an alicyclic group, and a di-carboxylic anhydride having an alicyclic group, it is possible to improve the heat resistance and transparency of the cured film by the heat resistance and transparency of the alicyclic group.

[0512] As the tetra-carboxylic acid having an alicyclic group, the tri-carboxylic acid having an alicyclic group, the tri-carboxylic anhydride having an alicyclic group, the di-carboxylic acid having an alicyclic group, or the di-carboxylic anhydride having an alicyclic group, a compound included in the aforementioned alicyclic tetra-carboxylic acid and / or derivatives thereof, alicyclic tri-carboxylic acid and / or derivatives thereof, alicyclic di-carboxylic acid and / or derivatives thereof can be mentioned.

[0513] In the (A2c-3) carboxylic acid-modified epoxy resin, the contained ratio of the structural unit derived from one or more selected from the group consisting of a tetra-carboxylic acid having an alicyclic group, a tri-carboxylic acid having an alicyclic group, a tri-carboxylic anhydride having an alicyclic group, a di-carboxylic acid having an alicyclic group, and a di-carboxylic anhydride having an alicyclic group, among the structural units derived from all of the tetra-carboxylic acids and all of the di-carboxylic acids and their derivatives, is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 15 mol% or more. When the contained ratio is within the above range, it is possible to improve the heat resistance and transparency of the cured film. On the other hand, the contained ratio is preferably 90 mol% or less, more preferably 85 mol% or less, and further preferably 75 mol% or less. When the contained ratio is within the above range, it is possible to improve the mechanical properties of the cured film.

[0514] <Acidic group derived from tetra-carboxylic acid, tri-carboxylic acid, tri-carboxylic anhydride, and di-carboxylic anhydride>

[0515] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, it is preferable to contain a structural unit derived from a tetra-carboxylic acid, a tri-carboxylic acid, a tri-carboxylic anhydride, and a di-carboxylic anhydride. It is preferable that the (A2c-3) carboxylic acid-modified epoxy resin have an acidic group. By making the (A2c-3) carboxylic acid-modified epoxy resin have an acidic group, it is possible to improve the pattern processing properties with an alkaline developer and the resolution after development.

[0516] As the acidic group, a group showing acidity with pH less than 6 is preferred. As the group showing acidity with pH less than 6, for example, a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a phenolic hydroxyl group or a hydroxyimide group can be given. From the viewpoint of improving the pattern processing property with an alkaline developer and improving the resolution after development, a carboxyl group, a carboxylic anhydride group or a phenolic hydroxyl group is preferred, and a carboxyl group or a carboxylic anhydride group is more preferred.

[0517] As the tetracarboxylic acid, the tricarboxylic acid, the tricarboxylic anhydride or the dicarboxylic anhydride, the aforementioned compounds can be given.

[0518] The contained ratio of the structural unit from each monomer component in the (A2c-3) carboxylic acid-modified epoxy resin can be combined 1 H-NMR, 13 C-NMR, 29 Si-NMR, IR, TOF-MS, elemental analysis and ash determination, etc. are measured.

[0519] <Specific examples of carboxylic acid-modified epoxy resins>

[0520] As the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, for example, "KAYARAD" (registered trademark) PCR-1222H, KAYARAD PCR-1173H, KAYARAD PCR-1221H, KAYARAD PCR-1220H, KAYARAD CCR-1171H, KAYARAD CCR-1307H, KAYARAD CCR-1309H, KAYARAD CCR-1291H, KAYARAD CCR-1235, KAYARAD TCR-1348H, KAYARAD TCR-1323H, KAYARAD TCR-1347H, KAYARAD TCR-1338H, KAYARAD TCR-1352H, KAYARAD TCR-1353H, KAYARAD TCR-1354H, KAYARAD TCR-1355H, KAYARAD TCR-1356H, KAYARAD ZAR-1494H, KAYARAD ZAR-2001H, KAYARAD ZAR-1035, KAYARAD ZAR-2000, KAYARAD ZFR-1401H, KAYARAD ZFR-1491H, KAYARAD ZCR-1797H, KAYARAD ZCR-1798H, KAYARAD ZCR-1569H, KAYARAD ZCR-1798H, KAYARAD ZCR-1761H, KAYARAD ZCR-1601H, KAYARAD ZXR-1807H, KAYARAD ZXR-1816H, KAYARAD ZXR-1810H, KAYARAD ZCR-6001H, KAYARAD ZCR-6002H, KAYARAD ZCR-8001H, or KAYARAD ZCR-8002H (all of which are manufactured by Nippon Kayaku Co., Ltd.), or "NK OLIGO" (registered trademark) EA-6340, NK OLIGO EA-7140, or NK OLIGO EA-7340 (all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.) can be mentioned.

[0521] <Properties of the carboxylic acid-modified epoxy resin>

[0522] As the Mw of the (A2c-3) carboxylic acid-modified epoxy resin used in the present application, the value measured by GPC and calculated as polystyrene is preferably 500 or greater, more preferably 1,000 or greater, and further preferably 1,500 or greater. When the Mw is within the above range, the resolution after development can be improved. On the other hand, the Mw is preferably 100,000 or less, more preferably 50,000 or less, and further preferably 20,000 or less. When the Mw is within the above range, the planarity at the time of coating and the pattern processing properties using an alkaline developer can be improved.

[0523] <Novolac resin>

[0524] As the (Alb-4) Novolac resin, a resin having a weakly acidic group, which can be contained in the negative photosensitive resin composition of the present application, a general Novolac resin described below is meant.

[0525] As the (Alb-4) Novolac resin, a resin having a weakly acidic group, which can be contained in the negative photosensitive resin composition of the present application, a general Novolac resin described below is meant.

[0526] The (Alb-4) Novolac resin used in the present application is a resin obtained by reacting a phenol compound with an aldehyde compound or a ketone compound, and has an aromatic structure from the phenol compound. When the aldehyde compound and / or the ketone compound has an aromatic structure, it also has an aromatic structure from them. Therefore, by containing the (Alb-4) Novolac resin in the resin composition, the heat resistance of the obtained cured film can be improved. Thus, it is suitable for cases where the cured film is used for a use requiring heat resistance, and the like.

[0527] The (Alb-4) Novolac resin used in the present application has a phenolic hydroxyl group as a base-soluble group. By having a phenolic hydroxyl group, the half-tone characteristics can be improved. In addition to the phenolic hydroxyl group, a weakly acidic group such as a hydroxyimide group can be further present.

[0528] In the (Ala-4) carboxylic acid-modified Novolac resin used in the present application, as the base-soluble group, not only a phenolic hydroxyl group but also a carboxyl group and / or a carboxylic anhydride group are present. By having a carboxyl group and / or a carboxylic anhydride group, not only the half-tone characteristics but also the resolution after development can be improved.

[0529] As the phenolic compound, for example, phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 4-n-propylphenol, 4-n-butylphenol, 4-t-butylphenol, 1-naphthol, 2-naphthol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane, o-dihydroxybenzene, m-dihydroxybenzene, 1,4-hydroquinone, o-trihydroxybenzene, 1,2,4-benzene triol, or m-trihydroxybenzene can be given.

[0530] As the aldehyde compound, for example, formaldehyde, paraformaldehyde, acetaldehyde, triacetaldehyde, propionaldehyde, benzaldehyde, or salicylaldehyde can be given.

[0531] As the ketone compound, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, or benzophenone can be given.

[0532] As the Novolac resin used in the present application, a Novolac resin obtained by reacting a phenolic compound with an aldehyde compound and / or a ketone compound in the presence of an acid catalyst is preferred. The reaction of the phenolic compound with the aldehyde compound and / or the ketone compound is carried out in a solvent or without a solvent.

[0533] In addition, as the Novolac resin, a (Alb-4b) Resol resin obtained by the same reaction except that a base catalyst is used instead of the acid catalyst can be used.

[0534] As the acid catalyst, for example, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, or a polycarboxylic acid or an anhydride thereof or an ion exchange resin can be given. As the base catalyst, for example, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, diethylamine, triethanolamine, diethanolamine, N,N-dimethyl-4-aminopyridine, sodium hydroxide, potassium hydroxide, or an ion exchange resin can be given.

[0535] As the (Ala-4) carboxylic acid-modified Novolac resin used in the present application, a (Ala-4) carboxylic acid-modified Novolac resin of (I) and / or (II) below is preferred.

[0536] As the (Ala-4) carboxylic acid-modified Novolac resin of (I), a (Ala-4) carboxylic acid-modified Novolac resin obtained by reacting a part of the phenolic hydroxyl group of a (Alb-4) Novolac resin with a polyfunctional carboxylic anhydride (one or more selected from tetracarboxylic dianhydride, tricarboxylic anhydride, and dicarboxylic anhydride) and / or a polyfunctional carboxylic acid (one or more selected from tetracarboxylic acid, tricarboxylic acid, and dicarboxylic acid) can be given.

[0537] As the (II) (A1a-4) carboxylic acid-modified Novolac resin, there can be mentioned (A1a-4) carboxylic acid-modified Novolac resins obtained by reacting a phenolic compound having a carboxyl group and / or a carboxylic anhydride group with an aldehyde compound and / or a ketone compound in the presence of an acid catalyst.

[0538] In addition, as the (II) (A1a-4) carboxylic acid-modified Novolac resin, there can be mentioned (A1a-4b) carboxylic acid-modified Resol resins obtained by reacting the aforementioned (A1b-4b) Resol resin.

[0539] As the tetracarboxylic acid, tetracarboxylic dianhydride, tricarboxylic acid, tricarboxylic anhydride, dicarboxylic acid or dicarboxylic anhydride, there can be mentioned compounds contained in the aforementioned tetracarboxylic acid and / or derivative thereof, tricarboxylic acid and / or derivative thereof, or dicarboxylic acid and / or derivative thereof.

[0540] As the phenolic compound having a carboxyl group and / or a carboxylic anhydride group, there can be mentioned, for example, 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 4-hydroxy-3-methylbenzoic acid, 4-hydroxy-2-methylbenzoic acid, 5-hydroxy-2-methylbenzoic acid, 4-carboxy-1-naphthol, 3,3'-dicarboxy-4,4'-dihydroxydiphenyl, 4-carboxyhydroquinone, 2-carboxyhydroquinone, 4-hydroxyphenylacetic acid or salicylic acid.

[0541] <Properties of Novolac resin>

[0542] As the Mw of the Novolac resin used in the present application, it is preferably 500 or more, more preferably 1,000 or more, and further preferably 1,500 or more, as measured by GPC and calculated as polystyrene. When the Mw is within the above range, the resolution after development can be improved. On the other hand, as the Mw, it is preferably 100,000 or less, more preferably 50,000 or less, and further preferably 20,000 or less. When the Mw is within the above range, the leveling property at the time of coating and the pattern processing property with an alkaline developer can be improved.

[0543] <Polyhydroxystyrene>

[0544] As the (I) resin containing a weakly acidic group in the negative photosensitive resin composition of the present application, there can be mentioned (A1) polyhydroxystyrene. The (A1) polyhydroxystyrene is a compound having a weakly acidic group and having a structure represented by the following general formula (1).

[0545] The (Alb-5) polyhydroxystyrene used in the present application is a resin obtained by subjecting one or more copolymerization components selected from a hydroxystyrene compound copolymerization component, a styrene compound copolymerization component, and other copolymerization components to radical copolymerization, and has an aromatic structure derived from the hydroxystyrene compound copolymerization component and the styrene compound copolymerization component. Therefore, by incorporating the polyhydroxystyrene into the resin composition, the heat resistance of the obtained cured film can be improved. Thus, the cured film is suitable for use in applications requiring heat resistance, and the like.

[0546] The (Alb-5) polyhydroxystyrene used in the present application has a phenolic hydroxyl group as an alkali-soluble group. By having a phenolic hydroxyl group, the halftone characteristics can be improved. In addition to having a phenolic hydroxyl group, a weakly acidic group such as a hydroxyimide group can be further included.

[0547] In the (Ala-5) carboxylic acid-modified polyhydroxystyrene used in the present application, in addition to a phenolic hydroxyl group, a carboxyl group and / or a carboxylic anhydride group are included as alkali-soluble groups. By having a carboxyl group and / or a carboxylic anhydride group, the halftone characteristics and the resolution after development can be improved.

[0548] As the hydroxystyrene compound copolymerization component, for example, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2,4-dihydroxystyrene, 2,6-dihydroxystyrene, 2,4,6-trihydroxystyrene, 2,3,4,5-tetrahydroxystyrene, penta-hydroxystyrene, 2-hydroxy-a-methylstyrene, 3-hydroxy-a-methylstyrene, 4-hydroxy-a-methylstyrene, 1-(2-hydroxyphenyl)propene, 1-(3-hydroxyphenyl)propene, or 1-(4-hydroxyphenyl)propene can be given.

[0549] As the styrene compound copolymerization component, for example, styrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, a-methylstyrene, 1-phenylpropene, or 4-phenylstyrene (meth)acrylate can be given.

[0550] As the other copolymerization components, methyl (meth)acrylate, ethyl (meth)acrylate, (2-hydroxy)ethyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecyl (meth)acrylate, tetracyclodecyl (meth)acrylate, phenyl (meth)acrylate, or benzyl (meth)acrylate can be given.

[0551] As the polyhydroxystyrene used in the present application, a polyhydroxystyrene obtained by subjecting one or more copolymerization components selected from a hydroxystyrene compound copolymerization component, a styrene compound copolymerization component, and other copolymerization components to radical copolymerization in the presence of a radical polymerization initiator or an anionic polymerization initiator is preferred.

[0552] Examples of free radical polymerization initiators include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanitrile), or 2,2'-azobis(4-methoxy-2,4-dimethylpentanitrile), as well as organic peroxides such as lauroyl peroxide, di-tert-butyl peroxide, bis(4-tert-butylcyclohexane-1-ester) peroxydicarbonate, tert-butyl 2-ethylperoxyhexanoate, methyl ethyl ketone peroxide, benzoyl peroxide, or cumene hydroperoxide.

[0553] Preferred conditions for free radical copolymerization include, for example, thoroughly replacing the nitrogen in the reaction vessel under air or by bubbling, degassing, or other methods, adding the copolymerizing component and free radical polymerization initiator to the reaction solvent, and reacting at 60–110°C for 30–500 minutes. When using a copolymerizing component with a carboxylic anhydride group, it is preferable to add the theoretical amount of water and react at 30–60°C for 30–60 minutes. Additionally, chain transfer agents such as thiols and / or polymerization inhibitors such as phenols can be used as needed.

[0554] Examples of organic base compounds that can be used as anionic polymerization initiators include n-butyllithium, sec-butyllithium, tert-butyllithium, ethyllithium, sodium ethyl, 1,1-diphenylhexyllithium, or 1,1-diphenyl-3-methylpentyllithium.

[0555] As conditions for anionic polymerization, for example, it is preferable to fully replace the nitrogen in the reaction vessel by bubbling, degassing under reduced pressure, etc., and then add the copolymerizing component and the anionic polymerization initiator to the reaction solvent and react at -100 to 50°C for 30 to 500 minutes.

[0556] As the (A1a-5) carboxylic acid modified polyhydroxystyrene used in this invention, the following (I) and / or (II) types of (A1a-5) carboxylic acid modified polyhydroxystyrene are preferred.

[0557] As (I), (A1a-5) carboxylic acid modified polyhydroxystyrene can be exemplified by reacting a portion of the phenolic hydroxyl groups of (A1b-5) polyhydroxystyrene with a polyfunctional carboxylic anhydride (selected from one or more of tetracarboxylic dianhydride, tricarboxylic anhydride and dicarboxylic anhydride) and / or a polyfunctional carboxylic acid (selected from one or more of tetracarboxylic acid, tricarboxylic acid and dicarboxylic acid).

[0558] As (II), (A1a-5) carboxylic acid modified polyhydroxystyrene can be exemplified by free radical copolymerization of one or more copolymers selected from hydroxystyrene compounds, styrene compounds, other copolymers, and copolymers having carboxyl groups and / or carboxylic anhydride groups.

[0559] As the tetracarboxylic acid, tetracarboxylic dianhydride, tricarboxylic acid, tricarboxylic anhydride, dicarboxylic acid, or dicarboxylic anhydride, a compound included in the aforementioned tetracarboxylic acid and / or derivative thereof, tricarboxylic acid and / or derivative thereof, or dicarboxylic acid and / or derivative thereof can be exemplified.

[0560] As the copolymerization component having a carboxyl group and / or carboxylic anhydride group, for example, a hydroxystyrene compound such as 2-hydroxy-4-vinylbenzoic acid, 3-hydroxy-4-vinylbenzoic acid, 4-hydroxy-2-vinylbenzoic acid, 4-hydroxy-3-vinylbenzoic acid, 3-hydroxy-4-vinylbenzoic acid, 2-hydroxy-4-carboxy-a-methylstyrene, or 1-(2-hydroxy-4-carboxy)phenylpropene, a styrene compound such as 2-vinylbenzoic acid, 3-vinylbenzoic acid, or 4-vinylbenzoic acid, or other copolymerization components such as (meth)acrylic acid, (meth)acrylic anhydride, itaconic acid, itaconic anhydride, maleic acid, fumaric acid, succinic acid mono(2-acryloyloxyethyl ester), phthalic acid mono(2-acryloyloxyethyl ester), tetrahydrophthalic acid mono(2-acryloyloxyethyl ester), 2-vinylacetic acid, 2-vinylcyclohexanecarboxylic acid, 3-vinylcyclohexanecarboxylic acid, or 4-vinylcyclohexanecarboxylic acid can be exemplified.

[0561] <Properties of polyhydroxystyrene>

[0562] As the Mw of the polyhydroxystyrene used in the present application, preferably 500 or more, more preferably 1,000 or more, and further preferably 1,500 or more, in terms of polystyrene equivalent, as measured by GPC. When the Mw is within the above range, the resolution after development can be improved. On the other hand, as the Mw, preferably 100,000 or less, more preferably 50,000 or less, and further preferably 20,000 or less. When the Mw is within the above range, the leveling property at the time of coating and the pattern processing property with an alkaline developer can be improved.

[0563] <Content ratio of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polysiloxane, resin having polycyclic side chain, and carboxylic acid-modified epoxy resin>

[0564] In the negative photosensitive resin composition of the present application, the content ratio of one or more selected from the group consisting of (Ala-l) polyimide, (Ala-2) polyimide precursor, (Ala-3) carboxylic acid-modified polysiloxane, (Alb-l) polybenzoxazole, (Alb-2) polybenzoxazole precursor, and (Alb-3) polysiloxane in 100 mass% of the resin having a weak acid group (Al) is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, further preferably 70 to 100 mass%, further more preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass%. When the content ratio is within the above range, the heat resistance of the cured film can be improved.

[0565] In the negative photosensitive resin composition of the present application, the content ratio of one or more selected from the group consisting of (A2a-1) unsaturated group-containing polyimide, (A2a-2) unsaturated group-containing polyimide precursor, (A2a-3) carboxylic acid-modified unsaturated group-containing polysiloxane, (A2b-1) unsaturated group-containing polybenzoxazole, (A2b-2) unsaturated group-containing polybenzoxazole precursor, (A2b-3) unsaturated group-containing polysiloxane, (A2c-1) aromatic resin having polycyclic side chains, and (A2c-3) carboxylic acid-modified epoxy resin in 100 mass% of (A2) unsaturated group-containing resin is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, further preferably 70 to 100 mass%, further more preferably 80 to 100 mass%, and particularly preferably 90 to 100 mass%. When the content ratio is within the above range, the heat resistance of the cured film can be improved.

[0566] When the content ratio of (A1) weak acid group-containing resin and (A2) unsaturated group-containing resin in the negative photosensitive resin composition of the present application is within the above range, the heat resistance of the cured film can be improved, and the sensitivity and halftone characteristics at the time of exposure can be improved. Thus, it is possible to maintain high sensitivity while forming a cured film having a step-shaped form in which there is a sufficient film thickness difference between thick film portions and thin film portions. Therefore, the cured film obtained from the negative photosensitive resin composition of the present application is suitable for an insulating layer such as a pixel partition layer of an organic EL display, and the like, which requires high heat resistance and a step-shaped form. Particularly in applications in which problems due to heat resistance (element malfunctions or property reductions due to gas generation by thermal decomposition, and the like) are expected to occur, by using the cured film of the negative photosensitive resin composition of the present application, it is possible to manufacture an element of high reliability in which the above problems do not occur. Furthermore, when the negative photosensitive resin composition of the present application contains (D) colorant described later, it is possible to prevent visibility of electrode wiring or reduce external light reflection, and it is possible to improve the contrast of image display.

[0567] <(B) Radical polymerizable compound>

[0568] As the negative photosensitive resin composition of the present application, it is preferable to further contain (B) radical polymerizable compound.

[0569] (B) Radical polymerizable compound" means a compound having a plurality of ethylenic unsaturated double bond groups in the molecule. At the time of exposure, radical polymerization of (B) radical polymerizable compound proceeds by means of radicals generated from (C1) photopolymerization initiator described later, so that the exposed portion of the resin composition film becomes insoluble in an alkali developer, and thus a negative pattern can be formed.

[0570] By containing (B) a radical polymerizable compound, UV curing at the time of exposure can be promoted, and sensitivity at the time of exposure can be improved. Furthermore, crosslinking density after thermal curing is improved, and the hardness of the cured film can be improved.

[0571] As (B) a radical polymerizable compound, a compound having a (meth)acrylic group that easily undergoes radical polymerization is preferable. From the viewpoint of improving sensitivity at the time of exposure and improving the hardness of the cured film, a compound having two or more (meth)acrylic groups in the molecule is more preferable. As the double bond equivalent of (B) a radical polymerizable compound, from the viewpoint of improving sensitivity at the time of exposure and improving the hardness of the cured film, 80 to 400 g / mol is preferable.

[0572] As the (B) radical polymerizable compound, for example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ethoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloyloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloyloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)phenyl]fluorene, or 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, or acid-modified, oxirane-modified, or propylene oxide-modified products thereof can be mentioned.From the viewpoint of improving sensitivity at the time of exposure and improving the hardness of the cured film, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloyloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloyloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)phenyl]fluorene, or 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, or an acid-modified product, an oxirane-modified product, or an epoxy propane-modified product thereof are preferable, and from the viewpoint of improving the resolution after development, an acid-modified product or an oxirane-modified product thereof is more preferable. In addition, from the viewpoint of improving the resolution after development, a compound obtained by subjecting a compound having two or more epoxy propoxy groups in the molecule to ring-opening addition reaction with an unsaturated carboxylic acid having an ethylenic unsaturated double bond group, and then reacting the obtained compound with a polycarboxylic acid or a polycarboxylic anhydride is also preferable.

[0573] The content of the (B) free radical polymerizable compound in the negative photosensitive resin composition of the present application is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, further preferably 25 parts by mass or more, and particularly preferably 30 parts by mass or more, based on 100 parts by mass of the total amount of the (A) alkali-soluble resin and the (B) free radical polymerizable compound. When the content is within the above range, the sensitivity at the time of exposure can be improved, and a low-tapered pattern shape can be obtained. On the other hand, the content of the (B) free radical polymerizable compound is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, further preferably 55 parts by mass or less, and particularly preferably 50 parts by mass or less. When the content is within the above range, the half-tone characteristics can be improved. In addition, the heat resistance of the cured film can be improved, and a low-tapered pattern shape can be obtained.

[0574] <Negative photosensitivity>

[0575] The negative photosensitive resin composition of the present application preferably further contains a (C) photosensitizer. In addition, it is preferable to contain the (B) free radical polymerizable compound and the (C) photosensitizer. As the (C) photosensitizer, a (C1) photopolymerization initiator and / or a (C2) photoacid generator are preferable.

[0576] By containing (C1) a photopolymerization initiator and / or (C2) a photoacid generator, a negative photosensitivity can be imparted to the resin composition of the present application.

[0577] <(C1) Photopolymerization initiator>

[0578] The (C1) photopolymerization initiator refers to a compound that generates radicals by bond cleavage and / or reaction upon exposure to light.

[0579] By containing (C1) a photopolymerization initiator, radical polymerization of the above-mentioned (B) radical polymerizable compound is allowed to proceed, and the exposed portion of the resin composition film becomes insoluble in an alkali developer, thereby forming a negative pattern. In addition, UV curing at the time of exposure can be promoted, and the sensitivity can be improved.

[0580] As the (C1) photopolymerization initiator, for example, a benzil ketal-based photopolymerization initiator, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, an acyloxyphosphine-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, an acridine-based photopolymerization initiator, a titanocene-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an aromatic ketone ester-based photopolymerization initiator, or a benzoic acid ester-based photopolymerization initiator is preferred from the viewpoint of improving the sensitivity at the time of exposure, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, an acyloxyphosphine-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, an acridine-based photopolymerization initiator, or a benzophenone-based photopolymerization initiator is more preferred, and an α-aminoketone-based photopolymerization initiator, an acyloxyphosphine-based photopolymerization initiator, or an oxime ester-based photopolymerization initiator is further preferred.

[0581] As the benzil ketal-based photopolymerization initiator, for example, 2,2-dimethoxy-1,2-diphenylethane-1-one can be mentioned.

[0582] As the α-hydroxyketone-based photopolymerization initiator, for example, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropane-1-one, or 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl]-2-methylpropane-1-one can be mentioned.

[0583] As the α-amino ketone-based photopolymerization initiator, for example, 2-methyl-1- [4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- morpholinophenyl)butan-1-one, or 3,6-bis(2-methyl-2-morpholinopropanoyl)-9-octyl- 9H-carbazole can be given.

[0584] As the acylphosphine oxide-based photopolymerization initiator, for example, 2,4,6- trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide can be given.

[0585] As the oxime ester-based photopolymerization initiator, for example, 1-phenylpropane-1,2- dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4- (phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4- (carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2- methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2- methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methoxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, or 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2- methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime can be given.

[0586] As the acridine-based photopolymerization initiator, for example, 1,7-bis(acridin-9-yl)- n-heptane can be given.

[0587] As the titanocene-based photopolymerization initiator, for example, bis(η 5 -2,4-cyclopentadien-1-yl)-bis[2,6-difluoro)-3-(1H-pyrrol-1-yl)phenyl]titanium(IV) or bis(η 5 -3-methyl-2,4-cyclopentadien-1-yl)-bis(2,6-difluorophenyl)titanium(IV).

[0588] As the benzophenone-based photopolymerization initiator, for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, 4-hydroxybenzophenone, alkylated benzophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4-methylbenzophenone, dibenzylketone, or fluorenone can be given.

[0589] As the acetophenone-based photopolymerization initiator, for example, 2,2-diethoxyacetophenone, 2,3-diethoxyacetophenone, 4-tert-butyl-dichloroacetophenone, benzalacetophenone, or 4-azidedbenzalacetophenone can be given.

[0590] As the aromatic ketone ester-based photopolymerization initiator, for example, 2-phenyl-2-oxoacetate methyl can be given.

[0591] As the benzoic acid ester-based photopolymerization initiator, for example, ethyl 4-dimethylaminobenzoate, (2-ethyl)hexyl 4-dimethylaminobenzoate, ethyl 4-diethylaminobenzoate, or methyl 2-benzoylbenzoate can be given.

[0592] In the case where the total amount of (A) the alkali-soluble resin and (B) the radical polymerizable compound is 100 parts by mass, the content of (C1) the photopolymerization initiator in the negative photosensitive resin composition of the present application is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 0.7 parts by mass or more, and particularly preferably 1 part by mass or more. When the content is within the above range, the sensitivity at the time of exposure can be improved. On the other hand, the content of (C1) the photopolymerization initiator is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, further preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content is within the above range, the half-tone characteristics can be improved. In addition, the resolution after development can be improved, and a pattern shape with low taper can be obtained.

[0593] <(C2) photoacid generator>

[0594] The (C2) photoacid generator refers to a compound that generates an acid by bond cleavage upon exposure.

[0595] By containing the (C2) photoacid generator, the UV curing at the time of exposure is promoted, and the sensitivity can be improved. In addition, the crosslinking density after thermal curing of the resin composition is improved, and the chemical resistance of the cured film can be improved.

[0596] As the (C2) photoacid generator, there are ionic compounds and non-ionic compounds.

[0597] As the ionic compound, a compound not containing a heavy metal, a halogen ion is preferred, and a triorganosulfonium salt compound is more preferred. As the triorganosulfonium salt compound, for example, a methanesulfonic acid salt, a trifluoromethanesulfonic acid salt, a camphorsulfonic acid salt, or a 4-toluenesulfonic acid salt of triphenylsulfonium; a methanesulfonic acid salt, a trifluoromethanesulfonic acid salt, a camphorsulfonic acid salt, or a 4-toluenesulfonic acid salt of dimethyl-1-naphthylsulfonium; a methanesulfonic acid salt, a trifluoromethanesulfonic acid salt, a camphorsulfonic acid salt, or a 4-toluenesulfonic acid salt of dimethyl(4-hydroxy-1-naphthyl)sulfonium; a methanesulfonic acid salt, a trifluoromethanesulfonic acid salt, a camphorsulfonic acid salt, or a 4-toluenesulfonic acid salt of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; a methanesulfonic acid salt, a trifluoromethanesulfonic acid salt, a camphorsulfonic acid salt, or a 4-toluenesulfonic acid salt of diphenyliodonium can be given.

[0598] As the non-ionic (C2) photoacid generator, for example, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate compound, a carboxylate compound, a sulfoximine compound, a phosphate compound, or a sulfone benzotriazole compound can be given.

[0599] As the halogen-containing compound, for example, a halogenated alkyl-containing hydrocarbon compound or a halogenated alkyl-containing heterocyclic compound can be given. As the halogen-containing compound, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane, 2-phenyl-4,6-bis(trichloromethyl) s-triazine, or 2-naphthyl-4,6-bis(trichloromethyl) s-triazine is preferred.

[0600] As the diazomethane compound, for example, bis(trifluoromethylsulfonyl) diazomethane, bis(cyclohexylsulfonyl) diazomethane, bis(phenylsulfonyl) diazomethane, bis(4-methylphenylsulfonyl) diazomethane, bis(2,4-dimethylphenylsulfonyl) diazomethane, bis(4-chlorophenylsulfonyl) diazomethane, methylsulfonyl-4-methylphenylsulfonyl diazomethane, cyclohexylsulfonyl(1,1-dimethylethylsulfonyl) diazomethane, bis(1,1-dimethylethylsulfonyl) diazomethane, or phenylsulfonyl(benzoyl) diazomethane can be given.

[0601] As the sulfone compound, for example, a β-ketosulfone compound, a β-sulfonylsulfone compound, or a diaryl disulfone compound can be given. As the sulfone compound, 4-tolylbenzoylmethyl sulfone, mesitylbenzoylmethyl sulfone, bis(phenylsulfonyl)methane, or a 4-chlorophenyl-4-tolyl disulfone compound is preferred.

[0602] As the sulfonate compound, for example, an alkyl sulfonate, a halogenated alkyl sulfonate, an aryl sulfonate, or an imino sulfonate compound can be given. As the sulfonate compound, benzoin-4-tolyl sulfonate, pyrogallol tris(methyl sulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, or 2,6-(dinitrobenzyl) phenyl sulfonate is preferred.

[0603] As an imidic sulfonate compound, for example, benzyl monoxime-4-tolylsulfonate, benzyl monoxime-4-dodecylphenylsulfonate, benzyl monoxime hexadecylsulfonate, 4-nitroacetophenone oxime-4-tolylsulfonate, 4,4'-dimethylbenzyl monoxime-4-tolylsulfonate, 4,4'-dimethylbenzyl monoxime-4-dodecylphenylsulfonate, dibenzyl ketoxime-4-tolylsulfonate, α-(4-tolylsulfonyloxy)imino-α-cyanoacetic acid ethyl ester, furanyl monoxime-4-(aminocarbonyl)phenylsulfonate, acetone oxime-4-benzoylphenylsulfonate, 3-(benzylsulfonyloxy)iminoacetylacetone, bis(benzyl monoxide) dioctyl naphthylsulfonate, α-(4-tolylsulfonyloxy)imino phenylacetonitrile, α-(4-tolylsulfonyloxy)imino-4-methoxyphenylacetonitrile, α-(10-camphorsulfonyloxy)imino-4-methoxyphenylacetonitrile, or 5-(4-tolylsulfonyloxy)imino-5H-thiophene-2-ylidene-(2-methylphenyl)acetonitrile.

[0604] As a carboxylic acid ester compound, for example, 2-nitrobenzyl carboxylate can be mentioned.

[0605] As the sulfimide compound, for example, N-(trifluoromethylsulfonyloxy)succinimide, N-(10-camphorsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(10-camphorsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(10-camphorsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(trifluoromethylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(2-trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid imide, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylic acid imide, N-(10-camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylic acid imide, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylic acid imide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylic acid imide, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxo-2,3-dicarboxylic acid imide,1] heptane-5, 6-oxyl-2, 3-dicarboxylic imide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylic imide, N- (10-camphorsulfonyloxy) naphthyl dicarboxylic imide, N- (4-tolylsulfonyloxy) naphthyl dicarboxylic imide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylic imide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylic imide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylic imide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylic imide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylic imide, N- (ethylsulfonyloxy) naphthyl dicarboxylic imide, N- (propylsulfonyloxy) naphthyl dicarboxylic imide, N- (butylsulfonyloxy) naphthyl dicarboxylic imide, N- (pentylsulfonyloxy) naphthyl dicarboxylic imide, N- (hexylsulfonyloxy) naphthyl dicarboxylic imide, N- (heptylsulfonyloxy) naphthyl dicarboxylic imide, N- (octylsulfonyloxy) naphthyl dicarboxylic imide, or N- (nonylsulfonyloxy) naphthyl dicarboxylic imide, and the like.

[0606] Among these (C2) photo-acid generators, from the viewpoints of solubility and insulation of the cured film, a non-ionic compound is preferred compared to an ionic compound. From the viewpoint of the strength of the generated acid, a compound that generates benzenesulfonic acid, 4-toluenesulfonic acid, a perfluoroalkylsulfonic acid, or phosphoric acid is more preferred. From the viewpoints of high sensitivity resulting from high quantum yield with respect to the j-line (wavelength 313 nm), the i-line (wavelength 365 nm), the h-line (wavelength 405 nm), or the g-line (wavelength 436 nm), and transparency of the cured film, a sulfonic acid ester compound, a sulfonylimine compound, an imino sulfonic acid ester compound is further preferred.

[0607] When the total amount of the (A) alkali-soluble resin and the (B) radical polymerizable compound is 100 parts by mass, the content of the (C2) photo-acid generator in the negative photosensitive resin composition of the present application is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 0.7 parts by mass or more, and particularly preferably 1 part by mass or more. When the content is within the above range, the sensitivity at the time of exposure can be improved. On the other hand, the content of the (C2) photo-acid generator is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, further preferably 17 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content is within the above range, the half-tone characteristics can be improved. In addition, the resolution after development can be improved, and a low-tapered pattern shape can be obtained.

[0608] <(D) colorant>

[0609] The negative photosensitive resin composition of the present application preferably further contains a (D) colorant.

[0610] The so-called (D) colorant is a compound that absorbs light of a specific wavelength, and particularly refers to a compound that colors by absorbing light of a visible light wavelength (380 to 780 nm).

[0611] By containing the (D) colorant, it is possible to color the film obtained from the resin composition, and it is possible to impart coloration (coloring the light that has passed through the resin composition film or the light that has been reflected by the resin composition film into a desired color). In addition, it is possible to impart light shielding properties (shielding the light of a wavelength that is absorbed by the (D) colorant from the light that has passed through the resin composition film or the light that has been reflected by the resin composition film).

[0612] As the (D) colorant, a compound that colors white, red, orange, yellow, green, blue, or purple by absorbing light of a visible light wavelength can be given. By combining two or more of these colorants of different colors, it is possible to improve the desired color matching properties (matching the color coordinates of the light that has passed through the resin composition film or the light that has been reflected by the resin composition film to desired color coordinates) of the resin composition.

[0613] As the negative photosensitive resin composition of the present application, it is preferable that the above-mentioned (D) colorant contain the following (D1) pigment and / or (D2) dye. As the negative photosensitive resin composition of the present application, it is preferable that the above-mentioned (D) colorant contain (Da) a black colorant and / or (Db) a colorant other than black.

[0614] The so-called (Da) black colorant refers to a compound that colors black by absorbing light of a visible light wavelength.

[0615] By containing the (Da) black colorant, it is possible to blacken the film of the resin composition, and thus it is possible to improve the light shielding properties (shielding the light that has passed through the resin composition film or the light that has been reflected by the resin composition film). As a result, it is suitable for use in the black matrix of a color filter, the light shielding film such as the black columnar spacer of a liquid crystal display, and the pixel partition layer or the TFT flattening layer of an organic EL display, and the like, which require high contrast achieved by suppressing the reflection of external light.

[0616] As the (Da) black colorant, from the viewpoint of light shielding properties, it is preferable to be a compound that colors black by absorbing light of the entire visible light wavelength. In addition, it is also preferable to be a mixture of two or more (D) colorants selected from among colorants of white, red, orange, yellow, green, blue, or purple. By combining two or more of these (D) colorants of different colors, it is possible to color black in a pseudo manner, and it is possible to improve the light shielding properties.

[0617] As the negative photosensitive resin composition of the present application, the above-mentioned (Da) black agent preferably contains one or more selected from the group consisting of the following (Dla) black pigment, (D2a-1) black dye, and (D2a-2) two or more kinds of dye mixture, and more preferably contains the following (Dla) black pigment from the viewpoint of light shielding property.

[0618] The so-called (Db) coloring agent other than black is a compound that colors by absorbing light of a visible light wavelength. That is, the coloring agent whose color is white, red, orange, yellow, green, blue, or violet (excluding black).

[0619] By containing the (Da) black agent and the (Db) coloring agent other than black, the resin composition film can be imparted with light shielding property, and coloring property and / or toning property.

[0620] As the negative photosensitive resin composition of the present application, the above-mentioned (Db) coloring agent other than black preferably contains the following (Dlb) coloring agent other than black and / or (D2b) coloring agent other than black, and more preferably contains the following (Dlb) coloring agent other than black from the viewpoint of light shielding property, and heat resistance or weather resistance.

[0621] In the negative photosensitive resin composition of the present application, the inclusion ratio of the (D) coloring agent in the total amount of 100 mass% of the (A) alkali-soluble resin, the (D) coloring agent, and the following (E) dispersant is preferably 15 mass% or more, more preferably 20 mass% or more, further preferably 25 mass% or more, and particularly preferably 30 mass% or more. When the inclusion ratio is within the above range, light shielding property, coloring property, or toning property can be improved. On the other hand, the inclusion ratio of the (D) coloring agent is preferably 80 mass% or less, more preferably 75 mass% or less, further preferably 70 mass% or less, and particularly preferably 65 mass% or less. When the inclusion ratio is within the above range, sensitivity at the time of exposure can be improved.

[0622] In addition, the inclusion ratio of the (D) coloring agent in the entire solid content (excluding a solvent) of the negative photosensitive resin composition of the present application is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, and particularly preferably 20 mass% or more. When the inclusion ratio is within the above range, light shielding property, coloring property, or toning property can be improved. On the other hand, the inclusion ratio of the (D) coloring agent in the entire solid content is preferably 70 mass% or less, more preferably 65 mass% or less, further preferably 60 mass% or less, further more preferably 55 mass% or less, and particularly preferably 50 mass% or less. When the inclusion ratio is within the above range, sensitivity at the time of exposure can be improved.

[0623] <(D1) Pigment>

[0624] As the negative photosensitive resin composition of the present application, it is preferable that the above-mentioned (D) colorant contain (D1) pigment. As a means of containing (D1) pigment, it is preferable that the above-mentioned (D) colorant contain (D1) pigment as the above-mentioned (Da) black colorant and / or (Db) colorant other than black.

[0625] (D1) pigment is a compound that colors an object by causing (D1) pigment to be physically adsorbed to the surface of the object or (D1) pigment to interact with the surface of the object, etc., and is generally insoluble in solvents, etc. In addition, the coloration by (D1) pigment is highly concealing and is not easily discolored by ultraviolet rays, etc.

[0626] By containing (D1) pigment, it is possible to color an excellent color in terms of concealing property, and it is possible to improve the light shielding property and weather resistance of the resin composition film.

[0627] The number average particle diameter of (D1) pigment is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and further preferably 10 to 200 nm. When the number average particle diameter of (D1) pigment is within the above-mentioned range, it is possible to improve the light shielding property of the resin composition film and the dispersion stability of (D1) pigment.

[0628] Here, the number average particle diameter of (D1) pigment can be found by using a submicron particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter) or a Zeta potential / particle diameter / molecular weight measuring device (Zetasizer NanoZS; manufactured by Sysmex Corporation) to measure laser scattering (dynamic light scattering method) caused by Brownian motion of (D1) pigment in solution. In addition, the number average particle diameter of (D1) pigment in a cured film obtained from a resin composition can be found by measuring using SEM and TEM. The magnification is set to 50,000 to 200,000 times, and the number average particle diameter of (D1) pigment is directly measured. When (D1) pigment is a round sphere, the diameter of the round sphere is measured and taken as the number average particle diameter. When (D1) pigment is not a round sphere, the longest diameter (hereinafter referred to as "major axis diameter") and the longest diameter in a direction orthogonal to the major axis diameter (hereinafter referred to as "minor axis diameter") are measured, and the average of the major axis diameter and the minor axis diameter is taken as the number average particle diameter.

[0629] (D1) pigment, for example, an organic pigment or an inorganic pigment can be mentioned.

[0630] By containing an organic pigment in the resin composition, coloration or toning can be imparted to the resin composition film. Furthermore, since it is organic, the transmission spectrum or absorption spectrum of the resin composition film can be adjusted (transmission of light of a desired specific wavelength or shielding of light of a desired characteristic wavelength, etc.) by chemical structure change or functional transformation, improving toning. In addition, since the insulating property and low dielectric property of organic pigments are excellent compared to general inorganic pigments, by containing an organic pigment, the resistance value of the film can be improved. Especially in the case of use as an insulating layer such as a pixel partition layer of an organic EL display, etc., light emission failure, etc. can be suppressed, improving reliability.

[0631] As the organic pigment, for example, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, pyranthrone pigments, dioxazine pigments, thioindigo pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, threne-type pigments, indolinine pigments, isoindolinine pigments, isoindolinone pigments, benzofuranone pigments, perylene pigments, aniline pigments, azo pigments, azomethine pigments, azo condensation pigments, carbon black, metal complex pigments, lake pigments, toner pigments, or fluorescent pigments can be given. From the viewpoint of heat resistance, anthraquinone pigments, quinacridone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, benzofuranone pigments, perylene pigments, azo condensation pigments, and carbon black are preferred.

[0632] As the phthalocyanine pigment, for example, phthalocyanine copper compounds, halogenated phthalocyanine copper compounds, or metal-free phthalocyanine compounds can be given.

[0633] As the anthraquinone pigment, for example, aminoanthraquinone compounds, diaminoanthraquinone compounds, anthrapyrimidine compounds, flavanthrone compounds, anthanthrone compounds, indathrone compounds, pyranthrone compounds, or violanthrone compounds can be given.

[0634] As the azo pigment, for example, disazo compounds or polyazo compounds can be given.

[0635] By containing an inorganic pigment in the resin composition, coloration or toning can be imparted to the resin composition film. Furthermore, since it is inorganic, heat resistance and weather resistance are more excellent, so the heat resistance and weather resistance of the resin composition film can be improved.

[0636] As the inorganic pigment, for example, titanium oxide, barium carbonate, zirconium oxide, zinc white, zinc sulfide, white lead, calcium carbonate, barium sulfate, white carbon, alumina white, silica, kaolin, talc, bentonite, red iron oxide, molybdenum chromium red, molybdenum chromium orange, chromium vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, chromium green, titanium cobalt green, cobalt green, cobalt chromium green, victoria green, ultramarine, prussian blue, cobalt blue, sky blue, cobalt silica dioxide blue, cobalt zinc silica dioxide blue, manganese violet, cobalt violet, graphite, or silver-tin alloy; or fine particles, oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, or oxynitrides of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver can be mentioned.

[0637] As the negative photosensitive resin composition of the present application, it is preferable that the above-mentioned (D1) pigment contains (D1a) black pigment described later, or contains (D1a) black pigment and / or (D1b) pigment other than black.

[0638] The content ratio of (D1) pigment in the total solid content (excluding the solvent) of the negative photosensitive resin composition of the present application is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more. When the content ratio is within the above-mentioned range, the light shielding property, coloring property, or toning property can be improved. On the other hand, the content ratio of (D1) pigment in the total solid content is preferably 70% by mass or less, more preferably 65% by mass or less, further preferably 60% by mass or less, further more preferably 55% by mass or less, particularly preferably 50% by mass or less. When the content ratio is within the above-mentioned range, the sensitivity at the time of exposure can be improved.

[0639] <(D1a) Black Pigment and (D2a) Pigment Other Than Black>

[0640] As the negative photosensitive resin composition of the present application, it is preferable that the above-mentioned (D1) pigment contains (D1a) black pigment, or contains (D1a) black pigment and / or (D1b) pigment other than black.

[0641] (D1a) Black Pigment means a pigment which is colored black by absorbing light of a visible light wavelength.

[0642] By containing (D1a) black pigment, the resin composition film is blackened, and the hiding property is excellent, so that the light shielding property of the resin composition film can be improved.

[0643] As the negative photosensitive resin composition of the present application, it is preferable that the above-mentioned (D1a) black pigment is one or more selected from (D1a-1) black organic pigment, (D1a-2) black inorganic pigment, and (D1a-3) mixture of two or more kinds of coloring pigments described later.

[0644] The so-called (D1b) pigments other than black are pigments that are colored in purple, blue, green, yellow, orange, red, or white (excluding black) by absorbing light of a visible light wavelength.

[0645] By containing (D1b) pigments other than black, the resin composition film can be colored, and colorability or toning can be imparted. By combining two or more kinds of (D1b) pigments other than black, the resin composition film can be toned to a desired color coordinate, and toning can be improved.

[0646] As (D1b) pigments other than black, pigments that are colored in white, red, orange, yellow, green, blue, or purple (excluding black) as described later can be given.

[0647] As the negative photosensitive resin composition of the present application, it is preferable that the above (D1b) pigments other than black be (D1b-1) organic pigments other than black and / or (D1b-2) inorganic pigments other than black as described later.

[0648] <(D1a-1) black organic pigments, (D1a-2) black inorganic pigments, and (D1a-3) two or more kinds of pigment mixtures>

[0649] As the negative photosensitive resin composition of the present application, it is preferable that the above (D1a) black pigments be one or more kinds selected from (D1a-1) black organic pigments, (D1a-2) black inorganic pigments, and (D1a-3) two or more kinds of colored pigment mixtures.

[0650] The so-called (D1a-1) black organic pigments are organic pigments that are colored in black by absorbing light of a visible light wavelength.

[0651] By containing (D1a-1) black organic pigments, the resin composition film is blackened, and the hiding property is excellent, and thus the light shielding property of the resin composition film can be improved. Furthermore, since it is an organic substance, the transmission spectrum or the absorption spectrum of the resin composition film can be adjusted (transmission of light of a desired specific wavelength or shielding of light of a desired specific wavelength, etc.) by chemical structural change or functional group conversion, and toning can be improved. In addition, compared to general inorganic pigments, (D1a-1) black organic pigments are excellent in insulating property and low dielectric property, and thus by containing (D1a-1) black organic pigments, the resistance value of the film can be improved. Especially in the case of being used as an insulating layer such as a pixel partition layer of an organic EL display, light emission failure and the like can be suppressed, and reliability can be improved.

[0652] As the (Dla-1) black organic pigment, for example, an anthraquinone-based black pigment, a benzofuranone-based black pigment, a perylene-based black pigment, an aniline-based black pigment, an azomethine-based black pigment, or carbon black can be given.

[0653] As the carbon black, for example, channel black, furnace black, thermal black, acetylene black, and lamp black can be given. From the viewpoint of light shielding property, channel black is preferred.

[0654] <Carbon black surface-treated>

[0655] As the carbon black, a carbon black surface-treated is preferred. As the surface treatment, a surface treatment for introducing an acidic group, a surface treatment using a silane coupling agent, or a coating treatment using a resin is preferred.

[0656] By applying the surface treatment for introducing an acidic group or the surface treatment using a silane coupling agent, it is possible to modify the surface state of the carbon black particles (acidify, hydrophilize, or hydrophobize the particle surface, etc.), and it is possible to improve the dispersion stability brought about by the resin contained in the resin composition, the (E) dispersant described later.

[0657] As the acidic group introduced into the carbon black by the surface treatment for introducing an acidic group, a substituent showing acidity in the Bronsted definition is given. As specific examples of the acidic group, a carboxyl group, a sulfonic acid group, or a phosphoric acid group can be given.

[0658] The acidic group introduced into the carbon black can form a salt. As the cation forming a salt with the acidic group, various metal ions, cations of nitrogen-containing compounds, arylammonium ions, alkylammonium ions, or ammonium ions can be given. From the viewpoint of the insulation property of the cured film, arylammonium ions, alkylammonium ions, or ammonium ions are preferred.

[0659] The number of moles of the acidic group introduced into the carbon black is preferably 1 mmol or more, more preferably 5 mmol or more, relative to 100 g of the carbon black. When the number of moles is within the above range, it is possible to improve the dispersion stability of the carbon black. On the other hand, the number of moles is preferably 200 mmol or less, more preferably 150 mmol or less. When the number of moles is within the above range, it is possible to improve the dispersion stability of the carbon black.

[0660] As the substituent introduced into the carbon black by the surface treatment using a silane coupling agent (hereinafter referred to as "surface-treated organosilane") which modifies the surface state of the carbon black particles, for example, an acidic group, a basic group, a hydrophilic group, or a hydrophobi...

Claims

1. A negative photosensitive resin composition, comprising at least (A1) a resin containing a weakly acidic group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin, and further comprising (B) a free radical polymerizable compound, (C) a photosensitizer and (D) a colorant. The (A1) resin containing a weakly acidic group has an acidic group in dimethyl sulfoxide with an acid dissociation constant in the range of 13.0 to 23.0, and the (A1) resin containing a weakly acidic group comprises one or more selected from (A1a-4) carboxylic acid modified Novolac resin, (A1a-5) carboxylic acid modified polyhydroxystyrene, (A1b-4) Novolac resin, and (A1b-5) polyhydroxystyrene. The resin containing unsaturated groups (A2) has olefinic unsaturated double bonds as free radical polymerizable groups. The resin containing unsaturated groups (A2) comprises one or more selected from the following: (A2a-1) polyimide containing unsaturated groups; (A2a-2) polyimide precursor containing unsaturated groups; (A2a-3) carboxylic acid-modified polysiloxane containing unsaturated groups; (A2b-1) polybenzoxazole containing unsaturated groups; (A2b-2) polybenzoxazole precursor containing unsaturated groups; (A2b-3) polysiloxane containing unsaturated groups; (A2c-1) aromatic resin containing polycyclic side chains; and (A2c-2) acrylic resin. The double bond equivalent of the (A2c-2) acrylic resin is 150 to 10,000 g / mol.

2. A negative photosensitive resin composition, comprising at least (A1) a resin containing a weakly acidic group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin, and further comprising (B) a free radical polymerizable compound, (C) a photosensitizer and (D) a colorant. The (A1) resin containing a weakly acidic group has an acidic group in dimethyl sulfoxide with an acid dissociation constant in the range of 13.0 to 23.0, and the (A1) resin containing a weakly acidic group comprises one or more selected from (A1a-4) carboxylic acid modified Novolac resin, (A1a-5) carboxylic acid modified polyhydroxystyrene, (A1b-4) Novolac resin, and (A1b-5) polyhydroxystyrene. The resin containing unsaturated groups (A2) has olefinic unsaturated double bonds as free radical polymerizable groups. The resin containing unsaturated groups (A2) comprises one or more selected from the following: (A2a-1) polyimide containing unsaturated groups; (A2a-2) polyimide precursor containing unsaturated groups; (A2a-3) carboxylic acid-modified polysiloxane containing unsaturated groups; (A2b-1) polybenzoxazole containing unsaturated groups; (A2b-2) polybenzoxazole precursor containing unsaturated groups; (A2b-3) polysiloxane containing unsaturated groups; (A2c-1) aromatic resin containing polycyclic side chains; and (A2c-2) acrylic resin. The (A2c-2) acrylic resin contains structural units represented by general formula (61) and / or structural units represented by general formula (62). In general formulas (61) and (62), Rd 1 and Rd 2 Each of these groups independently represents an alkyl group with 1 to 10 carbon atoms having an olefinic unsaturated double bond, a cycloalkyl group with 4 to 15 carbon atoms having an olefinic unsaturated double bond, or an aryl group with 6 to 15 carbon atoms having an olefinic unsaturated double bond; R 200 ~R 205 Each of these can independently represent hydrogen, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms; X 90 and X 91 Each can be independently represented as a direct linking bond, an alkylene chain with 1 to 10 carbon atoms, a cycloalkylene chain with 4 to 10 carbon atoms, or an arylene chain with 6 to 15 carbon atoms.

3. A negative photosensitive resin composition, comprising at least (A1) a resin containing a weakly acidic group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin, and further comprising (B) a free radical polymerizable compound, (C) a photosensitizer and (D) a colorant. The (A1) resin containing a weakly acidic group has an acidic group in dimethyl sulfoxide with an acid dissociation constant in the range of 13.0 to 23.0, and the (A1) resin containing a weakly acidic group comprises one or more selected from (A1a-4) carboxylic acid modified Novolac resin, (A1a-5) carboxylic acid modified polyhydroxystyrene, (A1b-4) Novolac resin, and (A1b-5) polyhydroxystyrene. The resin containing unsaturated groups (A2) has olefinic unsaturated double bonds as free radical polymerizable groups. The resin containing unsaturated groups (A2) comprises one or more selected from the following: (A2a-1) polyimide containing unsaturated groups; (A2a-2) polyimide precursor containing unsaturated groups; (A2a-3) carboxylic acid-modified polysiloxane containing unsaturated groups; (A2b-1) polybenzoxazole containing unsaturated groups; (A2b-2) polybenzoxazole precursor containing unsaturated groups; (A2b-3) polysiloxane containing unsaturated groups; (A2c-1) aromatic resin containing polycyclic side chains; and (A2c-2) acrylic resin. The (A2c-2) acrylic resin is obtained by further reacting a resin obtained by free radical copolymerization of a copolymer component with acidic groups with an unsaturated compound of general formula (60) having olefinic unsaturated double bond groups and epoxy groups through a ring-opening addition reaction. In general formula (60), X 87 Indicates a direct linker, an alkylene chain with 1-10 carbon atoms, a cycloalkylene chain with 4-10 carbon atoms, or an arylene chain with 6-15 carbon atoms; X 87 In the case of direct bonding or arylene chains with 6-15 carbon atoms, X 88 Indicates a direct connection key; X 87 In the case of an alkylene chain with 1 to 10 carbon atoms or a cycloalkylene chain with 4 to 10 carbon atoms, X 88 Indicates a direct linker or an aryl chain with 6-15 carbon atoms; R 198 It indicates a vinyl or (meth)acrylic group.

4. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein, The (D) colorant contains (D1) pigment. The (D1) pigment contains (D1a) black pigment.

5. The negative photosensitive resin composition as described in claim 4, wherein, The (D1a) black pigment contains (D1a-1a) benzofuranone-based black pigment and / or (D1a-1b) perylene-based black pigment as (D1a-1) black organic pigment.

6. The negative photosensitive resin composition as described in claim 5, wherein, The (D1a-1) black organic pigment contains (D1a-1a) benzofuranone-based black pigment.

7. The negative photosensitive resin composition of claim 4, further comprising (E) a dispersant. The (E) dispersant includes a dispersant having only an amine value, a dispersant having both an amine value and an acid value, or a dispersant having a structure in which an amino and / or acidic group forms a salt with an acid and / or a base.

8. The negative photosensitive resin composition of claim 4, further comprising (E) a dispersant and a solvent. The (E) dispersant comprises a dispersant having only an amine value, or a dispersant having a structure in which amino and / or acidic groups form salts with acids and / or bases. The negative photosensitive resin composition contains a solvent having a carbonyl or ester bond as the solvent. The solvent having a carbonyl or ester bond contains solvents having an acetate bond. The solvent having a carbonyl or ester bond accounts for 50 to 100% of the content of the solvent.

9. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein, The resin containing weak acid groups (A1) includes a resin containing two acid groups (A1a) and a second resin containing weak acid groups (A1b). The (A1a) resin containing two acidic groups comprises one or more selected from (A1a-4) carboxylic acid modified Novolac resin and (A1a-5) carboxylic acid modified polyhydroxystyrene. The second resin containing a weakly acidic group (A1b) comprises one or more selected from (A1b-4) Novolac resin and (A1b-5) polyhydroxystyrene.

10. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein, The resin containing weakly acidic groups (A1) has one or more acidic groups selected from phenolic hydroxyl and hydroxyimide groups.

11. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein, The resin (A1) containing weakly acidic groups does not have olefinic unsaturated double bond groups. The resin containing weak acid groups in (A1) accounts for 30% to 99% by mass of the alkali-soluble resin in (A).

12. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein, The acid equivalent of the resin containing weakly acidic groups (A1) is in the range of 200 to 1,200 g / mol.

13. A negative photosensitive resin composition comprising at least (A1) a resin containing a weakly acidic group and (A2) a resin containing an unsaturated group as (A) an alkali-soluble resin, and further comprising (B) a free radical polymerizable compound, (C) a photosensitizer, (E) a dispersant and a solvent. The (A1) resin containing a weakly acidic group has an acidic group in dimethyl sulfoxide with an acid dissociation constant in the range of 13.0 to 23.0, and the (A1) resin containing a weakly acidic group comprises one or more selected from (A1a-1) polyimide, (A1a-2) polyimide precursor, (A1a-3) carboxylic acid modified polysiloxane, (A1a-4) carboxylic acid modified Novolac resin, (A1a-5) carboxylic acid modified polyhydroxystyrene, (A1b-1) polybenzoxazole, (A1b-2) polybenzoxazole precursor, (A1b-3) polysiloxane, (A1b-4) Novolac resin, and (A1b-5) polyhydroxystyrene. The resin containing unsaturated groups (A2) has olefinic unsaturated double bonds as free radical polymerizable groups, and the resin containing unsaturated groups (A2) comprises one or more selected from polyimide containing unsaturated groups (A2a-1), polyimide precursor containing unsaturated groups (A2a-2), polybenzoxazole containing unsaturated groups (A2b-1), and polybenzoxazole precursor containing unsaturated groups (A2b-2). The negative photosensitive resin composition also contains (D1) pigment as (D) colorant. The (D1) pigment comprises (D1a) black pigment. The (D1a) black pigment contains (D1a-1a) benzofuranone-based black pigment and / or (D1a-1b) perylene-based black pigment as (D1a-1) black organic pigment. The (E) dispersant comprises a dispersant having only an amine value. The negative photosensitive resin composition contains a solvent having a carbonyl or ester bond as the solvent. The solvent having a carbonyl or ester bond contains solvents having an acetate bond. The solvent having a carbonyl or ester bond accounts for 50 to 100% of the content of the solvent.

14. A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 13.

15. The cured film as claimed in claim 14, wherein, The optical density per 1 μm of cured film thickness is in the range of 0.3 to 5.

0. The cured film comprises a cured pattern with a stepped shape, wherein the thickness of the thick film portion in the stepped shape of the cured pattern is set to (T). FT ) μm, and set the film thickness of the thin film portion as (T) μm. HT At μm, The (T) FT ) and (T HT ) film thickness difference (ΔT FT-HT The μm range is from 1.0 to 10.0 μm. The (T) FT ) and (T HT It also satisfies the relationship represented by the general formula (δ) ~ (ζ). 3.0≤(T FT )≤9.0 (d) 0.20≤(T HT )≤7.0 (e) 0.20×(T FT )≤(T HT )≤0.70×(T FT ) (ζ)。 16. An organic EL display comprising a cured film as claimed in claim 14 or 15, wherein the organic EL display comprises the cured film as one or more selected from a pixel segmentation layer, a color filter, a black matrix of the color filter, and a planarization film for a TFT.

17. A method for manufacturing an organic EL display, comprising the following steps: Step (1): Forming a coating film of the negative photosensitive resin composition according to any one of claims 1 to 13 on a substrate; Step (2): Irradiate the resin composition with active photochemical rays through a photomask; Step (3) involves developing a coating of the negative photosensitive resin composition using an alkaline solution to form a pattern of the resin composition with a stepped shape; and Step (4) involves heating the pattern to obtain a cured pattern of the resin composition with a stepped shape. in, The photomask is a halftone photomask having a pattern including a light-transmitting portion and a light-shielding portion, and the photomask has a semi-transparent portion between the light-transmitting portion and the light-shielding portion, wherein the transmittance of the semi-transparent portion is lower than that of the light-transmitting portion and higher than that of the light-shielding portion.

Images