Negative-type photosensitive composition containing a reflectance adjuster

Abstract

To provide a negative photosensitive composition capable of forming a cured film having high resolution, excellent light-shielding properties, and high reflectance. The negative photosensitive composition comprises an alkali-soluble resin having a specific structure, a reflectance adjuster, a polymerization initiator, and a solvent.

Description

[Technical Field]

[0001] The present invention relates to a negative-type photosensitive composition containing a reflectance adjuster. The present invention also relates to a method for producing a cured film using the composition, a cured film formed from the composition, and a device including the cured film. [Background technology]

[0002] In display devices such as organic electroluminescence devices (OLEDs), partition walls are formed to separate pixels, and these partition walls are generally formed by photolithography using a photosensitive resin composition. Transparent materials have been used as partition wall materials, but in order to further increase contrast, colored partition walls that have light-shielding properties have been studied. For example, the formation of black partition walls using a photosensitive resin composition containing a black colorant has been studied. White partition walls are also desired.

[0003] When a photosensitive resin composition containing a white colorant is used, the white colorant reflects light during exposure, preventing the light from reaching the bottom of the coating film of the photosensitive resin composition, adversely affecting patterning and making it difficult to achieve high resolution. Materials that can achieve thicker films are needed as materials for OLED partition walls and overcoats in display devices, but when a photosensitive resin composition containing a white colorant is made into a thick film, the effect of reflection from the white colorant becomes even greater than when a thin film is made. In the case of white partition walls, high reflectance is also required. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 056189 [Patent Document 2] Japanese Patent Application Laid-Open No. 2015-69085 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in light of the above-mentioned circumstances, and an object of the present invention is to provide a negative-type photosensitive composition capable of forming a cured film having high resolution, excellent light-shielding properties, and high reflectance. [Means for solving the problem]

[0006] The negative photosensitive composition according to the present invention comprises: (I) an alkali-soluble resin comprising a polymer containing a repeating unit represented by formula (A); [ka] (In the formula, X is independently C 1~27 is a substituted or unsubstituted hydrocarbon group of the formula a1 is 1 to 2, a2 is 0 to 3) (II) a reflectance adjuster, (III) a polymerization initiator, and (IV) Solvent The compound comprises:

[0007] The method for producing a cured film according to the present invention comprises applying the above-mentioned negative photosensitive composition to a substrate to form a film, exposing the film to light, and heating the film.

[0008] The cured film according to the present invention is produced by the method described above.

[0009] The device according to the present invention comprises the above-described cured film. [Effects of the Invention]

[0010] The negative photosensitive composition of the present invention can form a cured film having high resolution, excellent light-shielding properties, and high reflectance. Furthermore, the negative photosensitive composition of the present invention can achieve a thick film. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail. In this specification, unless otherwise specified, the symbols, units, abbreviations and terms have the following meanings. In this specification, unless otherwise specified, the singular includes the plural, and "one" and "the" mean "at least one." In this specification, unless otherwise specified, elements of a concept may be expressed by a plurality of species, and when an amount (e.g., mass % or mole %) is described, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of elements and also includes the use of a single element.

[0012] In this specification, when a numerical range is indicated using ~ or -, it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.

[0013] As used herein, hydrocarbon refers to a group containing carbon and hydrogen, and optionally oxygen or nitrogen. A hydrocarbon group refers to a monovalent or polyvalent hydrocarbon. As used herein, aliphatic hydrocarbon refers to a linear, branched, or cyclic aliphatic hydrocarbon, and aliphatic hydrocarbon group refers to a monovalent or polyvalent aliphatic hydrocarbon. Aromatic hydrocarbon refers to a hydrocarbon containing an aromatic ring, which may optionally have an aliphatic hydrocarbon group as a substituent or may be condensed with an alicyclic ring. Aromatic hydrocarbon group refers to a monovalent or polyvalent aromatic hydrocarbon. Furthermore, an aromatic ring refers to a hydrocarbon having a conjugated unsaturated ring structure, and an alicyclic ring refers to a hydrocarbon having a ring structure but not containing a conjugated unsaturated ring structure.

[0014] In this specification, alkyl refers to a group in which any one hydrogen atom has been removed from a linear or branched saturated hydrocarbon, and includes linear alkyl and branched alkyl. Cycloalkyl refers to a group in which one hydrogen atom has been removed from a saturated hydrocarbon containing a cyclic structure, and the cyclic structure may optionally contain a linear or branched alkyl atom as a side chain.

[0015] As used herein, aryl refers to a group obtained by removing one arbitrary hydrogen from an aromatic hydrocarbon. Alkylene refers to a group obtained by removing two arbitrary hydrogens from a linear or branched saturated hydrocarbon. Arylene refers to a hydrocarbon group obtained by removing two arbitrary hydrogens from an aromatic hydrocarbon.

[0016] As used herein, "C x~y "," "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1~6 Alkyl refers to an alkyl having 1 to 6 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). In addition, as used herein, fluoroalkyl refers to an alkyl in which one or more hydrogen atoms have been replaced with fluorine atoms, and fluoroaryl refers to an aryl in which one or more hydrogen atoms have been replaced with fluorine atoms.

[0017] In the present specification, when a polymer has multiple types of repeating units, these repeating units are copolymerized. The copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. In this specification, % means mass % and ratio means mass ratio.

[0018] In this specification, the unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0019] <Negative Photosensitive Composition> The negative-working photosensitive composition according to the present invention (hereinafter simply referred to as the "composition") comprises a specific alkali-soluble resin, a reflectance adjuster, a polymerization initiator, and a solvent. Each component contained in the composition according to the present invention will be described in detail below. The composition of the present invention is effective for films of 100 μm or less, but is a negative photosensitive composition for thick films that is particularly effective for applications involving the formation of thick films such as partition wall materials. Here, in the present invention, a thick film means a film having an average film thickness of 5 to 100 μm (preferably 5 to 25 μm, more preferably 8 to 20 μm). In the present invention, the average film thickness is determined by measuring the film thickness at three to five locations using a stylus-type surface profiler manufactured by ULBAC Corporation, and averaging the measurements.

[0020] (I) Alkali-soluble resin The alkali-soluble resin used in the present invention comprises a specific polymer containing a repeating unit represented by formula (A). Hereinafter, the alkali-soluble resin containing a repeating unit represented by formula (A) may be referred to as polymer A. [ka] During the ceremony, X is independently C 1~27 is a substituted or unsubstituted hydrocarbon group of the formula a1 is 1 to 2, preferably 1; a2 is 0 to 3, preferably 1. This polymer A may be a novolak polymer commonly used in lithography, such as one obtained by the condensation reaction of a phenol with formaldehyde.

[0021] The composition according to the present invention contains a reflectance modifier. White colorants generally reflect not only visible light but also ultraviolet light. In this case, when a composition containing a white colorant is applied to a substrate to form a coating film, the white colorant reflects ultraviolet light emitted by exposure, which may prevent the light from reaching the bottom of the coating film, resulting in failure to form a pattern. However, the composition according to the present invention can achieve high-resolution patterns by containing a polymer having the structure of formula (A) in addition to a reflectance adjuster. Without being bound by theory, when a composition containing a polymer having the structure of formula (A) is applied to a substrate to form a coating film, the ultraviolet light has low absorption and high transmittance during exposure, allowing the ultraviolet light to reach the bottom of the coating film and form a pattern. It is believed that subsequent heating at high temperatures oxidizes the methylene group in formula (A), increasing the absorption of ultraviolet light, and in combination with the reflectance adjuster, a cured film having low transmittance and high reflectance can be formed.

[0022] When it is desired to make the film thicker, X preferably contains a bulky group, and specifically, at least one X is preferably represented by -L-Ar, where L is C 1~8 is a straight or branched alkylene, preferably C 3~6 Specific examples of L include -C(CH3)2- and cyclohexane. Ar is C 6~22 substituted or unsubstituted aryl, preferably C 6~10 wherein the substituents are hydroxy or C 1~8 Specific examples of Ar include the following: [ka]

[0023] In a preferred embodiment, the alkali-soluble resin used in the present invention comprises a repeating unit represented by formula (A-1). [ka] wherein L and Ar are as defined above.

[0024] The alkali-soluble resin used in the present invention more preferably further contains a repeating unit represented by the following formula (A-2) in addition to the repeating unit represented by formula (A-1). [ka] During the ceremony, X' each independently represents C 1~8 unsubstituted alkyl, preferably methyl and ethyl; and a3 is 0 to 3, preferably 0 to 2, and more preferably 1.

[0025] The proportion of repeating units of formula (A-1) in polymer A is preferably 1 to 100%, more preferably 10 to 90%, and even more preferably 40 to 80%, based on the total number of repeating units in polymer A. The proportion of repeating units of formula (A-2) in polymer A is preferably 0 to 99%, more preferably 10 to 90%, based on the total number of repeating units in polymer A. Polymer A may also contain repeating units other than (A-1) and (A-2). Here, based on the total number of all repeating units contained in polymer A, the proportion of repeating units other than (A-1) and (A-2) is preferably 20% or less, and more preferably 10% or less. A preferred embodiment of the present invention is one in which polymer A does not contain repeating units other than (A-1) and (A-2).

[0026] The weight average molecular weight (hereinafter sometimes referred to as Mw) of polymer A is preferably 5,000 to 30,000, more preferably 6,000 to 15,000, and even more preferably 8,200 to 11,500. Here, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight, which can be measured by gel permeation chromatography using polystyrene as the standard. The same applies hereinafter.

[0027] The alkali-soluble resin used in the present invention may be a mixture of two or more types of polymer A, or may be a mixture further containing a polymer different from polymer A, i.e., a polymer not containing a repeating unit represented by formula (A). Preferably, the alkali-soluble resin used in the present invention further contains polysiloxane and / or acrylic polymer. From the viewpoint of dispersibility of the reflectance adjuster and heat resistance, it is more preferable to use polysiloxane.

[0028] (Polysiloxane) The polysiloxane used in the present invention is not particularly limited and can be selected from any suitable ones depending on the purpose. The skeletal structure of polysiloxane can be classified into a silicone skeleton (2 oxygen atoms bonded to silicon atom), a silsesquioxane skeleton (3 oxygen atoms bonded to silicon atom), and a silica skeleton (4 oxygen atoms bonded to silicon atom) depending on the number of oxygen atoms bonded to silicon atom. In the present invention, any of these may be used. The polysiloxane molecule may contain a combination of multiple of these skeletal structures.

[0029] Preferably, the polysiloxane used in the present invention comprises a repeating unit represented by the following formula (Ia): [ka] During the ceremony, R Ia is hydrogen, C 1~30 (Preferably C 1~10 ) represents a linear, branched or cyclic, saturated or unsaturated, aliphatic or aromatic hydrocarbon group; The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or C 1~8 is substituted with alkoxy, and In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, no methylene is replaced, or one or more methylenes are replaced by oxy, imino, or carbonyl, provided that R Iais not hydroxy or alkoxy. Here, the above methylene includes the terminal methyl. In addition, the above "fluorine, hydroxy or C 1~8 "Alkoxy-substituted" means that a hydrogen atom directly bonded to a carbon atom in the aliphatic hydrocarbon group or aromatic hydrocarbon group is substituted with a fluorine atom, a hydroxyl atom, or a C 1~8 The same applies to other similar descriptions in this specification.

[0030] In the repeating unit represented by formula (Ia), R Ia Examples of R include (i) alkyls such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryls such as phenyl, tolyl, and benzyl; (iii) fluoroalkyls such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl; (iv) fluoroaryls; (v) cycloalkyls such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure such as isocyanate and amino; and (vii) oxygen-containing groups having an epoxy structure such as glycidyl, or an acryloyl or methacryloyl structure. Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl, and phenyl. Ia When R is methyl, it is preferable because the raw material is easily available, the hardness of the film after curing is high, and the film has high chemical resistance. Ia When is phenyl, the solubility of the polysiloxane in a solvent is increased, and the cured film is less likely to crack, which is preferable.

[0031] The polysiloxane used in the present invention may further contain a repeating unit represented by the following formula (Ib): [ka] During the ceremony, R Ibis a group formed by removing multiple hydrogens from a nitrogen- and / or oxygen-containing cycloaliphatic hydrocarbon compound, including amino, imino, and / or carbonyl.

[0032] In formula (Ib), R Ib R is preferably a group in which multiple hydrogen atoms, preferably two or three hydrogen atoms, have been removed from a nitrogen-containing aliphatic hydrocarbon ring containing imino and / or carbonyl, more preferably a five- or six-membered ring containing nitrogen as a constituent member. Examples of R include groups in which two or three hydrogen atoms have been removed from piperidine, pyrrolidine, and isocyanurate. Ib connects Si atoms contained in multiple repeating units together.

[0033] The polysiloxane used in the present invention may further contain a repeating unit represented by the following formula (Ic): [ka]

[0034] If the compounding ratio of the repeating units represented by formula (Ib) and formula (Ic) is high, the sensitivity of the composition may decrease, the compatibility with solvents and additives may decrease, and the film stress may increase, making cracks more likely to occur. Therefore, the compounding ratio is preferably 40 mol % or less, and more preferably 20 mol % or less, of the total number of repeating units of the polysiloxane.

[0035] The polysiloxane used in the present invention may further contain a repeating unit represented by the following formula (Id): [ka] During the ceremony, R Id are each independently hydrogen, C 1~30 (Preferably C 1~10 ) represents a linear, branched or cyclic, saturated or unsaturated, aliphatic or aromatic hydrocarbon group; The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or C 1~8 is substituted with alkoxy, and In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced or one or more methylenes are replaced by oxy, imido or carbonyl, provided that R Id is not hydroxy or alkoxy.

[0036] In the repeating unit represented by formula (Id), R Id Examples of R include (i) alkyls such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryls such as phenyl, tolyl, and benzyl; (iii) fluoroalkyls such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl; (iv) fluoroaryls; (v) cycloalkyls such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure such as isocyanate and amino; and (vii) oxygen-containing groups having an epoxy structure such as glycidyl, or an acryloyl or methacryloyl structure. Methyl, ethyl, propyl, butyl, pentyl, hexyl, and phenyl are preferred. R Id When R is methyl, it is preferable because the raw material is easily available, the hardness of the film after curing is high, and the film has high chemical resistance. Id When is phenyl, the solubility of the polysiloxane in a solvent is increased, and the cured film is less likely to crack, which is preferable.

[0037] By including the repeating unit of formula (Id), the polysiloxane of the present invention can have a partially linear structure. However, since this reduces heat resistance, it is preferable to have a small linear structure portion. Specifically, the repeating unit of formula (Id) is preferably 30 mol % or less, more preferably 5 mol % or less, of the total number of repeating units of the polysiloxane. Having no repeating unit of formula (Id) (0 mol %) is also an embodiment of the present invention.

[0038] The polysiloxane used in the present invention may contain two or more types of repeating units. For example, R Ia is methyl, phenyl, and a repeating unit represented by formula (Ia), and a repeating unit represented by formula (Ic).

[0039] The polysiloxane used in the present invention preferably has silanol. Here, silanol refers to a compound in which an OH group is directly bonded to the Si skeleton of the polysiloxane, and is a compound in which a hydroxy group is directly bonded to a silicon atom in a polysiloxane containing repeating units such as those of the formulas (Ia) to (Id). That is, -O in the formulas (Ia) to (Id) 0.5 -O 0.5 Silanol is formed by bonding H. The silanol content in polysiloxane varies depending on the synthesis conditions of polysiloxane, such as the monomer ratio and the type of reaction catalyst.

[0040] The weight-average molecular weight of the polysiloxane used in the present invention is not particularly limited. However, higher molecular weights tend to improve coatability. On the other hand, lower molecular weights are easier to synthesize because fewer restrictions are placed on synthesis conditions, while polysiloxanes with very high molecular weights are difficult to synthesize. For these reasons, the weight-average molecular weight of the polysiloxane is usually 500 to 25,000, and from the viewpoint of solubility in organic solvents, it is preferably 1,000 to 20,000. Here, the weight-average molecular weight is the weight-average molecular weight in terms of polystyrene and can be measured by gel permeation chromatography using polystyrene as the standard.

[0041] The method for synthesizing the polysiloxane used in the present invention is not particularly limited, but it can be synthesized by the method disclosed in Japanese Patent No. 6639724, for example.

[0042] (acrylic polymer) The acrylic polymer used in the present invention can be selected from commonly used acrylic polymers, such as polyacrylic acid, polymethacrylic acid, alkyl polyacrylate, alkyl polymethacrylate, etc. The acrylic polymer used in the present invention preferably contains a repeating unit containing an acryloyl group, and also preferably further contains a repeating unit containing a carboxyl group and / or a repeating unit containing an alkoxysilyl group.

[0043] The repeating unit containing a carboxyl group is not particularly limited as long as it is a repeating unit containing a carboxyl group in the side chain, but is preferably a repeating unit derived from an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or a mixture thereof.

[0044] The repeating unit containing an alkoxysilyl group may be any repeating unit containing an alkoxysilyl group in the side chain, but is preferably a repeating unit derived from a monomer represented by the following formula (B). X B -(CH2) a -Si(OR B ) b (CH3) 3-b (B) In the formula, X B is a vinyl group, a styryl group, or a (meth)acryloyloxy group, and R B is a methyl group or an ethyl group, a is an integer of 0 to 3, and b is an integer of 1 to 3.

[0045] The polymer preferably contains a repeating unit containing a hydroxyl group, which is derived from a hydroxyl group-containing unsaturated monomer.

[0046] The weight-average molecular weight of the alkali-soluble resin according to the present invention is not particularly limited, but is preferably 1,000 to 40,000, and more preferably 2,000 to 30,000. Here, the weight-average molecular weight is the polystyrene-equivalent weight-average molecular weight determined by gel permeation chromatography. Furthermore, the number of acid groups is, from the viewpoints of enabling development with a low-concentration alkaline developer and achieving both reactivity and storage stability, typically a solids acid value of 40 to 190 mgKOH / g, and more preferably 60 to 150 mgKOH / g.

[0047] When a mixture of polymer A, polysiloxane, and acrylic polymer is used as the alkali-soluble resin, the blending ratio of the acrylic polymer to the polysiloxane is not particularly limited, but a higher blending ratio of the acrylic polymer is preferred when a thick coating film is desired, while a higher blending ratio of the polysiloxane is preferred when the coating is applied to a high-temperature process or from the viewpoint of transparency and chemical resistance after curing. For these reasons, the blending ratio of the polysiloxane to the acrylic-soluble resin is preferably 90:10 to 10:90, and more preferably 85:15 to 25:75. The polymer (A) may be a copolymer further containing repeating units represented by the above formulas (Ia) to (Id) which are the skeleton structure of polysiloxane, or repeating units which are the skeleton structure of the above acrylic polymer.

[0048] Furthermore, the composition of the present invention forms a cured film by coating on a substrate, imagewise exposing, and developing. It is necessary for the solubility of the exposed and unexposed portions to differ, and the unexposed portions of the coating film should have a certain level of solubility in a developer. For example, if the dissolution rate of the prebaked coating film in a 2.38% aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) (hereinafter sometimes referred to as alkaline dissolution rate or ADR, described in detail below) is 50 Å / sec or higher, it is believed that pattern formation by exposure and development is possible. However, since the required solubility varies depending on the average film thickness of the cured film to be formed and the development conditions, an alkali-soluble resin should be appropriately selected depending on the development conditions. Although this will vary depending on the type and amount of photosensitizer and silanol condensation catalyst contained in the composition, for example, if the average film thickness is 0.1 to 100 μm (1,000 to 1,000,000 Å), the dissolution rate in a 2.38% TMAH aqueous solution is preferably 50 to 20,000 Å / sec, and more preferably 100 to 10,000 Å / sec.

[0049] [Method for measuring and calculating alkaline dissolution rate (ADR)] The alkaline dissolution rate of an alkali-soluble resin is measured and calculated as follows using an aqueous TMAH solution as the alkaline solution.

[0050] The alkali-soluble resin was diluted to 35% by mass in propylene glycol monomethyl ether acetate (PGMEA) and dissolved at room temperature for 1 hour while stirring. In a clean room at a temperature of 23.0±0.5°C and a humidity of 50±5.0%, 1 cc of the prepared alkali-soluble resin solution was pipetted onto the center of a 4-inch, 525 μm-thick silicon wafer. The wafer was spin-coated to a thickness of 2±0.1 μm, and then heated on a hot plate at 100°C for 90 seconds to remove the solvent. The coating thickness was measured using a spectroscopic ellipsometer (JA Woollam).

[0051] Next, the silicon wafer with this film was gently immersed in a 6-inch diameter glass Petri dish containing 100 ml of a TMAH solution of a specified concentration adjusted to 23.0±0.1°C and left to stand. The time until the coating disappeared was measured. The dissolution rate was calculated by dividing the time by the time it took for the film to disappear from a portion 10 mm inward from the wafer edge. If the dissolution rate was significantly slow, the wafer was immersed in the TMAH solution for a certain period of time and then heated on a hot plate at 200°C for 5 minutes to remove any moisture absorbed into the film during the dissolution rate measurement. The film thickness was then measured and the change in film thickness before and after immersion was divided by the immersion time to calculate the dissolution rate. This measurement method was performed five times, and the average of the obtained values was used as the dissolution rate of the alkali-soluble resin.

[0052] (II) Reflectance adjuster The composition according to the present invention comprises a reflectance modifier. In the present invention, the reflectance modifier is a substance that can be combined with polymer A to form a cured film that achieves low transmittance and high reflectance. The color of the reflectance modifier itself is not particularly limited, but it is preferable that it be colored white by absorbing light with a wavelength of 370 to 740 nm. The reflectance adjuster may be an inorganic pigment or an organic pigment, or a combination of two or more pigments. In the present invention, since high scattering properties are desirable, an inorganic pigment is preferred.

[0053] Examples of inorganic pigments include alumina, magnesium oxide, antimony oxide, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, barium carbonate, calcium carbonate, lead sulfate, lead phosphate, zinc phosphate, silicon dioxide, zinc oxide, tin oxide, strontium sulfide, strontium titanate, barium tungstate, lead metasilicate, talc, kaolin, clay, bismuth oxide chloride, silica (e.g., hollow silica particles), titanium oxide, titanium oxynitride, and titanium nitride. Among these, at least one pigment selected from the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, titanium oxynitride, titanium nitride, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate is preferred. Titanium oxide is particularly preferred from the viewpoint of particle size control. These pigments may be core-shell type. Examples of organic pigments include organic compound salts disclosed in JP-A-11-129613, alkylenebismelamine derivatives, hollow particles made of thermoplastic resins such as styrene-acrylic copolymers, and the like.

[0054] The volume-based average particle size (hereinafter simply referred to as average particle size) of the reflectance adjuster is preferably 50 to 900 nm, more preferably 50 to 700 nm. By setting the average particle size within this range, good light-blocking properties and good film quality of the cured film can be obtained. Note that such average particle size can be measured in accordance with dynamic light scattering (DLS) using an apparatus such as a Nanotrac particle size analyzer manufactured by Nikkiso Co., Ltd.

[0055] The content of the reflectance adjuster used in the present invention is preferably 10 to 150% by mass, more preferably 20 to 110% by mass, based on the total mass of the alkali-soluble resin. The content of the reflectance adjuster is based on the mass of the pigment itself. In other words, although the reflectance adjuster may be obtained in a dispersed state using a dispersant, in this case, the mass of the reflectance adjuster does not include anything other than the pigment.

[0056] The reflectance adjuster used in the present invention can also be used in combination with a dispersant, such as an organic compound-based dispersant such as the polymer dispersant described in JP-A-2004-292672.

[0057] (III) Polymerization initiator The composition according to the present invention comprises a polymerization initiator. The polymerization initiator may be one that generates an acid, a base, or a radical when exposed to radiation, or one that generates an acid, a base, or a radical when exposed to heat. In the present invention, the reaction starts immediately after radiation exposure, eliminating the need for a reheating step that is performed after radiation exposure and before the development step. Therefore, the former is preferred in terms of shortening the process and reducing costs, and a photoradical generator is more preferred.

[0058] The photoradical generator can improve the resolution by strengthening the pattern shape and increasing the development contrast. The photoradical generator used in the present invention is a photoradical generator that releases radicals when irradiated with radiation. Here, examples of the radiation include visible light, ultraviolet light, infrared light, X-rays, electron beams, α rays, and γ rays.

[0059] The optimal amount of photoradical generator added varies depending on the type and amount of active substance generated by the decomposition of the photoradical generator, the required sensitivity, and the dissolution contrast between exposed and unexposed areas. However, it is preferably 0.001 to 50% by mass, more preferably 0.01 to 30% by mass, based on the total mass of the alkali-soluble resin. If the amount added is less than 0.001% by mass, the dissolution contrast between exposed and unexposed areas may be too low, resulting in ineffective addition. On the other hand, if the amount added is more than 50% by mass, cracks may occur in the formed coating, or discoloration due to decomposition of the photoradical generator may become noticeable. Furthermore, if the amount added is too high, thermal decomposition of the photoradical generator may cause deterioration of the electrical insulation of the cured product or gas emission, resulting in problems in subsequent processes. Furthermore, the resistance of the coating to photoresist stripping solutions, such as those containing monoethanolamine as a main component, may be reduced.

[0060] Examples of photoradical generators include azo-based, peroxide-based, acylphosphine oxide-based, alkylphenone-based, oxime ester-based, and titanocene-based initiators. Among them, alkylphenone-based, acylphosphine oxide-based, and oxime ester-based initiators are preferred, such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one. 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), and the like.

[0061] (IV) Solvent The composition according to the present invention contains a solvent. The solvent is not particularly limited as long as it can uniformly dissolve or disperse the alkali-soluble resin, reflectance adjuster, polymerization initiator, and additives added as needed. Examples of solvents that can be used in the present invention include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; and propane glycols such as propylene glycol monomethyl ether and propylene glycol monoethyl ether. Examples of suitable solvents include propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates such as PGMEA, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin; esters such as ethyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; and cyclic esters such as γ-butyrolactone. Among these, propylene glycol alkyl ether acetates or esters are preferred from the viewpoints of availability, ease of handling, and polymer solubility. From the viewpoints of coatability and storage stability, the solvent ratio of alcohol is preferably 5 to 80% by mass.

[0062] The solvent content of the composition of the present invention can be adjusted as desired depending on the method of applying the composition. For example, when applying the composition by spray coating, the solvent content of the composition can be 90% by mass or more. In addition, in slit coating, which is used for applying to large substrates, the solvent content is usually 60% by mass or more, preferably 70% by mass or more. The properties of the composition of the present invention do not change significantly depending on the amount of solvent.

[0063] The composition of the present invention essentially comprises the above-mentioned (I) to (IV), but can be combined with additional compounds as needed. The materials that can be combined are described below.

[0064] (V) Compounds containing two or more (meth)acryloyloxy groups The composition according to the present invention may further contain a compound containing two or more (meth)acryloyloxy groups (hereinafter, for simplicity, sometimes referred to as a (meth)acryloyloxy group-containing compound). Here, the (meth)acryloyloxy group is a general term for an acryloyloxy group and a methacryloyloxy group. This compound is a compound that can react with the acryloyl group-containing polysiloxane and the alkali-soluble resin to form a crosslinked structure. In order to form a crosslinked structure, a compound containing two or more reactive groups, acryloyloxy groups or methacryloyloxy groups, is required, and it is preferable that the compound contain three or more acryloyloxy groups or methacryloyloxy groups to form a higher-order crosslinked structure.

[0065] As such a compound containing two or more (meth)acryloyloxy groups, an ester obtained by reacting (α) a polyol compound having two or more hydroxyl groups with (β) two or more (meth)acrylic acids is preferably used. Examples of the polyol compound (α) include compounds having a basic skeleton of a saturated or unsaturated aliphatic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon, a primary, secondary, or tertiary amine, or an ether, and having two or more hydroxyl groups as a substituent. The polyol compound may contain other substituents, such as a carboxyl group, a carbonyl group, an amino group, an ether bond, a thiol group, or a thioether bond, as long as the effects of the present invention are not impaired.

[0066] Preferred polyol compounds include alkyl polyols, aryl polyols, polyalkanolamines, cyanuric acid, and dipentaerythritol. When the polyol compound (α) has three or more hydroxyl groups, not all of the hydroxyl groups need to be reacted with meth(acrylic acid), and they may be partially esterified. In other words, the ester may have unreacted hydroxyl groups. Examples of such esters include tris(2-acryloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, polytetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, tricyclodecane dimethanol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate, and 1,10-decanediol diacrylate. Among these, tris(2-acryloxyethyl)isocyanurate and dipentaerythritol hexaacrylate are preferred in terms of reactivity and the number of crosslinkable groups. Furthermore, two or more of these compounds can be combined to adjust the shape of the resulting pattern. Specifically, it is preferable to combine a compound containing three (meth)acryloyloxy groups with a compound containing two (meth)acryloyloxy groups.

[0067] From the viewpoint of reactivity, it is preferable that such compounds have relatively smaller molecules than the alkali-soluble resin, and therefore the molecular weight is preferably 2,000 or less, and more preferably 1,500 or less.

[0068] The content of the (meth)acryloyloxy group-containing compound is adjusted depending on the type of polymer and (meth)acryloyloxy group-containing compound used, but from the viewpoint of compatibility with the resin, it is preferably 5 to 300 mass %, more preferably 20 to 100 mass %, based on the total mass of the alkali-soluble resin. When a low-concentration developer is used, it is preferably 20 to 200 mass %. Furthermore, these (meth)acryloyloxy group-containing compounds may be used alone or in combination of two or more.

[0069] The content of components other than (I) to (V) in the entire composition is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less, based on the total mass of the composition.

[0070] (VI) Other additives The composition according to the present invention may contain other additives, if necessary. Such additives include developer dissolution promoters, scum removers, adhesion promoters, polymerization inhibitors, antifoaming agents, surfactants, sensitizers, crosslinking agents, and hardeners.

[0071] The developer dissolution promoter or scum remover adjusts the solubility of the formed film in the developer and prevents scum from remaining on the substrate after development. Crown ethers can be used as such additives. The crown ether with the simplest structure has the general formula (-CH2-CH2-O-) nAmong these, those in which n is 4 to 7 are preferred in the present invention. Crown ethers are sometimes called x-crown-y-ethers, where x is the total number of atoms constituting the ring and y is the number of oxygen atoms contained therein. In the present invention, crown ethers in which x=12, 15, 18, or 21 and y=x / 3, as well as those selected from the group consisting of their benzo-condensation products and cyclohexyl-condensation products, are preferred. More preferred examples of crown ethers include 21-crown-7 ether, 18-crown-6 ether, 15-crown-5 ether, 12-crown-4 ether, dibenzo-21-crown-7 ether, dibenzo-18-crown-6 ether, dibenzo-15-crown-5 ether, dibenzo-12-crown-4 ether, dicyclohexyl-21-crown-7 ether, dicyclohexyl-18-crown-6 ether, dicyclohexyl-15-crown-5 ether, and dicyclohexyl-12-crown-4 ether. Among these, 18-crown-6 ether and 15-crown-5 ether are most preferred. The content of the crown ether is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the alkali-soluble resin.

[0072] The adhesion promoter has the effect of preventing peeling of the pattern due to stress applied after baking when a cured film is formed using the composition according to the present invention. As the adhesion promoter, imidazoles and silane coupling agents are preferred, and among imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, and 2-aminoimidazole are preferred, and 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, and imidazole are particularly preferred.

[0073] Known silane coupling agents are suitably used, and examples thereof include epoxy silane coupling agents, amino silane coupling agents, and mercapto silane coupling agents. Specific examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane. These can be used alone or in combination, and the amount added is preferably 0.05 to 15% by mass based on the total mass of the alkali-soluble resin.

[0074] Furthermore, a silane compound or siloxane compound having an acid group can also be used as the silane coupling agent. Examples of the acid group include a carboxyl group, an acid anhydride group, and a phenolic hydroxyl group. When a monobasic acid group such as a carboxyl group or a phenolic hydroxyl group is contained, it is preferable that a single silicon-containing compound has multiple acid groups.

[0075] Specific examples of such silane coupling agents include those represented by formula (C): X n Si(OR 3 ) 4-n (C) or a polymer having the same as a repeating unit. In this case, X or R 3 A combination of multiple repeating units with different repeating units can be used.

[0076] In the formula, R 3 Examples of R include hydrocarbon groups, such as alkyl groups such as methyl, ethyl, n-propyl, isopropyl, and n-butyl. 3 There are multiple R 3may be the same or different.

[0077] Examples of X include those having an acid group such as phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, sulfo, and alcohol groups, as well as those in which the acid group is protected with an acetyl, aryl, amyl, benzyl, methoxymethyl, mesyl, tolyl, trimethoxysilyl, triethoxysilyl, triisopropylsilyl, or trityl group, and acid anhydride groups.

[0078] Of these, R 3 Preferred are those having a methyl group as X and a carboxylic acid anhydride group as X, such as an acid anhydride group-containing silicone. More specifically, a compound represented by the following formula (X-12-967C (trade name, Shin-Etsu Chemical Co., Ltd.)) or a polymer containing a corresponding structure at the end or side chain of a silicon-containing polymer such as silicone is preferred. [ka] Also preferred are compounds in which an acid group such as thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, or sulfo group is attached to the terminal of dimethyl silicone. Examples of such compounds include the compounds represented by the following formula (X-22-2290AS and X-22-1821 (both trade names, Shin-Etsu Chemical Co., Ltd.)). [ka]

[0079] When the silane coupling agent contains a silicone structure, if the molecular weight is too large, it may have poor compatibility with the polysiloxane contained in the composition, resulting in poor solubility in the developer, and reactive groups may remain in the film, potentially resulting in adverse effects such as an inability to maintain chemical resistance sufficient for post-processing. For this reason, the mass-average molecular weight of the silane coupling agent is preferably 5,000 or less, more preferably 4,000 or less. The content of the silane coupling agent is preferably 0.01 to 15 mass% based on the total mass of the alkali-soluble resin.

[0080] Examples of polymerization inhibitors that can be added include nitrones, nitroxide radicals, hydroquinone, catechol, phenothiazine, phenoxazine, hindered amines, and derivatives thereof, as well as ultraviolet absorbers. Among these, methylhydroquinone, catechol, 4-t-butylcatechol, 3-methoxycatechol, phenothiazine, chlorpromazine, phenoxazine, and hindered amines such as TINUVIN 144, 292, and 5100 (BASF), and ultraviolet absorbers such as TINUVIN 326, 328, 384-2, 400, and 477 (BASF) are preferred. These can be used alone or in combination, and the content is preferably 0.01 to 20% by mass based on the total mass of the alkali-soluble resin.

[0081] As a defoaming agent, alcohol (C1- 18 ), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerin monolaurate, polyethers such as polyethylene glycol (PEG) (Mn 200 to 10,000) and polypropylene glycol (PPG) (Mn 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil, and fluorosilicone oil, and organosiloxane surfactants, details of which are given below. These can be used alone or in combination, and the content is preferably 0.1 to 3 mass% based on the total mass of the alkali-soluble resin.

[0082] The composition of the present invention may also contain a surfactant, if necessary. The surfactant is added for the purpose of improving coating properties, developability, water repellency and oil repellency of the film surface, etc. Examples of surfactants that can be used in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0083] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; acetylene glycol derivatives such as polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, acetylene alcohol, acetylene glycol, polyethoxylates of acetylene alcohol, and polyethoxylates of acetylene glycol; fluorine-containing surfactants such as Fluorad (trade name, Sumitomo 3M Limited), Megafac (trade name, DIC Corporation), and Sulfuron (trade name, Asahi Glass Co., Ltd.); and organic siloxane surfactants such as KP341 (trade name, Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,5-dimethyl-2,5-hexanediol, etc. Among them, the Megafac RS series contributes to improving the water repellency and oil repellency of the membrane surface, and is therefore suitable for forming membranes for partition walls.

[0084] Examples of anionic surfactants include ammonium salts or organic amine salts of alkyldiphenyletherdisulfonic acids, ammonium salts or organic amine salts of alkyldiphenylethersulfonic acids, ammonium salts or organic amine salts of alkylbenzenesulfonic acids, ammonium salts or organic amine salts of polyoxyethylene alkylethersulfonic acids, and ammonium salts or organic amine salts of alkylsulfuric acids.

[0085] Further, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauric acid amidopropyl hydroxysulfone betaine.

[0086] These surfactants can be used alone or in combination of two or more, and the content thereof is preferably 0.005 to 1 mass %, more preferably 0.01 to 0.5 mass %, based on the total mass of the composition.

[0087] If necessary, a sensitizer may be added to the composition of the present invention. Sensitizers preferably used in the composition of the present invention include coumarin, ketocoumarin and derivatives thereof, thiopyrylium salts, acetophenones, and the like, specifically, p-bis(o-methylstyryl)benzene, 7-dimethylamino-4-methylquinolone-2, 7-amino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2-(p-dimethylaminostyryl)-pyridylmethyl iodide, 7-diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 2,3,5,6-1H,4H-tetrahydro-8-methylquinolizino-<9,9a,1-gh>coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7-amino-4-trifluoro ... Examples of sensitizing dyes include tetrahydroquinolidino-<9,9a,1-gh>coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 2,3,5,6-1H,4H-tetrahydro-9-carbethoxyquinolidino-<9,9a,1-gh>coumarin, 3-(2'-N-methylbenzimidazolyl)-7-N,N-diethylaminocoumarin, N-methyl-4-trifluoromethylpiperidino-<3,2-g>coumarin, 2-(p-dimethylaminostyryl)-benzothiazolylethyl iodide, 3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin, 3-(2'-benzothiazolyl)-7-N,N-diethylaminocoumarin, and pyrylium salts and thiopyrylium salts represented by the following chemical formulas. The addition of a sensitizing dye enables patterning using an inexpensive light source such as a high-pressure mercury lamp (360 to 430 nm). The content of the sensitizing dye is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the alkali-soluble resin. [ka]

[0088] Furthermore, an anthracene skeleton-containing compound can also be used as the sensitizer. Specific examples include compounds represented by the following formula: [ka] In the formula, R 31 each independently represents a substituent selected from the group consisting of an alkyl group, an aralkyl group, an allyl group, a hydroxyalkyl group, an alkoxyalkyl group, a glycidyl group, and a halogenated alkyl group; R 32 each independently represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group, and a carboalkoxy group; Each k is independently an integer selected from 0 and 1 to 4.

[0089] When such a sensitizer having an anthracene skeleton is used, the content thereof is preferably 0.01 to 5% by mass based on the total mass of the alkali-soluble resin.

[0090] <Method for forming a cured film> The method for forming a cured film according to the present invention comprises applying the composition described above to a substrate to form a film, exposing the film to light, and heating the film. The method for forming a cured film will be described below in order of steps.

[0091] (1) Coating process First, the composition described above is applied to a substrate. The formation of a coating film of the composition in the present invention can be carried out by any conventionally known method for applying a photosensitive composition. Specifically, the method can be selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, and the like. The substrate to which the composition is applied can be any suitable substrate, such as a silicon substrate, glass substrate, or resin film. These substrates may have various semiconductor elements formed thereon, if necessary. When the substrate is a film, gravure coating can also be used. If desired, a drying step can be separately performed after the coating. If necessary, the coating step can be repeated once or twice or more times to form a coating film with a desired thickness.

[0092] (2) Pre-baking process After forming a coating film by applying the composition, the coating film is preferably prebaked (preheated) to dry it and reduce the amount of solvent remaining in the coating film. The prebaking step can be carried out generally at a temperature of 50 to 150°C, preferably 90 to 120°C, for 10 to 300 seconds, preferably 30 to 120 seconds, using a hot plate, or for 1 to 30 minutes using a clean oven.

[0093] (3) Exposure process After the coating film is formed, the surface of the coating film is irradiated with light. The light source used for light irradiation can be any light source conventionally used in pattern formation methods. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, laser diodes, LEDs, etc. Ultraviolet rays such as g-line, h-line, and i-line are usually used as the irradiated light. Except for ultrafine processing such as semiconductors, light of 360 to 430 nm (high-pressure mercury lamps) is generally used for patterning of several μm to several tens of μm. The energy of the irradiated light varies depending on the light source and the thickness of the coating film, but is generally 5 to 2000 mJ / cm. 2 , preferably 10 to 1000 mJ / cm 2The irradiation light energy is 5 mJ / cm 2 If it is lower than 2000mJ / cm, sufficient resolution may not be obtained. 2 If it is higher than this, overexposure may occur, which may result in the occurrence of halation.

[0094] A general photomask can be used to irradiate light in a pattern. Such a photomask can be arbitrarily selected from well-known photomasks. The environment during irradiation is not particularly limited, but generally, the ambient atmosphere (air) or a nitrogen atmosphere can be used. Furthermore, when a film is formed on the entire surface of a substrate, the entire surface of the substrate can be irradiated with light. In the present invention, the patterned film also includes such a case where a film is formed on the entire surface of a substrate.

[0095] (4) Post-exposure baking process After exposure, post-exposure baking can be performed as needed to promote the interpolymer reaction within the film using a polymerization initiator. Unlike the heating step (6) described below, this heating treatment is not performed to completely harden the coating film, but rather to leave only the desired pattern on the substrate after development, allowing the remaining parts to be removed by development.

[0096] When post-exposure baking is performed, a hot plate, oven, furnace, or the like can be used. The heating temperature should not be excessively high, since it is undesirable for the acid generated in the exposed region by light irradiation to diffuse to the unexposed region. From this perspective, the post-exposure heating temperature range is preferably 40°C to 150°C, more preferably 60°C to 120°C. Stepwise heating can also be applied, if necessary, to control the curing rate of the composition. The heating atmosphere is not particularly limited, but can be selected from an inert gas such as nitrogen, under vacuum, under reduced pressure, or in oxygen gas, for the purpose of controlling the curing rate of the composition. The heating time is preferably at least a certain time to maintain a high degree of uniformity in the temperature history within the wafer surface, and is preferably not excessively long to suppress the diffusion of the generated acid. From this perspective, the heating time is preferably 20 to 500 seconds, more preferably 40 to 300 seconds.

[0097] (5)Developing process After exposure, if necessary, post-exposure baking can be performed, and the coating film can then be developed. The present invention can be used in cases where a development step is not performed and no pattern is not formed, but development is performed when a pattern is formed. The developer used during development can be any developer conventionally used for developing photosensitive compositions. Preferred developers include alkaline developers, which are aqueous solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicate (hydrates), alkali metal phosphate (hydrates), aqueous sodium carbonate, ammonia, alkylamines, alkanolamines, and heterocyclic amines. Particularly preferred alkaline developers are aqueous tetramethylammonium hydroxide, aqueous potassium hydroxide, aqueous sodium hydroxide, and aqueous sodium carbonate. These alkaline developers may further contain a water-soluble organic solvent such as methanol or ethanol, or a surfactant, as necessary. In the present invention, development can be performed using a developer with a lower concentration than the 2.38% by weight TMAH developer typically used as a developer. Examples of such developers include a 0.05 to 1.5 mass % TMAH aqueous solution, a 0.1 to 2.5 mass % sodium carbonate aqueous solution, a 0.01 to 1.5 mass % potassium hydroxide aqueous solution, etc. The development time is usually 10 to 300 seconds, and preferably 30 to 180 seconds. The developing method can also be arbitrarily selected from conventionally known methods. Specific examples include immersion in a developer (dipping), puddle, shower, slit, cap coat, spray, etc. This development can obtain a pattern. After development with a developer, it is preferable to wash with water.

[0098] (6)Heating process After development, the resulting patterned film is heated to cure it. The heating device used in the heating step can be the same as that used for the post-exposure baking described above. This heating step colorizes the polymer A, reducing the overall film transparency, i.e., improving the light-blocking properties. Without being bound by theory, this is thought to be due to the oxidation of methylene groups in the repeating unit of formula (A) in polymer A. To further improve the light-blocking properties, the heating temperature in this heating step is preferably 150 to 300°C, more preferably 180 to 250°C. Furthermore, this heating step promotes the curing reaction of the coating film. When the alkali-soluble resin contains polysiloxane, residual silanol groups can result in insufficient chemical resistance of the cured film or an increased dielectric constant. From these perspectives, a relatively high heating temperature is generally selected, preferably 150 to 300°C, more preferably 180 to 280°C. The heating time is not particularly limited and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. Note that this heating time is the time after the temperature of the pattern film reaches the desired heating temperature. Usually, it takes several minutes to several hours for the pattern film to reach the desired temperature from the temperature before heating.

[0099] The cured film thus formed exhibits the effects of the present invention as long as it has an average film thickness of 100 μm or less, preferably 5 to 100 μm, more preferably 5 to 25 μm, and even more preferably 8 to 20 μm. The optical density (OD) of the cured film is preferably at least 1 on average at wavelengths of 400 to 700 nm. The optical density is measured, for example, by a Spectrophotometer CM-5 (Konica Minolta). Regarding the reflectance of the cured film, the average reflectance measured by the SCI method, which measures diffuse reflected light without removing specular reflected light at a wavelength of 370 to 740 nm, is preferably at least 30, more preferably at least 40. Here, the reflectance is measured, for example, using a Spectrophotometer CM-5 (Konica Minolta). The cured film according to the present invention has excellent light-blocking properties and high reflectance, and can be used as a barrier rib material or overcoat material with high reflectance (or high refractive index) for devices. The color of the cured film is not particularly limited, but is preferably white. Because the cured film according to the present invention can be made thick, it can be suitably used in micro LEDs, quantum dot displays, and organic electroluminescence devices, which require thicker barrier rib materials.

[0100] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

[0101] Gel permeation chromatography (GPC) was performed using an HLC-8220GPC high-speed GPC system (product name, Tosoh Corporation) and two Super Multipore HZ-N GPC columns (product name, Tosoh Corporation). Measurements were performed using monodisperse polystyrene as the standard sample, tetrahydrofuran as the developing solvent, and a flow rate of 0.6 mL / min at a column temperature of 40°C.

[0102] <Synthesis of Polysiloxane> A 2L flask equipped with a stirrer, thermometer, and condenser was charged with 49.0 g of 25% by weight TMAH aqueous solution, 600 ml of isopropyl alcohol (IPA), and 4.0 g of water. A mixed solution of 68.0 g of methyltrimethoxysilane, 79.2 g of phenyltrimethoxysilane, and 15.2 g of tetramethoxysilane was then prepared in a dropping funnel. The mixed solution was added dropwise at 40°C and stirred at the same temperature for 2 hours, after which a 10% by weight HCl aqueous solution was added for neutralization. 400 ml of toluene and 600 ml of water were added to the neutralized solution, which was separated into two phases. The aqueous phase was removed. The solution was washed three times with 300 ml of water, and the resulting organic phase was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate to adjust the solids concentration to 35% by weight, yielding a polysiloxane solution. The molecular weight (polystyrene equivalent) of the obtained polysiloxane was measured by gel permeation chromatography, and the mass average molecular weight (hereinafter sometimes abbreviated as "Mw") was found to be 1,700. The obtained polysiloxane solution was applied to a silicon wafer using a spin coater (MS-A100 (manufactured by Mikasa)) so that the film thickness after pre-baking would be 2 μm, and the dissolution rate in a 2.38 mass % TMAH aqueous solution after pre-baking was measured and found to be 1,200 Å / sec.

[0103] <Synthesis of Acrylic Polymer A> A 1L flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube was charged with 16.4g of azobisisobutyronitrile and 120g of butanol. Under a nitrogen gas atmosphere, the temperature was raised to the appropriate temperature based on the initiator's 10-hour half-life temperature. Separately, a mixture of 13.0g of methacrylic acid, 46.5g of KBM-502, 6.5g of 2-hydroxyethyl methacrylate, and 60.0g of methyl methacrylate was prepared and added dropwise to the solvent over 4 hours. The mixture was then allowed to react for 3 hours to yield acrylic polymer A with a molecular weight of 7,000.

[0104] <Synthesis of Acrylic Polymer B> A 1L flask equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet tube was charged with 16.4g of azobisisobutyronitrile and 120g of butanol. Under a nitrogen gas atmosphere, the temperature was raised to the appropriate temperature based on the initiator's 10-hour half-life temperature. Separately, a mixture of 5.16g of methacrylic acid, 46.5g of KBM-502, 6.5g of 2-hydroxyethyl methacrylate, and 70.08g of methyl methacrylate was prepared and added dropwise to the solvent over 4 hours. The mixture was then allowed to react for 3 hours to obtain Acrylic Polymer B with a molecular weight of 7,350.

[0105] Example 1 A solution containing 15 parts by mass of a novolac polymer having the following two repeating units at 50% each based on the number of all repeating units, 30 parts by mass of the polysiloxane obtained above, 35 parts by mass of the acrylic polymer A obtained above, and 35 parts by mass of the acrylic polymer B obtained above was mixed with 1 part by mass of polymerization initiator A (ADEKA Corporation "NCI-831E"), 12 parts by mass of polymerization initiator B (IGM Resins BV "Omnirad 819"), 50 parts by mass of a (meth)acryloyloxy group-containing compound dipentaerythritol hexaacrylate (Shin-Nakamura Chemical Co., Ltd. "A-DPH"), 100 parts by mass of a surfactant (DIC Corporation "Megafac"), and 100 parts by mass of a copolymer of acrylic polymer A and acrylic polymer B. 0.3 parts by mass of titanium dioxide (RS-72A) and 44.6 parts by mass of titanium oxide (Sigma-Aldrich "TiO2", titanium dioxide particles with a primary particle size of 50 to 100 nm) as a reflectance adjuster were added, and PGMEA was further added to make the final concentration 30% by mass, followed by stirring to obtain the composition of Example 1. [ka] (wherein one of the two R's is methyl) Novolac polymer (Aica Kogyo Co., Ltd., mass average molecular weight 9,750)

[0106] <Examples 2 to 9, Comparative Examples 1 and 2> Compositions were prepared by changing the composition of Example 1 as shown in Table 1. In the table, the numerical values for the compositions indicate parts by mass. [Table 1] In the table, The cyclic olefin polymer has the following structure (mass average molecular weight 11,600): [ka] R1=Me, R2=H Other materials are as described in Example 1.

[0107] Each of the obtained compositions was applied to alkali-free glass by spin coating, and after application, it was prebaked on a hot plate at 100°C for 90 seconds to give an average film thickness of 10 μm. Using a mask with a 10 μm contact hole (C / H) pattern, it was exposed to an i-line exposure machine at 200 mJ / cm 2 The pattern was exposed to 1000 kJ / cm², developed using a 2.38% TMAH aqueous solution, and rinsed with pure water for 30 seconds. It was then heated at 250°C in air for 30 minutes. The cross-section of the resulting pattern was observed using an SEM and evaluated as follows. The results are shown in Table 1. A: The pattern was formed and there was no peeling. B: A pattern was formed, and some peeling was observed. C: The film was dissolved and no pattern could be formed.

[0108] Each composition was spin-coated onto alkali-free glass, prebaked on a hot plate at 100°C for 90 seconds to form a coating film with an average thickness of 10 μm. The coating film was then heated in air at 250°C for 30 minutes, after which the transmittance was measured using a Spectrophotometer CM-5 (Konica Minolta) and the OD was calculated. The OD values obtained are shown in Table 1.

[0109] Each of the obtained compositions was applied to alkali-free glass by spin coating, and after application, the glass was prebaked on a hot plate at 100°C for 90 seconds to form a coating film with an average film thickness of 10 μm. The coating film was then exposed to 200 mJ / cm using an i-line exposure machine. 2 The film was exposed to UV light, developed using a 2.38% TMAH aqueous solution, and rinsed with pure water for 30 seconds. It was then heated at 250°C in air for 30 minutes. The average reflectance was measured using the SCI and SCE (Specular Components Exclude) methods at wavelengths of 370 to 740 nm using a Spectrophotometer CM-5 (Konica Minolta). The resulting reflectances are listed in Table 1. Some aspects of the present invention are set out below. [Aspect 1] (I) an alkali-soluble resin comprising a polymer containing a repeating unit represented by formula (A);

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Claims

1. (I) an alkali-soluble resin comprising a polymer containing a repeating unit represented by formula (A); 【Chemical 1】 (In the formula, Each X is independently C １～２７ is a substituted or unsubstituted hydrocarbon group of the formula a1 is 1 to 2, a2 is 0 to 3. (II) a reflectance adjuster selected from at least one of the group consisting of alumina, magnesium oxide, antimony oxide, titanium oxide, titanium oxynitride, titanium nitride, zirconium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, and barium carbonate; (III) a polymerization initiator, (IV) a solvent, (V) a compound containing two or more (meth)acryloyloxy groups, and comprising polysiloxane, A negative-type photosensitive composition, wherein the polysiloxane comprises a repeating unit represented by formula (Ia): 【Chemistry 2】 (In the formula, R Ｉａ is hydrogen, C １～３０ represents a linear, branched or cyclic, saturated or unsaturated, aliphatic hydrocarbon group or aromatic hydrocarbon group; The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or C １～６ is substituted with alkoxy, and In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced or one or more methylenes are replaced by oxy, imino or carbonyl, provided that R Ｉａ is not hydroxy or alkoxy).

2. At least one X is -L-Ar (In the formula, L is C １～８ is a linear or branched alkylene; Ar is C ６～２２ substituted or unsubstituted aryl) 2. The composition of claim 1, wherein:

3. The composition of claim 1 or 2, wherein the alkali-soluble resin further comprises an acrylic polymer.

4. The composition according to any one of claims 1 to 3, wherein the content of the reflectance adjuster is 10 to 150 mass % based on the total mass of the alkali-soluble resin.

5. A method for producing a cured film, comprising applying the composition according to any one of claims 1 to 4 to a substrate to form a film, exposing the film to light, and heating the film.

6. The method of claim 5, further comprising developing the film, wherein the heating temperature after development is 150 to 300°C.

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