Negative photosensitive resin composition, pattern forming method, cured film forming method, interlayer insulating film, surface protective film, and electronic component

Abstract

To provide a negative type photosensitive resin composition which is soluble in alkali aqueous solution, enables formation of a fine pattern and can obtain high resolution, and has good mechanical characteristics such as elongation at break and tensile strength even when cured at low temperature.SOLUTION: A negative type photosensitive resin composition contains (A) an alkali-soluble resin including at least one or more structures selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure and precursor structures thereof, (B) a polymer compound having a structural unit obtained by cyclic polymerization, (C) a compound for generating an acid by light, and (D) a heat crosslinking agent.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a negative photosensitive resin composition, a pattern forming method using the negative photosensitive resin composition which enables development with an alkaline aqueous solution, a cured film forming method, an interlayer insulating film, a surface protective film, and an electronic component. [Background technology]

[0002] As various electronic devices such as personal computers, digital cameras, and mobile phones become smaller and more powerful, there is a rapidly growing demand for semiconductor elements to be smaller, thinner, and denser. Accordingly, the interlayer insulating film and surface protective film of semiconductor elements are required to have superior electrical properties, heat resistance, mechanical properties, etc.

[0003] In high-density packaging technologies such as three-dimensional stacking, photosensitive insulating materials that can be patterned on substrates have long been used as protective coatings or insulating layers, such as polyimide films. Their insulating properties, mechanical properties, and adhesion to substrates have continued to attract attention, and they are still being actively developed.

[0004] In order to further improve the above-mentioned required properties, various approaches have been taken. In particular, photosensitive resin compositions using ring-closed polyimide resins have been proposed for the purpose of lowering the post-curing temperature (Patent Document 1, Patent Document 2). However, it is difficult to simultaneously achieve the physical properties of the cured film, such as resolution, mechanical properties (elongation and tensile strength), and adhesion, and there is room for improvement.

[0005] In addition, in order to improve the mechanical strength of the cured film, it has been proposed to add a (meth)acrylic resin to achieve both lithography properties and cured film properties (Patent Documents 3, 4, and 5). However, since the purpose is to modify the main resin, there is room for improvement in the mechanical strength of the cured film.

[0006] On the other hand, in order to improve this, in addition to polyimide, its precursor, polybenzoxazole, and its precursor, studies are being conducted on structural units derived from cyclic olefins (norbornene type monomers, maleic anhydride, and maleimide) and resins in which a cyclic structure has been introduced into the main chain skeleton, such as cyclic polymerization monomer units (Patent Document 6, Patent Document 7, Patent Document 8, Patent Document 9).

[0007] Patent Documents 6 and 7 propose positive-type photosensitive resin compositions using an alkali-soluble resin containing an N-hydroxymaleimide unit and a norbornene unit, and further a novolak resin, and a quinone diazide compound, but do not provide any detailed discussion of micronization, and no description is made of the physical properties of the cured film.

[0008] Furthermore, Patent Document 8 proposes a negative type photosensitive resin composition using a copolymer consisting of a (meth)acrylate unit and a maleimide, a compound having a difunctional or higher polymerizable group, and a photopolymerization initiator, but makes no mention of the resolution or mechanical strength of fine patterns.

[0009] In addition, Patent Document 9 proposes a negative photosensitive resin composition using a copolymer of a monomer having an acid group introduced in the side chain, maleimides, and a cyclic cyclized monomer, an alkali-soluble resin having an unsaturated double bond introduced in the acid group in the side chain, and a photopolymerization initiator, and the material has excellent mechanical properties such as elastic recovery rate and breaking strength of the cured film. However, due to the photosensitive properties using radical crosslinking, there is room for improvement in terms of fineness.

[0010] As described above, in the future, as chips become increasingly dense and highly integrated, the rewiring technology for insulating protective films will likely require increasingly finer patterns. For this reason, there is a strong demand for photosensitive resin compositions that can realize high resolution without compromising the excellent mechanical properties of the protective coating obtained by low-temperature heating. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Patent No. 4530284 [Patent Document 2] JP 2006-313237 A [Patent Document 3] Patent No. 5884837 [Patent Document 4] JP 2015-129791 A [Patent Document 5] JP 2015-200819 A [Patent Document 6] JP 2019-045622 A [Patent Document 7] JP 2020-170103 A [Patent Document 8] Patent No. 6315204 [Patent Document 9] Patent No. 6694230 Summary of the Invention [Problem to be solved by the invention]

[0012] The present invention has been made in view of the above circumstances, and has an object to provide a negative type photosensitive resin composition that is soluble in an alkaline aqueous solution, can form a fine pattern with high resolution, and has good mechanical properties such as breaking elongation and tensile strength even when cured over a wide low temperature range. [Means for solving the problem]

[0013] In order to solve the above problems, the present invention provides a negative photosensitive resin composition, comprising: (A) an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a polymer compound having a structural unit formed by cyclopolymerization; (C) a compound that generates an acid when exposed to light; (D) a thermal crosslinker; The present invention provides a negative type photosensitive resin composition comprising:

[0014] Such a negative type photosensitive resin composition is soluble in an alkaline aqueous solution, is capable of forming a fine pattern and achieving high resolution, and exhibits good mechanical properties such as breaking elongation and tensile strength even when cured over a wide low temperature range.

[0015] In the negative photosensitive resin composition of the present invention, the structural unit formed by cyclopolymerization in the component (B) is preferably at least one of structural units represented by the following general formula (1), the following general formula (2), the following general formula (3), and the following general formula (4). [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0016] By having such a ring structure in the main chain, mechanical properties such as breaking elongation and tensile strength become good even when cured at low temperatures, and further heat resistance is improved.

[0017] In the negative photosensitive resin composition of the present invention, the component (B) is preferably an alkali-soluble polymeric compound further comprising a structural unit represented by the following general formula (5) or (5'). [ka] (In the formula, R 7 represents a hydrogen atom or a methyl group, and X 1 are -C(=O)-O- and -C(=O)-OR, respectively. 8 -, -C(=O)-NH-, -C(=O)-NH-R 8 - or -C(=O)-N(R 8 OH)-. 8is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. In addition, a hydrogen atom of the aromatic hydrocarbon group in the formula may be replaced with a methyl group. p is 0 or 1.

[0018] Such a negative photosensitive resin composition is soluble in an alkaline aqueous solution, and is capable of forming a fine pattern with high resolution.

[0019] Furthermore, the component (B) is preferably a crosslinked alkali-soluble polymer compound further containing either or both of a structural unit represented by the following general formula (6) and a structural unit represented by the following general formula (α): [ka] (In the formula, R 9 represents a hydrogen atom or a methyl group, and X 2 R is -C(=O)-O-, or a phenylene or naphthylene group. 10 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an ester group, an ether group or an aromatic hydrocarbon group; R 11 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R 10 R may be bonded to form a ring. 12 is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; R 13 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and R 10 may be bonded to form a ring. m is 0 or 1. p is 0 or 1. In the formula, R 1 ' represents a hydrogen atom or a methyl group, and R 2 ' represents a single bond or an alkylene group; R 3 ' is a blocked isocyanate group.

[0020] Such alkali-soluble polymer compounds have crosslinking groups with excellent crosslinking properties, and therefore undergo a crosslinking reaction with the phenolic hydroxyl groups of the alkali-soluble resin of component (A). Even when cured at low temperatures, the compounds have good mechanical properties such as breaking elongation and tensile strength, and also have improved heat resistance.

[0021] Furthermore, the component (B) is preferably a crosslinked alkali-soluble polymer compound further comprising a structural unit represented by the following general formula (7). [ka] (In the formula, R 14 represents a hydrogen atom or a methyl group, R 15 X is a single bond or a (l+1)-valent linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the saturated aliphatic hydrocarbon group may be replaced with an oxygen atom. 3 are -C(=O)-O- and -C(=O)-OR, respectively. 16 -, -C(=O)-NH-, -C(=O)-N(R 16 OH)-, or a phenylene group or a naphthylene group. 16 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. 1 is 0 or 1.

[0022] Such a polymer compound maintains its alkali solubility while reacting with the thermal crosslinking agent (D), making it possible to obtain a high-resolution pattern.

[0023] Furthermore, the component (B) is preferably a crosslinked alkali-soluble polymer compound containing structural units represented by any one or both of the following general formula (3), the following general formula (5), the following general formula (6), and the following general formula (α), and the following general formula (7). [ka] (In the formula, R 4R is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. 7 represents a hydrogen atom or a methyl group, and X 1 are -C(=O)-O- and -C(=O)-OR, respectively. 8 -, -C(=O)-NH-, -C(=O)-NH-R 8 - or -C(=O)-N(R 8 OH)-. 8 R is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. In addition, a hydrogen atom of the aromatic hydrocarbon group in the formula may be replaced with a methyl group. 9 represents a hydrogen atom or a methyl group, and X 2 R is -C(=O)-O-, or a phenylene or naphthylene group. 10 is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an ester group, an ether group or an aromatic hydrocarbon group; R 11 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R 10 R may be bonded to form a ring. 12 is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; R 13 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and R 10 R may be bonded to form a ring. 1 ' represents a hydrogen atom or a methyl group, and R 2 ' represents a single bond or an alkylene group; R 3 R' is a blocked isocyanate group. 14 represents a hydrogen atom or a methyl group, R 15 X is a single bond or a (l+1)-valent linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the saturated aliphatic hydrocarbon group may be replaced with an oxygen atom. 3 are -C(=O)-O- and -C(=O)-OR, respectively. 16 -, -C(=O)-NH-, -C(=O)-N(R 16OH)-, or a phenylene group or a naphthylene group. R 16 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and the carbon atoms of the aliphatic saturated hydrocarbon group may be replaced by oxygen atoms. p is 0 or 1. m is 0 or 1. l is 0 or 1. 0 < a1 < 1.0, 0 < a2 < 1.0, 0 ≤ a3 < 1.0, 0 ≤ b1 < 1.0, 0 < a3 + b1 < 1.0, 0 < a4 < 1.0, and any one of 0 < a1 + a2 + a3 + a4 ≤ 1.0, 0 < a1 + a2 + b1 + a4 ≤ 1.0, 0 < a1 + a2 + a3 + b1 + a4 ≤ 1.0 is satisfied.)

[0024] For such a crosslinkable polymer compound, a high-resolution pattern can be obtained while maintaining sufficient alkali solubility. In addition, a ring structure is introduced into the main chain skeleton, and there is also a crosslinkable group with excellent crosslinkability, so even when cured at a low temperature, mechanical properties such as elongation at break and tensile strength are good.

[0025] Further, it is preferable that the component (D) contains one or more crosslinking agents selected from amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenol compounds having an average of 2 or more methylol groups or alkoxymethylol groups in one molecule.

[0026] For such a component (D), the alkali solubility of the photosensitive resin composition becomes suitable, and the crosslinking reaction proceeds sufficiently at the PEB (Post Exposure Bake) temperature in lithographic patterning, enabling good lithographic patterning.

[0027] Further, it is preferable that the component (B) is contained in an amount of 10 to 100 parts by mass with respect to 100 parts by mass of the component (A).

[0028] Within this range, sufficient mechanical properties of the cured film, particularly elongation and tensile strength, can be obtained while maintaining lithography characteristics.

[0029] It is preferable that the composition further contains one or more of (E) a basic compound, (F) a thermal acid generator, (G) an antioxidant, and (H) a silane compound.

[0030] By including the basic compound of component (E), not only can the dissolution contrast during lithographic patterning be improved, but also the pattern shape can be controlled. In addition, the thermal acid generator of component (F) can further advance the crosslinking and curing reaction, thereby further improving the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or coating. Furthermore, the antioxidant of component (G) can suppress the deterioration of physical properties due to oxidation deterioration of the cured film during reliability tests such as high humidity tests and thermal shock tests, and can form a more suitable cured film. In addition, the silane compound of component (H) can further improve the adhesion of the obtained pattern or coating to the substrate.

[0031] The present invention also provides a method for producing a photosensitive film comprising the steps of: (1) applying the negative photosensitive resin composition onto a substrate to form a photosensitive film; (2) subsequently, exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask after the heat treatment; (3) developing the irradiated and heat-treated substrate with an aqueous alkaline developer; The present invention provides a pattern forming method comprising the steps of:

[0032] In such a pattern forming method, by using the above-mentioned negative photosensitive resin composition, which is soluble in an alkaline aqueous solution, it is possible to form a fine pattern and obtain high resolution.

[0033] The present invention also provides a method for forming a cured coating, comprising the step of heating the patterned coating obtained by the above-mentioned pattern formation method at a temperature of 100 to 300° C. and post-curing it.

[0034] Such a method for forming a cured coating makes it possible to form a cured coating (pattern) that has good mechanical properties even when cured at low temperatures.

[0035] The present invention also provides an interlayer insulating film comprising a cured film obtained by curing the above negative photosensitive resin composition.

[0036] The present invention also provides a surface protective film comprising a cured coating formed by curing the above negative photosensitive resin composition.

[0037] The cured coating obtained by curing the negative type photosensitive resin composition of the present invention has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength, and chemical resistance against alkaline stripping solutions and the like, and also has excellent reliability for semiconductor elements using it as a protective coating. Therefore, the cured coating is suitable as a protective coating (interlayer insulating film or surface protective film) for electric / electronic components, semiconductor elements, etc.

[0038] The present invention also provides an electronic component having the above interlayer insulating film or the above surface protective film.

[0039] Such protective coatings (interlayer insulating films or surface protective films) are effective as insulating films for semiconductor elements, including rewiring applications, and insulating films for multilayer printed circuit boards, due to their heat resistance, chemical resistance, and insulating properties, and can be used to produce electronic components with excellent reliability. Effect of the Invention

[0040] As described above, the present invention can provide a negative type photosensitive resin composition that is soluble in an alkaline aqueous solution, can form a fine pattern with high resolution, and has good mechanical properties such as high elongation and high strength even when cured over a wide low temperature range, and also has excellent adhesion. [Brief description of the drawings]

[0041] [Figure 1] FIG. 2 is an explanatory diagram showing a method for measuring adhesion. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0042] As described above, there has been a demand for a photosensitive resin composition that is soluble in an alkaline aqueous solution, capable of forming fine patterns with high resolution, and has good mechanical properties even when cured at low temperatures.

[0043] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above-mentioned object, and have found that a pattern obtained using a negative-type photosensitive resin composition comprising: (A) an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a polymeric compound having a structural unit formed by cyclic polymerization; (C) a compound that generates an acid when exposed to light; and (D) a thermal crosslinking agent, is capable of forming a fine pattern and provides a cured film having good mechanical properties.

[0044] Furthermore, it was found that a protective film obtained by forming a pattern using the negative photosensitive resin composition and heating the pattern had excellent adhesion after a high-temperature, high-humidity test. That is, it was found that a cured film having a pattern formed using the negative photosensitive resin composition is excellent as a protective film for electric and electronic components and an insulating protective film, and the present invention was completed. In this specification, electric and electronic components are also collectively referred to as "electronic components".

[0045] That is, the present invention is a negative type photosensitive resin composition, (A) an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof; (B) a polymer compound having a structural unit formed by cyclopolymerization; (C) a compound that generates an acid when exposed to light; (D) a thermal crosslinker; The negative type photosensitive resin composition contains

[0046] The present invention will be described in detail below, but the present invention is not limited thereto.

[0047] [Negative-type photosensitive resin composition] The negative photosensitive resin composition of the present invention will now be described.

[0048] The negative photosensitive resin composition of the present invention comprises: The negative photosensitive resin composition contains (A) an alkali-soluble resin containing at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof, (B) a polymeric compound having a structural unit formed by cyclic polymerization, (C) a compound that generates an acid by light, and (D) a thermal crosslinking agent. The negative photosensitive resin composition is alkali developable. In addition to the above components (A), (B), (C), and (D), the negative photosensitive resin composition may further contain (E) a basic compound, (F) a thermal acid generator, (G) an antioxidant, (H) a silane compound, and the like, as necessary. These components will be described in detail below.

[0049] [(A) Alkali-soluble resin] The alkali-soluble resin (A) used in the present invention contains at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and precursor structures thereof. The resin (A) is not particularly limited as long as it is an alkali-soluble resin containing the above structure, but it is preferable that the resin (A) contains a structure represented by the following general formula (8) and / or (9).

[0050] [ka] (In the formula, X 4 is a tetravalent organic group, s represents 0 or 1, Z is a divalent linking group, and when s=0, the two aromatic rings in the formula are directly linked without a linking group. [ka] (In the formula, X 5 is a divalent organic group, and s and Z are the same as above.

[0051] X in the above general formula (8) 4 is a tetravalent organic group, but is not limited thereto as long as it is a tetravalent organic group. It is preferably a tetravalent organic group of an alicyclic aliphatic group or an aromatic group having 4 to 40 carbon atoms, and more preferably a tetravalent organic group represented by the following formula (10). X 4 The structure may be one type or a combination of two or more types.

[0052] [ka] (In the formula, the dotted line represents a bond.)

[0053] In the above general formula (8), s represents 0 or 1, and when s=0, the two aromatic rings in the above general formula (8) are directly bonded without the divalent bonding group Z therebetween.

[0054] On the other hand, when s=1, the two aromatic rings in the above general formula (8) are bonded via a divalent bonding group Z. There are no limitations on Z as long as it is a divalent group. It is preferably a divalent organic group of an alicyclic aliphatic group or aromatic group having 4 to 40 carbon atoms, and more preferably a divalent bonding group represented by the following formula (11). Furthermore, the structure of Z may be one type or a combination of two or more types.

[0055] [ka] (In the formula, q 1 , q 2 , and q 3 represents an integer from 1 to 6, and q 4 and q 5 represents an integer from 1 to 10. The dotted line represents a bond.)

[0056] Particularly preferred divalent linking groups Z are divalent groups represented by the following formula (12) or (13). [ka] (In the formula, the dotted line represents a bond.)

[0057] As the structural unit represented by the above general formula (8), when Z in the above general formula (8) is a group represented by the above formula (12), a structural unit represented by the following general formula (8-1) is preferred, and when Z in the above general formula (8) is a group represented by the above formula (13), a structural unit represented by the following general formula (8-2) is preferred. [ka] [ka] (In the formula, X 4 is the same as above.)

[0058] As in the above general formula (8-1), when the divalent linking group Z is a hexafluoropropylene group represented by the above formula (12) and is located at the p-position of the phenolic hydroxyl group, the hexafluoropropylene group is an electron-withdrawing group, so that the acidity of the phenolic hydroxyl group is increased and the solubility in an alkaline aqueous developer is improved, which is preferable.

[0059] Similarly, as in the above general formula (8-2), when the divalent linking group Z is a sulfone group represented by the above formula (13) and is located at the p-position of the phenolic hydroxyl group, the sulfone group is also an electron-withdrawing group, so that the acidity of the phenolic hydroxyl group is increased and the solubility in an alkaline aqueous developer is improved, which is preferable.

[0060] X in the above general formula (9) 5 is a divalent organic group, and is not limited as long as it is a divalent organic group. It is preferably a divalent organic group having an aliphatic chain structure having 4 to 40 carbon atoms, an alicyclic aliphatic group, or an aromatic group. It is more preferably a divalent organic group represented by the following formula (14). In addition, X 5 The structure may be one type or a combination of two or more types.

[0061] [ka] (In the formula, R 17 , R 18 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 6 carbon atoms; q 6 is an integer from 1 to 30, and the dotted line represents a bond.

[0062] X in the above general formula (9) 5 is a divalent organic group having an aliphatic chain structure, this is preferred because it increases the mechanical strength, particularly the elongation, of the cured film of the negative photosensitive resin composition of the present invention.

[0063] In the above general formula (9), s and Z are the same as above, and from the viewpoint of solubility in an alkaline aqueous developer, Z is preferably the above formula (12) or (13). In this case, as in the case of the above general formulas (8-1) and (8-2), the acidity of the phenolic hydroxyl group becomes high, and the solubility in an alkaline aqueous developer is improved, which is preferable.

[0064] The alkali-soluble resin (A) used in the present invention may contain, in addition to the structural units represented by the above general formulas (8) and (9), a structural unit represented by the following general formula (15) (hereinafter also referred to as structural unit (15)). [ka] (In the formula, X 6 isX 5 Same as X 7 is a divalent organic group.

[0065] X in the above general formula (15) 7 is a divalent organic group, and is not limited as long as it is a divalent organic group, but is preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a cyclic organic group containing 1 to 4 aromatic or aliphatic rings having a substituent, or an aliphatic group or siloxane group having no cyclic structure. 7 Examples of the structure represented by the following formula (16) or the following general formula (17) are given. 7 The structure may be one type or a combination of two or more types.

[0066] [ka] (In the formula, the dotted line represents a bond to an amino group.)

[0067] [ka] (In the formula, the dotted line represents a bond to an amino group, and R 19 each independently represents a methyl group, an ethyl group, a propyl group, an n-butyl group, or a trifluoromethyl group; q 7 represents an integer from 2 to 20.)

[0068] In addition, the alkali-soluble resin (A) used in the present invention preferably contains, in addition to the structural units represented by the above general formulas (8) and (9), a structural unit represented by the following general formula (18) (hereinafter also referred to as structural unit (18)): [ka] (In the formula, X 8 is the above X 4 is a tetravalent organic group that may be the same or different from X 9 is a group represented by the following general formula (19). [ka] (In the formula, R 20 ~R 23 each independently represents a linear or branched alkylene group having 2 to 10 carbon atoms; 1 is an integer between 1 and 40, m 2、 m 3 are each independently an integer from 0 to 40.

[0069] X in the above general formula (18) 8 X 4 For example, the tetravalent organic group represented by the above formula (10) may be used. 9In the group represented by the above general formula (19), specific examples of the organic group that can be preferably used include the following, although the group is not limited thereto. [ka]

[0070] When the alkali-soluble resin (A) contains such a structural unit (19), flexibility is imparted, and a cured film having high elongation and low warpage can be obtained.

[0071] Furthermore, the alkali-soluble resin (A) used in the present invention can contain a structural unit represented by the following general formula (20) or (21) (hereinafter referred to as structural unit (20) or structural unit (21)). [ka] [ka] (In the formula, X 10 is the above X 4 is a tetravalent organic group that may be the same or different from X 11 isX 7 is a divalent organic group that may be the same or different from , and s and Z are the same as above. 24 and R 25 are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following general formula (22), 24 and R 25 At least one of the above is an organic group represented by the following general formula (22). [ka] (In the formula, the dotted lines represent bonds. R 26 is a hydrogen atom or an organic group having 1 to 3 carbon atoms, and R 27 and R 28 each independently represents a hydrogen atom or an organic group having 1 to 3 carbon atoms, and o represents an integer of 2 to 10.

[0072] X in the above structural units (20) and (21) 10 is a tetravalent organic group, but the above X 4 and may be the same as or different from each other, and are not limited as long as they are tetravalent organic groups. They are preferably tetravalent organic groups of alicyclic aliphatic groups or aromatic groups having 4 to 40 carbon atoms, and more preferably tetravalent organic groups represented by the above formula (10). 10 The structure may be one type or a combination of two or more types.

[0073] On the other hand, X in the structural unit (21) 11 is a divalent organic group, but the above X 7 and may be the same or different, and are not limited as long as they are divalent organic groups. Preferably, they are divalent organic groups having 6 to 40 carbon atoms, and more preferably, they are cyclic organic groups containing 1 to 4 aromatic or aliphatic rings having a substituent, or aliphatic groups or siloxane groups having no cyclic structure. More preferably, X 11 Examples of the structure represented by the above formula (16) or general formula (17) include X 11 The structure may be one type or a combination of two or more types.

[0074] R in the above structures (20) and (21) 24 and R 25 are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an organic group represented by the above general formula (22), and R 24 and R 25 At least one of them is an organic group represented by the above general formula (22).

[0075] R in the above general formula (22) 26 is not limited as long as it is a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but is preferably a hydrogen atom or a methyl group from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0076] R in the above general formula (22) 27 and R 28are not limited as long as they are each independently a hydrogen atom or a monovalent organic group having 1 to 3 carbon atoms, but are preferably a hydrogen atom from the viewpoint of the photosensitive properties of the negative photosensitive resin composition.

[0077] In the above general formula (22), o is an integer of 2 to 10, and from the viewpoint of photosensitive characteristics, is preferably an integer of 2 to 4. More preferably, o is 2.

[0078] [(B) Polymer compound having structural units obtained by cyclopolymerization] The polymer compound (B) used in the present invention is not particularly limited as long as it has a structural unit formed by cyclopolymerization.

[0079] Examples of monomers that can be preferably used to obtain structural units by cyclopolymerization include diallyl quaternary ammonium salts, ether-type perfluoro-1,6-dienes, and α-(allyloxymethyl)acrylic esters.

[0080] Furthermore, in order to improve adhesion to a substrate, it is more preferable that the structural unit formed by cyclopolymerization in the component (B) is at least one of structural units represented by the following general formula (1), the following general formula (2), the following general formula (3) and the following general formula (4). [ka]

[0081] Wherein, R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.

[0082] As the monomer unit for forming the structural unit obtained by cyclopolymerization, the monomer units represented by the following general formulae (23) and (24) are particularly preferred. These monomers may be used alone or in combination of two or more kinds.

[0083] [ka] (In the formula, R 4 , R 5 , and R 6 As mentioned above.)

[0084] In particular, specific examples of commercially available products include the ACRYCURE RD series and the ACRYCURE RE series (product names, manufactured by Nippon Shokubai Co., Ltd.).

[0085] In particular, from the viewpoints of polymerizability and stability, the structural unit of the above general formula (3) and the above monomer unit (23) are more preferred.

[0086] Furthermore, in order to impart alkali solubility and improve the crosslink density, the polymer compound of component (B) more preferably contains a structural unit represented by the following general formula (5) or (5'). [ka]

[0087] Wherein, R 7 represents a hydrogen atom or a methyl group, and X 1 are -C(=O)-O- and -C(=O)-OR, respectively. 8 -, -C(=O)-NH-, -C(=O)-NH-R 8 - or -C(=O)-N(R 8 OH)-. 8 is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. In addition, a hydrogen atom of the aromatic hydrocarbon group in the formula may be replaced with a methyl group. p is 0 or 1.

[0088] In addition, the structure represented by the general formula (5) preferably has an ester group or an amide group, which is an electron-withdrawing group, at the p-position of the phenolic hydroxyl group, and in this case, the acidity of the phenolic hydroxyl group is increased, and the solubility in an alkaline aqueous developer is improved. Specific examples of monomers that can be preferably used to form the structural units of the general formulae (5) and (5') are given below. However, they are not limited to these.

[0089] [ka] (In the formula, R 7 is as above.)

[0090] [ka] (In the formula, R 7 is as above.)

[0091] The structures represented by general formulas (5) and (5') are effective as units that promote crosslinking in addition to improving alkali solubility, and by using them in combination with structural units obtained by cyclopolymerization, it is possible to further improve the mechanical properties of the cured film.

[0092] Furthermore, in order to improve the crosslink density, it is preferable to copolymerize a monomer having an epoxy group or an oxetanyl group represented by the following general formula (6) or a monomer having a blocked isocyanate group represented by the following general formula (α) with the polymer compound of component (B). [ka]

[0093] Wherein, R 9 represents a hydrogen atom or a methyl group, and X 2 R is -C(=O)-O-, or a phenylene or naphthylene group. 10is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an ester group, an ether group or an aromatic hydrocarbon group; R 11 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R 10 R may be bonded to form a ring. 12 is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; R 13 is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and R 10 may be bonded to form a ring. m is 0 or 1. p is 0 or 1. In addition, R 1 ' represents a hydrogen atom or a methyl group, and R 2 ' represents a single bond or an alkylene group; R 3 ' is a blocked isocyanate group.

[0094] Examples of monomers for forming the structural unit of the above general formula (6) include the following. [ka] (In the formula, R 9 is as above.)

[0095] [ka] (In the formula, R 9 is as above.)

[0096] [ka] (In the formula, R 9 is as above.)

[0097] In addition, some of the monomers for obtaining repeating units having an epoxy group or an oxetanyl group are disclosed in Japanese Patent Application Laid-Open No. 2003-55362, Japanese Patent Application Laid-Open No. 2005-8847, and Japanese Patent Application Laid-Open No. 2005- This is disclosed in Publication No. 18012.

[0098] In the general formula (α), R 1 ' represents a hydrogen atom or a methyl group, and R 2 ' represents a single bond or an alkylene group; R 3 ' is a blocked isocyanate group.

[0099] The blocked isocyanate group is an organic group in which an isocyanate group (-N=C=O) is blocked with a suitable protecting group. The blocked isocyanate group can be formed by reacting an isocyanate group with a blocking agent.

[0100] The blocked isocyanate group is stable at room temperature, but above a certain temperature, the blocking agent is eliminated (deblocked), and the hydroxyl or carboxyl group in component (A) reacts with the isocyanate group to form a crosslinked structure. The blocking agent is an active hydrogen-containing compound capable of reacting with isocyanate, such as alcohol, phenol, polycyclic phenol, amide, imide, imine, thiol, oxime, lactam, active hydrogen-containing heterocycle, and active methylene-containing compound.

[0101] Suitable blocked isocyanate groups are described in paragraphs

[0015] to

[0025] of Japanese Patent No. 6601628, and the compounds therein can be used.

[0102] In particular, the following monomer units are more preferred because they have good polymerizability and can be used commercially. These monomers may be used alone or in combination of two or more. [ka] (In the formula, R 1 ' is as above.)

[0103] Furthermore, it is preferable that the photosensitive composition is not deblocked by a post-exposure bake (PEB) or a post-spin coating bake treatment, but is deblocked by post-curing with a post-development bake treatment, and crosslinked with the alkali-soluble resin.

[0104] Therefore, the following monomer units which are unblocked in the range of 140° C. to 200° C. are more preferred.

[0105] [ka] (In the formula, R 1 ' is as above.)

[0106] In particular, specific examples of commercially available products include the Karenz MOI series and AOI series (product names, manufactured by Showa Denko KK).

[0107] Furthermore, from the viewpoints of further improving the crosslinking reactivity during lithographic patterning and improving the dissolution contrast between the exposed and unexposed areas in an alkaline developer, it is preferable that the polymer compound of component (B) is copolymerized with a structural unit represented by the following general formula (7): [ka]

[0108] Wherein, R 14 represents a hydrogen atom or a methyl group, R 15 X is a single bond or a (l+1)-valent linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the saturated aliphatic hydrocarbon group may be replaced with an oxygen atom. 3 are -C(=O)-O- and -C(=O)-OR, respectively. 16 -, -C(=O)-NH-, -C(=O)-N(R 16 OH)-, or a phenylene group or a naphthylene group. 16 is a divalent linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which a carbon atom of the saturated aliphatic hydrocarbon group may be replaced by an oxygen atom.

[0109] Examples of monomers for forming the structural unit of the above general formula (7) include the following. [Chemical formula] (wherein, R 14 is as described above.)

[0110] [Chemical formula] (wherein, R 14 is as described above.)

[0111] [Chemical formula] (wherein, R 14 is as described above.)

[0112] Here, the structural units formed by cyclopolymerization represented by the above general formulas (1) to (4) are excellent in mechanical strength and heat resistance, but have no crosslinkability or alkali solubility. Therefore, the polymer of component (B) preferably copolymerizes with the structural units represented by the above general formulas (5), (5'), and (7) which are excellent in alkali solubility, and the structural units represented by the epoxy group, oxetanyl group represented by the above general formula (6), and the block isocyanate group represented by the above general formula (α) having crosslinkability. If it is such a thing, it is easier to balance all of mechanical properties, alkali solubility, and crosslinkability than a polymer composed only of the structural units represented by the above general formulas (1) to (7).

[0113] Therefore, when copolymerizing repeating units in this way, it is preferable to have the repeating unit of the following formula (1a). position. [Chemical formula] (wherein, 0 < a1 < 1.0, 0 < a2 < 1.0, 0 ≦ a3 < 1.0, 0 ≦ b1 < 1.0, 0 < a3 + b1 < 1.0, 0 < a4 < 1.0, and any one of 0 < a1 + a2 + a3 + a4 ≦ 1.0, 0 < a1 + a2 + b1 + a4 ≦ 1.0, 0 < a1 + a2 + a3 + b1 + a4 ≦ 1.0 is satisfied. R 4 , R 7 , R 9~R 13 , R 14 , R 15 , R 1 '~R 3 ', X 1 , X 2 , X 3 , m, p and l are the same as above.

[0114] The polymer compound of component (B) used in the present invention can be based on repeating units derived from a monomer (hereinafter referred to as a) for obtaining structural units obtained by cyclopolymerization represented by the above general formulas (1) to (4), a monomer (hereinafter referred to as b or c) for obtaining repeating units having a hydroxyl group represented by the above general formulas (5) and (7), and a monomer (hereinafter referred to as d) for obtaining repeating units having a group that crosslinks with the alkali-soluble resin of component (A) represented by general formula (6) and general formula (α). In order to improve adhesion to the substrate and flexibility of the cured film, and to further improve mechanical properties and thermal shock resistance, a monomer (hereinafter referred to as e) for obtaining a repeating unit represented by the following general formula (25) may be copolymerized.

[0115] [ka] In the general formula (25), R 29 represents a hydrogen atom or a methyl group, R 30 may have a monovalent organic group having a primary, secondary or tertiary amino group, an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alicyclic group having 6 to 10 carbon atoms. 12 is preferably -C(=O)-O- or -C(=O)-NH-, where 0≦e<1.

[0116] Specific examples of monomers from which the repeating unit represented by the above general formula (25) is obtained include the following: aminoethyl (meth)acrylate, N-methylaminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N-ethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N-methylaminopropyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N-ethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, aminoethyl (meth)acrylamide, N-methylaminoethyl (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylamide, N-ethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, aminopropyl (meth)acrylamide, N-methylaminopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, amide, N-ethylaminopropyl(meth)acrylamide, N,N-diethylaminopropyl(meth)acrylamide, piperidin-4-yl(meth)acrylate, 1-methylpiperidin-4-yl(meth)acrylate, 2,2,6,6-tetramethylpiperidin-4-yl(meth)acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl(meth)acrylate, (piperidin-4-yl)methyl(meth)acrylate, 2-( (piperidin-4-yl)ethyl (meth)acrylate, piperidin-4-yl (meth)acrylate, 1-methylpiperidin-4-yl (meth)acrylate, 2,2,6,6-tetramethylpiperidin-4-yl (meth)acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth)acrylate, (piperidin-4-yl)methyl (meth)acrylate, 2-(piperidin-4-yl)ethyl (meth)acrylate, and the like.

[0117] Furthermore, as a monomer for obtaining the repeating unit represented by the above general formula (25), it is possible to use an alkyl (meth)acrylate ester. Specific examples include butyl (meth)acrylate ester, pentyl (meth)acrylate ester, hexyl (meth)acrylate ester, heptyl (meth)acrylate ester, octyl (meth)acrylate ester, nonyl (meth)acrylate ester, decyl (meth)acrylate ester, undecyl (meth)acrylate ester, dodecyl (meth)acrylate ester, tridecyl (meth)acrylate ester, tetradecyl (meth)acrylate ester, pentadecyl (meth)acrylate ester, hexadecyl (meth)acrylate ester, heptadecyl (meth)acrylate ester, octadecyl (meth)acrylate ester, nonadecyl (meth)acrylate ester, and eicosyl (meth)acrylate ester.

[0118] Furthermore, for the purpose of improving the mechanical strength of the cured film, olefins f having an aromatic group, such as styrenes, vinylnaphthalenes, vinylanthracenes, vinylcarbazoles, acenaphthylenes, and indenes, and alicyclic olefins g, such as norbornenes and norbornadienes, may be copolymerized.

[0119] In the repeating units a1, a2, a3, a4, b1, e, f, and g, the ratio of the repeating units preferably satisfies 0 < a1 < 0.8, 0 < a2 ≤ 0.8, 0 ≤ a3 ≤ 0.8, 0 < a4 ≤ 0.8, 0 ≤ b1 ≤ 0.6, 0 ≤ e ≤ 0.8, 0 ≤ f ≤ 0.8, and 0 ≤ g ≤ 0.8. More preferably, 0 < a1 ≤ 0.5, 0.1 ≤ a2 ≤ 0.6, 0.1 ≤ a3 ≤ 0.6, 0.1 ≤ a4 ≤ 0.7, 0 ≤ b1 ≤ 0.4, 0 ≤ e ≤ 0.4, 0 ≤ f ≤ 0.4, and 0 ≤ g ≤ 0.4. Even more preferably, it is in the range of 0 < a1 ≤ 0.4, 0.1 ≤ a2 ≤ 0.4, 0.1 ≤ a3 ≤ 0.4, 0.2 ≤ a4 ≤ 0.7, 0 ≤ b1 ≤ 0.2, 0 ≤ e ≤ 0.4, 0 ≤ f ≤ 0.4, and 0 ≤ g ≤ 0.4. Note that it is preferably one that satisfies any of a1 + a2 + a3 + a4 = 1, a1 + a2 + b1 + a4 = 1, a1 + a2 + a3 + b1 + a4 = 1, and a1 + a2 + a3 + b1 + a4 + e + f + g = 1, and the total of these repeating units is preferably 100 mol% of the total amount of all repeating units.

[0120] The (crosslinkable) polymer compound (B) used in the negative photosensitive composition of the present invention preferably has a polystyrene-equivalent weight average molecular weight of 1,000 to 500,000, particularly 2,000 to 30,000, as determined by gel permeation chromatography (GPC). If the weight average molecular weight is 1,000 or more, the glass transition temperature is sufficiently high, and the pattern does not deform during the thermal crosslinking after development of the negative photosensitive resin composition. If it is 500,000 or less, there is no risk of causing pinhole defects during coating or layer separation with the alkali-soluble resin in the pattern formed by the lithographic pattern. It is also possible to blend two or more polymers having different composition ratios, molecular weight distributions, and molecular weights.

[0121] In addition, the amount of the (crosslinkable) polymer compound (B) added is preferably 10 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the alkali-soluble resin (A). If the amount added is 10 parts by mass or more, the toughness of the cured film with the alkali-soluble resin (A) as described above is high, and if it is 100 parts by mass or less, the tensile strength of the cured film does not decrease, so the amount of the (crosslinkable) polymer compound (B) added is preferably within the above range. The amount of the (B) component added is more preferably 10 parts by mass or more and 70 parts by mass or less, and even more preferably 30 parts by mass or more and 50 parts by mass or less. By setting it in this range, the balance between the lithography patterning performance and the cured film properties is good.

[0122] [(C) Compounds that generate acid when exposed to light] The compound (C) that generates an acid by light (photoacid generator) used in the present invention may be any compound that generates an acid by irradiation with high energy rays. Suitable compounds include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide type, benzoin sulfonate type, pyrogallol trisulfonate type, nitrobenzyl sulfonate type, sulfone type, and glyoxime derivative type acid generators. As described in detail below, these can be used alone or in combination of two or more types.

[0123] Sulfonium salts are salts of sulfonium cations and sulfonates, and the sulfonium cations include triphenylsulfonium, (4-tert-butoxyphenyl)diphenylsulfonium, bis(4-tert-butoxyphenyl)phenylsulfonium, tris(4-tert-butoxyphenyl)sulfonium, (3-tert-butoxyphenyl)diphenylsulfonium, bis(3-tert-butoxyphenyl)phenylsulfonium, tris(3-tert-butoxyphenyl)sulfonium, and (3,4- (di-tert-butoxyphenyl)diphenylsulfonium, bis(3,4-di-tert-butoxyphenyl)phenylsulfonium, tris(3,4-di-tert-butoxyphenyl)sulfonium, diphenyl(4-thiophenoxyphenyl)sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl)diphenylsulfonium, tris(4-tert-butoxycarbonylmethyloxyphenyl)sulfonium, (4-tert-butoxyphenyl)bis(4-dimethylaminophenyl)sulfonium , tris(4-dimethylaminophenyl)sulfonium, 2-naphthyldiphenylsulfonium, dimethyl 2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, tribenzylsulfonium, and the like. Examples of the sulfonate include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octane sulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, and the like, and sulfonium salts of combinations thereof.

[0124] The iodonium salt is a salt of an iodonium cation and a sulfonate. Examples of the iodonium cation include aryl iodonium cations such as diphenyliodonium, bis(4-tert-butylphenyl)iodonium, 4-tert-butoxyphenylphenyliodonium, and 4-methoxyphenylphenyliodonium, and examples of the sulfonates include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, 4-(4-toluenesulfonyloxy)benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate, and examples of iodonium salts of combinations of these include iodonium salts.

[0125] Sulfonyldiazomethanes include bis(ethylsulfonyl)diazomethane, bis(1-methylpropylsulfonyl)diazomethane, bis(2-methylpropylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(perfluoroisopropylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(4-methylphenylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane. Examples of the sulfonyldiazomethane include bissulfonyldiazomethanes and sulfonylcarbonyldiazomethanes such as methane, bis(2-naphthylsulfonyl)diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, and tert-butoxycarbonyl-4-methylphenylsulfonyldiazomethane.

[0126] Examples of the N-sulfonyloxyimide type photoacid generator include compounds having an imide skeleton, such as succinimide, naphthalenedicarboxylic imide, phthalic imide, cyclohexyldicarboxylic imide, 5-norbornene-2,3-dicarboxylic imide, or 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxylic imide, in combination with trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, or methanesulfonate.

[0127] Benzoin sulfonate type photoacid generators include benzoin tosylate, benzoin mesylate, and benzoin butanesulfonate.

[0128] Examples of pyrogallol trisulfonate type photoacid generators include compounds in which all of the hydroxy groups of pyrogallol, phloroglycine, catechol, resorcinol, and hydroquinone are substituted with trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octane sulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, or the like.

[0129] Examples of the nitrobenzyl sulfonate type photoacid generator include 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and 2,6-dinitrobenzyl sulfonate. Specific examples of the sulfonate include trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octane sulfonate, dodecylbenzenesulfonate, butanesulfonate, and methanesulfonate. Compounds in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used.

[0130] Examples of sulfone-type photoacid generators include bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane, bis(2-naphthylsulfonyl)methane, 2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane, 2,2-bis(2-naphthylsulfonyl)propane, 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one.

[0131] Examples of the photoacid generator of the glyoxime derivative type include bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluenesulfonyl)-α-diphenylglyoxime, bis-o-(p-toluenesulfonyl)-α-dicyclohexylglyoxime, bis-o-(p-toluenesulfonyl)-2,3-pentanedione glyoxime, and bis-o-(p-toluenesulfonyl)-2-methyl-3,4- Pentanedione glyoxime, bis-o-(n-butanesulfonyl)-α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexylglyoxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione glyoxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4-pentanedione glyoxime, bi Examples of such compounds include bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, bis-o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(tert-butanesulfonyl)-α-dimethylglyoxime, bis-o-(perfluorooctanesulfonyl)-α-dimethylglyoxime, bis-o-(cyclohexylsulfonyl)-α-dimethylglyoxime, bis-o-(benzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-fluorobenzenesulfonyl)-α-dimethylglyoxime, bis-o-(p-tert-butylbenzenesulfonyl)-α-dimethylglyoxime, bis-o-(xylenesulfonyl)-α-dimethylglyoxime, and bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

[0132] Among these, the photoacid generators preferably used are bissulfonyldiazomethane and N-sulfonyloxyimide.

[0133] Furthermore, an oxime-type acid generator as disclosed in WO2004 / 074242 A2 is added. It is also possible.

[0134] The acid generators can be used alone or in combination of two or more. Onium salts are excellent in improving rectangularity, and diazomethane derivatives and glyoxime derivatives are excellent in reducing standing waves, so that the profile can be finely adjusted by combining both.

[0135] The amount of the photoacid generator in the negative photosensitive resin composition of the present invention is preferably 0.05 to 20 parts by mass, particularly 1 to 10 parts by mass, per 100 parts by mass of component (A). If the amount is 0.05 parts by mass or more, sufficient contrast (difference in dissolution rate in a developer between exposed and unexposed parts) can be obtained, and if it is 20 parts by mass or less, there is no risk of the resolution being deteriorated due to light absorption by the photoacid generator itself.

[0136] [(D) Thermal crosslinking agent] The thermal crosslinking agent (D) used in the present invention may be any compound having a group that crosslinks with the component (A) other than the component (B).Specific examples of the crosslinking agent that can be used here include melamine compounds substituted with at least one group selected from methylol groups, alkoxymethyl groups, and acyloxymethyl groups, guanamine compounds, glycoluril compounds, or urea compounds, epoxy compounds, oxetane compounds, isocyanate compounds, azide compounds, compounds containing double bonds such as alkenyl ether groups, compounds containing benzyl alcohol, and oxazoline-based crosslinking agents described in JP-A-2-60941, JP-A-2-99537, and JP-A-2-115238.

[0137] Among the specific examples of the crosslinking agent, the epoxy compound is further exemplified by tris(2,3-epoxy). (xypropyl) isocyanurate, trimethylolmethane triglycidyl ether, tri Methylolpropane triglycidyl ether, Triethylolethane triglycidyl ether Teru etc. are examples.

[0138] Or phenol, o-cresol, m-cresol, p-cresol, 2,3-di Methylphenol, 2,5-dimethylphenol, 3,4-dimethylphenol, 3,5 -Dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2 ,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2-t-butyl Phenol, 3-t-butylphenol, 4-t-butylphenol, 2-phenylphenol phenol, 3-phenylphenol, 4-phenylphenol, 3,5-diphenylphenol phenol, 2-naphthylphenol, 3-naphthylphenol, 4-naphthylphenol, 4 -Tritylphenol, resorcinol, 2-methylresorcinol, 4-methylresorcinol resorcinol, 5-methylresorcinol, catechol, 4-t-butylcatechol, 2-methyl Toxophenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol Phenol, 4-propylphenol, 2-isopropylphenol, 3-isopropylphenol phenol, 4-isopropylphenol, 2-methoxy-5-methylphenol, 2-t -Butyl-5-methylphenol, pyrogallol, thymol, isothymol, 4,4'- (9H-fluoren-9-ylidene)bisphenol, 2,2'dimethyl-4,4'-( 9H-fluoren-9-ylidene)bisphenol, 2,2'diallyl-4,4'-(9 H-fluoren-9-ylidene)bisphenol, 2,2'difluoro-4,4'-(9 H-fluoren-9-ylidene)bisphenol, 2,2'-diphenyl-4,4'-(9 H-fluoren-9-ylidene)bisphenol, 2,2'-dimethoxy-4,4'-(9 H-fluoren-9-ylidene)bisphenol, 2,3,2',3'-tetrahydro- (1,1')-Spirobiindene-6,6'-diol, 3,3,3',3'-tetramethyl 2,3,2',3'-Tetrahydro-(1,1')-spirobiindene-6,6' -diol, 3,3,3',3',4,4'-hexamethyl-2,3,2',3'-tetramethyl Hydro-(1,1')-spirobiindene-6,6'-diol, 2,3,2',3' -Tetrahydro-(1,1')-spirobiindene-5,5'-diol, 5,5'-di Methyl-3,3,3',3'-tetramethyl-2,3,2',3'-tetrahydro-(1 ,1')-Spirobiindene-6,6'-diol hydroxy group is converted to glycidyl ether or the hydroxy group of the novolak resin of the phenolic compound is glycerinated. Examples include those which have been di-etherified.

[0139] Specific examples of melamine compounds include hexamethylolmelamine, hexamethoxymelamine, 1 to 6 methylol groups of methylol melamine and hexamethylol melamine are methoxymethylated. Compounds or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine 1 to 6 of the methylol groups of melamine and hexamethylolmelamine are acyloxymethylated. The guanamine compounds include tetramethylol guanamine, ... 1-4 methylguanamine, tetramethoxymethylguanamine, tetramethylolguanamine Compounds or mixtures thereof in which the thiol group is methoxymethylated, tetramethoxyethylguanidine 1 to 4 methyl groups of guanamine, tetraacyloxyguanamine, and tetramethylolguanamine Examples of the compounds include compounds in which the aryl group is acyloxymethylated, and mixtures thereof. Compounds such as tetramethylol glycol uril, tetramethoxy glycol uril, Tetramethoxymethylglycoluril, methylol of tetramethylolglycoluril Compounds in which 1 to 4 of the alkyl groups are methoxymethylated or mixtures thereof, tetramethylolglycol A compound in which 1 to 4 methylol groups of acyluril are acyloxymethylated or a mixture thereof Examples of the urea compound include tetramethylol urea and tetramethoxymethyl urea. A compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated or or a mixture thereof, tetramethoxyethyl urea, etc.

[0140] The isocyanate compounds include tolylene diisocyanate and diphenylmethane diisocyanate. cyanate, hexamethylene diisocyanate, cyclohexane diisocyanate, etc. The azide compounds are 1,1'-biphenyl-4,4'-bisazide, 4,4 4,4'-methylidenebisazide, and 4,4'-oxybisazide.

[0141] Examples of compounds containing an alkenyl ether group include ethylene glycol divinyl ether, Triethylene glycol divinyl ether, 1,2-propanediol divinyl ether , 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether Neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether Pentaerythritol trivinyl ether, Pentaerythritol tetravinyl ether ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether.

[0142] Further, JP-A-11-100378, JP-A-2003-231860, JP2005-146038A, JP2005-290052A, JP2006-1 99790 and cyclic epoxy compounds described in JP-A-2006-273748; Crosslinking agents having an oxirane ring bonded to a ring as described in JP-A-2006-348252, particularly Based on the dendrimer and hyperbranched polymer shown in Japanese Patent Application Laid-Open No. 2008-24920, Epoxy crosslinking agents having a hydroxyl group as described in JP-A-2001-310937 A crosslinking agent having both an oxetanyl group and a hydroxyl group is described in Japanese Patent No. 3824286. Examples of crosslinking agents include those having both a carboxyl group and a hydroxyl group.

[0143] The epoxy group has a large ring distortion and is highly reactive, but the oxetane is highly basic and does not bond with acids. The cationic polymerization reaction is improved by combining the epoxy group with the oxetanyl group. Significant improvements have been reported.

[0144] Furthermore, the component (D) in the negative photosensitive resin composition of the present invention is more preferably one or more crosslinking agents selected from the group consisting of amino condensates modified with formaldehyde or formaldehyde-alcohol, and phenol compounds having, on average, two or more methylol groups or alkoxymethylol groups per molecule.

[0145] Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

[0146] The above-mentioned melamine condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, by first modifying a melamine monomer with formalin by methylolation according to a known method, or by further modifying the melamine monomer by alkoxylation with an alcohol to obtain a modified melamine represented by the following general formula (26).The above-mentioned alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[0147] [ka] (In the formula, R 31 may be the same or different and are a methylol group, an alkoxymethyl group containing an alkoxy group having 1 to 4 carbon atoms, or a hydrogen atom, provided that at least one of them is a methylol group or the above alkoxymethyl group.

[0148] Above R 31 Examples of the alkyl group include a methylol group, an alkoxymethyl group such as a methoxymethyl group or an ethoxymethyl group, and a hydrogen atom.

[0149] Specific examples of the modified melamine represented by the above general formula (26) include trimethoxymethyl monomethylol melamine, dimethoxymethyl monomethylol melamine, trimethylol melamine, hexamethylol melamine, and hexamethoxymethylol melamine.

[0150] Next, the modified melamine represented by the above general formula (26) or its multimer (for example, an oligomer such as a dimer or trimer) is subjected to addition condensation polymerization with formaldehyde in a conventional manner until a desired molecular weight is reached, thereby obtaining a melamine condensate modified with formaldehyde or a formaldehyde-alcohol.

[0151] The above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol can be prepared, for example, according to a known method, by modifying a urea condensate having a desired molecular weight with formaldehyde by methylolation, or by further modifying the urea condensate by alkoxylation with an alcohol.

[0152] Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate.

[0153] The modified melamine condensates and modified urea condensates may be used alone or in combination of two or more.

[0154] Next, examples of phenol compounds having an average of two or more methylol groups or alkoxymethylol groups per molecule include (2-hydroxy-5-methyl)-1,3-benzenedimethanol, 2,2',6,6'-tetramethoxymethylbisphenol A, and compounds represented by the following formulas (D-3) to (D-7). [ka]

[0155] The above crosslinking agents can be used alone or in combination of two or more.

[0156] The component (D) undergoes a crosslinking reaction with the components (A) and (B) in the PEB process of the negative photosensitive resin composition of the present invention, using the acid generated from the component (C) as a catalyst. Furthermore, the component (D) undergoes a crosslinking reaction in the subsequent post-curing, thereby further increasing the strength of the cured product. From the viewpoints of photocurability and heat resistance, the weight-average molecular weight of such a component (D) is preferably 150 to 10,000, and particularly preferably 200 to 3,000.

[0157] Furthermore, the blend amount of the component (D) in the negative photosensitive resin composition of the present invention is preferably 0.5 to 50 parts by mass, and particularly preferably 1 to 30 parts by mass, per 100 parts by mass of the component (A).

[0158] [(E) Basic compound] The negative photosensitive resin composition of the present invention may further contain (E) a basic compound in addition to the essential components (A), (B), (C), and (D). The basic compound of component (E) is preferably a compound capable of suppressing the diffusion rate of the acid generated by the photoacid generator when it diffuses into the resist film. The incorporation of such a basic compound suppresses the diffusion rate of the acid in the resist film, improving the resolution, suppressing the change in sensitivity after exposure, reducing the dependency on the substrate and environment, and improving the exposure margin and pattern profile.

[0159] Examples of the basic compound include primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives and imide derivatives.

[0160] Specific examples of primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, and tetraethylenepentamine. Specific examples of secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, and the like. Examples of the tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N,N,N',N'-tetramethylmethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyltetraethylenepentamine, and the like.

[0161] Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of the aromatic amines and heterocyclic amines include aniline derivatives (e.g., aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, and N,N-dimethyltoluidine), diphenyl(p-tolyl)amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, and pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (e.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazan derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4-(1-butylpentyl)pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives Examples of the conductors include quinoline derivatives (e.g., quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, and uridine derivatives.

[0162] Further, examples of nitrogen-containing compounds having a carboxy group include aminobenzoic acid, indole carboxylic acid, and amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycyl leucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine). Examples of nitrogen-containing compounds having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate. Examples of nitrogen-containing compounds having a hydroxy group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indole methanol hydrate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, and the like. amine, N,N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-(2-hydroxyethyl)morpholine, 2-(2-hydroxyethyl)pyridine, 1-(2-hydroxyethyl)piperazine, 1-[2-(2-hydroxyethoxy)ethyl]piperazine, piperidineethanol, 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)-2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyjurolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N-(2-hydroxyethyl)phthalimide, N-(2-hydroxyethyl)isonicotinamide, and the like. Examples of the amide derivatives include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, etc. Examples of the imide derivatives include phthalimide, succinimide, maleimide, etc.

[0163] The basic compound can be used alone or in combination of two or more, and the amount of the basic compound is preferably 0 to 2 parts by mass, more preferably 0.01 to 2 parts by mass, and particularly preferably 0.01 to 1 part by mass, per 100 parts by mass of the alkali-soluble resin of component (A). If the amount is 2 parts by mass or less, the sensitivity is sufficiently maintained.

[0164] [(F) Thermal acid generator] The negative type photosensitive resin composition of the present invention may further contain (F) a compound that generates an acid by heat (thermal acid generator). The component (F) compound that generates an acid by heat can be added for the purpose of thermally promoting the crosslinking reaction of the components (A), (B), and (D) in the step of heating and post-curing at a temperature of 100 to 300°C that is carried out after the above pattern formation.

[0165] In particular, the (F) component is preferably one that does not promote the curing of the film until a pattern is formed by development and does not inhibit pattern formation. In order to achieve this, the (F) component is preferably one that does not generate acid at the temperature of the process of removing the solvent and drying after coating the photosensitive resin composition, but generates acid only by heat treatment after pattern formation, thereby promoting the curing of the pattern or coating of the negative photosensitive resin composition. Specifically, it is preferable that the (F) component is a compound that decomposes and generates acid by heat treatment at 100°C to 300°C, preferably 150°C to 300°C. By containing such an (F) component, the pattern or coating of the negative photosensitive resin composition can be changed to a pattern or coating in which the crosslinking and curing reaction has progressed further in the process of heating and post-curing at a temperature of 100 to 300°C applied after pattern formation. The (F) component further advances the crosslinking and curing reaction, making it possible to further improve the mechanical strength, chemical resistance, adhesion, etc. of the obtained pattern or coating.

[0166] As a compound that generates an acid by suitable heat, the compounds described in paragraphs

[0061] to

[0085] of JP-A-2007-199653 can be used.

[0167] The amount of the compound that generates an acid by heat is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 30 parts by mass or less, more preferably 5 parts by mass or less, per 100 parts by mass of the component (A) in the negative photosensitive resin composition of the present invention. When the content is 0.1 parts by mass or more, the crosslinking reaction is promoted. When the content is 30 parts by mass or less, the alkali developability of the composition is not deteriorated, and development residue is not generated.

[0168] [(G) Antioxidants] The negative photosensitive resin composition of the present invention may further contain an antioxidant as component (G). By containing the antioxidant as component (G), oxidative deterioration of the aliphatic group and phenolic hydroxyl group of component (A) is suppressed. In addition, due to the rust-preventing effect on metal materials, it is possible to suppress metal oxidation caused by external moisture, photoacid generators, thermal acid generators, etc., and the associated decrease in adhesion and peeling.

[0169] Specific examples of usable antioxidants include hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. However, the antioxidants are not limited to these. These antioxidants may be used alone or in combination of two or more.

[0170] Among the specific examples of the antioxidants, further examples of hindered phenol-based antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan Ltd., Irganox 1010 (trade name)), thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (BASF Japan Ltd., Irganox 1035 (trade name)), octadecyl[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate (BASF Japan Ltd., Irganox 1076 (trade name)), octyl 1-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate (BASF Japan Ltd., Irganox 1135 (trade name)), 4,6-bis(octylthiomethyl-o-cresol) (BASF Japan Ltd., Irganox 1520L), Sumilizer GA80 (Sumitomo Chemical Co., Ltd., trade name), Adeka STAB Examples of the hindered phenol-based antioxidant include AO-20 (manufactured by ADEKA Corporation, product name), ADK STAB AO-30 (manufactured by ADEKA Corporation, product name), ADK STAB AO-40 (manufactured by ADEKA Corporation, product name), ADK STAB AO-50 (manufactured by ADEKA Corporation, product name), ADK STAB AO-60 (manufactured by ADEKA Corporation, product name), ADK STAB AO-80 (manufactured by ADEKA Corporation, product name), ADK STAB AO-330 (manufactured by ADEKA Corporation, product name), and the hindered phenol-based antioxidants described in JP2017 / 188153A1A.

[0171] Among the specific examples of the antioxidants, further examples of phosphorus-based antioxidants include triphenyl phosphite, tris(methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(nonylphenyl) phosphite, tris(octylphenyl) phosphite, trisdecylpoly(oxyethylene) phosphite, tris(cyclohexylphenyl) phosphite, tricyclohexyl phosphite, tri(decyl)thiophosphite, triisodecylthiophosphite, phenyl-bis(2-ethylhexyl) phosphite, phenylhexyl) phosphite, phenyl-diisodecyl phosphite, tetradecylpoly(oxyethylene)-bis(ethylphenyl) phosphite, phenyl-dicyclohexyl phosphite, phenyl-diisooctyl phosphite, phenyl-di(tridecyl) phosphite, diphenyl-cyclohexyl phosphite, diphenyl-isooctyl phosphite, diphenyl-2-ethylhexyl phosphite, diphenyl-isodecyl phosphite, diphenyl-cyclohexyl phenyl phosphite, diphenyl-(tridecyl) thiophosphite, and the like.

[0172] Further examples of sulfur-based antioxidants among the specific examples of the antioxidants include ADK STAB AO-412S (manufactured by ADEKA CORPORATION, product name), AO-503S (manufactured by ADEKA CORPORATION, product name), and Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd., product name).

[0173] The sulfur-based antioxidant and phosphorus-based antioxidant are expected to have the effect of decomposing peroxides.

[0174] The content of the antioxidant (G) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, per 100 parts by mass of the alkali-soluble resin (A). When the content is 0.1 part by mass or more, adhesion to metal materials is improved and peeling is suppressed. When the content is 10 parts by mass or less, the alkali developability of the composition and the toughness of the cured film are not deteriorated.

[0175] [(H) Silane compounds] The negative photosensitive resin composition of the present invention may further contain a silane compound as component (H). By containing the silane compound as component (H), not only can the adhesion to metal materials be improved, but also peeling of the cured film can be suppressed during reliability tests such as thermal shock tests and high temperature and high humidity tests.

[0176] The silane compound that can be used here may be any compound having an alkoxysilyl group. Preferred specific examples are shown below. γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxy ...propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis(2-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis(2-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis(2-hydroxypropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl Examples of the silane compounds include N-phenyl-3-aminopropyltriethoxysilane, triethoxysilylpropylethylcarbamate, 3-(triethoxysilyl)propylsuccinic anhydride, phenyltriethoxysilane, phenyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, silane compounds containing amide groups as described in Japanese Patent No. 6414060, silane compounds containing thiourea groups as described in Japanese Patent No. WO2016 / 140024 and Japanese Patent No. 5987984, and silane compounds containing thiol groups as described in Japanese Patent No. 2017-044964. However, the examples are not limited to these. Furthermore, these silane compounds can be used alone or in combination of two or more.

[0177] The content of the silane compound (H) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 3 to 6 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). When the content is 0.1 part by mass or more, more sufficient adhesion to the substrate can be imparted, and when the content is 20 parts by mass or less, problems such as an increase in viscosity during storage at room temperature can be more effectively suppressed. When the content is less than 10 parts by mass, development residues due to deterioration of the alkali developability of the composition can be more reliably suppressed.

[0178] [Other ingredients] The negative photosensitive resin composition of the present invention may further contain components other than the components (A), (B), (C), (D), (E), (F), (G) and (H). Examples of the other components include a dissolution inhibitor (I), a surfactant (J) and a solvent (K). The compounds exemplified below can be suitably used. However, they are not limited to these.

[0179] Examples of the (I) dissolution inhibitor include a compound having a weight-average molecular weight of 100 to 1,000, preferably 150 to 800, in which the hydrogen atoms of the phenolic hydroxyl groups of a compound having two or more phenolic hydroxyl groups in the molecule are substituted with acid labile groups in an average ratio of 0 to 100 mol % as a whole, and a compound having a carboxy group in the molecule in which the hydrogen atoms of the carboxy groups are substituted with acid labile groups in an average ratio of 50 to 100 mol % as a whole.

[0180] The substitution rate of hydrogen atoms of phenolic hydroxyl groups with acid labile groups is, on average, 0 mol % or more, preferably 30 mol % or more, with an upper limit of 100 mol %, more preferably 80 mol % of all phenolic hydroxyl groups. The substitution rate of hydrogen atoms of carboxyl groups with acid labile groups is, on average, 50 mol % or more, preferably 70 mol % or more, with an upper limit of 100 mol % of all carboxyl groups.

[0181] In this case, the compound having two or more phenolic hydroxyl groups or the compound having a carboxy group is preferably one represented by the following formulae (I1) to (I15).

[0182] [ka]

[0183] However, in the above formula, R 201 , R 202 R represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. 203 R represents a hydrogen atom, or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. 204 Ha-(CH 2 ) i -(i=2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom. 205 R represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom. 206 R represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a phenyl group or naphthyl group each substituted with a hydroxyl group. 208 represents a hydrogen atom or a hydroxyl group. j is an integer of 0 to 5. u and h are 0 or 1. s, t, s', t', s'', and t'' are numbers which satisfy s+t=8, s'+t'=5, and s''+t''=4, respectively, and each phenyl skeleton has at least one hydroxyl group. a is a number which makes the molecular weight of the compound of formula (I8) or (I9) 100 to 1,000.

[0184] The amount of the dissolution inhibitor is 0 to 50 parts by mass, preferably 5 to 50 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of the alkali-soluble resin of component (A), and may be used alone or in combination of two or more. If the amount is 5 parts by mass or more, the resolution is improved more reliably, and if it is 50 parts by mass or less, no film loss of the pattern occurs and high resolution is obtained.

[0185] The (J) surfactant is preferably a nonionic surfactant, such as a fluorine-based surfactant, specifically, perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, fluorine-containing organosiloxane compound, or non-fluorine-containing organosiloxane compound.

[0186] As these surfactants, commercially available ones can be used, and examples thereof include Fluorad FC-4430 (trade name, manufactured by Sumitomo 3M Limited), PF-6320 (trade name, manufactured by OMNOVA), PF-636 (trade name, manufactured by OMNOVA), Surflon S-141 and S-145 (all of which are trade names, manufactured by Asahi Glass Co., Ltd.), Unidyne DS-401, DS-4031 and DS-451 (all of which are trade names, manufactured by Daikin Industries, Ltd.), Megafac F-8151 (trade name, manufactured by DIC Corporation), and X-70-093 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Among these, Fluorad FC-4430 (trade name, manufactured by Sumitomo 3M Limited), PF-6320 (trade name, manufactured by OMNOVA), PF-636 (trade name, manufactured by OMNOVA), and X-70-093 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) are preferable.

[0187] The amount of the surfactant added is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 3 parts by mass, per 100 parts by mass of the alkali-soluble resin of the component (A).

[0188] There are no limitations on the solvent (K) so long as it dissolves the components (A), (B), (C) and (D). Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; and esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol-mono-tert-butyl ether acetate, and γ-butyrolactone. One or more of these may be used. Particularly, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone, or a mixed solvent thereof is preferred.

[0189] The blend amount of the (K) component is preferably 50 to 2,000 parts by mass, and particularly preferably 100 to 1,000 parts by mass, per 100 parts by mass of the total blend amounts of the (A), (B), (C) and (D) components.

[0190] (Pattern formation method) The present invention provides a pattern forming method comprising the following steps. (1) applying the negative photosensitive resin composition onto a substrate to form a photosensitive film; (2) subsequently, after heat treatment, exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; (3) A step of developing the heat-treated substrate after irradiation using an aqueous alkaline developer.

[0191] Hereinafter, a pattern forming method using the negative photosensitive resin composition of the present invention will be described.

[0192] In the negative photosensitive resin composition of the present invention, a pattern can be formed by using a known lithography technique. For example, the pattern can be formed on a silicon wafer or a SiO 2 A negative photosensitive resin composition is applied by spin coating onto a substrate, a SiN substrate, or a substrate on which a pattern of copper wiring or the like has been formed, and pre-baked at 80 to 130°C for about 50 to 600 seconds to form a photosensitive film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 1 to 20 μm.

[0193] In the spin coating method, the negative photosensitive resin composition is applied onto a silicon substrate by dispensing about 5 mL of the negative photosensitive resin composition onto the substrate and then rotating the substrate. At this time, the thickness of the photosensitive film on the substrate can be easily adjusted by adjusting the rotation speed.

[0194] Next, a mask for forming a desired pattern is placed over the photosensitive film, and high-energy rays such as i-rays and g-rays with wavelengths of 190 to 500 nm or electron beams are irradiated at an exposure dose of 1 to 5,000 mJ / cm. 2 Approximately, preferably 100 to 2,000 mJ / cm 2 Irradiate to a degree.

[0195] Next, post-exposure bake (PEB) is performed on a hot plate at, for example, 60 to 150° C. for 50 to 600 seconds, preferably 80 to 120° C. for 60 to 300 seconds.

[0196] In the negative type photosensitive resin composition of the present invention, alkaline development using an aqueous alkaline solution is possible.

[0197] On the other hand, a suitable alkaline aqueous solution that can be used for alkaline development is a 2.38% aqueous solution of tetramethylhydroxyammonium (TMAH). Development can be carried out by a normal method such as a spray method or a paddle method, or by immersion in a developer. Thereafter, washing, rinsing, drying, etc. can be carried out as necessary to obtain a resist film having a desired pattern.

[0198] (Hardened film formation method) In addition, the patterned coating obtained by the above pattern forming method can be heated and post-cured using an oven or a hot plate at a temperature of 100 to 300°C, preferably 150 to 300°C, and more preferably 180 to 250°C, to form a cured coating. If the post-curing temperature is 100 to 300°C, the crosslink density of the coating of the negative photosensitive resin composition can be increased and residual volatile components can be removed, which is preferable from the viewpoints of adhesion to the substrate, heat resistance and strength, and further electrical properties. The post-curing time can be 10 minutes to 10 hours.

[0199] The above-mentioned formed patterns are used for the purpose of forming protective coatings to cover wiring, circuits, substrates, etc., and these formed patterns and protective coatings have excellent insulating properties and exhibit excellent adhesion to the metal layers, such as Cu, of the wiring or circuit they cover, metal electrodes present on the substrate, or insulating substrates, such as SiN, present on the wiring or circuit they cover, and can significantly improve resolution performance to enable the formation of even finer patterns while retaining the mechanical strength suitable for a protective coating.

[0200] (hardened film) The cured coating thus obtained has excellent adhesion to the substrate, heat resistance, electrical properties, mechanical strength and chemical resistance to alkaline stripping solutions and the like, and also has excellent reliability for semiconductor elements using it as a protective coating, particularly in preventing cracks during temperature cycle tests. Thus, it is suitable for use as a protective coating (interlayer insulating film or surface protective film) for electrical / electronic components, semiconductor elements, etc.

[0201] That is, the present invention provides an interlayer insulating film or a surface protective film which is a cured film obtained by curing the above-mentioned negative photosensitive resin composition.

[0202] The protective coating is effective for applications such as insulating films for semiconductor elements including rewiring, insulating films for multilayer printed circuit boards, solder masks, and coverlay films due to its heat resistance, chemical resistance, and insulating properties.

[0203] Furthermore, the present invention provides an electronic component having the above-mentioned interlayer insulating film or the above-mentioned surface protective film. Such an electronic component has excellent reliability because it has a protective coating (interlayer insulating film or surface protective film) that has heat resistance, chemical resistance, and insulating properties. EXAMPLES

[0204] The present invention will be described in detail below with reference to Synthesis Examples, Examples and Comparative Examples. The weight average molecular weight (Mw) is determined by GPC. The weight average molecular weight is calculated based on styrene.

[0205] I. Synthesis of alkali-soluble resin (A) The chemical structures and names of the compounds used in the synthesis examples are shown below. [ka]

[0206] [Synthesis Example 1] Synthesis of polyimide resin (A1) In a 1L flask equipped with a stirrer and a thermometer, 30g (81.9mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9g (8.6mmol) of 4-aminophenol (PAP), and 125g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, a solution of 26.7g (86.2mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) dissolved in 270g of N-methyl-2-pyrrolidone was added dropwise at room temperature, and the mixture was stirred at room temperature for 3 hours after the dropwise addition. Then, 40g of xylene was added to the reaction solution, and the mixture was heated to reflux at 170°C for 3 hours while removing the water generated from the system. After cooling to room temperature, the reaction solution was dropped into 2 L of ultrapure water under stirring, and the precipitate was filtered off, appropriately washed with water, and then dried under reduced pressure at 40° C. for 48 hours to obtain polyimide resin (A1). The molecular weight of this polymer was measured by GPC and found to be 35,000 in terms of polystyrene.

[0207] [Synthesis Example 2] Synthesis of polyimide resin (A2) Polyimide resin (A2) was obtained in the same manner as in Synthesis Example 1, except that 30 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP) was replaced with 21.2 g (81.9 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP). The molecular weight of this polymer was measured by GPC and found to be 34,000 in terms of polystyrene.

[0208] [Synthesis Example 3] Synthesis of polyamide-imide resin (A3) In a 500 ml flask equipped with a stirrer and a thermometer, 28.5 g (77.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.2 mmol) of 4-aminophenol (PAP), and 118 g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, a solution of 19.0 g (61.4 mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA) dissolved in 192 g of N-methyl-2-pyrrolidone was added dropwise at room temperature, and the mixture was stirred at room temperature for 3 hours after the dropwise addition. Then, 40 g of xylene was added to the reaction solution, and the mixture was heated to reflux at 170°C for 3 hours while removing the water generated from the system. After cooling to room temperature, 3.2 g (41.0 mmol) of pyridine was added, and 4.9 g (20.5 mmol) of sebacic acid dichloride (DC-1) was added dropwise while maintaining the temperature below 5° C. After the dropwise addition, the mixture was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water under stirring, and the precipitate was filtered off, appropriately washed with water, and then dried under reduced pressure at 40° C. for 48 hours to obtain polyamideimide resin (A3). The molecular weight of this polymer was measured by GPC, and was found to be 35,000 in terms of weight average molecular weight in terms of polystyrene.

[0209] [Synthesis Example 4] Synthesis of polyamide resin (A4) In a 500 ml flask equipped with a stirrer and a thermometer, 28.5 g (77.8 mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 0.9 g (8.2 mmol) of 4-aminophenol (PAP), and 118 g of N-methyl-2-pyrrolidone were added and stirred at room temperature to dissolve. Next, 13.0 g (163.8 mmol) of pyridine was added, and 19.6 g (81.9 mmol) of sebacic acid dichloride (DC-1) was added dropwise to keep the temperature below 5°C. After the dropwise addition, the mixture was returned to room temperature, and the reaction solution was added dropwise to 2 L of ultrapure water under stirring. The precipitate was filtered, washed appropriately, and then dried under reduced pressure at 40°C for 48 hours to obtain polyamide resin (A4). The molecular weight of this polymer was measured by GPC, and the weight average molecular weight was 38,000 in terms of polystyrene.

[0210] [Synthesis Example 5] Synthesis of tetracarboxylic acid diester compound (X-1) In a 3L flask equipped with a stirrer and a thermometer, 100g (322mmol) of 3,3',4,4'-oxydiphthalic dianhydride (s-ODPA), 65.2g (644mmol) of triethylamine, 39.3g (322mmol) of N,N-dimethyl-4-aminopyridine, and 400g of γ-butyrolactone were added, and 83.8g (644mmol) of hydroxyethyl methacrylate (HEMA) was added dropwise while stirring at room temperature, and the mixture was stirred at room temperature for 24 hours. Then, 370g of 10% aqueous hydrochloric acid was added dropwise under ice cooling to stop the reaction. 800g of 4-methyl-2-pentanone was added to the reaction solution, and the organic layer was separated, and then washed six times with 600g of water. The solvent of the obtained organic layer was distilled off, and 180g of tetracarboxylic acid diester compound (X-1) was obtained.

[0211] [Synthesis Example 6] Synthesis of polyimide precursor (A5) In a 1L flask equipped with a stirrer and a thermometer, 57.1g (100mmol) of (X-1) and 228g of N-methyl-2-pyrrolidone were added and dissolved by stirring at room temperature. Next, 24.4g (205mmol) of thionyl chloride was added dropwise under ice cooling so that the reaction solution temperature was kept below 10℃, and after the dropwise addition, the mixture was stirred for 2 hours under ice cooling. Next, a solution of 34.8g (95mmol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 1.1g (10mmol) of 4-aminophenol (PAP), and 32.4g (410mmol) of pyridine dissolved in 144g of N-methyl-2-pyrrolidone was added dropwise under ice cooling so that the reaction solution temperature was kept below 10℃. After the dropwise addition, the mixture was cooled to room temperature, and the reaction solution was dropped into 3 L of water under stirring, and the precipitate was filtered off, appropriately washed with water, and then dried under reduced pressure at 40° C. for 48 hours to obtain a polyimide precursor (A5). The molecular weight of this polymer was measured by GPC and found to be 36,000 in terms of polystyrene.

[0212] II. Synthesis of polymer compound (B) [Synthesis example] As a crosslinkable polymer compound (polymer additive), each monomer was combined and copolymerized in tetrahydrofuran solvent, crystallized in hexane, and dried to obtain the polymer compounds (Polymers B1 to B14, Comparative Polymers C1 and C2) with the compositions shown below. The compositions of the obtained polymer compounds were confirmed by 1H-NMR, and the molecular weights were confirmed by gel permeation chromatography.

[0213] [Synthesis Example 7] Polymer B1 Molecular weight (Mw)=11,400 [ka]

[0214] [Synthesis Example 8] Polymer B2 Molecular weight (Mw)=11,000 [ka]

[0215] [Synthesis Example 9] Polymer B3 Molecular weight (Mw)=11,500 [ka]

[0216] [Synthesis Example 10] Polymer B4 Molecular weight (Mw)=11,400 [ka]

[0217] [Synthesis Example 11] Polymer B5 Molecular weight (Mw)=10,300 [ka]

[0218] [Synthesis Example 12] Polymer B6 Molecular weight (Mw)=12,000 [ka]

[0219] [Synthesis Example 13] Polymer B7 Molecular weight (Mw)=11,800 [ka]

[0220] [Synthesis Example 14] Polymer B8 Molecular weight (Mw)=10,800 [ka]

[0221] [Synthesis Example 15] Polymer B9 Molecular weight (Mw)=12,300 [ka]

[0222] [Synthesis Example 16] Polymer B10 Molecular weight (Mw)=11,800 [ka]

[0223] [Synthesis Example 17] Polymer B11 Molecular weight (Mw)=10,700 [ka]

[0224] [Synthesis Example 18] Polymer B12 Molecular weight (Mw)=10,400 [ka]

[0225] [Synthesis Example 19] Polymer B13 Molecular weight (Mw)=9,400 [ka]

[0226] [Synthesis Example 20] Polymer B14 Molecular weight (Mw)=11,000 [ka]

[0227] [Synthesis Example 21] Comparative Polymer C1 Molecular weight (Mw)=11,300 [ka]

[0228] [Synthesis Example 22] Comparative Polymer C2 Molecular weight (Mw)=11,800 [ka]

[0229] III. Preparation of negative photosensitive resin composition (Examples 1 to 20, Comparative Examples 1 and 2) A resin composition of 20 mass% resin equivalent was prepared using the base resin in the composition and blending amount shown in Table 1, using 70 mass parts of the alkali-soluble resins (A1) to (A5) synthesized in Synthesis Examples 1 to 6 and 30 mass parts of the crosslinkable polymer compounds (B1) to (B14), (C1), and (C2) synthesized in Synthesis Examples 7 to 22. The mixture was then stirred, mixed, and dissolved, and then microfiltered with a 1.0 μm Teflon (registered trademark) filter to obtain a negative photosensitive resin composition. In the table, the solvent PGMEA stands for propylene glycol monomethyl ether acetate, and GBL stands for gamma-butyrolactone.

[0230] [Table 1]

[0231] In Table 1, the details of the photoacid generator (PAG-1), which is an oxime sulfonate compound, the crosslinking agents (CL-1) (CL-2) (CL-3), the basic compound (E-1), the thermal acid generators (F-1) and (F-2), the antioxidant (G-1), the silane compound (H-1), the dissolution inhibitor (I-1), and the surfactant (J-1) are as follows:

[0232] Photoacid generator (PAG-1) [ka]

[0233] Crosslinker (CL-1) [ka]

[0234] Crosslinker (CL-2) [ka]

[0235] Crosslinker (CL-3) Oxetane resin: OXT-121 manufactured by Toagosei Co., Ltd.

[0236] Basic Compound (E-1) [ka]

[0237] Thermal acid generator (F-1) [ka]

[0238] Thermal acid generator (F-2) [ka]

[0239] Antioxidant (G-1) Hindered phenol-based antioxidant: Sumilizer GA-80 manufactured by Sumitomo Chemical Co., Ltd.

[0240] Silane Compound (H-1) Aminosilane coupling agent: KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.

[0241] Dissolution inhibitor (I-1) [ka]

[0242] Surfactant (J-1) Fluorosurfactant: OMNOVA PF-6320

[0243] IV. Pattern Formation The above-mentioned photosensitive resin compositions 1 to 20 and comparative photosensitive resin compositions 1 and 2 were dispensed in an amount of 5 mL onto a silicon substrate treated with hexamethylsilazane, and then the substrate was rotated, i.e., by a spin coating method, so that the film thickness would be 2 μm after heating for post-curing performed after pattern formation. That is, after considering in advance that the film thickness would decrease after the post-curing process, the rotation speed during application was adjusted so that the finished film thickness after post-curing would be 2 μm.

[0244] Next, the substrate was prebaked on a hot plate at 100°C for 2 minutes. Next, i-line exposure was performed using a Veeco i-line stepper AP300E. After exposure, the substrate was post-exposure baked (PEB) at 110°C for 2 minutes, and then cooled. A mask for negative patterns was used for pattern formation. The mask had a pattern capable of forming a 2 μm line and space pattern (hereinafter referred to as LS pattern) with a 1:1 vertical and horizontal arrangement, and was capable of forming an LS pattern in 1 μm increments from 10 μm to 2 μm.

[0245] Thereafter, paddle development was carried out for 1 minute using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer until the coating film in the unexposed areas was dissolved, and then rinsing was carried out with ultrapure water.

[0246] The patterned substrate was then post-cured in an oven at 180° C. for 2 hours with a nitrogen purge.

[0247] Next, each substrate was cut out so that the shape of the obtained LS pattern could be observed, and the line pattern shape was observed using a scanning electron microscope (SEM). The shape of the 2 μm LS line pattern after post-curing was evaluated. Together with these results, the sensitivity and number of developments required to form the 2 μm pattern are shown in Table 2.

[0248] The shape of the LS pattern was evaluated according to the following criteria, and the evaluation results are shown in Table 2. The cross section of the pattern with the smallest LS line was observed, and the width of the top and bottom of the cross section of the pattern was compared. Patterns with a difference between 0 μm and 0.2 μm were rated A, those with a difference between 0.2 μm and 0.5 μm were rated B, those with a difference between 0.5 μm and 1.0 μm were rated C, and those with a difference over 1.0 μm were rated D.

[0249] V. Breaking elongation and tensile strength The above-mentioned photosensitive resin compositions 1 to 20 and comparative photosensitive resin compositions 1 and 2 were spin-coated onto an aluminum substrate so that the final film thickness after curing was 10 μm. Then, the coating was pre-baked on a hot plate at 100° C. for 4 minutes to obtain a photosensitive resin film.

[0250] Then, using a Quintel contact aligner UL-7000, a broadband wavelength of 500 mJ / cm 2The entire substrate was contact exposed to light with an exposure dose of 1000 nm. After irradiation, PEB treatment was performed at 110°C for 4 minutes, and then cooled. Then, curing was performed using an oven under two conditions: 180°C and 240°C for 2 hours with nitrogen purging, to obtain a photosensitive resin cured film. Next, the wafer with the cured film was cut into strips with a width of 10 mm and a length of 60 mm, and the cured film was peeled off from the substrate by immersing it in 20% by mass hydrochloric acid. The breaking elongation and tensile strength of the obtained cured film were measured using an autograph AGX-1KN manufactured by Shimadzu Corporation. The measurement was performed 10 times for each sample, and the average values ​​are shown in Table 2.

[0251] [Table 2]

[0252] VI. Adhesion Using the same procedure as the above pattern formation, the above photosensitive resin compositions 1 to 20 and comparative photosensitive resin compositions 1 and 2 were exposed to i-line to form a 1 cm square pattern on a SiN substrate so that the final film thickness after curing was 5 μm, and a pattern was obtained in a lattice shape over the entire surface of the substrate. The exposure dose was the exposure dose at which the minimum pattern determined by the above LS pattern evaluation could be formed. In addition, pre-baking was performed at 100°C for 4 minutes, and PEB was performed at 110°C for 4 minutes. In addition, development was performed by paddle development for 1 minute until the coating film in the unexposed area was dissolved, and was performed a specified number of times.

[0253] After that, nitrogen purging was performed at 180°C for 2 hours to post-cure the patterned substrate. Next, the cured substrate was cut into individual pieces along the 1 cm square pattern to obtain chips with a cured film. Aluminum pins with epoxy resin were set on the obtained chips, and the chips were heated at 150°C for 1 hour to bond the aluminum pins to the chips, and a measurement sample was prepared. After cooling, the adhesion force was measured using a ROMULUS manufactured by Quad Group by the method shown in Figure 1 (hereinafter referred to as the Stud-pull method). The measurement speed was 20 N / sec as a measurement condition. Figure 1 is an explanatory diagram showing the adhesion force measurement method. In Figure 1, 1 is the SiN substrate (substrate), 2 is the cured film, 3 is the aluminum pin with adhesive, 4 is the support base, 5 is the grip, and 6 is the tensile direction. The obtained value is the average value of 10 points, and the higher the value, the higher the adhesion of the cured film to the SiN substrate. In addition, the peel interface of the cured film / adhesive has a higher adhesion than the substrate / cured film. The adhesion was evaluated by comparing the obtained values ​​and the peeled interface.

[0254] Furthermore, as a high temperature and high humidity test, the obtained chips were left in a pressure cooker at 120°C and 100% RH for 168 hours under saturated 2 atmospheres pressure. The adhesion strength after the test was then evaluated by the stud-pull method, and the results before the test and the adhesion strength to the substrate are shown in Table 3.

[0255] [Table 3]

[0256] As shown in Table 2, it was found that the negative photosensitive resin composition of the present invention gave a cured film having good mechanical properties even when cured at a low temperature of 200° C. or less. The negative photosensitive composition of the present invention also had good mechanical properties even when cured at a high temperature of 240° C. within the low temperature range (100° C. to 300° C.). On the other hand, Comparative Examples 1 and 2 had inferior mechanical properties at 240° C. compared to the negative photosensitive composition of the present invention.

[0257] Furthermore, as shown in Table 3, it was found that the negative type photosensitive resin composition of the present invention gave a cured film having adhesion and high temperature and high humidity resistance even when cured at a low temperature of 200° C. or less. On the other hand, Comparative Examples 1 and 2 had inferior adhesion to the negative type photosensitive composition of the present invention.

[0258] As a result of the above, the compositions of Examples 1 to 20 exhibited good rectangularity and excellent resolution capable of resolving fine patterns of 2 μm, and exhibited sufficient properties as photosensitive materials. In addition, the cured films produced from the compositions exhibited good substrate adhesion and resistance to high temperatures and high humidity, and were therefore useful as protective films for circuits and electronic components.

[0259] The present invention is not limited to the above-described embodiment. The above-described embodiment is merely an example, and any embodiment that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included in the technical scope of the present invention. [Explanation of symbols]

[0260] 1...SiN substrate (substrate), 2...hardened film, 3...aluminum pin with adhesive, 4...support base, 5...grasp, 6...tensile direction.

Claims

1. A negative photosensitive resin composition comprising: (A) an alkali-soluble resin including at least one structure selected from a polyimide structure, a polyamide structure, a polybenzoxazole structure, a polyamideimide structure, and a precursor structure thereof; (B) a polymer compound having a structural unit formed by cyclopolymerization; (C) a compound that generates an acid when exposed to light; (D) a thermal crosslinking agent; It contains A negative type photosensitive resin composition, characterized in that the structural unit formed by cyclopolymerization in the component (B) is at least one of structural units represented by the following general formula (1), the following general formula (2), the following general formula (3), and the following general formula (4): 【Chemistry 1】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.)

2. 2. The negative photosensitive resin composition according to claim 1, wherein the component (B) is an alkali-soluble polymeric compound further comprising a structural unit represented by the following general formula (5) or (5'): 【Chemistry 2】 (In the formula, R ７ represents a hydrogen atom or a methyl group; X １ are respectively -C(=O)-O- and -C(=O)-O-R ８ -, -C(=O)-NH-, -C(=O)-NH-R ８ - or -C(=O)-N(R ８ OH)-. ８ is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. In addition, a hydrogen atom of the aromatic hydrocarbon group in the formula may be replaced with a methyl group. p is 0 or 1.

3. The negative type photosensitive resin composition according to claim 1 or 2, characterized in that the component (B) is a crosslinkable polymer compound further containing either one or both of a structural unit represented by the following general formula (6) and a structural unit represented by the following general formula (α): 【Chemistry 3】 (In the formula, R ９ represents a hydrogen atom or a methyl group; X ２ R is —C(═O)—O—, or a phenylene or naphthylene group. １０ is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an ester group, an ether group or an aromatic hydrocarbon group; R １１ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R １０ may be bonded to form a ring. １２ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; R １３ is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms; R １０ may be bonded to form a ring. m is 0 or 1. p is 0 or 1. R １ R ′ represents a hydrogen atom or a methyl group; ２ ' represents a single bond or an alkylene group; R ３ ' is a blocked isocyanate group.)

4. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the component (B) is a crosslinked alkali-soluble polymer compound further comprising a structural unit represented by the following general formula (7): 【Chemistry 4】 (In the formula, R １４ represents a hydrogen atom or a methyl group, R １５ X is a single bond or a (l+1)-valent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. ３ are respectively -C(=O)-O- and -C(=O)-O-R １６ -, -C(=O)-NH-, -C(=O)-N(R １６ OH)-, or a phenylene group or a naphthylene group. １６ is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom; and l is 0 or 1.

5. The negative type photosensitive resin composition according to any one of claims 1 to 4, characterized in that the component (B) is a crosslinked alkali-soluble polymer compound containing structural units represented by any one or both of the following general formula (3), the following general formula (5), the following general formula (6), or the following general formula (α), and the following general formula (7): 【Chemistry 5】 (In the formula, R ４ R is a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. ７ represents a hydrogen atom or a methyl group; X １ are respectively -C(=O)-O- and -C(=O)-O-R ８ -, -C(=O)-NH-, -C(=O)-NH-R ８ - or -C(=O)-N(R ８ OH)-. ８ R is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, in which a carbon atom of the aliphatic saturated hydrocarbon group may be replaced by an oxygen atom. In addition, a hydrogen atom of the aromatic hydrocarbon group in the formula may be replaced by a methyl group. ９ represents a hydrogen atom or a methyl group; X ２ R is —C(═O)—O—, or a phenylene or naphthylene group. １０ is a linear, branched or cyclic alkylene group having 1 to 15 carbon atoms which may contain an ester group, an ether group or an aromatic hydrocarbon group; R １１ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R １０ may be bonded to form a ring. １２ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; R １３ is a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms; R １０ may be bonded to form a ring. １ ' represents a hydrogen atom or a methyl group; R ２ ' represents a single bond or an alkylene group; R ３ R′ is a blocked isocyanate group. １４ represents a hydrogen atom or a methyl group, R １５ X is a single bond or a (l+1)-valent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 13 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. ３ are respectively -C(=O)-O- and -C(=O)-O-R １６ -, -C(=O)-NH-, -C(=O)-N(R １６ OH)-, or a phenylene group or a naphthylene group. １６ is a divalent linear, branched or cyclic aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a carbon atom of the aliphatic saturated hydrocarbon group may be replaced with an oxygen atom. p is 0 or 1. m is 0 or 1. l is 0 or 1. 0<a1<1.0, 0<a2<1.0, 0≦a3<1.0, 0≦b1<1.0, 0<a3+b1<1.0, 0<a4<1.0, and any one of 0<a1+a2+a3+a4≦1.0, 0<a1+a2+b1+a4≦1.0, 0<a1+a2+a3+b1+a4≦1.0 is satisfied.

6. The negative type photosensitive resin composition according to any one of claims 1 to 5, wherein the component (D) contains one or more crosslinking agents selected from the group consisting of an amino condensate modified with formaldehyde or a formaldehyde-alcohol, and a phenol compound having, on average, two or more methylol groups or alkoxymethylol groups per molecule.

7. The negative type photosensitive resin composition according to any one of claims 1 to 6, characterized in that the negative type photosensitive resin composition contains 10 to 100 parts by mass of the component (B) relative to 100 parts by mass of the component (A).

8. 8. The negative type photosensitive resin composition according to claim 1, further comprising one or more of a basic compound (E), a thermal acid generator (F), an antioxidant (G), and a silane compound (H).

9. (1) A step of applying the negative type photosensitive resin composition according to any one of claims 1 to 8 onto a substrate to form a photosensitive film; (2) subsequently, after the heat treatment, exposing the photosensitive film to high-energy rays or electron beams having a wavelength of 190 to 500 nm through a photomask; (3) developing the irradiated and heat-treated substrate with an aqueous alkaline developer; A pattern forming method comprising the steps of:

10. 10. A method for forming a cured film, comprising a step of heating and post-curing the patterned film obtained by the method for forming a pattern according to claim 9 at a temperature of 100 to 300°C.

11. 9. An interlayer insulating film comprising a cured film obtained by curing the negative photosensitive resin composition according to claim 1.

12. A surface protective film comprising a cured coating formed by curing the negative photosensitive resin composition according to any one of claims 1 to 8.

13. An electronic component comprising the interlayer insulating film according to claim 11 or the surface protective film according to claim 12.

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