TWI598364B - Photosensitive resin composition, method for producing cured film, cured film, organic EL display device, and liquid crystal display device - Google Patents

Description

Photosensitive resin composition, method for producing cured film, cured film, organic EL display device, and liquid crystal display device

The present invention relates to a photosensitive resin composition (hereinafter sometimes referred to simply as "the composition of the present invention"). Further, there is a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing a photosensitive composition, and various image display devices using the cured film.

More specifically, it is a photosensitive resin composition and a use of a flattening film, a protective film, or an interlayer insulating film which are suitable for forming electronic components such as a liquid crystal display device, an organic EL display device, an integrated circuit device, and a solid-state imaging device. A method of producing a cured film thereof.

A patterned interlayer insulating film is provided in an organic electroluminescence (EL) display device or a liquid crystal display device. In order to form the interlayer insulating film, the number of steps for obtaining a necessary pattern shape is small, and sufficient flatness is obtained, and the photosensitive resin composition is widely used. The photosensitive resin composition is described, for example, in Japanese Laid-Open Patent Publication No. 2011-209681.

Further, in the use of the photoresist, the photosensitive resin composition is also known as described in Japanese Laid-Open Patent Publication No. 2000-66406.

Here, the photosensitive resin composition is required to have a certain level of sensitivity, and on the other hand, it is required to improve the adhesion and chemical resistance at the time of development. In order to solve the above problems, an object of the present invention is to provide a photosensitive resin composition which is excellent in adhesion and chemical resistance at the time of development, in addition to maintaining high sensitivity.

Further, an object of the invention is to provide a method for forming a cured film using such a photosensitive resin composition, a cured film, an organic EL display device, and a liquid crystal display device.

Based on the above, it has been found that a polymer which is soluble in a specific alkali solution is formulated in a certain ratio by a composition of a polymer comprising a constituent unit including a group having an acid group-protected group. Surprisingly, not only the sensitivity but also the adhesion at the time of development and the chemical resistance can be improved, thereby completing the present invention.

Specifically, the above problem is solved by the following solution <1>, preferably by <2> to <11>.

<1> A photosensitive resin composition comprising: (A) a polymer component comprising at least one of the following (1) and (2), and a polymer component of the following (S) polymer: (1) a polymer comprising (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a constituent unit having a crosslinkable group, (2) a polymer comprising (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and a polymer comprising (a2) a constituent unit having a crosslinkable group, and (S) a weight average molecular weight a polymer of 1000 to 50000, and further comprising a constituent unit containing a carboxyl group; (B) a photoacid generator; and (C) a solvent; and the value of the (S) polymer represented by the formula (1) is 50. ~3000: solid acid value of the polymer of the formula (1) (S) (unit: mgKOH/g) × content ratio of (S) polymer relative to all solid components in the photosensitive resin composition (unit: mass%) )‥(1).

<2> The photosensitive resin composition according to <1>, wherein the content of the (S) polymer is from 0.5% by mass to 20.0% by mass based on the total solid content.

The photosensitive resin composition as described in <1>, wherein the (S) polymer is a polymer including at least one of the following constituent unit A groups: constituent unit A group

The photosensitive resin composition of any one of the above-mentioned (a2) which has a bridge|crosslinking group is the bridge|crosslinking group which can react with a carboxyl group.

The photosensitive resin composition of any one of the above-mentioned (a2) which has a crosslinkable group is selected from the group consisting of having an epoxy group and/or an oxygen hetero ring. A constituent unit of a butyl group and a constituent unit having a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).

The photosensitive resin composition as described in any one of <1> to <5> which is a positive type.

<7> A method for producing a cured film, comprising: (1) a step of applying the photosensitive resin composition according to any one of <1> to <6> on a substrate; a step of removing a solvent from the applied photosensitive resin composition; (3) a step of exposing the photosensitive resin composition from which the solvent is removed by using activic rays; (4) exposing the exposed photosensitive resin composition a step of developing the photosensitive resin composition; and (5) a post-baking step of thermally hardening the developed photosensitive resin composition Step.

<8> The method for producing a cured film according to <7>, wherein after the step of performing the above development, the step of performing the full exposure of the developed photosensitive resin composition is performed before the post-baking step.

<9> A cured film formed by a method as described in <7> or <8>.

<10> The cured film according to <9>, which is an interlayer insulating film.

<11> An organic EL display device or a liquid crystal display device comprising the cured film according to <9> or <10>.

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in adhesion and chemical resistance at the time of development while maintaining high sensitivity.

1‧‧‧TFT (thin film transistor)

2‧‧‧Wiring

3,8‧‧‧Insulation film

4‧‧‧Flat film

5‧‧‧First electrode

6‧‧‧ glass substrate

7, 18‧‧‧ contact holes

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

FIG. 1 is a conceptual diagram showing an example of a liquid crystal display device. A schematic cross-sectional view showing an active matrix substrate in a liquid crystal display device, including a cured film 17 as an interlayer insulating film.

FIG. 2 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, including a planarization film 4.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below is based on a representative embodiment of the present invention, but the present invention It is not limited to such an embodiment. In addition, the "~" in the specification of the present application is used in the meaning of including the numerical values described before and after the lower limit value and the upper limit value.

Further, in the expression of the group (atomic group) in the present specification, the description that the substituted or unsubstituted is not described includes not only a substituent but also a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The photosensitive resin composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") is preferably used as a positive photosensitive resin composition.

The photosensitive resin composition of the present invention contains (A) a polymer component which satisfies at least one of the following (1) and (2) and a polymer component of the following (S) polymer, (B) a photoacid generator, and (C) a solvent, and the (S) polymer has a value represented by the formula (1) of 50 to 3000; (1) includes (a1) having an acid group protected by an acid-decomposable group a constituent unit of the group, and (a2) a polymer having a structural unit having a crosslinkable group, and (2) a polymer comprising (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and a polymer comprising (a2) a constituent unit having a crosslinkable group, and (S) a polymer having a weight average molecular weight of from 1,000 to 50,000, and further comprising a constituent unit containing a carboxyl group, and formula (1) (S) Solid acid value of the polymer (unit: mgKOH/g) × content ratio (unit: mass%) of the (S) polymer relative to all solid components in the photosensitive resin composition. (1).

According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in adhesion and chemical resistance at the time of development, in addition to maintaining high sensitivity.

Hereinafter, the composition of the present invention will be described in detail.

<(A) Polymer component>

The composition of the present invention contains the following polymer as a polymer component (hereinafter referred to as "(A) component"): (1) includes (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, and/or (2) a polymer comprising (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and including (a2) having crosslinkability The polymer of the constituent unit of the group, and the (S) weight average molecular weight is from 1,000 to 50,000, and further includes a polymer comprising a constituent unit of a carboxyl group. Further, the value of the (S) polymer represented by the formula (1) is 50 to 3,000.

The solid acid value (unit: mgKOH/g) of the polymer of the formula (1) (S) × the content (unit: mass %) of the (S) polymer relative to all the solid components in the photosensitive resin composition. 1)

In the present invention, the polymer component means those other polymers which are added as needed in addition to the above (1) and/or (2) and (S) components.

(1) A polymer comprising (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, and/or (2) including (a1) having an acid a polymer of a constituent unit of a group protected by an acid-decomposable group and a polymer comprising (a2) a constituent unit having a crosslinkable group

<<constitution unit (a1)>>

Component A includes at least (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group. By including the constituent unit (a1) as the component (A), a photosensitive resin composition having an extremely high sensitivity can be obtained.

In the present invention, the "acid group-protected group which is protected by an acid-decomposable group" can be used as an acid group and an acid-decomposable group, and is not particularly limited. The specific acid group is preferably a carboxyl group and a phenolic hydroxyl group. Further, as the acid-decomposable group, a group which is relatively easily decomposed by an acid (for example, an ester structure, a tetrahydropyranyl ester group, or an acetal functional group such as a tetrahydrofuranyl ester group) can be used or compared by an acid. A group which is difficult to decompose (for example, a tertiary alkyl carbonate group such as a tertiary alkyl group such as a third butyl ester group or a tertiary butyl carbonate group such as a third butyl carbonate group).

(a1) The constituent unit having a group having an acid group protected by an acid-decomposable group is preferably a constituent unit having a protective carboxyl group protected by an acid-decomposable group or a protective phenolic hydroxyl group having an acid-decomposable group. unit.

Hereinafter, the composition of the protected carboxyl group having the acid-decomposable group is protected in order The unit (a1-1) and the constituent unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group will be described separately.

<<<(a1-1) constituent unit having a protected carboxyl group protected by an acid-decomposable group>>>

The structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit having a protective carboxyl group which is protected by an acid-decomposable group described below in detail.

The constituent unit having a carboxyl group which can be used in the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is not particularly limited, and a known constituent unit can be used. For example, a constituent unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid; or A constituent unit (a1-1-2) having an ethylenically unsaturated group and an acid anhydride-derived structure.

In the following, (a1-1-1), which is a constituent unit having a carboxyl group, is derived from a constituent unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) The constituent units of the ethylenically unsaturated group and the structure derived from the acid anhydride will be separately described.

<<<<(a1-1-1) is derived from a constituent unit of an unsaturated carboxylic acid having at least one carboxyl group in a molecule>>>>

As the constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, the following may be used as the unsaturated carboxylic acid used in the present invention. That is, examples of the unsaturated monocarboxylic acid include acrylic acid and methacrylic acid. Butenoic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloxyethyl-succinic acid, 2-(methyl)acryloxyethyl hexahydrophthalic acid, 2- (Meth) propylene methoxyethyl-phthalic acid, and the like. Further, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Further, the unsaturated polycarboxylic acid used to obtain a constituent unit having a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and dibutyl Acid mono(2-methylpropenyloxyethyl) ester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate Ester and the like. Further, the unsaturated polycarboxylic acid may be a mono(meth)acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethyl group. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4- Carboxy styrene and the like.

In view of the developability, in order to form the structural unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, and 2 are preferably used. -(Meth)propenyloxyethyl-succinic acid, 2-(methyl)propenyloxyethylhexahydrophthalic acid, 2-(methyl)propenyloxyethyl-o-benzene An acid anhydride such as dicarboxylic acid or an unsaturated polycarboxylic acid, or the like, more preferably acrylic acid, methacrylic acid or 2-(meth)acryloxyethyl hexahydrophthalic acid.

The constituent unit (a1-1-1) derived from the unsaturated carboxylic acid having at least one carboxyl group in the molecule may be contained alone or in combination of two or more.

<<<<(a1-1-2) A constituent unit having both an ethylenically unsaturated group and an acid anhydride-derived structure>>>>

The constituent unit (a1-1-2) having both an ethylenically unsaturated group and an acid anhydride-derived structure is preferably obtained by reacting a hydroxyl group present in a constituent unit having an ethylenically unsaturated group with an acid anhydride. Monomer unit.

As the acid anhydride, a known acid anhydride can be used, and specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. a dibasic acid anhydride such as chlorendic anhydride; an acid anhydride such as trimellitic anhydride, pyromellitic anhydride, diphenylketone tetracarboxylic anhydride or biphenyltetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability.

The reaction rate of the above acid anhydride to the hydroxyl group is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%, from the viewpoint of developability.

<<<<Acidolytic Groups Usable in Building Unit (a1-1)>>>>

The acid-decomposable group which can be used in the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group can be used.

From the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity, the pattern shape, the contact hole formation property, and the storage stability of the photosensitive resin composition, among the acid-decomposable groups, the carboxyl group is preferably The protected carboxyl group is protected in the form of an acetal. Further, from the viewpoint of sensitivity, the acid-decomposable group is more preferably a carboxyl group which is a protected carboxyl group protected by an acetal represented by the following formula (a1-10). Further, in the case where the carboxyl group is a protected carboxyl group protected by the form of an acetal represented by the following general formula (a1-10), the entire protective carboxyl group is formed -(C=O)-O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ) structure.

(In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, wherein R ¹⁰¹ and R ¹⁰² are each a hydrogen atom; R ¹⁰³ represents an alkyl group; R ¹⁰¹ or R ¹⁰² and R ¹⁰³ can be linked to form a cyclic ether.)

In the above formula (a1-10), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, there is no case where both of R ¹⁰¹ and R ¹⁰² represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the above formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be any of a linear chain, a branched chain or a cyclic group.

The linear or branched alkyl group is preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, and particularly preferably a carbon number of 1 to 4. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, neopentyl, n-hexyl, 2 ,3-dimethyl-2-butyl (thexvl), n-heptyl, positive Octyl, 2-ethylhexyl, n-decyl, n-decyl and the like.

The above cyclic alkyl group preferably has a carbon number of 3 to 12, more preferably a carbon number of 4 to 8, and particularly preferably a carbon number of 4 to 6. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The above alkyl group may have a substituent, and the substituent may, for example, be a halogen atom, an aryl group or an alkoxy group. When a halogen atom is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ^{103 are} a halogenated alkyl group, and when an aryl group is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ^{103 are} aralkyl groups.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these halogen atoms, a fluorine atom or a chlorine atom is preferred.

Further, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a carbon number of 6 to 12, and specifically, a phenyl group, an α-methylphenyl group, a naphthyl group or the like may be exemplified by an aryl group. The alkyl group as a whole, that is, an aralkyl group, may, for example, be a benzyl group, an α-methylbenzyl group, a phenethyl group or a naphthylmethyl group.

The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably a methoxy group or an ethoxy group.

Further, when the alkyl group is an alkyl group having a cyclic structure, the alkyl group having a cyclic structure may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the group is a linear or branched alkyl group, it may have an alkyl group having a cyclic structure of 3 to 12 carbon atoms as a substituent.

These substituents may be further substituted by the above substituents.

In the above formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group is preferably a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The aryl group may have a substituent, and the above substituent is preferably an alkyl group having 1 to 6 carbon atoms. The aryl group may, for example, be phenyl, tolyl, xylyl, cumenyl or 1-naphthyl.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring together with the carbon atoms to which they are bonded. To R ¹⁰¹ and R ^102, in the case of a ring structure with R ¹⁰¹ R ¹⁰³ or R ¹⁰² and R ¹⁰³ bonded include, for example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantane Base and tetrahydropyranyl group and the like.

Further, in the above formula (a1-10), it is preferred that any of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

The radical polymerizable monomer for forming a structural unit having a protective carboxyl group represented by the above formula (a1-10) can be used commercially, or can be synthesized by a known method. For example, it can be synthesized by the synthesis method described in Paragraph No. 0037 to Paragraph No. 0040 of JP-A-2011-221494.

The first preferred embodiment of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a constituent unit represented by the following formula.

(wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, and R ¹ or R ² , R ³ can be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an extended aryl group.

When R ¹ and R ² are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. In the case where R ¹ and R ² are an aryl group, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

X represents a single bond or an extended aryl group, preferably a single bond.

A second preferred embodiment of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is a structural unit of the following formula.

(wherein R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; L ¹ represents a carbonyl group or a phenyl group; and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

R ^{121 is} preferably a hydrogen atom or a methyl group.

L ^{1 is} preferably a carbonyl group.

R ¹²² to R ^{128 are} preferably a hydrogen atom.

A preferred specific example of the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is exemplified by the following constituent unit. Further, R represents a hydrogen atom or a methyl group.

<<<(a1-2) constituent unit having a protective phenolic hydroxyl group protected by an acid-decomposable group>>>

The structural unit (a1-2) having a phenolic hydroxyl group protected by an acid-decomposable group is a constituent unit having a phenolic hydroxyl group and a constituent unit having a phenolic hydroxyl group protected by an acid-decomposable group described below. .

<<<<(a1-2-1) constitutive unit having a phenolic hydroxyl group>>>>

The constituent unit having a phenolic hydroxyl group may be a constituent unit in a hydroxystyrene-based constituent unit or a novolak-based resin, and among these constituent units, from the viewpoint of sensitivity, it is preferably derived from hydroxystyrene or α. a constituent unit of methyl hydroxystyrene. In addition, from the viewpoint of sensitivity, the constituent unit having a phenolic hydroxyl group is also preferably a constituent unit represented by the following formula (a1-20).

General formula (a1-20)

(In the formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. A, a represents an integer from 1 to 5, b represents an integer from 0 to 4, and a+b is 5 or less. Further, when two or more R ²²² are present, the R ²²² may be different from each other or the same.

In the above formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, preferably a methyl group.

Further, R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, the sensitivity can be improved, and the transparency of the cured film can be improved, which is preferable. Specific examples of the divalent linking group of R ²²¹ may be an alkylene group, and R ²²¹ is an alkylene group: methylene, ethyl, propyl, isopropyl, n-butyl, and isobutylene. Stretching the third butyl group, stretching the pentyl group, stretching the isoamyl group, stretching the neopentyl group, and stretching the hexyl group. Among them, R ^{221 is} preferably a single bond, a methylene group or an ethyl group. Further, the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group and the like. Further, a represents an integer of 1 to 5. However, from the viewpoint of the effects of the present invention or the ease of production, a is preferably 1 or 2, and more preferably a is 1.

Further, when the carbon atom bonded to R ²²¹ is used as a reference (1 position), the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4 position.

R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Base. Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferred in terms of ease of production.

In addition, b represents an integer of 0 or 1 to 4.

<<<<Acidolytic Groups Usable in Building Unit (a1-2)>>>>

The acid-decomposable group which can be used in the structural unit (a1-2) having a phenolic hydroxyl group which is protected by an acid-decomposable group, and the above-mentioned constituent unit having a protective carboxyl group protected by an acid-decomposable group (a1-1) The acid-decomposable group which can be used in the above is similarly used, and is not particularly limited. The acid-decomposable group preferably has acetal protection from the viewpoint of the basic physical properties of the photosensitive resin composition, particularly the sensitivity or the pattern shape, the storage stability of the photosensitive resin composition, and the formation of contact pores. A constituent unit that protects a phenolic hydroxyl group. Further, from the viewpoint of sensitivity, the acid-decomposable group is more preferably a phenolic hydroxyl group protected by a form of an acetal represented by the above formula (a1-10). Further, in the case where the phenolic hydroxyl group is a phenolic hydroxyl group protected in the form of an acetal represented by the above formula (a1-10), the overall formation of the phenolic hydroxyl group is protected - Ar-O-CR ¹⁰¹ R ¹⁰² The structure of (OR ¹⁰³ ). Further, Ar represents an aryl group.

A preferred example of the acetal ester structure of the phenolic hydroxyl group is exemplified by a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl or R ¹⁰¹ = R ¹⁰² = methyl and R ¹⁰³ = benzyl.

In addition, the radically polymerizable monomer which forms a structural unit which protects a phenolic hydroxyl group which has a phenolic hydroxyl group in the form of an acetal is described, for example, as described in Paragraph No. 0044 of JP-A-2011-215590. Monomers, etc.

Among these monomers, from the viewpoint of transparency, a 1-alkoxyalkyl protecting agent of 4-hydroxyphenyl methacrylate or a tetrahydropyranyl group of 4-hydroxyphenyl methacrylate is preferred. Protector.

Specific examples of the acetal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, and examples thereof include 1-ethoxyethyl, 1-methoxyethyl, and 1-n-butoxyethyl. 1-isobutoxyethyl, 1-(2-chloroethoxy)ethyl, 1-(2-ethylhexyloxy)ethyl, 1-n-propoxyethyl, 1-cyclohexyloxy Ethyl ethyl group, 1-(2-cyclohexylethoxy)ethyl group, 1-benzyloxyethyl group, etc., these groups may be used individually or in combination of 2 or more types.

The radical polymerizable monomer for forming the structural unit (a1-2) having the above-mentioned protective phenolic hydroxyl group protected by an acid-decomposable group can be used commercially, or can be synthesized by a known method. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with a vinyl ether in the presence of an acid catalyst. The above synthesis allows a monomer having a phenolic hydroxyl group to be previously copolymerized with another monomer and then reacted with a vinyl ether in the presence of an acid catalyst.

A preferred specific example of the structural unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group is exemplified by the following constituent unit, but the present invention is not limited to the constituent units.

<<<The preferred aspect of the constituent unit (a1)>>>

In the case where the polymer containing the above-mentioned structural unit (a1) does not substantially contain the structural unit (a2), the constituent unit (a1) preferably contains 20 mol% to 100% of the polymer containing the structural unit (a1). Molar%, more preferably 30% by mole to 90% by mole.

In the case where the polymer containing the above-mentioned structural unit (a1) contains the following structural unit (a2), the polymer including the structural unit (a1) and the structural unit (a2) has a constituent unit in terms of sensitivity. (a1) is preferably 3 mol% ~70% by mole, more preferably 10% by mole to 60% by mole. Further, in particular, in the case where the acid-decomposable group which can be used in the above-mentioned structural unit (a1) is a constituent unit having a protective carboxyl group in which a carboxyl group is protected by an acetal, it is preferably 20 mol% to 50 mol. %.

The constituent unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group has a feature of rapid development as compared with the above-mentioned constituent unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group. Therefore, in the case of rapid development, it is preferably a constituent unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group. On the contrary, in the case where the development is to be slowed down, it is preferred to use a constituent unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group.

<<(a2) constituent unit having a crosslinkable group>>

The component (A) includes a constituent unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group which undergoes a curing reaction by heat treatment. The aspect of the constituent unit having a preferred crosslinkable group is preferably a group reactive with a carboxylic acid. By using such a crosslinkable group, a crosslinked structure is formed together with the polymer (S) component, so that different types of polymers can be well compatible with each other. Therefore, the film quality can be made uniform, and the chemical resistance can be further improved.

Examples of the crosslinkable group include a group selected from an epoxy group, an oxetanyl group, an —NH—CH ₂ —OR (R is an alkyl group having 1 to 20 carbon atoms), and an ethylenically unsaturated group. The constituent unit of at least one of the constituent groups is preferably selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). At least one of the groups. In the photosensitive resin composition of the present invention, the component (A) preferably contains at least one of an epoxy group and an oxetanyl group. More specifically, the following structural unit is mentioned.

<<<(a2-1) constituent unit having an epoxy group and/or an oxetanyl group>>>

The (A) polymer preferably contains a structural unit (constituting unit (a2-1)) having an epoxy group and/or an oxetanyl group. The cyclic ether group of the above 3-membered ring is also called an epoxy group, and the cyclic ether group of the 4-membered ring is also called an oxetanyl group.

The constituent unit (a2-1) having an epoxy group and/or an oxetanyl group may have at least one epoxy group or oxetanyl group in one constituent unit, and may have one or more members. The epoxy group and one or more oxetanyl groups, two or more epoxy groups, or two or more oxetanyl groups are not particularly limited, and preferably have a total of one to three The epoxy group and/or oxetanyl group is more preferably an epoxy group and/or an oxetanyl group having a total of 1 or 2, and particularly preferably having 1 epoxy group or an oxocyclic group. Butyl.

Specific examples of the radical polymerizable monomer for forming a constituent unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α-n-propyl group. Glycidyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Hexylmethyl ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexylmethyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl Glycidyl ether, p-vinylbenzyl glycidyl ether, paragraph number 0031~paragraph number of Japanese Patent No. 4,184,443 The compound containing an alicyclic epoxy skeleton described in 0035, and the like, are incorporated in the specification of the present application.

Specific examples of the radically polymerizable monomer for forming a structural unit having an oxetanyl group include an oxygen heterocyclic ring described in Paragraph No. 0011 to Paragraph No. 0016 of JP-A-2001-330953. Butyl (meth) acrylates and the like, which are incorporated in the specification of the present application.

A specific example of the radical polymerizable monomer for forming the above-mentioned structural unit (a2-1) having an epoxy group and/or an oxetanyl group is preferably a monomer having a methacrylate structure and containing an acrylate. The monomer of the structure.

Among these monomers, preferred are: glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxa) Cyclobutane-3-yl)methyl ester, and (3-ethyloxetan-3-yl)methyl methacrylate. These constituent units may be used alone or in combination of two or more.

A preferred specific example of the structural unit (a2-1) having an epoxy group and/or an oxetanyl group is exemplified by the following constituent unit. Further, R represents a hydrogen atom or a methyl group.

<<<(a2-2) constituent unit having an ethylenically unsaturated group>>>

One type of the structural unit (a2) having the above crosslinkable group can be exemplified A structural unit (a2-2) of an ethylenically unsaturated group (hereinafter also referred to as "constituting unit (a2-2)"). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal group and having a carbon number of 3 to 16. The constituent unit of the side chain is particularly preferably a constituent unit having a side chain represented by the following formula (a2-2-1).

(In the formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * represents a constituent unit (a2) having a crosslinkable group. The part where the main chain is connected.)

R ³⁰¹ is a divalent linking group having 1 to 13 carbon atoms, and includes an alkenyl group, a cycloalkenyl group, an extended aryl group or a group obtained by combining the groups, and may further contain an ester bond, an ether bond, or a guanamine bond. a bond such as a urethane bond. Further, the divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at any position. Specific examples of R ³⁰¹ include the following divalent linking groups.

The side chain represented by the above formula (a2-2-1) includes the divalent linking group represented by the above R ³⁰¹ , and is preferably an aliphatic side chain.

In addition, the constituent unit having an ethylenically unsaturated group (a2-2) can be referred to the description of Paragraph No. 0072 to Paragraph No. 0090 of JP-A-2011-215580, which is incorporated in the specification of the present application. .

<<<(a2-3) A constituent unit of a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>>

The polymer used in the present invention is also preferably a constituent unit (a2-3) having a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-3), the hardening reaction can be caused by a slow heat treatment, and a cured film excellent in characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. The constituent unit (a2) is more preferably a constituent unit having a group represented by the following formula (a2-30).

(In the formula (a2-30), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

R ^{2 is} preferably an alkyl group having 1 to 9 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group.

Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and a n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

<<<The preferred aspect of the constituent unit (a2)>>>

In the case where the polymer containing the above-mentioned structural unit (a2) does not substantially contain the structural unit (a1), in the polymer containing the above-mentioned structural unit (a2), the structural unit (a2) is preferably 5 mol% to 90%. More than 20% of the moles, more preferably 20% by mole to 80% by mole.

When the polymer containing the structural unit (a2) contains the structural unit (a1), the structural unit (a1) and the structural unit (a2) are contained. In the polymer, from the viewpoint of chemical resistance, the constituent unit (a2) is preferably from 3 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%.

In the present invention, in any of the constituent elements of the component (A), it is preferable to contain a structural unit (a2) of 3 mol% to 70 mol%, more preferably 10 mol%. ~60% by mole.

When it is in the above numerical range, the cured film obtained from the photosensitive resin composition has good transparency and chemical resistance.

<<(a3) Other constituent units>>

In the present invention, the polymer component (1) and the polymer component (2) may include other constituent units other than the constituent units (a3) in addition to the constituent unit (a1) and/or the constituent unit (a2). .

The monomer to be another constituent unit (a3) is not particularly limited, and examples thereof include styrenes, alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, and aryl (meth)acrylates. Ester, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid , unsaturated dicarboxylic anhydride, other unsaturated compounds. Further, as will be described later, a constituent unit having an acid group may also be included. The monomers which are other constituent units (a3) may be used singly or in combination of two or more.

Hereinafter, preferred embodiments of the polymer component (1) and/or the polymer component (2) of the present invention are listed, but the present invention is not limited to the embodiments.

(First embodiment)

The polymer component (1) further includes one or two or more kinds of other constituent units (a3).

(Second embodiment)

The polymer of the polymer component (2) including (a1) a constituent unit having a group in which the acid group is protected by an acid-decomposable group further includes one or two or more kinds of other constituent units (a3).

(Third embodiment)

The polymer of the polymer component (2) including (a2) a constituent unit having a crosslinkable group further includes one or two or more kinds of other constituent units (a3).

(Fourth embodiment)

In any of the first to third embodiments, the constituent unit including at least an acid group is included as the other constituent unit (a3).

(Fifth Embodiment)

The form of the combination of two or more types of the above-described first to fourth embodiments is included.

(Sixth embodiment)

At least the aspect of the polymer component (2) is included. In particular, the first embodiment to the fourth embodiment include at least the polymer component (2).

Specifically, the constituent unit (a3) includes constituent units derived from the following compounds: styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, ethoxylated. Styrene, methoxystyrene, ethoxystyrene, Chlorostyrene, methyl benzoate, ethyl vinyl benzoate, 4-hydroxypropoxypropyl 4-hydroxybenzoate, (meth)acrylic acid, methyl (meth)acrylate , ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ( Benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetic acid monoester (meth) acrylate, and the like. In addition, the compound described in Paragraph No. 0021 to Paragraph No. 0024 of JP-A-2004-264623 is mentioned.

Further, from the viewpoint of electrical properties, the other constituent unit (a3) is preferably a styrene group or a group having an alicyclic skeleton. Specific examples thereof include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, and cyclohexyl (meth)acrylate. Ester, isobornyl (meth)acrylate, benzyl (meth)acrylate, and the like.

Further, from the viewpoint of adhesion, the other constituent unit (a3) is preferably an alkyl (meth)acrylate. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. . In the constituent unit constituting the polymer (A), the content of the constituent unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and particularly preferably 40 mol% or less. The lower limit value may be 0 mol%, and may be, for example, 1 mol% or more, and may be 5 mol% or more. When it is in the above numerical range, the characteristics of the cured film obtained from the photosensitive resin composition become good.

The other constituent unit (a3) preferably contains an acid group. Good sensitivity is obtained by including an acid group in the polymer component (1) and the polymer component (2). The acid group in the present invention means a proton dissociative group having a pKa of less than 7. Usually, a monomer capable of forming an acid group is used as a constituent unit containing an acid group, and an acid group is incorporated into the polymer. When such a structural unit containing an acid group is contained in a polymer, it tends to be easily dissolved in an alkaline developing solution.

The acid group used in the present invention can be exemplified by those derived from a carboxylic acid group, those derived from a sulfonylamino group, those derived from a phosphonic acid group, those derived from a sulfonic acid group, those derived from a phenolic hydroxyl group, and sulfonylamino groups. The sulfonimide group or the like is preferably one derived from a carboxylic acid group and/or derived from a phenolic hydroxyl group.

The constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth)acrylic acid and/or an ester thereof.

In the present invention, in particular, from the viewpoint of sensitivity, a constituent unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group is preferable.

The constituent unit containing an acid group is preferably from 1 mol% to 80 mol%, more preferably from 1 mol% to 50 mol%, more preferably from 5 mol% to 40 mol% of the constituent units of all the polymer components. Ear %, particularly preferably 5 mole % to 30 mole %, optimally 5 mole % ~ 20 mole %.

<<Molecular weight of polymer component (1) and polymer component (2)>>

The molecular weight of the polymer component (1) and the polymer component (2) is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene-equivalent weight average molecular weight. If it is within the above numerical range, the characteristics are good. The ratio (dispersion) of the number average molecular weight to the weight average molecular weight is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.

<<Method for Producing Polymer Component (1) and Polymer Component (2)>>

Further, various methods are also known for the synthesis of the polymer component (1) and the polymer component (2), and if an example is used, at least the above-mentioned (a1) can be formed by using a radical polymerization initiator. The radically polymerizable monomer mixture of the radical polymerizable monomer of the constituent unit represented by the above (a3) is synthesized by polymerization in an organic solvent. Further, it can also be synthesized by a so-called polymer reaction.

The photosensitive resin composition of the present invention preferably contains the polymer component (1) and the polymer component (2) in a proportion of 50 parts by mass to 99.9 parts by mass, more preferably 70% by mass based on 100 parts by mass of all the solid components. The proportion of the mass parts to 98 parts by mass includes the polymer component (1) and the polymer component (2).

<(S) component>

The photosensitive resin composition of the present invention contains (S) a polymer represented by the formula (1) and having a value of 50 to 3,000, a weight average molecular weight of 1,000 to 50,000, and a constituent unit including a carboxyl group (in the present specification, sometimes It is called "(S) component").

(S) solid acid value of the polymer (unit: mgKOH/g) × content ratio of (S) polymer relative to all solid components in the photosensitive resin composition (unit: mass%). (1)

All solid components refer to all components other than the solvent.

By formulating such a polymer, it is possible to provide not only high sensitivity but also A photosensitive resin composition having excellent adhesion to a substrate during development and further excellent chemical resistance. Furthermore, transparency can also be improved.

For example, the (S) component is a polymer having a solid acid value of 200 mg KOH/g, and the content of the (S) component is 5% by mass based on all components other than the solvent of the photosensitive resin composition of the present invention. Next, the formula (1) is 200 × 5 = 1000.

The solid acid value in the formula (1) was measured by the following method.

1 g of a solution of the (S) component of Propylene Glycol Monomethyl Ether Acetate (PGMEA) (40% by mass) was dissolved in 54 ml of propylene glycol monomethyl ether and 6 ml of pure water, and 0.1 mol/l of KOH aqueous solution was used. The titration was performed by potentiometric titration, and the acid value of the solution of 40% by mass was determined. Only the acid value of the (S) component is calculated as the solid acid value based on the acid value of the above solution.

The calculated value of the above formula (1) is 50 to 3,000, preferably 100 to 2,000, and particularly preferably 150 to 1,000. By setting it as the above range, the ratio of the acid group (especially a carboxyl group) in the polymer component in the photosensitive resin composition becomes an appropriate amount, and the high sensitivity can be maintained, and the substrate adhesiveness at the time of image development can be improved, and further. Improve chemical resistance. In the composition comprising a polymer comprising a constituent unit having a group in which an acid group is protected by an acid-decomposable group, it is surprisingly possible to achieve the above effect by formulating a component (S) which is soluble in a base.

The solid acid value of the component (S) is preferably from 100 mgKOH/g to 350 mgKOH/g, more preferably from 140 mgKOH/g to 300 mgKOH/g, still more preferably from 180 mgKOH/g to 250 mgKOH/g. In the case of the above range, both sensitivity and Adhesion to the substrate.

The component (S) in the present invention is a polymer different from the polymer component (1) and the polymer component (2). Therefore, (a1) a structural unit having a group having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group are not usually contained.

The component (S) is a polymer having a weight average molecular weight of from 1,000 to 50,000, preferably from 1,250 to 40,000, more preferably from 1,500 to 30,000. When the weight average molecular weight is in the above range, the compatibility with the resin of the polymer (1) and the polymer (2) component is excellent, and the chemical resistance is improved. On the other hand, when the molecular weight of the (S) component is less than 1,000, it is rapidly mixed in the developer, and the effects of the present invention are not exhibited. Further, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.

<<Composition unit containing a carboxyl group>>

The (S) component includes at least a constituent unit containing a carboxyl group. When the component (S) includes a constituent unit containing a carboxyl group, not only the high sensitivity but also the adhesion is excellent, and the chemical resistance is also improved, and a preferred embodiment of the present invention can be achieved.

The constituent unit having a carboxyl group is not particularly limited as long as it has at least one carboxyl group in the molecule, and a known constituent unit can be used. For example, a constituent unit derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid can be used.

The constituent unit having a carboxyl group can be used as the unsaturated carboxylic acid listed below. The unsaturated carboxylic acid or the like used in the present invention. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloyloxyethyl-succinic acid, and 2-(A). Base) propylene methoxyethyl hexahydrophthalic acid, 2-(meth) propylene methoxyethyl-phthalic acid, and the like. Further, examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Further, the unsaturated polycarboxylic acid used to obtain a constituent unit having a carboxyl group may also be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. Further, the unsaturated polycarboxylic acid may be a mono(2-methylpropenyloxyalkyl)ester of a polyvalent carboxylic acid, and examples thereof include succinic acid mono(2-propenyloxyethyl) ester and butyl Di(2-methylpropenyloxyethyl) diester, mono(2-propenyloxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate ) esters, etc. Further, the unsaturated polycarboxylic acid may be a mono(meth)acrylate of a di-carboxyl polymer at both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethyl. Acrylate and the like. Further, as the unsaturated carboxylic acid, 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, monoalkyl maleate, monoalkyl fumarate, 4- Carboxy styrene and the like.

The constituent unit containing the carboxyl group may be contained alone or in combination of two or more.

Further, as the constituent unit having a carboxyl group, the constituent units listed below can also be used.

The (S) component in the present invention is preferably a polymer including at least one of the following constituent unit A groups. Among them, when a carboxyl group is directly bonded to the main chain, the crosslinking density of the cured film is improved, and thus the chemical resistance is excellent.

Therefore, a constituent unit in which a carboxyl group is directly bonded to a straight chain as described below is preferred.

Constituent unit A group

The (S) component may be included in addition to the constituent unit having a carboxyl group. Other constituent units other than the constituent units are included.

The monomer to be another constituent unit is not particularly limited, and examples thereof include styrene, benzyl methacrylate, alkyl (meth)acrylate, and cyclic alkyl (meth)acrylate. Aryl acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, Unsaturated dicarboxylic acid, unsaturated dicarboxylic anhydride, and other unsaturated compounds. Among them, from the viewpoint of easily controlling the penetration of the developer, a monomer containing an aromatic ring is preferable, and for example, styrene or benzyl methacrylate is more preferable.

In the present invention, it is particularly preferred that the (S) component contains the following constituent unit B group. Such a constituent unit is hydrophobic, and the developer can be more appropriately infiltrated into the polymer component of the photosensitive resin composition. Further, such a structure is also preferable in terms of not impeding the coordination of the resin component to the substrate.

Constituent unit B group

The monomers which are other constituent units may be used singly or in combination of two or more.

In the component (S), the content of the constituent unit containing a carboxyl group is preferably 70 mol. The ear is below the ear%, more preferably 60% by mole or less, and particularly preferably 50% by mole or less.

Specific examples of the structure of the component (S) include the following structures, but the scope of the invention is not particularly limited thereto. Further, in the formula, Et represents an ethyl group.

The polymers may also preferably be commercially available: ARUFON UC-3080 (solid acid value 230, weight average molecular weight 14000), ARUFON UC-3900 (solid acid value 108, weight average molecular weight 4600), ARUFON UC-3910 (solid acid value 200, weight average molecular weight 8500), ARUFON UC-3920 (solid acid value 240, weight average molecular weight 15500) (above manufactured by East Asia Synthetic Co., Ltd.), Joncryl 67 (solid acid value 213) , weight average molecular weight of 12,500), Joncryl 678 (solid acid value of 215, weight average molecular weight of 8,500), Joncryl 586 (solid acid value of 108, weight average molecular weight of 4,600), Joncryl 680 (solid acid value of 215, weight The average molecular weight is 4900), Joncryl 682 (solid acid value 238, weight average molecular weight 1700), Joncryl 690 (solid acid value 240, weight average molecular weight 16500), Joncryl JDX-C3080 (solid acid value 230, weight The average molecular weight is 14,000) (the above is manufactured by BASF) and the like.

The content of the (S) component relative to all the solid components is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, even more preferably 0.7% by mass to 5% by mass. In the case of the above range, the crosslinking reaction of the components (1) and (2) proceeds satisfactorily, and the chemical resistance is improved.

<<Method for manufacturing (S) component>>

There are various methods for synthesizing the component (S), and for example, it can be synthesized by the same method as the components (1) and (2).

In the composition of the present invention, the content of the carboxylic acid having a weight average molecular weight of less than 1,000 is preferably 3% by mass or less, more preferably 1% by mass or less, and preferably substantially no carboxylic acid having a weight average molecular weight of less than 1,000. An example of such a low molecular carboxylic acid is exemplified by the carboxylic acid described in JP-A-2000-66406, which is incorporated herein by reference.

<<<Other polymerizable ingredients>>>

In the present invention, other polymers which do not satisfy the above polymer component (1) or polymer components (2) and (S) may also be contained. For example, a polymer including substantially no constituent unit (a1) and constituent unit (a2) and including other constituent unit (a3) may be mentioned. For example, the following copolymers which are not (S) components: benzyl (meth)acrylate/(meth)acrylic acid copolymer, 2-hydroxyethyl (meth)acrylate/benzyl (meth)acrylate /(Meth)acrylic acid copolymer, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxy-3-phenoxy acrylate Propyl ester/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methyl Acrylic copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like. These polymers are used to fine tune the sensitivity or film quality. Therefore, the amount of the other polymer component as described above is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less based on the total amount of the polymer component.

Commercially available ones of these polymers are SMA 1000P, SMA 2000P, SMA 3000P (manufactured by Cray Valley), and the like.

The total amount of the polymer component (the component (A) and the component (S)) in the present invention is preferably 60% by mass or more, and more preferably 65% by mass or more, based on all the solid components of the photosensitive resin composition of the present invention. More preferably, it is 70% by mass or more.

<(B) Photoacid generator>

The photosensitive resin composition of the present invention contains (B) a photoacid generator. this The photoacid generator (also referred to as "(B) component") used in the invention is preferably a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more, preferably a wavelength of 300 nm to 450 nm, but There is no limit to the chemical structure. In addition, the photoacid generator which does not directly induce the actinic ray having a wavelength of 300 nm or more is a compound which generates an acid by inducing an actinic ray having a wavelength of 300 nm or more by using it together with a sensitizer. It can then be used in combination with a sensitizer. The photoacid generator used in the present invention is preferably a photoacid generator which produces an acid having a pKa of 4 or less, more preferably a photoacid generator which produces an acid having a pKa of 3 or less, and preferably has a pKa of 2 or less. Acid photoacid generator.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium or phosphonium salt, quaternary ammonium salt, diazomethane compound, sulfhydryl sulfonate compound, and sulfonate compound. Wait. Among these compounds, an oxime sulfonate compound is preferably used from the viewpoint of insulating properties. These photoacid generators may be used alone or in combination of two or more. Specific examples of the trichloromethyl-s-triazine, the diarylsulfonium salt, the triarylsulfonium salt, the quaternary ammonium salt, and the diazomethane derivative can be exemplified by Japanese Patent Laid-Open Publication No. 2011-221494. The compound described in paragraph number 0083 to paragraph number 0008.

The oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, is preferably a compound containing an oxime sulfonate structure represented by the following formula (B1).

General formula (B1)

(In the formula (B1), R ²¹ represents an alkyl group or an aryl group; a wavy line indicates a bond with another group.)

In the general formula (B1), any of the groups may be substituted, and the alkyl group in R ²¹ may be linear, may be branched, or may be cyclic. The permitted substituents will be described below.

The alkyl group of R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ may be an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a bridged ring such as 7,7-dimethyl-2-oxonorbornyl). The alicyclic group is preferably substituted with a bicycloalkyl group or the like.

The aryl group of R ²¹ is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The above compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B2).

(In the formula (B2), R ⁴² represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group or a halogen atom, m4 represents an integer of 0 to 3, and when m4 is 2 or 3, a plurality of X may be the same It can be different.)

The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.

The halogen atom as X is preferably a chlorine atom or a fluorine atom.

M4 is preferably 0 or 1. In the above formula (B2), it is particularly preferred that m4 is 1, X is a methyl group, the substitution position of X is an ortho position, and R ⁴² is a linear alkyl group having a carbon number of 1 to 10, and 7,7-dimethyl group. a compound of 2-oxo norbornylmethyl or p-tolylmethyl.

The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably an oxime sulfonate compound represented by the following formula (B3).

(In the formula (B3), R ⁴³ has the same meaning as R ⁴² in the formula (B2), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cyano group. Or nitro, n4 represents an integer from 0 to 5.)

R ⁴³ in the above formula (B3) is preferably: methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, all Fluorine-n-butyl, p-tolyl, 4-chlorophenyl or pentafluorophenyl, particularly preferably n-octyl.

X ^{1 is} preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group.

N4 is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the above formula (B3) include α-(methylsulfonyloxyimino)benzylcarbonitrile and α-(ethylsulfonyloxyimino)benzylcarbonitrile. --(n-propylsulfonyloxyimino)benzylcarbonitrile, α-(n-butylsulfonyloxyimino)benzylcarbonitrile, α-(4-toluenesulfonyloxyimino) Benzonitrile, α-[(methylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(ethylsulfonyloxyimino)-4-methoxybenzene Acetonitrile, α-[(n-propylsulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α-[(n-butylsulfonyloxyimino)-4-methoxy Phenyl phenyl] acetonitrile, α-[(4-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile.

Specific examples of the preferred oxime sulfonate compound include the following compounds (i) to (viii), and the like, and may be used alone or in combination of two or more. The compound (i) to the compound (viii) can be obtained as a commercial product. Further, it can also be used in combination with other types of (B) photoacid generators.

The compound containing the oxime sulfonate structure represented by the above formula (B1) is also preferably a compound represented by the following formula (OS-1).

In the above formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a decyl group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a cyano group, or the like. Aryl or heteroaryl. R ¹⁰² represents an alkyl group or an aryl group.

X ¹⁰¹ represents -O-, -S-, -NH-, -NR ¹⁰⁵ -, -CH ₂ -, -CR ¹⁰⁶ H-, or -CR ¹⁰⁵ R ¹⁰⁷ -, and R ¹⁰⁵ to R ¹⁰⁷ represent an alkyl group or an aromatic group. base.

R ¹²¹ to R ¹²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amine group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, a decylamino group, a sulfo group or a cyano group. Or aryl. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

R ¹²¹ to R ^{124 are} preferably a hydrogen atom, a halogen atom, and an alkyl group. Further, it is preferable to exemplify a state in which at least two of R ¹²¹ to R ¹²⁴ are bonded to each other to form an aryl group. Among them, from the viewpoint of sensitivity, it is preferred that all of R ¹²¹ to R ¹²⁴ are hydrogen atoms.

The functional groups described may each further have a substituent.

The compound represented by the above formula (OS-1) is more preferably a compound represented by the following formula (OS-2).

In the above formula (OS-2), R ¹⁰¹ , R ¹⁰² and R ¹²¹ to R ¹²⁴ have the same meanings as in the formula (OS-1), and preferred examples are also the same.

In these preferred embodiments, it is more preferred that the above formula (OS-1) and R ¹⁰¹ in the above formula (OS-2) are in the form of a cyano group or an aryl group, and it is most preferred from the above formula ( The aspect represented by OS-2) and R ¹⁰¹ is a cyano group, a phenyl group or a naphthyl group.

Further, the steric structure (E, Z, etc.) of the hydrazine or benzothiazole ring in the above sulfonate compound may be either a mixture or a mixture.

Specific examples of the compound represented by the above formula (OS-1) which can be suitably used in the present invention include the compounds described in Paragraph No. 0128 to Paragraph No. 0132 of JP-A-2011-221494 (exemplified compound b- 1 to the exemplified compound b-34), but the present invention is not limited thereto.

In the present invention, the compound containing the oxime sulfonate structure represented by the above formula (B1) is preferably a compound of the following formula (OS-3), the following formula (OS-4) or the following formula (OS). -5) The oxime sulfonate compound represented.

(In the general formula (OS-3) to (OS-5), R ²² , R ²⁵ and R ²⁸ each independently represent an alkyl group, an aryl group or a heteroaryl group, and R ²³ , R ²⁶ and R ²⁹ are each independently The ground represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonate. The thiol group, X ¹ to X ³ each independently represents an oxygen atom or a sulfur atom, and n ¹ to n ³ each independently represent 1 or 2, and m ¹ to m ³ each independently represent an integer of 0 to 6.

In the above formula (OS-3) to formula (OS-5), the alkyl group, the aryl group or the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²² , R ²⁵ and R ²⁸ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ¹ is preferably a heteroaryl group having a total carbon number of 4 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), the heteroaryl group in R ²² , R ²⁵ and R ²⁸ may be at least one ring which is a heteroaromatic ring, for example, a heteroaromatic ring and benzene. The ring can also be condensed.

In the above formula (OS-3) to formula (OS-5), R ²³ , R ²⁶ and R ^{29 are} preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

In the above formula (OS-3) to formula (OS-5), two or more of R ²³ , R ²⁶ and R ²⁹ are present in the compound, and preferably one or two are alkyl groups, aryl groups or More preferably, one halogen atom is an alkyl group, an aryl group or a halogen atom, and particularly preferably one is an alkyl group, and the balance is a hydrogen atom.

The alkyl group in R ²³ , R ²⁶ and R ²⁹ is preferably an alkyl group having a total carbon number of 1 to 12 which may have a substituent, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent.

The aryl group in R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having a total carbon number of 6 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), X ¹ to X ³ each independently represent O or S, and is preferably O.

In the above formula (OS-3) to formula (OS-5), the ring including X ¹ to X ³ as a ring member is a 5-membered ring or a 6-membered ring.

In the above formula (OS-3) to formula (OS-5), n ¹ to n ³ each independently represent 1 or 2, and when X ¹ to X ³ are 0, n ¹ to n ³ are each independently The ground is preferably 1, and when X ¹ to X ³ are S, n ¹ to n ³ are each independently preferably 2.

In the above formula (OS-3) to formula (OS-5), R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or Alkoxysulfonyl. Wherein R ²⁴ , R ²⁷ and R ³⁰ are each independently preferably an alkyl group or an alkoxy group.

The alkyl group, alkoxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R ²⁴ , R ²⁷ and R ³⁰ may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkyl group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.

In the above formula (OS-3) to formula (OS-5), the alkoxy group in R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkoxy group having a total carbon number of 1 to 30 which may have a substituent.

Further, in the above formula (OS-3) to formula (OS-5), m ¹ to m ³ each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1. , especially good is 0.

Further, regarding the respective substituents of the above (OS-3) to (OS-5), (OS-3) to (OS-, as described in Paragraph No. 0092 to Paragraph No. 0109 of JP-A-2011-221494 The preferred range of the substituent of 5) is also preferably preferred.

In addition, the compound containing the oxime sulfonate structure represented by the above formula (B1) is particularly preferably an oxime sulfonate represented by any one of the following formula (OS-6) to (OS-11). Compound.

(In the formula (OS-6)~(OS-11), R ³⁰¹ to R ³⁰⁶ represent an alkyl group, an aryl group or a heteroaryl group, and R ³⁰⁷ represents a hydrogen atom or a bromine atom, and R ³⁰⁸ to R ³¹⁰ and R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ³¹¹ and ^R314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group.

The preferred range of the above-mentioned general formula (OS-6) to the general formula (OS-11) and (OS-6) to (OS) described in Paragraph No. 0110 to Paragraph No. 0112 of JP-A-2011-221494 The preferred range of -11) is the same.

Specific examples of the oxime sulfonate compound represented by the above formula (OS-3) to the above formula (OS-5) include those described in paragraph No. 0114 to paragraph number 0120 of JP-A-2011-221494. A compound, but the invention is not limited to the compounds.

a compound containing the oxime sulfonate structure represented by the above formula (B1) The oxime sulfonate compound represented by the following formula (B4) is preferred.

(In the formula (B4), R ¹ represents an alkyl group or an aryl group, R ² represents an alkyl group, an aryl group or a heteroaryl group; and R ³ to R ⁶ each represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom; Wherein R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form an alicyclic or aromatic ring; X represents -O- or S-.

R ¹ represents an alkyl group or an aryl group. The alkyl group is preferably an alkyl group having a branched structure or an alkyl group having a cyclic structure.

The alkyl group preferably has a carbon number of from 3 to 10. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferred, and when it has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferred.

The alkyl group may, for example, be propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, 1,1-dimethylpropane. The group, the hexyl group, the 2-ethylhexyl group, the cyclohexyl group, the octyl group and the like are preferably an isopropyl group, a tert-butyl group, a neopentyl group or a cyclohexyl group.

The carbon number of the aryl group is preferably from 6 to 12, more preferably from 6 to 8, and particularly preferably from 6 to 7. The aryl group may, for example, be a phenyl group or a naphthyl group, and is preferably a phenyl group.

The alkyl group and the aryl group represented by R ¹ may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a linear, branched or cyclic alkyl group (e.g., a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, or an alkynyl group. , aryl, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, aminemethanyl, cyano, carboxyl, hydroxy, alkoxy, aryloxy, alkylthio, arylthio, heterocycle An oxy group, a decyloxy group, an amine group, a nitro group, a fluorenyl group, a heterocyclic group or the like. In addition, these groups may be further substituted. A halogen atom or a methyl group is preferred.

In view of the transparency of the photosensitive resin composition of the present invention, R ^{1 is} preferably an alkyl group, and R ^{1 is} preferably a carbon number of 3 to 6 from the viewpoint of storage stability and sensitivity. An alkyl group having a branched structure, an alkyl group having a cyclic structure of 5 to 7 carbon atoms, or a phenyl group, more preferably an alkyl group having a branched structure having a carbon number of 3 to 6, or a cyclic structure having a carbon number of 5 to 7. alkyl. By using such a large volume group (especially a large volume of alkyl group) as R ¹ , transparency can be further improved.

Among the large-volume substituents, preferred are isopropyl, tert-butyl, neopentyl, cyclohexyl, and more preferred are tert-butyl or cyclohexyl.

R ² represents an alkyl group, an aryl group or a heteroaryl group. The alkyl group represented by R ² is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group or a cyclohexyl group, and is preferably a methyl group.

The aryl group is preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, a p-tolylmethyl group (p-methylphenyl group), and the like, and a phenyl group and a p-tolylmethyl group are preferable.

Examples of the heteroaryl group include a pyrrolyl group, a fluorenyl group, a carbazolyl group, a furyl group, a thienyl group and the like.

The alkyl group, the aryl group, and the heteroaryl group represented by R ² may have a substituent. The substituent has the same meaning as the substituent which the alkyl group and the aryl group represented by R ¹ may have.

R ^{2 is} preferably an alkyl group or an aryl group, more preferably an aryl group, and even more preferably a phenyl group. The substituent of the phenyl group is preferably a methyl group.

R ³ to R ⁶ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom). The alkyl group represented by R ³ to R ⁶ has the same meaning as the alkyl group represented by R ² , and the preferred range is also the same. Further, the aryl group represented by R ³ to R ⁶ has the same meaning as the aryl group represented by R ¹ , and the preferred range is also the same.

In R ³ to R ⁶ , R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form a ring, and the ring preferably forms an alicyclic ring or an aromatic ring, more preferably a benzene ring.

R ³ to R ^{6 are} preferably a hydrogen atom, an alkyl group, a halogen atom (a fluorine atom, a chlorine atom or a bromine atom), or R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ^{6 are} bonded to each other. The benzene ring is more preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a bromine atom or R ³ and R ⁴ , R ⁴ and R ⁵ or R ⁵ and R ^{6 are} bonded to each other to form a benzene ring.

Preferred aspects of R ³ to R ⁶ are as follows.

(Stage 1) At least two are hydrogen atoms.

(Section 2) The number of the alkyl group, the aryl group or the halogen atom is one or less.

(Form 3) R ³ and R ⁴ , R ⁴ and R ⁵ , or R ⁵ and R ^{6 are} bonded to each other to form a benzene ring.

(Stage 4) The aspect of the above-described aspect 1 and aspect 2 is satisfied, and/or the aspect of the above-described aspect 1 and aspect 3 is satisfied.

X represents -O- or S-.

Specific examples of the above formula (B4) include the following compounds, but the present invention is not particularly limited thereto. Further, in the exemplified compound, Ts represents a toluenesulfonyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.

In the photosensitive resin composition of the present invention, all the resin components in the photosensitive resin composition (preferably a solid component, more preferably a total of copolymers) The (B) photoacid generator is preferably used in an amount of from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 10 parts by mass, per 100 parts by mass. Two or more types may be used in combination.

<(C) Solvent>

The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared by dissolving an essential component of the present invention and further optional components described below in (C) a solvent.

The (C) solvent used in the photosensitive resin composition of the present invention may be a known solvent, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, and ethylene glycol monoalkyl ether acetate. Esters, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol Monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, guanamines, lactones, and the like. In addition, as a specific example of the solvent (C) used in the photosensitive resin composition of the present invention, a solvent described in Paragraph No. 0174 to Paragraph No. 0178 of JP-A-2011-221494 can be cited, and these contents are incorporated. In the specification of the present application.

In addition, if necessary, it may be further added to the solvents: benzyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophor Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, carbonic acid A solvent such as ethylene glycol or propylene carbonate. These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably used singly or in combination of two, and particularly preferably propylene glycol monoalkyl ether acetate or dialkyl ether. And diacetate and diethylene glycol dialkyl ether, or ester and butanediol alkyl ether acetate.

Further, the solvent (C) is preferably a solvent having a boiling point of 130 ° C or more and less than 160 ° C, a solvent having a boiling point of 160 ° C or higher, or a mixture of the solvents.

The solvent having a boiling point of 130 ° C or more and less than 160 ° C can be exemplified by propylene glycol monomethyl ether acetate (boiling point: 146 ° C), propylene glycol monoethyl ether acetate (boiling point: 158 ° C), propylene glycol methyl-n-butyl ether (boiling point) 155 ° C), propylene glycol methyl-n-propyl ether (boiling point 131 ° C).

The solvent having a boiling point of 160 ° C or higher can be exemplified by ethyl 3-ethoxypropionate (boiling point: 170 ° C), diethylene glycol methyl ether (boiling point: 176 ° C), and propylene glycol monomethyl ether propionate (boiling point: 160 ° C), dipropylene glycol methyl ether acetate (boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), two Diol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C ), 1,3-butanediol diacetate (boiling point: 232 ° C).

The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably 50 parts by mass to 95 parts by mass, particularly preferably 60 parts by mass, based on 100 parts by mass of all the resin components in the photosensitive resin composition. 90 parts by mass.

<Other ingredients>

In addition to the above components, the photosensitive resin composition of the present invention may preferably contain (D) an alkoxydecane compound, (E) a crosslinking agent, (F) a sensitizer, and (G) a surfactant. (H) a basic compound, (I) an antioxidant. and then, An acid proliferating agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, a UV absorber, a tackifier, and an organic or inorganic precipitation preventive agent may be added to the photosensitive resin composition of the present invention. And other known additives.

(D) alkoxydecane compound

The photosensitive resin composition of the present invention preferably contains (D) an alkoxydecane compound (also referred to as "(D) component"). When an alkoxy decane compound is used, the adhesiveness of the film formed from the photosensitive resin composition of this invention and a board|substrate can be improved, or the film of the photosensitive resin composition of this invention can be adjusted. The alkoxydecane compound is preferably a dialkoxy decane compound or a trialkoxy decane compound, more preferably a trialkoxy decane compound. The alkoxy group of the alkoxydecane compound preferably has 1 to 5 carbon atoms.

The (D) alkoxydecane compound which can be used in the photosensitive resin composition of the present invention is preferably an inorganic substance which is a base material, for example, an antimony compound such as cerium, cerium oxide or cerium nitride, which improves gold, copper, molybdenum, A compound having adhesion to a metal such as titanium or aluminum and an insulating film. Specifically, a known decane coupling agent or the like is also effective.

Examples of the decane coupling agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrialkoxydecane, and γ-glycidyloxy group. Propyl alkyl dialkoxy decane, γ-methyl propylene methoxy propyl trialkoxy decane, γ-methyl propylene methoxy propyl alkyl dialkoxy decane, γ-chloropropyl three Alkoxydecane, γ-mercaptopropyltrialkoxydecane, β-(3,4-epoxycyclohexyl)ethyltrialkoxydecane, vinyltrialkoxydecane. Among these compounds, more preferred is γ-glycidoxypropyltrialkoxydecane or γ-methacryloxypropyltrialkoxide The decane, particularly preferably gamma-glycidoxypropyltrialkoxydecane, is more preferably 3-glycidoxypropyltrimethoxydecane. These compounds may be used alone or in combination of two or more.

Further, the following compounds can also be preferably used.

In the above, Ph is a phenyl group.

The (D) alkoxydecane compound in the photosensitive resin composition of the present invention is not particularly limited to these compounds, and a known compound can be used.

Commercially available products such as KBM-3103 and KBM-846 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be suitably used.

In the case where the photosensitive resin composition of the present invention contains the (D) alkoxydecane compound, the content of the (D) alkoxydecane compound is preferably 100 parts by mass based on 100 parts by mass of all the solid components in the photosensitive resin composition. It is 0.1 parts by mass to 30 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass.

(E) crosslinker

The photosensitive resin composition of the present invention preferably contains a crosslinking agent as needed. The cured film obtained from the photosensitive resin composition of the present invention can form a stronger film by adding a crosslinking agent.

The crosslinking agent is not limited as long as it is a crosslinking reaction by heat. (except for component A). For example, a compound having two or more epoxy groups or oxetanyl groups, a crosslinking group containing an alkoxymethyl group, or a compound having at least one ethylenically unsaturated double bond in the molecule described below may be added. , block isocyanate compounds, and the like.

When the photosensitive resin composition of the present invention contains (E) a crosslinking agent, the amount of the crosslinking agent added is preferably 0.01 parts by mass to 50% by mass based on 100 parts by mass of all the solid components of the photosensitive resin composition. The portion is more preferably 0.1 part by mass to 30 parts by mass, particularly preferably 0.5 part by mass to 20 parts by mass. By adding in this range, a cured film excellent in mechanical strength and solvent resistance is obtained. A plurality of crosslinking agents may be used in combination, and in this case, the total amount of the crosslinking agents is totaled to calculate the content.

<Compound having two or more epoxy groups or oxetanyl groups in the molecule>

Specific examples of the compound having two or more epoxy groups in the molecule include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolak type epoxy resin. Aliphatic epoxy resin, etc.

These compounds are available as commercial products. For example, commercially available products such as JER157S70, JER157S65, and JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), paragraph number 0189 of JP-A-2011-221494.

Other than this, ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKA RESIN EP-4010S, ADEKA RESIN EP-4011S (above manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above manufactured by Eddy Co.), Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B , Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-211, Denacol EX-212 , Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-911, Denacol EX-941 , Denacol EX-920, Denacol EX-931, Denacol EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-321L, Denacol EX-850L, Denacol DLC-201, Denacol DLC-203, Denacol DLC-204 , Denacol DLC-205, Denacol DLC-206, Denacol DLC-301, Denacol DLC-402 (above manufactured by Nagase ChemteX), YH-300, YH-301, YH-302, YH- 315, YH-324, YH-325 (above manufactured by Nippon Steel Chemical Co., Ltd.), Celloxide 2021P, Celloxide 2081, Celloxide 3000, Celloxide EHPE3150, Epolead GT400, Celvenus B0134, Celvenus B0177 ( Celluloid (Daicel) (shares)) and so on.

These commercially available products may be used alone or in combination of two or more.

Among these compounds, preferred are bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and aliphatic epoxy resins, and particularly preferred are bisphenol A type epoxy resins. Resin.

Specific examples of a compound having two or more oxetanyl groups in the molecule can be used. Use: Aron Oxetane OXT-121, Aron Oxetane OXT-221, Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.).

Further, the compound containing an oxetanyl group is preferably used singly or in combination with a compound containing an epoxy group.

Further, the other crosslinking agent may preferably be an alkoxymethyl group-containing crosslinking agent described in Paragraph No. 0107 to Paragraph No. 0108 of JP-A-2012-8223, and having at least one ethylenic property. Compounds of unsaturated double bonds, etc., are incorporated herein by reference. The alkoxymethyl group-containing crosslinking agent is preferably an alkoxymethylated glycoluril.

<Block isocyanate compound>

In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably used as the crosslinking agent. The block isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, and is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.

In addition, the block isocyanate group in the present invention means a group which can form an isocyanate group by heat, and for example, a group which reacts with an isocyanate group to protect an isocyanate group is preferably exemplified. Further, the blocked isocyanate group is preferably a group capable of forming an isocyanate group by heat of from 90 ° C to 250 ° C.

Further, the blocked isocyanate compound is not particularly limited as long as it has two isocyanate groups in one molecule, and is preferably an aliphatic, alicyclic or aromatic polyisocyanate, and is suitable, for example. Use: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-six Methylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-three Methylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate , diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3- Dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4' -diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-benzenedimethyl diisocyanate, hydrogenated 1,4-benzyldimethyl An isocyanate compound such as a diisocyanate and a compound of a prepolymer type skeleton derived from the compounds. Among these compounds, particularly preferred is tolylene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate. (isophorone diisocyanate, IPDI).

The parent structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention may be a biuret type, an isocyanurate type, an adduct type or a bifunctional type. Polymer type, etc.

Examples of the block forming the block structure of the above-mentioned blocked isocyanate compound include an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, and an imidazole system. Compound a substance, a quinone imine compound or the like. Among these compounds, a block agent selected from the group consisting of an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.

Examples of the above hydrazine compound include hydrazine and ketoxime, and specific examples thereof include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketoxime, cyclohexanone oxime, and benzophenone. Hey.

The above-mentioned indoleamine compound can be exemplified by ε-caprolactam, γ-butylide or the like.

The phenol compound may, for example, be phenol, naphthol, cresol, xylenol or halogen-substituted phenol.

The alcohol compound may, for example, be methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether or alkyl lactate.

Examples of the amine compound include a primary amine and a secondary amine, and may be any of an aromatic amine, an aliphatic amine, and an alicyclic amine, and examples thereof include aniline, diphenylamine, and ethylenimine. Polyethylenimine and the like.

The active methylene compound may, for example, be diethyl malonate, dimethyl malonate, ethyl acetate or ethyl acetate.

The above pyrazole compound can be exemplified by pyrazole, methylpyrazole, dimethylpyrazole and the like.

The above thiol compound can be exemplified by an alkylthiol, an arylthiol or the like.

The blocked isocyanate compound which can be used in the photosensitive resin composition of the present invention can be obtained as a commercial product, and for example, Coronate AP Stable M, Coronate 2503, Coronate 2515, Coronate 2507, Coronate can be preferably used. 2513, Coronate 2555, Millionate MS-50 (above manufactured by Nippon Polyurethane Industry), Takenate B-830, Takenate B-815N, Takenate B-820NSU, Takenate B-842N , Takenate B-846N, Takenate B-870N, Takenate B-874N, Takenate B-882N (above manufactured by Mitsui Chemicals Co., Ltd.), Duranate 17B-60PX, Duranate 17B-60P, Duranate TPA-B80X, Duranate TPA-B80E ,Duranate MF-B60X,Duranate MF-B60B,Duranate MF-K60X,Duranate MF-K60B,Duranate E402-B80B,Duranate SBN-70D,Duranate SBB-70P,Duranate K6000 (above manufactured by Asahi Kasei Chemicals Co., Ltd.), Desmodur BL1100, Desmodur BL1265 MPA/X, Desmodur BL3575/1, Desmodur BL3272MPA, Desmodur BL3370MPA, Desmodur BL3475BA/SN, Desmodur BL5375MPA, Desmodur VPLS2078/2, Desmodur BL4265SN, Desmodur PL340, Desmodur PL350, Sumidur BL3175 (above by Bayeramine Sumika Bayer Urethane (manufactured by the company) and the like.

(F) sensitizer

In combination with the (B) photoacid generator, the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote decomposition thereof. The sensitizer absorbs actinic rays or radiation and becomes an electronically excited state. The sensitizer that is in an electronically excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like. Thereby, the photoacid generator generates a chemical change to decompose and generate an acid. Examples of preferred sensitizers include the following compounds and are in the wavelength region of 350 nm to 450 nm. A compound having an absorption wavelength at any wavelength of the domain.

Polynuclear aromatics (eg, pyrene, perylene, extended triphenyl, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxy Base, 9,10-dipropoxypurine, xanthene (eg fluorescein, eosin, erythrosine, rose B) Rhodamine B), rose bengal, xanthone (eg xanthonesone, thioxanthone, dimethylthiazolone, dithionone) ), cyanine (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (eg, merocyanine, carbocyanine (carbomerocyanine) )), rhodacyanine, oxonol, thiazine (eg, thionine, methylene blue, toluidine blue), Acridines (eg, acridine orange, chloroflavin, acriflavine), acridone (eg acridone, 10-butyl) Keal-2-chloroacridone, 10-butyl acridone Anthraquinone (eg 蒽醌), squaric acid ylide (eg squaraine sulphate), styryl, basic styryl (eg 2-[2-[4 -(Dimethylamino)phenyl]vinyl]benzoxazole), coumarin (eg 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methyl) Coumarin, 2,3,6,7-tetrahydro-9-methyl-1H,5H,11H[1]benzopyrano[6,7,8-ij]quinolizin-11-one) .

Among the sensitizers, preferred are polynuclear aromatics, acridone, and styrene. The alkenyl group, the basic styryl group, and the coumarin are more preferably polynuclear aromatics. Among the polynuclear aromatics, the most preferred is an anthracene derivative.

When the photosensitive resin composition of the present invention contains (F) a sensitizer, the amount of the sensitizer added is preferably 0 parts by mass to 1000 parts by mass based on 100 parts by mass of the photoacid generator of the photosensitive resin composition. The mass fraction is more preferably 10 parts by mass to 500 parts by mass, particularly preferably 50 parts by mass to 200 parts by mass.

Two or more types may be used in combination.

(G) surfactant

The photosensitive resin composition of the present invention may contain (G) a surfactant. (G) The surfactant may be any of an anionic, cationic, nonionic or amphoteric surfactant, and a preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, anthrone series, and fluorine interface. Active agent. In addition, the following product names are listed: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), Eftop (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafac (DIC ) (manufacturing), Fluorad (manufactured by Sumitomo 3M), Asahi Guard, Surflon (made by Asahi Glass), PoIyFox (made by OMNOVA), SH-8400 (Toray Dow Corning) (Toray Dow Corning Silicone)) and other series.

Further, the surfactant is preferably a copolymer comprising a constituent unit A represented by the following formula (G-1) and a constituent unit B, In addition, the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography in the case of using tetrahydrofuran (THF) as a solvent is 1,000 or more and 10,000 or less.

(In the formula (G-1), R ⁴⁰¹ and R ⁴⁰³ each represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon number of 1 or more. 4 or less alkyl groups, L represents an alkylene group having 3 or more and 6 or less carbon atoms, p and q are mass percentages indicating a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass. The above numerical value of 90% by mass or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.)

The above L is preferably a branched alkyl group represented by the following formula (G-2). R ⁴⁰⁵ in the formula (G-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and is preferably a carbon number of 1 or more in terms of compatibility and wettability to a surface to be coated. An alkyl group of 3 or less is more preferably an alkyl group having 2 or 3 carbon atoms. The sum of p and q (p+q) is preferably p+q=100, that is, 100% by mass.

General formula (G-2)

The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

These surfactants may be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention contains (G) a surfactant, the amount of the (G) surfactant added is preferably 10% by mass based on 100 parts by mass of all the solid components in the photosensitive resin composition. The amount is preferably 0.001 parts by mass to 10 parts by mass, particularly preferably 0.01 parts by mass to 3 parts by mass.

(H) basic compound

The photosensitive resin composition of the present invention may contain (H) a basic compound. (H) The basic compound can be arbitrarily selected from the users of the chemical amplification resist. For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a quaternary ammonium salt of a carboxylic acid, etc. are mentioned. Specific examples of such a compound include the compounds described in Paragraph No. 0204 to Paragraph No. 0207 of JP-A-2011-221494.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, and triethanolamine. Dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N,N-dimethylaniline, and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and N-methyl. 4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine ), nicotinic acid, nicotinic acid decylamine, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, hydrazine, pyrrolidine, piperidine, piperazine, morpholine, 4-methyl? Porphyrin, N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-di Azabicyclo[5.3.0]-7-undecene and the like.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

Examples of the quaternary ammonium salt of the carboxylic acid include tetramethylammonium acetate, ammonium tetramethylbenzoate, tetra-n-butylammonium acetate, and tetra-n-butylbenzoic acid ammonium.

The basic compound which can be used in the present invention may be used alone or in combination of two or more.

When the (H) basic compound is contained in the photosensitive resin composition of the present invention, the content of the (H) basic compound is preferably 0.001 part by mass based on 100 parts by mass of all the solid components in the photosensitive resin composition. ~3 parts by mass, more preferably 0.005 parts by mass to 1 part by mass.

(I) Antioxidants

The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant The agent may contain a known antioxidant. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or reduction in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.

Examples of such an antioxidant include phosphorus-based antioxidants, guanamines, guanidines, hindered amine-based antioxidants, sulfur-based antioxidants, phenolic antioxidants, ascorbic acid, zinc sulfate, saccharides, nitrites, and sub- Sulfate, thiosulfate, hydroxylamine derivative, and the like. Among these compounds, a phenolic antioxidant, a guanamine antioxidant, a lanthanoid antioxidant, and a sulfur-based antioxidant are particularly preferable from the viewpoint of coloring and film thickness reduction of the cured film. These compounds may be used alone or in combination of two or more.

Commercial products of phenolic antioxidants include, for example, Adekastab AO-15, Adekastab AO-18, Adekastab AO-20, Adekastab AO-23, Adekastab AO-30, Adekastab AO-37, Adekastab AO-40, Adekastab AO- 50. Adekastab AO-51, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-330, Adekastab AO-412S, Adekastab AO-503, Adekastab A-611, Adekastab A-612, Adekastab A- 613, Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-8W, Adekastab PEP-24G, Adekastab PEP-36, Adekastab PEP-36Z, Adekastab HP-10, Adekastab 2112, Adekastab 260, Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP, Adekastab CDA-1, Adekastab CDA-6, Adekastab ZS-27, Adekastah ZS-90, Adekastab ZS-91 (above manufactured by Eddy Co., Ltd.), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168 , Irgamod 295 (made by BASF). Among them, Adekastab AO-60, Adekastab AO-80, Irganox 1726, Irganox 1035, Irganox 1098 can be suitably used.

When the photosensitive resin composition of the present invention contains (I) an antioxidant, the content of the antioxidant is preferably 0.1% by mass to 10% by mass, more preferably 0.2%, based on the total solid content of the photosensitive resin composition. The mass %~5 mass%, particularly preferably 0.5 mass%~4 mass%. By setting it as this range, the transparency of the formed film is acquired, and the sensitivity at the time of pattern formation also becomes favorable.

In addition, as the additive other than the antioxidant, various ultraviolet absorbers, metal passivators, and the like described in "New Development of Polymer Additives" (Nikkei Kogyo Co., Ltd.) may be added to the photosensitive resin of the present invention. In the composition.

[acid proliferator]

The photosensitive resin composition of the present invention can use an acid multiplier for the purpose of improving sensitivity.

The acid multiplying agent which can be used in the present invention is a compound which can further generate an acid by an acid catalyst reaction and raise the acid concentration in the reaction system, and is a compound which is stably present in the absence of an acid. Since such a compound is increased by one or more acids by one reaction, the reaction is accelerated as the reaction progresses, but since the generated acid itself causes self-decomposition, the strength of the acid generated here is The acid dissociation constant and pKa are preferably 3 or less, and particularly preferably 2 or less.

Specific examples of the acid-proliferating agent include paragraph number 0203 to paragraph number 0223 of JP-A-10-1508, paragraph number 0016 to paragraph number 0055 of Japanese Patent Laid-Open No. Hei 10-282642, and Japanese Patent Special Table. The compounds described in Japanese Patent Publication No. Hei 9-512498, page 39, line 12 to page 47, line 2, are incorporated herein by reference.

The acid multiplying agent which can be used in the present invention is decomposed by using an acid generated by an acid generator to produce dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, or the like. A compound having an acid having a pKa of 3 or less.

Specifically, it can be enumerated:

Wait.

When the photosensitive resin composition of the present invention contains an acid-proliferating agent, the content of the acid-proliferating agent is preferably from 100 parts by mass of the photo-acid generator from the viewpoint of the dissolution ratio of the exposed portion and the unexposed portion. It is preferably 10 parts by mass to 1,000 parts by mass, and more preferably 20 parts by mass to 500 parts by mass.

[development accelerator]

The photosensitive resin composition of the present invention may contain a development accelerator.

The development accelerator can be referred to the description of Paragraph No. 0171 to Paragraph No. 0172 of Japanese Patent Laid-Open No. 2012-042837, which is incorporated herein by reference.

One type of the development accelerator may be used alone or two or more types may be used in combination.

When the photosensitive resin composition of the present invention contains a development accelerator, the amount of the development accelerator is increased by 100 parts by mass based on 100 parts by mass of all the solid components of the photosensitive resin composition from the viewpoint of the sensitivity and the residual film ratio. It is preferably 0 parts by mass to 30 parts by mass, more preferably 0.1 parts by mass to 20 parts by mass, most preferably 0.5 parts by mass to 10 parts by mass.

In addition, as the other additive, the thermal radical generating agent described in Paragraph No. 0120 to Paragraph No. 0121 of JP-A-2012-8223, the nitrogen-containing compound described in WO2011/136074A1, and a thermal acid generator may be used. The content is incorporated into the specification of the present application.

<Method for Preparing Photosensitive Resin Composition>

The components are mixed at a predetermined ratio and by any method, and stirred and dissolved to prepare a photosensitive resin composition. For example, after the components are each dissolved in a solvent to prepare a solution, the solutions are mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared in the above manner can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

[Method for producing cured film]

Next, a method of producing the cured film of the present invention will be described.

The method for producing a cured film of the present invention preferably comprises the following (1)~ Steps of (5).

(1) a step of applying the photosensitive resin composition of the present invention onto a substrate; (2) a step of removing a solvent from the applied photosensitive resin composition; and (3) removing a solvent by an actinic ray pair a step of exposing the photosensitive resin composition; (4) a step of developing the exposed photosensitive resin composition with an aqueous developing solution; (5) post-baking for thermally curing the developed photosensitive resin composition Baking steps.

Each step will be described in order below.

In the coating step of (1), it is preferred to apply the photosensitive resin composition of the present invention onto a substrate to form a wet film containing a solvent. It is preferred to perform cleaning of the substrate such as alkali cleaning or plasma cleaning before applying the photosensitive resin composition onto the substrate, and it is more preferable to treat the surface of the substrate with hexamethyldiaziridine after the substrate is cleaned. By performing this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved. The method of treating the surface of the substrate with hexamethyldioxane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldioxane vapor in advance.

Examples of the substrate include an inorganic substrate, a resin, a resin composite material, and the like.

Examples of the inorganic substrate include glass, quartz, anthrone, and tantalum nitride, and a composite substrate obtained by depositing molybdenum, titanium, aluminum, copper, or the like on the substrate as described above.

Examples of the resin include: polybutylene terephthalate and polyparaphenylene. Ethylene dicarboxylate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polyfluorene, polyether oxime, polyarylate, allyl diol carbonate, poly Fluorine, polyimine, polyamidimide, polyether phthalimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, etc. Resin, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic ether, maleic acid A substrate of a synthetic resin such as a quinone imine, an olefin, a cellulose, or an episulfide compound.

These substrates are rarely used as they are in the above-described form, and a multilayer laminated structure such as a thin film transistor (TFT) element is usually formed by the form of the final product.

The method of applying the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, a slit, and a spin method (slit-and- Spin method) and other methods. Further, a so-called pre-wet method described in Japanese Laid-Open Patent Publication No. 2009-145395 can also be applied.

The wet film thickness at the time of application is not particularly limited, and it can be applied in accordance with the film thickness of the application, and is usually used in the range of 0.5 μm to 10 μm.

In the solvent removal step of (2), a solvent is removed from the applied film by pressure reduction (vacuum) and/or heating to form a dried coating film on the substrate. The heating condition in the solvent removal step is preferably from 70 ° C to 130 ° C and from about 30 seconds to about 300 seconds. When the temperature and time are in the above range, the adhesion of the pattern is further improved, and the residue tends to be further reduced.

In the exposure step of (3), the substrate on which the coating film is provided is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. The acid-decomposable group contained in the coating film component is hydrolyzed by the catalytic action of the generated acid to form a carboxyl group or a phenolic hydroxyl group.

The exposure light source by actinic ray can be used: a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, etc., which can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as g-ray (436 nm), i-ray (365 nm), and h-ray (405 nm). Further, the illumination light may be adjusted by a long-wavelength cut filter, a short-wavelength cut filter, or a band pass filter such as a band pass filter as needed.

The exposure device can be used: a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, Various types of exposure machines such as laser exposure.

In the region where the acid catalyst is formed, in order to accelerate the hydrolysis reaction, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") may be performed. By PEB, it is possible to promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature in the case of performing PEB is preferably 30° C. or higher and 130° C. or lower, more preferably 40° C. or higher and 110° C. or lower, and particularly preferably 50° C. or higher and 100° C. or lower.

Among them, the acid-decomposable group in the present invention has a low activation energy due to acid decomposition, and is easily decomposed by an acid derived from an acid generator generated by exposure to produce a carboxyl group. Alternatively, the phenolic hydroxyl group may be formed by developing to form a positive image without performing PEB.

In the developing step of (4), a polymer having a free carboxyl group or a phenolic hydroxyl group is developed using an alkaline developing solution. A positive image is formed by removing an exposed portion region containing a resin composition having a carboxyl group or a phenolic hydroxyl group which is easily dissolved in an alkaline developing solution.

The developing solution used in the developing step is preferably an aqueous solution containing a basic compound. As the basic compound, for example, an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide or potassium hydroxide; an alkali metal carbonate such as sodium carbonate, potassium carbonate or cesium carbonate; or a base such as sodium hydrogencarbonate or potassium hydrogencarbonate; Metal hydrogencarbonate; tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, diethyldimethylhydrogen a tetraalkylammonium hydroxide such as ammonium oxide; a (hydroxyalkyl) trialkylammonium hydroxide such as choline; a citrate such as sodium citrate or sodium metasilicate; ethylamine, propylamine, and Alkylamines such as ethylamine and triethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-di An alicyclic amine such as azabicyclo-[4.3.0]-5-nonene.

Among these compounds, preferred are: sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, 2-hydroxyethyl Trimethylammonium hydroxide (commonly known as: choline).

Further, an aqueous solution of an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the above-mentioned alkali as a developing solution.

The pH of the developer is preferably from 9.0 to 15.0, more preferably from 10.0 to 14.0. The concentration of the developer is preferably from 0.1% by mass to 20% by mass. More preferably, it is 0.1 mass% - 5.0 mass%. For example, a 0.4% aqueous solution of tetramethylammonium hydroxide, a 0.5% aqueous solution, a 0.7% aqueous solution, and a 2.38% aqueous solution can be mentioned.

The development time is preferably from 30 seconds to 180 seconds, and the development method may be any one of a puddle method, a dipping method, and a shower method. After development, a running water rinse of 30 seconds to 90 seconds can be performed to form a desired pattern.

After development, a rinsing step can also be performed. In the rinsing step, the developed substrate is cleaned by pure water or the like, and the adhered developer is removed and the development residue is removed. A known method can be used for the rinsing method. For example, spray rinsing, immersion rinsing, etc. are mentioned.

In the post-baking step of (5), the acid-decomposable group is thermally decomposed by heating the obtained positive image to form a carboxyl group or a phenolic hydroxyl group, and cross-linking with a crosslinkable group, a crosslinking agent, or the like. Thereby, a cured film can be formed. Preferably, the heating is performed by a heating means such as a hot plate or an oven at a predetermined temperature, for example, 180 ° C to 250 ° C, for a predetermined period of time, for example, 5 minutes to 90 minutes on a hot plate, if The oven is carried out for 30 minutes to 120 minutes. By performing such a crosslinking reaction, a protective film or an interlayer insulating film which is more excellent in heat resistance and hardness can be formed. Further, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

Before baking, it is also possible to perform post-baking after baking at a relatively low temperature (addition of the intermediate baking step). In the case of performing intermediate baking, it is preferably heated at 90 ° C to 150 ° C for 1 minute to 60 minutes, and then at a temperature of 200 ° C or higher. Post-baking. Further, the intermediate baking and the post-baking may be divided into three or more stages to perform heating. The taper angle of the pattern can be adjusted by the intermediate baking and post-baking operations as described above. A known heating method such as a hot plate, an oven, or an infrared heater can be used for the heating.

Further, after performing overall re-exposure (post-exposure) on the patterned substrate by actinic rays before post-baking, post-baking is performed, whereby acid is generated from the photo-acid generator present in the unexposed portion, It functions as a catalyst for promoting the crosslinking step, and promotes the hardening reaction of the film. The preferable exposure amount in the case of including the post-exposure step is preferably from 100 mJ/cm ² to 3,000 mJ/cm ² , particularly preferably from 100 mJ/cm ² to 500 mJ/cm ² .

Further, the cured film obtained from the photosensitive resin composition of the present invention can also be used as an anti-dry etchant. In the case where the cured film obtained by heat-hardening by the post-baking step is used as an anti-dry etchant, the etching treatment may be subjected to dry etching treatment such as ashing, plasma etching, or ozone etching.

[hardened film]

The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.

The cured film of the present invention can be suitably used as an interlayer insulating film. Further, the cured film of the present invention is preferably a cured film obtained by the method for forming a cured film of the present invention.

According to the photosensitive resin composition of the present invention, an interlayer insulating film which is excellent in insulating properties and has high transparency even when baked at a high temperature is obtained. use The interlayer insulating film of the photosensitive resin composition of the present invention has high transparency and excellent physical properties of the cured film, and thus can be used for an organic EL display device or a liquid crystal display device.

[Liquid Crystal Display Device]

The liquid crystal display device of the present invention is characterized by comprising the cured film of the present invention.

The liquid crystal display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and a known liquid crystal display device having various structures can be cited.

Specific examples of the thin film transistor (TFT) included in the liquid crystal display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

Further, examples of the liquid crystal driving method that can be employed in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and an in-plane switching (IPS). Mode, Frings Field Switching (FFS) mode, Optical Compensated Bend (OCB) mode, etc.

In the panel structure, the cured film of the present invention can also be used in a color filter on Allay (COA) type liquid crystal display device, for example, as an organic insulating film of Japanese Laid-Open Patent Publication No. 2005-284291 ( 115) or an organic insulating film (212) of JP-A-2005-346054.

Moreover, the specific alignment of the liquid crystal alignment film which can be taken by the liquid crystal display device of the present invention is, for example, a rubbing alignment method or a photoalignment method. In addition, the polymer alignment support can be carried out by the Polymer Sustained Alignment (PSA) technique described in JP-A-2003-149647 or JP-A-2011-257734.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above applications, and can be used for various purposes. For example, in addition to the planarization film or the interlayer insulating film, a protective film suitable for a color filter or a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device fixed may be provided in the solid-state imaging element. Microlenses and the like on a color filter.

FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel is provided with an element of the TFT 16, and an element of the TFT 16 is disposed between two glass substrates 14 and 15 to which a polarizing film is attached. All pixels correspond. On each element formed on the glass substrate, an ITO transparent electrode 19 on which a pixel electrode is formed is wired through a contact hole 18 formed in the cured film 17. A layer of the liquid crystal 20 and a red green blue (RGB) color filter 22 in which a black matrix is disposed are disposed on the ITO transparent electrode 19.

The light source of the backlight is not particularly limited, and a known light source can be used. For example, a multi-color LED such as a white LED, a blue ‧ red ‧ green, a fluorescent lamp (cold cathode tube), an organic EL, or the like can be given.

In addition, the liquid crystal display device can also be made into three dimensions (three dimensional, 3D) (stereoscopic) type device, or made into a touch panel type device. Further, it can be made into a flexible type, and can be used as the second interphase insulating film (48) of JP-A-2011-145686 or the interphase insulating film (520) of JP-A-2009-258758.

[Organic EL display device]

The organic EL display device of the present invention is characterized by comprising the cured film of the present invention.

The organic EL display device of the present invention is not particularly limited as long as it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices having various structures or Liquid crystal display device.

Specific examples of the thin film transistor (TFT) included in the organic EL display device of the present invention include amorphous germanium-TFT, low-temperature polycrystalline germanium-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.

FIG. 2 is a conceptual diagram showing an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, including a planarization film 4.

A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . After the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 is formed on the insulating film 3 via the contact hole. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or in the step described later to the TFT 1.

Further, in order to planarize the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried.

A bottom emission type organic EL element is formed on the planarization film 4. That is, on the planarizing film 4, the first electrode 5 including ITO is formed by being connected to the wiring 2 via the contact hole 7. Further, the first electrode 5 corresponds to the anode of the organic EL element.

The insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and by providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, in FIG. 2, a hole transport layer, an organic light-emitting layer, and an electron transport layer are sequentially deposited by vapor deposition through a desired pattern mask, and then a second electrode including Al is formed on the entire upper surface of the substrate. An ultraviolet-curable epoxy resin is bonded to the glass plate for sealing and sealed, and an active matrix organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained.

Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a microelectromechanical system (MEMS) device is used. It is made into a partition or assembled as part of a mechanically driven part. Examples of such a MEMS element include a surface acoustic wave (SAW) filter, a bulk acoustic wave (BAW) filter, a gyro sensor, and a microshutter for display. , image sensor, electronic paper, inkjet head (inkjet head), biochip, sealant and other parts. More specific examples are exemplified in JP-A-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.

The photosensitive resin composition of the present invention is excellent in flatness and transparency, and can be used, for example, in forming a bank layer (16) and planarization described in Fig. 2 of JP-A-2011-107476. The partition (12) and the flattening film (102) described in Fig. 4 (a) of the Japanese Patent Publication No. 2010-9793, and the description of Fig. 10 of Japanese Patent Laid-Open Publication No. 2010-27591 The deposition layer (221) and the third interlayer insulating film (216b), the second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4(a) of JP-A-2009-128577 The flattening film (12) and the pixel separation insulating film (14) described in Fig. 3 of Japanese Laid-Open Patent Publication No. 2010-182638.

Example

The present invention will be further specifically described below by way of examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, "parts" and "%" are quality standards unless otherwise specified.

In the following synthesis examples, the following symbols represent the following compounds, respectively.

MATHF: 2-tetrahydrofuran methacrylate (synthetic)

MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

OXF-30: 3-ethyl-3-oxetanylmethyl methacrylate (Osaka Organicization) Industrial company manufacturing)

GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

NBMA: n-Butoxymethyl propylene decylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

HEMA: Hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

MAA: Methacrylic Acid (manufactured by Wako Pure Chemical Industries, Ltd.)

MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

DCPM: Dicyclopentyl Methacrylate

V-601: 2,2'-azobis(2-methylpropionic acid) dimethyl ester (manufactured by Wako Pure Chemical Industries, Ltd.)

V-65: 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)

PGMEA: methoxypropyl acetate (manufactured by Showa Denko)

MEDG: Diethylene glycol methyl ether

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was previously cooled to 15 ° C, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution was added dropwise 2-dihydrofuran (71 g, 1 mol, 1.0 eq.). After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added, and ethyl acetate (500 mL) was evaporated. After ethyl sulfate (500 mL), and dried over magnesium sulfate, the insolubles were filtered, and then concentrated under reduced pressure at 40 ° C. The product was distilled under reduced pressure to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) of 54 to 56 ° C / 3.5 mmHg as a colorless oil (yield 80). %).

<Synthesis Example of Polymer P-1>

PGMEA (89 g) was added to a three-necked flask and the temperature was raised to 90 ° C under a nitrogen atmosphere. MAA (in an amount of 9.5 mol% of all monomer components), MATHF (amount of 43 mol% of all monomer components), and GMA (corresponding to 47.5 mol% of all monomer components) were dissolved in the solution. V-65 (corresponding to 100 mol% of all monomer components, equivalent to 4 mol%) was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, the polymer P-1 was obtained. Further, the ratio of the total amount of PGMEA to other components was set to 60:40. Namely, a polymer solution having a solid concentration of 40% was prepared.

The other types of polymers were synthesized by changing the monomer type and the like to the following table.

In the above table, the values of the units not specifically marked in the table are in mol%. The numerical values of the polymerization initiator and the additive are mol% in the case where the monomer component is made 100 mol%. The solid content concentration is expressed as monomer mass / (monomer mass + solvent mass) × 100 (unit: mass%). When V-601 was used as a polymerization initiator, the reaction temperature was 90 ° C, and when V-65 was used, 70 ° C was set as the reaction temperature.

<Preparation of photosensitive resin composition>

The polymer ((A) component, (S) component), photoacid generator, and other components are dissolved and mixed in a solvent (PGMEA) so as to have a solid content ratio as shown in the following table. The photosensitive resin composition of each of Examples and Comparative Examples was obtained by filtration using a filter made of polytetrafluoroethylene having a diameter of 0.2 μm. The amount of each component in the table is expressed as a ratio (% by mass) of each solid component when the total of the solid components is 100% by mass.

The details of the abbreviations of the respective compounds used in the examples and the comparative examples are as follows.

(Component (A) other than those described in Table 1)

P-14: Joncryl JDX-C3000 (manufactured by BASF) (solid acid value 85, weight average molecular weight 10000)

P-15: SMA 1000P (manufactured by Crayville) (without carboxyl group)

P-16: SMA 3000P (manufactured by Crayville) (without carboxyl group)

((S) component)

S-1: Joncryl 67 (manufactured by BASF, styrene acrylic resin, solid acid value) 213, weight average molecular weight is 12,500)

S-2: ARUFON UC-3910 (manufactured by East Asia Synthetic Co., Ltd., styrene acrylic resin, solid acid value 200, weight average molecular weight 8500)

S-3: Joncryl 680 (manufactured by BASF, styrene acrylic resin, solid acid value 215, weight average molecular weight 4,900)

S-4: The following polymer: (solid acid value: 112, weight average molecular weight is 10000)

S-5: Joncryl 682 (manufactured by BASF, solid acid value 238, weight average molecular weight 1700)

S-6: The following polymer (solid acid value: 168, weight average molecular weight: 8,000)

S-7: the following polymer (solid acid value: 197, weight average molecular weight: 12,000)

S'-1: Salicylic acid

(photoacid generator)

B-1: Structure shown below (the synthesis example will be described below)

B-2: PAG-103 (trade name, structure shown below, manufactured by BASF Corporation)

B-3: α-(hydroxyimino)-2-phenylacetonitrile (described below for synthesis)

B-4: TPS-TF (trade name, structure shown below, manufactured by Toyo Seiki Co., Ltd.)

B-5: Structure shown below (Ts represents toluenesulfonyl (p-toluenesulfonyl))

<Synthesis of B-1>

Add aluminum chloride (10.6g) and 2-chloropropionyl chloride (10.1g) to a suspension solution of 2-naphthol (10g) and chlorobenzene (30mL), and heat the mixture to 40 °C. It reacted for 2 hours. 4N HCl aqueous solution (60 mL) was added dropwise to the reaction mixture under ice-cooling, and ethyl acetate (50 mL) was added. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 ° C for 1 hour. Then, a 2N aqueous HCl solution (60 mL) was added and the mixture was partitioned. The organic layer was concentrated and then crystallised from diisopropyl ether (10 mL) Slurry, filtration, and drying to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated under reflux. After standing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain a hydrazine compound (2.4 g).

The obtained hydrazine compound (1.8 g) was dissolved in acetone (20 mL), and triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added thereto under ice cooling, and the mixture was heated to room temperature for 1 hour. Water (50 mL) was added to the reaction liquid, and the precipitated crystals were filtered, and then re-slurryed with methanol (20 mL), filtered, and dried to obtain a compound (the above structure) (2.3 g) of B-1.

Further, the ¹ H-NMR spectrum of B-1 (300 MHz, CDCl ₃ ) was: δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B-3>

Phenyl acetonitrile (5.85 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with tetrahydrofuran (50 ml, manufactured by Wako Pure Chemical Industries, Ltd.), and the reaction liquid was cooled to 5 ° C or lower in an ice bath. Then, SM-28 (sodium methoxide 28% methanol solution, 11.6 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred for 30 minutes in an ice bath to carry out a reaction. Then Isoamyl nitrate (7.03 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining the internal temperature at 20 ° C. After the completion of the dropwise addition, the reaction solution was allowed to react at room temperature for 1 hour. The obtained reaction liquid was poured into water (150 mL) in which sodium hydroxide (1 g) was dissolved, and completely dissolved. Then, ethyl acetate (100 ml) was added and liquid-separated to obtain about 180 ml of an aqueous layer containing the target. Further, ethyl acetate (100 ml) was added again, and the aqueous layer was made acidic with a pH of 3 or less with concentrated hydrochloric acid, and the product was extracted and concentrated. When the obtained crude crystals were washed with hexane, α-(hydroxyimino)-2-phenylacetonitrile (4.6 g) was obtained in a yield of 63%.

(alkoxydecane compound)

D-1: γ-glycidoxypropyl trialkoxy decane (manufactured by Tokyo Chemical Industry Co., Ltd.)

D-2: KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.)

D-3: KBE-846 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(alkaline compound)

H-1: 2,4,5-triphenylimidazole

H-2: 1,5-diazabicyclo[4.3.0]-5-nonene

H-3: N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea

(surfactant)

G-1: a perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by Di Aisheng)

(sensitizer)

DBA: Dibutoxy oxime of the following structure (manufactured by Kawasaki Chemical Co., Ltd.)

(other additives)

E-1: JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)

E-2: JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.)

E-3: Celloxide 2021P (manufactured by Daicel Co., Ltd.)

E-4: Duranate 17B-60P (made by Asahi Kasei Chemicals Co., Ltd.)

E-5: Denacol EX-321L (manufactured by Changchun Huacheng Co., Ltd.)

E-6: Takenate B-870N (manufactured by Mitsui Chemicals Co., Ltd.)

I-1: Irganox 1098 (manufactured by BASF Corporation)

I-2: Irganox 1035 (made by BASF Corporation)

I-3: Adekastab AO-60 (made by Eddy Co.)

Each of the obtained compositions was subjected to the following evaluation.

<Evaluation of sensitivity>

A glass substrate (EAGLE XG, 0.7 mm thick (manufactured by Corning)) was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was spin-coated at 90 ° C. The resin was prebaked on a hot plate for 120 seconds to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3.0 μm.

Then, the obtained photosensitive resin composition layer was exposed using a mask of a hole pattern of 10 μmφ using MPA 5500CF (high pressure mercury lamp) manufactured by Canon. Next, the exposed photosensitive resin composition layer was developed by an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C / 60 seconds, and then rinsed with ultrapure water for 20 seconds. The exposure amount (monitoring by i-ray) when the hole of 10 μmφ was analyzed by these operations was taken as the sensitivity. The evaluation above D is a practical level.

A: less than 40mJ/cm ²

B: 40 mJ/cm ² or more and less than 120 mJ/cm ²

C: 120 mJ/cm ² or more and less than 200 mJ/cm ²

D: 200 mJ/cm ² or more and less than 280 mJ/cm ²

E: 280 mJ/cm ² or more

<Evaluation of adhesion during development>

A film of Mo (molybdenum) was formed in a half area (10 cm × 5 cm) of one side of the substrate, and a glass substrate of SiNx film was formed on the other half of the same surface (10 cm × 5 cm) (10 cm × 10 cm × 0.5). Mm), exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and applied to each photosensitive resin composition solution by a spin coater to have a dry film thickness of 3 μm, and then at 90 ° C Preheat the plate on the hot plate for 2 minutes to evaporate the solvent. Then, after exposure to a mask capable of reproducing a space of 10 μm line/10 μm, an ultrahigh pressure mercury lamp was used for exposure at a cumulative irradiation amount of 40 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and an alkali developing solution (0.4) was used. The mass% of the TMAH aqueous solution was developed at 23 ° C for 60 seconds, and then rinsed with ultrapure water for 1 minute. The obtained substrate was observed with an optical microscope, and the pattern of the 10 μm line/10 μm space was observed and peeled off in the Mo portion and the SiNx portion. The results are shown in the following table. The less the peeling, the better, A or B is particularly good, and D is a practically problem-free level.

A: No defect, no peeling

B: Defect, peeling is less than 10%

C: defect, peeling more than 10% and less than 20%

D: defect, peeling more than 20% and less than 30%

E: Defect, peeling more than 30% and less than 60%

F: defect, peeling more than 60% and less than 100%

<Evaluation of chemical resistance>

The glass substrate (10 cm × 10 cm × 0.5 mm) was exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and then each photosensitive resin composition was spin-coated, and then preheated at 90 ° C on a hot plate. After baking for 2 minutes, the solvent was volatilized to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, using an ultrahigh pressure mercury lamp, the total exposure was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and then the substrate was heated in an oven at 230 ° C for 30 minutes. A cured film is obtained.

The film thickness (T ¹ ) of the obtained cured film was measured. Next, the substrate on which the cured film was formed was immersed in a solution of dimethyl hydrazine:monoethanolamine=7:3 whose temperature was controlled at 60 ° C for 10 minutes, and then the film thickness (t ¹ ) of the cured film after immersion was measured. The film thickness change rate {|t ¹ -T ¹ |/T ¹ }×100 [%] caused by the immersion was calculated. The results are shown in the following table. The smaller the calculated value, the better, and A and B are practically problem-free.

A: less than 2%

B: 2% or more and less than 3%

C: 3% or more and less than 4%

D: 4% or more and less than 6%

E: 6% or more

As is apparent from the above results, the photosensitive resin compositions of the present invention are all practical levels of sensitivity D or higher, and the adhesion is a practical level of A to D, and further, resistance is achieved. The technical level is also the practical level of A or B (Examples 1 to 54). On the other hand, in the photosensitive resin composition of the comparative example, the sensitivity was a practical level, but the adhesion at the time of development was E or F, which was inferior (Comparative Example 1, Comparative Example 2, Comparative Example 4 to Comparative Example 7). Or the chemical resistance is D, which is outside the practical level (Comparative Example 3).

<Example 55>

Example 55 is the same as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Co., Ltd. to FX-803M (gh-Line, stepper) manufactured by Nikon Co., Ltd. The way to proceed. The evaluation of the sensitivity was the same as that of Example 1.

<Example 56>

Example 56 was carried out in the same manner as in Example 1 except that the exposure machine was changed from a MPA 5500CF manufactured by Canon to a 355 nm laser exposure machine to perform 355 nm laser exposure. Here, the 355 nm laser exposure machine uses "AEGIS" (wavelength: 355 nm, pulse width: 6 nsec) manufactured by V-Technology Co., Ltd., and uses "PE10B-V2" manufactured by OPHIR to measure the exposure amount. .

The evaluation of the sensitivity was the same as that of Example 1.

<Example 57>

In the active matrix liquid crystal display device of FIG. 1 of the Japanese Patent No. 3,321,003, the cured film 17 is formed as an interlayer insulating film in the following manner, and the liquid crystal display device of the fifty-seventh embodiment is obtained. That is, the cured film 17 was formed using the photosensitive resin composition of Example 22 as an interlayer insulating film.

In other words, as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0057 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldioxane (HMDS) vapor for 30 seconds, and then, After the photosensitive resin composition of Example 22 was spin-coated, it was prebaked on a hot plate at 90 ° C for 2 minutes to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 μm. Then, using the MPA 5500CF (high-pressure mercury lamp) manufactured by Canon Co., Ltd., the resulting photosensitive light was obtained by a mask of a hole pattern of 10 μmφ to reach 40 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray). The resin composition layer was exposed. Next, the exposed photosensitive resin composition layer was developed at 23 ° C for 60 seconds using an alkali developing solution (0.4% tetramethylammonium hydroxide aqueous solution), and then rinsed with ultrapure water for 20 seconds. Then, using an ultrahigh pressure mercury lamp, the total exposure was 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and then the substrate was heated in an oven at 230 ° C for 30 minutes. A cured film is obtained.

The coating property at the time of applying the photosensitive resin composition was good, and the occurrence of wrinkles or cracks was not confirmed on the cured film obtained after exposure, development, and firing.

When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibits excellent display characteristics and high reliability.

<Example 58>

The liquid crystal display device of Example 58 was obtained in the same manner except that the hexamethyldioxane (HMDS) treatment was omitted in Example 57. The obtained liquid crystal display device is a liquid crystal display device which is free from defects or peeling of the pattern of the cured film, exhibits good display characteristics, and has high reliability.

<Example 59>

A liquid crystal display device of Example 59 was obtained in the same manner as in Example 57 except that the alkali developing solution was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a tetramethylammonium hydroxide aqueous solution of 2.38%. The obtained liquid crystal display device is a liquid crystal display device which is free from defects or peeling of the pattern of the cured film, exhibits good display characteristics, and has high reliability.

<Example 60>

The liquid crystal display device of Example 60 was obtained in the same manner as in Example 57 except that the alkali developing solution was changed from a 0.4% aqueous solution of tetramethylammonium hydroxide to a 0.04% aqueous KOH solution. The obtained liquid crystal display device is a liquid crystal display device which is free from defects or peeling of the pattern of the cured film, exhibits good display characteristics, and has high reliability.

<Example 61>

Development was omitted except in Example 57. The liquid crystal display device of Example 61 was obtained in the same manner except for the step of full exposure after rinsing. The obtained liquid crystal display device is a liquid crystal display device which exhibits excellent display characteristics and is highly reliable.

<Example 62>

Except in Example 57, the examples were obtained in the same manner except for the step of heating at 230 ° C / 30 minutes in the oven and the heating step at 100 ° C for 3 minutes. A liquid crystal display device of 62. The obtained liquid crystal display device is a liquid crystal display device which exhibits excellent display characteristics and is highly reliable.

<Example 63>

Except in Example 57, in development. The liquid crystal display device of Example 63 was obtained in the same manner except that the step of rinsing was performed by adding a step of heating on a hot plate at 100 ° C for 3 minutes. The obtained liquid crystal display device is a liquid crystal display device which exhibits excellent display characteristics and is highly reliable.

<Example 64>

The same liquid crystal display device was obtained by changing only the following coating process as compared with Example 57. Specifically, the photosensitive resin composition of Example 22 was applied by a slit coating method, and then the solvent was removed by heating on a hot plate at 90 ° C / 120 seconds to form a photosensitive resin composition having a film thickness of 3.0 μm. Floor. The obtained coating film was a flat surface which was flat and had no unevenness. Further, the performance as a liquid crystal display device was also good as in Example 57.

<Example 65>

The same liquid crystal display device was obtained by changing only the following coating process as compared with Example 57. . Specifically, the photosensitive resin composition of Example 22 was applied by a slit and a spin method, and then the solvent was removed by heating on a hot plate at 90 ° C / 120 seconds to form a photosensitive resin composition having a film thickness of 3.0 μm. Floor. The obtained coating film was a flat surface which was flat and had no unevenness. Further, the performance as a liquid crystal display device was also good as in Example 65.

<Example 66>

Embodiment 66 is the same as in Embodiment 1, except that the exposure machine is changed from the MPA 5500CF manufactured by Canon to the UV-LED source exposure machine. Way to proceed. Further, the performance as a liquid crystal display device was also good as in Example 57.

<Example 67>

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).

A bottom gate type TFT 1 is formed on the glass substrate 6 to cover the TFT 1 to form an insulating film 3 containing Si ₃ N ₄ . Then, after the contact hole (not shown) is formed on the insulating film 3, the wiring 2 (having a height of 1.0 μm) connected to the TFT 1 via the contact hole is formed on the insulating film 3. This wiring 2 is for connecting the organic EL element formed in the TFT 1 or in the step described later to the TFT 1.

Further, in order to planarize the unevenness caused by the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state in which the unevenness caused by the wiring 2 is buried. The formation of the planarizing film 4 on the insulating film 3 is performed by spin-coating the photosensitive resin composition of Example 22 on a substrate and pre-baking (90 ° C / 120 seconds) on a hot plate. On the self-shield, an i-ray (365 nm) of 45 mJ/cm ² (energy intensity: 20 mW/cm ² ) was irradiated with a high-pressure mercury lamp, and then developed by using a 0.4% TMAH aqueous solution to form a pattern, and an ultrahigh pressure mercury lamp was used for total irradiation. The exposure was carried out in such a manner that the amount reached 300 mJ/cm ² (energy intensity: 20 mW/cm ² , i-ray), and heat treatment was performed at 230 ° C for 30 minutes.

When the photosensitive resin composition was applied, the coating property was good, and no occurrence of wrinkles or cracks was observed on the cured film obtained after exposure, development, and firing. Further, the average step of the wiring 2 was 500 nm, and the thickness of the produced planarizing film 4 was 2,000 nm.

Then, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 containing ITO is formed on the planarization film 4 via the contact hole 7 and connected to the wiring 2. Then, the resist is applied and prebaked, and exposed and developed through a mask of a desired pattern. This resist pattern was used as a mask, and pattern processing was performed by wet etching using an ITO etchant. Then, the resist pattern was peeled off at 50 ° C using a resist stripper (Remover 100, manufactured by AZ Electronic Materials Co., Ltd.). The first electrode 5 obtained in the above manner corresponds to the anode of the organic EL element.

Then, an insulating film 8 covering the shape of the periphery of the first electrode 5 is formed. The insulating film 8 was formed on the insulating film 8 by using the photosensitive resin composition of Example 22 in the same manner as described above. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent step can be prevented.

Further, a hole transport layer, an organic light-emitting layer, and an electron transport layer are provided by sequentially depositing a mask in a vacuum vapor deposition apparatus with a desired pattern. Then, a second electrode containing Al is formed on the entire surface above the substrate. The obtained substrate was taken out from a vapor deposition machine, and bonded to a glass plate for sealing by using an ultraviolet curable epoxy resin, and sealed.

In the above manner, an active matrix organic EL display device in which the TFTs 1 for driving the organic EL elements are connected to each other is obtained. When a voltage was applied via a drive circuit, it was found that the organic EL display device exhibits excellent display characteristics and high reliability.

10‧‧‧Liquid crystal display device

12‧‧‧Backlight unit

14, 15‧‧‧ glass substrate

16‧‧‧TFT

17‧‧‧ hardened film

18‧‧‧Contact hole

19‧‧‧ITO transparent electrode

20‧‧‧LCD

22‧‧‧Color filters

Claims (14)

A photosensitive resin composition comprising: (A) a polymer comprising at least one of the following (1) and (2), and a polymer component of the following (S) polymer: (1) Including (a1) a constituent unit having a group in which an acid group is protected by an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group, (2) including (a1) having an acid group decomposable by acid a polymer of a constituent unit of the group-protected group, and a polymer comprising (a2) a constituent unit having a crosslinkable group, and (S) a weight average molecular weight of from 1,000 to 50,000, and further including a constituent unit including a carboxyl group a polymer; (B) a photoacid generator; and (C) a solvent, and the solid acid value of the (S) polymer is from 180 mgKOH/g to 250 mgKOH/g, and the value represented by the formula (1) is from 50 to 2000. The solid acid value (unit: mgKOH/g) of the polymer of the formula (1) (S) × the content (unit: mass%) of the (S) polymer with respect to all solid components in the photosensitive resin composition. The photosensitive resin composition according to the first aspect of the invention, wherein the content of the (S) polymer is from 0.5% by mass to 20.0% by mass based on the total solid content. The photosensitive resin composition according to claim 1 or 2, wherein the (S) polymer is a polymer including at least one of the following constituent unit A groups: a constituent unit group A The photosensitive resin composition according to the first or second aspect of the invention, wherein the component (a2) having a crosslinkable group is a crosslinkable group capable of reacting with a carboxyl group. The photosensitive resin composition according to claim 1 or 2, wherein the structural unit having a crosslinkable group (a2) is a constituent unit selected from the group consisting of an epoxy group and/or an oxetanyl group. And a constituent unit having a group represented by -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The photosensitive resin composition according to claim 1 or 2, wherein the (S) polymer is a polymer including at least one of the following constituent unit A groups, and (a2) has cross-linking The constituent unit of the group is a crosslinkable group capable of reacting with a carboxyl group, and constitutes a group A group The photosensitive resin composition according to claim 1 or 2, wherein the (S) polymer is a polymer including at least one of the following constituent unit A groups, and (a2) has cross-linking The constituent unit of the group is selected from a constituent unit having an epoxy group and/or an oxetanyl group, and a group having -NH-CH ₂ -OR (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) In the constituent unit of the represented group, the constituent unit A group The photosensitive resin composition as described in claim 1 or 2, which is a positive type. A method for producing a cured film, comprising: (1) a step of applying a photosensitive resin composition according to any one of claims 1 to 7 to a substrate; (2) a step of removing a solvent in the applied photosensitive resin composition; (3) a step of exposing the solvent-removed photosensitive resin composition by actinic rays; (4) using an aqueous developing solution to expose the photosensitive resin a step of developing the composition; and (5) a post-baking step of thermally curing the developed photosensitive resin composition. The method for producing a cured film according to claim 9, wherein the step of performing the development and the step of the post-baking step include a step of performing total exposure on the developed photosensitive resin composition. A cured film formed by a method for producing a cured film according to claim 9 or 10. The cured film according to claim 11, which is an interlayer insulating film. An organic EL display device comprising the cured film according to claim 11 or claim 12. A liquid crystal display device comprising the cured film according to claim 11 or 12 of the patent application.