KR20150103210A - Photosensitive resin composition, production method for cured film using same, cured film, liquid crystal display device, and organic el display device - Google Patents

Abstract

Provided is a photosensitive resin composition which can maintain high sensitivity and good chemical resistance and adhesion to a cured film. (a1) a polymer having a structural unit having a group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group (excluding a block isocyanate group and an OH group), or a polymer having a structural unit (a1) (A1) and a structural unit (a2) among the polymer components, a polymer containing a polymer satisfying at least one of the structural unit (a2), a photoacid generator and a solvent, (a4) at least one structural unit having a block isocyanate group is contained in at least one of the polymer having a structural unit (a1) and the polymer having a structural unit (a2), or a structural unit and at least one polymer containing no structural unit (a1) and structural unit (a2).

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a cured film, a cured film, a liquid crystal display device, and an organic EL display device using the same,

The present invention relates to a photosensitive resin composition, a method for producing a cured film, a cured film, an organic EL display, and a liquid crystal display. More particularly, the present invention relates to a planarizing film for electronic parts such as a liquid crystal display, an organic EL display, an integrated circuit element, and a solid-state imaging element, a positive photosensitive resin composition suitable for forming a protective film or an interlayer insulating film, and a process for producing a cured film using the same. will be.

An organic EL display device, a liquid crystal display device, or the like is provided with a patterned interlayer insulating film. In order to form this interlayer insulating film, a photosensitive resin composition is widely used because it has few steps for obtaining a required pattern shape and has sufficient flatness.

The interlayer insulating film in the display device is required to have high transparency in addition to physical properties of a cured film excellent in insulating property, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputter suitability. For this reason, it has been attempted to use an acrylic resin having excellent transparency as a film forming component. For example, those described in Patent Documents 1 to 3 are known.

Japanese Patent Laid-Open Publication No. 2011-209681 Japanese Patent Application Laid-Open No. 2009-288343 Japanese Patent Application Laid-Open No. 2008-286924

However, there is a demand for a photosensitive resin composition capable of maintaining a higher sensitivity than that of recent years, while improving the chemical resistance and adhesion of the cured film. An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a photosensitive resin composition capable of improving chemical resistance and adhesion to a cured film while maintaining a higher sensitivity.

Under these circumstances, the inventor of the present invention has found that, by blending a structural unit having a block isocyanate group in the photosensitive resin composition, the chemical resistance and the adhesion of the cured film can be improved while maintaining high sensitivity. Although the mechanism below is not sure, the incorporation of a polymer containing a constituent unit having a block isocyanate group in the photosensitive resin composition improves the affinity between the composition of the present invention and the ground substrate by the block isocyanate group, It is presumed that the adhesion of the base substrate can be improved and the adhesion of the cured film can be improved. Also, by including a structural unit having a block isocyanate group as a polymer in the photosensitive resin composition, structural units having a block isocyanate group are uniformly distributed in the composition of the present invention, and even when the composition of the present invention has a block isocyanate group It is presumed that the group derived from the constituent unit is uniformly distributed and that the chemical resistance can be improved.

More specifically, the above problem is solved by the following solving means <1>, preferably by <2> - <12>.

&Lt; 1 > (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2)

(1) a polymer having (a1) a structural unit having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group (excluding a block isocyanate group and an OH group)

(2) a polymer having the structural unit (a1) and a polymer having the structural unit (a2)

(B) a photoacid generator,

(C) a solvent,

(A4) at least one member selected from the group consisting of a block (a4), a block (a2), and a polymer having the structural unit (a1) At least one constituent unit having an isocyanate group is contained,

(3) A photosensitive resin composition containing at least one polymer containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2).

<2> The photosensitive resin composition according to <1>, wherein the structural unit (a4) is represented by the following general formula (a4-1).

In general formula (a4-1)

[In the formula (a4-1), R ⁴ represents a hydrogen atom or a methyl group, W represents a divalent linking group, and Z represents a monovalent organic group.]

<3> The photosensitive resin composition according to <2>, wherein the structural unit (a4) is represented by the following general formula (a4-2).

In general formula (a4-2)

[In the formula (a4-2), R ⁴ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and Z represents a monovalent organic group.]

<4> The positive resist composition according to any one of <1> to <3>, wherein the crosslinking group contained in the structural unit (a2) is at least one selected from the group consisting of an epoxy group, oxetanyl group and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) Wherein the photosensitive resin composition is a photosensitive resin composition.

<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid-decomposable group is a group having a protected structure in the form of acetal.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the structural unit (a1) is a repeating unit represented by the following general formula (A2 ').

Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or an aryl group, , R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

(7) A method for producing a photosensitive resin composition, comprising the steps of (1) applying the photosensitive resin composition described in any one of (1) to (6)

(2) a step of removing the solvent from the applied photosensitive resin composition,

(3) a step of exposing the photosensitive resin composition from which the solvent has been removed with an actinic ray,

(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and

(5) A post-baking step of thermally curing the developed photosensitive resin composition.

&Lt; 8 > A method for producing a cured film according to < 7 >, comprising a step of performing a front exposure before the post-baking step after the development step.

<9> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <6>.

&Lt; 10 > A cured film obtained by the process for producing a cured film according to < 7 > or < 8 >.

<11> The cured film according to <9> or <10> which is an interlayer insulating film.

<12> A liquid crystal display device or organic EL display device having the cured film according to any one of <9> to <11>.

(Effects of the Invention)

According to the present invention, it is possible to provide a photosensitive resin composition that can maintain high sensitivity and good chemical resistance and adhesion to a cured film.

Fig. 1 shows a configuration diagram of an example of a liquid crystal display device. Sectional view of an active matrix substrate in a liquid crystal display device and has a cured film 17 as an interlayer insulating film.
2 shows a configuration diagram of an example of the organic EL display device. Sectional schematic view of a substrate in a bottom emission type organic EL display device and has a planarization film 4. [

Hereinafter, the contents of the present invention will be described in detail. The following description of the constituent elements described below may be made on the basis of exemplary embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, &quot; &quot; is used to mean that the numerical values described before and after that are included as the lower limit value and the upper limit value.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having no substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

(A) a polymer component containing a polymer satisfying at least one of the following (1) and (2) [hereinafter referred to as (A) a polymer component ) Polymer component or (A) component]

  (1) a composition comprising (a1) a structural unit having an acid group protected with an acid-decomposable group (hereinafter also referred to as a structural unit (a1)) and (a2) a crosslinkable group (excluding a block isocyanate group and an OH group) (Hereinafter also referred to as a polymer (1)) having a unit (hereinafter also referred to as a constituent unit (a2)), or

  (2) The polymer having the structural unit (a1) and the polymer having the structural unit (a2) [hereinafter also referred to as the polymer (2)],

(B) a photoacid generator,

(C) a solvent,

(A) at least one of the polymer having the constituent unit (a1) and the constituent unit (a2), the polymer having the constituent unit (a1) and the polymer having the constituent unit (a2) (a4) at least one structural unit having a block isocyanate group (hereinafter also referred to as a structural unit (a4)),

(3) at least one polymer containing the above-mentioned structural unit (a4) and containing neither the structural unit (a1) nor the structural unit (a2) (hereinafter also referred to as the polymer (3)).

The photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition.

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

<(A) Polymer Component>

The composition of the present invention contains at least one of the polymer (1) and the polymer (2) as the polymer component (A). The composition of the present invention may further comprise a polymer having the constituent unit (a1) and the constituent unit (a2), the polymer having the constituent unit (a1) and the polymer having the constituent unit (a2) At least one of the polymers contains at least one of the structural units (a4), or further contains the polymer (3) in the polymer component (A).

The composition of the present invention may contain (A) a polymer other than these as the polymer component.

The polymer component (A) in the present invention means that, in addition to the polymer (1) and / or the polymer (2), other polymer added as needed is added, unless otherwise specified.

<< Constituent unit (a1) >>

The component (A) has at least a structural unit (a1) in which the acid group has a group protected with an acid-decomposable group. The component (A) has the structural unit (a1), whereby a highly sensitive photosensitive resin composition can be obtained.

In the present invention, the "group protected with an acid-decomposable group" can be any group known as an acid group and an acid decomposable group, and is not particularly limited. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. Examples of the acid decomposable group include groups which are relatively easily decomposed by an acid (for example, an ester structure of a group represented by the formula (A1) described below, an acetal such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group (Tertiary alkyl group such as tert-butyl ester group, tertiary alkylcarbonate group such as tert-butyl carbonate group) can be used.

(a1) The constituent unit in which the acid group has a group protected by an acid-decomposable group is preferably a constituent unit having a protected carboxyl group protected with an acid-decomposable group or a constituent unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.

Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order.

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

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

The structural unit having a carboxyl group which can be used as the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is not particularly limited and a known structural unit can be used. (A1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid; , And a structural unit (a1-1-2) having both an ethylenic unsaturated group and an acid anhydride derived structure.

(A1-1-1) a constituent unit derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule and (a1-1-2) a constituent unit derived from an ethylenic unsaturated group and an acid And structural units having both structures derived from anhydride will be described in order.

<<<< (a1-1-1) Constituent units derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, etc. >>>>

As the constituent unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule, the same as exemplified below is used as the unsaturated carboxylic acid used in the present invention. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl Hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid used to obtain the structural unit having a carboxyl group may be an acid anhydride thereof. Specific examples thereof include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polycarboxylic acid, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono Mono (2-acryloyloxyethyl) phthalate mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymers thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have. Examples of the unsaturated carboxylic acid include acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester and 4-carboxystyrene.

Among them, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule from the viewpoint of developability, acrylic acid, methacrylic acid, 2- (meth) acryloyl (Meth) acryloyloxyethyl-phthalic acid, or anhydride of an unsaturated polycarboxylic acid, and the like, and acrylic acid, methacrylic acid, Methacrylic acid and 2- (meth) acryloyloxyethylhexahydrophthalic acid are more preferably used.

The structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone, or two or more kinds.

<<<< (a1-1-2) Constituent units having both structures derived from an ethylenic unsaturated group and an acid anhydride >>>>

The structural unit (a1-1-2) having both the ethylenic unsaturated group and the structure derived from an acid anhydride is preferably a unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride present in a structural unit having an ethylenic unsaturated group.

As the acid anhydrides, known ones can be used, and specific examples include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and anhydrous chlorendic acid; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, and biphenyltetracarboxylic acid anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride are preferable from the viewpoint of developability.

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

<<<< Acid decomposable group which can be used as the structural unit (a1-1) >>>>

As the acid decomposable group which can be used as the structural unit (a1-1) having a protected carboxyl group protected with the acid decomposable group, the acid decomposable group described above can be used.

Among these acid decomposable groups, it is preferable that the carboxyl group is a protected carboxyl group protected in the form of an acetal from the viewpoints of the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the formability of the contact hole, and the storage stability of the photosensitive resin composition. Among the acid decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity. When the carboxyl group is a protected carboxyl group protected in the form of acetal represented by the following general formula (a1-10), the structure of - (C═O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) .

The general formula (a1-10)

[In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, provided that R ¹⁰¹ and R ¹⁰² are not both hydrogen atoms. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether.]

In the general 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 linear, branched and cyclic. Here, in the case where both of R ¹⁰¹ and R ¹⁰² represent a hydrogen atom is not, at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

The straight-chain or branched-chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec- Butyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and more preferably 4 to 6 carbon atoms. 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 isobonyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When a halogen atom is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are haloalkyl groups. When an aryl group is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are an aralkyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Specifically, a phenyl group, an? -Methylphenyl group, a naphthyl group, etc. may be exemplified, and an alkyl group substituted with an aryl group As the whole, that is, the aralkyl group, benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like can be exemplified.

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

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the alkyl group is a straight chain or branched chain alkyl group, Or a cycloalkyl group having 1 to 12 carbon atoms.

These substituents may be further substituted by the above substituents.

When R ¹⁰¹ , R ¹⁰² and R ^{103 in} the general formula (a1-10) represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. As the aryl group, for example, a phenyl group, a tolyl group, a silyl group, a cumenyl group, a 1-naphthyl group and the like can be mentioned.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may bond together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, and a tetrahydropyranyl group.

In the general formula (a1-10), it is preferable that one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

As the radical polymerizable monomer used for forming the constitutional unit having a protective carboxyl group represented by the general formula (a1-10), a commercially available one may be used, or a compound synthesized by a known method may be used. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of Japanese Patent Laid-Open Publication No. 2011-221494.

The first preferred form of the structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is a structural unit represented by the following general formula:

(A2 ')

Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or an aryl group, , R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

When R ¹ and R ² are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each independently 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 arylene group, with a single bond being preferred.

A second preferred form of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following general 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 phenylene 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 hydrogen atoms.

Preferable specific examples of the structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

<<< (a1-2) Protecting Protected by Acid-Decomposable Group Constituent with a phenolic hydroxyl group >>>

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

<<<< (a1-2-1) Constituent with phenolic hydroxyl group >>>>

Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolak-based resin. Of these, structural units derived from hydroxystyrene or? -Methylhydroxystyrene Is preferable from the viewpoint of sensitivity. The structural unit represented by the following general formula (a1-20) as a structural unit having a phenolic hydroxyl group is also preferable from the viewpoint of sensitivity.

In general formula (a1-20)

Wherein 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 represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less. When two or more R ²²² are present, these R ²²² may be the same or different.]

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

R ²²¹ represents a single bond or a divalent linking group. In the case of single-crystal combination, it is preferable since the sensitivity can be improved and the transparency of the cured film can be improved. Examples of the divalent linking group of R ²²¹ include alkylene groups and specific examples of R ²²¹ is an alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, Pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among them, R &lt; ²²¹ &gt; is preferably a single bond, a methylene group or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. Although a represents an integer of 1 to 5, a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of the effects of the present invention and ease of production.

It is preferable that the bonding position of the hydroxyl group in the benzene ring is bonded to the 4-position when the carbon atom bonded to R ²²¹ is set as the reference (1 position).

R ²²² is a halogen atom or a straight or branched alkyl group having 1 to 5 carbon atoms.

Specific examples include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- butyl group, a pentyl group, an isopentyl group and a neopentyl group . Among them, a chlorine atom, a bromine atom, a methyl group or an ethyl group is preferable in view of easiness of production.

B represents 0 or an integer of 1 to 4;

<<<< Acid decomposable group which can be used as constituent unit (a1-2) >>>>

The acid decomposable group which can be used as the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group is preferably an acid decomposable group which can be used as the structural unit (a1-1) having a protected carboxyl group protected with the acid- As well as the acid-decomposable group, known ones can be used, and they are not particularly limited. Among the acid decomposable groups, structural units having a protected phenolic hydroxyl group protected by an acetal are preferable from the viewpoints of basic physical properties of the photosensitive resin composition, in particular, sensitivity and pattern shape, storage stability of the photosensitive resin composition, and formation of contact holes. Among the acid decomposable groups, the phenolic hydroxyl group is more preferably a protective phenolic hydroxyl group protected in the form of an acetal represented by the above general formula (a1-10) from the viewpoint of sensitivity. In addition, when the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of the acetal represented by the general formula (a1-10), -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) .

Ar represents an arylene group.

Preferable examples of the acetal ester structure of the phenolic hydroxyl group are R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group, R ¹⁰¹ = R ¹⁰² = methyl group, and R ¹⁰³ = benzyl group.

Examples of the radically polymerizable monomer used to form a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include those described in Japanese Patent Laid-Open Publication No. 2011-215590 And the like.

Of these, a 1-alkoxyalkyl protected derivative of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protected derivative of 4-hydroxyphenyl methacrylate are preferred from the viewpoint of transparency.

Specific examples of the acetal protecting group of the phenolic hydroxyl group include 1-alkoxyalkyl groups, and examples thereof include a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, 1-cyclohexyloxy) ethyl group, 1- (2-cyclohexyloxy) ethyl group, 1-naphthyloxy group, Oxyethyl group, etc. These may be used alone or in combination of two or more.

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

Specific preferred examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group include the following structural units, but the present invention is not limited thereto.

<<< Preferable Form of Constituent Unit (a1) >>>

When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is preferably 20 to 100 mol% in the polymer containing the structural unit (a1) And more preferably 30 to 90 mol%.

When the polymer containing the structural unit (a1) contains the following structural unit (a2), the structural unit (a1) is preferably a polymer containing the structural unit (a1) and the structural unit (a2) Is preferably 3 to 70 mol%, more preferably 10 to 60 mol%. In particular, when the acid-decomposable group usable as the constituent unit (a1) is a constituent unit having a protected carboxyl group protected in the form of an acetal, the content is preferably 20 to 50 mol%.

The structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is characterized in that the phenomenon is faster than that of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid decomposable group. Therefore, when a rapid development is desired, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

The structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group is characterized in that the phenomenon is faster than that of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid decomposable group. Therefore, when a rapid development is desired, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferable. On the contrary, when it is desired to slow the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.

<< Constituent unit (a2) >>

The component (A) has (a2) a structural unit having a crosslinkable group (excluding a block isocyanate group and an OH group). The crosslinkable group in the present invention is at least one selected from the group capable of initiating the crosslinking reaction with the carboxylic acid or the phenolic hydroxyl group at 90 占 폚 or higher, for example. However, OH group has low crosslinking reactivity with carboxylic acid and phenolic hydroxyl group and can not sufficiently improve chemical resistance, so that it is excluded from the crosslinkable group of the present invention. Preferable examples of the structural unit having a crosslinking group include at least one selected from the group consisting of an epoxy group, an oxetanyl group, a group represented by -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) and an ethylenic unsaturated group , And is preferably at least one member 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). Among them, the photosensitive resin composition of the present invention preferably contains a constituent unit containing at least one of an epoxy group and an oxetanyl group, and particularly preferably contains a constituent unit containing an epoxy group . More specifically, the following can be mentioned.

<<< (a2-1) Constituent Unit Having an Epoxy Group and / or an Oxetanyl Group >>>

The polymer component (A) preferably contains a structural unit (structural unit (a2-1)) having an epoxy group and / or an oxetanyl group.

The structural unit (a2-1) having an epoxy group and / or an oxetanyl group is preferably a structural unit having an alicyclic epoxy group and / or an oxetanyl group, and more preferably a structural unit having an oxetanyl group.

The structural unit (a2-1) having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may contain at least one epoxy group and at least one oxetanyl group, Or more oxetanyl group, and it is not particularly limited, but it is preferable to have 1 to 3 epoxy groups and / or oxetanyl groups in total, and it is preferable that a total of one epoxy group and / or oxetanyl group More preferably two, and more preferably one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicyclohexylmethyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, -Epoxy cyclohexylmethyl,? -Ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, Compounds having an alicyclic epoxy skeleton described in paragraphs [0031] to [0035] of Japanese Patent No. 4168443, and the like.

Specific examples of the radically polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylate esters having an oxetanyl group as described in paragraphs 0011 to 0016 of JP 2001-330953 A And compounds described in paragraph No. 0027 of Japanese Patent Application Laid-Open No. 08-088459, the contents of which are incorporated herein by reference.

Specific examples of the radically polymerizable monomer used to form the structural unit (a2-1) having an epoxy group and / or an oxetanyl group are monomers containing a methacrylic acid ester structure and monomers containing an acrylic ester structure Do.

More preferred among these monomers are compounds containing an alicyclic epoxy skeleton described in paragraphs [0034] to [0035] of Japanese Patent No. 4168443 and oxetanyls described in paragraphs 0011 to 0016 of JP-A No. 2001-330953 (Meta) acrylic acid ester having an oxetanyl group as described in paragraphs 0011 to 0016 of JP 2001-330953 A is particularly preferable. Of these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl, and most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl and methacrylic acid (3-ethyloxetan-3-yl) methyl. These constituent units may be used alone or in combination of two or more.

As the above-mentioned structural unit (a2-1) having an epoxy group and / or an oxetanyl group, the description of paragraphs 0053 to 0055 of Japanese Patent Laid-Open Publication No. 2011-215590 may be taken into consideration.

Preferable specific examples of the above-mentioned structural unit (a2-1) having an epoxy group and / or an oxetanyl group include the following constitutional units. R represents a hydrogen atom or a methyl group.

In the present invention, an oxetanyl group is preferred from the viewpoint of sensitivity. From the viewpoint of transmittance (transparency), alicyclic epoxy groups and oxetanyl groups are preferred. From the above, as the epoxy group and / or oxetanyl group in the present invention, an alicyclic epoxy group and an oxetanyl group are preferable, and an oxetanyl group is particularly preferable.

<<< (a2-2) Structural unit having an ethylenic unsaturated group >>>

As one of the structural unit (a2) having a crosslinking group, a structural unit (a2-2) having an ethylenic unsaturated group (hereinafter also referred to as &quot; structural unit (a2-2) &quot; As the structural unit (a2-2) having an ethylenically unsaturated group, a structural unit having an ethylenic unsaturated group at the side chain is preferable, and a structural unit having an ethylenic unsaturated group at the terminal and having a side chain of 3 to 16 carbon atoms is more preferable.

For the other structural unit having (a2-2) ethylenically unsaturated group, the description of paragraphs 0077 to 0090 of Japanese Patent Laid-Open Publication No. 2011-215580 and the description of paragraphs 0013 to 0031 of Japanese Patent Application Laid-Open No. 2008-256974 , The contents of which are incorporated herein by reference.

<< Structural unit having a group represented by (a2-3) -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) >>>

Copolymer used in the present invention is -NH-CH ₂ -OR is also preferred structural units (a2-3) having a group represented by (R is an alkyl group having 1 to 20 carbon atoms). By having the structural unit (a2-3), a curing reaction can be caused by a gentle heat treatment, and a cured film excellent in various properties 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. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group. The structural unit (a2) is more preferably a structural unit having a group represented by the following general formula (1).

In general formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms.)

R ² is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a linear or branched alkyl group.

Specific examples of R ² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group and an n-hexyl group. Of these, an i-butyl group, an n-butyl group and a methyl group are preferable.

<<< Preferable Form of Constituent Unit (a2) >>>

When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is preferably from 5 to 90 mol% in the polymer containing the structural unit (a2) And more preferably 20 to 80 mol%.

When the polymer containing the structural unit (a2) contains the structural unit (a1), the structural unit (a2) is a polymer containing the structural unit (a1) and the structural unit (a2) To 70 mol%, and more preferably 10 to 60 mol%.

In the present invention, regardless of the form, the content of the structural unit (a2) in the total structural units of the component (A) is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.

Within the above range, the transparency, chemical resistance and ITO sputtering resistance of the cured film obtained from the photosensitive resin composition are improved.

<< (a4) Structural unit having a block isocyanate group >>

The composition of the present invention can improve the chemical resistance and the adhesion of the cured film (particularly, the adhesion of the cured film after the PCT test) by containing the (a4) polymer containing the constituent unit having a block isocyanate group.

Although the following mechanism is not clear, by blending a polymer containing a constituent unit having a block isocyanate group in the photosensitive resin composition, the affinity between the composition of the present invention and the ground substrate is improved by the block isocyanate group, It is presumed that the adhesion of the base substrate can be improved and the adhesion of the cured film can be improved. Also, by including a structural unit having a block isocyanate group as a polymer in the photosensitive resin composition, structural units having a block isocyanate group are uniformly distributed in the composition of the present invention, and even when the composition of the present invention has a block isocyanate group The groups derived from the constituent units are uniformly distributed, and thus the chemical resistance can be improved.

In the present invention, the block isocyanate group is a protecting group that protects an isocyanate group by reacting a compound (usually called a block agent) having a hydrogen atom capable of reacting with an isocyanate group. The introduced protecting group is one in which a hydrogen atom has been removed from a block agent and is usually called a block group. For example, in the structure represented by A-C (= O) -NH-, A is a protecting group.

As the block agent used in the present invention, for example, the blocking agent described in paragraph 0009 of Japanese Patent Application Laid-Open No. 5-186564 and the blocking agent disclosed in paragraph 0022 of Japanese Patent Application Laid-Open No. 2002-275231 can be used, Are incorporated herein by reference.

Specifically, a compound having a phenolic hydroxyl group such as phenol, naphthol, cresol, xylenol, and halogen-substituted phenol; Oxime compounds such as acetoxime, formaldehyde, cyclohexanoxime and methylethylketoxime; Compounds having a pyrazole structure such as pyrazole, methylpyrazole, and dimethylpyrazole; Alcohol-based compounds such as methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether and alkyl lactate; Compounds having active methylene such as ethyl acetoacetate, diethyl malonate, and acetylacetone; Mercapane compounds such as alkyl mercaptans and aryl mercaptans; lactam compounds such as? -lactam,? -lactam,? -lactam and? -lactam, and other imide compounds, imidazole compounds, primary amines, and secondary amines.

The block group used in the present invention is preferably a group derived from, for example, a compound having a phenolic hydroxyl group, a oxime compound or an alcohol compound, more preferably a group derived from an oxime compound or an alcohol compound, A group derived from a compound is more preferable.

The polymer component (A) used in the present invention may contain at least one block isocyanate group in the structural unit having one (a4) block isocyanate group, but may contain two or more kinds of block isocyanate groups, Is more preferable.

The upper limit of the number of the block isocyanate group in the constituent unit having one block isocyanate group is not particularly limited, but is preferably 5 or less among the constituent units having one block isocyanate group, More preferably 3 or less, and particularly preferably 1.

As the structural unit having a block isocyanate group (a4) used in the present invention, a vinyl-based polymer is preferable, and a repeating unit represented by the following general formula (a4-1) is more preferable.

In general formula (a4-1)

[In the formula (a4-1), R ⁴ represents a hydrogen atom or a methyl group, W represents a divalent linking group, and Z represents a monovalent organic group.]

In the general formula (a4-1), W represents a divalent linking group. Examples of the divalent linking group include a linear, branched or cyclic alkylene group, a divalent group such as -O-, -COO-, -S-, -NR-, -CO-, -NRCO-, and -SO ₂ - And a combination of these groups. Here, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. The divalent linking group is - (CH ₂ ) _m - (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4), a cyclic alkylene group having 5 to 10 carbon atoms, Or a group formed by combining these groups with at least one of -O-, -COO-, -S-, -NH-, and -CO-.

In the general formula (a4-1), Z is a group (the above-mentioned block group) which is eliminated by heating. Here, the group which is desorbed by heating means a group which is desorbed when heated, for example, at 90 to 250 ° C.

In the general formula (a4-1), Z is not particularly limited, and for example, a monovalent organic group is preferable. Examples of the monovalent organic group include an alkyl group or an aryl group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a combination thereof. Specific examples of such monovalent organic groups are preferably -N═R ', -OR', -NR ', -SR' or a combination of at least one of these groups and -O-, -CO- and -COOR ' . Here, R 'is a straight chain having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms (preferably a straight chain having 1 to 7 carbon atoms, a branched chain having 3 to 7 carbon atoms, (Preferably a cyclic alkyl group having 3 to 7 carbon atoms), an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), or a combination of an aryl group having 6 to 10 carbon atoms and an alkylene group having 1 to 10 carbon atoms.

When the monovalent organic group represents -NR ', it is preferable that -NR' form a heterocyclic structure. The hetero atom in the heterocyclic structure preferably contains a nitrogen atom, more preferably contains two or more nitrogen atoms, and more preferably contains two nitrogen atoms. The heterocyclic structure is preferably a 5- to 8-membered ring structure, more preferably a 5- to 7-membered ring structure. A condensed ring may be used, but a monocyclic ring is preferred. When the monovalent organic group represents -NR ', it is preferable that the substituent includes a -CO group or an alkyl group (preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group) as a substituent.

In formula (a4-1), the amount of Z is preferably from 20 to 300, more preferably from 30 to 150. It is preferable that the amount of Z is not excessively large so that unnecessary components of the final cured film can be reduced.

Here, the term &quot; Z &quot; refers to the mass of the Z portion per constituent unit having a block isocyanate group.

As the structural unit having a block isocyanate group (a4) used in the present invention, a repeating unit represented by the following general formula (a4-1-2) is more preferable.

In general formula (a4-1-2)

[In formula (a4-2), R ⁴ represents a hydrogen atom or a methyl group, X represents an arylene group or a -C (= O) - group, Y represents a divalent linking group, and Z represents a monovalent organic group .]

In the general formula (a4-2), X represents an arylene group or a -C (= O) - group, and when X is an arylene group, a phenylene group is preferable.

In the general formula (a4-2), Y represents a divalent linking group. Examples of the divalent linking group include a linear, branched or cyclic alkylene group, a divalent group such as -O-, -COO-, -S-, -NR-, -CO-, -NRCO-, and -SO ₂ - And a combination of these groups. Here, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom. The divalent linking group is - (CH ₂ ) _m - (m is an integer of 1 to 10, preferably an integer of 1 to 6, more preferably an integer of 1 to 4), a cyclic alkylene group having 5 to 10 carbon atoms, Or a group formed by combining these groups with at least one of -O-, -COO-, -S-, -NH-, and -CO-.

In the general formula (a4-2), Z represents a monovalent organic group, agrees with Z in the general formula (a4-2) described above, and the preferable range is also the same.

As the structural unit having a block isocyanate group (a4) used in the present invention, a repeating unit represented by the following general formula (a4-2) is more preferable.

In general formula (a4-2)

[In the formula (a4-2), R ⁴ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and Z represents a monovalent organic group.]

In the general formula (a4-2), Y and Z are synonymous with Y and Z in the general formula (a4-1-2) described above, and preferable ranges are also the same.

(a4) Specific examples of the structural unit having a block isocyanate group are illustrated below, but the present invention is not limited thereto. In the following specific examples, Rx is a hydrogen atom or a methyl group.

<<< Preferable Form of Constituent Unit (a4) >>>

When the structural unit (a4) is contained in the polymer (1), the content of the structural unit (a4) in the polymer containing the structural unit (a4) is preferably from 0.1 to 30 mol%, more preferably from 1 to 20 mol% , More preferably 2 to 15 mol%.

When the structural unit (a4) is contained in the polymer (2), that is, the structural unit (a4) is contained in at least one of the polymer having the structural unit (a1) or the polymer having the structural unit (a2) , The content of the structural unit (a4) in the polymer containing the structural unit (a4) is preferably from 0.1 to 40 mol%, more preferably from 1 to 30 mol%, still more preferably from 2 to 25 mol%.

When the above structural unit (a4) is contained in the polymer (3), the content of the structural unit (a4) is preferably 1 to 90 mol%, more preferably 2 to 70 mol% , More preferably from 3 to 50 mol%.

In the present invention, regardless of the form, the content of the structural unit (a4) in the total structural units of the component (A) is preferably from 0.1 to 30 mol%, more preferably from 1 to 20 mol% More preferably 15 mol% or less. The content of the structural unit (a4) in the total structural units of the component (A) may be 5 mol% or less. In this case, the residual film ratio after the post-baking is advantageous.

Within the above range, the transparency, chemical resistance and ITO sputtering resistance of the cured film obtained from the composition of the present invention are improved.

When the structural unit (a4) is contained in at least one of the polymer (1), the polymer (2) and the polymer (3), the content of the structural unit (a4) is preferably 100 to 500, More preferably from 150 to 400.

The polymer containing the structural unit (a4) preferably has a molecular weight of 8,000 or more, preferably 9,000 or more, for example. The upper limit of the molecular weight of the polymer containing the structural unit (a4) is not particularly limited, but is preferably, for example, 50,000 or less, more preferably 30,000 or less.

When the molecular weight of the polymer containing the structural unit (a4) is 8000 or more, the constituent units having a block isocyanate group are more uniformly distributed in the composition of the present invention, and even in the cured film of the present invention, The unit derived from the constituent unit is more uniformly distributed, and it is presumed that the chemical resistance effect of the present invention is more effectively exerted throughout the film.

The composition of the present invention preferably contains substantially no polymer containing the structural unit (a4) having a molecular weight of less than 8000. When the content of the polymer containing the structural unit (a4) having a molecular weight of less than 8000 is less than 0% Is more preferable.

<< (a3) Other constituent units >>

In the present invention, the component (A) may contain, in addition to the above structural unit (a1), the structural unit (a2) and the structural unit (a4), another structural unit (a3). The structural unit (a3) may contain any of the polymer (1), the polymer (2) and the polymer (3). Further, apart from the polymer (1), the polymer (2) and the polymer (3), the composition of the present invention may contain another polymer component having the constituent unit (a3). When the other polymer having the constituent unit (a3) is contained separately from the polymer (1), the polymer (2) and the polymer (3), the blending amount of the polymer component is preferably 60 mass% By mass, more preferably 40% by mass or less, and still more preferably 20% by mass or less.

The monomer to be the constituent unit (a3) is not particularly limited and includes, for example, styrenes, alkyl (meth) acrylates, cyclic alkyl methacrylates, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters Unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds can be given as examples of the unsaturated dicarboxylic acids. Further, as described later, it may have a structural unit having an acid group. The monomers to be the constituent unit (a3) may be used alone or in combination of two or more.

Hereinafter, preferred embodiments of the polymer component of the present invention are illustrated, but it is needless to say that the present invention is not limited to these.

(First Embodiment)

Wherein the polymer (1) further comprises one or more of the structural units (a3).

(Second Embodiment)

Wherein the polymer having the structural unit (a1) in the polymer (2) further comprises one or more of the structural units (a3).

(Third Embodiment)

Wherein the polymer having the structural unit (a2) in the polymer (2) further comprises one or more of the structural units (a3).

(Fourth Embodiment)

Wherein the polymer (3) further comprises one or more of the structural units (a3).

(Fifth Embodiment)

In any one of the first to fourth embodiments, the structural unit (a3) includes a structural unit containing at least an acid group.

(Sixth Embodiment)

Wherein at least any one of the polymer (1), the polymer (2) and the polymer (3) as the structural unit (a3) comprises at least an acid group-containing structural unit Lt; / RTI &gt;

(Seventh Embodiment)

A form having a polymer having the structural unit (a3), separately from the polymer (1), the polymer (2) and the polymer (3). Examples of the structural unit (a3) in this case include a structural unit containing an acid group, a structural unit having a group capable of crosslinking other than the structural unit (a2), and the like.

(Eighth embodiment)

A mode in which two or more of the first to seventh embodiments are combined.

Specific examples of the structural unit (a3) include styrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, Acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-methacryloyl (Meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, ethylene glycol (meth) acrylate, isobutyl (meth) acrylate, Monoacetoacetate mono (meth) acrylate, and the like. In addition, the compounds described in paragraphs 0021 to 0024 of Japanese Patent Application Laid-Open No. 2004-264623 can be mentioned.

In addition, as the structural unit (a3), a group having a styrene group or an alicyclic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, hydroxystyrene,? -Methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, benzyl .

Further, as the structural unit (a3), a (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and n-butyl (meth) acrylate. More preferred is methyl (meth) acrylate. The content of the structural unit (a3) in the polymer (A) is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less. The lower limit value may be 0 mol%, for example, 1 mol% or more, and may be 5 mol% or more. Within the range of the above-mentioned numerical values, various properties of the cured film obtained from the photosensitive resin composition are improved.

The structural unit (a3) preferably contains an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developing solution, and the effect of the present invention is more effectively exerted. The acid group in the present invention means a proton dissociable group having a pKa smaller than 7. The acid group is usually introduced into the polymer as a constituent unit containing an acid group by using a monomer capable of forming an acid group. When such a structural unit containing an acid group is contained in a polymer, it tends to be easily soluble in an alkaline developer.

Examples of the acid group used in the present invention include those derived from a carboxylic acid group, those derived from a sulfonamide group, those derived from a phosphonic acid group, those derived from a sulfonic acid group, those derived from a phenolic hydroxyl group, sulfonamide groups, And the like, and those derived from a carboxylic acid group and / or derived from a phenolic hydroxyl group are preferable.

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, and a constituent unit derived from (meth) acrylic acid and / or an ester thereof. For example, compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP-A-2012-88459 can be used, the contents of which are incorporated herein by reference. Among them, a constituent unit derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid and maleic anhydride is preferable.

In the present invention, it is particularly preferable to contain a constituent unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group from the viewpoint of sensitivity.

The constituent unit containing an acid group is preferably from 1 to 80 mol%, more preferably from 1 to 50 mol%, still more preferably from 5 to 40 mol%, and particularly preferably from 5 to 30 mol%, of the constituent units of the whole polymer component , And particularly preferably from 5 to 20 mol%.

In the present invention, in addition to the polymer component (1), the polymer component (2) or the polymer component (3), the constitutional unit (a1), the constitutional unit (a2) And may contain a polymer having no other structural unit (a3).

As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, Japanese Patent Publication No. 54-25957, Japanese Patent Application Laid-open No. 59-53836, Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like as disclosed in the respective publications of Japanese Patent Application Laid-Open No. 59-71048 Acidic cellulose derivatives having a carboxyl group in a side chain, acid anhydride added to a polymer having a hydroxyl group, and the like, and a polymer having a (meth) acryloyl group in the side chain is also preferable.

(Meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (Meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / Benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl Methacrylate / methacrylic acid copolymer, and the like.

In addition, Japanese Patent Application Laid-Open Nos. 7-207211, 8-259876, 10-300922, 11-140144, 11-174224 Publicly known high molecular compounds described in JP-A-2000-56118, JP-A-2003-233179, and JP-A-2009-52020 can be used.

These polymers may be contained only in one kind or in two or more kinds.

As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (manufactured by Satoruma Corporation), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC- ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 (manufactured by BASF).

<< (A) Molecular weight of polymer >>

The molecular weight of the polymer (A) is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, and still more preferably from 10,000 to 50,000, in terms of polystyrene reduced weight average molecular weight. Within the range of the above numerical values, various characteristics are good. The ratio (number of dispersions) of the number average molecular weight to the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< (A) Method of producing polymer >>

Various methods are also known for the method of synthesizing the component (A). For example, there is a method in which a radical-polymerizable monomer used for forming a structural unit represented by at least the structural unit (a1) and the structural unit (a3) Can be synthesized by polymerization in an organic solvent using a radical polymerization initiator. It may also be synthesized by a so-called polymer reaction.

The polymer (A-1) preferably contains a structural unit derived from (meth) acrylic acid and / or an ester thereof in an amount of 50 mol% or more, more preferably 80 mol% or more.

The photosensitive resin composition of the present invention preferably contains the component (A) in an amount of 50 to 99.9 parts by mass, more preferably 70 to 98 parts by mass, based on 100 parts by mass of the total solid content.

&Lt; (B) Photo acid generator >

The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as &quot; component (B) &quot;) used in the present invention, a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or longer, preferably 300-450 nm, . Also, with respect to a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer if the compound is used in combination with a sensitizer to generate an acid in response to an actinic ray having a wavelength of 300 nm or more. As the photoacid generator used in the present invention, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, a photoacid generator that generates an acid with a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid of 2 or less is most preferable Do.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds . Of these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazine, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives are described in paragraphs 0083 to 0088 of JP-A No. 2011-221494 The compounds described can be exemplified.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following general formula (B1) can be preferably exemplified.

In general formula (B1)

[In the formula (B1), R ²¹ represents an alkyl group or an aryl group. The dashed line indicates the combination with other tiles.]

The alkyl group in R &lt; ²¹ &gt; may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R &lt; ²¹ &gt; is preferably a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (preferably containing a bridged alicyclic group such as a 7,7- May be 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.

It is also preferable that the compound containing an oxime sulfonate structure represented by the general formula (B1) is an oxime sulfonate compound represented by the following general formula (B2).

Wherein (B2) of, R ⁴² represents an alkyl group or an aryl group, X is an alkyl group, an alkoxy group, or a halogen atom, m4 is an integer of 0 to 3, a plurality of X When m4 is 2 or 3 is It may or may not be the same.]

The preferable range of R &lt; ⁴² &gt; is the same as the preferable range of R &lt; ²¹ &gt;

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 general formula (B2), and m4 are 1, X is a methyl group, the substitution position of X is the ortho-position, R ⁴² is a straight chain alkyl group, a 7,7-dimethyl-2-oxo-norbornyl group having 1 to 10 carbon atoms Methyl group, or p-toluyl group is particularly preferable.

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

Equation (B3) of, R ⁴³ is R ⁴² and agreed in the formula (B2), X ¹ is the group of a halogen atom, a hydroxyl group, having from 1 to 4 carbon atoms, having from 1 to 4 carbon atoms, an alkoxy group, a cyano group or a nitro group And n4 represents an integer of 0 to 5.]

Examples of R ⁴³ in the general formula (B3) include methyl, ethyl, n-propyl, n-butyl, n-octyl, A perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.

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

As n4, 0 to 2 is preferable, and 0 to 1 is particularly preferable.

As specific examples of the compound represented by the above general formula (B1-3) and specific examples of the preferable oxime sulfonate compounds, mention may be made of the description of paragraphs 0080 to 0082 of Japanese Patent Application Laid-Open No. 163937/1989, Are incorporated herein by reference.

As the compound containing an oxime sulfonate structure represented by the above general formula (B1), it is also preferable to be a compound represented by the following general formula (OS-1).

In the general formula (OS-1), R ¹⁰¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Lt; / RTI &gt; R ¹⁰² represents an alkyl group or an aryl group.

¹⁰¹ X is ^{-O-, -S-, -NH-, -NR 105} -, -CH 2 -, -CR 106 H-, or -CR ¹⁰⁵ R ¹⁰⁷ - represents a, R ¹⁰⁵ ~ R ¹⁰⁷ is an alkyl group, or Lt; / RTI &gt;

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

As R ¹²¹ to R ¹²⁴ , a hydrogen atom, a halogen atom, and an alkyl group are preferable, and at least two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form an aryl group. Among them, a form in which all of R ¹²¹ to R ¹²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

All of the functional groups described above may further have a substituent.

The compound represented by the above general formula (OS-1) is preferably a compound represented by the general formula (OS-2) described in, for example, paragraphs 0087 to 0089 of Japanese Patent Application Laid- , The contents of which are incorporated herein by reference.

Specific examples of the compound represented by the above general formula (OS-1) that can be preferably used in the present invention include compounds (exemplified compounds b-1 to b-1) described in paragraphs 0128 to 0132 of Japanese Patent Application Laid- 34), but the present invention is not limited to this.

In the present invention, the compound having an oxime sulfonate structure represented by the general formula (B1) is represented by the following general formula (OS-3), the following general formula (OS-4) It is preferable that the luminescent oxime sulfonate compound is a luminescent oxime sulfonate compound.

In the formulas (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 each represent An alkyl group, an aryl group or a halogen atom; R ²⁴ , R ²⁷ and R ³⁰ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group; ¹ to X ³ each independently represent an oxygen atom or a sulfur atom, n ¹ to n ³ each independently represents 1 or 2, and m ¹ to m ³ each independently represent an integer of 0 to 6.

With respect to the above general formulas (OS-3) to (OS-5), for example, the description of paragraphs 0098 to 0115 of Japanese Patent Application Laid-Open No. 163937/1974 can be taken into consideration, .

The compound containing an oxime sulfonate structure represented by the general formula (B1-1) can be produced by using a compound represented by the general formula (OS-6) described in Paragraph 0117 of Japanese Patent Application Laid- To (OS-11), and this content is incorporated herein by reference.

Preferable ranges in the above general formulas (OS-6) to (OS-11) are as described in (OS-6) to (OS-11) described in paragraphs 0110 to 0112 of Japanese Patent Application Laid- Range.

Specific examples of the oxime sulfonate compound represented by the above general formulas (OS-3) to (OS-5) include the compounds described in paragraphs 0114 to 0120 of JP-A No. 2011-221494 , But the present invention is not limited to these.

In the photosensitive resin composition of the present invention, the photoacid generator (B) is used in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total resin component (preferably solid content, more preferably the total amount of the copolymer) in the photosensitive resin composition More preferably 0.5 to 10 parts by mass. Two or more species may be used in combination.

&Lt; (D) Solvent >

The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential component of the present invention and any of the components described below are dissolved in the (D) solvent.

As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, 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, di Propylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like. Specific examples of the solvent (D) used in the photosensitive resin composition of the present invention include the solvent described in paragraphs 0174 to 0178 of JP-A-2011-221494, paragraphs 0167 to 0168 of JP-A-2012-194290 Solvents listed, and the contents of these are incorporated herein by reference.

In these solvents, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, Benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like may be further added. 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 one type alone or two types in combination, more preferably two kinds, more preferably propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and di It is more preferable to use ethylene glycol dialkyl ethers or esters in combination with butylene glycol alkyl ether acetates.

The component D 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 more, or a mixture thereof.

Propylene glycol monomethyl ether acetate (boiling point: 146 占 폚), propylene glycol monoethyl ether acetate (boiling point: 158 占 폚), propylene glycol methyl n-butyl ether (boiling point: 155 占 폚), propylene glycol Methyl-n-propyl ether (boiling point 131 占 폚).

As the solvent having a boiling point of 160 캜 or more, ethyl 3-ethoxypropionate (boiling point: 170 캜), diethylene glycol methyl ethyl ether (boiling point: 176 캜), propylene glycol monomethyl ether propionate (boiling point: 160 캜), dipropylene glycol methyl ether acetate (Boiling point: 213 占 폚), 3-methoxybutyl ether acetate having a boiling point of 171 占 폚, diethylene glycol diethanol ether having a boiling point of 189 占 폚, diethylene glycol dimethyl ether having a boiling point of 162 占 폚, propylene glycol diacetate having a boiling point of 190 占 폚 ), Diethylene glycol monoethyl ether acetate (boiling point 220 占 폚), dipropylene glycol dimethyl ether (boiling point 175 占 폚), and 1,3-butylene glycol diacetate (boiling point 232 占 폚).

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, more preferably 60 to 90 parts by mass, per 100 parts by mass of the total resin component in the photosensitive resin composition.

&Lt; Other components >

To the photosensitive resin composition of the present invention, other crosslinking agents, alkoxysilane compounds, sensitizers, basic compounds, surfactants and antioxidants may be added, if necessary, in addition to the above components. The photosensitive resin composition of the present invention may contain known additives such as an acid generator, a development accelerator, a plasticizer, a heat radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. As these compounds, mention may also be made of the description of paragraphs 0201 to 0224 of Japanese Patent Application Laid-Open No. 88459/1987, the contents of which are incorporated herein by reference.

Other cross-linking agents

The photosensitive resin composition of the present invention preferably contains a crosslinking agent other than the alicyclic epoxy compound, if necessary. By adding a crosslinking agent other than the alicyclic epoxy compound, the cured film obtained by the photosensitive resin composition of the present invention can be made into a stronger film.

As the crosslinking agent, there is no limitation as long as a crosslinking reaction occurs by heat [excluding the above (A) polymer component). For example, a compound having at least two epoxy groups or oxetanyl groups in the molecule, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, the compound (a4) used in the present invention described above, A block isocyanate compound different from the constitutional unit having a block isocyanate group may be added.

The amount of the crosslinking agent to be added in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition desirable. When added in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. A plurality of crosslinking agents may be used together, and in that case, the total amount of the crosslinking agents is to be calculated.

<Low molecular weight crosslinkable compound>

Specific examples of the low molecular weight crosslinkable compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, aliphatic epoxy resin and the like.

These are available as commercial products. For example, commercial products described in paragraph 0189 of Japanese Patent Application Laid-Open Publication No. 2011-221494 such as JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.) EX-614, EX-621, EX-621, EX-621, EX- EX-920, EX-820, EX-820, EX-810, EX-810, EX- DLC-204, DLC-205, DLC-206, DLC-301, DLC-201, EX- 402, YH-300, YH-301, YH-302, YH-315, YH-324 and YH-325 manufactured by Shinnitetsu Kagaku Co.,

These may be used singly or in combination of two or more.

Among them, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.

As specific examples of the compound having two or more oxetanyl groups in the molecule, Aromoxetane OXT-121, OXT-221, OX-SQ and PNOX [manufactured by Toagosei Co., Ltd.] can be used.

The oxetanyl group-containing compound is preferably used alone or in combination with a compound containing an epoxy group.

As other crosslinking agents, there can be preferably used an alkoxymethyl group-containing crosslinking agent and at least one compound having an ethylenically unsaturated double bond as described in paragraphs 0107 to 0108 of Japanese Patent Application Laid-Open Publication No. 2012-8223. Which is incorporated herein by reference. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

Alkoxysilane compound

The photosensitive resin composition of the present invention may contain an alkoxysilane compound. When the alkoxysilane compound is used, the adhesion between the film formed by the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed by the photosensitive resin composition of the present invention can be adjusted. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group of the alkoxysilane compound preferably has 1 to 5 carbon atoms.

The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an alkoxysilane compound which can be used as a base material, for example, an inorganic substance such as silicon, a silicon compound such as silicon oxide, silicon nitride, or the like and a metal such as gold, copper, molybdenum, titanium, Or the like. Specifically, known silane coupling agents and the like are also effective.

Examples of the silane coupling agent include? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacrylate, (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane, , And vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is even more preferable, and 3-glycidoxypropyltrimethoxy Silane is even more preferred. These may be used singly or in combination of two or more.

Further, a compound represented by the following general formula can also be preferably employed.

(R ¹ ) _4-n- Si- (OR ² ) _n

R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 1 to 3.) In the general formula, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms and no reactive group,

Specific examples thereof include the following compounds.

In the above, Ph is a phenyl group.

The alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited to these, and known alkoxysilane compounds may be used.

The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the total solid content in the photosensitive composition.

Increase / decrease agent

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator (B) in order to accelerate the decomposition thereof. The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron excited state comes into contact with the photoacid generator to generate electron transfer, energy transfer, heat generation, and the like. As a result, the photoacid generator causes a chemical change and decomposes to generate an acid. Examples of preferred sensitizers include compounds having an absorption wavelength in any one of the wavelength ranges of 350 nm to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Anthracene, xanthone, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, and the like), xanthone Oxanols, thiazides, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, thiocarbamates, (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, acridine, acridine), acridine (for example, thionine, methylene blue, toluidine blue) 2-chloroacridone), anthraquinones (for example, anthraquinone), squaryliums (for example, squarylium), styryls, bases But are not limited to, styrenes such as 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (e.g., 7-diethylamino 4-methylcoumarin, Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-pne).

Of these sensitizers, polynuclear aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatic compounds are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

The amount of the sensitizer to be added to the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass, more preferably 10 to 500 parts by mass, more preferably 50 to 200 parts by mass relative to 100 parts by mass of the photoacid generator of the photosensitive resin composition Is more preferable.

Two or more species may be used in combination.

Basic compound

The photosensitive resin composition of the present invention may contain a basic compound. As the basic compound, any of those used as chemical amplification resistors can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples of these compounds include the compounds described in paragraphs 0204 to 0207 of Japanese Patent Laid-Open Publication No. 2011-221494, the contents of which are incorporated herein by reference.

The basic compounds usable in the present invention may be used singly or in combination of two or more kinds.

The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 1 part by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition, when the other basic compound is contained Do.

Surfactants

The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants. Examples of the surfactant used in the composition of the present invention include those described in paragraphs 0201 to 0205 of JP-A-2012-88459, and those described in paragraphs 0185 to 0188 of JP-A-2011-215580 And descriptions of these are incorporated herein by reference.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. Further, KP-341 and X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.) (Manufactured by Mitsubishi Materials Kasei Co., Ltd.), Megapack (manufactured by DIC Corporation), Fluorad nooba FC-4430 (manufactured by Sumitomo 3M Ltd.) (Manufactured by NEOS), FRONT S-242 (made by AGC Seiyam Chemical Co., Ltd.), PolyFoxPF-6320 (made by OMNOVA), SH-8400 (Dorey Dow Corning silicone) and POTGENT FTX-218G

Further, it is preferable that the surfactant contains a constitutional unit A and a constitutional unit B represented by the following general formula (I-1) as a surfactant and the polystyrene-reduced polystyrene- Average molecular weight (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

In general formula (I-1)

Wherein R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴⁰⁴ represents a hydrogen atom or a C1-C4 alkyl group having 1 to 4 carbon atoms, P represents an alkylene group having 3 to 6 carbon atoms, p and q represent percentages of mass indicating a polymerization ratio, p represents a value of 10 mass% or more and 80 mass% or less, q represents a mass of 20 mass % Or more and 90 mass% or less, r is an integer of 1 or more and 18 or less, and s is an integer of 1 or more and 10 or less.

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

In general formula (I-2)

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

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

The amount of the surfactant added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 parts by mass to 10 parts by mass, and most preferably 0.01 parts by mass to 3 parts by mass relative to 100 parts by mass of the total solid content in the photosensitive resin composition desirable.

Antioxidant

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. Addition of an antioxidant can prevent coloring of the cured film or reduce film thickness reduction due to decomposition and has an advantage of excellent heat-resistant transparency.

Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite salts, Sulfates, hydroxylamine derivatives, and the like. Of these, a phenol-based antioxidant, an amide-based antioxidant, a hydrazide-based antioxidant, and a sulfuric acid-based antioxidant are particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used singly or in combination of two or more kinds.

Specific examples include the compounds described in paragraphs 0026 to 0031 of Japanese Patent Application Laid-Open No. 2005-29515, the contents of which are incorporated herein by reference. Preferred commercial products include Adekastab AO-60, Adekastab AO-80, Igarox 1726, Igarox 1035, Igarox 1098.

The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.5 to 4% by mass based on the total solid content of the photosensitive resin composition. With this range, sufficient transparency of the film formed can be obtained, and sensitivity at the time of pattern formation becomes good.

Various ultraviolet absorbers, metal deactivators, and the like described in "New developments of polymer additives " (Nikkan Kogyo Shinbunsha Co., Ltd.) may be added to the photosensitive resin composition of the present invention as additives other than the antioxidant.

[Acid growth agent]

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

The acid-proliferator which can be used in the present invention is a compound capable of raising the acid concentration in the reaction system by further generating an acid by an acid catalytic reaction, and is a compound stably present in the absence of acid.

Specific examples of such an acid-proliferating agent include the acid-proliferating agents described in paragraphs 0226 to 0228 of Japanese Patent Application Laid-Open No. 2011-221494, the contents of which are incorporated herein by reference.

[Development promoter]

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

As the phenomenon promoter, reference may be made to paragraphs 0171 to 0172 of Japanese Patent Application Laid-Open Publication No. 2012-042837, the contents of which are incorporated herein by reference.

The development accelerator may be used alone or in combination of two or more.

The addition amount of the development accelerator in the photosensitive resin composition of the present invention is preferably 0 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive composition, from the viewpoints of sensitivity and residual film ratio. Most preferably 10 parts by mass.

As other additives, there can be used a thermal radical generator described in paragraphs 0120 to 0121 of Japanese Patent Application Laid-Open Publication No. 2012-8223, a nitrogen-containing compound described in WO2011 / 136074A1, and a thermal acid generation system, .

&Lt; Preparation method of photosensitive resin composition >

The respective components are mixed in a predetermined ratio and by an arbitrary method, and the mixture is stirred and dissolved to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which each of the components is previously dissolved in a solvent, and then mix them in a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered using, for example, a filter having a pore diameter of 0.2 mu m or the like.

[Process for producing a cured film]

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

The method for producing the cured film of the present invention preferably includes the following steps (1) to (5).

 (1) a step of applying the photosensitive resin composition of the present invention onto a substrate;

 (2) removing the solvent from the applied photosensitive resin composition;

 (3) exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray;

 (4) developing the exposed photosensitive resin composition with an aqueous developing solution;

 (5) a post-baking step of thermally curing the developed photosensitive resin composition.

Each step will be described below in order.

(1), it is preferable that the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent. It is preferable to clean the substrate such as alkali washing or plasma cleaning before applying the photosensitive resin composition to the substrate, and more preferably, the substrate surface is treated with hexamethyldisilazane after the substrate cleaning. This treatment tends to improve the adhesion of the photosensitive resin composition to the substrate. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and for example, a method of exposing the substrate to hexamethyldisilazane vapor may be mentioned.

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

Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and composite substrates obtained by depositing molybdenum, titanium, aluminum, copper, or the like on a substrate such as glass, quartz, silicon or silicon nitride.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyldiglycol carbonate, polyamide, polyimide, polyamide Acrylic resin, epoxy resin, silicone resin, ionomer resin, polyimide resin, polyimide resin, polyimide resin, polyimide resin, And a synthetic resin such as a cyanate resin, a crosslinked fumaric acid diester, a cyclic polyolefin, an aromatic ether, a maleimide olefin, a cellulose, or an episulfide compound

These substrates are rarely used in the above-described form, and a multi-layered laminate structure such as a TFT element is usually formed depending on the shape of the final product.

The method of application to the substrate is not particularly limited, and for example, slit coat method, spray method, roll coating method, spin coating method, spin coating method, slit-and-spin method and the like can be used.

The wet film thickness at the time of application is not particularly limited, and it can be applied with a film thickness according to applications, but it is usually used in the range of 0.5 to 10 mu m.

Also, before applying the composition for use in the present invention to the substrate, it is also possible to apply the so-called pre-wet method as described in JP-A-2009-145395.

In the solvent removal step (2), the solvent is removed from the applied film by reduced pressure (bacitcum) and / or by heating to form a dry film on the substrate. The heating condition of the solvent removing step is preferably about 70 to 130 DEG C for about 30 to 300 seconds. When the temperature and the time are in the above ranges, the pattern adhesion tends to be better and the residue tends to be lowered.

In the exposure step of the step (3), the substrate on which the coating film is formed is irradiated with an actinic ray of a predetermined pattern. In this process, the photoacid generator is decomposed to generate acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.

(436 nm), i-line (365 nm), h-line (405 nm), and the like can be used as the exposure light source by the actinic light ray. Examples of the exposure light source include a low pressure mercury lamp, a high pressure mercury lamp, Nm) or the like having a wavelength of 300 nm or more and 450 nm or less can be preferably used. If necessary, the irradiation light may be adjusted by passing through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter. The exposure dose is preferably 1 to 500 mj / cm &lt; 2 &gt;.

As the exposure apparatus, various types of exposure apparatus such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.

Post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) may be performed to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote the generation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 100 占 폚.

However, since the acid decomposable group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group, Thereby forming a positive image.

(4), the liberated carboxyl group or the polymer having a phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the exposed region containing a resin composition having a carboxyl group or phenolic hydroxyl group that is easily dissolved in an alkaline developer.

It is preferable that the developer used in the developing process contains a basic compound. Examples of the basic compound include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate or the like can be used. An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

As a preferable developing solution, 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide can be mentioned.

The pH of the developing solution is preferably 10.0 to 14.0.

The developing time is preferably 30 to 500 seconds, and the developing method may be puddle method, dipping method, or the like. After the development, a desired pattern can be formed by conducting water washing for 30 to 300 seconds in general.

After the development, a rinsing process may be performed. In the rinsing step, the developed substrate is cleaned with pure water or the like to remove the attached developing solution and remove the developing residue. As the rinsing method, known methods can be used. Examples thereof include shower rinses and deep rinses.

In the post-baking step of the step (5), the obtained positive image is heated to decompose the acid-decomposable group to generate a carboxyl group or a phenolic hydroxyl group, and crosslinked with an epoxy group, a crosslinking agent or the like. This heating is carried out by using a heating apparatus such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C for a predetermined time, for example, 5 to 90 minutes in the case of a hot plate and 30 to 120 minutes in the case of an oven . By carrying out such crosslinking reaction, it is possible to form a protective film or an interlayer insulating film which is more excellent in heat resistance, hardness and the like. In addition, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

Post-baking may be performed after baking at a relatively low temperature before the post-baking (addition of the middle baking process). In the case of performing the middle baking, post baking is preferably performed at a high temperature of 200 ° C or higher after heating at 90 to 150 ° C for 1 to 60 minutes. In addition, middle baking and post baking may be divided into three or more stages and heated. The taper angle of the pattern can be adjusted by devising such a middle baking and post baking. These can be heated by a known heating method such as a hot plate, an oven, or an infrared heater.

In addition, as a catalyst for promoting the crosslinking process by generating an acid from the photoacid generator present in the unexposed portion by post-exposure (post exposure) to the substrate on which the pattern has been formed before the postbaking, And the curing reaction of the film can be promoted. When the post exposure step is included, the preferable exposure amount is preferably 100 to 3,000 mJ / cm2, and particularly preferably 100 to 500 mJ / cm2.

The cured film obtained from the photosensitive resin composition of the present invention may also be used as a dry etching resist. When the cured film obtained by thermal curing by the post-baking step is used as a dry etching resist, dry etching such as etching, plasma etching, ozone etching, or the like can be performed as the etching processing.

[Coating 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 preferably used as an interlayer insulating film. It is preferable that the cured film of the present invention is a cured film obtained by the method for producing a cured film of the present invention.

With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent transparency can be obtained even when the insulating resin is baked at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention is useful for an organic EL display device or a liquid crystal display device because it has high transparency and excellent physical properties of a cured film.

[Liquid crystal display device]

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

The liquid crystal display device of the present invention is not particularly limited, except that it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and includes a known liquid crystal display device employing various structures.

For example, specific examples of a TFT (Thin-film Transistor) included in the liquid crystal display of the present invention include an amorphous silicon-TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention has excellent electric characteristics, it can be preferably used in combination with these TFTs.

As a liquid crystal driving method that can be adopted in the liquid crystal display of the present invention, a TN (Twisted Nematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) Optical Compensated Bend) method.

In the panel structure, the cured film of the present invention can also be used in a COA (Color Filter on All) type liquid crystal display device. For example, the organic insulating film 115 of Japanese Patent Application Laid-Open No. 2005-284291, And can be used as the organic insulating film 212 of JP-A-346054.

Specific examples of the alignment method of the liquid crystal alignment film that can be employed in the liquid crystal display device of the present invention include a rubbing alignment method and a light distribution method. It may also be polymer-oriented supported by the PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.

In addition, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-described applications, and can be used for various purposes. For example, in addition to a planarizing film and an interlayer insulating film, a protective film for a color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, and a microlens provided on the color filter in the solid- Can be used.

Fig. 1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. Fig. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its back surface and the liquid crystal panel is constituted by a TFT corresponding to all pixels arranged between two glass substrates 14, (16) devices are arranged. An ITO transparent electrode 19 for passing through the contact hole 18 formed in the cured film 17 and forming the pixel electrode is wired to each element formed on the glass substrate. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal layer 20 and a black matrix are arranged is provided.

The light source of the backlight is not particularly limited and a known light source can be used. For example, white LEDs, multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), and organic ELs.

The liquid crystal display device may be of a 3D (stereoscopic) type or a touch panel type. It can also be used as a flexible type, and can be used as a second interlayer insulating film 48 of JP-A-2011-145686 or an inter-phase insulating film 520 of JP-A-2009-258758.

[Organic EL display device]

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

The organic EL display device of the present invention is not particularly limited, except that it has a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known organic EL display devices and liquid crystal display devices .

For example, specific examples of a TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include an amorphous silicon-TFT, a low-temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention has excellent electric characteristics, it can be preferably used in combination with these TFTs.

2 is a conceptual diagram showing an example of an organic EL display device. Sectional schematic view of a substrate in a bottom emission type organic EL display device and has a planarization film 4. [

A bottom gate type TFT 1 is formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ is formed in a state in which the TFT 1 is covered. A contact hole (not shown) is formed in the insulating film 3 and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 . The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

The flattening layer 4 is formed on the insulating film 3 in a state in which the irregularities by the wiring 2 are buried in order to planarize the irregularities due to the formation of the wiring 2. [

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the flattening film 4 by being connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.

An insulating film 8 is formed so as to cover the periphery of the first electrode 5. By forming the insulating film 8, a short circuit is formed between the first electrode 5 and the second electrode formed in a subsequent step .

Although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited by evaporation through a desired pattern mask. Then, a second electrode made of Al is formed on the entire upper surface of the substrate, And an ultraviolet curable epoxy resin are used to bond the organic EL element to each organic EL element so that the TFT 1 for driving the organic EL element is connected to the active matrix type organic EL display device.

Since the photosensitive resin composition of the present invention is excellent in curability and cured film properties, a resist pattern formed by using the photosensitive resin composition of the present invention as a structural member of a MEMS device is used as a partition wall or as a part of a mechanical driving component . Examples of such MEMS devices include SAW filters, BAW filters, gyro sensors, micro-shutters for displays, image sensors, electronic paper, inkjet heads, biochips, and sealants. More specific examples are exemplified in Japanese Patent Publication Nos. 2007-522531, 2008-250200, and 2009-263544.

Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer 16 and the planarization film 57 shown in Fig. 2 of Japanese Patent Laid-Open Publication No. 2011-107476, Japanese Patent Application Laid- The bank layer 221 and the third interlayer insulating film 216b shown in Fig. 10 of Japanese Patent Application Laid-Open No. 2010-27591, the barrier layer 12 and the planarization film 102 described in Fig. 4 (a) The second interlayer insulating film 125 and the third interlayer insulating film 126 described in FIG. 4A of JP 2009-128577 A, the planarization film 12 described in FIG. 3 of JP 2010-182638 A, The insulating film 14 and the like.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, the amounts used, the ratios, the contents of processing, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless specifically stated, &quot; part &quot; and &quot;% &quot; are based on mass.

In the following Synthesis Examples, the following symbols respectively represent the following compounds.

MATHF: 2-Tetrahydrofuranyl methacrylate (Synthesis)

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

MACHOE: 1- (cyclohexyloxy) ethyl methacrylate

MATHP: tetrahydro-2H-pyran-2-yl methacrylate

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

OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Yuki Kagaku Osaka)

NBMA: n-butoxymethyl acrylamide [manufactured by Mitsubishi Rayon Co., Ltd.]

MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

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

St: Styrene (made by Wako Junyakuko)

DCPM: dicyclopentanyl methacrylate

HEMA: hydroxyethyl methacrylate (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 K.K.)

PGME: Propylene glycol monomethyl ether (manufactured by Nippon Nyukazai Co., Ltd.)

MEDG: Diethylene glycol ethyl methyl ether: Hyosolve EDM (manufactured by Toho Chemical Industry Co., Ltd.)

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was cooled to 15 占 폚 and camphorsulfonic acid (4.6 g, 0.02 mol) was added. 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise to the solution. After stirring for 1 hour, saturated sodium hydrogencarbonate (500 ml) was added, the mixture was extracted with ethyl acetate (500 ml) and dried over magnesium sulfate. The insoluble material was filtered and concentrated under reduced pressure to 40 ° C or lower. 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% .

The monomer having a block isocyanate group

MOI-BM: (manufactured by Showa Denko K.K.)

MOI-BP: (manufactured by Showa Denko K.K.)

[Synthesis of a4-1]

(27 g, 0.31 mol), bismuth tris (2-ethylhexanoate) (manufactured by Nitto Kasei Co., Ltd., Neo, Japan) was added to a commercially available car lens AOI (manufactured by Showa Denko KK) Stann U-600, Bi content 18.0 to 19.0%) (0.1 g) and tetrahydrofuran (200 g) were added at room temperature, and the mixture was heated to 60 占 폚 and stirred for 5 hours.

After cooling to room temperature, 500 ml of water was added to the reaction solution, and the organic layer was extracted with 200 ml of ethyl acetate. Magnesium sulfate was added to the obtained organic layer, followed by dehydration. After filtration and concentration under reduced pressure, 62.3 g (yield: 91.0%) of the compound a4-1 was obtained.

¹ H-NMR spectrum (300 MHz, CDCl ₃ ). 2H), 3.59 (m, 2H), 2.49 (q, 2H), 6.99 (d, , 2.02 (s. 3H), 1.18 (t, 3H).

[Synthesis of a4-2 to a4-12]

a4-2 to a4-12 were also synthesized by the same method as in a4-1.

<Synthesis Example of Polymer A-1>

PGMEA (89 g) was placed in a three-necked flask, and the temperature was raised to 90 占 폚 under a nitrogen atmosphere. The amount of MATHF (amount to be 30 mol% in the total monomer components), GMA (amount to become 30 mol% in the total monomer components), MOI-BM (amount to be 10 mol% (Corresponding to 10 mol% in the monomer component), MMA (20 mol% in the total monomer component) and V-65 (corresponding to 4 mol% based on the total 100 mol% of the total monomer components) Over a period of time. After completion of dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby, Polymer A-1 was obtained. Further, the ratio of the total amount of PGMEA to the other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared.

&Lt; Synthesis Example of Polymers A-2 to A-25 >

The monomer types and the like were changed as shown in the following table to synthesize other polymers. In the following Tables, PGMEA was used for all the polymerization solvents of A2 to A23, MEDG for the polymerization solvent of A-24, and PGME for the polymerization solvent of A-25. The solid concentration was 40 parts by mass.

&Lt; Adjustment of Photosensitive Resin Composition >

A polymer component, a photoacid generator, an alkoxysilane compound, a crosslinking agent, a sensitizer, a basic compound, a surfactant and other components were dissolved and mixed in a PGMEA to a solid content of 25% so as to have a solid content ratio shown in the following table, Of a polytetrafluoroethylene filter to obtain photosensitive resin compositions of various examples and comparative examples. In the following table, the addition amount is in parts by mass.

Details of the abbreviations used for the compounds used in Examples and Comparative Examples are as follows.

(Polymer component)

A-1 to A-25: The polymer

(Photo acid generator)

B-1: DTS-105, (triarylsulfonium salt) (Midorikagaku)

B-2: CGI1397 (manufactured by BASF Japan Ltd.)

B-3: PAI101 (manufactured by Midori Kagaku Co., Ltd.)

B-4: Compound

[Synthesis of B-4]

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 ml), and the mixture was heated to 40 캜 for reaction for 2 hours. A 4N HCl aqueous solution (60 ml) was added dropwise to the reaction solution under ice-cooling, and ethyl acetate (50 ml) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 占 폚 for 1 hour. 2N HCl aqueous solution (60 ml) was added to separate the liquid layer. The organic layer was concentrated, and the crystals were reslurried with diisopropyl ether Filtered, and dried to obtain a ketone compound (6.5 g).

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

The obtained oxime compound (1.8 g) was dissolved in acetone (20 ml), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the temperature was raised to room temperature and reacted for 1 hour. Water (50 ml) was added to the reaction solution, and the precipitated crystals were filtered, and then slurry was rinsed with methanol (20 ml), followed by filtration and drying to obtain B-4 (2.3 g).

In addition, ¹ H-NMR spectrum of _{B-4 (300㎒, CDCl 3} ) is δ = 8.3 (d, 1H) , 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (d, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

(Sensitizer)

E-1: Dibutoxyanthracene of the following structure (manufactured by Kawasaki Chemical Industry Co., Ltd.)

(Crosslinking agent)

F-1: JER157S65 (manufactured by Mitsubishi Chemical Holdings, Inc.) (bisphenol type epoxy compound)

F-2: JER828 (manufactured by Mitsubishi Chemical Holdings, Inc.) (bisphenol type epoxy compound)

(Alkoxysilane compound)

G-1: γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-2: Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Basic compound)

H-1: Diazabicyclononene (manufactured by Tokyo Kasei Co., Ltd.)

H-2: 2,4,5-Triphenylimidazole (manufactured by Tokyo Kasei Co., Ltd.)

H-3: The following compound

(Surfactants)

I-1: Perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC) represented by the following structural formula:

(Antioxidant)

J-1: Igarox 1098 (manufactured by BASF)

&Lt; Evaluation of sensitivity &

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), pre-baked on a hot plate at 95 deg. C / 140 seconds to volatilize the solvent to obtain a photosensitive resin composition layer .

Subsequently, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (ultra-high pressure mercury lamp) manufactured by Canon Inc. Then, the exposed photosensitive resin composition layer was developed in an alkali developing solution (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 占 폚 for 60 seconds, and rinsed with ultrapure water for 20 seconds.

The optimum i-line exposure dose Eopt when resolving a hole of 5 mu m by these operations was taken as the sensitivity. C or higher is a practical level.

A: less than 20 mJ / cm 2

B: 20 mJ / cm 2 or more, less than 40 mJ / cm 2

C: 40 mJ / cm 2 or more, less than 80 mJ / cm 2

D: 80 mJ / cm2 or more, less than 160 mJ / cm2

E: 160 mJ / cm 2 or more

&Lt; Evaluation of chemical resistance (release liquid resistance) >

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a 90 ° C / 120 sec hot plate to obtain a photosensitive resin composition layer .

The resulting photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) by a PLA-501F exposure device (ultra high pressure mercury lamp) manufactured by Canon Inc., At 230 占 폚 for 1 hour to obtain a cured film.

The cured film was immersed in monoethanolamine at 60 DEG C for 5 minutes, and the film was pulled up to wipe off the liquid on the surface, and the film thickness was immediately measured. The film thickness before immersion and the film thickness after immersion were compared, and the increased ratio was expressed as a percentage. The results are shown in the following table. The smaller the numerical value, the better the peel solution resistance of the cured film, and A or B is the practical level.

Swelling rate (%) = film thickness after immersion (占 퐉) / film thickness before immersion (占 퐉) 占 100

A: 100% or more and less than 105%

B: 105% or more and less than 110%

C: 110% or more

D: 115% or more

&Lt; Evaluation of chemical resistance (NMP resistance) >

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)), and then the solvent was removed by heating on a 90 ° C / 120 sec hot plate to obtain a photosensitive resin composition layer .

The resulting photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) by a PLA-501F exposure device (ultra high pressure mercury lamp) manufactured by Canon Inc., At 230 占 폚 for 1 hour to obtain a cured film.

The cured film was immersed in NMP at 80 DEG C for 10 minutes, and the film was pulled up to wipe out the liquid on the surface, and the film thickness was measured immediately. The film thickness before immersion and the film thickness after immersion were compared, and the increased ratio was expressed as a percentage. The results are shown in the following table. The smaller the numerical value, the better the NMP resistance of the cured film, and A or B is the practical level.

Swelling rate (%) = film thickness after immersion (占 퐉) / film thickness before immersion (占 퐉) 占 100

A: 100% or more and less than 105%

B: 105% or more and less than 110%

C: 110% or more

D: 115% or more

&Lt; Evaluation of adhesion of cured film after PCT test >

Each of the photosensitive resin compositions was coated with a slit on an ITO (indium tin oxide) substrate, a Mo (molybdenum) substrate, a titanium (Ti) substrate, an aluminum (Al) substrate, and a copper The solvent was removed by heating to form a photosensitive resin composition layer having a film thickness of 4.0 占 퐉. The resulting photosensitive resin composition layer was exposed to light with an integrated irradiation amount of 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) by a PLA-501F exposure device (ultra high pressure mercury lamp) manufactured by Canon Inc., At 230 占 폚 for 1 hour to obtain a cured film. This cured film was treated with an unsaturated super accelerated life test device PC-304R8 (manufactured by Hirayama Seisakusho Co., Ltd.) for 150 hours under conditions of a temperature of 121 占 폚, a humidity of 100% and a pressure of 2.1 atm. The resulting cured film was cut at intervals of 1 mm vertically and horizontally using a cutter, and a tape peeling test was conducted using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred on the back side of the tape. The results are shown in the following table. The smaller the numerical value is, the higher the adhesion to the substrate is, and the practical level is A, B or C.

A: Less than 1% of transferred area

B: Transferred area is 1% or more and less than 3%

C: Transferred area is 3% or more and less than 5%

D: Transferred area of 5% or more

As is apparent from the above results, the photosensitive resin composition of the present invention was excellent in sensitivity, excellent in chemical resistance after thermosetting, and in substrate adhesion after PCT, all of which were above the practical level. On the other hand, the photosensitive resin composition of the comparative example was outside the practical level of chemical resistance or substrate adhesion after PCT.

&Lt; Example 28 >

Example 25 was carried out in the same manner as in Example 1 except that the exposure machine was changed to MPA 5500CF manufactured by Canon Inc. and FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The evaluation of the sensitivity was at the same level as in Example 1.

&Lt; Example 29 >

Example 29 was carried out in the same manner as in Example 1 except that 355 nm laser exposure was performed by changing the exposure apparatus to a 355 nm laser exposure apparatus in MPA 5500CF manufactured by Canon Inc. Here, as a 355 nm laser exposure device, "AEGIS" (wavelength 355 nm, pulse width 6 nsec) manufactured by Kabushiki Kaisha V Technology was used, and the exposure amount was measured using "PE10B-V2" manufactured by OPHIR Co.,

The evaluation of the sensitivity was at the same level as in Example 1.

&Lt; Example 30 >

In the active matrix type liquid crystal display device shown in Fig. 1 of Japanese Patent No. 3321003, a cured film 17 as an interlayer insulating film is formed as follows to obtain a liquid crystal display device. That is, the photosensitive resin composition of Example 1 was used to form a cured film 17 as an interlayer insulating film.

As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited good display characteristics and was highly reliable.

&Lt; Example 31 >

Only the coating process of Example 30 and the following was changed to obtain the same liquid crystal display device. That is, the photosensitive resin composition of Example 1 was applied by a slit coat method, and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to form a photosensitive resin composition layer having a film thickness of 3.0 mu m. The obtained coating film was flat and had a good surface without any unevenness. The performance as a liquid crystal display device was also good as in Example 30. [

&Lt; Example 32 >

Example 32 was carried out in the same manner as in Example 1, except that the exposure device was changed to a UV-LED light source exposing device by MPA 5500CF manufactured by Canon Inc. The evaluation of the sensitivity was at the same level as in Example 1.

As described above, it was found that the photosensitive resin composition of the examples was excellent in the shape of the pattern formed regardless of the substrate and the exposure apparatus.

&Lt; Example 33 >

The same liquid crystal display device was obtained by changing only the coating process of Example 32 and the following. That is, the photosensitive resin composition of Example 1 was applied by a slit-and-spin method, and then the solvent was removed by heating on a hot plate at 90 DEG C for 120 seconds to form a photosensitive resin composition layer having a film thickness of 3.0 mu m. The obtained coating film was flat and had a good surface without any unevenness. The performance as a liquid crystal display device was also good as in Example 27. [

&Lt; Example 34 >

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 was formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ was formed with the TFT 1 covered. Subsequently, a contact hole (not shown) is formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 did. This wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

In order to planarize the irregularities due to the formation of the wirings 2, the flattening film 4 was formed on the insulating film 3 with the irregularities formed by the wirings 2 embedded. The planarizing film 4 was formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on a substrate, pre-baking (90 DEG C / 120 seconds) on a hot plate, (365 mm) was irradiated with 45 mJ / cm 2 (light intensity: 20 mW / cm 2), and then developed with an aqueous alkaline solution to form a pattern and subjected to heat treatment at 230 캜 for 30 minutes.

The coating properties upon application of the photosensitive resin composition were satisfactory, and wrinkles and cracks were not observed in the cured films obtained after exposure, development and firing. In addition, the average step of the wiring 2 was 500 nm, and the film thickness of the prepared planarization film 4 was 2,000 nm.

Subsequently, a bottom-emission organic EL device was formed on the obtained planarization film 4. Then, First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, the resist was applied, pre-baked, exposed through a desired pattern mask, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using ITO etchant. Thereafter, the resist pattern was peeled off at 50 占 폚 using a resist stripping solution (Remover 100, manufactured by AZ Electronic Materials Co., Ltd.). The thus obtained first electrode 5 corresponds to the anode of the organic EL element.

Then, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed using the photosensitive resin composition of Example &lt; RTI ID = 0.0 &gt; (@) &lt; / RTI &gt; By forming the insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in a subsequent step.

Further, a hole transporting layer, an organic light emitting layer, and an electron transporting layer were sequentially evaporated through a desired pattern mask in a vacuum evaporation apparatus. Then, a second electrode made of Al was formed on the entire upper surface of the substrate. The obtained substrate was taken out from the evaporator, and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements were connected to each organic EL element was obtained. As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibits good display characteristics and is highly reliable.

1: TFT (thin film transistor) 2: wiring
3: insulating film 4: planarization film
5: first electrode 6: glass substrate
7: Contact hole 8: Insulating film
10: liquid crystal display device 12: backlight unit
14, 15: glass substrate 16: TFT
17: curing film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: Color filter

Claims (12)

(A) a polymer component containing a polymer satisfying at least one of the following (1) and (2)
(1) a polymer having (a1) a structural unit having an acid group protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group (excluding a block isocyanate group and an OH group)
(2) a polymer having the structural unit (a1) and a polymer having the structural unit (a2)
(B) a photoacid generator,
(C) a solvent,
(A4) at least one member selected from the group consisting of a block (a4), a block (a2), and a polymer having the structural unit (a1) At least one constituent unit having an isocyanate group is contained,
(3) A photosensitive resin composition comprising at least one polymer containing the structural unit (a4) and not containing the structural unit (a1) and the structural unit (a2). The method according to claim 1,
Wherein the structural unit (a4) is represented by the following general formula (a4-1).
In general formula (a4-1)

[In the formula (a4-1), R ⁴ represents a hydrogen atom or a methyl group, W represents a divalent linking group, and Z represents a monovalent organic group.] 3. The method of claim 2,
Wherein the structural unit (a4) is represented by the following general formula (a4-2).
In general formula (a4-2)

[In the formula (a4-2), R ⁴ represents a hydrogen atom or a methyl group, Y represents a divalent linking group, and Z represents a monovalent organic group.] 4. The method according to any one of claims 1 to 3,
Wherein the crosslinking group contained in the structural unit (a2) is at least one 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). 5. The method according to any one of claims 1 to 4,
Wherein the acid-decomposable group is a group having a protected structure in the form of an acetal. 6. The method according to any one of claims 1 to 5,
Wherein the structural unit (a1) is a repeating unit represented by the following general formula (A2 ').

Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or an aryl group, , R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 6 onto a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition,
(3) a step of exposing the photosensitive resin composition from which the solvent has been removed with an actinic ray,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) a post-baking step of thermally curing the developed photosensitive resin composition. 8. The method of claim 7,
And a step of performing front exposure before the post-baking step after the developing step. A cured film formed by curing the photosensitive resin composition according to any one of claims 1 to 6. A cured film characterized by being obtained by the method for producing a cured film according to claim 7 or 8. 11. The method according to claim 9 or 10,
Wherein the cured film is an interlayer insulating film. A liquid crystal display device or an organic EL display device having the cured film according to any one of claims 9 to 11.

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