KR101763685B1 - Photosensitive resin composition, method for manufacturing cured film, cured film, organic el display device, and liquid crystal display device - Google Patents

Abstract

And to provide a photosensitive resin composition capable of achieving adhesion to a substrate during development and use as a cured film.
The present invention relates to a polymer composition comprising (A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2), (1) a polymer component comprising (a1) a structural unit having an acid group protected with an acid- (2) a polymer having (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group, (B) a polymer having a structural unit having a non- , (C) a compound represented by the following general formula (S) (wherein R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group), ( D) a solvent and (E) an alkoxysilane compound.
In general formula (S)

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a method of producing a cured film, a cured film, an organic EL display device, and a liquid crystal display device. BACKGROUND ART [0002]

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

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

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 the interlayer insulating film, a photosensitive resin composition is widely used because the number of processes for obtaining a desired pattern shape is small, and furthermore, sufficient flatness is obtained.

The interlayer insulating film in the display device is required to have high transparency in addition to physical properties of a cured film which is excellent in insulating property, solvent resistance, heat resistance, hardness and indium tin oxide (ITO) sputter suitability. For this reason, attempts have been made to use an acrylic resin having excellent transparency as a film forming component, for example, as disclosed in Patent Document 1. As the photosensitive resin composition, there is also known that described in Patent Document 2.

Japanese Patent Laid-Open Publication No. 2011-209681 Japanese Patent Application Laid-Open No. 2005-234449

As the important characteristics of the photosensitive resin composition constituting the interlayer insulating film, the adhesiveness to the substrate is enumerated. Film peeling " from the substrate occurs in the developing process, which is one of the problems. In recent years, it has become difficult to perform fine pattern processing according to the high performance and high definition of the display device, and it is also required to improve the adhesion of the interlayer insulating film material after curing.

As described above, the photosensitive resin composition is required to have adhesion with a base substrate in the state of being developed and a cured film. Particularly, since the substrate itself is made of a plurality of kinds of materials, the interlayer insulating film material formed on the surface of the wiring substrate is also formed to have adhesiveness to a plurality of kinds of substrates.

An object of the present invention is to provide a photosensitive resin composition having good adhesion to a substrate. In particular, it is an object of the present invention to provide a photosensitive resin composition having high adhesion to a substrate during development and high adhesion to various substrates after curing.

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

As a result of the studies conducted by the present inventors, it has been found that the adhesion of the photosensitive resin composition to a substrate when used as a cured film at the time of development by containing a nonionic photoacid generator, a compound represented by a specific general formula and an alkoxysilane And significantly improved.

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

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

(1) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group,

(2) a polymer having (a1) a polymer having a structural unit having a group protected with an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group,

(B) a nonionic photoacid generator,

(C) a compound represented by the following general formula (S)

In general formula (S)

(In the formula (S), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group)

(D) a solvent and

(E) an alkoxysilane compound.

&Lt; 2 > In the general formula (S), R ¹ is -NR ³ R ⁴ (provided that R ³ and R ⁴ are each an organic group and may form a ring by bonding with each other) Of the photosensitive resin composition.

<3> The photosensitive resin composition according to <1> or <2>, wherein R ¹ in the general formula (S) is a cyclic group of a 5-membered ring or a 6-membered ring.

<4> The photosensitive resin composition according to <1> or <2>, wherein, in formula (S), R ¹ is a morpholino group.

<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the photoacid generator (B) is an oxime sulfonate compound.

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the alkoxysilane compound is a dialkoxysilane compound or a trialkoxysilane compound.

(7) The photosensitive resin composition according to any one of (1) to (6), which comprises (F) a crosslinking agent.

(8) A process for producing a photosensitive resin composition, comprising the steps of: (1) applying a photosensitive resin composition according to any one of (1) to (7)

(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 by an actinic ray,

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

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

<9> A method for producing a cured film, which comprises a step of exposing a developed photosensitive resin composition to a front exposure before the post-baking step after the development step.

&Lt; 10 > A cured film formed by the method of < 8 > or < 9 >.

<11> A cured film of <10> which is an interlayer insulating film.

<12> An organic EL display device or liquid crystal display device having a cured film of <10> or <11>.

The above problem has also been solved by the following means.

(13) A photosensitive resin composition according to any one of the above items, wherein (A) the polymer component is contained in an amount of 50 to 99.9 parts by mass, (B) the nonionic photoacid generator is contained in an amount of 0.1 to 10 parts by mass, C) A composition comprising 0.001 to 5 parts by mass of a compound represented by the formula (S) and 0.1 to 30 parts by mass of an alkoxysilane compound.

<14> The photosensitive resin composition according to any one of the above-mentioned items, wherein R ¹ in the compound represented by formula (S) is a group represented by -NR ³ R ⁴ , R ³ and R ⁴ each represent an alkyl group, A group formed by combining at least one of these with -O-, -S-, and -N-,

Wherein R &lt; ^{1 &gt;} is a cyclic group of a 5-membered or 6-membered ring.

(Effects of the Invention)

According to the present invention, it is possible to provide a photosensitive resin composition capable of achieving high adhesiveness to a substrate at the time of development and when used as 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. 1 is a schematic cross-sectional 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 is based on a representative embodiment of the present invention, but the present invention is not limited to these embodiments. In the present specification, &quot; &quot; is used to mean that the numerical values described before and after the numerical value 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 which does not include substitution and non-substitution includes not only a substituent but also 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).

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

The photosensitive resin composition of the present invention comprises (A) a polymer component comprising a polymer satisfying at least one of the following (1) and (2)

(1) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group,

(2) a polymer having (a1) a structural unit having a group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group,

(B) a nonionic photoacid generator,

(C) a compound represented by the above general formula (S)

(D) a solvent and

(E) an alkoxysilane compound.

According to the present invention, it becomes possible to provide a photosensitive resin composition excellent in adhesion with a substrate when used as a cured film at the time of development. Also, the chemical resistance can be improved.

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

<(A) Polymer Component>

The composition of the present invention comprises as polymer components: (1) a polymer having (a1) a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group, and (2) A polymer having a structural unit having a group protected with a group and (a2) a polymer having a structural unit having a crosslinkable group. It may also contain other polymers. The polymer component (A) (hereinafter referred to as the "component (A)") in the present invention may contain, in addition to the above-mentioned (1) and / or (2) .

<< Constituent unit (a1) >>

Component A has at least (a1) a structural unit having a group whose acid group is protected with an acid-decomposable group. When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.

The "acid-decomposable group-protected group" in the present invention 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 functional group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group ) Or a group which is relatively difficult to decompose by an acid (for example, a tertiary alkyl group such as a tert-butyl ester group, or a tertiary alkylcarbonate group such as a tert-butylcarbonate group).

(a1) The constituent unit in which the acid group has a group protected with 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 sequence.

<<< (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 having a carboxyl group of the structural unit having a carboxyl group and having 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 for the structural unit (a1-1) having a protected carboxyl group protected with the 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 a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid; (A1-1-2) having a structure derived from an unsaturated group and an acid anhydride group.

(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) an ethylenically unsaturated group and an acid anhydride And the constitutional unit having a structure derived from the same will be sequentially described.

<<<< (a1-1-1) Constituent derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule >>>>

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, those listed below are 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- Oxyethylhexahydrophthalic 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 for obtaining 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, mono (2-acryloyloxyethyl) succinate, mono Mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate, and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the both terminal dicarboxylic polymer, and examples thereof include ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like . 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, acrylic acid, methacrylic acid, 2- (meth) acryloyl (meth) acrylate and the like are preferable from the viewpoint of developability in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule. (Meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid or anhydrides of unsaturated polycarboxylic acids, and the like, and acrylic 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 may be composed of two or more kinds.

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

The structural unit (a1-1-2) having a structure derived from an ethylenic unsaturated group and 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; 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 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 in the structural unit (a1-1) >>>>

As the acid decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected with the acid decomposable group, the acid decomposable group may be used.

Among these acid decomposable groups, the carboxyl group is preferably a protected carboxyl group protected by an acetal form from the viewpoints of the basic physical properties of the photosensitive resin composition, particularly from the viewpoints of sensitivity and pattern shape, contact hole formation, and storage stability of the photosensitive resin composition. Among the acid decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected by an acetal form represented by the following general formula (a1-10) from the viewpoint of sensitivity. When the carboxyl group is a protected carboxyl group protected by an acetal form 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 &lt; ¹⁰¹ &gt; And R ¹⁰² each independently represent a hydrogen atom or an alkyl group except when R ¹⁰¹ and R ¹⁰² together are a hydrogen atom. 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, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

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

The straight-chain or branched-chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even 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- (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-texyl group.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still 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 isobornyl 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 R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are a haloalkyl group and have an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are an aralkyl group when they have a halogen atom as a substituent.

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 an aryl group having 6 to 12 carbon atoms, more preferably a phenyl group, an? -Methylphenyl group or a naphthyl group. An alkyl group substituted with an aryl group Examples of the aralkyl group as a whole include benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like.

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 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, And may have 12 cycloalkyl groups.

These substituents may be further substituted by the above substituents.

In the general formula (a1-10), R ¹⁰¹ , R ¹⁰² And R ¹⁰³ represents 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 combine with each other to form a ring together with the carbon atoms 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, And examples thereof include a t-butyl group and a tetrahydropyranyl group.

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

The radically polymerizable monomer used for forming the structural unit having a protective carboxyl group represented by the general formula (a1-10) may be a commercially available one, or a compound synthesized by a known method may be used. For example, it can be synthesized by the synthesis method described in the paragraphs Nos. 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 an acid-decomposable group is a structural unit represented by the following general formula.

(Wherein R ¹ and R ² each 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, R ³ is an alkyl group or an aryl group, and 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 alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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

X represents a single bond or an arylene group, and a single bond is preferable.

A second 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:

(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 a hydrogen atom.

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 by the acid-decomposable group is a structural unit having a protected phenolic hydroxyl group, the structural unit having a phenolic hydroxyl group being protected by an acid-decomposable group described in detail below.

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

In general formula (a1-20)

(In the general formula (a1-20), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms A is an integer of 1 to 5, b is an integer of 0 to 4, and a + b is not more than 5. When two or more R ²²² are present, these R ²²² may be different from each other , May be the same.)

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

Furthermore, R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, 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. Of these, 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 from the standpoint of 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 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 fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, do. 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 in the structural unit (a1-2) >>>>

The acid decomposable group which can be used for 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 for the structural unit (a1-1) having a protected carboxyl group protected with the acid- A known acid such as an acid-decomposable group can be used, and it is not particularly limited. Among the acid decomposable groups, structural units having a protective phenolic hydroxyl group protected by an acetal are preferred from the viewpoints of basic physical properties of the photosensitive resin composition, particularly from the viewpoints of sensitivity and pattern shape, storage stability of the photosensitive resin composition, and formability of contact holes. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is a protective phenolic hydroxyl group protected by an acetal type represented by the above general formula (a1-10). When the phenolic hydroxyl group is an acetal-protected protected phenolic hydroxyl group represented by the general formula (a1-10), the total of the protected phenolic hydroxyl groups may be -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) Structure.

Ar represents an arylene group.

Preferred examples of the acetal ester structure of the phenolic hydroxyl group may include a combination of R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group or R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group.

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

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 1-ethoxyethyl, 1-methoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1- 1-cyclohexyloxy) ethyl group, 1- (2-cyclohexyloxy) ethyl group, 1-naphthyloxy group, And an oxyethyl group. These may be used alone or in combination of two or more.

The radically polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group may be commercially available or may be synthesized by a known method. 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 carried out 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 from 20 to 100 mol% in the polymer containing the structural unit (a1) And more preferably from 30 to 90 mol%.

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

The structural unit (a1-1) having a protected carboxyl group protected with the acid-decomposable group has a feature that the development 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 an acid-decomposable group has a feature that the development 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.

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

(A) has a structural unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as far as it is a group that causes a curing reaction by a heat treatment. Preferable examples of the structural unit having a crosslinkable group include at least one group 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 from 1 to 20 carbon atoms) Is preferably 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 from 1 to 20 carbon atoms). Among them, the photosensitive resin composition of the present invention preferably contains the structural unit (A) containing at least one of an epoxy group and an oxetanyl group. More specifically, the following are listed.

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

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

The 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 that a total of 1 to 3 epoxy groups and / or oxetanyl groups are contained, and a total of one epoxy group and / or oxetanyl group More preferably two, and still more preferably one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used to form 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 containing an alicyclic epoxy skeleton described in paragraph numbers &lt; RTI ID = 0.0 &gt; 0031 to 0035 &lt; / RTI &gt; of EP-A-4168443, and the like are enumerated in the present specification.

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 001 of JP-A No. 2001-330953 Etc., 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.

Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl. These constituent units may be used alone or in combination of two or more.

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.

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

(A2-2) having an ethylenic unsaturated group as one of the structural units (a2) having a crosslinkable group (hereinafter also referred to as &quot; structural unit (a2-2) &quot;). The structural unit (a2-2) having an ethylenically unsaturated group is preferably a structural unit having an ethylenic unsaturated group in its side chain, more preferably a structural unit having an ethylenic unsaturated group at its terminal and having 3 to 16 carbon atoms, And more preferably a structural unit having a side chain represented by the following general formula (a2-2-1).

(A2-2-1)

(General formula (a2-2-1) of, R ³⁰¹ represents a 1 to 13 carbon atoms of a divalent connecting group, R ³⁰² represents a hydrogen atom or a methyl group, and * is the main chain of the structural unit (a2) having a crosslinking group Indicates the connecting site.)

R ³⁰¹ is a divalent linking group having 1 to 13 carbon atoms, and may include an alkenyl group, a cycloalkenyl group, an arylene group, or a combination thereof, and may include a bond such as an ester bond, an ether bond, an amide bond or a urethane bond. The divalent linking group may have a substituent such as a hydroxyl group or a carboxyl group at an arbitrary position. Specific examples of R ³⁰¹ include the following divalent linking groups.

Of the side chains represented by the general formula (a2-2-1), aliphatic side chains including the divalent linking group represented by R ³⁰¹ are preferable.

Other examples of the structural units having an ethylenically unsaturated group (a2-2) may be those described in Japanese Patent Application Laid-Open No. 2011-215580, paragraphs 0072 to 0090, the contents of which are incorporated herein by reference.

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

Polymer used in the present invention are also preferred structural units (a2-3) having a group represented by -NH-CH ₂ -OR (R is alkyl group having 1 to 20 carbon atoms). By having the structural unit (a2-3), the curing reaction can be caused by a gentle heat treatment, and a cured film excellent in various characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. 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 (a2-30).

(A2-30)

(In the general formula (a2-30), 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 constituent unit (a2) does not substantially contain the constituent unit (a1), the constituent unit (a2) is preferably from 5 to 90 mol% in the polymer containing the constituent unit (a2) , More preferably from 20 to 80 mol%.

When the polymer containing the constituent unit (a2) contains the above-mentioned constituent unit (a1), the single constituent unit (a2) is a polymer having a drug resistance of the polymer containing the constituent unit (a1) , It is preferably from 3 to 70 mol%, more preferably from 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 and chemical resistance of the cured film obtained from the photosensitive resin composition become favorable.

<< (a3) Other building blocks >>

In the present invention, the component (A) may contain, in addition to the above-mentioned structural units (a1) and / or (a2), other structural units (a3). These constituent units may contain the polymer components (1) and / or (2). In addition, apart from the polymer component (1) or (2), a polymer component having substantially no structural units (a1) and (a2) and having another structural unit (a3) may be contained. In the case of containing a polymer component having substantially no other components (a1) and (a2) and having another constituent unit (a3), apart from the polymer component (1) or (2) Is preferably 60 mass% or less, more preferably 40 mass% or less, and even more preferably 20 mass% or less.

The monomer to be the other 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 di An unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, and other unsaturated compounds. Further, as described later, it may have a structural unit having an acid group. The monomers to be the other constituent units (a3) may be used alone or in combination of two or more.

Hereinafter, preferred embodiments of the polymer component of the present invention are described, but the present invention is not limited thereto.

(First Embodiment)

The polymer component (1) has one or more other structural units (a3).

(Second Embodiment)

(A1) a form in which the polymer having a constituent unit having a group protected with an acid-decomposable group further comprises one or more other constituent units (a3) in the polymer component (2).

(Third Embodiment)

The form (a2) of the polymer component (2) further comprises one or more other structural units (a3) having a structural unit having a crosslinkable group.

(Fourth Embodiment)

In any one of the first to third embodiments, as the other structural unit (a3), a structure further comprising at least a structural unit containing an acid group.

(Fifth Embodiment)

A form further comprising a polymer having substantially no (a1) and (a2) and having another structural unit (a3), apart from the polymer component (1) or (2).

(Sixth Embodiment)

And a combination of two or more of the first to fifth embodiments.

(Seventh Embodiment)

A form comprising at least the polymer component (2). Particularly, in the first to sixth embodiments, at least a form containing the polymer component (2).

Specific examples of the structural unit (a3) include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetate mono 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.

Further, as the other structural unit (a3), a styrene group or a group having an alicyclic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specific examples include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (Meth) acrylate, and the like.

In addition, as the other 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, and methyl (meth) acrylate is more preferred. The content of the structural unit (a3) in the polymer (A) is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less. The lower limit value may be 0 mol%, for example, 1 mol% or more, or 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 become favorable.

As the other structural unit (a3), it is preferable to include an acid group. By incorporating an acid group, it is easy to dissolve in an alkaline developing solution, and the effect of the present invention is more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa smaller than 7. The acid group is usually contained in the polymer as a constituent unit containing an acid group by using a monomer capable of forming an acid group. By incorporating such a structural unit containing an acid group in the polymer, it tends to be easily dissolved 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 those 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.

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) or (2), a polymer having substantially no structural units (a1) and (a2) and having another structural unit (a3) may be contained.

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 polymer polymers having a (meth) acryloyl group in the side chain.

(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 A publicly known polymer compound described in JP-A-2000-56118, JP-A-2003-233179, and JP-A-2009-52020 can be used.

These polymers may be contained singly or in a combination of two or more.

As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F, SMA EF-30, SMA EF-40, SMA EF- ARUFON UC-3900, ARUFON UC-3920, ARUFON UC-3080 (manufactured by Toagosei Co., Ltd.), Joncryl (product of CRAY VALLEY USA, LLC), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC- 690, Joncryl 678, Joncryl 67, and Joncryl 586 (manufactured by BASF).

<< (A) Molecular weight of polymer >>

The molecular weight of the (A) polymer is a polystyrene reduced weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000. If the value is within the above range, various characteristics are good. The ratio of the number average molecular weight to the weight average molecular weight (dispersion degree) is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5.

<< (A) Method of producing polymer >>

In addition, although various methods are known for the synthesis of the component (A), for example, a radical containing a radical polymerizable monomer used for forming at least the structural units represented by (a1) and (a3) Can be synthesized by polymerization of a polymerizable monomer mixture in an organic solvent using a radical polymerization initiator. It may also be synthesized by a so-called polymer reaction.

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) Nonionic photoacid generator >

The photosensitive resin composition of the present invention contains (B) a nonionic photoacid generator.

As the nonionic photoacid generator (also referred to as &quot; component (B) &quot;) used in the present invention, a compound which responds to an actinic ray having a wavelength of 300 nm or longer, preferably 300-450 nm, But is not limited to a structure. Also, with respect to the photoacid generator which does not directly react with the actinic ray having a wavelength of 300 nm or more, a compound capable of reacting with an actinic ray having a wavelength of 300 nm or more and generating an acid by being used in combination with a sensitizer can be preferably used in combination with a sensitizer. 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 with 2 or less is the most preferable .

Examples of the nonionic photoacid generator include trichloromethyl-s-triazine, a diazomethane compound, an iminosulfonate compound and an oxime sulfonate compound. Among them, from the viewpoint of the insulating property, it is preferable to use an oxime sulfonate compound. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazine and diazomethane derivatives include the compounds described in paragraphs [0083] to [0088] of JP-A No. 2011-221494.

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, and the contents thereof are described in detail in the specification .

In general formula (B1)

(In the general formula (B1), R ²¹ represents an alkyl group or an aryl group, and the broken line represents a bond with another group)

The alkyl group in R ²¹ 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 ²¹ is preferably an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a cycloalkyl group (including a polycyclic alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, An alkyl group or the like).

As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. 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 halogen atom, m4 is an integer of 0 to 3, when m4 is 2 or 3, a plurality of X May be the same or different)

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

The halogen atom as X is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In the above general formula (B2), and m4 are 1, X is a methyl group, the substitution position of X is the ortho position, R ⁴² is 1 to 10 carbon atoms of straight chain alkyl, 7,7-dimethyl-2-oxo-norbornyl A n-methyl group or a p-toluyl group is particularly preferable.

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

(In the formula (B3), R ⁴³ is the same as R ⁴² in the formula (B2), and X ¹ represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 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.

n4 is preferably 0 to 2, and particularly preferably 0 to 1.

Specific examples of the compound represented by the above general formula (B3) include? - (methylsulfonyloxyimino) benzyl cyanide,? - (ethylsulfonyloxyimino) benzyl cyanide,? - (n-propylsulfonyloxyimino) Benzyl cyanide,? - (methylsulfonyloxyimino) -4-methoxyphenyl, benzyl cyanide,? - (n-butylsulfonyloxyimino) benzyl cyanide, - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, alpha - [(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, and? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

Specific examples of the preferable oxime sulfonate compound include the following compounds (i) to (viii), and they may be used alone or in combination of two or more. The compounds (i) to (viii) are commercially available. It may also be used in combination with other types of (B) photoacid generators.

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

R ¹⁰¹ in the general formula (OS-1) 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, an aryl group or a heteroaryl group . 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 an aryl group .

R ¹²¹ to R ¹²⁴ 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 ^{1 24} are 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 more preferably a compound represented by the following general formula (OS-2).

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

Of these, R ^{101 in} the general formulas (OS-1) and (OS-2) is preferably a cyano group or an aryl group, more preferably a form represented by the general formula (OS-2) ¹⁰¹ is a cyano group, a phenyl group or a naphthyl group is most preferable.

In the oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or both of them.

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

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.

(Formula (OS-3) ~ formula (OS-5) of, R ^22, R ²⁵ and R ²⁸ are each alkyl group independently represents an aryl group or a heteroaryl group, R ^23, R ²⁶ and R ²⁹ are each 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; X ^{1 to} X ³ each independently represent an oxygen atom or a sulfur atom, n ^{1 to} n ³ each independently represent 1 or 2, and m ^{1 to} m ³ each independently represent an integer of 0 to 6.

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

The alkyl group for R ²² , R ²⁵ and R ²⁸ in the formulas (OS-3) to (OS-5) is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.

Of the above general formulas (OS-3) to (OS-5), the aryl group in R ²² , R ²⁵ and R ²⁸ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

Among the above-mentioned general formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent.

The heteroaryl group in R ²² , R ²⁵ and R ²⁸ in the general formulas (OS-3) to (OS-5) may be any of a heteroaromatic ring having at least one ring. For example, do.

R ²³ , R ²⁶ and R ²⁹ in the general formulas (OS-3) to (OS-5) are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

One or two of R ²³ , R ²⁶ and R ²⁹ in which at least two of the compounds in the general formulas (OS-3) to (OS-5) are present are preferably an alkyl group, an aryl group or a halogen atom, More preferably an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

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

The aryl group for R ²³ , R ²⁶ and R ²⁹ is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.

In the general formulas (OS-3) to (OS-5), X ^{1 to} X ³ each independently represents O or S, and is preferably O.

In the general formulas (OS-3) to (OS-5), the ring containing X ^{1 to} X ³ as a reduction is a 5-membered ring or a 6-membered ring.

If the formula of (OS-3) ~ (OS -5) of, n1~n3 each independently represents 1 or 2, X ¹ ~X ³ is O, n1~n3 is preferably each independently 1 And when X ^{1 to} X ³ are S, n ^{1 to} n ³ are each independently preferably 2.

In the general formulas (OS-3) to (OS-5), 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. Among them, R ²⁴ , R ²⁷ and R ³⁰ are each independently preferably an alkyl group or an alkyloxy group.

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

Of the general formulas (OS-3) to (OS-5), the alkyl group for R ²⁴ , R ²⁷ and R ³⁰ is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.

The alkyloxy group in R ²⁴ , R ²⁷ and R ³⁰ in formulas (OS-3) to (OS-5) is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent.

In the general formulas (OS-3) to (OS-5), m1 to m3 each independently represent an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, , 0 &lt; / RTI &gt;

The substituents (OS-3) to (OS-5) described in paragraphs 0092 to 0109 of Japanese Patent Laid-Open Publication No. 2011-221494 Is also preferable.

The compound containing an oxime sulfonate structure represented by the general formula (B1) is particularly preferably an oxime sulfonate compound represented by any one of the following general formulas (OS-6) to (OS-11) .

(Wherein (OS-6) ~ (OS -11), R 301 ~R 306 represents an alkyl group, an aryl group or a heteroaryl group, R ³⁰⁷ represents a hydrogen atom or a bromine atom, R ³⁰⁸ ~R ^310, R ³¹³ , R ³¹⁶ and R ³¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ³¹¹ and R ³¹⁴ A halogen atom, a methyl group or a methoxy group, and R ³¹² , R ³¹⁵ , R ³¹⁷ and R ³¹⁹ each independently represent a hydrogen atom or a methyl group)

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

Specific examples of the oxime sulfonate compounds 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, The invention is not limited to these.

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

In the present invention, (B ') an ionic photoacid generator may be included. Examples of (B ') ionic photoacid generators include sulfonium salts, iodonium salts and quaternary ammonium salts. Among them, from the viewpoint of the insulating property, it is preferable to use an oxime sulfonate compound. These ionic photoacid generators may be used singly or in combination of two or more. Specific examples of diaryliodonium salts, triarylsulfonium salts and quaternary ammonium salts include compounds described in paragraphs [0083] to [0088] of JP-A No. 2011-221494.

In the photosensitive resin composition of the present invention, when the (B ') ionic photoacid generator is contained, the total amount of the resin component (preferably solid content, more preferably Is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, based on 100 parts by mass of the total amount of the polymer (A). The amount of the ionic photoacid generator (B ') to be added is preferably not more than the amount of (B) the nonionic photoacid generator, more preferably not more than 10% by mass. However, in the present invention, a form substantially containing no (B ') ionic photoacid generator is preferable.

&Lt; (C) Compound represented by the following general formula (S)

The composition of the present invention comprises (C) a compound represented by the following general formula (S).

In general formula (S)

(In the formula (S), R ¹ represents a group containing at least one nitrogen atom, A represents a divalent linking group, and R ² represents an organic group)

R ¹ represents a group containing at least one nitrogen atom, preferably a group containing 1 to 3 nitrogen atoms, more preferably a group represented by -NR ³ R ⁴ .

R ¹ is preferably a group consisting of ¹ to 10 carbon atoms and 1 to 3 hetero atoms including an oxygen atom and at least one nitrogen atom. The hetero atom in this case includes an oxygen atom and a sulfur atom, and an oxygen atom is preferable. R ¹ is preferably a cyclic group, more preferably a cyclic group of a 5-membered ring or a 6-membered ring.

R ³ and R ⁴ each represent an organic group. The organic group is preferably an alkyl group, an alkenyl group or a group formed by combining at least one of -O-, -S-, and -N-. R ³ and R ⁴ are each preferably a group having 1 to 3 carbon atoms. R ³ and R ⁴ may be bonded to each other to form a ring, and preferably form a ring.

Preferred examples of R ¹ include the following forms.

(1) a form wherein R ¹ is a group represented by -NR ³ R ⁴ , R ³ and R ⁴ are bonded to each other to form a ring, or R ³ and R ⁴ are each an aliphatic hydrocarbon group.

(2) a form wherein R ¹ is a group represented by -NR ³ R ⁴ , R ³ and R ⁴ are bonded to each other to form a 5-membered ring or a 6-membered ring, or R ³ and R ⁴ are each a straight- Or branched aliphatic hydrocarbon group.

(3) wherein R ¹ is a group represented by -NR ³ R ⁴ , R ³ and R ⁴ are bonded to each other to form two or more hetero atoms (at least one of them is a nitrogen atom and the remainder is an oxygen atom or a nitrogen atom) Or a form in which R ³ and R ⁴ are each a straight chain aliphatic hydrocarbon group of 1 to ⁴ carbon atoms.

Specific examples of R ¹ include, for example, morpholino, hydrazino, pyridyl, imidazolyl, quinolyl, piperidyl, pyrrolidinyl, pyrazolyl, oxazolyl, thiazolyl, Benzoxazolyl group, benzimidazolyl group, benzthiazolyl group, pyrazinyl group, diethylamino group and the like. Among them, a morpholino group is preferable.

R ² represents an organic group. As the organic group, a group consisting of a combination of a hydrocarbon group or a hydrocarbon group and at least one of -O- and -C (= O) - is preferable. The number of carbon atoms of R ² is preferably 1 to 20, more preferably 1 to 10.

R ² is more preferably a group consisting of an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms, or a combination of at least one of -O- and -C (= O) -. These groups may have a substituent, and as the substituent, a halogen atom is exemplified.

When R ² is an alkyl group, a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group is preferred. When R ² is a cyclic alkyl group, a cyclic alkyl group of 5-membered ring or 6-membered ring is preferred.

When R ² is an aryl group, a phenyl group and a naphthyl group are exemplified, and a phenyl group is more preferable.

Preferred examples of R &lt; ² &gt; include the following forms.

(1) a form of a straight chain alkylene group having 1 to 4 (preferably 2 or 3) carbon atoms.

A represents a divalent linking group, preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and still more preferably a hydrocarbon group having 2 to 6 carbon atoms. As the hydrocarbon group, an alkylene group and an arylene group are exemplified, and an alkylene group is preferable.

Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a cyclohexylene group, and a cyclopentylene group. Examples of the arylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group and a naphthylene group. In the present invention, a methylene group, an ethylene group and a propylene group are particularly preferable, and an ethylene group or a propylene group is more preferable.

As a preferable form of A, the following forms are enumerated.

(1) a form of a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 5 or 6 ring members, or a phenyl group.

The compound represented by the general formula (S) is exemplified as a particularly preferred form in which the combination of the preferable form of R ^1, the preferable form of R ^{2, and} the preferable form of A is as described above.

The compound represented by the general formula (S) is preferably represented by the general formula (S1).

In general formula (S1)

(In the general formula (S1), R ² represents an organic group, and A represents a divalent linking group)

R ² is the same meaning as R ² in the formula (S), it is also the same preferable range.

A is the same as A in the above formula (S), and the preferable range is also the same.

Particularly, in the general formula (S1), the following form is preferable.

(1) A is a straight-chain alkylene group having 1 to 4 carbon atoms, and R ² is a linear, branched or cyclic alkyl group.

(2) A is a C 2 -C 3 alkylene group, and R ² is a linear, branched or cyclic alkyl group having 2 to 6 carbon atoms.

Specific examples of the above-mentioned general formula (S) include the following compounds, but the present invention is not particularly limited thereto. Also, Et in the exemplified compounds represents an ethyl group.

The photosensitive resin composition of the present invention preferably contains the component (C) in an amount of 0.001 to 5 parts by mass, more preferably 0.003 to 2 parts by mass, and more preferably 0.005 to 1 part by mass relative to 100 parts by mass of the total solid content More preferably in a proportion of the mass part. The component (C) may be one kind or two or more kinds. In the case of two or more types, the total is preferably in the above range.

&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 solvents described in paragraphs 0174 to 0178 of JP-A No. 2011-221494, the contents of which 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, 1 Solvents such as octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may also be 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 used alone or in combination of two or more, more preferably two kinds of solvents, more preferably propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates and diethylene It is more preferable to use the 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 diethyl 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), 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.

(E) alkoxysilane compound

The photosensitive resin composition of the present invention is characterized by containing (E) an alkoxysilane compound (also referred to as &quot; component (E) &quot;). 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 (E) alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is an alkoxysilane compound that can be used as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, molybdenum, And is preferably a compound that improves the adhesion of the insulating film. Specifically, known silane coupling agents and the like are also effective.

As the silane coupling agent, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Meta (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 alone or in combination of two or more.

The following compounds can also be preferably employed.

In the above, Ph is a phenyl group.

The (E) alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited to these, and known ones can be used.

The content of the (E) 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.

<Other ingredients>

(G) a sensitizer, (H) a basic compound, (I) a surfactant and (J) an antioxidant may be preferably added to the photosensitive resin composition of the present invention 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.

(F) Crosslinking agent

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

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

The amount of the crosslinking agent added to 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, and most preferably 0.5 to 20 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition More preferable. When added in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. The crosslinking agent may be used in combination with a plurality of the crosslinking agents, in which case the crosslinking agents are all added to calculate the content.

&Lt; Compounds having two or more epoxy groups or oxetanyl groups in the molecule &

Specific examples of the compound having two or more epoxy groups in the molecule include 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, JER157S70, JER157S65 (manufactured by MITSUBISHI CHEMICAL HOLDINGS CORPORATION), etc., and commercial products described in paragraph 0189 of Japanese Patent Application Laid-Open No. 2011-221494.

NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501 and EP-4011S (manufactured by ADEKA CORPORATION) EXPENSIBLE EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX- EX-821, EX-821, EX-821, EX-821, EX-821, DLC-203, DLC-204, DLC-202, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX- YH-315, YH-324, and YH-325 (all of which are manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH- EPICLON EXA-4850-150 (manufactured by DIC Corporation), EPICLON EXA-4850-150 (manufactured by Nippon Steel Chemical Co., Ltd.), Celloxide 2021P, 2081, 3000, EHPE3150, Epolide GT400, Selbinase B0134, B0177 4850-1000 (manufactured by DIC Corporation).

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

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

Specific examples of the compound having two or more oxetanyl groups in the molecule include alonoxetane OXT-121, OXT-221, OX-SQ and PNOX (manufactured by Toagosei Co., Ltd.).

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 ethylenically unsaturated double bond-containing compound described in paragraphs 0107 to 0108 of JP-A-2012-8223, Are included in the specification. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

&Lt; Block isocyanate compound >

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

The block isocyanate group in the present invention is a group capable of forming an isocyanate group by heat, and for example, a group in which an isocyanate group is protected by reacting a blocking agent with an isocyanate group can be preferably exemplified. The block isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 to 250 캜.

The skeleton of the block isocyanate compound is not particularly limited, and any skeleton may be used as long as it has two isocyanate groups in one molecule. The skeleton may be an aliphatic, alicyclic or aromatic polyisocyanate. For example, 2,4- 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexyl isocyanate, Hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-di Ethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p- 1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylenediisocyanate, 3, 3'-methylene ditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylenediisocyanate, norbornadiisocyanate, hydrogenated 1,3-xylylene diisocyanate, Xylylene diisocyanate and the like, and prepolymer type skeleton compounds derived from these compounds can be preferably used. Of these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are particularly preferable.

As the parent structure of the block isocyanate compound in the photosensitive resin composition of the present invention, buret type, isocyanurate type, adduct type, bifunctional prepolymer type and the like can be exemplified.

Examples of the block agent forming the block structure of the block isocyanate compound include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, . Among them, a block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable.

Examples of the oxime compounds include oxime and keto oxime. Specific examples thereof include acetoxime, formaldehyde, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.

Examples of the lactam compound include ε-caprolactam, γ-butyrolactam, and the like.

Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.

Examples of the amine compound include primary amines and secondary amines, and may be any of aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole, and the like.

Examples of the mercaptan compound include alkyl mercaptans, aryl mercaptans, and the like.

The block isocyanate compound that can be used in the photosensitive resin composition of the present invention is available as a commercially available product. Examples of the block isocyanate compound include Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, B-820N, B-842N, B-846N, B-870N, B-874N and B-882N (all products of Mitsui Chemicals Inc.), manufactured by Nihon Polyurethan Inudstrial Ltd.), TAKENATE B-830, B-815N, B- B40B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (Manufactured by Asahi Kasei Corporation), Desmodule BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidule BL3175 Coporation products) can be preferably used.

(G) Thinner

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 is brought into contact with the photoacid generator, and electron transfer, energy transfer, heat generation and the like are generated. As a result, the photoacid generator decomposes by causing a chemical change 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- ), Xanthines (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (e.g., xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone ), Cyanines (for example, thiacarbocyanine, oxacarbocyanine), melocyanines (for example, melocyanine, carbomeroxy), rhodacyanines, oxonols, (For example, thionine, methylene blue, toluidine blue), acridines (such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, 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 (for example, 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 added in 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 photo- It is more desirable to be negative.

Two or more species may be used in combination.

(H) Other basic compounds

The photosensitive resin composition of the present invention may further contain (H) a basic compound in addition to the compound represented by the above general formula (S). (H) As the basic compound, any of those used in the chemically amplified resist may 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. As specific examples thereof, the compounds described in paragraphs 0204 to 0207 of Japanese Patent Laid-Open Publication No. 2011-221494 are enumerated, and the contents thereof are included in the specification of this application.

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

The content of the (H) other 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, Mass part is more preferable. However, since the photosensitive resin composition of the present invention contains a compound represented by the general formula (S), it may be a form which does not substantially contain other basic compounds.

(I) Surfactant

The photosensitive resin composition of the present invention may contain (I) a surfactant. As the (I) surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants.

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, in the following trade names, KP (product of Shin-Etsu Chemical Co., Ltd.), POLYFLOW (product of Kyoeisha Chemical Co., Ltd.), F-top (product of JEMCO), Megafac (product of DIC) (Manufactured by Sumitomo 3M, Inc.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (Dow Corning Toray Silicone) .

The weight ratio in terms of polystyrene measured by gel permeation chromatography in the case of using tetrahydrofuran (THF) as a solvent and containing the constituent unit A and the constituent unit B represented by the following general formula (I-1) as a surfactant A preferred example is a copolymer having an average molecular weight (Mw) of 1,000 or more and 10,000 or less.

In general formula (I-1)

  Construction unit A Construction unit B

(In the formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represents 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 P and q are mass percentages indicating polymerization ratios, and p is a number of not less than 10 mass% and not more than 80 mass% , Q represents a numerical value of 20 mass% or more and 90 mass% or less, r represents an integer of 1 or more and 18 or less, and s represents an integer of 1 or more and 10 or less.

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 of 1 to 4 carbon atoms, and from the viewpoint of compatibility and wettability to a surface to be coated, an alkyl group of 1 to 3 carbon atoms is preferable, Two or three alkyl groups are more preferred. It is preferable that the sum (p + q) of p and q is p + q = 100, that is, 100 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 (I) added to the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass, and most preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition. Mass part is more preferable.

(J) Antioxidant

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

Examples of the antioxidant include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiosulfate, And hydroxylamine derivatives. Of these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants and sulfur-based antioxidants are particularly preferred 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.

Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO- 40, ADK STAB AO-50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO- ADK STAB PEP-24, ADK STAB PEP-36, ADK STABA-611, ADK STABA-612, ADK STABA-613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP- ADK STAB HP-10, ADK STAB 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP, ADK STAB CDA- 1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90, ADK STAB ZS-91 (from ADEKA CORPORATION), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035 , Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, and Irgamod 295 (manufactured by BASF Corporation). Among them, ADK STABAO-60, ADK STABAO-80, Irganox 1726, Irganox 1035 and Irganox 1098 can be preferably used.

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

As the additives other than the antioxidant, various ultraviolet absorbers or metal deactivators described in &quot; NIKKAN KOGYO SHIMBUN, LTD. &Quot; may be added to the photosensitive resin composition of the present invention.

[Acid proliferating agent]

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

The acid-proliferating agent which can be used in the present invention is a compound capable of increasing the acid concentration in the reaction system by further generating an acid by an acid catalytic reaction and stably exists in a state in which no acid exists. Since these compounds proliferate more than one acid in one reaction, the reaction progresses acceleratively according to the progress of the reaction. However, since the generated acid itself induces self-decomposition, the strength of the acid generated here is the acid- The pKa is preferably 3 or less, and particularly preferably 2 or less.

Specific examples of acid proliferating agents are described in paragraphs [0203] to [0203] of JP-A No. 10-1508, paragraphs 0016 to 0055 of JP-A No. 10-282642, and JP-A No. 9-512498 Line 12 to page 47, the second line, and the contents of these are incorporated herein by reference.

Examples of the acid growth agent that can be used in the present invention include acids decomposed by an acid generated from an acid generator and formed from an acid having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, . &Lt; / RTI &gt;

Specifically, the following can be mentioned.

The content of the acid proliferating agent in the photosensitive composition is preferably from 10 to 1,000 parts by mass based on 100 parts by mass of the photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion, more preferably from 20 to 500 parts by mass .

[Development promoter]

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

As the phenomenon promoter, the description of paragraphs 0171 to 0172 of Japanese Patent Application Laid-Open Publication No. 2012-042837 may be taken into consideration, 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 from 0 to 30 parts by mass, more preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 20 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive composition, And most preferably 0.5 to 10 parts by mass.

As other additives, thermal radical generating agents described in paragraphs 0120 to 0121 of Japanese Patent Application Publication No. 2012-8223, nitrogen containing compounds described in WO2011 / 136074 A1, and thermal acid generation systems can be used. .

&Lt; Preparation method of photosensitive resin composition >

The respective components are mixed in a predetermined ratio in any manner, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which each component is dissolved in each solvent in advance, 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 a filter having a diameter of 0.2 탆 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, which is called alkali cleaning or plasma cleaning, before the photosensitive resin composition is applied to the substrate, and more preferably, the substrate surface is treated with hexamethyldisilazane after the substrate cleaning. By carrying out this treatment, the adhesion of the photosensitive resin composition to the substrate tends to be improved. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and examples thereof include a method of exposing the substrate to hexamethyldisilazane vapor, and the like.

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 and silicon nitride.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, aryldiglycol carbonate, polyamide, polyimide, polyamide A fluororesin such as polyetherimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin and polychlorotrifluoroethylene, a liquid crystal polymer, an acrylic resin, an epoxy resin, a silicone resin, an ionomer resin , A cyanate resin, a crosslinked fumaric acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, and an episulfide compound.

These substrates are rarely usable 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 coating method on the substrate is not particularly limited, and for example, a slit coating method, a spraying method, a roll coating method, a rotation coating method, a cast coating method, a slit and spin method and the like can be used. It is also possible to apply the so-called pre-wet method as described in JP-A-2009-145395.

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

In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry film on the substrate. The heating condition of the solvent removing step is preferably about 70 to 130 占 폚 for 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.

The substrate on which the coating film is formed is irradiated with an actinic ray through a mask having a predetermined pattern. In this step, 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 form a carboxyl group or a phenolic hydroxyl group.

(436 nm), an i-ray (365 nm), an h-ray (405 nm), and the like can be used as an exposure light source by an active light beam, such as a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, Of an active ray 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 through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

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;) can be performed to accelerate the above-described hydrolysis reaction in an acid-generated region. 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, PEB is not necessarily performed, A positive image may be formed by development.

In the developing step of (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 including a resin composition having a carboxyl group or a phenolic hydroxyl group which is liable to dissolve in an alkaline developer.

The developing solution used in the developing step preferably 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 development time is preferably 30 to 500 seconds, and the developing method may be any of a puddle method, a dipping method and the like. After the development, a desired pattern can be formed by conducting water-washing with water, usually for 30 to 300 seconds. 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, a known method can be used. For example, shower rinsing or dipping rinsing.

In the post-baking step of (5), the obtained positive image is heated to pyrolyze the acid-decomposable group to produce a carboxyl group or phenolic hydroxyl group, and the cured film can be formed by crosslinking with a crosslinkable group or a crosslinking agent. The heating is carried out at a predetermined temperature, for example, 180 to 250 DEG C for a predetermined time, for example, 5 to 90 minutes in the case of a hot plate or 30 to 120 minutes in the case of an oven by using a heating apparatus such as a hot plate or an oven. It is preferable to carry out the treatment. By carrying out such a crosslinking reaction, an excellent protective film or an interlayer insulating film can be formed by heat resistance, hardness and the like. Further, when the heat treatment is performed, 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 such a study of the middle baking and the post baking. These heating can be performed by a known heating method such as a hot plate, an oven, or an infrared heater.

In addition, prior to post-baking, the substrate having the pattern formed thereon is subjected to a front re-exposure (post exposure) by an actinic ray, and then post baking to generate an acid from the photoacid generator present in the unexposed portion to accelerate the cross- Can function as a catalyst, and can accelerate the curing reaction of the film. As a preferred exposure dose in the case of including a post-exposure step 100~3,000mJ / cm ² are preferred, 100~500mJ / cm ² is particularly preferred.

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 ashing, plasma etching, and ozone etching 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 of forming a cured film of the present invention.

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

[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 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 having various structures.

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

As a liquid crystal driving method that can be adopted by the liquid crystal display of the present invention, twisted nematic (TN), VA (virtual alignment), IPS (in-place 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 the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. It may also be polymer-oriented supported by PSA (Polymer Sustained Alignment) technology described in Japanese Patent 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-mentioned applications and can be used for various applications. For example, in addition to a planarizing film and an interlayer insulating film, a protective film for a color filter, a spacer for maintaining the thickness of the liquid crystal layer in a liquid crystal display device constantly, and a microlens formed on a color filter in a solid- Can be used.

1 is a conceptual cross-sectional view showing an example of an active matrix type liquid crystal display device 10. Fig. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the backside thereof and the liquid crystal panel is constituted by a TFT corresponding to all the pixels arranged between two glass substrates 14 and 15 to which a polarizing film is adhered (16) are disposed on the substrate. An ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17 in each element formed on the glass substrate. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of a liquid crystal 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 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 comprising 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 by using the photosensitive resin composition of the present invention, and various known organic EL display devices and liquid crystal display devices .

For example, as specific examples of TFTs (Thin-Film Transistors) included in the organic EL display device of the present invention, amorphous silicon TFT, low temperature polysilicon TFT, oxide semiconductor TFT, and the like are listed. Since the cured film of the present invention is excellent in 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. 1 is a schematic cross-sectional 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 of covering the TFT 1. 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 planarization layer 4 is formed on the insulating film 3 in a state of embedding unevenness by the wiring 2 in order to planarize the unevenness due to the formation of the wiring 2. [

On the planarizing film 4, a bottom emissive type organic EL element is formed. That is, a first electrode 5 made of ITO is formed on the planarization 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 edge of the first electrode 5. By forming the insulating film 8, a short circuit is prevented between the first electrode 5 and the second electrode formed in the subsequent step can do.

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, An active matrix type organic EL display device in which a glass plate and an ultraviolet curing type epoxy resin are used to seal each other and the TFT 1 for driving each organic EL element is connected is obtained.

Since the photosensitive resin composition of the present invention has excellent curability and cured film properties, it is possible to use a resist pattern formed by using the photosensitive resin composition of the present invention as a structural member of a MEMS device, as a partition wall, do. Examples of such MEMS devices include SAW filters, BAW filters, xylo sensors, micro-shutters for displays, image sensors, electronic paper, inkjet heads, biochips, encapsulants and the like. 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 white layer 16 and the planarization film 57 described in Fig. 2 of Japanese Patent Laid-Open Publication No. 2011-107476, Japanese Patent Application Laid- The back layer 221 and the third interlayer insulating film 216b described 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 shown in Fig. 4 (a) of JP-A No. 128577, the planarization film 12 described in Fig. 3 of JP-A No. 2010-182638, (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 processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the following specific examples. Unless otherwise 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.)

OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Ltd.)

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

NBMA: n-butoxymethyl acrylamide (manufactured by Tokyo Chemical Co., Ltd.)

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

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

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

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

DCPM: dicyclopentanyl methacrylate

V-601: Dimethyl-2,2'-azobis (2-methylpropionate) (available from Wako Pure Chemical Industries, Ltd.)

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

MEDG: methyl ethyl diglycol (manufactured by Nippon Nyukazai Co., Ltd.)

PGMEA: Methoxypropylacetate (product of Showa Denko K.K.)

<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. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added. The mixture was extracted with ethyl acetate (500 mL) and dried over anhydrous magnesium sulfate. The insoluble material was filtered off and concentrated under reduced pressure at 40 ° C or lower. 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 distillate was obtained as a colorless oil (yield: 80%).

&Lt; Synthesis Example of Polymer P-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 MAA (amount to be 9.5 mol% of total monomer components), MATHF (amount to become 43 mol% of total monomer components), GMA (corresponding to 47.5 mol% of total monomer components), V-65 Of the total amount of 100 mol%) was dissolved and dissolved dropwise over 2 hours. After completion of dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Polymer P-1 was thus obtained. 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.

The monomer types and the like were changed as shown in the following table, and other polymers were synthesized.

In the above table, the numerical values not specifically given in the table are in mol%. The numerical values of the polymerization initiator and the additive are mol% based on 100 mol% of the monomer component. The solid content concentration is expressed as monomer mass / (monomer mass + solvent mass) x 100 (unit mass%). In the case of using V-601 as the polymerization initiator, the reaction temperature was set at 90 占 폚, and in the case of using V-65, the reaction temperature was set at 70 占 폚.

&Lt; Adjustment of Photosensitive Resin Composition >

(S), a compound represented by the general formula (S), an alkoxysilane compound, a surfactant, and a compound represented by the general formula (S) The basic compound and other components were dissolved and mixed in a solvent (MEDG) until a solid content concentration reached 32%, and the mixture was filtered through a polytetrafluoroethylene filter having a pore size of 0.2 탆 to obtain photosensitive resin compositions of various examples and comparative examples . The amount added in the table is mass%.

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

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

P-21: Joncryl 67 (product of BASF)

P-22: ARUFON UC-3910 (manufactured by Toagosei Co., Ltd.)

P-23: SMA 1000P (manufactured by CRAY VALLEY USA, LLC)

P-24: SMA 2000P (manufactured by CRAY VALLEY USA, LLC)

P-25: SMA 3000P (manufactured by CRAY VALLEY USA, LLC)

P-26: SMA EF-30 (manufactured by CRAY VALLEY USA, LLC)

P-27: SMA EF-40 (manufactured by CRAY VALLEY USA, LLC)

P-28: SMA EF-60 (manufactured by CRAY VALLEY USA, LLC)

P-29: SMA EF-80 (product of CRAY VALLEY USA, LLC)

P-30: SMA 2625P (manufactured by CRAY VALLEY USA, LLC)

P-31: SMA 3840F (manufactured by CRAY VALLEY USA, LLC)

(Nonionic photo acid generator)

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

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

B-3: Synthesis of? - (hydroxyimino) -2-phenylacetonitrile (synthesis example will be described later)

<Synthesis of B-1>

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 at 40 占 폚 for 2 hours. Under ice cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, 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 thereto to separate the liquid. 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 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 resulting 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 mixture was allowed to react at room temperature for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered and then slurry with methanol (20 mL), followed by filtration and drying to obtain the compound B-1 (2.3 g).

(D, 1H), 7.8 (d, 1H), 7.8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6

<Synthesis of B-3>

Phenylacetonitrile (5.85 g, manufactured by Tokyo Chemical Co., Ltd.) was mixed with tetrahydrofuran (50 ml, manufactured by Wako Pure Chemical Industries, Ltd.), and the reaction solution was cooled to 5 캜 or lower in an ice bath. Next, SM-28 (28% methanol solution of sodium methoxide, 11.6 g, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and stirred for 30 minutes under an ice bath. Next, isopentyl nitrite (7.03 g, manufactured by Tokyo Chemical Co., Ltd.) was added dropwise while keeping the internal temperature at 20 占 폚 or lower, and after completion of dropwise addition, the reaction solution was allowed to react at room temperature for 1 hour. The obtained reaction solution was poured into water (150 mL) in which sodium hydroxide (1 g) was dissolved, followed by easy dissolution, followed by addition of ethyl acetate (100 mL) to obtain about 180 mL of an aqueous layer having the desired product. Further, ethyl acetate (100 ml) was added again, and the aqueous layer was acidified to a pH of 3 or less with concentrated hydrochloric acid, and the product was extracted and concentrated. The obtained crude crystals were washed with hexane to obtain? - (hydroxyimino) -2-phenylacetonitrile (4.6 g) in a yield of 63%.

(A compound represented by the formula (S)

S-1: Structure shown below

S-2: Structure shown below

S-3: Structure shown below

(solvent)

MEDG: Hyosolve EDM (manufactured by TOHO Chemical Industry Co., Ltd.)

1,3-BGDA: 1,3-butylene glycol diacetate (DAICEL Corporation)

(Alkoxysilane compound)

G-1: γ-glycidoxypropyltrialkoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

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

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

G-4: KBM-3063 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Sensitizer)

DBA: dibutoxyanthracene of the following structure (product of KAWASAKI KASEI CHEMICALS LTD.)

(Other basic compounds)

H-1: 2,4,5-triphenylimidazole (available from Tokyo Chemical Industry Co., Ltd.)

H-2: 1,5-diazabicyclo [4.3.0] -5-nonene (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Surfactants)

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

            20 wt% 80 wt%

                           Mw = 1,500

(Other components)

(Crosslinking agent)

F-1: JER828 (manufactured by MITSUBISHI CHEMICAL HOLDINGS CORPORATION)

F-2: JER1007 (manufactured by MITSUBISHI CHEMICAL HOLDINGS CORPORATION)

F-3: JER157S65 (manufactured by MITSUBISHI CHEMICAL HOLDINGS CORPORATION)

F-4: Dyuranate 17B-60P (manufactured by Asahi Kasei Corporation)

F-5: Celllock 2021P (manufactured by DAICEL Corporation)

F-6: Denacol EX-321L (manufactured by Nagase ChemteX Corporation)

F-7: EPICLON EXA-4850-150 (manufactured by DIC Corporation)

F-8: Takenate B-870N (manufactured by Mitsui Chemicals Inc.)

F-9: Nika Rack MW-100LM (available from Sanwa Chemical Co., Ltd.)

F-10: NIKARAK MX-270 (available from Sanwa Chemical Co., Ltd.)

F-11: Kaya Rad DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(Antioxidant)

J-1: ADK STAB AO-60 (product of ADEKA CORPORATION)

J-2: Irganox 1035 (product of BASF)

J-3: Irganox 1098 (product of BASF)

&Lt; Evaluation of adhesion at the time of development &

A glass substrate (10 cm x 10 cm (10 cm x 10 cm) on which a Mo (molybdenum) thin film was formed on a half area (10 cm x 5 cm) of one side of the substrate and a SiN x thin film was formed on the other half × 0.5 mm) was exposed for 30 seconds under the steam of hexamethyldisilazane (HMDS). Each of the photosensitive resin composition solutions was applied using a spin coater so as to have a dry film thickness of 3 μm, And the solvent was volatilized. Thereafter, an exposure dose of 40 mJ / cm ² (illuminance: 20 mW / cm ² , i-line) was exposed to light through a mask capable of reproducing 10 탆 lines / 10 탆 space using an ultra high pressure mercury lamp, TMAH aqueous solution) at 23 DEG C for 60 seconds, and rinsed with ultra-pure water for 1 minute. The obtained substrate was observed with an optical microscope, and the Mo part and the SiNx part were observed for defects and peeling of the pattern of 10 mu m line / 10 mu m space. The results are shown in the following table. The less the peeling, the better, and A or B is preferable.

A: There is no defect or peeling.

B: Defects and peeling less than 30%

C: Defects and delaminations exceed 30% and not more than 60%

D: Defects and peels exceeding 60% and not more than 100%

&Lt; Cohesion of cured film: Mo>

A glass substrate (10 cm x 10 cm x 0.5 mm) on which a Mo (molybdenum) thin film was formed was exposed for 30 seconds under steam of hexamethyldisilazane (HMDS), and then each photosensitive resin composition was coated with a spin coat, The solution was prebaked on a 2 minute hot plate to volatilize the solvent to form a photosensitive resin composition layer having a thickness of 3 m. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the cumulative dose was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C for 30 minutes to obtain a cured film .

Subsequently, the cured film was cut at intervals of 1 mm vertically and horizontally using a cutter, and subjected to a tape peeling test (100 mass cross cut method: according to JIS 5600) 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 surface 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 A or B is preferable.

A: Less than 1% of transferred area

B: Transferred area is 1% or more and less than 5%

C: Transferred area is 5% or more and less than 10%

D: Transferred area is 10% or more and less than 50%

E: Over 50% of transferred area

&Lt; Cured film adhesion property: Ti>

A glass substrate (10 cm x 10 cm x 0.5 mm) on which a Ti (titanium) thin film was formed was exposed for 30 seconds under steam of hexamethyldisilazane (HMDS), and then each photosensitive resin composition was coated with a spin coat, The solution was prebaked on a 2 minute hot plate to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 m. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the cumulative dose was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C for 30 minutes to obtain a cured film .

Subsequently, the cured film was cut at intervals of 1 mm vertically and horizontally using a cutter, and subjected to a tape peeling test (100 mass cross cut method: according to JIS 5600) 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 surface 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 A or B is preferable.

A: Less than 1% of transferred area

B: Transferred area is 1% or more and less than 5%

C: Transferred area is 5% or more and less than 10%

D: Transferred area is 10% or more and less than 50%

E: Over 50% of transferred area

&Lt; Cured film adhesion property: SiNx >

A glass substrate (10 cm x 10 cm x 0.5 mm) on which a SiNx (silicon nitride) thin film was formed was exposed for 30 seconds under steam of hexamethyldisilazane (HMDS), and then each photosensitive resin composition was coated with a spin coat, On a 2 minute hot plate to volatilize the solvent to form a photosensitive resin composition layer having a film thickness of 3 占 퐉. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the cumulative dose was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C for 30 minutes to obtain a cured film .

Subsequently, the cured film was cut at intervals of 1 mm vertically and horizontally using a cutter, and subjected to a tape peeling test (in accordance with JIS 5600 of 100 mass crossing method) 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 surface 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 A or B is preferable.

A: Less than 1% of transferred area

B: Transferred area is 1% or more and less than 5%

C: Transferred area is 5% or more and less than 10%

D: Transferred area is 10% or more and less than 50%

E: Over 50% of transferred area

&Lt; Evaluation of Chemical Resistance &

A glass substrate (10 cm x 10 cm x 0.5 mm) was exposed for 30 seconds under the steam of hexamethyldisilazane (HMDS), and then each photosensitive resin composition was spin-coated and then prebaked on a hot plate at 90 DEG C for 2 minutes The solvent was volatilized to form a photosensitive resin composition layer having a film thickness of 3 m. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the cumulative dose was 300 mJ / cm ² (illuminance: 20 mW / cm ² , i-line), and then the substrate was heated in an oven at 230 ° C for 30 minutes to obtain a cured film .

The film thickness (T ¹ ) of the obtained cured film was measured. Subsequently, the substrate on which the cured film was formed was dipped in a dimethylsulfoxide: monoethanolamine = 7: 3 solution controlled at a temperature of 60 캜 for 10 minutes, and then the film thickness (t ¹ ) of the cured film after immersion was measured. The film thickness change rate {| t ¹ -T ¹ | / T ¹ } x 100 [%] was calculated. The results are shown in the following table. The smaller the rate of change, the better, and A and B are levels at which there is no practical problem.

A: less than 2%

B: 2% or more and less than 3%

C: 3% to less than 4%

D: 4% to less than 6%

E: 6% or more

As is apparent from the above results, it was confirmed that the photosensitive resin composition of the present invention was excellent in adhesion at the time of development, and that the cured film of the photosensitive resin composition of the present invention also had excellent adhesion with the substrate. Particularly, in a plurality of kinds of substrates, all of them are excellent in adhesion to a high hardened film, and therefore can be suitably used for wiring boards such as display devices. Further, it is highly valuable to have the adhesion of the evaluation "A" to the molybdenum substrate.

In addition, the cured film of the photosensitive resin composition of the present invention has merit that the chemical resistance is high.

&Lt; Example 65 >

Example 65 was the same as Example 1 except that the exposure apparatus was replaced by Canon Inc. Except that the product was changed from MPA 5500CF to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The adhesion between the cured film and the developing film was evaluated at the same level as in Example 1.

&Lt; Example 66 >

Example 66 was the same as Example 1 except that the developing solution was changed from an alkaline developing solution (0.4 mass% of TMAH aqueous solution) to an alkaline developing solution (2.38 mass% of TMAH aqueous solution). The evaluation of the adhesion at the time of development was at the same level as in Example 1.

&Lt; Example 67 >

Example 67 was the same as Example 1 except for omitting the entire exposure process using an ultra-high pressure mercury lamp before heating in an oven. The adhesion of the cured film and the evaluation of chemical resistance were at the same level as in Example 1.

&Lt; Example 68 >

Example 68 was prepared in the same manner as in Example 1 except that the exposure apparatus was replaced by Canon Inc. Except that the product was changed from MPA 5500CF to a 355nm laser exposure apparatus and 355nm laser exposure was performed. Here, as the 355 nm laser exposure device, "AEGIS" (wavelength 355 nm, pulse width 6 nsec) manufactured by V Technology Co., Ltd. was used and the exposure amount was measured using "PE10B-V2" manufactured by OPHIR.

The adhesion between the cured film and the developing film was evaluated at the same level as in Example 1.

&Lt; Example 69 >

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 was formed as follows to obtain a liquid crystal display device of Example 69. Fig. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.

When the driving voltage was applied to the obtained liquid crystal display device, it was confirmed that the liquid crystal display device exhibited good display characteristics and was highly reliable.

&Lt; Example 70 >

Only the coating process of Example 69 and the following was changed to obtain the same liquid crystal display device. That is, the photosensitive resin composition of Example 1 was coated by a slit coating 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 69. [

&Lt; Example 71 >

Example 71 was the same as Example 1 except that the exposure apparatus was replaced by Canon Inc. Except that the product was changed from MPA 5500CF to a UV-LED light source exposer. The adhesion between the cured film and the developing film was evaluated at the same level as in Example 1.

As described above, it was confirmed 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.

<Example 72>

The same liquid crystal display device was obtained by changing only the coating process of Example 69 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 69.

&Lt; Example 73 >

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 in a state of covering the TFT 1. Next, a contact hole (not shown) was formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole was 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. [

In order to planarize the irregularities formed by the formation of the wirings 2, the planarization film 4 was formed on the insulating film 3 in a state in which irregularities due to the wirings 2 were embedded. The formation of the planarization film 4 on the insulating film 3 was performed by spin-coating the photosensitive resin composition of Example 16 on a substrate, prebaking (90 DEG C / 120 seconds) on a hot plate, , Irradiated with i-line (365 nm) at 45 mJ / cm ² (illuminance: 20 mW / cm ² ), developed with an aqueous alkaline solution to form a pattern, and subjected to heat treatment at 230 ° C 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. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Next, a bottom emissive organic EL device was formed on the planarization film 4 obtained. 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 mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using ITO as a catalyst. Thereafter, the resist pattern was peeled off at 50 占 폚 using a resist stripping solution (manufactured by AZ Electronic Materials Co., Ltd.). The thus obtained first electrode 5 corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the edge of the first electrode 5 was formed. An insulating film 8 was formed in the same manner as above using the photosensitive resin composition of Example 1 for the insulating film 8. By forming the insulating film 8, a short circuit can be prevented between the first electrode 5 and the second electrode formed in the 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 of the evaporator and sealed by 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. When a voltage was applied through the driving circuit, it was confirmed that the organic EL display device exhibited good display characteristics and was 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 (16)

A polymer component comprising a polymer that satisfies at least one of the following first and second aspects:
(1) a polymer having a structural unit having a crosslinkable group as a structural unit and a structural unit having a group in which an acid group is protected with an acid-decomposable group,
(2) a polymer having a structural unit having a group protected with an acid-decomposable group and a polymer having a structural unit having a crosslinkable group as the structural unit a2,
Nonionic photoacid generators,
A compound represented by the following general formula S,
Solvent, and
Wherein the photosensitive resin composition contains an alkoxysilane compound.
General formula S

(In the general formula S, R ¹ represents a group selected from the group consisting of a hydrazino group, a pyridyl group, an imidazolyl group, a quinolyl group, a piperidyl group, a pyrrolidinyl group, a pyrazolyl group, an oxazolyl group, a thiazolyl group, , A benzimidazolyl group, a benzthiazolyl group, a pyrazinyl group, or a diethylamino group, A represents a divalent linking group, and R ² represents an organic group) delete delete delete The method according to claim 1,
Wherein the photoacid generator is an oxime sulfonate compound. The method according to claim 1,
Wherein the alkoxysilane compound is at least one of a dialkoxysilane compound and a trialkoxysilane compound. delete delete delete The method according to claim 1,
A photosensitive resin composition comprising a crosslinking agent. A step of applying the photosensitive resin composition according to claim 1 onto a substrate,
A step of removing the solvent from the applied photosensitive resin composition,
A step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray,
A step of developing the exposed photosensitive resin composition by an aqueous developing solution, and
And a post-baking step of thermally curing the developed photosensitive resin composition. 12. The method of claim 11,
And a step of exposing the developed photosensitive resin composition to the whole before the post-baking step after the developing step. A cured film formed by the method for producing a cured film according to claim 11. 14. The method of claim 13,
Wherein the cured film is an interlayer insulating film. An organic EL display device having the cured film according to claim 13. A liquid crystal display device having the cured film according to claim 13.

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