KR20140147847A - Photosensitive resin composition, process for producing cured film, cured film, organic el display device, and liquid-crystal display device - Google Patents

Abstract

A photosensitive resin composition excellent in sensitivity and adhesion, and heat-resistant transparency.
(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 an acid group protected by 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 residue protected by an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group,
(B) a photoacid generator,
(C) a compound represented by the following general formula (I), and
(D) a solvent.

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,

The present invention relates to a photosensitive resin composition. In particular, the present invention relates to a chemically amplified positive photosensitive resin composition. The present invention also relates to a method for producing a cured film using a photosensitive resin composition, a cured film obtained by curing the photosensitive composition, and various image display devices using the cured film.

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

In an organic EL display device, a liquid crystal display device, or the like, an interlayer insulating film is formed from the viewpoints of luminance improvement, power consumption reduction, and the like. A photosensitive resin composition is widely used because of the small number of steps for obtaining a pattern shape required for formation of the interlayer insulating film and sufficient flatness is obtained.

Here, it is required that the patterned interlayer insulating film using the photosensitive resin composition as described above is a highly reliable effect film having excellent adhesion after development and after heat curing, and excellent heat-resistant transparency. In addition, in recent years, in order to produce an organic EL display device and a liquid crystal display device with good productivity, a high sensitivity of a photosensitive resin composition is required.

Conventionally, as a photosensitive resin composition having a high sensitivity, for example, Patent Document 1 using a binder having an acetal structure or a ketal structure is known. Although a silane coupling agent is noticeable as a contact improver, satisfactory adhesion can not be achieved with these compositions. In addition, there is an idea that adhesiveness is improved by using amines in consideration of the interaction with the substrate, but there is a drawback that the sensitivity is lowered with an increase in the amount of addition, and thus both sensitivity and adhesion can not be achieved. Further, the binder having an acetal structure generally has a storage stability that is not so high, and therefore it has been desired to find an adhesion improver that does not impair the stability.

Japanese Patent Application Laid-Open No. 2011-221494

It is an object of the present invention to solve the above problems, and an object thereof is to provide a photosensitive resin composition which is excellent in both sensitivity and adhesion, and heat-resistant transparency.

As a result of intensive research conducted by the present inventors to solve the above problems, it has been found that the above problems can be solved by adding a compound represented by the following general formula (I) (hereinafter also referred to as "specific sulfur-containing compound") in the photosensitive resin composition I found that I could. That is, it has been found that radicals are generated by decomposition of an S-S bond of a specific sulfur-containing compound to attack a compound having an adverse effect on transparency, and as a result, transparency and the like are improved.

Specifically, the above problems are solved by the following method <1>, preferably by <2> to <15>.

&Lt; 1 > A polymer composition comprising (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 an acid group protected by 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 residue protected by an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group,

(B) a photoacid generator,

(C) a compound represented by the following general formula (I), and

(D) Solvent

By weight based on the total weight of the photosensitive resin composition.

(In the general formula (I), R ¹¹ and R ¹² each represent a group containing at least one of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group, and n represents an integer of 2 to 4.)

&Lt; 2 > The method according to < 1 &

In the general formula (I), R ¹¹ and R ¹² are each an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

<3> The photosensitive resin composition according to <1>, wherein in the general formula (I), R ¹¹ and R ¹² each are an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 11 carbon atoms.

&Lt; 4 > The photosensitive resin composition according to < 1 >, wherein the compound (C) represented by the general formula (I) is represented by the following general formula (II).

(Wherein R ²¹ and R ²² each represent a hydrogen atom, an alkyl group or an aryl group, L ¹ and L ² each represent an alkylene group or an arylene group, and L ¹¹ and L ²² each represent * -OC ( = O) - or * -NH-C (= O) - and coupled to L ¹ or L ² shown in the side *).

<5> A photosensitive resin composition according to any one of <1> to <4>, wherein the structural unit (a1) is a structural unit having a carboxyl group in a form of acetal protected moiety.

<6> A photosensitive resin composition according to any one of <1> to <4>, wherein the structural unit (a1) is a structural unit represented by the following formula (A2 ').

The formula (A2 ')

(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, R ¹ or R ² And R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

<7> The positive resist composition according to any one of <1> to <6>, wherein the crosslinkable group is at least one selected from the group consisting of an epoxy group, oxetanyl group and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) Wherein the photosensitive resin composition is a photosensitive resin composition.

<8> A photosensitive resin composition according to any one of <1> to <7>, wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition.

<9> A photosensitive resin composition according to any one of <1> to <8>, wherein the photoacid generator (B) is an oxime sulfonate compound or an onium salt compound.

(10) A process for producing a photosensitive resin composition, comprising the steps of applying the photosensitive resin composition according to any one of < 1 > to <

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

(3) a step of exposing by actinic radiation,

(4) a step of developing with an aqueous developer, and

(5) a post-baking step of thermally curing the cured film.

<11> The method for producing a cured film according to <10>, which comprises a step of performing front exposure before the post-baking step after the development step.

<12> The method for producing a cured film according to <10> or <11>, wherein the substrate is a metal substrate.

<13> A cured film formed by curing the photosensitive resin composition according to any one of <1> to <9>.

<14> The cured film according to <13>, which is an interlayer insulating film.

&Lt; 15 > A liquid crystal display device or organic EL display device characterized by having a cured film according to < 13 > or < 14 >.

(Effects of the Invention)

According to the present invention, it is possible to provide a photosensitive resin composition excellent in both adhesion and heat-resistant transparency.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. Sectional schematic view of a substrate in a bottom emission type organic EL display device and has a planarization film 4. [
2 is a conceptual diagram showing an example of the configuration 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.

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

[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), (B) a photoacid generator, (C) Compound, and

(D) a solvent.

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

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

The compound of formula (I)

(In the general formula (I), R ¹¹ and R ¹² each represent a group containing at least one of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group, and n represents an integer of 2 to 4.)

The photosensitive resin composition of the present invention is a positive photosensitive resin composition. Further, the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition (chemically amplified positive photosensitive resin composition).

Hereinafter, preferred embodiments of the components of the photosensitive resin composition of the present invention will be described in order.

&Lt; Component (A) >

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

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

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

Here, in the above-mentioned form (1), at least one kind of polymer is included, and the polymer is composed of (a1) a structural unit having an acid group having a residue protected by an acid-decomposable group and (a2) a structural unit having a crosslinkable group to be. Such a polymer may further contain other repeating units. Two or more kinds of the structural units (a1) and (a2) may be contained.

In the above-mentioned form (2), at least one kind of the polymer contains the constituent unit (a1) and at least one other kind of the polymer has the constituent unit (a2).

Further, in the form of (2), the polymer containing the structural unit (a1) may further contain the structural unit (a2) or another structural unit. Similarly, the polymer containing the structural unit (a2) may contain the structural unit (a1) or another structural unit. In such a case, a form satisfying both (1) and (2) is obtained. The term &quot; component A &quot; in the present specification is intended to include any of the above polymer components.

As a first preferred embodiment of the present invention, at least one kind of the polymer includes two or more kinds of polymers as the component (A), and the polymer is a polymer having a constitutional unit having at least an acid group- The other at least one kind of polymer is a polymer having a constituent unit having at least a crosslinkable group. From the viewpoint of freedom of molecular design, it is preferable that the polymer having a constituent unit having at least an acid group-protected residue by an acid-decomposable group does not substantially contain the constituent unit (a2), and the polymer having a constituent unit having at least a crosslinkable group More preferably does not contain the structural unit (a1). Here, the term "substantially free" means that the proportion of the total structural units is 3 mol% or less and 1 mol% or less.

As a second preferred embodiment of the present invention, from the viewpoint of compatibility, a form in which the polymer containing the structural unit (a1) contains the structural unit (a2) is exemplified.

As a third aspect, a mode in which the polymer of the first embodiment and the polymer of the second embodiment coexist is considered as the polymer component (A).

The component (A) is preferably an addition polymerization type resin, more preferably a polymer comprising a constituent unit derived from (meth) acrylic acid and / or an ester thereof. Further, it may contain a structural unit other than the structural unit derived from (meth) acrylic acid and / or an ester thereof, for example, a structural unit derived from styrene or a structural unit derived from a vinyl compound.

The component (A) preferably contains a constituent unit derived from (meth) acrylic acid and / or an ester thereof in an amount of 50 mol% or more, more preferably 90 mol% or more, relative to all the constituent units in the polymer , (Meth) acrylic acid and / or an ester thereof.

Further, the "structural unit derived from (meth) acrylic acid and / or its ester" is also referred to as "acrylic structural unit". Further, "(meth) acrylic acid" means "methacrylic acid and / or acrylic acid".

The component (A) is preferably alkali-insoluble, and is preferably a resin that becomes alkali-soluble when the acid-decomposable group of the structural unit (a1) is decomposed. Herein, the acid-decomposable group means a functional group capable of decomposing in the presence of an acid. That is, a constituent unit having a protective carboxyl group protected by an acid-decomposable group in a carboxyl group is a constituent unit in which a protective group is decomposed by an acid to form a carboxyl group and the phenolic hydroxyl group is protected by an acid- The protecting group is decomposed by an acid to generate a phenolic hydroxyl group. In the present invention, the term "alkali-soluble" means that the coating solution (thickness: 3 μm) of the compound (resin) formed by applying a solution of the compound (resin) onto a substrate and heating it at 90 ° C. for 2 minutes, Means that the dissolution rate of the compound (resin) in an aqueous solution of 0.4% tetramethylammonium hydroxide at 23 캜 is 0.01 탆 / second or more. "Alkali insoluble" means that the solution of the compound (resin) Means that the dissolution rate of the coating film (thickness 3 占 퐉) of the compound (resin) formed by heating during the heating to 0.4% tetramethylammonium hydroxide aqueous solution at 23 占 폚 is less than 0.01 占 퐉 / second.

The (A) copolymer may have a structure derived from a carboxyl group, a carboxylic acid anhydride, and / or other structural units having a phenolic hydroxyl group, which will be described later. However, in the case of introducing an acidic group, it is preferable to introduce the acidic group within the range of keeping the entire copolymer (A) insoluble in alkali.

<< (a1) Structural unit having an acid group protected by an acid-decomposable group >>

(A) has at least a constitutional unit (a1) in which the acid group has a residue protected by an acid-decomposable group. The component (A) has the constituent unit (a1), so that a photosensitive resin composition having extremely high sensitivity can be obtained.

The constituent unit (a1) in the present invention preferably contains a constituent unit having a protected carboxyl group protected by an acid-decomposable group or a constituent unit having a protected phenolic hydroxyl group protected by an acid-decomposable group.

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

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

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

As the structural unit having a carboxyl group, which can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, a known structural unit can be used without particular limitation. (A1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid and an unsaturated tricarboxylic acid; , And a structural unit (a1-1-2) having both an ethylenic unsaturated group and a structure derived from an acid anhydride.

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

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

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

Among them, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule from the viewpoint of developability, anhydrides of acrylic acid, methacrylic acid or unsaturated polycarboxylic acid Or the like is preferably used, and acrylic acid or methacrylic acid is more preferably used.

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

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

The structural unit (a1-1-2) having both the ethylenic unsaturated group and the structure derived from an acid anhydride is preferably a unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride which are present in the 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 with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.

<<<< Acid-decomposable groups available for the structural unit (a1-1) >>>>

The acid-decomposable group which can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group may be any known acid-decomposable group and is not particularly limited. Conventionally, examples of the acid-decomposable group include a group which is relatively easily decomposed by an acid (for example, an acetal-based functional group such as a tetrahydropyranyl group) or a group which is relatively difficult to decompose by an acid (for example, tert- Butyl-based functional group such as a tert-butyl-carbonate group) are known.

Among these acid-decomposable groups, acetal-based functional groups are preferable from the viewpoints of the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the formation of contact holes, and the storage stability of the photosensitive resin composition. Among the protected carboxyl groups protected by an acid-decomposable group, the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-1) from the viewpoint of sensitivity. When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-1), the structure of - (C = O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) .

In general formula (a1-1)

(Formula (a1-1) of, R ¹⁰¹ and R ¹⁰² represents a hydrogen atom or an alkyl group, each independently, other than the R-stage ¹⁰¹ and, if R ¹⁰² is a hydrogen atom together. 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 (a1-1), 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 or cyclic. Here, R ¹⁰¹ and R ¹⁰² do not both represent a hydrogen atom, at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

When R ¹⁰¹ , R ¹⁰² and R ^{103 in} the general formula (a1-1) 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 more preferably 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec- Butyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and even more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, and isobonyl.

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 have a haloalkyl group as a substituent and R ¹⁰¹ , R ¹⁰² and R ¹⁰³ have an aralkyl group when they have an aryl group 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, and more specifically, a phenyl group, an -methylphenyl group, a naphthyl group, etc., As the whole, that is, the aralkyl group, benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like can be exemplified.

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

When the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent. When the alkyl group is a linear or branched alkyl group, the cycloalkyl group may have 3 to 12 carbon atoms And may have a cycloalkyl group.

These substituents may be further substituted by the above substituents.

In the general formula (a1-1), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms may be 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 a carbon atom to which they are bonded. Examples of the ring structure in the case where R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, An adamantyl group, and a tetrahydropyranyl group.

In the general formula (a1-1), it is preferable that either R ¹⁰¹ or R ¹⁰² is a hydrogen atom or a methyl group.

The preferred form of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the formula (A2 ').

The formula (A2 ')

(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, R ¹ or R ² And R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group.

When R ¹ and R ² are an alkyl group, the alkyl group preferably has 1 to 10 carbon atoms. When R ¹ and R ² are aryl groups, a phenyl group is preferred. Each of R ¹ and R ² is 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 allylene group, and a single bond is preferable.

The radically polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-1) may be a commercially available one, or a compound synthesized by a known method may be used.

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

<<< (a1-2) Structural unit having a protective phenolic hydroxyl group protected by an acid-decomposable 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 protected by an acid-decomposable group described below in detail in a structural unit having a phenolic hydroxyl group .

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

Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolak-based resin. Of these structural units, hydroxystyrene or a structural unit derived from -methylhydroxystyrene has transparency . Among the structural units having a phenolic hydroxyl group, structural units represented by the following general formula (a1-2) are preferable from the viewpoints of transparency and sensitivity.

In general formula (a1-2)

(In the general formula (a1-2), 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 the same or different .)

In the general formula (a1-2), 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 methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, Pentylene group, isopentylene group, neopentylene group, and xylene group. 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. In addition, a represents an integer of 1 to 5, but a is preferably 1 or 2, and more preferably a is 1, from the viewpoint of the effects of the present invention or from the standpoint of ease of production.

The bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R &lt; ²²¹ &gt; is the reference (1 position).

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

Specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group and a neopentyl group do. Of these, 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 available for the structural unit (a1-2) >>>>

As 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, the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group A known acid decomposable group can be used, and there is no particular limitation. Among the acid-decomposable groups, structural units having a protected phenolic hydroxyl group protected in the form of acetal are preferable from the viewpoints of the basic physical properties of the resist, in particular, the sensitivity and pattern shape, the storage stability of the photosensitive resin composition, and the formability of the contact hole.

Among the acid-decomposable groups, from the viewpoint of sensitivity, it is more preferable that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-1). Further, when the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-1), -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) . Furthermore, AR represents an allylene group.

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

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

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

Specific examples of the acetal protecting group of the phenolic hydroxyl group include 1-alkoxyalkyl groups, for example, 1-ethoxyethyl, 1-methoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1- (1-cyclohexyloxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, Ethyl group, etc. These may be used singly or in combination of two or more kinds.

The radically polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group may be either commercially available or 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 other monomers, 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 by 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 5 to 90 mol% in the polymer containing the structural unit (a1) And more preferably 20 to 80 mol%.

When the polymer containing the structural unit (a1) contains the structural unit (a2), the structural unit (a1) is preferably a polymer containing the structural unit (a1) and the structural unit (a2) Is preferably 3 to 70 mol%, more preferably 10 to 60 mol%. In particular, in the case where the acid-decomposable group usable in the structural unit (a1) is a structural unit having a carboxyl group protected in the form of an acetal in the form of an acetal, it is more preferably 10 to 40 mol%.

In the present invention, regardless of the form, the content of the structural unit (a1) in the total structural units of the component (A) is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.

The structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group has a characteristic that the development is faster than that of the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group. Therefore, when a rapid development is desired, the structural unit (a1-1) having a protected carboxyl group protected by an acid-decomposable group is preferable. On the contrary, when it is intended to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected by an acid-decomposable group.

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

(A) has a structural unit (a2) having a crosslinking group. The crosslinking group is not particularly limited as long as it is a group which causes a curing reaction by a heat treatment. Preferable examples of the form of the structural unit having a crosslinking group include a structural unit containing at least one selected from the group consisting of oxiranyl, oxetanyl, -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) and ethylenic unsaturated group .

Among them, the photosensitive resin composition of the present invention preferably contains a constituent unit in which the component (A) includes at least one of an oxiranyl group and an oxetanyl group, and more preferably contains a constituent unit containing an oxetanyl group Is particularly preferable. More specifically, the following are exemplified.

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

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

The structural unit (a2-1) having an oxiranyl group and / or an oxetanyl group may have at least one oxiranyl group or oxetanyl group in one structural unit, and may contain at least one oxiranyl group and at least one oxirane group A pentanyl group, a pentanyl group, a pentanyl group, a pentanyl group, a pentanyl group, a pentanyl group, a pentanyl group, a pentanyl group, / Or oxetanyl groups in total, and more preferably one oxiranyl group or oxetanyl group.

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

Specific examples of the radically polymerizable monomer used for forming the oxetanyl group-containing structural unit include (meth) acrylate esters having an oxetanyl group as described in paragraphs 0011 to 0016 of JP 2001-330953 A And the like.

Specific examples of the radically polymerizable monomer used for forming the oxiranyl and / or oxetanyl group-containing structural unit (a2-1) include monomers containing a methacrylate ester structure, monomers containing an acrylic ester structure .

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

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

Preferable specific examples of the oxiranyl and / or oxetanyl group-containing structural unit (a2-1) include the following structural units. R represents a hydrogen atom or a methyl group.

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

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

As the structural unit (a2) having a crosslinking group, a structural unit (a2-2) having an ethylenic unsaturated group is exemplified (hereinafter also referred to as "structural unit (a2-2)"). 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)

(In the general formula (a2-2-1), R ³⁰¹ represents a divalent linking group having 1 to 13 carbon atoms, R ³⁰² represents a hydrogen atom or a methyl group, and * represents a linking group to the main chain of the structural unit (a2) .)

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.

Others (a2-2) For the structural unit having an ethylenic unsaturated group, the description of paragraphs 0077 to 0090 of Japanese Patent Laid-Open Publication No. 2011-215580 may be taken into consideration.

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

Copolymer used in this invention is -NH-CH ₂ -OR is also preferred structural units (a2-3) having a partial structure represented by (R is an alkyl group having 1 to 20 carbon atoms). By having the constituent unit (a2-3), a 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 (1).

In general formula (1)

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

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

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

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

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

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

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

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

<< (a3) Other building blocks >>

In the present invention, the component (A) may contain other structural unit (a3) in addition to the structural unit (a1) and the structural unit (a2). The monomer constituting the other constituent unit (a3) is not particularly limited. (Meth) acrylic acid alkyl ester, a (meth) acrylic acid aryl ester, an unsaturated dicarboxylic acid diester, a bicyclo unsaturated compound, a maleimide compound, an unsaturated aromatic Compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds.

Specific examples include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, tert (Meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, 2-hydroxyethyl And the like. Other compounds listed in paragraphs 0021 to 0024 of JP-A-2004-264623 can be exemplified.

Among them, other structural units (a3) having a group which reacts with the structural unit (a2) or a separately added crosslinking agent by the (final) heat treatment are preferable from the viewpoint of film strength.

Specifically, a group having an alcoholic hydroxyl group is preferable, and 2-hydroxyethyl methacrylate is particularly preferable. The proportion of the other structural unit (a3) having a group which reacts with the structural unit (a2) or the separately added crosslinking agent to the total (A) component by the (final) heat treatment is preferably 1 to 50 mol% To 40 mol%, and particularly preferably from 10 to 30 mol%.

In addition, the component (A) has a constitutional unit having an unprotected carboxyl group or a constitutional unit having a phenolic hydroxyl group which is not protected in an amount of 1 to 50 mol% based on the total of the component (A) , More preferably from 3 to 40 mol%, and particularly preferably from 5 to 20 mol%. As the structural unit having an unprotected carboxyl group or phenolic hydroxyl group, a monomer having a known acidic group can be exemplified. Of these, hydroxystyrene and (meth) acrylic acid are preferable, and methacrylic acid is more preferable.

The monomers constituting the other structural unit (a3) may be used alone or in combination of two or more.

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 thereof include styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene,? -Methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate and benzyl .

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.

(A3) in any of the above-described embodiments with respect to the component (A), and it is also possible to use a plurality of the component (A3) in combination.

In the present invention, it is preferable that a structural unit having a carboxyl group or a phenolic hydroxyl group protected in the acetal form and a structural unit having an unprotected carboxyl group or a phenolic hydroxyl group are included together.

In the photosensitive resin composition of the present invention, the polymer component (A) preferably accounts for 70 wt% or more of the components excluding the solvent, and more preferably 90 wt% or more.

<< (A) Molecular Weight of Copolymer >>

The molecular weight of the (A) copolymer is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, in terms of polystyrene reduced weight average molecular weight. Within the above range of values, sensitivity and ITO suitability are good.

The ratio (number of dispersions) of the number average molecular weight to the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

<< Process for producing (A) copolymer >>

Various methods are also known for the synthesis of the component (A). For example, at least the radically polymerizable (meth) acrylate compound containing a radically polymerizable monomer used for forming the constituent unit represented by the above (a1) Can be synthesized by polymerization of a monomer mixture in an organic solvent using a radical polymerization initiator. It may also be synthesized by so-called polymer reaction.

As specific examples of the copolymer (A), for example, (1) is satisfied,

Methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid 2-hydroxyethyl copolymer (45/8/35/12), 1-ethoxyethyl methacrylate /

Methacrylic acid / glycidyl methacrylate / allyl methacrylate / dicyclopentanyl methacrylate / styrene copolymer (35/10/30/5/15/15), 1-ethoxyethyl methacrylate /

1-cyclohexyloxyethyl methacrylate / methacrylic acid / glycidyl methacrylate / 2-hydroxyethyl methacrylate / styrene copolymer (40/8/35/12/5),

Methacrylic acid (3-ethyloxetan-3-yl) methyl / glycidyl methacrylate / 2-hydroxyethyl / styrene copolymer of methacrylic acid / tetrahydrofuran-2-yl methacrylate / methacrylic acid / (35/10/15/15/15/10),

Methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / N-methoxymethylacrylamide / 2-hydroxyethyl methacrylate copolymer (40 / 5/40/5/10),

Methacrylic acid / 3-ethyloxetane-3-yl) methyl methacrylate / 2-hydroxyethyl methacrylate / dicyclopentyl methacrylate copolymer (42 / 11/25/18/4).

As an example satisfying equation (2)

Methoxyethyl methacrylate / methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (60/10/10/20) and methacrylic acid (3-ethyloxetane-3- A combination of methyl / methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (60/10/10/20)

Methacrylic acid tetrahydropyran-2-yl / methacrylic acid / 2-hydroxyethyl methacrylate / dicyclopentyl methacrylate copolymer (65/5/10/20) and glycidyl methacrylate / N -Methoxymethylacrylamide / methacrylic acid / dicyclopentanyl methacrylate / styrene copolymer (50/15/5/15/15) can be exemplified.

&Lt; (B) Photo acid generator >

The photoacid generator used in the present invention is preferably a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but is not limited to the chemical structure thereof. Further, in the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, it can be preferably used in combination with a sensitizer if it is used in combination with a sensitizer so as to generate an acid in response to an actinic ray having a wavelength of 300 nm or more. As the photoacid generator used in the present invention, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, and a photoacid generator that generates an acid with a pKa of 3 or less is more preferable.

The component (B) is preferably an onium salt compound or an oxime sulfonate compound from the viewpoint of sensitivity. Of these, oxime sulfonate is more preferable from the viewpoint of electric characteristics. When an oxime sulfonate compound is used as an acid generator, a compound in which imine is dimerized as a by-product to be colored is by-produced. It is thought that the coloring material is suppressed by attacking the radicals generated by the decomposition of S-S of the compound represented by the general formula (C).

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. have. Among them, it is preferable to use an oxime sulfonate compound from the standpoint of insulation. These photoacid generators may be used alone or in combination of two or more. Specific examples of trichloromethyl-s-triazine, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts and diazomethane derivatives are described in paragraphs 0077 to 0078 of JP-A No. 2011-221494 The compounds described can be exemplified.

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

In general formula (B1)

(In the general formula (B1), R ²¹ represents an alkyl group, an aryl group or an alkyl fluoride 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-oxononyl 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 by 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).

(In the formula (B2), R ⁴² represents an alkyl group, an aryl group or an alkyl fluoride group; X represents an alkyl group, an alkoxy group or a halogen atom; m4 represents an integer of 0 to 3; when m4 is 2 or 3, Multiple Xs 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 dimethyl 1 to 10 carbon atoms of straight chain alkyl, 7,7-carbonyl-2-oxo-Nord Methyl group or p-toluyl group is particularly preferable.

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

(Formula (B3) of, R ⁴³ is R ⁴² and agreed in the formula (B2), X ¹ is a halogen atom, a hydroxyl group, a C 1 -C 4 alkyl group, a 1-4C alkoxy group, a cyano group or a nitro group And n4 represents an integer of 0 to 5.)

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

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

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

Specific examples of the compound represented by the 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 (vii), which may be used alone or in combination of two or more. The compounds (i) to (III) 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).

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

X ¹⁰¹ represents O-, -S-, -NH-, -NR ¹⁰⁵ -, -CH ₂ -, -CR ¹⁰⁶ H- or -CR ¹⁰⁵ R ¹⁰⁷ , and R ¹⁰⁵ to R ¹⁰⁷ represent an alkyl group or an 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 amido group, a sulfo group, a cyano group or an aryl group. Two of R ¹²¹ to R ¹²⁴ may be bonded to each other to form a ring.

As R ¹²¹ to R ¹²⁴ , a hydrogen atom, a halogen atom and an alkyl group are preferable, and at least two of R ¹²¹ to R ¹²⁴ 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.

Preferable examples of the compound represented by the above general formula (OS-1) include the general formulas described in paragraphs 0194 to 0202 of JP-A No. 2011-221496 and exemplified compounds thereof.

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 represents 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)

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

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

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

Of the above 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 as long as at least one of the heteroaryl rings is a heteroaromatic ring, and examples thereof include a heteroaromatic ring and a benzene ring Or may be corrugated.

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

Of the above-mentioned general formulas (OS-3) to (OS-5), one or two of R ²³ , R ²⁶ and R ²⁹ present in two or more of the compounds are preferably an alkyl group, More preferably one 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.

In the general formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have a substituent. Here, examples of the substituent which the alkyl group or aryl group in R ²³ , R ²⁶ and R ²⁹ may have include the same groups as the substituent which the alkyl group or aryl group in R ²² , R ²⁵ and R ²⁸ may have .

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.

Examples of the halogen atom for R ²³ , R ²⁶ and R ²⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Of these, a chlorine atom and a bromine atom are preferable.

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.

The formula (OS-3) ~ formula (OS-5) of, n1 ~ n3 each independently represents 1 or 2, when X ¹ ~ X ³ is O, n1 ~ n3 are, respectively independently 1 When X ¹ to X ³ are S, it is preferable that n ¹ to n ³ are each independently 2.

The formula (OS-3) ~ formula (OS-5) of, R ^24, R ²⁷ and R ³⁰ are each independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group, or an alkoxy sulfonyl . Among them, it is preferable that R ²⁴ , R ²⁷ and R ³⁰ are each independently 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 the general formulas (OS-3) to (OS-5) is preferably an alkyloxy group having 1 to 30 carbon atoms which may have a substituent .

For the preferable ranges or exemplary compounds of the general formulas (OS-3) to (OS-5), reference may be made to the description of paragraphs 0171 to 0200 of JP-A No. 2011-227449.

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

The photosensitive resin composition of the present invention may contain a 1,2-quinonediazide compound as a photoacid generator which is sensitive to an actinic ray. The 1,2-quinonediazide compound generates a carboxyl group by a sequential photochemical reaction, but its quantum yield is necessarily 1 or less.

&Lt; (C) The compound represented by the general formula (I) (specific sulfur-containing compound)

The photosensitive resin composition of the present invention comprises (C) a compound represented by the following general formula (I). By employing a specific sulfur-containing compound, it is possible to improve the sensitivity while achieving the improvement of the adhesion, and to obtain a cured product having high heat-resistant transparency.

The compound of formula (I)

(In the general formula (I), R ¹¹ and R ¹² each represent a group containing at least one of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group, and n represents an integer of 2 to 4.)

R ¹¹ and R ¹² each represent a group containing at least one of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group, and is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an alkyl group or an aryl group. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent.

The aliphatic hydrocarbon group is preferably an alkyl group. The alkyl group may have a substituent, and may be any of alkyl groups of straight chain, branched chain and cyclic. The number of carbon atoms of the alkyl group is preferably 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, in the absence of a substituent. (R is a hydrogen atom or a substituent), -NHCOR (R is a hydrogen atom or a substituent (s), and the substituent is not particularly limited as long as it does not deviate from the object of the present invention. ), A halogen atom, a cyano group, a sulfide group and an aryl group. R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.

The aromatic hydrocarbon group is preferably an aryl group. The aryl group may have a substituent, may be monocyclic or condensed. The number of carbon atoms in the aryl group is preferably from 6 to 11, more preferably 6. The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. Examples of the substituent which the aryl group may have include -OH, -C (= O) -OR (R is a hydrogen atom or a substituent), -NHCOR (R is a hydrogen atom or a substituent), an alkyl group, a halogen atom, a cyano group, Aryl groups are exemplified. R is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.

The group containing a heterocyclic group preferably contains a nitrogen atom. The heterocyclic ring may be an aromatic heterocyclic ring, an aliphatic heterocyclic ring, or a 5-membered ring or a 6-membered ring. The ring may be monocyclic or condensed.

n is preferably 2 or 3, and more preferably 2.

(C) The compound represented by the general formula (I) is preferably represented by the following general formula (II).

(Wherein R ²¹ and R ²² each represent a hydrogen atom, an alkyl group or an aryl group, L ¹ and L ² each represent an alkylene group or an arylene group, and L ¹¹ and L ²² each represent * -OC ( = O) - or * -NH-C (= O) - and coupled to L ¹ or L ² shown in the side *).

R ²¹ and R ²² are preferably a hydrogen atom or an alkyl group, more preferably an alkyl group, and more preferably an alkyl group having from 1 to 10 carbon atoms.

L ¹ and L ² each represent an alkylene group or an arylene group, and an alkylene group is preferable. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and particularly preferably 2 carbon atoms. The alkylene group may be substituted with an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a sulfide group or a carbonyl group. However, the alkylene group is represented by - (CH ₂ ) _m -, and m is preferably an integer of 2 or more. m is more preferably 2 to 4.

The number of carbon atoms of the arylene group is preferably 6 to 12, more preferably 6. The allylene group may be substituted by an unsubstituted alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a sulfide group, a carbonyl group or the like. The arylene group is preferably a phenylene group.

L ¹¹ and L ²² each represents * -OC (= O) - or * -NH-C (= O) -, and more preferably * -OC (= O) -.

The specific sulfur-containing compound used in the present invention preferably has a molecular weight of 100 to 1,000, more preferably 200 to 800, and even more preferably 200 to 600. With such a range, the adhesion can be promoted without being volatilized under the baking condition, and the sensitivity can be improved.

In the photosensitive resin composition of the present invention, the specific sulfur-containing compound (C) is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the solid content in the photosensitive resin composition , And 1.0 to 4.0 parts by mass are most preferably used. Two or more species may be used in combination. In the case of two or more species, the total amount is in the above range.

Hereinafter, preferred examples of the specific sulfur-containing compound (C) usable in the present invention are shown. It is needless to say that the present invention is not limited to these.

&Lt; (D) Solvent >

The photosensitive resin composition of the present invention contains (D) a solvent. The photosensitive resin composition of the present invention is produced by dissolving the components (A) to (D) as essential components, the components (E) to (I) It is preferable to prepare it as a solution.

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, and lactones.

As the solvent (D) used in the photosensitive resin composition of the present invention, for example, the description of paragraphs 0166 to 0169 of Japanese Patent Laid-Open Publication No. 2011-215580 may be taken into consideration.

These solvents may be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably one or two kinds of solvents in combination, 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, and it is most preferable to use propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether in combination.

The component D is preferably a solvent having a boiling point of 130 캜 or more and less than 160 캜, a solvent having a boiling point of 160 캜 or more, or a mixture thereof, a solvent having a boiling point of 130 캜 or more and less than 160 캜, More preferably a mixture of a solvent having a boiling point of 130 ° C or more and less than 160 ° C and a solvent having a boiling point of 160 ° C or more and 200 ° C or less.

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 DEG C) can be exemplified.

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 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), and 1,3-butylene glycol diacetate (boiling point 232 ° C).

The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by mass per 100 parts by mass of the total resin component (preferably solid content, more preferably the above-mentioned (A) copolymer) in the photosensitive resin composition More preferably 100 to 2,000 parts by mass, and still more preferably 150 to 1,500 parts by mass.

<Other ingredients>

(E) a sensitizer, (F) a cross-linking agent, (G) a contact improving agent (B), (C) , (H) a basic compound, and (I) a surfactant. Further, known additives such as plasticizers, heat radical generators, antioxidants, thermal acid generators, ultraviolet absorbers, thickeners, development promoters, and organic or inorganic precipitation inhibitors may be added to the positive photosensitive resin composition of the present invention .

(E) 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 the actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator to generate electron movement, energy transfer, heat generation, and the like. As a result, the photoacid generator is decomposed by a chemical change to generate an acid. Examples of preferred sensitizers include compounds having an absorption wavelength in any one of the wavelength ranges from 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- Xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone (e.g., anthracene), xanthene (such as fluorescein, eosin, erythrosine, rhodamine B and rose bengal) Tonnes), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines (e.g., merocyanine, carbomerocyanine), rhodacyanines, (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, acridine, acridine), acridine (for example, thionine, methylene blue, toluidine blue) 2-chloroacridone), anthraquinones (for example, anthraquinone), squaryliums (for example, squarylium), styryls, (For example, 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).

Among 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 to the photosensitive resin composition of the present invention is preferably 0 to 1,000 parts by weight, more preferably 10 to 500 parts by weight, and still more preferably 50 to 200 parts by weight per 100 parts by weight of the photoacid generator of the photosensitive resin composition Is more preferable.

Two or more species may be used in combination.

(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 the crosslinking reaction is caused 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, or a compound having at least one ethylenically unsaturated double bond in the molecule described below may be added.

Of these crosslinking agents, compounds having two or more epoxy groups or oxetanyl groups in the molecule are preferable, and epoxy resins are particularly preferable.

The amount of the crosslinking agent added to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, more preferably 2 to 10 parts by weight, relative to 100 parts by weight of the total solid content of the photosensitive resin composition desirable. When added in this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. The crosslinking agent may be used in combination with a plurality of the crosslinking agents. In that 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, a commercially available product described in paragraph No. 0189 of Japanese Patent Laid-Open Publication No. 2011-221494 can be given.

In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- 501, EPPN-502 (manufactured by ADEKA), Denacol EX-611, EX-612, EX- EX-821, EX-821, EX-821, EX-821, EX-821, DLC-203, DLC-203, EX-841, EX-911, EX-941, EX-920, EX- YH-302, YH-315, YH-324 and YH-325 (manufactured by NAGASE CAM TEXT), YH-300, YH-301, (Shinnetsu Tetsukagaku Co., Ltd.), and the like.

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

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

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

As the other crosslinking agent, the crosslinking agent containing an alkoxymethyl group and compounds having at least one ethylenically unsaturated double bond described in paragraphs 0107 to 0108 of JP-A-2012-8223 may be preferably used.

(G) Adhesion improver

The photosensitive resin composition of the present invention may contain (G) an adhesion improver. The adhesion modifier (G) that can be used in the photosensitive resin composition of the present invention improves the adhesion of an inorganic substance to be a base material, for example, a silicon compound such as silicon, silicon oxide, silicon nitride, and metal such as gold, . Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the adhesion improver (G) used in the present invention is for the purpose of improving the interface, and any known one can be used without particular limitation.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? - Methacryloxypropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? - Silane, and vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is even more preferable, and 3-glycidoxypropyltrimethoxy Silane is even more preferred. These may be used singly or in combination of two or more. These are effective in improving the adhesion to the substrate and also in adjusting the taper angle with the substrate.

The content of the (G) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition.

(H) Basic compound

The photosensitive resin composition of the present invention may contain (H) a basic compound. (H) As the basic compound, any of those used in the chemically amplified resist can be used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids and the like. Specific examples of these compounds include the compounds described in paragraphs 0204 to 0207 of JP-A No. 2011-221494.

The basic compounds usable in the present invention may be used singly or in combination of two or more kinds, but it is preferable to use two or more kinds of them in combination, more preferably two kinds of them, It is more preferable to use them in combination.

The content of the (H) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.2 part by mass based on 100 parts by mass of the total solid content in the photosensitive resin composition.

(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 can be used, but preferred surfactants are nonionic surfactants.

Examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid esters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Trade name) manufactured by Shin-Etsu Chemical Co., Ltd.), polyfluoro (manufactured by Kyowa Chemical Co., Ltd.), F-top (manufactured by JEMCO), megapack (manufactured by DIC) (Manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA) and SH-8400 (Toray Dow Corning Silicon).

Further, compounds described in paragraphs 0185 to 0188 of Japanese Patent Laid-Open Publication No. 2011-215580 as a surfactant can also be employed.

These surfactants may be used alone 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 parts by mass to 10 parts by mass, more preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the total solid content in the photosensitive resin composition More preferably 0.01 to 3 parts by mass, still more preferably 0.01 to 1 part by mass.

Antioxidant

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

As such an antioxidant, for example, reference may be made to paragraph No. 0104 of Japanese Patent Application Laid-Open No. 2007-073609, the contents of which are incorporated herein by reference.

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

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

In the present invention, it is also preferable to use a sulfonic acid ester which generates an acid by heat without generating an acid substantially by irradiation with exposure light.

The fact that the acid is not substantially generated by the irradiation of the exposure light can be judged to be no change in the spectrum by IR spectrum or NMR spectrum measurement before and after exposure of the compound.

The molecular weight of the sulfonic acid ester is preferably from 230 to 1,000, more preferably from 230 to 800.

The sulfonic acid ester which can be used in the present invention may be commercially available or may be synthesized by a known method. The sulfonic acid ester can be synthesized, for example, by reacting sulfonyl chloride or sulfonic anhydride with the corresponding polyhydric alcohol under basic conditions.

The content of the thermal acid generator in the photosensitive resin composition is preferably 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the total content of the component (A).

[Acid proliferating agent]

An acid generator can be used for the purpose of improving the sensitivity of the photosensitive resin composition of the present invention.

The acid-proliferating agent usable 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 is a compound stably present in the absence of acid. Such a compound accelerates the reaction in accordance with the progress of the reaction because one or more acids are increased by one reaction. However, since the generated acid itself causes self-decomposition, the intensity of the acid generated here is the acid dissociation constant pKa Is preferably 3 or less, and particularly preferably 2 or less.

Specific examples of acid proliferating agents are described in paragraphs 0203 to 0223 of Japanese Patent Application Laid-Open No. 10-1508, paragraphs 0016 to 0055 of Japanese Patent Application Laid-Open No. 10-282642, and Japanese Patent Publication No. 9-512498, On page 47 to the second line.

Specifically,

And the like.

Examples of the acid growth agent usable in the present invention include acids having a pKa of 3 or less such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, phenylphosphonic acid, etc., Can be exemplified.

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

[Development promoter]

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

As the development accelerator, any compound having a phenomenon of promoting development may be used. However, it is preferably a compound having at least one structure selected from the group consisting of a carboxyl group, a phenolic hydroxyl group and an alkyleneoxy group, and a carboxyl group or a phenolic hydroxyl group Is more preferable, and a compound having a phenolic hydroxyl group is most preferable.

The molecular weight of the development accelerator (M) is preferably 100 to 2,000, more preferably 100 to 1,000, and most preferably 100 to 800.

As an example of the phenomenon promoter, reference may be made to paragraphs 0217 to 0217 of Japanese Patent Laid-Open Publication No. 2011-221496, 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 0.5 to 30 parts by mass, from the viewpoint of sensitivity and residual film ratio, when 100 parts by mass of the component (A) Most preferably 10 to 10 parts by mass.

As the other additives, the heat radical generator and thermal acid generation system described in paragraphs 0120 to 0121 of Japanese Patent Application Laid-Open Publication No. 2012-8223 can be used.

[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 positive photosensitive resin composition of the present invention onto a substrate

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

(3) a step of exposing by an actinic ray

(4) Step of developing with aqueous developer

(5) Post-baking process for thermosetting

Each step will be described below in order.

(1), it is preferable to apply the positive photosensitive resin composition of the present invention to a substrate to form a wet film containing a solvent.

In the solvent removal step (2), the solvent is removed from the applied film by reduced pressure (vacuum) and / or heating to form a dried coating film on the substrate.

(3), an actinic ray having a wavelength of 300 nm or more and 450 nm or less is irradiated to the obtained coating film. In this step (B), the photoacid generator is decomposed to generate acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the (A) copolymer is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.

Post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) is performed to accelerate the hydrolysis reaction in the region where the acid catalyst is generated. PEB can promote the generation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for PEB 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.

The acid decomposable group in the constituent unit represented by the formula (a1-1) 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 A positive image can be formed by development without necessarily performing PEB. However, in the method for producing a cured film of the present invention, the cured film obtained by performing the post-baking step (5) using the photosensitive resin composition of the present invention The heat flow can be reduced. Therefore, when the cured film obtained by the method for producing a cured film of the present invention is used, for example, on a substrate as a resist, the resolution of the pattern hardly deteriorates even if the cured film of the present invention is heated together with the substrate. In the present specification, the term &quot; heat flow &quot; means that the cross-sectional shape of the patterned cured film formed by the exposure and development processes is deformed when the cured film is heated (preferably 180 ° C or higher, more preferably 200 ° C to 240 ° C) , Taper angle, and the like are deteriorated.

In the developing step of (4), the liberated copolymer having a carboxyl group or 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 phenolic hydroxyl group which is easily dissolved in an alkaline developer.

(A1) by thermally decomposing an acid-decomposable group in the constituent unit (a1) to produce a carboxyl group or a phenolic hydroxyl group in the post-baking step of the step (5) to cross the crosslinking group, the crosslinking agent and the like of the constituent unit A cured film can be formed. The heating is preferably performed at a high temperature of 150 ° C or higher, more preferably 180 ° C to 250 ° C, and particularly preferably 200 ° C to 240 ° C. The heating time can be suitably set according to the heating temperature and the like, but is preferably within a range of 10 to 120 minutes.

When a step of irradiating the development pattern with an actinic ray, preferably ultraviolet light, to the development pattern is added before the postbaking process, the crosslinking reaction can be promoted by the acid generated by the actinic light irradiation.

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 thermosetting by the post baking process of step (5) is used as a dry etching resist, dry etching such as ashing, plasma etching, ozone etching and the like can be performed as the etching process.

 Next, a method for forming a cured film using the photosensitive resin composition of the present invention will be described in detail.

&Lt; Preparation method of photosensitive resin composition >

The essential components of (A) to (D) are mixed in a predetermined ratio in an arbitrary manner, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which the components (A) and (C) are respectively dissolved in a solvent (D), and then they are mixed at a predetermined ratio to prepare a resin composition. The composition solution prepared as described above can be provided for use after being filtered using a filter having a pore diameter of 0.2 mu m or the like.

<Application Process and Solvent Removal Process>

A desired dry film can be formed by applying the photosensitive resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). Examples of the substrate include a polarizing plate in the production of a liquid crystal display device, and a glass plate in which a black matrix layer and a color filter layer are formed as required and a transparent conductive circuit layer is formed thereon. The method of applying the photosensitive resin composition to the substrate is not particularly limited, but in the present invention, it is preferable to apply the photosensitive resin composition to the substrate. The method of applying the composition to the substrate is not particularly limited, and for example, slit coating, spraying, roll coating, spin coating and the like can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large-size substrate. If it is manufactured on a large substrate, it is preferable because productivity is high. Here, a large substrate means a substrate having a size of 1 m or more and 5 m or less on each side.

(2) The heating conditions in the solvent removal step are those in which the acid-decomposable groups in the constituent unit (a1) in the component (A) in the unexposed portion are decomposed to make the component (A) not soluble in the alkali developer, But it is preferably about 80 to 130 DEG C for about 30 to 120 seconds.

&Lt; Exposure step and development step (pattern formation method) >

In the exposure step, the substrate on which the coating film is formed is irradiated with an actinic ray through a mask having a predetermined pattern. After the exposure step, the substrate is subjected to heat treatment (PEB) as required, and in the development step, the exposed area is removed using an alkaline developer to form an image pattern.

(436 nm), i-line (365 nm), h-line (405 nm), and the like can be used for exposure by the active light beam. Examples of the exposure light include a low pressure mercury lamp, a high pressure mercury lamp, ) Can be preferably used as the active light ray having a wavelength of 300 nm or more and 450 nm or less. If necessary, the irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

The developing solution used in the developing step preferably contains a basic compound. Examples of the basic compound include alkali metal oxides 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.

The developer pH is preferably 10.0 to 14.0.

The development time is preferably 30 to 180 seconds, and the developing method may be any of a puddle method and a dipping method. After the development, the flowing water is cleaned for 30 to 90 seconds to form a desired pattern.

After the development, a rinsing process may be performed. In the rinsing step, the developed substrate is cleaned with pure water or the like to remove the attached developing solution and remove the developing residue. As the rinsing method, known methods can be used. For example, a shower rinse or a dipping rinse can be exemplified.

&Lt; Post baking step (crosslinking step) >

The pattern corresponding to the unexposed area obtained by the development is heated at a predetermined temperature, for example, 180 to 250 DEG C for a predetermined time, for example, 5 to 90 minutes on a hot plate, using a heating apparatus such as a hot plate or an oven And in the case of an oven for 30 to 120 minutes, a crosslinking reaction is carried out to form a protective film or an interlayer insulating film excellent in heat resistance and hardness. In addition, when the heat treatment is performed, transparency can be 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 can 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 may be performed using a known heating method such as a hot plate, an oven, or an infrared heater.

Further, an acid is generated from the component (B) present in the unexposed portion by post-baking (re-exposure / post-baking) after re-exposure to the substrate on which the pattern has been formed before the heat treatment by an actinic ray, As a catalyst for accelerating the reaction.

That is, it is preferable that the method of forming a cured film of the present invention includes a re-exposure step of re-exposing by the actinic ray between the developing step and the post-baking step. The exposure in the re-exposure step may be performed by the same means as in the exposure step, but in the re-exposure step, it is preferable to perform the entire exposure on the side of the substrate where the film is formed by the photosensitive resin composition of the present invention.

The preferable exposure amount of the re-exposure process is 100 to 1,000 mJ / cm &lt; 2 &gt;.

[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 suitably 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.

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

[Organic EL display device, liquid crystal display device]

The organic EL display device and the liquid crystal display device of the present invention are characterized by including the cured film of the present invention.

The organic EL display device or the liquid crystal display device of the present invention is not particularly limited but may be any of various known organic EL display devices having various structures, such as a liquid crystal display device having a flattening film or an interlayer insulating film formed using the photosensitive resin composition of the present invention A liquid crystal display device can be exemplified.

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 purposes. For example, a protective film for a color filter, a spacer for keeping the thickness of the liquid crystal layer constant in a liquid crystal display device, a microlens formed on a color filter in a solid-state image pickup device or the like Can be used.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. Sectional schematic view of a substrate in a bottom-emission organic EL display device, and has a planarizing film 4. Fig.

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

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

On the planarizing film 4, a bottom-emission organic EL element is formed. That is, the 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 periphery of the first electrode 5. By forming the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in a subsequent step Can be prevented.

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

Fig. 2 is a conceptual cross-sectional view showing an example of the 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 its back surface and the liquid crystal panel is composed of a TFT corresponding to all pixels arranged between two glass substrates 14, 16 are disposed on the substrate. In each element formed on the glass substrate, an ITO transparent electrode 19 for forming a pixel electrode is wired through a contact hole 18 formed in the cured film 17. 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 formed.

Example

Hereinafter, the present invention will be described in more detail by way of examples. The materials, amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be suitably 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 specified, &quot; part &quot; and &quot;% &quot; are based on mass.

(A) the polymer component

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

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

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

MATHF: tetrahydro-2H-furan-2-yl methacrylate (synthetic)

MAEVE: 1-ethoxyethyl methacrylate (synthetic)

MATHP: tetrahydro-2H-pyran-2-yl methacrylate (Shin Nakamura Kagaku Kogyo Co., Ltd.)

StOEVE: 4- (1-ethoxyethyloxy) styrene (synthetic)

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

OXE-30: Methacrylic acid (3-ethyloxetan-3-yl) methyl (Osaka Yukikagaku Kogyo Co., Ltd.)

NBMA: n-butoxymethyl acrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)

HEMA: 2-hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

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

DCPM: dicyclopentanyl methacrylate (Hitachi Kasei High School)

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

PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)

HS-EDM: Hyosolve EDM (manufactured by Tohoku Kagaku Kogyo Co., Ltd.)

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was cooled to 15 DEG C 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 magnesium sulfate. The insoluble material was filtered off and concentrated under reduced pressure at 40 ° C or lower. The oil was distilled under reduced pressure to obtain 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg as a colorless oil 80%).

<Synthesis of MAEVE>

Phenothiazine (0.5 part) was added to ethyl vinyl ether (144.2 parts, 2 molar equivalents), methacrylic acid (86.1 parts, 1 molar equivalent) was added dropwise while cooling the reaction system to 10 DEG C or lower, ) For 4 hours. After adding pyridinium p-toluenesulfonate (5.0 parts), the mixture was stirred at room temperature for 2 hours and allowed to stand at room temperature overnight. To the reaction mixture, 5 parts of sodium hydrogencarbonate and 5 parts of sodium sulfate were added and the mixture was stirred at room temperature for 1 hour. The insoluble materials were filtered off and concentrated under reduced pressure at 40 DEG C or lower. The residue was distilled under reduced pressure, bp.) 43 ~ 45 占 폚 / 7 mmHg fraction 1-ethoxyethyl methacrylate (MAEVE) (134.0 parts) was obtained as a colorless oil.

&Lt; Synthesis of Copolymer (A) A-1 >

HS-EDM (82 parts) was heated and stirred in a nitrogen stream at 90 占 폚. , MAA [6 parts (9.5 mol% equivalent)], HEMA [11 parts (12.5 mol% equivalent)], MATFF [43 parts (45.5 mol% equivalent)], OXE- A mixed solution of a radical polymerization initiator V-601 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 4.3 parts) and PGMEA (82 parts) was added dropwise over 2 hours and further reacted at 90 DEG C for 2 hours to obtain polymer A- Of PGMEA solution (solid concentration: 40%).

The polymer A-1 thus obtained had a weight average molecular weight of 15,000 as determined by gel permeation chromatography (GPC).

&Lt; Synthesis of other polymer >

Each of the copolymers was synthesized in the same manner as in the synthesis of the polymer A-1, except that each of the monomers used and the amounts thereof were changed to those described in the following table.

In the above table, numerical values in the tables without specific units are in units of mol%. The numerical value of the polymerization initiator is mol% based on 100 mol% of the monomer component. The solid concentration is expressed as monomer weight / (monomer weight + solvent weight) x 100 (unit weight%). When V-601 was used as the polymerization initiator, the reaction temperature was set at 90 ° C, and when V-65 was used, the reaction temperature was set at 70 ° C.

(B)

B-1: Irgacure PAG-103 (manufactured by BASF)

B-2: PAI-101 (trade name, manufactured by Midori Kagaku)

B-3: Structure shown below (Synthesis example will be described later)

B-4: Structure shown below, TPS-1000 (manufactured by Midori Kagaku)

Ts represents a tosyl group (p-toluenesulfonyl group).

<Synthesis of B-3>

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 ml), and the mixture was heated to 40 占 폚 for 2 hours. 4N HCl aqueous solution (60 ml) was added dropwise to the reaction solution under ice-cooling, and ethyl acetate (50 ml) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 DEG C for 1 hour. 2N HCl aqueous solution (60 mL) was added thereto to separate the layers. The organic layer was concentrated, and crystals were dissolved in 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 cooling, 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 heated to room temperature and reacted for 1 hour. Water (50 ml) was added to the reaction solution, and the precipitated crystals were filtered and then slurry was rinsed with methanol (20 ml), followed by filtration and drying to obtain 2.3 g of B-6 (the above structure).

In addition, ¹ H-NMR spectrum of _{B-6 (300MHz, CDCl 3} ) is δ = 8.3 (d, 1H) , 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 ( (d, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6

(C) a specific sulfur-containing compound (a compound represented by the general formula (I)

C-2: dibutyl disulfide, manufactured by Aldrich Co.

C-5: Diisopentyl disulfide, manufactured by Tokyo Kasei Co., Ltd.

C-10: dimethyl dithiodipropionate, manufactured by Wako Pure Chemical Industries, Ltd.

C-11: dithiodipropionic acid, manufactured by Tokyo Kasei Co., Ltd.

C-16: diphenyl disulfide, manufactured by Aldrich Co.

C-20: bis (2-benzamidophenyl) disulfide, manufactured by Tokyo Kasei Co., Ltd.

C-31: dipropyltrisulfide, synthetic

C-32: diphenyltrisulfide, synthetic product

C-33: diphenyl tetrasulfide, synthetic

C-31 is described in J. Am. Chem. Soc. 1952, 74, 3982, and C-32 are described in J. Org. Chem. 1980, 45, 5155, and C-33 are described in J. Org. Chem. 2003, 68, 2489.

(D) Solvent

HS-EDM (diethylene glycol ethyl methyl ether) manufactured by Toho Kagaku Co.,

(E) Thinner

E-1: DBA (dibutoxyanthracene) manufactured by Kawasaki Kasei Kogyo Co., Ltd.

(F) Crosslinking agent

F-1: JER157S65 (trade name, phenol novolak type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd.)

F-2: NIKARAK MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)

F-3: Trimethylolpropane triacrylate (Toocosece)

(G) Adhesion improver

G-1: KBM-403 (trade name, 3-glycidoxypropyltrimethoxysilane, structure shown below, manufactured by Shin-Etsu Chemical Co., Ltd.)

(H) Basic compound

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

H-2: Triphenylimidazole

(I) Surfactant

I-1: polyoxyethylene sorbitan fatty acid ester type surfactant (Solzhen 90, Daiichi Kogyo Seiyaku Co., Ltd.)

I-2: Silicone surfactant SH-8400 (Toray, Dow Corning Silicone)

(R) Comparative compound

In the comparative examples, the following compounds were used as substitute components of (C) compounds represented by the general formula (I).

R-1: Dibutylthiourea, manufactured by Wako Pure Chemical Industries, Ltd.

R-2: Diorophenylthiourea, manufactured by Wako Pure Chemical Industries, Ltd.

R-3: methyl-3-mercaptopropionate, manufactured by SC Yuki Kagaku Co., Ltd., trade name MPM

R-4: dimethyl thiodipropionate, SC, manufactured by Yuki Kagaku Co., Ltd., TDM

R-5: diphenyl sulfide, manufactured by Wako Pure Chemical Industries, Ltd.

R-6: Dibutyl sulfide, manufactured by Wako Pure Chemical Industries, Ltd.

R-7: thiodipropionic acid, manufactured by Wako Pure Chemical Industries, Ltd.

[Example 1]

Each component was dissolved and mixed so that the composition of the table was obtained and filtered through a polytetrafluoroethylene filter having a pore size of 0.2 탆 to obtain a photosensitive resin composition of Example 1.

[Other Embodiments and Comparative Examples]

A photosensitive resin composition of the following examples and comparative examples was prepared by dissolving and mixing in the same amount as in Example 1, except that each compound used in Example 1 was changed to the compound shown in the following table.

&Lt; Evaluation of sensitivity &

Each of the photosensitive resin compositions was coated with a slit on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) surface-treated with hexamethyldisilazane vapor for 1 minute, baked on a hot plate at 85 deg. C / And the solvent was volatilized to form a photosensitive resin composition layer having a film thickness of 4.0 m.

Subsequently, the resultant photosensitive resin composition layer was exposed through a mask of 9 mu m hole pattern using PLA-501F exposure device (super high pressure mercury lamp) manufactured by Canon Inc. Then, the exposed photosensitive composition layer was developed with an alkaline developer (0.4 mass% of tetramethylammonium hydroxide aqueous solution) at 24 DEG C for 60 seconds and then rinsed with ultrapure water for 20 seconds.

By these operations, the optimum exposure amount (Eopt) at the time of forming the hole pattern of 9 mu m was taken as the sensitivity. The evaluation criteria are as follows. A larger value is preferable, and a range of 6 to 4 is practical.

6: Less than 30 mJ / cm2

5: 30 mJ / cm2 or more and less than 60 mJ / cm2

4: 60mJ / cm2 or more and less than 90mJ / cm2

3: 90 mJ / cm 2 or more and less than 120 mJ / cm 2

2: 120 mJ / cm 2 or more and less than 150 mJ / cm 2

1: 150 mJ / cm 2 or more

<Evaluation of transparency>

A coating film having a film thickness of 3.0 占 퐉 was formed on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)). Subsequently, exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 + manufactured by Canon Inc.). Puddle development with an alkaline developer (2.38 wt% tetramethylammonium hydroxide aqueous solution) at 23 DEG C for 65 seconds and rinsed with ultrapure water for 1 minute. The coated film after development was irradiated with light of 300 mJ / cm 2 at a wavelength of 365 nm using an ultra-high pressure mercury lamp, and then heated in an oven at 220 캜 for 45 minutes. The transmittance of this cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: Hitachi, Ltd.). The lowest transmittance is shown in the table (fresh transparency).

Further, it was heated in an oven at 230 DEG C for 2 hours. The transmittance of the cured film was similarly measured (permeability after heat resistance).

&Lt; Evaluation of adhesion &

Each of the photosensitive resin compositions was coated with a slit on an ITO (indium tin oxide) substrate, a Mo (molybdenum) substrate, and a titanium (Ti) substrate and then the solvent was removed by heating on a hot plate at 90 ° C for 120 seconds. Mu m of the photosensitive resin composition layer. The thus-obtained photosensitive resin composition layer was exposed in a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc. so that the cumulative irradiation dose was 300 mJ / cm 2 (illuminance: 20 mW / cm 2, i-line) Lt; 0 &gt; C for 1 hour to obtain a cured film. Sheets were inserted into the cured films at intervals of 1 mm vertically and horizontally using a cutter, and a tape peeling test was conducted using a scotch tape. The adhesion between the cured film and the substrate was evaluated from the area of the cured film transferred on the back surface of the tape. The results are shown in the following table. The smaller the numerical value is, the higher the adhesion with the underlying 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 of 5% or more

<Evaluation of preservability>

The obtained photosensitive resin composition was allowed to stand in a thermostatic chamber at 30 占 폚 for 2 weeks, and the above sensitivity evaluation was carried out again. The results are shown in the following table. The smaller the variation in sensitivity is, the more excellent the storage stability is.

A: Sensitivity variation less than 5%

B: Sensitivity fluctuation is 5% or more

<Overall evaluation>

When the photosensitive resin composition and the cured film were evaluated for sensitivity, transparency, adhesion, and storage stability, the following comprehensive evaluation was performed.

5: The best performance, the practicality is abundant

4: Good performance and practicality

3: Practical coverage, but expected improvement

2: Difficulty in practical use due to limited storage period or usage

1: Not practicable

As is clear from the above results, the photosensitive resin composition of the present invention is excellent in sensitivity, heat-resistant transparency, adhesion, and storage stability. On the other hand, in the photosensitive resin composition of the comparative example, one of the characteristics was remarkably deteriorated. Concretely, the sensitivity decreases when the basic compound is added. Further, the sensitivity of the thiourea compound is deteriorated due to its basicity, and the thiol compound has a problem that the sensitivity is changed by an acetal exchange reaction with a resin having an acetal structure.

[Example 30]

An organic EL display device using a thin film transistor (TFT) was produced by the following method (see Fig. 1).

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. Subsequently, a contact hole (not shown) is formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 did. The wiring 2 is for connecting the organic EL element formed between the TFTs 1 or the subsequent steps and the TFT 1. [

The flattening film 4 was formed on the insulating film 3 in a state in which irregularities due to the wirings 2 were filled in order to planarize the irregularities due to the formation of the wirings 2. 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, pre-baking (90 DEG C x 2 minutes) on a hot plate, (365 nm) was irradiated with 45 mJ / cm 2 (illuminance: 20 mW / cm 2) and then developed with an aqueous alkali solution to form a pattern, and heat treatment was performed at 230 ° C. for 60 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 film thickness of the prepared planarizing film 4 was 2,000 nm.

Subsequently, a bottom-emission organic EL device was formed on the obtained planarization film 4. Then, First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, resist was applied, prebaked, 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 etchant. Thereafter, the resist pattern was separated at 50 캜 by using a resist stripper (Remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Then, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. An insulating film 8 was formed on the insulating film 8 by the same method as above using the photosensitive resin composition of Example 18. By forming the insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in a subsequent step.

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

An active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements are connected as described above was obtained. As a result of applying a voltage through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was highly reliable.

[Example 31]

In the active matrix type liquid crystal display device shown in Fig. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows to obtain a liquid crystal display device of Example 31. Fig.

That is, the photosensitive resin composition of Example 18 was used to form a cured film 17 as an interlayer insulating film in the same manner as the method of forming the planarizing film 4 of the organic EL display device in the above-mentioned example.

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

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 (15)

(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 an acid group protected by 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 residue protected by an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group,
(B) a photoacid generator,
(C) a compound represented by the following general formula (I), and
(D) a solvent.
The compound of formula (I)

(In the general formula (I), R ¹¹ and R ¹² each represent a group containing at least one of an aliphatic hydrocarbon group, an aromatic hydrocarbon group and a heterocyclic group, and n represents an integer of 2 to 4.) The method according to claim 1,
In the general formula (I), R ¹¹ and R ¹² are each an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The method according to claim 1,
In the general formula (I), each of R ¹¹ and R ¹² is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 11 carbon atoms. The method according to claim 1,
(C) A photosensitive resin composition characterized in that the compound represented by the general formula (I) is represented by the following general formula (II).

(Wherein R ²¹ and R ²² each represent a hydrogen atom, an alkyl group or an aryl group, L ¹ and L ² each represent an alkylene group or an arylene group, L ¹¹ and L ²² each represent a * -OC (= O) - or * -NH-C (= O). * On the * side binds to L ¹ or L ² . 5. The method according to any one of claims 1 to 4,
Wherein the constituent unit (a1) is a constituent unit in which the carboxyl group has a moiety protected in an acetal form. 5. The method according to any one of claims 1 to 4,
Wherein the structural unit (a1) is a structural unit represented by the following formula (A2 ').
The formula (A2 ')

(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, R ¹ or R ² And R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group. 7. The method according to any one of claims 1 to 6,
Wherein the crosslinkable group is at least one member selected from the group consisting of an epoxy group, an oxetanyl group and -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). 8. The method according to any one of claims 1 to 7,
Wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition. 9. The method according to any one of claims 1 to 8,
(B) the photoacid generator is an oxime sulfonate compound or an onium salt compound. (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 9 on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition,
(3) a step of exposing by actinic radiation,
(4) a step of developing with an aqueous developer, and
(5) a post-baking step of thermally curing the cured film. 11. The method of claim 10,
And a step of performing front exposure before the post-baking step after the developing step. The method according to claim 10 or 11,
Wherein the substrate is a metal substrate. A cured film characterized by being formed by curing the photosensitive resin composition according to any one of claims 1 to 9. 14. The method of claim 13,
Wherein the cured film is an interlayer insulating film. A liquid crystal display device or an organic EL display device having the cured film according to claim 13 or 14.

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