KR101703718B1 - Photosensitive resin composition, method for producing cured film, cured film, organic el display device and liquid crystal display device - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a cured film and a process for producing the same, an organic EL display device, and a process for producing the same, which can provide a cured film excellent in solvent resistance and heat resistance and transparency, , And a liquid crystal display device.
(A) a structure represented by the formula (Ia) for producing a carboxy group by an acid or a structure represented by the formula (Ib) for producing a phenolic hydroxyl group by an acid, (A2) having a structure represented by the formula (IIb) that generates a phenolic hydroxyl group by an acid, and a monomer unit (a3) having a structure represented by the formula A polymer containing a monomer unit (a3) having an epoxy group and / or an oxetanyl group, (B) a photoacid generator, and (C) a solvent.

Description

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

In an organic EL display device, a liquid crystal display device, or the like, a patterned interlayer insulating film is provided. In forming the interlayer insulating film, the number of steps for obtaining a desired pattern shape is small, and furthermore, a sufficient level of flatness is obtained, so that a photosensitive resin composition is widely used.

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

As such a photosensitive resin composition, for example, Patent Document 1 discloses a composition comprising (A) an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) a radically polymerizable compound having an epoxy group, and (c) A resin soluble in an aqueous chain alkaline solution and (B) a radiation-sensitive (radiation-sensitive) acid-generating compound.

Patent Document 2 discloses a resin composition comprising (A) a high molecular weight substance having an acetal structure and / or a ketal structure and an epoxy structure, and having a weight average molecular weight of 2000 or more in terms of polystyrene measured by gel permeation chromatography, and (B) A compound capable of generating an acid having a pKa of 4.0 or less has been proposed.

Patent Document 3 discloses a resin composition containing (A) a structural unit represented by the following general formula (1) having an acid-dissociable group and a structural unit having a functional group capable of reacting with a carboxyl group to form a covalent bond, (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, characterized in that the positive photosensitive resin composition contains at least one compound selected from the group consisting of .

In the general formula (1), R ¹ represents a hydrogen atom, a methyl group, a halogen atom or a cyano group. R ² and R ³ each independently represent a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group. Provided that at least one of R ² and R ³ represents a linear or branched alkyl group or a cycloalkyl group. R ⁴ represents a linear or branched alkyl group, a cycloalkyl group or an aralkyl group which may be substituted. R ² or R ³ and R ⁴ may be connected to form a cyclic ether.

Japanese Patent Application Laid-Open No. 5-165214 Japanese Patent Application Laid-Open No. 2004-264623 Japanese Patent Application Laid-Open No. 2009-98616

The photosensitive resin composition described in Patent Document 1 is not satisfactory in producing a liquid crystal display device of high quality without sufficient sensitivity, resolution and stability over time, and is not satisfactory in terms of pattern shape There has been a problem in that the change is large.

In addition, the photosensitive resin compositions described in Patent Documents 2 and 3 have a problem of low sensitivity and / or a large change in pattern shape due to a change in exposure amount.

An object of the present invention is to provide a photosensitive resin composition which has a cured film excellent in solvent resistance and heat resistance and transparency, has a high sensitivity, has a small change in pattern shape with respect to a change in exposure amount (also referred to as "wide exposure latitude" A cured film using the photosensitive resin composition, a manufacturing method thereof, an organic EL display device, and a liquid crystal display device.

The above object of the present invention is solved by the means described in the following <1>, <10>, <11>, <13> or <14>. Are described below together with <2> to <9> and <12> which are preferred embodiments.

(A) a monomer unit (a1) having a structure represented by the formula (Ia) for producing a carboxy group by an acid or a structure represented by the formula (Ib) for producing a phenolic hydroxyl group by an acid, A monomer unit (a2) having a structure represented by the formula (IIa) for producing a carboxy group or a structure represented by the formula (IIb) for producing a phenolic hydroxyl group by an acid, and a monomer unit having an epoxy group and / or an oxetanyl group A photosensitive resin composition comprising a polymer containing a unit (a3), (B) a photoacid generator, and (C) a solvent,

(Wherein, R ¹ represents an alkyl group or a cycloalkyl group independently, R ² are, each independently, an alkyl group, R ³ represents a tertiary alkyl group or a 2-tetrahydropyranyl, R ⁴ is the Ar ¹ and Ar ² each independently represent an aryl group, and the broken line portion represents a bonding site to another structure. Further, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, R ² may be connected to form a cyclic ether (except for a 6-membered ring structure))

<2> The photosensitive resin composition according to <1>, wherein the monomer unit (a1) is a monomer unit represented by the formula (III) and the monomer unit (a2) is a monomer unit represented by the formula (IV)

(Wherein R ⁵ represents an alkyl group or a cycloalkyl group, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a tertiary alkyl group or a 2-tetrahydropyranyl group, and R ⁸ represents a hydrogen atom or a methyl group )

<3> The photosensitive resin composition according to <1> or <2>, which is a chemically amplified positive-working photosensitive resin composition,

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the monomer unit (a3) is a monomer unit having an alicyclic epoxy group and / or a oxetanyl group,

(5) The positive resist composition as described in any one of (1) to (3) above, wherein the monomer unit (a3) in the polymer (A) is at least one monomer selected from the group consisting of 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 1] to [4], wherein the monomer unit derived from at least one member selected from the group consisting of methyl (meth) acrylate and methyl methacrylate Photosensitive resin composition,

<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the photoacid generator (B) is a compound having an oxime sulfonate residue,

The photoacid generator according to any one of <1> to <6>, wherein the photoacid generator (B) is a compound represented by formula (OS-3), formula (OS- Photosensitive resin composition,

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each of R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents 0 to 6 Lt; / RTI &gt;

<8> The photosensitive resin composition according to any one of <1> to <7>, further containing (D) an antioxidant,

<9> The photosensitive resin composition according to any one of <1> to <8>, further containing (E) a crosslinking agent,

(2) a solvent removing step of removing the solvent from the applied photosensitive resin composition, (3) a step of removing the solvent from the coated photosensitive resin composition, (4) a step of applying the photosensitive resin composition described in any one of (4) a developing step of developing with an aqueous developer, and (5) a post-baking step of thermally curing,

<11> A cured film formed by the method according to <10>

<12> The cured film according to <11> which is an interlayer insulating film,

&Lt; 13 > An organic EL display device comprising the cured film according to < 11 > or < 12 &

<14> A liquid crystal display device comprising the cured film according to <11> or <12>.

According to the present invention, a curable film excellent in solvent resistance and heat resistance transparency can be obtained, a photosensitive resin composition having high sensitivity and little change in pattern shape with respect to change in exposure amount, a cured film using the photosensitive resin composition, Method, an organic EL display device, and a liquid crystal display device.

Fig. 1 shows a configuration diagram of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.
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.

(Photosensitive resin composition)

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

The photosensitive resin composition of the present invention comprises (A) a monomer unit (a1) having a structure represented by formula (Ia) for producing a carboxy group by an acid or a structure represented by formula (Ib) for producing a phenolic hydroxyl group by an acid ), A monomer unit (a2) having a structure represented by the formula (IIa) for producing a carboxy group by an acid or a structure represented by the formula (IIb) for producing a phenolic hydroxyl group by an acid, and an epoxy group and / (B) a photo acid generator, and (C) a solvent.

(Wherein, R ¹ represents an alkyl group or a cycloalkyl group independently, R ² are, each independently, an alkyl group, R ³ represents a tertiary alkyl group or a 2-tetrahydropyranyl, R ⁴ is the Ar ¹ and Ar ² each independently represent an aryl group, and the broken line portion represents a bonding site to another structure. Further, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, R ² may be connected to form a cyclic ether (except for a 6-membered ring structure))

Hereinafter, each of the components represented by (A) to (C) is also referred to as "(A) component" to "(C) component".

In the polymer (A), it is preferable that the monomer unit (a1) is a monomer unit represented by the formula (III), and the monomer unit (a2) is a monomer unit represented by the formula desirable.

In the formula, R ⁵ represents an alkyl group or a cycloalkyl group, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a tertiary alkyl group or a 2-tetrahydropyranyl group, and R ⁸ represents a hydrogen atom or a methyl group.

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

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

It is preferable that the photosensitive resin composition of the present invention does not contain a 1,2-quinonediazide compound as a photoacid generator sensitive to an actinic ray. The 1,2-quinonediazide compound generates a carboxy group by a sequential photochemical reaction, but its quantum yield is necessarily 1 or less.

On the other hand, the photoacid generator (B) used in the present invention acts as a catalyst for deprotection of an acid-protected acid generated in response to an actinic ray, Contributing to the deprotection reaction, the quantum yield exceeds 1, for example, becomes a large value such as several powers of 10, and high sensitivity is obtained as a result of so-called chemical amplification.

In the photosensitive resin composition of the present invention, it is preferable that the polymer (A) contains a monomer unit having an alicyclic epoxy group and / or an oxetanyl group from the viewpoint of the solvent resistance, and the crosslinking agent (E) .

By containing the components (A) to (C), the photosensitive resin composition of the present invention can provide a photosensitive resin composition having a high sensitivity and a small change in pattern shape to a change in the exposure amount, . Further, it is possible to provide a photosensitive resin composition which can obtain a cured film excellent in solvent resistance and heat-resistant transparency.

Hereinafter, components (A) to (C) constituting the photosensitive resin composition will be described.

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

The method of introducing the monomer unit contained in the copolymer used in the present invention may be a polymerization method or a polymer reaction method. In the polymerization method, monomers containing a predetermined functional group are synthesized in advance, and then these monomers are copolymerized. In the polymer reaction method, a necessary functional group is introduced into the monomer unit using a reactive group contained in the monomer unit of the obtained copolymer after the polymerization reaction. Examples of the functional group include a protecting group for protecting the phenolic hydroxyl group or the carboxyl group and decomposing in the presence of strong acid and liberating them, a crosslinkable group such as an epoxy group or an oxetanyl group, an alkali soluble group such as a phenolic hydroxyl group or a carboxy group (Acidic group), and the like.

The introduction of the monomer units (1) to (3) into the polymer (A) may be carried out by a polymerization method or a polymer reaction method, or both of these methods may be used in combination.

In the polymerization method, for example, an ethylenically unsaturated compound having a structure represented by formula (Ia) or (Ib), an ethylenically unsaturated compound having a structure represented by formula (IIa) or formula (IIb) An ethylenically unsaturated compound having an epoxy group or an oxetanyl group is mixed and subjected to addition polymerization to obtain a desired polymer (A).

In the polymer reaction method, epichlorohydrin may be reacted with a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate to introduce an epoxy group. (Ia), (Ib), (IIa) and / or (IIb) can be obtained by copolymerizing the ethylenically unsaturated compound having a reactive group with a reactive group remaining in the side chain, A functional group such as a structure or a crosslinkable group to be displayed can be introduced into the side chain.

(A) Polymer

The photosensitive resin composition of the present invention contains the polymer (A).

The polymer (A) contained in the photosensitive resin composition of the present invention,

(A1) having a structure represented by the formula (Ia) for producing a carboxy group by an acid or a structure represented by the formula (Ib) for producing a phenolic hydroxyl group by an acid,

A monomer unit (a2) having a structure represented by the formula (IIa) for producing a carboxy group by an acid or a structure represented by the formula (IIb) for producing a phenolic hydroxyl group by an acid,

(A3) having an epoxy group and / or an oxetanyl group,

Lt; / RTI &gt;

The polymer (A) is an alkali-insoluble resin and is a resin which becomes alkali-soluble when the acid-decomposable groups in each of the formula (Ia) or the formula (Ib) and the formula (IIa) or the formula . Herein, the acid-decomposable group in the present invention refers to a functional group capable of decomposing in the presence of an acid to form a carboxyl group or a phenolic hydroxyl group.

"Alkali solubility" in the present invention means that the solution of the compound (resin) is coated on a substrate and the coating film (thickness: 3 μm) of the compound (resin) formed by heating at 90 ° C. for 2 minutes is 23 Means that the dissolution rate of the compound (resin) in an aqueous solution of 0.4% tetramethylammonium hydroxide at 0 占 폚 is 0.005 占 퐉 / sec or more. The term "alkali insoluble" means that the solution of the compound Refers to a dissolution rate of a coating film (thickness 3 占 퐉) of the compound (resin) formed by heating for minutes in an aqueous solution of 0.4% tetramethylammonium hydroxide at 23 占 폚 of less than 0.005 占 퐉 / second.

The polymer (A) does not exclude the introduction of an acidic group, but may contain a monomer unit having a carboxyl group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group (a4 ) Or the like.

The polymer (A) is preferably an acrylic polymer.

The "acrylic polymer" in the present invention is a polymer of addition polymerization type and is a polymer containing a monomer unit derived from (meth) acrylic acid and / or an ester thereof, and is a polymer obtained by copolymerizing (meth) acrylic acid and / A monomer unit other than a monomer unit, for example, a monomer unit derived from a styrene or a monomer unit derived from a vinyl compound.

The polymer (A) preferably has a monomer unit derived from (meth) acrylic acid and / or an ester thereof in an amount of 50 mol% or more, more preferably 80 mol% or more with respect to all monomer units in the polymer, (Meth) acrylic acid and / or an ester thereof.

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

<Monomer unit (a1)>

The polymer (A) contains a monomer unit (a1) having a structure represented by the formula (Ia) for producing a carboxy group by an acid or a structure represented by the formula (Ib) for producing a phenolic hydroxyl group by an acid . In the formula, the broken line represents a bonding site with another structure.

In the formulas (Ia) and (Ib), R ¹ independently represents an alkyl group or a cycloalkyl group.

The alkyl group for R &lt; ¹ &gt; may be linear or branched.

The preferable number of carbon atoms of the alkyl group in R ¹ is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 7.

The preferable number of carbon atoms of the cycloalkyl group in R ¹ is preferably 3 to 20, more preferably 3 to 10, and still more preferably 5 to 7.

When these carbon atoms have a substituent, they include the carbon number of the substituent.

The alkyl group for R ¹ may be, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group.

Examples of the cycloalkyl group for R ¹ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group and an isobornyl group.

The alkyl group and cycloalkyl group in R ¹ may have a substituent.

Examples of the substituent in the alkyl group and the cycloalkyl group include an alkyl group having 1 to 10 carbon atoms (such as a methyl group, an ethyl group, a propyl group or a butyl group), a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, A halogen atom, a chlorine atom, a bromine atom and an iodine atom), a cyano group, a nitro group, a hydroxy group, and an alkoxy group having 1 to 10 carbon atoms. These substituents may be further substituted by the above substituents.

The alkyl group or cycloalkyl group in R ¹ is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms, an alkyl group having 1 to 6 carbon atoms , A cycloalkyl group having 3 to 6 carbon atoms, or a benzyl group, more preferably an ethyl group or a cyclohexyl group, and particularly preferably an ethyl group.

In the formulas (Ia) and (Ib), R ² represents an alkyl group.

The alkyl group for R ² may be linear or branched.

The preferable number of carbon atoms of the alkyl group in R ² is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 7.

When these carbon atoms have a substituent, they include the carbon number of the substituent.

As the alkyl group for R ² , an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.

In the formulas (Ia) and (Ib), R ¹ and R ² may be connected to form a cyclic ether structure (except for a 6-membered ring structure). The cyclic ether structure is preferably a 4-membered ring, 5-membered ring, 7-membered ring, or 8-membered ring structure, particularly preferably a 5-membered ring structure. In the present invention, the 6-membered ring structure is not included in the monomer unit (a1) because the activation energy of deprotection is high.

In formula (Ib), Ar ¹ represents a divalent aromatic group and has OCH (OR ¹ ) (R ² ) on the aromatic ring.

The bivalent aromatic group in Ar ¹ is not particularly limited and examples thereof include a phenylene group, a substituted phenylene group, a naphthylene group, and a substituted naphthylene group, and examples thereof include a phenylene group or a substituted phenylene group More preferably a phenylene group, still more preferably a 1,4-phenylene group.

The divalent aromatic group in Ar ¹ may have a substituent on the aromatic ring. Examples of the substituent include alkyl groups having 1 to 10 carbon atoms (such as methyl, ethyl, propyl and butyl), cycloalkyl groups having 3 to 10 carbon atoms , A halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, a nitro group, a hydroxyl group, and an alkoxy group having 1 to 10 carbon atoms. May be further substituted by the substituent.

The monomer unit (a1) in the present invention contains the structure represented by the formula (Ia) and / or the formula (Ib), which is a structure in which a carboxyl group or a phenolic hydroxyl group is protected.

The carboxylic acid monomer capable of forming a monomer unit having the structure represented by the formula (Ia) by protecting the carboxyl group can be used as long as it can be a monomer unit (a1) by protecting the carboxyl group. Examples of the carboxylic acid monomer include acrylic acid, Monocarboxylic acids such as methacrylic acid, crotonic acid, and? -Methyl-p-carboxystyrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. The monomer unit (a1) is preferably a monomer unit derived from a carboxylic acid in which these carboxyl groups are protected.

As the monomer having a phenolic hydroxyl group capable of forming a monomer unit having the structure represented by the formula (Ib) by protecting the phenolic hydroxyl group, there can be used a monomer having a phenolic hydroxyl group which can be a monomer unit (a1) For example, hydroxystyrenes such as p-hydroxystyrene and? -Methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of Japanese Patent Laid-Open Publication No. 2008-40183, compounds disclosed in Japanese Patent No. 2888454 Hydroxybenzoic acid derivative as described in paragraphs 0007 to 0010 of the above-mentioned, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, .

Of these, α-methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, Addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, and addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

Of these structures, particularly preferred as the monomer unit (a1) is a monomer unit represented by the formula (III).

In the formula (III), R ⁵ represents an alkyl group or a cycloalkyl group, and preferred embodiments of R ⁵ are the same as those of R ¹ in formulas (Ia) and (Ib).

In the formula (III), R ⁶ represents a hydrogen atom or a methyl group.

Specific preferred examples of the radical polymerizable monomer used for forming the monomer unit represented by the formula (III) include 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl Methoxyethyl acrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, Propyl methacrylate, 1-n-propyl methacrylate, 1-n-propyl methacrylate, 1- 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1- Benzyloxyethyl methacrylate, 1-benzyloxyethyl acrylate, and the like, Particularly preferred are 1-ethoxyethyl methacrylate and 1-ethoxyethyl acrylate. These monomer units may be used alone or in combination of two or more.

As the radically polymerizable monomer used for forming the monomer unit (a1), a commercially available one may be used, or a compound synthesized by a known method may be used. For example, it can be synthesized by reacting (meth) acrylic acid with a vinyl ether compound in the presence of an acid catalyst as shown below.

Here, R ⁵ and R ⁶ each correspond to R ⁵ and R ⁶ in the formula (III).

The monomer unit (a1) is obtained by polymerizing a protected carboxyl group or a phenolic hydroxyl group-containing monomer with a monomer unit (a2) to (a5) described below or a precursor thereof and then reacting the carboxyl group or the phenolic hydroxyl group with a vinyl ether compound Can also be formed. Specific examples of the preferable monomer unit thus formed are the same as the monomer units derived from the preferred specific examples of the radical polymerizable monomer.

As specific preferred examples of the monomer unit (a1), the following monomer units can be exemplified.

The content of the monomer unit (a1) in the total monomer units constituting the polymer (A) is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and particularly preferably 20 to 60 mol% . By containing the monomer unit (a1) together with the monomer unit (a2) in the above ratio, a photosensitive resin composition having high sensitivity and a large exposure latitude can be obtained.

&Lt; Monomer unit (a2) >

The polymer (A) contains a monomer unit (a2) having a structure represented by the formula (IIa) for producing a carboxy group by an acid or a structure represented by the formula (IIb) for producing a phenolic hydroxyl group by an acid .

In the formulas (IIa) and (IIb), R ³ represents a tertiary alkyl group or a 2-tetrahydropyranyl group, and R ⁴ represents a tertiary alkyl group, a tert-butoxycarbonyl group or a 2-tetrahydropyranyl group , Ar ² represents a divalent aromatic group, and the broken line represents a bonding site with another structure.

The tertiary alkyl group for R ³ and R ⁴ preferably has 4 to 20 carbon atoms, more preferably 4 to 14 carbon atoms, and more preferably 4 to 8 carbon atoms.

The tertiary alkyl group and the 2-tetrahydropyranyl group in R ³ , the tertiary alkyl group in R ⁴ , the tert-butoxycarbonyl group or the 2-tetrahydropyranyl group, and the bivalent aromatic group in Ar ² , (Such as a methyl group, an ethyl group, a propyl group or a butyl group), a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen atom (a fluorine atom, A chlorine atom, a bromine atom and an iodine atom), a cyano group, a nitro group, a hydroxyl group, and an alkoxy group having 1 to 10 carbon atoms. These substituents may be further substituted by the above substituents.

The tertiary alkyl group in R ³ and R ⁴ is more preferably at least one selected from the group consisting of the groups represented by the following formula (V).

^{-C (R 9 R 10 R 11} ) (V)

In the formulas, R ⁹ , R ¹⁰ and R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, , R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other to form a ring with the carbon atom to which they are bonded.

The alkyl group having 1 to 12 carbon atoms represented by R ⁹ , R ¹⁰ and R ^{11 in} the formula (V) may be straight chain or branched chain, and examples thereof include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, texyl group (2,3-dimethyl-2-butyl group), n -Hexyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group and an isobornyl group.

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.

Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group,? -Methylbenzyl group, phenethyl group, naphthylmethyl group and the like.

Further, R ⁹ , R ¹⁰ and R ¹¹ may bond to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ⁹ and R ¹⁰ , R ⁹ and R ¹¹ , or R ¹⁰ and R ¹¹ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuran An adamantyl group, and a tetrahydropyranyl group.

In the formula (IIa), R ³ is preferably a tertiary alkyl group having 4 to 12 carbon atoms or a 2-tetrahydropyranyl group, more preferably a tertiary alkyl group having 4 to 8 carbon atoms or a 2-tetrahydropyranyl More preferably a t-butyl group or a 2-tetrahydropyranyl group, and a t-butyl group is particularly preferable.

R ⁴ in the formula (IIb) is preferably a tertiary alkyl group having 4 to 12 carbon atoms, a 2-tetrahydropyranyl group, a tert-butoxycarbonyl group, a tertiary alkyl group having 4 to 12 carbon atoms, More preferably a 2-tetrahydropyranyl group, still more preferably a t-butyl group or a 2-tetrahydropyranyl group, and particularly preferably a 2-tetrahydropyranyl group.

In the formula (IIb), Ar ² represents a divalent aromatic group and has OCH (OR ¹ ) (R ² ) on the aromatic ring.

A preferable embodiment of Ar ^{2 in} the formula (IIb) is the same as the preferred embodiment of Ar ¹ in the formula (IIa).

The monomer unit (a2) in the present invention contains a protected carboxyl group represented by the formula (IIa) and / or a protected phenolic hydroxyl group represented by the formula (IIb).

Examples of the carboxylic acid monomer capable of forming a monomer unit having a structure represented by the formula (IIa) by protecting the carboxyl group include those capable of forming a monomer unit (a2) by protecting the carboxyl group, and examples thereof include acrylic acid, Monocarboxylic acids such as methacrylic acid, crotonic acid, and? -Methyl-p-carboxystyrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. The monomer unit (a2) is preferably a monomer unit derived from a carboxylic acid protected with these carboxyl groups.

As the monomer having a phenolic hydroxyl group capable of forming a monomer unit having the structure represented by the above formula (IIb) by protecting the phenolic hydroxyl group, there can be used a monomer having a phenolic hydroxyl group which can be a monomer unit (a2) And examples thereof include hydroxystyrenes such as p-hydroxystyrene and? -Methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of Japanese Patent Laid-Open Publication No. 2008-40183, compounds described in Japanese Patent No. 2888454 4-hydroxybenzoic acid derivative as described in paragraphs 0007 to 0010, an addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, an addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate, .

Of these, α-methyl-p-hydroxystyrene, compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, Addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, and addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

Of these structures, particularly preferable as the monomer unit (a2) is a monomer unit represented by the following formula (IV).

In the formula (IV), R ⁷ represents a tertiary alkyl group or a 2-tetrahydropyranyl group, and R ⁸ represents a hydrogen atom or a methyl group.

In formula (IV), preferred examples of R ⁷ are the same as those of R ³ in formula (IIa).

Specific preferred examples of the radical polymerizable monomer used for forming the monomer unit represented by the formula (IV) include, for example, tert-butyl methacrylate, tert-butyl acrylate, tetrahydro- Methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, acrylic acid 1-methylcyclohexyl, and the like. Of these, tert-butyl methacrylate and tert-butyl acrylate are particularly preferable. These monomer units may be used alone or in combination of two or more.

As specific preferred examples of the monomer unit (a2), the following monomer units can be exemplified.

The content of the monomer unit (a2) in the total monomer units constituting the polymer (A) is preferably from 5 to 60 mol%, more preferably from 10 to 50 mol%, and particularly preferably from 10 to 40 mol% . By containing the monomer unit (a2) together with the monomer unit (a1) in the above ratio, a photosensitive resin composition having high sensitivity and a large exposure latitude can be obtained.

<Monomer Unit (a3) Having an Epoxy Group and / or Oxetanyl Group>

The polymer (A) contains a monomer unit (a3) having an epoxy group and / or an oxetanyl group.

The monomer unit (a3) having an epoxy group and / or an oxetanyl group is preferably a monomer unit having an alicyclic epoxy group and / or an oxetanyl group, and more preferably a monomer unit having an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring, and specific examples thereof include 3,4-epoxycyclohexyl group, 2,3-epoxycyclohexyl group, 2,3-epoxycyclopentyl group And the like.

The group having an oxetanyl group is not particularly limited as long as it has an oxetanyl ring, but a (3-ethyloxetan-3-yl) methyl group can be preferably exemplified.

The monomer unit having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one monomer unit, and may contain at least one epoxy group and at least one oxetanyl group, two or more epoxy groups, And it is preferable to have one to three epoxy groups and / or oxetanyl groups in total, more preferably one or two epoxy groups and / or oxetanyl groups in total, more preferably epoxy group or oxetanyl group, More preferably has one aryl group.

Specific examples of the radical polymerizable monomer used for forming the monomer unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Epoxycyclohexyl methacrylate, glycidyl acrylate, glycidyl? -N-butyl acrylate,? -Epoxybutyl acrylate,? -Epoxybutyl methacrylate, Epoxy heptyl,? -Ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and Japanese Patent No. 4168443 Compounds containing an alicyclic epoxy skeleton described in Nos. 0031 to 0035, and the like.

Examples of the radically polymerizable monomer used to form the monomer unit having an oxetanyl group include (meth) acrylic acid esters having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953 .

Examples of the radically polymerizable monomer used for forming a monomer unit having an epoxy group and / or an oxetanyl group are monomers containing a methacrylate ester structure and monomers containing an acrylic ester structure.

Of these monomers, compounds having an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and compounds having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A-2001-330953 (Meth) acrylic acid ester, and particularly preferred is a (meth) acrylic acid ester having an oxetanyl group as described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2001-330953. Among these, preferred are acrylic esters such as 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These monomer units may be used alone or in combination of two or more.

As specific preferred examples of the monomer unit (a3), the following monomer units can be exemplified.

The content of the monomer unit (a3) having an epoxy group and / or an oxetanyl group is preferably from 10 to 80 mol%, more preferably from 15 to 70 mol%, and most preferably from 10 to 70 mol%, of all the monomer units constituting the polymer (A) And particularly preferably from 20 to 65 mol%. By containing the monomer unit having an epoxy group and / or an oxetanyl group in the above ratio, the physical properties of the cured film become good.

<Monomer Unit (a4) Having Carboxyl Group, Carboxylic Acid Anhydride Residue and / or Phenolic Hydroxyl Group>

The polymer (A) preferably contains a monomer unit having a carboxyl group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group within the range that the polymer (A) does not become alkali soluble, and the carboxyl group and / or the phenolic hydroxyl group Is more preferable.

Examples of the radically polymerizable monomers used for forming the monomer unit having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid are preferable.

As the radical polymerizable monomer used for forming the monomer unit having a carboxylic acid anhydride residue, for example, maleic anhydride, itaconic anhydride and the like are preferably used.

Examples of the radical polymerizable monomer used for forming the monomer unit having a phenolic hydroxyl group include hydroxystyrenes such as p-hydroxystyrene and? -Methyl-p-hydroxystyrene, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, 4 - addition reaction product of hydroxybenzoic acid and glycidyl acrylate, and the like are preferably used.

Of these, methacrylic acid, acrylic acid, compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, Addition reaction products of benzoic acid and glycidyl methacrylate, and addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate are more preferred, and compounds described in paragraphs 0011 to 0016 of Japanese Patent Application Laid-Open No. 2008-40183, 4-hydroxybenzoic acid derivative as described in paragraphs 0007 to 0010 of the Japanese Patent No. 2888454, addition reaction product of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate Is particularly preferable. These monomer units may be used alone or in combination of two or more.

As specific preferred examples of the monomer unit (a4), the following monomer units can be exemplified.

When the monomer unit (a4) having a carboxyl group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group is contained among all the monomer units constituting the polymer (A), the content of the component (a4) is 1 to 25 mol %, More preferably 2 to 25 mol%, and particularly preferably 3 to 20 mol%. By containing a monomer unit having a carboxyl group, a carboxylic acid anhydride residue and / or a phenolic hydroxyl group at the above ratio, a high sensitivity can be obtained and also the developing property can be improved.

&Lt; Other monomer unit (a5) >

The polymer (A) may further contain monomer units (a5) other than the above (a1) to (a4) (hereinafter referred to as "component (a5)" or "other monomer units (a5 ) &Quot;).

Examples of the radically polymerizable monomer used for forming the component (a5) include the compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 (provided that (a1) to (a4) &Lt; / RTI &gt; except for the monomer units of &lt; RTI ID =

Among them, (meth) acrylic esters containing an alicyclic structure such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate and cyclohexyl acrylate, methyl (meth) acrylate, 2-hydroxyethyl Styrene and the like can be preferably exemplified. Of these, 2-hydroxyethyl (meth) acrylate is more preferably exemplified.

These (a5) components may be used singly or in combination of two or more.

The content of the component (a5) in the case where the component (a5) is contained in the total monomer units constituting the polymer (A) is preferably 1 to 50 mol%, more preferably 5 to 40 mol% , And particularly preferably from 5 to 30 mol%.

The weight average molecular weight of the polymer (A) is preferably 1,000 to 100,000, more preferably 2,000 to 50,000. The weight average molecular weight in the present invention is preferably a polystyrene reduced weight average molecular weight determined by gel permeation chromatography (GPC).

Various methods are also known for the synthesis of the polymer (A). For example, there are known methods for synthesizing the polymer (A), and examples thereof include a radical polymerizable monomer (a2) used for forming at least a monomer unit (a1), a monomer unit Can be synthesized by polymerization of a radical polymerizable monomer mixture containing a radical polymerization initiator in an organic solvent.

Preferable examples of the polymer (A) used in the present invention are illustrated below, but the present invention is not limited thereto.

The weight average molecular weight of the polymer (A) shown below is preferably 2,000 to 50,000.

1-ethoxyethyl methacrylate / tert-butyl methacrylate / glycidyl methacrylate copolymer

1-ethoxyethyl methacrylate / tert-butyl methacrylate / glycidyl methacrylate / methacrylic acid copolymer

1-ethoxyethyl methacrylate / tert-butyl methacrylate / glycidyl methacrylate / methacrylic acid / styrene copolymer

Methyl methacrylate tetrahydrofuran-2-yl / methacrylic acid tert-butyl / glycidyl methacrylate / methacrylic acid copolymer

1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / glycidyl methacrylate / methacrylic acid copolymer

1-ethoxyethyl methacrylate / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer

Methacrylic acid 1-ethoxyethyl / methacrylic acid tert-butyl / methacrylic acid 3,4-epoxycyclohexylmethyl / methacrylic acid copolymer

Methacrylic acid 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxy- coalescence

Methacrylic acid 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl)

Methacrylic acid 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2- Hydroxyethyl copolymer

Methacrylic acid 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methyl methacrylate coalescence

Methacrylic acid 1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / 3,4-epoxycyclohexylmethyl 4-hydroxybenzoate (3-methacryloyloxypropyl) Ester copolymer

Methacrylic acid 1-ethoxyethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / 3,4-epoxycyclohexylmethyl 4-hydroxybenzoate (3-methacryloyloxypropyl) Ester / 2-hydroxyethyl methacrylate copolymer

(3-methacryloyloxypropyl) ester copolymer of 1-ethoxyethyl methacrylate / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl acrylate / 4-hydroxybenzoic acid

Methacrylic acid 1-ethoxyethyl / methacrylic acid tert-butyl acrylate 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxy Ethyl copolymer

Ethyl methacrylate / methacrylic acid tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl copolymer

Butyl methacrylate / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid copolymer

Methacrylic acid tetrahydrofuran-2-yl / methacrylic acid tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid copolymer

Methyl methacrylate / methacrylic acid / styrene copolymer (3-ethyloxetan-3-yl) methyl methacrylate tetrahydrofuran-2-yl / methacrylic acid tert-

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxy Propyl) ester copolymer

(3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer of 1-ethoxyethyl methacrylate / tert-butyl methacrylate /

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyl Oxypropyl) ester copolymer

(3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxy) methacrylic acid 1-methyl-1-cyclohexyl methacrylate / Propyl) ester copolymer

(2-methacryloyloxyethyl) ester copolymer of 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoate

(6-methacryloyloxyhexyl) ester copolymer of 1-ethoxyethyl methacrylate / tert-butyl methacrylate / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoate

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl methacrylate copolymer

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid Methyl acrylate copolymer

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxyethyl) 1-oxypropyl) ester copolymer

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxyethyl) 1-oxypropyl) ester / 2-hydroxyethyl methacrylate copolymer

(3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester copolymer of 1-ethoxyethyl methacrylate / tert-butyl methacrylate /

(3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer

Ethyl methacrylate / 1- (cyclohexyloxy) ethyl methacrylate / tert-butyl methacrylate / 3,4-epoxycyclohexylmethyl methacrylate copolymer

(Methacryloyloxy) ethyl methacrylate / tert-butyl methacrylate / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl methacrylate copolymer

Methyl (meth) acrylate / methacrylic acid / 1- (cyclohexyloxy) ethyl methacrylate / tert-butyl methacrylate /

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl methacrylate / ) Ester / 2-hydroxyethyl methacrylate copolymer

Methacrylic acid 1 - (cyclohexyloxy) ethyl methacrylate / tetrahydro-2H-pyran-2-yl methacrylate / 3,4-epoxycyclohexylmethyl 4-hydroxybenzoic acid 1-oxypropyl) ester / 2-hydroxyethyl methacrylate copolymer

Methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3 (ethylcyclohexyloxy) ethyl methacrylate / tetrahydro- - methacryloyloxypropyl) ester / 2-hydroxyethyl methacrylate copolymer

Ethoxyethyl ether of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / tert-butyl methacrylate / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid Copolymer

Ethoxyethyl ether of? -Hydroxybenzoic acid (3-methacryloyloxypropyl) ester / tert-butoxycarbonyl protecting group of? -Methyl-p-hydroxystyrene / methacrylic acid Cetane-3-yl) methyl / methacrylic acid copolymer

Ethoxyethyl ether of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester / protected tert-butyl group of 4-hydroxyphenyl methacrylate / methacrylic acid (3-ethyloxetane- 3-yl) methyl / methacrylic acid copolymer

The polymer (A) may be used singly or in combination of two or more.

The molar amount of the monomer unit (a1) represented by the formula (I) in the polymer (A) is preferably larger than the molar amount of the monomer unit (a2) represented by the formula (II).

The content ratio of the monomer unit (a1) represented by the formula (I) and the monomer unit (a2) represented by the formula (II) in the polymer (A) (a2) is preferably 100: 200 to 100: 5, more preferably 100: 100 to 100: 10, and even more preferably 100: 90 to 100: 20.

The monomer unit (a1) represented by the formula (I), the monomer unit (a2) represented by the formula (II) and the monomer unit having an epoxy group and / or oxetanyl group in the polymer (A) (a1): monomer unit (a2): monomer unit (a3) = 100: (5 to 200) :( 10 to 200) More preferably 100: (20 to 90) :( 50 to 150).

The content of the polymer (A) in the photosensitive resin composition of the present invention is preferably 20 to 99% by weight, more preferably 40 to 97% by weight, and more preferably 60 to 95% by weight based on the total solid content of the photosensitive resin composition %. When the content is within this range, pattern formation property upon development becomes good. The solid content of the photosensitive resin composition means an amount excluding volatile components such as a solvent.

In the photosensitive resin composition of the present invention, resins other than the polymer (A) may be used in combination within the range not hindering the effect of the present invention. However, the content of the resin other than the polymer (A) is preferably smaller than the content of the polymer (A) from the viewpoint of developability.

(B)

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

As the photoacid generator (also referred to as "component (B)") used in the present invention, a compound which generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or longer, preferably 300-450 nm is preferable, . In the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid upon exposure to an actinic ray having a wavelength of 300 nm or more by using in combination with a sensitizer can be preferably used in combination with a sensitizer.

As the photoacid generator used in the present invention, a photoacid generator that generates an acid with a pKa of 4 or less is preferable, and a photoacid generator that generates an acid with a pKa of 3 or less is more preferable.

Examples of the photoacid generator include trichloromethyl-s-triazine, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds have. Of these, oxime sulfonate compounds are preferably used from the viewpoint of insulating properties. These photoacid generators may be used alone or in combination of two or more.

Specific examples thereof include the following.

As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) Triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan- (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, or 2- (4-methylphenyl) ethenyl] -bis Naphthyl) -bis (4,6-trichloromethyl) -s-triazine;

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenylphenyl iodonium trifluoromethane sulfonate, 4-methoxy (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium trifluoromethanesulfonate, phenyl 4- (2'-hydroxy-1'- -Tetradecaoxy) phenyliodonium hexafluoroantimonate or phenyl-4- (2'-hydroxy-1'-tetradecarboxy) phenyl iodonium p-toluenesulfonate;

As the triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenyl Sulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate; and the like;

Examples of the quaternary ammonium salts include tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) (P-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, and the like can be used. ;

Diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like;

As the imide sulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] -hept-5-ene-dicarboxyimide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfone N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidopropane sulfonate and the like;

As the oxime sulfonate compound, the following compounds.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate moiety, a compound containing an oxime sulfonate moiety represented by the formula (2) can be preferably exemplified.

In the formula (2), R ⁵ represents an alkyl group or an aryl group. The alkyl group in R &lt; ⁵ &gt; may be linear, branched or cyclic. The permissible substituents are described below.

As the alkyl group for R ⁵ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable.

The alkyl group of R ⁵ 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 bridged alicyclic groups such as a 7,7-dimethyl-2-oxonorbornyl group) Preferably a bicycloalkyl group, etc.).

As the aryl group for R ^5, 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 ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

The compound containing an oxime sulfonate residue represented by the formula (2) is more preferably an oxime sulfonate compound represented by the following formula (3).

In the formula (3), R ⁵ has the same meaning as R ⁵ in the formula (2), X represents an alkyl group, an alkoxy group or a halogen atom, m represents an integer of 0 to 3 , and when m is 2 or 3, plural Xs may be the same or different.

As the alkyl group represented by X, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable.

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

The halogen atom represented by X is preferably a chlorine atom or a fluorine atom.

m is preferably 0 or 1.

In the formula (3), m is 1, X is a methyl group, X is a substituted position in an ortho position, R ⁵ is a linear alkyl group having 1 to 10 carbon atoms, a 7,7-dimethyl-2-oxonorbornylmethyl group , Or a p-tolyl group.

Specific examples of the oxime sulfonate compound include the following compounds (i), (ii), (iii), (iv) and the like, and they can be used singly or in combination of two or more kinds. have. The compounds (i) to (iv) are commercially available. It may also be used in combination with other types of (B) photoacid generators.

As the photoacid generator, a photoacid generator represented by the formula (II) is also preferable.

In formula (II), R ^4A represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and L represents an integer of 0 to 5 . R ^3A is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, A phenyl group, a naphthyl group which may be substituted with W, or an anthranyl group which may be substituted with W, W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, An alkoxy group, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms.

Examples of R ^3A in the formula (II) include methyl, ethyl, n-propyl, n-butyl, n-octyl, N-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and methyl group, ethyl group, n-propyl group, n-butyl group or p-tolyl group is particularly preferable.

As the halogen atom represented by R ^4A , a fluorine atom, a chlorine atom or a bromine atom is preferable.

The alkyl group having 1 to 4 carbon atoms represented by R ^4A is preferably a methyl group or an ethyl group.

As the alkoxy group having 1 to 4 carbon atoms represented by R ^4A , a methoxy group or an ethoxy group is preferable.

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

Preferred examples of the compound included in the photoacid generator represented by the formula (II) include a compound wherein R ^3A represents a methyl group, an ethyl group, an n-propyl group, an n-butyl group or a 4-tolyly group, R ^4A represents a hydrogen atom or a methoxy group And L is a number of 0 to 1.

Hereinafter, particularly preferred examples of the compound included in the photoacid generator represented by the formula (II) are shown, but the present invention is not limited thereto.

? - (methylsulfonyloxyimino) benzyl cyanide (R ^3A = methyl group, R ^4A = hydrogen atom)

? - (ethylsulfonyloxyimino) benzyl cyanide (R ^3A = ethyl group, R ^4A = hydrogen atom)

? - (n-propylsulfonyloxyimino) benzyl cyanide (R ^3A = n-propyl group, R ^4A = hydrogen atom)

? - (n-butylsulfonyloxyimino) benzyl cyanide (R ^3A = n-butyl group, R ^4A = hydrogen atom)

? - (4-toluenesulfonyloxyimino) benzyl cyanide (R ^3A = 4-tolyl group, R ^4A = hydrogen atom)

? - [(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = methyl group, R ^4A = methoxy group)

? - [(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = ethyl group, R ^4A = methoxy group)

methoxyphenyl] acetonitrile (R ^3A = n-propyl group, R ^4A = methoxy group)

? - [(n-butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = n-butyl group, R ^4A =

? - [(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile (R ^3A = 4-tolyl group, R ^4A =

The compound containing an oxime sulfonate residue represented by the above formula (4) is also preferably a compound represented by the formula (OS-1).

In the formula (OS-1), R ¹ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Lt; / RTI &gt; R ² represents an alkyl group or an aryl group.

X is ^{-O-, -S-, -NH-, -NR 5} -, -CH 2 -, -CR 6 H-, or, -CR ⁶ R ⁷ - represents a, R ⁵ ~R ⁷ is an alkyl group, or , And an aryl group.

R ²¹ to R ²⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group . Two of R ²¹ to R ²⁴ may be bonded to each other to form a ring.

As R ²¹ to R ²⁴ , a hydrogen atom, a halogen atom and an alkyl group are preferable, and at least two of R ²¹ to R ²⁴ are bonded to each other to form an aryl group. Among them, the case where all of R ²¹ to R ²⁴ are hydrogen atoms is preferable from the viewpoint of sensitivity.

Each of the above-mentioned functional groups may further have a substituent.

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

In the formula (OS-2), R ¹ , R ² and R ²¹ to R ²⁴ are the same as those in the formula (OS-1), and preferred examples are also the same.

Of these, formula (OS-1) and the equation is R ¹ in (OS-2) a cyano group, or, more preferably an aryl group sun, and is represented by the expression (OS-2), R ¹ is a cyano group , A phenyl group or a naphthyl group is most preferable.

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

Specific examples (Exemplary Compounds b-1 to b-34) of a compound represented by the formula (OS-1) which can be suitably used in the present invention are shown below, but the present invention is not limited thereto . Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

Of these compounds, b-9, b-16, b-31 and b-33 are preferred from the viewpoint of compatibility between sensitivity and stability.

The oxime sulfonate residue-containing compound represented by the formula (4) is preferably an oxime sulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5).

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each of R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents 0 to 6 Lt; / RTI &gt;

In the above formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group for R ¹ may have a substituent.

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

Examples of the substituent which the alkyl group in R ¹ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, N-decyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, A phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Of these, preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

Among the above-mentioned formulas (OS-3) to (OS-5), the aryl group in R ¹ is preferably an aryl group having 6 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the aryl group in R ¹ may have include halogen atoms, alkyl groups, alkyloxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, aminocarbonyl groups, An alkoxy group, an alkoxy group, an alkoxy group, an alkoxy group,

Examples of the aryl group for R ¹ include a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, Phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group.

Among them, a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group and p-phenoxyphenyl group are preferable.

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

The substituent which R ¹ may have as a heteroaryl group may be a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, A sulfonyl group, and an alkoxysulfonyl group.

Of the above-mentioned formulas (OS-3) to (OS-5), the heteroaryl group for R ¹ may be at least one of the rings may be a heteroaromatic ring. For example, the heteroaromatic ring and the benzene ring may be coordinated.

Examples of the heteroaryl group for R ¹ include a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzoimidazole ring which may have a substituent A group in which one hydrogen atom is removed from the ring selected in the group.

In the formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.

Of the formulas (OS-3) to (OS-5), one or two of R ² present in two or more of the compounds are preferably an alkyl group, an aryl group or a halogen atom, And it is particularly preferable that one is an alkyl group and the remainder is a hydrogen atom.

In the above formulas (OS-3) to (OS-5), the alkyl group or aryl group in R ² may have a substituent.

Examples of the substituent which the alkyl group or the aryl group in R ² may have include a group such as the substituent which the alkyl group or aryl group in R ¹ may have.

The alkyl group in R ² is preferably an alkyl group having 1 to 12 carbon atoms in total which may have a substituent and more preferably an alkyl group having 1 to 6 carbon atoms in total which may have a substituent.

Specific examples of the alkyl group for R ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, A perfluorohexyl group, a chloromethyl group, a bromomethyl group, a methoxymethyl group, a benzyl group, a phenoxyethyl group, a methylthioethyl group, a naphthyl group, a naphthyl group, , A phenylthioethyl group, an ethoxycarbonylethyl group, a phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Among them, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s- , A benzyl group is preferable and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- butyl group, Propyl group, n-butyl group and n-hexyl group are more preferable, and methyl group is particularly preferable.

The aryl group in R ² is preferably an aryl group having a total of 6 to 30 carbon atoms which may have a substituent.

Specific examples of the aryl group for R ² include a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, Thiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group.

Among them, a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group and a p-phenoxyphenyl group are preferable.

Examples of the halogen atom in R ² 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.

Of the above formulas (OS-3) to (OS-5), X represents O or S, and is preferably O.

In the formulas (OS-3) to (OS-5), the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.

In the formulas (OS-3) to (OS-5), n represents 1 or 2, and when X is O, n is preferably 1. When X is S, n is 2 desirable.

In the above formulas (OS-3) to (OS-5), the alkyl group and alkyloxy group in R ⁶ may have a substituent.

Of the above-mentioned formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the alkyl group in R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

Examples of the alkyl group for R ⁶ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- N-decyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group, phenoxyethyl group, methylthioethyl group, phenylthioethyl group, ethoxycarbonylethyl group, A phenoxycarbonylethyl group, and a dimethylaminocarbonylethyl group.

Of these, preferred are a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s- An n-dodecyl group, a trifluoromethyl group, a perfluoropropyl group, a perfluorohexyl group, and a benzyl group are preferable.

Of the above formulas (OS-3) to (OS-5), the alkyloxy group in R ⁶ is preferably an alkyloxy group having 1 to 30 total carbon atoms which may have a substituent.

Examples of the substituent which the alkyloxy group of R ⁶ may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group and an aminocarbonyl group.

Examples of the alkyloxy group for R ⁶ include a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, an ethoxyethyloxy group, a methylthioethyloxy group, A phenylthioethyloxy group, an ethoxycarbonylethyloxy group, a phenoxycarbonylethyloxy group, and a dimethylaminocarbonylethyloxy group.

Of these, methyloxy, ethyloxy, butyloxy, hexyloxy, phenoxyethyloxy, trichloromethyloxy or ethoxyethyloxy groups are preferred.

In the formulas (OS-3) to (OS-5), examples of the aminosulfonyl group for R ⁶ include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, .

Of the above-mentioned formulas (OS-3) to (OS-5), examples of the alkoxysulfonyl group for R ⁶ include a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxycarbonyl group, a propyloxysulfonyl group and a butyloxysulfonyl group.

In the formulas (OS-3) to (OS-5), m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, Do.

The oximesulfonate residue-containing compound represented by the formula (4) is particularly preferably an oxime sulfonate compound represented by any of the following formulas (OS-6) to (OS-11).

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, R ⁷ represents a hydrogen atom or a bromine atom, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, R ¹⁰ represents a hydrogen atom or a lower alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, Methyl group)

Expression (OS-6) ~ R ¹ in (OS-11) is, and R ¹ and agreed in the formula (OS-3) ~ (OS -5), as a preferred aspect.

R ⁷ in the formula (OS-6) represents a hydrogen atom or a bromine atom and is preferably a hydrogen atom.

R ⁸ in formulas (OS-6) to (OS-11) represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, More preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group, and is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, .

R ⁹ in formulas (OS-8) and (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.

R ¹⁰ in formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group and is preferably a hydrogen atom.

In the oxime sulfonate compound, either or both of the stereostructure (E, Z) of oxime may be used.

Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.

In the photosensitive resin composition of the present invention, the photoacid generator as the component (B) is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the component (A) Do.

The photosensitive resin composition of the present invention preferably contains a sensitizer in combination with the photoacid generator (B) in order to accelerate the decomposition thereof.

The sensitizer absorbs an actinic ray or radiation to become an electron-excited state. The sensitizer in the electron-excited state comes into contact with the photoacid generator to generate electron transfer, energy transfer, heat generation, and the like. As a result, the photoacid generator decomposes by causing a chemical change to generate an acid.

Examples of preferred sensitizers include compounds having an absorption wavelength anywhere in the range of 350 nm to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Anthracene, xanthone, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone, and the like), xanthone Thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, (For example, thionine, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acriflavine), acridones -Butyl-2-chloroacridone), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squalium), 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.

(C) Solvent

The photosensitive resin composition of the present invention contains (C) a solvent.

The photosensitive resin composition of the present invention can be produced by mixing the components (A) and (B) as essential components, the component (D) and / or the component (E) It is preferably prepared as a solution in a solvent.

As the solvent (C) 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, Dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like.

As the solvent (C) used in the photosensitive resin composition of the present invention, for example,

(A) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether;

(B) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and ethylene glycol dipropyl ether;

(C) ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate and ethylene glycol monobutyl ether acetate;

(D) propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

(E) propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;

(F) propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate;

(G) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

(A) diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate and diethylene glycol monobutyl ether acetate;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

(Carboxy) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol ethyl methyl ether;

(K) dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate and dipropylene glycol monobutyl ether acetate;

(L) Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, isobutyl lactate, isobutyl lactate, n-amyl lactate, and lactic acid /

(Par) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetic acid, ethyl propionate, n-propyl propionate, isopropyl propionate, n- Aliphatic carboxylic acid esters such as isobutyl propionate, methyl butyrate, ethyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate and isobutyl butyrate;

(Lower) ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxypropionate, Methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, and ethyl pyruvate;

(Er) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;

Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;

(More) lactones such as? -Butyrolactone.

These solvents may also contain, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, Solvents such as octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may also be added.

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

The solvent which can be used in the present invention is preferably one type alone or in combination of two types, more preferably two kinds of solvents, more preferably propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers It is more preferable to use them in combination.

The content of the solvent (C) in the photosensitive resin composition of the present invention is preferably 50 to 3,000 parts by weight, more preferably 100 to 2,000 parts by weight, and most preferably 150 to 1,500 parts by weight per 100 parts by weight of the component (A) More preferable.

&Lt; Other components >

(D) an antioxidant, (E) a cross-linking agent, (C) an antioxidant, and (C) an antioxidant as described below as optional components, in addition to the components (A) F) a contact modifier, (G) a basic compound, (H) a surfactant, (I) a plasticizer, and (J) a thermal radical generator and a thermal acid generator, an ultraviolet absorber, a thickener, A known additive such as an inhibitor may be added.

(D) Antioxidants

The photosensitive resin composition of the present invention preferably contains (D) an antioxidant.

As the antioxidant (D), a known antioxidant may be contained. (D) the 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.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, nitrite, sulfite, thiosulfate, And a hydroxyamine derivative. Among them, a phenol-based antioxidant is particularly preferable from the viewpoint of coloring of the cured film and reduction of the film thickness. These may be used alone, or two or more kinds may be mixed and used.

Examples of commercially available phenolic antioxidants include ADEKA STOP AO-60 (manufactured by ADEKA), ADEKA STOP AO-80 (manufactured by ADEKA), Irganox 1098 (manufactured by Chiba Japan Co., ).

The content of the antioxidant (D) is preferably 0.1 to 6% by weight, more preferably 0.2 to 5% by weight, and particularly preferably 0.5 to 4% by weight based on the total solid content of the photosensitive resin composition. When the content is in this range, sufficient transparency of the formed film can be obtained and sensitivity at the time of pattern formation can be improved.

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

(E) Crosslinking agent

The photosensitive resin composition of the present invention preferably contains a crosslinking agent (E), if necessary.

As the crosslinking agent (E), for example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond may be added. By adding the crosslinking agent (E), the cured film can be made into a stronger film.

&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 and aliphatic epoxy resin.

These are available as commercial products. Examples of the bisphenol A epoxy resin include epoxy resins such as JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (Manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON 830, EPICLON 835 (manufactured by DIC Co., Ltd.), and the like, as the bisphenol F type epoxy resin, JER806, JER807, JER4004, JER4005, JER4007, JER4010 JER152, JER154, JER157S70 (manufactured by Japan Epoxy Resin Co., Ltd.)), phenol novolak type epoxy resin (trade name, manufactured by Nippon Kayaku Co., Ltd.) Examples of the cresol novolak epoxy resin include EPICLONN-640, EPICLONN-665, EPICLONN-670, EPICLONN-770 (manufactured by DIC Corporation) EPICLONN-690, EPICLONN-690, EPICLONN-695 (manufactured by DIC Corporation) and EOCN-1020 (manufactured by NIPPON KAYAKU CO., LTD.). Examples of the aliphatic epoxy resin include ADEKARESINEP- EP-4085S, EP-408 8S (manufactured by ADEKA), Selenoxide 2021P, Selenoxide 2081, Selenoxide 2083, Selenoxide 2085, EHPE 3150, EPOLEADPB3600, and PB4700 (manufactured by Daicel Chemical Industries, Ltd.) . In addition, ADEKARESINEP-4000S, EP-4003S, EP-4010S and EP-4011S (manufactured by ADEKA), NC-2000, NC-3000, NC-7300, XD- , EPPN-502 (manufactured by ADEKA Co., Ltd.), and the like. These may be used alone or in combination of two or more.

Among these, preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenol novolak type epoxy resin. Particularly, a bisphenol A type epoxy resin is preferable.

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

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

The amount of the compound having two or more epoxy groups or oxetanyl groups in the molecule to be added to the photosensitive resin composition is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 100 parts by weight of the total amount of the component (A) .

<Crosslinking agent containing alkoxymethyl group>

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycolauryl and alkoxymethylated elements are preferable. These are obtained by converting methylol melamine, methylol benzoguanamine, methylol fatty acid glycoluril, or the methylol group of methylol moiety into an alkoxymethyl group, respectively. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of the amount of out-gas generation, , And particularly preferably a methoxymethyl group.

Of these crosslinking compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycolyuril are preferable crosslinking compounds, and from the viewpoint of transparency, alkoxymethylated glycolauryl is particularly preferable.

These alkoxymethyl group-containing crosslinking agents are commercially available, for example, from Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123 , 1170, 1174, UFR65, 300 (manufactured by Mitsui Cyanamid Co.), Nigalak MX-750, -032, -706, -708, -40, -31, -270, -280, -290 , Nicalac MS-11, Nicalac MW-30HM, -100 LM, -390 (manufactured by Sanwa Chemical Co., Ltd.), and the like can be preferably used.

When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the amount of the alkoxymethyl group-containing crosslinking agent to be added is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the component (A) desirable. The addition in this range provides a favorable alkali solubility at the time of development and excellent solvent resistance of the film after curing.

&Lt; Compounds having at least one ethylenically unsaturated double bond >

As the compound having at least one ethylenic unsaturated double bond, a (meth) acrylate compound such as monofunctional (meth) acrylate, bifunctional (meth) acrylate or trifunctional or higher functional (meth) have.

Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl And 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate.

Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, and bisphenoxyethanol fluorene diacrylate.

Examples of trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

These compounds having at least one ethylenic unsaturated double bond are used singly or in combination of two or more.

The proportion of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the component (A) Do. By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. When a compound having at least one ethylenically unsaturated double bond is added, (J) a heat radical generator is preferably added.

(F) Adhesion improver

The photosensitive resin composition of the present invention may contain (F) an adhesion improver.

The (F) adhesion improver that can be used in the photosensitive resin composition of the present invention can be obtained by reacting an inorganic substance to be a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, Thereby improving adhesion. Specific examples thereof include silane coupling agents and thiol compounds. The silane coupling agent as the (F) adhesion improver used in the present invention is intended to modify the interface and is not particularly limited, and a known silane coupling agent can be used.

Preferable silane coupling agents include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrialkoxysilane,? -Glycidoxypropylalkyldialkoxysilane,? -Methacryloxypropyltrialkoxysilane,? -Methacryloxypropylalkyldialkoxysilane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyl tri Alkoxysilane, and vinyltrialkoxysilane.

Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are more preferable, and? -Glycidoxypropyltrialkoxysilane is more preferable.

These may be used alone or in combination of two or more. These are effective for improving the adhesion with the substrate, and are also effective for adjusting the taper angle with the substrate.

The content of the (F) adhesion improver in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, per 100 parts by weight of the component (A).

(G) Basic compound

The photosensitive resin composition of the present invention may contain (G) a basic compound.

As the basic compound (G), any of those used as a chemically amplified resist may be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Examples of the aliphatic amine include aliphatic amines such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- , Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

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

Examples of heterocyclic amines include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, Benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8- 4-methyl morpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, pyrrolidine, piperidine, piperazine, morpholine, 1,8-diazabicyclo [5.3.0] -7-undecene and the like.

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

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

The basic compounds usable in the present invention may be used singly or in combination of two or more kinds, but two or more kinds thereof are preferably used in combination, more preferably two kinds of them, and heterocyclic amines are substituted with 2 More preferably in combination.

The content of the (G) basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.2 part by weight, per 100 parts by weight of the component (A).

(H) Surfactant

The photosensitive resin composition of the present invention may contain (H) a surfactant.

As the surfactant (H), any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Goeisha Chemical Co., Ltd.), F-top (manufactured by JEMCO), Megapack (manufactured by DIC Corporation) (Manufactured by Asahi Glass Co., Ltd.) and PolyFox (manufactured by OMNOVA Co., Ltd.), and the like.

The surfactant preferably has a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography when the surfactant contains the constituent unit A and the constituent unit B represented by the following formula (1) and tetrahydrofuran (THF) (Mw) of 1,000 or more and 10,000 or less can be mentioned as a preferable example.

(Wherein R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a straight chain alkylene group having 1 to 4 carbon atoms and R ⁴ represents a hydrogen atom or a C1- P represents an alkylene group having 3 to 6 carbon atoms, p and q represent weight percentages indicating polymerization ratios, p represents a value of 10 to 80 wt%, q represents 20 wt% Or more and 90% or less by weight, r is an integer of 1 or more and 18 or less, and n is an integer of 1 or more and 10 or less)

It is preferable that L is a branched alkylene group represented by the following formula (2). R ⁵ in the formula (2) represents an alkyl group having 1 to 4 carbon atoms and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to a surface to be coated, and an alkyl group having 2 or 3 carbon atoms More preferable. It is preferable that the sum (p + q) of p and q is p + q = 100, that is, 100% by weight.

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

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

The amount of the surfactant (H) added to the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 1 part by weight based on 100 parts by weight of the component (A) It is more desirable to be negative.

(I) a plasticizer

The photosensitive resin composition of the present invention may contain (I) a plasticizer.

Examples of the plasticizer (I) include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethyl glycerine phthalate, dibutyl tartrate, dioctyl adipate and triacetyl glycerin.

The amount of the plasticizer (I) added to the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the component (A).

(J) Thermal radical generator

The photosensitive resin composition of the present invention may contain (J) a thermal radical generator, and when it contains an ethylenically unsaturated compound such as a compound having at least one ethylenically unsaturated double bond as described above, (J) a thermal radical It is preferable to contain the generator.

As the thermal radical generator in the present invention, a known thermal radical generator may be used.

The thermal radical generator is a compound that generates radicals by heat energy to initiate or promote the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the resulting cured film becomes more tough, and heat resistance and solvent resistance are sometimes improved.

Preferred thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, A compound having a bond, an azo-based compound, and a non-benzyl compound.

As the thermal radical generator (J), one type may be used alone, or two or more types may be used in combination.

The amount of the heat radical generator (J) to be added to the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polymer (A) More preferably 0.5 to 10 parts by weight.

(Method of forming a cured film)

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

The method for forming a cured film of the present invention is characterized by including the following steps (1) to (5).

(1) a coating step of applying the photosensitive resin composition of the present invention on a substrate

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

(3) an exposure process for exposing by an actinic ray

(4) a development step of developing with an aqueous developer

(5) Post-baking process for thermosetting

Each step will be described below in order.

(1), the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent.

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

In the exposure step of (3), an active 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. The acid-decomposable group in the monomer unit represented by the formula (Ia) and / or the formula (Ib) and the formula (IIa) and / or the formula (IIb) contained in the polymer (A) And decomposed to produce a carboxyl group and / or a phenolic hydroxyl group.

Post-exposure heat treatment: Post Exposure Bake (hereinafter, also referred to as &quot; PEB &quot;) can be performed as needed in order to accelerate the hydrolysis reaction in the region where the acid catalyst is formed. By PEB, the generation of carboxyl groups from the acid decomposable group can be promoted.

The acid decomposable group in the monomer unit represented by the formula (Ia) and / or the formula (Ib) 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, Since a carboxyl group is generated, a positive image can be formed by development without necessarily performing PEB. Further, in the present invention, since monomer units represented by formula (IIa) and / or formula (IIb) having an acid-decomposable group having a relatively high acid decomposition activation energy are used in combination, stable photosensitive resin compositions Can be obtained.

By performing PEB at a relatively low temperature, the hydrolysis of the acid decomposable group can be promoted without causing a crosslinking reaction. The temperature at which PEB is carried out is preferably 30 占 폚 to 130 占 폚, more preferably 40 占 폚 to 110 占 폚, and particularly preferably 50 占 폚 to 80 占 폚.

(4), the polymer having a liberated carboxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed region containing a resin composition having a carboxyl group which is liable to dissolve in an alkaline developing solution.

(A1) and the monomer unit (a2) by thermal decomposition of the acid-decomposable group in the post-baking step of the step (5) by heating the obtained positive image to crosslink a carboxyl group with an epoxy group and / or an oxetanyl group, A cured film can be formed. This 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 250 ° C. The heating time can be appropriately set according to the heating temperature and the like, but it is preferably within a range of 10 to 90 minutes.

When a step of irradiating an entire surface of the development pattern with an actinic ray, preferably ultraviolet light, is carried out before the post-baking step, the cross-linking reaction can be promoted by an acid generated by actinic light irradiation.

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

&Lt; Method of producing photosensitive resin composition >

(A) to (C) are mixed in an arbitrary manner at a predetermined ratio, and dissolved by stirring to prepare a photosensitive resin composition. For example, it is also possible to prepare a solution in which the component (A) or (B) is dissolved in advance in the solvent (C), and then mix them in a predetermined ratio to prepare a resin composition. The composition solution prepared as described above may be used after being filtered using a filter having a pore diameter of 0.2 mu m or the like.

<Coating Process and Solvent Removal Process>

A desired dry film can be formed by applying the resin composition to a predetermined substrate and removing the solvent by reduced pressure and / or heating (prebaking). As the substrate, for example, in the production of a liquid crystal display element, a polarizing plate, a glass plate provided with a black matrix layer, a color filter layer and a transparent electroconductive circuit layer as required can be exemplified. The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spraying method, a roll coating method, and a spin coating method can be used. Among them, the slit coating method is preferable from the viewpoint of being suitable for a large substrate. Here, a large substrate refers to a substrate having a size of 1 m or more on each side.

The heating condition of the solvent removal step (2) is such that the acid decomposable group decomposes in the monomer unit (a1) and the monomer unit (a2) in the component (A) in the unexposed portion and the component (A) And it varies depending on the kind of each component and blending ratio, and 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, an active ray is irradiated onto a substrate provided with a coating film through a mask having a predetermined pattern. After the exposure process, a heating process (PEB) is carried out if necessary, and in the development process, an exposed area is removed by 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 the exposure by the active light beam, and a low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, chemical lamp, LED light source, Of an active ray having a wavelength of 300 nm or more and 450 nm or less can be preferably used. If necessary, the irradiation light can be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

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

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

The developing time is preferably 30 to 180 seconds, and the developing method may be any of a liquid method, a dipping method, and the like. After the development, a desired pattern can be formed by conducting an aqueous (water) cleaning for 30 to 90 seconds.

&Lt; Post baking step (crosslinking step) >

For example, at a predetermined temperature, for example, 180 to 250 DEG C, for a predetermined time, for example, in a hot plate state, by using a heating apparatus such as a hot plate or an oven to a pattern corresponding to the unexposed region, (A) is decomposed by decomposition of the acid-decomposable group in the component (A) by heating for 60 to 60 minutes in the case of an oven and 30 to 90 minutes in the case of an oven to react with a crosslinkable group which is an epoxy group and / By crosslinking, a protective film or an interlayer insulating film excellent in heat resistance, hardness and the like can be formed. In addition, transparency can be improved by performing the heat treatment in a nitrogen atmosphere.

Prior to the heat treatment, 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 is formed by an actinic ray , And to function as a catalyst promoting the crosslinking process.

That is, the method of forming a cured film of the present invention preferably 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 whole 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 step is 100 to 1,000 mJ / cm &lt; ^{2 &} gt ;.

By the photosensitive resin composition of the present invention, an interlayer insulating film having excellent transparency can be obtained even when it is baked at a high temperature with excellent insulating properties. The interlayer insulating film formed using 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.

The organic EL display device and the liquid crystal display device of the present invention are not particularly limited except that they have a planarizing film or an interlayer insulating film formed using the photosensitive resin composition of the present invention and may be various known organic EL displays Device or a liquid crystal display device.

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

1 is a conceptual diagram showing an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device, and has a planarization film 4.

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

The planarization layer 4 is formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 2.

On the planarizing film 4, a bottom emission type 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.

The insulating film 8 is formed so as to cover the periphery of the first electrode 5. By providing the insulating film 8, the first electrode 5 and the second electrode Can be prevented.

Although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited by a desired pattern mask, and 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 form an organic EL display device in which an active matrix type organic EL display device in which a TFT 1 for driving each organic EL element is connected to each organic EL element is sealed.

2 is a conceptual cross-sectional view showing an example of the liquid crystal display device 10 of the active matrix type. 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 a liquid crystal display panel in which all of the liquid crystal display panel 10 is disposed between two glass substrates 14, Elements of the TFT 16 corresponding to the pixel are disposed. 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 the liquid crystal 20 and a black matrix are arranged is provided.

[Example]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

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

tert-BMA: tert-butyl methacrylate

V-65: 2,2'-azobis (2,4-dimethylvaleronitrile)

GMA: glycidyl methacrylate

EDM: diethylene glycol ethyl methyl ether

&Lt; Synthesis of Polymer A-1 &

And 0.5 parts by weight of phenothiazine was added to 144.2 parts by weight (2 molar equivalents) of ethyl vinyl ether. 86.1 parts by weight (1 molar equivalent) of methacrylic acid was added dropwise while cooling the reaction system to 10 DEG C or lower, Lt; / RTI &gt; for 4 hours. 5.0 parts by weight of p-toluenesulfonic acid pyridinium was added, followed by stirring at room temperature for 2 hours, and the mixture was allowed to stand at room temperature overnight. 5 parts by weight of sodium hydrogencarbonate and 5 parts by weight of sodium sulfate were added to the reaction mixture, and the mixture was stirred at room temperature for 1 hour. The insoluble material was filtered and then concentrated under reduced pressure at 40 DEG C or lower to distill off the yellow oil- (bp.) 43 to 45 占 폚 / 7 mmHg of fraction (fraction) of 134.0 parts by weight of 1-ethoxyethyl methacrylate as a colorless oil.

(42.66 parts by weight (0.3 molar equivalents)) and EDM (126.6 parts by weight (0.3 molar equivalents)), tert-butyl methacrylate ) Was heated to 70 캜 under a nitrogen stream. While stirring the mixed solution, a mixed solution of radical polymerization initiator V-65 (4 parts by weight, manufactured by Wako Pure Chemical Industries, Ltd.) and EDM (100.0 parts by weight) was added dropwise over 2.5 hours. After completion of the dropwise addition, the reaction was carried out at 70 DEG C for 4 hours to obtain an EDM solution of polymer A-1 (solid concentration: 40% by weight). The polymer A-1 thus obtained had a weight average molecular weight of 18,000 as determined by gel permeation chromatography (GPC).

<Synthesis of Polymers A-2 to A-14, A'-15 and A'-16>

Polymers A-2 to A-14, A'-15, A'-16 and A-17 were synthesized in the same manner as in the synthesis of Polymer A-1 except that the respective monomers used and the amounts used were changed to those shown in Table 1. Respectively.

[Table 1]

The copolymerization ratios shown in Table 1 are molar ratios, and the abbreviations in Table 1 are as follows.

MAEVE: 1-ethoxyethyl methacrylate

t-BMA: tert-butyl methacrylate

GMA: glycidyl methacrylate

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

OXE-10: Acrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.)

HEMA: 2-hydroxyethyl methacrylate

M100: 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd.)

A400: 3,4-epoxycyclohexylmethyl acrylate (manufactured by Daicel Chemical Industries, Ltd.)

MAA: methacrylic acid

thpMA: methacrylic acid tetrahydro-2H-pyran-2-yl

Ph-2: 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester

Ph-3: 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester

Ph-6: 4-Hydroxybenzoic acid (6-methacryloyloxyhexyl) ester

Ph-3OH: 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester

CHOEMA: 1- (cyclohexyloxy) ethyl methacrylate

MATHF: tetrahydrofuran-2-yl methacrylate

P-Ph-3: 1-ethoxyethyl ether of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester

P-Ph-1: tetrahydropyranyl ether of 4-hydroxyphenyl methacrylate

St: Styrene

C1: Propylene glycol monomethyl ether acetate

C2: diethylene glycol ethyl methyl ether

Further, thpMA (tetrahydro-2 H-pyran-2-yl methacrylate) was synthesized by the method of Synthesis Example 1 described in paragraph 0018 of Japanese Patent Application Laid-Open No. 5-88367.

CHOEMA (1- (cyclohexyloxy) ethyl methacrylate) was also synthesized by the same method. The protection of other 1-ethoxyethyl ether and tetrahydropyranyl ether was also carried out in the same manner.

Ph-2, Ph-3, Ph-6, and Ph-3OH were synthesized by the following methods, respectively.

<Synthesis of Ph-2 (4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester]

20 ml of N, N-dimethylacetamide was added to a solution of 21 g of 4-hydroxybenzoic acid (2-hydroxyethyl) ester in 100 ml of acetonitrile with stirring, and 20 g of methacrylic chloride was further added. The reaction mixture was poured into ice water and the precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to obtain 4-hydroxybenzoic acid (2-methacryloyl Chloroyloxyethyl) ester.

Ph-3 (4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester) and Ph-6 (4-hydroxybenzoic acid (6-methacryloyloxyhexyl) And synthesized together.

<Synthesis of Ph-3OH (4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester]

100 g of p-hydroxybenzoic acid, 100 g of glycidyl methacrylate, and 9.7 g of tetrabutylammonium bromide were added to 250 ml of N-methylpyrrolidone and reacted at 90 DEG C for 6 hours while stirring. The reaction mixture was diluted with water / acetic acid Ethyl acetate mixed solvent. The precipitated crystals were collected by filtration and recrystallized from ethyl acetate / n-hexane to obtain 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester.

&Lt; Synthesis of MATHF (tetrahydrofuran-2-yl methacrylate)

Methacrylic acid (86 g, 1 mole) was cooled to 15 占 폚 and camphorsulfonic acid (4.6 g, 0.02 mole) was added. 2,3-dihydrofuran (71 g, 1 mole, 1.0 equivalent) was added dropwise to the solution. After stirring for 1 hour, a saturated aqueous solution of sodium hydrogencarbonate (500 ml) was added, 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. Distilled under reduced pressure to obtain 125 g of a tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg as a colorless oil (yield: 80%).

(Examples 1 to 53 and Comparative Examples 1 to 3)

(1) Preparation of photosensitive resin composition solution

The components shown in Tables 2 to 4 were mixed to prepare a homogeneous solution, which was then filtered using a polytetrafluoroethylene filter having a pore size of 0.2 mu m, The photosensitive resin composition solutions of Comparative Examples 1 and 2 were prepared.

[Table 2]

[Table 3]

[Table 4]

The abbreviations in Tables 2 to 4 are as follows.

B1: CGI1397 (manufactured by Chiba Japan Co., Ltd.)

B2: CGI1325 (manufactured by Chiba Japan Co., Ltd.)

B3: PAI-1001 (the structure shown below, manufactured by Midori Kagaku Co., Ltd.)

B4: DBA (9,10-dibutoxyanthracene, structure shown below, manufactured by Kawasaki Chemical Industry Co., Ltd.)

&Lt; Synthesis of Photoacid generator B5 >

1-1. Synthesis of Synthetic Intermediate B5-A

(25 占 폚) was dissolved in 100 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 31.3 g of 2-aminobenzenethiol (manufactured by Tokyo Chemical Industry Co., Ltd.). Subsequently, 40.6 g of phenylacetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the mixture was reacted by stirring at room temperature for 1 hour and then at 100 ° C for 2 hours. 500 mL of water was added to the obtained reaction solution to dissolve the precipitated salt, and the toluene oil was extracted. The extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B5-A.

1-2. Synthesis of B5

2.25 g of the thus-obtained synthetic intermediate B5-A was mixed with 10 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) and then immersed in an ice bath to cool the reaction solution to 5 캜 or lower. Next, 4.37 g of tetramethylammonium hydroxide (25% by weight methanol solution, manufactured by Alfa Acer Co.) was added dropwise, and the mixture was reacted with stirring for 0.5 hour in an ice bath. Further, 7.03 g of isopentyl nitrite was added dropwise while keeping the internal temperature at 20 캜 or lower. After completion of dropwise addition, the reaction solution was heated to room temperature and stirred for 1 hour.

Subsequently, the reaction solution was cooled to 5 캜 or lower, p-toluenesulfonyl chloride (1.9 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred for 1 hour while maintaining the temperature at 10 캜 or lower. Then, 80 mL of water was added, and the mixture was stirred at 0 ° C for 1 hour. The resultant precipitate was filtered, and 60 mL of isopropyl alcohol (IPA) was added. The mixture was heated to 50 캜 and stirred for 1 hour, filtered, and dried to obtain 1.8 g of (B5: the above structure).

The obtained ¹ H-NMR spectrum of the obtained B5 (300 MHz, DMSO ((D ₃ C) ₂ S = O)) was found to be δ = 8.2-8.17 (m, 1H), 8.03-8.00 (m, 2H), 7.6-7.45 (m, 9H), 2.45 (s, 3H).

From the ¹ H-NMR measurement results, it is estimated that the obtained B5 is a single geometric isomer.

<Synthesis of B6>

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

Acetic acid (7.3 g) and a 50 wt% aqueous solution of hydroxyamine (8.0 g) were added to the suspension of the obtained 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 obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the 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 off and then slurry was rinsed with methanol (20 mL), followed by filtration and drying to obtain B6 (2.3 g).

In addition, ¹ H-NMR spectrum of B6 (300MHz, CDCl ₃₎ is, δ = 8.3 (d, 1H ), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (dd 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

C1: Propylene glycol monomethyl ether acetate

C2: diethylene glycol ethyl methyl ether

D1: ADEKA STOP AO-60 (manufactured by ADEKA Corporation)

E1: JER-157S70 (polyfunctional novolac epoxy resin (epoxy equivalents: 200 to 220 g / eq), Japan Epoxy Resin Co., Ltd.)

E2: Nikalkak MW-100LM (manufactured by Sanwa Chemical Co., Ltd.)

Surfactant 1: Megapack R-08 (a nonionic surfactant containing a perfluoroalkyl group, manufactured by DIC Corporation)

Surfactant 2: Compound W-3 having the following structure

Basic compound 1: 4-dimethylaminopyridine

Basic compound 2: 1,5-Diazabicyclo [4.3.0] -5-nonene

Basic compound 3: Triphenylimidazole

Adhesion improving agent 1: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

The composition used in Comparative Example 3 is the composition described in Example 1 of JP-A-2004-264623. That is, the composition is prepared as follows.

A cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether were charged. Subsequently, 40 parts by weight of 1- (cyclohexyloxy) ethyl methacrylate, 5 parts by weight of styrene, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, After charging the parts by weight and replacing with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer. The polystyrene reduced weight average molecular weight (Mw) of the obtained copolymer was 11,000. The solid content concentration of the obtained polymer solution was 31.6% by weight.

The solution containing the copolymer synthesized above was dissolved in an amount corresponding to 100 parts by weight (solid content) of the copolymer and an amount of 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoro And 5 parts by weight of methane sulfonate were dissolved in diethylene glycol methyl ethyl ether to have a solid concentration of 30% by weight and then filtered through a membrane filter having a pore diameter of 0.2 탆 to prepare a photosensitive resin composition of Comparative Example 3.

(2) Evaluation of sensitivity

The solution of the photosensitive resin composition was spin-coated on a silicon wafer having a silicon oxide film and then pre-baked on a hot plate at 95 캜 for 90 seconds to form a coating film having a film thickness of 3 탆.

Next, exposure was performed through a predetermined mask using an i-line stepper (FPA-3000i5 ⁺ manufactured by Canon Inc.). After the exposure, the resist film was developed by a liquid method at 23 캜 for 60 seconds with a 0.4% by weight tetramethylammonium hydroxide aqueous solution, and rinsed with ultrapure water for 1 minute. With these operations, the optimum exposure amount (Eopt) at the time of resolving a line-and-space of 10 mu m at a ratio of 1: 1 was taken as sensitivity. The sensitivity can be said to be high sensitivity when the exposure amount is lower than 100 mJ / cm ² .

(3) Evaluation of exposure dose dependency

(Eopt-10%) of the exposure amount (Eopt-10%) and Eopt (+ 10% of the exposure amount) were obtained for the optimum exposure amount Eopt (Line width when exposed at an exposure amount of Eopt + 10%)) was set to &quot; 1 &quot; when it was less than 1 mu m and &quot; 2 &quot; In the case of &quot; 1 &quot;, it can be said that the exposure amount dependency is good.

The evaluation results of sensitivity and exposure dose dependency are shown in Tables 5 and 6.

It can be seen that the photosensitive resin composition of the present invention has high sensitivity and good exposure dose dependency.

[Table 5]

[Table 6]

(4) Evaluation of solvent resistance

The solution of the photosensitive resin composition was spin-coated on a silicon wafer having a silicon oxide film and then pre-baked on a hot plate at 95 캜 for 90 seconds to form a coating film having a film thickness of 3 탆. The obtained coating film was exposed with a PLA-501F exposure apparatus (ultra-high pressure mercury lamp) manufactured by Canon Inc. so as to have a cumulative dose of 200 mJ / cm ² (light intensity: 20 mW / cm ² ) And heated for a time to obtain a cured film. The film thickness (T1) of the obtained cured film was measured. Next, the silicon wafer on which the cured film was formed was immersed in N-methylpyrrolidone controlled at 25 占 폚 for 30 minutes, and then the film thickness t1 of the cured film was measured, and the rate of film thickness change {| t1 -T1 | / T1} x 100 (%). If the rate of change is less than 3%, the solvent resistance is good.

Table 7 shows the evaluation results of the solvent resistance.

All of the photosensitive compositions of the present invention exhibit good solvent resistance and are particularly good when a polymer containing an alicyclic epoxy group is used, when a resin containing an oxetanyl group is used, and when a crosslinking agent is used.

[Table 7]

(5) Evaluation of heat resistance transparency

(4) A cured film was formed on a glass substrate in the same manner as in (4) except that a glass substrate "Corning 1737 (manufactured by Corning)" was used instead of the silicon wafer in the evaluation of the solvent resistance. The obtained cured film was further heated in an oven at 230 DEG C for 2 hours and then the light transmittance was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer "150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.)" . Evaluation of the lowest light transmittance (evaluation of heat resistance and transparency) at that time is shown in Table 8. When this value is 81% or more, it can be said that heat-resistant transparency is good.

All of the photosensitive compositions of the present invention exhibit good heat-resistant transparency. Particularly, when the photoacid generator B6 is used, and when an antioxidant is used, the photosensitive composition of the present invention is particularly satisfactory.

[Table 8]

(Example 54)

Using the photosensitive resin composition of Example 51, the same evaluation as in Example 51 was conducted using a UV-LED light source exposing apparatus instead of an ultra-high pressure mercury lamp, and the same results as in Example 51 were obtained.

(Example 55)

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

A TFT 1 of a bottom gate type was formed on a glass substrate 6 and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and a wiring 2 (height 1.0 mu m) connected to the TFT 1 through the contact hole is formed on the insulating film 3 did. This wiring 2 is for connecting the organic EL element formed between the TFTs 1 or a later step to the TFT 1. [

The planarization layer 4 was formed on the insulating film 3 so as to fill the irregularities formed by the wirings 2 in order to planarize the irregularities formed by the formation of the wirings 2. The planarizing film 4 on the insulating film 3 was formed by spin-coating the photosensitive resin composition of Example 7 on a substrate, prebaking on a hot plate (90 占 폚 for 2 minutes), using a high-pressure mercury lamp on the mask Irradiated with i-line (365 nm) at 45 mJ / cm ² (illuminance of 20 mW / cm ² ), developed with an alkali aqueous solution to form a pattern, and subjected to heat treatment at 230 ° C for 60 minutes. The coating property when the photosensitive resin composition was applied was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and firing. The average step of the wiring 2 was 500 nm, and the thickness of the planarization film 4 was 2,000 nm.

Next, an organic EL device of a bottom emission type was formed on the obtained planarization film (4). First, a first electrode 5 made of ITO was formed on the flattening film 4 by connecting it to the wiring 2 through the contact hole 7. Thereafter, the resist was applied, pre-baked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, patterning was carried out by wet etching using ITO etchant. Thereafter, the resist pattern was peeled off using a resist stripping solution (a mixture of monoethanolamine and dimethyl sulfoxide (DMSO)). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed using the photosensitive resin composition of Example 7 by the same method as described above. By providing 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 deposited through a desired pattern mask in a vacuum vapor deposition apparatus. Then, a second electrode made of Al was formed on the entire upper surface of the substrate. The obtained substrate was taken out from the evaporator, and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix type organic EL display device in which TFTs 1 for driving the organic EL elements are connected to each organic EL element was obtained. When the voltage was applied through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was highly reliable.

(Example 56)

An organic EL device was prepared in the same manner as in Example 55 except that the photosensitive resin composition of Example 7 was changed to the photosensitive resin composition of Example 34. [ The organic EL display device exhibits good display characteristics and is highly reliable.

(Example 57)

An organic EL device was prepared in the same manner as in Example 55 except that the photosensitive resin composition of Example 7 was changed to the photosensitive resin composition of Example 51. [ The organic EL display device exhibits good display characteristics and is highly reliable.

(Example 58)

In the active matrix type liquid crystal display device shown in Figs. 1 and 2 of Japanese Patent No. 3321003, a cured film 17 as an interlayer insulating film was formed as follows to obtain a liquid crystal display device of Example 58. [

That is, the photosensitive resin composition of Example 7 was used to form a cured film 17 as an interlayer insulating film in the same manner as in the method of forming the planarization film 4 of the organic EL display device in Example 55.

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

(Example 59)

A liquid crystal display device was prepared in the same manner as in Example 58 except that the photosensitive resin composition of Example 7 was changed to the photosensitive resin composition of Example 34. [ The liquid crystal display device exhibits good display characteristics and is highly reliable.

(Example 60)

A liquid crystal display device was manufactured in the same manner as in Example 58 except that the photosensitive resin composition of Example 7 was changed to the photosensitive resin composition of Example 51. [ The liquid crystal display device exhibits good display characteristics and is highly reliable.

1: TFT (thin film transistor)
2: Wiring
3: Insulating film
4: Planarizing film
5: First electrode
6: glass substrate
7: Contact hole
8: Insulating film
10: Liquid crystal display
12: Backlight unit
14, 15: glass substrate
16: TFT
17:
18: Contact hole
19: ITO transparent electrode
20: liquid crystal
22: Color filter

Claims (14)

(A) a monomer unit (a1) having a structure represented by the formula (Ia) for producing a carboxy group by an acid or a structure represented by the formula (Ib) for producing a phenolic hydroxyl group by an acid, A monomer unit (a2) having a structure represented by the formula (IIa) or a structure represented by the formula (IIb) which generates a phenolic hydroxyl group by an acid, and a monomer unit having an epoxy group and / or oxetanyl group ), &Lt; / RTI &gt;
(B) a photoacid generator, and
(C) a solvent.
Sensitive resin composition.

(Wherein, R ¹ represents an alkyl group or a cycloalkyl group independently, R ² are, each independently, an alkyl group, R ³ represents a tertiary alkyl group or a 2-tetrahydropyranyl, R ⁴ is the Ar ¹ and Ar ² each independently represent a divalent aromatic group, and the broken line portion represents a bonding site to another structure. In addition, R 1, R 2, R 3, R 4, R 5, ¹ and R ² may be connected to form a cyclic ether (except for the 6-membered ring structure)) The method according to claim 1,
Wherein the monomer unit (a1) is a monomer unit represented by the formula (III), and the monomer unit (a2) is a monomer unit represented by the formula (IV).

(Wherein R ⁵ represents an alkyl group or a cycloalkyl group, R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a tertiary alkyl group or a 2-tetrahydropyranyl group, and R ⁸ represents a hydrogen atom or a methyl group ) 3. The method according to claim 1 or 2,
Wherein the photosensitive resin composition is a chemically amplified positive photosensitive resin composition. 3. The method according to claim 1 or 2,
Wherein the monomer unit (a3) is a monomer unit having an alicyclic epoxy group and / or a monomer unit having an oxetanyl group. 3. The method according to claim 1 or 2,
Wherein the monomer unit (a3) in the polymer (A) is at least one monomer selected from the group consisting of 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, Methyl methacrylate, and methyl methacrylate (3-ethyloxetan-3-yl) methyl. 3. The method according to claim 1 or 2,
Wherein the photoacid generator (B) is a compound having an oxime sulfonate residue. 3. The method according to claim 1 or 2,
Wherein the photoacid generator (B) is a compound represented by formula (OS-3), formula (OS-4) or formula (OS-5).

Wherein R ¹ represents an alkyl group, an aryl group or a heteroaryl group, each of R ² independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, R ⁶ each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents 0 to 6 Lt; / RTI &gt; 3. The method according to claim 1 or 2,
(D) an antioxidant. 3. The method according to claim 1 or 2,
(E) a crosslinking agent. (1) a coating step of applying the photosensitive resin composition according to any one of claims 1 to 3 on a substrate,
(2) a solvent removing step of removing the solvent from the applied photosensitive resin composition,
(3) an exposure step for exposing by an actinic ray,
(4) a developing step of developing by an aqueous developing solution, and
(5) a heat-curing post-baking step
Method of forming a cured film. A cured film formed by the method according to claim 10. 12. The method of claim 11,
A cured film which is an interlayer insulating film. An organic EL display device comprising the cured film according to claim 11. A liquid crystal display device comprising the cured film according to claim 11.

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