KR20110042006A - Photosensitive resin composition, method for producing cured film, cured film, organic el display device and liquid crystal display device - Google Patents

Abstract

PURPOSE: A photosensitive resin composition, a method for forming a cured film, the cured film, an organic electroluminescent display device, and a liquid crystal display device are provided to reduce the change of pattern shapes according to the change of exposure amounts. CONSTITUTION: A photosensitive resin composition includes polymer, a photoacid generator, and a solvent. The polymer includes a first monomer unit, a second monomer unit, and a third monomer unit. The first monomer unit is represented by chemical formula Ia or chemical formula Ib. The second monomer unit is represented by chemical formula IIa or chemical formula IIb. The third monomer unit includes epoxy group and/or oxetanyl group. The chemical formula Ia generates carboxylic group by acid. The chemical formula Ib generates phenolic hydroxyl group by acid. The chemical formula IIa generates carboxylic group by acid. The chemical formula IIb generates phenolic hydroxyl group by acid.

Description

Photosensitive resin composition, formation method of cured film, cured film, organic EL display device, and liquid crystal display device {PHOTOSENSITIVE RESIN COMPOSITION, METHOD FOR PRODUCING CURED FILM, CURED FILM, ORGANIC EL DISPLAY DEVICE AND LIQUID CRYSTAL DISPLAY DEVICE}

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

The organic EL display device, the liquid crystal display device, or the like is provided with a patterned interlayer insulating film. The photosensitive resin composition is widely used in the formation of this interlayer insulating film because the number of steps for obtaining the required pattern shape is small and sufficient flatness is obtained.

In the interlayer insulating film in the display device, high transparency is desired in addition to the physical properties of the cured film excellent in insulation, solvent resistance, heat resistance, and indium tin oxide (ITO) sputterability. For this reason, it is tried to use acrylic resin excellent in transparency as a film formation component.

As such a photosensitive resin composition, patent document 1 has copolymerization of (A) (a) unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, (b) radically polymerizable compound which has an epoxy group, and (c) other radically polymerizable compound, for example. There is proposed a photosensitive resin composition having a resin soluble in a chain alkali aqueous solution and (B) a radiation sensitive acid generating compound.

In addition, Patent Literature 2 has a (A) acetal structure and / or a ketal structure, and an epoxy structure, and a polystyrene reduced weight average molecular weight measured by gel permeation chromatography is 2000 or more, and (B) irradiation of radiation. There has been proposed a radiation sensitive resin composition containing a compound in which pKa generates an acid of 4.0 or less.

In addition, Patent Document 3 contains (A) a structural unit having a functional group capable of reacting with a structural unit represented by the following General Formula (1) having an acid dissociable group and a carboxyl group to form a covalent bond, and is alkali insoluble or alkali. The positive photosensitive resin composition which is poorly soluble and contains at least the compound which becomes alkali-soluble when the said acid dissociable group dissociates, and (B) the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation is described. It is.

In 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 linked to form a cyclic ether.

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

The photosensitive resin composition of the said patent document 1 does not have sufficient sensitivity, resolution, and time-lapse stability, and is not satisfactory in order to manufacture a high quality liquid crystal display element, and also pattern shape with respect to the change of exposure amount. There was a problem that the change was large.

Moreover, the photosensitive resin compositions of the said patent documents 2 and 3 had the problem that the sensitivity is low, and / or that the change of the pattern shape with respect to the change of exposure amount is large.

An object of the present invention is to provide a cured film having excellent solvent resistance and heat resistance, having high sensitivity, and having a small change in pattern shape with respect to a change in exposure dose (also referred to as "wide exposure latitude"), It is providing the cured film using the said photosensitive resin composition, its manufacturing method, an organic electroluminescence display, and a liquid crystal display device.

The said subject of this invention was solved by the means as described in the following <1>, <10>, <11>, <13>, or <14>. It describes below with <2>-<9> and <12> which are preferable embodiments.

<1> (A) monomer unit (a1) which has a structure represented by Formula (Ia) which produces | generates a carboxyl group by acid, or a structure represented by Formula (Ib) which produces | generates phenolic hydroxyl group by acid, and an acid Monomer unit (a2) which has a structure represented by Formula (IIb) which produces a phenolic hydroxyl group by the structure represented by Formula (IIa) which produces | generates a carboxyl group, and a monomer, and a monomer which has 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 each independently represents an alkyl group or a cycloalkyl group, R ² each independently represents an alkyl group, R ³ represents a tertiary alkyl group or 2-tetrahydropyranyl group, and R ⁴ represents tertiary alkyl group, tert- butoxycarbonyl group, or 2-tetrahydro pyranyl represents a group, Ar ¹ and Ar ² are, each independently, an aryl, a broken line portion represents a bond with other portions of the structure. in addition, R ¹ and R ² may be linked to form a cyclic ether (except for a 6-membered ring structure))

<2> Photosensitive resin composition as described in said <1> whose said monomer unit (a1) is a monomer unit represented by Formula (III), and whose said monomer unit (a2) is a monomer unit represented by 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) )

The photosensitive resin composition as described in said <1> or <2> which is a <3> chemically amplified positive type photosensitive resin composition,

<4> Photosensitive resin composition in any one of said <1>-<3> whose said monomer unit (a3) is a monomer unit which has an alicyclic epoxy group, and / or a monomer unit which has an oxetanyl group,

<5> The said monomer unit (a3) in the said (A) polymer is acrylic acid 3, 4- epoxycyclohexylmethyl, methacrylic acid 3, 4- epoxycyclohexylmethyl, and acrylic acid (3-ethyloxetane-3 -Yl) methyl and any one of said <1>-<4> which is a monomeric unit derived from at least 1 sort (s) chosen from the group which consists of methacrylic acid (3-ethyloxetan-3-yl) methyl. Photosensitive resin composition,

<6> Photosensitive resin composition in any one of said <1>-<5> whose said (B) photo-acid generator is a compound which has an oxime sulfonate residue,

<7> The said (B) photo-acid generator is a compound as described in any one of said <1>-<6> which is a compound represented by a formula (OS-3), a formula (OS-4), or a formula (OS-5). Photosensitive resin composition,

(In formula (OS-3)-Formula (OS-5), R <^1> represents an alkyl group, an aryl group, or a heteroaryl group, R <^2> respectively independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ⁶ are, each independently, a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group and represents an amino-sulfonyl group, or an alkoxy-sulfonyl, X represents O or S, n represents 1 or 2, m is 0 to 6 of Represents an integer)

<8> Photosensitive resin composition in any one of said <1>-<7> which further contains (D) antioxidant,

<9> Photosensitive resin composition in any one of said <1>-<8> which further contains (E) crosslinking agent,

<10> (1) The application | coating process of apply | coating the photosensitive resin composition in any one of said <1>-<9> on a board | substrate, (2) The solvent removal process which removes a solvent from the apply | coated photosensitive resin composition, (3) A method of forming a cured film including an exposure step of exposing with actinic light, (4) a developing step of developing with an aqueous developer, and (5) a postbaking step of thermosetting,

<11> Cured film formed by the method as described in said <10>,

The cured film as described in said <11> which is a <12> interlayer insulation film,

<13> The organic electroluminescence display provided with the cured film as described in said <11> or <12>,

<14> The liquid crystal display device which comprises the cured film as described in said <11> or <12>.

ADVANTAGE OF THE INVENTION According to this invention, the cured film excellent in solvent resistance and heat resistance transparency is obtained, it has high sensitivity, and the photosensitive resin composition with small change of pattern shape with respect to a change of exposure amount, the cured film using the said photosensitive resin composition, and its manufacture A method, an organic EL display device, and a liquid crystal display device can be provided.

1 shows a configuration conceptual diagram of an example of an organic EL display device. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4.
2 shows a configuration conceptual diagram of an example of a liquid crystal display device. Typical sectional drawing of the active-matrix board | substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.

(Photosensitive resin composition)

Hereinafter, the photosensitive resin composition of this invention is demonstrated in detail.

The photosensitive resin composition of this invention has a monomer unit (a1) which has a structure represented by Formula (Ia) which produces a carboxyl group by (A) acid, or a structure represented by Formula (Ib) which produces a phenolic hydroxyl group by acid. ), A monomer unit (a2) having a structure represented by formula (IIa) that generates a carboxyl group by an acid or a structure represented by formula (IIb) that produces a phenolic hydroxyl group by an acid, and an epoxy group and / or jade A polymer containing a monomer unit (a3) having a cetanyl group, (B) a photoacid generator, and (C) a solvent are contained.

(Wherein, R ¹ each independently represents an alkyl group or a cycloalkyl group, R ² each independently represents an alkyl group, R ³ represents a tertiary alkyl group or 2-tetrahydropyranyl group, and R ⁴ represents tertiary alkyl group, tert- butoxycarbonyl group, or 2-tetrahydro pyranyl represents a group, Ar ¹ and Ar ² are, each independently, an aryl, a broken line portion represents a bond with other portions of the structure. in addition, R ¹ and R ² may be linked to form a cyclic ether (except for a 6-membered ring structure))

Hereinafter, each component represented by these (A)-(C) is also called "(A) component"-"(C) component", respectively.

In the polymer (A), the monomer unit (a1) is preferably a monomer unit represented by formula (III), and the monomer unit (a2) is a monomer unit represented by formula (IV). 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 2-tetrahydropyranyl group, and R ⁸ represents a hydrogen atom or a methyl group.

The photosensitive resin composition of this invention is a positive photosensitive resin composition.

Moreover, it is preferable that the photosensitive resin composition of this invention is a chemical amplification type positive photosensitive resin composition (chemical amplification positive type photosensitive resin composition).

It is preferable that the photosensitive resin composition of this invention does not contain a 1, 2- quinonediazide compound as a photo-acid generator sensitive to actinic light. Although a 1, 2- quinonediazide compound produces | generates a carboxyl group by sequential photochemical reaction, the quantum yield is necessarily 1 or less.

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

Moreover, it is preferable that the photosensitive resin composition of this invention contains the monomer unit which the said (A) polymer has an alicyclic epoxy group and / or an oxetanyl group from a solvent resistance viewpoint, and also mentions the (E) crosslinking agent mentioned later It is preferable to further contain.

The photosensitive resin composition of this invention has high sensitivity by containing (A)-(C) component, and the change of the pattern shape with respect to the change of exposure amount is small, ie, the photosensitive resin composition with a large latitude with respect to an exposure amount. Becomes Moreover, the photosensitive resin composition from which the cured film excellent in solvent resistance and heat transparency can be obtained.

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

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In addition, the polymerization method may be sufficient as the method of introduce | transducing the monomeric unit which the copolymer used for this invention contains, and a polymer reaction method may be sufficient as it. In the polymerization method, the monomer containing a predetermined functional group is previously synthesized, and then these monomers are copolymerized. In a polymer reaction method, after performing a polymerization reaction, the required functional group is introduce | transduced into a monomer unit using the reactive group contained in the monomer unit of the obtained copolymer. Here, as a functional group, it is a crosslinkable group, such as a protecting group, an epoxy group, or an oxetanyl group, and a soluble hydroxyl group or a carboxyl group, protecting a phenolic hydroxyl group or a carboxy group, and decomposing | disassembling in the presence of a strong acid, and freeing them. (Acidic group) etc. can be illustrated.

The introduction of the monomer units (1) to (3) into the polymer (A) may be either a polymerization method or a polymer reaction method, or a combination of these two methods may be used.

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), and The ethylenically unsaturated compound which has an epoxy group or an oxetanyl group is mixed, and it superposes | polymerizes and the target (A) polymer can be obtained.

In the polymer reaction method, epichlorohydrin is reacted with a copolymer obtained by copolymerizing 2-hydroxyethyl methacrylic acid to introduce an epoxy group. Thus, after copolymerizing the ethylenically unsaturated compound which has a reactive group, it utilizes the reactive group which remained in the side chain, and by a polymer reaction, it is represented by Formula (Ia), Formula (Ib), Formula (IIa), and / or Formula (IIb). A functional group such as a structure or a crosslinkable group to be represented can be introduced into the side chain.

(A) polymer

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

(A) polymer which the photosensitive resin composition of this invention contains,

Monomer unit (a1) which has a structure represented by Formula (Ia) which produces | generates a carboxyl group by acid, or a structure represented by Formula (Ib) which produces | generates a phenolic hydroxyl group by acid,

A monomer unit (a2) having a structure represented by formula (IIa) that generates a carboxyl group by an acid or a structure represented by formula (IIb) that produces a phenolic hydroxyl group by an acid, and

Monomer unit (a3) having an epoxy group and / or an oxetanyl group,

It contains.

The polymer (A) is alkali insoluble and is a resin which becomes alkali-soluble when the acid-decomposable group in each of formula (Ia) or formula (Ib) and formula (IIa) or formula (IIb) decomposes. It is preferable. Here, in this invention, an acid-decomposable group shows the functional group which can decompose | dissolve in presence of an acid, and can produce a carboxyl group or phenolic hydroxyl group.

In addition, "alkali solubility" in this invention is 23 of the coating film (3 micrometers in thickness) of the said compound (resin) formed by apply | coating the solution of the said compound (resin) on a board | substrate, and heating at 90 degreeC for 2 minutes. The dissolution rate with respect to the 0.4% tetramethylammonium hydroxide aqueous solution in degreeC is 0.005 micrometer / sec or more, and "alkali insoluble" means the solution of the said compound (resin) is apply | coated on a board | substrate, and it is 2 at 90 degreeC. It says that the dissolution rate with respect to the 0.4% tetramethylammonium hydroxide aqueous solution in 23 degreeC of the coating film (3 micrometers in thickness) of this compound (resin) formed by heating for minutes is said to be less than 0.005 micrometer / sec.

As long as the said (A) polymer keeps the said (A) polymer whole alkali insoluble, the introduction of an acidic group is not excluded, The monomer unit (a4) which has a carboxy group, a carboxylic anhydride residue, and / or a phenolic hydroxyl group mentioned later is mentioned. ) May be used.

It is preferable that the said (A) polymer is an acrylic polymer.

"Acrylic-type polymer" in this invention is a polymer of addition polymerization type | mold, is a polymer containing the monomer unit derived from (meth) acrylic acid and / or its ester, and originates in (meth) acrylic acid and / or its ester You may have monomer units other than a monomer unit, for example, the monomer unit derived from styrene, the monomer unit derived from a vinyl compound, etc.

As for the said (A) polymer, it is preferable that it is 50 mol% or more, and, as for the monomer unit derived from (meth) acrylic acid and / or its ester with respect to all the monomer units in a polymer, it is more preferable that it is 80 mol% or more, It is especially preferable that it is a polymer which consists only of the monomeric unit derived from (meth) acrylic acid and / or its ester.

Moreover, "the monomer unit derived from (meth) acrylic acid and / or its ester" is also called "acrylic-type monomer unit." In addition, (meth) acrylic acid shall mean methacrylic acid and / or acrylic acid.

<Monomer unit (a1)>

The said (A) polymer contains the monomer unit (a1) which has a structure represented by Formula (Ia) which produces | generates a carboxyl group by acid, or a structure represented by Formula (Ib) which produces | generates phenolic hydroxyl group by acid. . In the formula, the broken line portion represents a bonding point with another structure.

In formula (Ia) and (Ib), R <^1> represents an alkyl group or a cycloalkyl group each independently.

The alkyl group in R ¹ may be linear or branched.

As preferable carbon number of the alkyl group in R <^1> , it is preferable that it is 1-20, It is more preferable that it is 1-10, It is further more preferable that it is 1-7.

As preferable carbon number of the cycloalkyl group in R <^1> , it is preferable that it is 3-20, It is more preferable that it is 3-10, It is further more preferable that it is 5-7.

Moreover, when these carbon number has a substituent, carbon number of a substituent is also included.

The alkyl group in R ¹ is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As a cycloalkyl group in R <^1> , a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, isobornyl group etc. are mentioned, for example.

In addition, the alkyl group and cycloalkyl group in R <^1> may have a substituent.

As a substituent in the said alkyl group and cycloalkyl group, a C1-C10 alkyl group (methyl group, an ethyl group, a propyl group, a butyl group etc.), a C3-C10 cycloalkyl group, a C6-C10 aryl group, a halogen atom (fluorine) Atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, alkoxy group having 1 to 10 carbon atoms, and the like, and these substituents may be further substituted with the above substituents.

Moreover, as an alkyl group or a cycloalkyl group in R <^1> , a C1-C10 alkyl group, a C3-C10 cycloalkyl group, or a C1-C11 aralkyl group is preferable, and a C1-C6 alkyl group is preferable. The cycloalkyl group having 3 to 6 carbon atoms or the benzyl group is more preferable, the ethyl group or the cyclohexyl group is more preferable, and the ethyl group is particularly preferable.

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

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

As preferable carbon number of the alkyl group in R <^2> , it is preferable that it is 1-20, It is more preferable that it is 1-10, It is further more preferable that it is 1-7.

Moreover, when these carbon number has a substituent, carbon number of a substituent is also included.

Moreover, as an alkyl group in R <^2> , a C1-C6 alkyl group is preferable and a methyl group is especially preferable.

In addition, in formula (Ia) and formula (Ib), R <^1> and R <^2> may connect and form a cyclic ether structure (except a 6-membered ring structure). As a cyclic ether structure, a 4-membered ring, a 5-membered ring, a 7-membered ring, or an 8-membered ring structure is preferable, and it is especially preferable that it is a 5-membered ring structure. In the present invention, in the case of a six-membered ring structure, since the deprotection activation energy is high, it is not included in the monomer unit (a1).

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

There is no restriction | limiting in particular as a bivalent aromatic group in Ar <^1> , A phenylene group, a substituted phenylene group, a naphthylene group, a substituted naphthylene group, etc. can be illustrated, What is a phenylene group or a substituted phenylene group? It is preferable that it is a phenylene group, and it is still more preferable that it is a 1, 4- phenylene group.

The divalent aromatic group in Ar ¹ may have a substituent on the aromatic ring, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.), and 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, an iodine atom), a cyano group, a nitro group, a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, and the like. May be further substituted with the above substituents.

The monomer unit (a1) in this invention contains the structure represented by said Formula (Ia) and / or Formula (Ib) which is a structure where the carboxy group or phenolic hydroxyl group was protected.

As a carboxylic acid monomer which can form the monomeric unit which has a structure represented by said Formula (Ia) by protecting a carboxyl group, if it can become a monomeric unit (a1) by protecting a carboxyl group, For example, acrylic acid, Monocarboxylic acids such as methacrylic acid, crotonic acid and α-methyl-p-carboxystyrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Moreover, as a monomer unit (a1), the monomer unit derived from the carboxylic acid in which these carboxy groups were protected is mentioned as a preferable thing.

As a monomer which has a phenolic hydroxyl group which can form the monomeric unit which has a structure represented by said Formula (Ib) by protecting a phenolic hydroxyl group, as long as it can become a monomeric unit (a1) by protecting a phenolic hydroxyl group, it can be used. For example, hydroxy styrene, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, the compound of Unexamined-Japanese-Patent No. 2008-40183 Paragraph 0011-0016, and Unexamined-Japanese-Patent No. 2888454. 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate, and the like are preferred. Can be mentioned.

Among these, α-methyl-p-hydroxystyrene, the compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, the 4-hydroxybenzoic acid derivatives of paragraphs 0007 to 0010 of JP 2888454, The addition reactant of 4-hydroxybenzoic acid and glycidyl methacrylate, and the addition reactant of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

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

In formula (III), R <^5> represents an alkyl group or a cycloalkyl group, and a preferable aspect of R <^5> is the same as that of R <^1> in Formula (Ia) and Formula (Ib).

In addition, in formula (III), R <^6> represents a hydrogen atom or a methyl group.

As a preferable specific example of the radically polymerizable monomer used in order to form the monomeric unit represented by Formula (III), For example, 1-ethoxyethyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl Methacrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl methacrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, 1-isobutoxyethyl acrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl methacrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl methacrylate, 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 can be used individually by 1 type or in combination of 2 or more types.

A commercially available radical may be used for the radically polymerizable monomer used in order to form a monomeric unit (a1), and what synthesize | combined by a well-known method can also be used. For example, it can synthesize | combine by making (meth) acrylic acid react with a vinyl ether compound in presence of an acid catalyst as shown below.

Here, R <^5> and R <^6> correspond to R <^5> and R <^6> in Formula (III), respectively.

In addition, the monomer unit (a1) is polymerized with the monomer units (a2) to (a5) to be described later or a precursor thereof to the carboxyl group or phenolic hydroxyl group-containing monomer to be protected, followed by reacting the carboxyl group or phenolic hydroxyl group with the vinyl ether compound. Can also be formed. Moreover, the specific example of the preferable monomeric unit formed in this way is the same as the monomeric unit derived from the preferable specific example of the said radically polymerizable monomer.

As a preferable specific example of monomer unit (a1), the following monomer unit can be illustrated.

In all the monomer units which comprise the said (A) polymer, 10-80 mol% is preferable, as for content of a monomer unit (a1), 15-70 mol% is more preferable, 20-60 mol% is especially preferable. . By including monomeric unit (a1) in the said ratio with monomeric unit (a2), the photosensitive resin composition with high sensitivity and a wide exposure latitude is obtained.

<Monomer unit (a2)>

The said (A) polymer contains the monomer unit (a2) which has a structure represented by Formula (IIb) which produces | generates a carboxyl group by acid, or a structure represented by Formula (IIb) which produces | generates phenolic hydroxyl group by acid. .

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

As a tertiary alkyl group in R <^3> and R <^4> , a C4-C20 thing is preferable, a C4-C14 thing is more preferable, a C4-C8 thing is still more preferable.

Group is a tertiary alkyl group, and 2-tetrahydropyranyl group, a divalent aromatic of the tertiary alkyl group, tert- butoxycarbonyl group or a 2-tetrahydropyranyl group, Ar ² in R ⁴ in R ^3, It may have a substituent, As a substituent, a C1-C10 alkyl group (methyl group, an ethyl group, a propyl group, a butyl group etc.), a C3-C10 cycloalkyl group, a C6-C10 aryl group, a halogen atom (fluorine atom, Chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxy group, alkoxyl group having 1 to 10 carbon atoms and the like. These substituents may further be substituted by the said substituent.

Moreover, as a tertiary alkyl group in R <^3> and R <^4> , it is more preferable that it is at least 1 sort (s) chosen from the group which consists of group represented by Formula (V) shown below.

-C (R ⁹ R ¹⁰ R ¹¹ ) (V)

In formula, R <^9> , R <^10> and R <^11> respectively independently represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C6-C12 aryl group, or a C7-C12 aralkyl group, and , R ⁹ , R ^10, and R ¹¹ may be bonded to each other to form a ring integrally with the carbon atom to which they are bonded.

The alkyl group of 1 to 12 carbon atoms of R ⁹ , R ¹⁰ and R ¹¹ in formula (V) may be linear or branched, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, texyl group (2,3-dimethyl-2-butyl group), n -Heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As a C3-C12 cycloalkyl group, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group etc. are mentioned, for example.

As a C6-C12 aryl group, a phenyl group, tolyl group, xylyl group, cumenyl group, 1-naphthyl group etc. are mentioned, for example.

As a C7-12 aralkyl group, a benzyl group, the (alpha)-methyl benzyl group, a phenethyl group, a naphthyl methyl group, etc. are mentioned, for example.

In addition, R ⁹ , R ¹⁰ and R ¹¹ may be bonded to each other and may be integrated with the carbon atom to which they are bonded to form a ring. As a ring structure when R <^9> and R <^10> , R <^9> and R <^11> or R <^10> and R <^11> couple | bond, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, tetrahydrofura And a methyl group, adamantyl group, and tetrahydropyranyl group.

In addition, it is preferable that R <^3> in Formula (IIa) is a C4-C12 tertiary alkyl group or 2-tetrahydropyranyl group, and it is a C4-C8 tertiary alkyl group or 2-tetrahydropyranyl It is more preferable that it is a group, It is still more preferable that it is a t-butyl group or 2-tetrahydropyranyl group, A t-butyl group is especially preferable.

Moreover, it is preferable that R <^4> in Formula (IIb) is a C4-C12 tertiary alkyl group, 2-tetrahydropyranyl group, tert-butoxycarbonyl group, C3-C12 tertiary alkyl group, or It is more preferable that it is a 2-tetrahydropyranyl group, It is still more preferable that it is a t-butyl group or 2-tetrahydropyranyl group, A 2-tetrahydropyranyl group is especially preferable.

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

Preferred embodiments 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 this invention contains the protected carboxy group represented by said formula (IIa), and / or the protected phenolic hydroxyl group represented by said formula (IIb).

As a carboxylic acid monomer which can form the monomeric unit which has a structure represented by said Formula (IIa) by protecting a carboxyl group, if it can become a monomeric unit (a2) by protecting a carboxyl group, For example, acrylic acid, Monocarboxylic acids such as methacrylic acid, crotonic acid and α-methyl-p-carboxystyrene; And dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Moreover, as a monomer unit (a2), the monomer unit derived from the carboxylic acid in which these carboxy groups were protected is mentioned as a preferable thing.

As a monomer which has a phenolic hydroxyl group which can form the monomeric unit which has a structure represented by said Formula (IIb) by protecting a phenolic hydroxyl group, as long as it can become a monomeric unit (a2) by protecting a phenolic hydroxyl group, it can be used. For example, hydroxy styrene, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, the compound of Unexamined-Japanese-Patent No. 2008-40183 Paragraph 0011-0016, and Unexamined-Japanese-Patent No. 2888454. The 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010, addition reaction products of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reaction products of 4-hydroxybenzoic acid and glycidyl acrylate are mentioned as preferred. Can be.

Among these, α-methyl-p-hydroxystyrene, the compounds described in paragraphs 0011 to 0016 of JP-A-2008-40183, the 4-hydroxybenzoic acid derivatives of paragraphs 0007 to 0010 of JP 2888454, The addition reactant of 4-hydroxybenzoic acid and glycidyl methacrylate, and the addition reactant of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable.

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

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

In addition, in Formula (IV), the preferable aspect of R <^7> is the same as that of R <^3> in Formula (IIa).

As a preferable specific example of the radically polymerizable monomer used in order to form the monomeric unit represented by Formula (IV), For example, tert- butyl methacrylate, tert- butyl acrylate, tetrahydro-2H methacrylic acid-pyran- 2-yl, tetrahydro-2H-pyran-2-yl acrylate, 2-methyl-2-adamantyl methacrylate, 2-methyl-2-adamantyl acrylate, 1-methylcyclohexyl methacrylate, acrylic acid 1-methylcyclohexyl etc. are mentioned, Especially tert- butyl methacrylate and tert- butyl acrylate are preferable. These monomer units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of a monomer unit (a2), the following monomer unit can be illustrated.

In all the monomer units which comprise the said (A) polymer, 5-60 mol% is preferable, as for content of a monomer unit (a2), 10-50 mol% is more preferable, 10-40 mol% is especially preferable. . By including monomeric unit (a2) in the said ratio with monomeric unit (a1), the photosensitive resin composition with high sensitivity and a wide exposure latitude is obtained.

<Monomer unit (a3) having an epoxy group and / or oxetanyl group>

The said (A) polymer contains the monomeric unit (a3) which has an epoxy group and / or an oxetanyl group.

As a monomer unit (a3) which has the said epoxy group and / or oxetanyl group, it is preferable that it is a monomer unit which has an alicyclic epoxy group and / or oxetanyl group, and it is more preferable that it is a monomer unit which has an oxetanyl group.

The alicyclic epoxy group is a group in which an aliphatic ring and an epoxy ring form a condensed ring, and specifically, for example, a 3,4-epoxycyclohexyl group, a 2,3-epoxycyclohexyl group, a 2,3-epoxycyclopentyl group Etc. are mentioned preferably.

The group having an oxetanyl group is not particularly limited as long as it has an oxetane 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 at least one epoxy group and at least one oxetanyl group, two or more epoxy groups, or two or more oxetas Although it may have a nil group and it is not specifically limited, It is preferable to have one or three epoxy groups and / or oxetanyl groups in total, It is more preferable to have one or two epoxy groups and / or oxetanyl groups in total, Epoxy group or oxeta It is more preferable to have one silyl group.

As a specific example of the radically polymerizable monomer used in order to form the monomer unit which has an epoxy group, it is the glycidyl acrylate, the glycidyl methacrylate, the (alpha)-ethyl acrylate glycidyl, the (alpha)-n-propyl acrylate, for example. Cydyl, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7- Epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, paragraphs of Japanese Patent No. 4168443 The compound containing the alicyclic epoxy frame | skeleton of 0031-0035, etc. are mentioned.

As an example of the radically polymerizable monomer used in order to form the monomer unit which has an oxetanyl group, the (meth) acrylic acid ester etc. which have the oxetanyl group of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2001-330953 are mentioned, for example. Can be mentioned.

As an example of the radically polymerizable monomer used in order to form the monomer unit which has an epoxy group and / or an oxetanyl group, it is preferable that it is a monomer containing a methacrylic acid ester structure, and a monomer containing an acrylate ester structure.

Among these monomers, more preferably, a compound containing an alicyclic epoxy skeleton described in paragraphs 0034 to 0035 of Japanese Patent No. 4168443 and an oxetanyl group described in paragraphs 0011 to 0016 of Japanese Patent Laid-Open No. 2001-330953 It is (meth) acrylic acid ester and it is a (meth) acrylic acid ester which has an oxetanyl group of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2001-330953. Among these, preferred are 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyl Oxetan-3-yl) methyl, most preferred are acrylic acid (3-ethyloxetan-3-yl) methyl, and methacrylic acid (3-ethyloxetan-3-yl) methyl. These monomer units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of monomer unit (a3), the following monomer unit can be illustrated.

10-80 mol% is preferable, as for the content rate of the monomer unit (a3) which has an epoxy group and / or oxetanyl group, in all the monomer units which comprise the said (A) polymer, 15-70 mol% is more preferable, 20-65 mol% is especially preferable. By containing the monomer unit which has an epoxy group and / or an oxetanyl group in the said ratio, the physical property of a cured film becomes favorable.

<Monomer unit (a4) which has a carboxyl group, a carboxylic anhydride residue, and / or a phenolic hydroxyl group>

It is preferable that the said (A) polymer contains the monomeric unit which has a carboxyl group, a carboxylic anhydride residue, and / or a phenolic hydroxyl group in the range in which the said (A) polymer does not become alkali-soluble, and a carboxyl group and / or phenolic hydroxyl group It is more preferable to contain the monomer unit which has a.

As a radically polymerizable monomer used in order to form the monomeric unit which has a carboxyl group, For example, Monocarboxylic acid, such as acrylic acid, methacrylic acid, a crotonic acid; Dicarboxylic acids, such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid, are mentioned as a preferable thing.

Moreover, as a radically polymerizable monomer used in order to form the monomeric unit which has a carboxylic acid anhydride residue, maleic anhydride, itaconic anhydride, etc. are mentioned as a preferable thing, for example.

As a radically polymerizable monomer used in order to form the monomeric unit which has a phenolic hydroxyl group, For example, hydroxystyrenes, such as p-hydroxy styrene and (alpha) -methyl- p-hydroxy styrene, Unexamined-Japanese-Patent No. 2008-40183 Compounds described in paragraphs 0011 to 0016 of the publication, 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Japanese Patent No. 2888454, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, 4 -An addition reaction product of hydroxybenzoic acid and glycidyl acrylate is mentioned as a preferable thing.

Among these, methacrylic acid, acrylic acid, the compound of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2008-40183, the 4-hydroxybenzoic acid derivatives of Paragraph 0007-0010 of Unexamined-Japanese-Patent No. 2888454, 4-hydroxy The addition reaction product of benzoic acid and glycidyl methacrylate, the addition reaction product of 4-hydroxybenzoic acid and glycidyl acrylate are more preferable, The compound of Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2008-40183, Japanese patent The 4-hydroxybenzoic acid derivatives described in paragraphs 0007 to 0010 of Publication No. 2888454, addition reactants of 4-hydroxybenzoic acid and glycidyl methacrylate, addition reactants of 4-hydroxybenzoic acid and glycidyl acrylate This is particularly preferred. These monomer units can be used individually by 1 type or in combination of 2 or more types.

As a preferable specific example of monomer unit (a4), the following monomer unit can be illustrated.

The content rate of (a4) component in the case of containing the monomeric unit (a4) which has a carboxyl group, a carboxylic anhydride residue, and / or a phenolic hydroxyl group among all the monomeric units which comprise the said (A) polymer is 1-25 mol. % Is preferable, 2-25 mol% is more preferable, 3-20 mol% is especially preferable. By containing the monomer unit which has a carboxyl group, a carboxylic acid anhydride residue, and / or a phenolic hydroxyl group in the said ratio, high sensitivity is obtained and developability becomes favorable also.

<Other monomer unit (a5)>

The said (A) polymer is a monomer unit (a5) other than said (a1)-(a4) (hereinafter "component (a5)" or "other monomer unit (a5) in the range which does not prevent the effect of this invention. May be referred to as ")".

As a radically polymerizable monomer used in order to form (a5) component, the compound of Paragraph 0021-0024 of Unexamined-Japanese-Patent No. 2004-264623 is mentioned, for example (a1)-(a4) And monomer units of) are excluded.

Among these, (meth) acrylic acid esters containing alicyclic structures, such as dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, and cyclohexyl acrylate, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Styrene etc. can be illustrated preferable. Among these, 2-hydroxyethyl (meth) acrylate can be illustrated more preferable.

These (a5) components can be used individually by 1 type or in combination of 2 or more types.

1-50 mol% is preferable, and, as for the content rate of (a5) component in the case of containing (a5) component among all the monomer units which comprise the said (A) polymer, 5-40 mol% is more preferable 5-30 mol% is especially preferable.

It is preferable that it is 1,000-100,000, and, as for the weight average molecular weight of the said (A) polymer, it is more preferable that it is 2,000-50,000. Moreover, it is preferable that the weight average molecular weight in this invention is a polystyrene conversion weight average molecular weight by gel permeation chromatography (GPC).

Moreover, although the various methods are known also about the synthesis | combining method of the said (A) polymer, For example, the radically polymerizable monomer used in order to form at least a monomer unit (a1), a monomer unit (a2), and a monomer unit (a3). It can be synthesize | combined by superposing | polymerizing the radically polymerizable monomer mixture containing containing using a radical polymerization initiator in the organic solvent.

Hereinafter, although a preferable thing is illustrated as said (A) polymer used by this invention, this invention is not limited to this.

Moreover, it is preferable that the weight average molecular weights of the said (A) polymer illustrated below are 2,000-50,000.

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

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

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

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

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

1-Ethoxyethyl Methacrylic Acid / Methacrylic Acid Tert-Butyl / Methacrylic Acid 3,4-Epoxycyclohexylmethyl Copolymer

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

Methacrylic acid 1-ethoxyethyl / methacrylate tert-butyl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester coalescence

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

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

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

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

Methacrylic acid 1-ethoxyethyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) Ester / Methacrylic Acid 2-hydroxyethyl Copolymer

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

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

Methacrylic acid 1-ethoxyethyl / methacrylate tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl copolymer

Methacrylic acid 1-ethoxyethyl / methacrylic acid tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid copolymer

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

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

Methacrylic acid 1-ethoxyethyl / methacrylate tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxy Propyl) ester copolymer

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

Methacrylic acid 1-ethoxyethyl / methacrylic acid 2-methyl-2-adamantyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyl Oxypropyl) ester copolymer

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

Methacrylic acid 1-ethoxyethyl / methacrylic acid tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester copolymer

Methacrylic acid 1-ethoxyethyl / methacrylic acid tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester copolymer

Methacrylic acid 1-ethoxyethyl / methacrylic acid tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / meta Krylic Acid 2-Hydroxyethyl Copolymer

Methacrylic acid 1-ethoxyethyl / methacrylic acid tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / meta Methyl acrylate copolymer

Methacrylic acid 1-ethoxyethyl / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacrylo) Iloxypropyl) Ester Copolymer

Methacrylic acid 1-ethoxyethyl / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacrylo) Yloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer

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

Methacrylic acid 1-ethoxyethyl / methacrylic acid tert-butyl / acrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylate tert-butyl / methacrylic acid 3,4-epoxycyclohexylmethyl copolymer

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylate tert-butyl / methacrylic acid 3,4-epoxycyclohexylmethyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester / meta Krylic Acid 2-Hydroxyethyl Copolymer

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylate tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl copolymer

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylate tert-butyl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3-methacryloyloxypropyl Ester / methacrylic acid 2-hydroxyethyl copolymer

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

Methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylic acid (3-ethyloxetan-3-yl) methyl / 4-hydroxybenzoic acid (3 Methacryloyloxypropyl) ester / methacrylic acid 2-hydroxyethyl copolymer

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

Tert-butoxycarbonyl group protector / methacrylic acid (3-ethyl jade of 1-ethoxyethyl ether / α-methyl-p-hydroxystyrene of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester Cetane-3-yl) methyl / methacrylic acid copolymer

Tert-butyl group protector / methacrylic acid (3-ethyl oxetane- of 1-ethoxyethyl ether / methacrylic acid 4-hydroxyphenyl of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester 3-yl) methyl / methacrylic acid copolymer

(A) A polymer can be used individually by 1 type or in combination of 2 or more types.

It is preferable that the molar content of the monomeric unit (a1) represented by Formula (I) in the said (A) polymer is larger than the molar content of the monomeric unit (a2) represented by Formula (II).

The content ratio of the monomer unit (a1) represented by Formula (I) in the said (A) polymer and the monomer unit (a2) represented by Formula (II) is a molar ratio, and a monomer unit (a1): monomer unit It is preferable that it is (a2) = 100: 200-100: 5, It is more preferable that it is 100: 100-100: 10, It is still more preferable that it is 100: 90-100: 20.

Moreover, the monomer unit (a1) represented by Formula (I) in the said (A) polymer, the monomer unit (a2) represented by Formula (II), and the monomer unit which has an epoxy group and / or oxetanyl group ( The content ratio with a3) is preferably a molar ratio of monomer unit (a1): monomer unit (a2): monomer unit (a3) = 100: (5 to 200): (10 to 200), and 100: (10 It is more preferable that it is -100) :( 50-150), and it is still more preferable that it is 100: (20-90) :( 50-150).

It is preferable that it is 20-99 weight% with respect to the total solid of the photosensitive resin composition, and, as for content of the said (A) polymer in the photosensitive resin composition of this invention, it is more preferable that it is 40-97 weight%, and 60-95 weight It is more preferable that it is%. If content is this range, the pattern formation property at the time of image development will become favorable. In addition, solid content of the photosensitive resin composition represents the quantity except volatile components, such as a solvent.

Moreover, in the photosensitive resin composition of this invention, you may use together resin other than the (A) polymer in the range which does not prevent the effect of this invention. However, it is preferable that content of resin other than (A) polymer is smaller than content of (A) polymer from a developable viewpoint.

(B) mine generator

The photosensitive resin composition of this invention contains the (B) photo-acid generator.

As a photo-acid generator (also called "(B) component") used by this invention, the compound which generate | occur | produces an acid in response to actinic light of wavelength 300nm or more, Preferably wavelength 300-450nm is preferable, but the chemical structure It is not limited to. Moreover, also about the photo-acid generator which does not directly react to actinic light of wavelength 300nm or more, if it is a compound which responds to actinic light of wavelength 300nm or more by using together with a sensitizer and produces | generates an acid, it can be used conveniently in combination with a sensitizer.

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

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imidesulfonate compounds, and oxime sulfonate compounds. have. Among these, it is preferable to use an oxime sulfonate compound from an insulating viewpoint. These photo-acid generators can be used individually by 1 type or in combination of 2 or more types.

As these specific examples, the following can be illustrated.

As trichloromethyl-s-triazines, 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -Bis (4,6-trichloromethyl) -s-triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (furan-2-yl ) Ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, or 2- (4-meth Methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine and the like;

As the diaryl iodonium salts, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxy Phenylphenyl iodonium trifluoroacetate, phenyl-4- (2'-hydroxy-1'-tetradecaoxy) phenyl iodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1 ' -Tetradecaoxy) phenyl iodonium hexafluoro antimonate, or phenyl-4- (2'-hydroxy-l'- tetradecaoxy) phenyl iodonium p-toluenesulfonate;

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

As quaternary ammonium salts, tetramethylammoniumbutyltris (2,6-difluorophenyl) borate, tetramethylammoniumhexyltris (p-chlorophenyl) borate, tetramethylammoniumhexyltris (3-trifluoromethylphenyl) Borate, benzyldimethylphenylammoniumbutyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammoniumhexyltris (p-chlorophenyl) borate, benzyldimethylphenylammoniumhexyltris (3-trifluoromethylphenyl) borate ;

Examples of diazomethane derivatives include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane and the like;

As imide sulfonate derivatives, trifluoromethylsulfonyloxybicyclo [2.2.1] -hepto-5-ene-dicarboxyimide, succinimidetrifluoromethylsulfonate, phthalimidetrifluoromethylsulfo Nate, N-hydroxynaphthalimide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidepropanesulfonate and the like;

As an oxime sulfonate compound, the compound shown below.

As an oxime sulfonate compound, ie, a compound which has an oxime sulfonate residue, the compound containing the oxime sulfonate residue represented by Formula (2) can be illustrated preferably.

In formula (2), R <^5> represents an alkyl group or an aryl group. Either group may be substituted and the alkyl group in R <^5> may be linear, branched chain, or cyclic may be sufficient as it. Acceptable substituents are described below.

As an alkyl group of R <^5> , a C1-C10 linear or branched alkyl group is preferable.

The alkyl group of R ⁵ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloaliphatic group such as a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group). Containing, preferably a bicycloalkyl group).

As an aryl group of R <^5> , a C6-C11 aryl group 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.

As for the said compound containing the oxime sulfonate residue represented by Formula (2), it is more preferable that it is an oxime sulfonate compound represented by following formula (3).

In formula (3), R <^5> is synonymous with R <^5> in Formula (2), X represents an alkyl group, an alkoxy group, or a halogen atom, m represents the integer of 0-3. When m is 2 or 3, some X may be same or different.

As an alkyl group represented by X, a C1-C4 linear or branched alkyl group is preferable.

As an alkoxy group represented by X, a C1-C4 linear or branched alkoxy group is preferable.

As the halogen atom represented by X, a chlorine atom or a fluorine atom is preferable.

As for m, 0 or 1 is preferable.

In formula (3), m is 1, X is a methyl group, a substitution position of X is an ortho position, R <^5> is a C1-C10 linear alkyl group, and 7- dimethyl- 2-oxonorbornylmethyl group Or a compound that is a p-tolyl group is particularly preferred.

As a specific example of an oxime sulfonate compound, following compound (i), compound (ii), compound (iii), compound (iv) etc. are mentioned, It can be used individually by 1 type, or can use two or more types together. have. Compound (i)-(iv) can be obtained as a commercial item. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.

It is preferable that it is a photo-acid generator represented by Formula (II) as a photo-acid generator.

In formula (II), R <^4A> represents a halogen atom, a hydroxyl group, a C1-C4 alkyl group, a C1-C4 alkoxy group, a cyano group, or a nitro group, and L represents the integer of 0-5. . R ^3A may be substituted with 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, or W; A phenyl group, a naphthyl group which may be substituted by W, or an anthranyl group which may be substituted by W, represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, and a carbon atom having 1 to 10 carbon atoms. It represents an alkoxy group, a halogenated alkyl group of 1 to 5 carbon atoms, or a halogenated alkoxy group of 1 to 5 carbon atoms.

As R <^3A> in Formula (II), a methyl group, an ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, purple A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferable, and it is especially preferable that they are a methyl group, an ethyl group, n-propyl group, n-butyl group, or p-tolyl group.

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

As the alkyl group having 1 to 4 carbon atoms represented by R ^4A , a methyl group or an ethyl group is preferable.

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

As L, 0-2 are preferable and 0-1 are especially preferable.

As a preferable aspect of the compound contained in the photo-acid generator represented by Formula (II), R <^3A> represents a methyl group, an ethyl group, n-propyl group, n-butyl group, or 4-tolyl group, and R <^4A> is a hydrogen atom or a methoxy group Represents L is 0-1.

Hereinafter, although the especially preferable example of the compound contained in the photo-acid generator represented by Formula (II) is shown, this invention is not limited to these.

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

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

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

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

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

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

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

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

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

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

It is preferable that it is a compound represented by a formula (OS-1) as a compound containing the oxime sulfonate residue represented by said Formula (4).

In said formula (OS-1), R <^1> is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or hetero An aryl group is shown. 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> -R <^24> , a hydrogen atom, a halogen atom, and an alkyl group are preferable, Moreover, the aspect which at least two of R <^21> -R <^24> couple | bonds with each other and forms an aryl group is also mentioned preferably. Especially, the aspect whose R <^21> -R <^24> is all hydrogen atoms is preferable from a viewpoint of a sensitivity.

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

As for the compound represented by said formula (OS-1), it is more preferable that it is a compound represented by a following formula (OS-2).

In said formula (OS-2), R <^1> , R <^2> , R <^21> -R <^24> is synonymous with the thing in Formula (OS-1), respectively, and a preferable example is also the same.

Among these, the aspect whose R <^{1> in a} formula (OS-1) and a formula (OS-2) is a cyano group or an aryl group is more preferable, It is represented by a formula (OS-2), R <^1> is a cyano group Most preferred is a phenyl group or a naphthyl group.

In addition, in the said oxime sulfonate compound, about either the three-dimensional structure (E, Z etc.) of an oxime and a benzothiazole ring, respectively, may be sufficient as it, or a mixture may be sufficient as it.

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

Among the above compounds, b-9, b-16, b-31 and b-33 are preferable from the viewpoint of compatibility with sensitivity and stability.

As a compound containing the oxime sulfonate residue represented by said formula (4), it is preferable that it is an oxime sulfonate compound represented by a formula (OS-3), a formula (OS-4), or a formula (OS-5).

(In formula (OS-3)-Formula (OS-5), R <^1> represents an alkyl group, an aryl group, or a heteroaryl group, R <^2> respectively independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ⁶ are, each independently, a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group and represents an amino-sulfonyl group, or an alkoxy-sulfonyl, X represents O or S, n represents 1 or 2, m is 0 to 6 of Represents an integer)

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

It is preferable that it is a C1-C30 alkyl group which may have a substituent as said alkyl group in R <^1> in said Formula (OS-3)-(OS-5).

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.

As an alkyl group in R <^1> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-jade Methyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl, phenoxyethyl, methylthioethyl, phenylthioethyl, ethoxycarbonylethyl, A phenoxycarbonylethyl group and a dimethylaminocarbonylethyl group are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-de The preferred group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

Moreover, as said aryl group in R <^1> , the aryl group of 6-30 total carbons which may have a substituent is preferable in said Formula (OS-3)-(OS-5).

Examples of the substituent which may be included in the aryl group in R ¹ include 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 sulfonic acid group, and an aminosulfo. A silyl group and an alkoxysulfonyl group are mentioned.

Examples of the aryl group in R ¹ include a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group, p-methylthiophenyl group and p- A phenylthiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group are mentioned.

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

Moreover, as said heteroaryl group in R <^1> , the heteroaryl group of 4-30 total carbons which may have a substituent is preferable in said Formula (OS-3)-(OS-5).

Examples of the substituent which the heteroaryl group in R ¹ may have include 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 sulfonic acid group, and an amino group. A sulfonyl group and an alkoxysulfonyl group are mentioned.

In the formulas (OS-3) to (OS-5), at least one ring may be a heteroaromatic ring in the heteroaryl group in R ¹ , and for example, the heteroaromatic ring and the benzene ring may be condensed.

As a heteroaryl group in R <^1> , it consists of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, which may have a substituent, and a benzoimidazole ring. The group remove | excluding one hydrogen atom from the ring selected from the group is mentioned.

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

In the formulas (OS-3) to (OS-5), one or two of R ² present in the compound is preferably an alkyl group, an aryl group or a halogen atom, and one is an alkyl group, an aryl group or a halogen atom. It is more preferable, it is especially preferable that one is an alkyl group and the other is a hydrogen atom.

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

As a substituent which the alkyl group or aryl group in R <^2> may have, the group similar to the substituent which the alkyl group or aryl group in said R <^1> may have can be illustrated.

As an alkyl group in R <^2> , it is preferable that it is a C1-C12 alkyl group which may have a substituent, and it is more preferable that it is a C1-C6 alkyl group which may have a substituent.

Specifically as an alkyl group in R <^2> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, allyl group, n- Pentyl group, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, perfluorohexyl group, chloromethyl group, bromomethyl group, methoxymethyl group, benzyl group, phenoxyethyl group, methylthioethyl group And phenylthioethyl group, ethoxycarbonylethyl group, phenoxycarbonylethyl group, and dimethylaminocarbonylethyl group.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group, bromomethyl group, methoxymethyl group , Benzyl group is preferable, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group is more preferable, and methyl group, ethyl group, n- The propyl group, n-butyl group and n-hexyl group are more preferable, and a methyl group is especially preferable.

As an aryl group in R <^2> , it is preferable that it is a C6-C30 aryl group which may have a substituent.

Specifically as an aryl group in R <^2> , a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, p-phenoxyphenyl group, p-methylthiophenyl group, p-phenyl A thiophenyl group, p-ethoxycarbonylphenyl group, p-phenoxycarbonylphenyl group, and p-dimethylaminocarbonylphenyl group are mentioned.

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

As a halogen atom in R <^2> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

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

In said formula (OS-3)-(OS-5), X represents O or S, and it is preferable that it is O.

In formulas (OS-3) to (OS-5), the ring containing X as a reduction 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, and when X is S, n is 2 desirable.

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

In the formulas (OS-3) to (OS-5), the alkyl group for R ⁶ is preferably an alkyl group having 1 to 30 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.

As an alkyl group in R <^6> , a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-jade Methyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl, benzyl, phenoxyethyl, methylthioethyl, phenylthioethyl, ethoxycarbonylethyl, A phenoxycarbonylethyl group and a dimethylaminocarbonylethyl group are mentioned.

Among these, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-de The preferred group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group are preferable.

In said formula (OS-3)-(OS-5), as an alkyloxy group in R <^6> , it is preferable that it is a C1-C30 alkyloxy group which may have a substituent.

Examples of the substituent which the alkyloxy 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 alkyloxy group in R ⁶ include a methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, ethoxyethyloxy group, methylthioethyloxy group, A phenylthio ethyl oxy group, an ethoxy carbonyl ethyl oxy group, a phenoxy carbonyl ethyl oxy group, and a dimethylamino carbonyl ethyl oxy group are mentioned.

Among these, methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, or ethoxyethyloxy group is preferable.

In the formulas (OS-3) to (OS-5), as the aminosulfonyl group for R ⁶ , a methylaminosulfonyl group, dimethylaminosulfonyl group, phenylaminosulfonyl group, methylphenylaminosulfonyl group, and aminosulfonyl group are mentioned. Can be.

Examples of the alkoxysulfonyl group for R ⁶ in the formulas (OS-3) to (OS-5) include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.

Moreover, in said formula (OS-3)-(OS-5), m shows the integer of 0-6, It is preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1, It is especially preferable that it is 0 Do.

Moreover, it is especially preferable that the compound containing the oxime sulfonate residue represented by said Formula (4) is an oxime sulfonate compound represented by either of following formula (OS-6)-(OS-11).

(In formula (OS-6)-(OS-11), 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> is a hydrogen atom, C1-C8 Represents an alkyl group, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ⁹ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ¹⁰ represents a hydrogen atom or Methyl group)

R ¹ in formulas (OS-6) to (OS-11) is synonymous with R ^{1 in} formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.

R <^7> in Formula (OS-6) represents a hydrogen atom or a bromine atom, and it is preferable that it is a hydrogen atom.

R ⁸ in formulas (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or chloro It is preferable that it is a C1-C8 alkyl group, a halogen atom, or a phenyl group, It is more preferable that it is a C1-C8 alkyl group, It is still more preferable that it is a C1-C6 alkyl group, It is especially preferable that it is a methyl 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 formula (OS-8)-(OS-11) represents a hydrogen atom or a methyl group, and it is preferable that it is a hydrogen atom.

In addition, in the said oxime sulfonate compound, any one or a mixture may be sufficient about the three-dimensional structure (E, Z) of an oxime.

Although the following exemplary compound is mentioned as a specific example of the oxime sulfonate compound represented by said formula (OS-3)-a formula (OS-5), This invention is not limited to these.

In the photosensitive resin composition of this invention, it is preferable to use 0.1-10 weight part with respect to 100 weight part of (A) component, and, as for the photo-acid generator which is (B) component, it is more preferable to use 0.5-10 weight part. Do.

It is preferable that the photosensitive resin composition of this invention contains a sensitizer in order to accelerate the decomposition | disassembly in combination with (B) photo-acid generator.

A sensitizer absorbs actinic light or a radiation and will be in an electronic excited state. A sensitizer which has become an electron excitation state comes into contact with a photoacid generator to generate an action such as electron transfer, energy transfer, and heat generation. As a result, the photoacid generator causes chemical change to decompose to produce an acid.

As an example of a preferable sensitizer, the compound which belongs to the following compounds, and has an absorption wavelength in 350 nm-450 nm region is mentioned.

Polynuclear aromatics (e.g., pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxy Anthracene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (e.g., xanthone, thioxanthone, dimethyl thioxanthone, diethylthioke) Santon), cyanines (e.g., tiacarbocyanine, oxacarbocyanine), melocyanines (e.g., melocyanine, carbomelocyanine), rhodyanine, oxonol, thiazines (E.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, acriflavin), acridones (e.g. acridon, 10 -Butyl-2-chloroacridone), anthraquinones (e.g., anthraquinones), squalariums (e.g., squaals), styryls, bases Reels (e.g. 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), Coumarins (e.g. 7-diethylamino4-methylcoumarin, 7-hydroxy4 Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizine-11-non).

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

(C) solvent

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

The photosensitive resin composition of this invention is the said (A) and (B) component which are essential components, (D) component mentioned later which is a preferable component, and / or (E) component, and the arbitrary component mentioned later further, (C) It is preferable to manufacture as a solution which melt | dissolved in the solvent.

As a solvent (C) used for the photosensitive resin composition of this invention, a well-known solvent can be used and 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, etc. can be illustrated.

As a (C) solvent used for the photosensitive resin composition of this 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;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

(Ethylene) 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;

(I) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether;

(Propylene) 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;

(E) lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, and isoamyl lactate;

(Wave) n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, 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;

(H) ethyl hydroxy acetate, 2-hydroxy-2-methylpropionate, 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxypropionate, 3-meth Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3 Other esters such as methyl-3-methoxybutylbutyrate, methyl acetoacetate, ethyl acetoacetate, methyl pirbate and ethyl pirbate;

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

(N) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpyrrolidone;

Lactone, such as (gamma) -butyrolactone, etc. are mentioned.

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

These solvents can be used individually by 1 type or in mixture of 2 or more types.

It is preferable to use together single 1 type or 2 types, the solvent which can be used for this invention, It is more preferable to use 2 types together, It is more preferable to use propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers. It is more preferable to use together.

It is preferable that content of (C) solvent in the photosensitive resin composition of this invention is 50-3,000 weight part per 100 weight part of (A) component, It is more preferable that it is 100-2,000 weight part, It is 150-1,500 weight part More preferred.

&Lt; Other components >

In the photosensitive resin composition of this invention, in addition to (A) component, (B) component, and (C) component, (D) antioxidant, (E) crosslinking agent, which are described below as arbitrary components as needed as needed, (( F) Adhesion improvers, (G) basic compounds, (H) surfactants, (I) plasticizers, and (J) thermal radical generators, and thermal acid generators, ultraviolet absorbers, thickeners, and organic or inorganic precipitations Known additives such as inhibitors can be added.

(D) antioxidant

It is preferable that the photosensitive resin composition of this invention contains the antioxidant (D).

(D) As antioxidant, a well-known antioxidant can be contained. By adding antioxidant (D), coloring of a cured film can be prevented, the film thickness reduction by decomposition can be reduced, and there is an advantage that it is excellent in heat transparency.

Examples of such antioxidants include phosphorus antioxidants, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, sugars, nitrites, sulfites, thiosulfates, and hydrides. And oxyamine derivatives. Among these, a phenolic antioxidant is especially preferable from a viewpoint of coloring of a cured film and a film thickness reduction. These may be used individually by 1 type, and may mix and use 2 or more types.

As a commercial item of a phenolic antioxidant, Adecas top AO-60 (made by ADEKA), Adecas top AO-80 (made by ADEKA), Irganox 1098 (Chiba Japan Co., Ltd.) 1) can be mentioned.

It is preferable that content of (D) antioxidant is 0.1-6 weight% with respect to the total solid of the photosensitive resin composition, It is more preferable that it is 0.2-5 weight%, It is especially preferable that it is 0.5-4 weight%. By setting it as this range, sufficient transparency of the formed film is obtained and the sensitivity at the time of pattern formation also becomes favorable.

In addition, as an additive other than antioxidant, you may add the various ultraviolet absorbers, metal deactivator, etc. which were described in "extension of polymer additive (Nikkan Kogyo Co., Ltd.)", etc. to the photosensitive resin composition of this invention.

(E) crosslinking agent

It is preferable that the photosensitive resin composition of this invention contains (E) crosslinking agent as needed.

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

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

As a specific example of the compound which has two or more epoxy groups in a molecule | numerator, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, an aliphatic epoxy resin, etc. are mentioned.

These can be obtained as a commercial item. For example, as bisphenol-A epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1055, EPICLON1055 (EPICLON1055) As mentioned above, DIC Corporation make, for example, JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, DIC Corporation) ), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.) are JER152, JER154, JER157S70 (above, Japan epoxy resin Co., Ltd. product), as a phenol novolak-type epoxy resin, EPICLONN-740, EPICLONN-740, EPICLONN-770, EPICLONN-775 (above, made by DIC Co., Ltd.) are cresol novolac-type epoxy resins such as EPICLONN-660, EPICLONN-665, EPICLONN-670, and EPICLONN-673. , EPICLONN-680, EPICLONN-690, EPICLONN-695 (above, made by DIC Corporation), EOCN-1020 (above, Nippon Kayaku Co., Ltd.) are ADEKARESINEP-4080S, copper ( EP-4085S, EP-408 8S (above, made by ADEKA Corporation), ceroxide 2021P, ceroxide 2081, ceroxide 2083, ceroxide 2085, EHPE3150, EPOLEADPB3600, copper PB4700 (above, manufactured by Daicel Chemical Co., Ltd.), and the like. . In addition, ADEKARESINEP-4000S, East EP-4003S, East EP-4010S, East EP-4011S (above, made by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501 And EPPN-502 (above, manufactured by ADEKA Corporation). These can be used individually by 1 type or in combination of 2 or more types.

Preferred among these are bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenol novolac type epoxy resins. In particular, a bisphenol-A epoxy resin is preferable.

As a specific example of a compound which has two or more oxetanyl groups in a molecule | numerator, Aaronoxetane OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd. product) can be used.

In addition, the compound containing an oxetanyl group can be used individually or in mixture with the compound containing an epoxy group.

1-50 weight part is preferable and, as for the addition amount of the compound which has two or more epoxy groups or oxetanyl group in a molecule | numerator to the photosensitive resin composition, when the total amount of (A) component is 100 weight part, 3-30 weight part is more preferable. .

<Alkoxymethyl group-containing crosslinking agent>

As the alkoxy methyl group-containing crosslinking agent, alkoxy methylated melamine, alkoxy methylated benzoguanamine, alkoxy methylated glycol lauryl, alkoxy methylated urea and the like are preferable. These are obtained by converting the methylol groups of methylolated melamine, methylolated benzoguanamine, methylolated glycol lauryl, or methylolated urea groups into alkoxymethyl groups, respectively. It does not specifically limit about the kind of this alkoxy methyl group, For example, although a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group etc. are mentioned, from a viewpoint of the outgas generation amount, In particular, a methoxymethyl group is preferable.

Among these crosslinkable compounds, alkoxy methylated melamine, alkoxy methylated benzoguanamine and alkoxy methylated glycol lauryl are mentioned as preferable crosslinkable compounds, and alkoxy methylated glycol lauryl is particularly preferable from the viewpoint of transparency.

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

It is preferable that it is 0.05-50 weight part with respect to 100 weight part of (A) component, and, as for the addition amount of the alkoxy methyl group containing crosslinking agent in the case of using an alkoxy methyl group containing crosslinking agent for the photosensitive resin composition of this invention, it is more preferable that it is 0.5-10 weight part. desirable. By adding in this range, preferable alkali solubility at the time of image development and the outstanding solvent resistance of the film | membrane after hardening are obtained.

<Compounds having at least one ethylenically unsaturated double bond>

As a compound which has at least 1 ethylenically unsaturated double bond, (meth) acrylate compounds, such as monofunctional (meth) acrylate, bifunctional (meth) acrylate, and trifunctional or more (meth) acrylate, can be used suitably. have.

As monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acryl The rate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned.

As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, and the like.

As (meth) acrylate more than trifunctional, for example, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

The compound which has these at least 1 ethylenically unsaturated double bond is used individually by 1 type or in combination of 2 or more types.

It is preferable that it is 50 weight part or less with respect to 100 weight part of (A) component, and, as for the usage ratio of the compound which has at least 1 ethylenically unsaturated double bond in the photosensitive resin composition of this invention, it is more preferable that it is 30 weight part or less. Do. By containing the compound which has at least 1 ethylenically unsaturated double bond in such a ratio, the heat resistance, surface hardness, etc. of the insulating film obtained from the photosensitive resin composition of this invention can be improved. When adding the compound which has at least 1 ethylenically unsaturated double bond, it is preferable to add (J) thermal radical generating agent.

(F) adhesion improver

The photosensitive resin composition of this invention may contain the (F) adhesive improving agent.

The (F) adhesion improving agent which can be used for the photosensitive resin composition of this invention is made from the inorganic substance used as a base material, for example, silicon compounds, such as a silicon, a silicon oxide, a silicon nitride, metal, such as gold, copper, aluminum, and an insulating film. It is a compound which improves adhesiveness. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent as the (F) adhesion improving agent used in the present invention is for the purpose of modifying the interface, and is not particularly limited and known ones can be used.

As a preferable silane coupling agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyl trialkoxysilane, (gamma)-glycidoxy propyl alkyl dialkoxysilane, (gamma), for example -Methacryloxypropyltrialkoxysilane, (gamma) -methacryloxypropylalkyl dialkoxysilane, (gamma) -chloropropyltrialkoxysilane, (gamma)-mercaptopropyltrialkoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl tree Alkoxysilane and vinyltrialkoxysilane are mentioned.

Among these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, and γ-glycidoxypropyltrialkoxysilane is more preferable.

These can be used individually by 1 type or in combination of 2 or more types. These materials are effective for improving adhesion with the substrate and also for adjusting the taper angle with the substrate.

0.1-20 weight part is preferable with respect to 100 weight part of (A) component, and, as for content of the (F) adhesion improving agent in the photosensitive resin composition of this invention, 0.5-10 weight part is more preferable.

(G) basic compounds

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

(G) It can be used selecting arbitrarily as a basic compound from what is used by chemically amplified resist. For example, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, quaternary ammonium salt of carboxylic acid, etc. are mentioned.

Examples of the aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, and diethanolamine. , Triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, etc. are mentioned.

As aromatic amine, aniline, benzylamine, N, N- dimethylaniline, diphenylamine, etc. are mentioned, for example.

As the heterocyclic amine, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8- Oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8- diazabicyclo [5.3.0] -7-undecene, etc. are mentioned.

As quaternary ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexyl ammonium hydroxide, etc. are mentioned, for example. have.

As quaternary ammonium salt of carboxylic acid, tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, etc. are mentioned, for example.

Although the basic compound which can be used for this invention may be used individually by 1 type, or may use 2 or more types together, It is preferable to use 2 or more types together, It is more preferable to use 2 types together, Heterocyclic amine 2 It is more preferable to use together species.

It is preferable that it is 0.001-1 weight part with respect to 100 weight part of (A) component, and, as for content of the (G) basic compound in the photosensitive resin composition of this invention, it is more preferable that it is 0.005-0.2 weight part.

(H) surfactant

The photosensitive resin composition of this invention may contain (H) surfactant.

As the (H) surfactant, any of anionic, cationic, nonionic, and amphoteric compounds can be used, but the preferred surfactant is a nonionic surfactant.

Examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone and fluorine-based surfactants. In addition, the following brand names are KP (made by Shin-Etsu Chemical Co., Ltd.), polyflow (made by Koeisha Chemical Co., Ltd.), F-Top (made by JEMCO Corporation), mega pack (made by DIC Corporation), and a flora. Each series, such as a figure (Sumitomo-Three Co., Ltd. make), Asahi Guard, a sufflon (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA Corporation), is mentioned.

Moreover, the weight average molecular weight of polystyrene conversion measured by the gel permeation chromatography in the case of containing the structural unit A and structural unit B represented by following formula (1) as a surfactant, and using tetrahydrofuran (THF) as a solvent. The copolymer whose (Mw) is 1,000 or more and 10,000 or less is mentioned as a preferable example.

(In formula (1), R <^1> and R <^3> respectively independently represents a hydrogen atom or a methyl group, R <^2> represents a C1-C4 linear alkylene group, R <^4> represents a hydrogen atom or C1-C4 or less Represents an alkyl group, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing the polymerization ratio, p represents a numerical value of 10% by weight to 80% by weight, and q is 20% by weight. The numerical value of 90 weight% or more is shown, r represents an integer of 1 or more and 18 or less, n represents an integer of 1 or more and 10 or less)

It is preferable that said L is a branched alkylene group represented by following formula (2). R <^5> in Formula (2) represents a C1-C4 alkyl group, From a compatibility and wettability with respect to a to-be-coated surface, C1-C3 alkyl group is preferable, A C2-C3 alkyl group is preferable. More preferred. It is preferable that sum (p + q) of p and q is p + q = 100, ie, 100 weight%.

As for the weight average molecular weight (Mw) of the said copolymer, 1,500 or more and 5,000 or less are more preferable.

These surfactant can be used individually by 1 type or in mixture of 2 or more types.

It is preferable that it is 10 weight part or less with respect to 100 weight part of (A) component, and, as for the addition amount of (H) surfactant in the photosensitive resin composition of this invention, it is more preferable that it is 0.01-10 weight part, and it is 0.01-1 weight More preferably denial.

(I) plasticizer

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

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

It is preferable that it is 0.1-30 weight part with respect to 100 weight part of (A) component, and, as for the addition amount of the (I) plasticizer in the photosensitive resin composition of this invention, it is more preferable that it is 1-10 weight part.

(J) thermal radical generating agent

The photosensitive resin composition of this invention may contain the (J) thermal radical generating agent, and when it contains the ethylenically unsaturated compound like the compound which has the at least 1 ethylenically unsaturated double bond mentioned above, (J) thermal radical It is preferable to contain a generator.

As a thermal radical generating agent in this invention, a well-known thermal radical generating agent can be used.

A thermal radical generating agent is a compound which generate | occur | produces a radical by the energy of heat, and starts or accelerates the polymerization reaction of a polymeric compound. By adding a thermal radical generating agent, the obtained cured film becomes stronger, and heat resistance and solvent resistance may improve.

Preferable thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds and carbon halogens. The compound which has a bond, an azo compound, a bibenzyl compound, etc. are mentioned.

(J) A thermal radical generating agent may be used individually by 1 type, and can also use 2 or more types together.

The amount of the (J) thermal radical generating agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by weight, and preferably 0.1 to 20 parts by weight based on 100 parts by weight of the polymer (A) from the viewpoint of improving film properties. Addition is more preferable and it is most preferable that it is 0.5-10 weight part.

(Formation method of hardened film)

Next, the formation method of the cured film of this invention is demonstrated.

The formation method of the cured film of this invention is characterized by including the process of the following (1)-(5).

(1) Coating process of apply | coating photosensitive resin composition of this invention on board | substrate

(2) Solvent removal process which removes solvent from apply | coated photosensitive resin composition

(3) Exposure process to expose by actinic light

(4) Developing process developed by aqueous developer

(5) thermosetting post-baking process

Each process is demonstrated in order below.

In the application | coating process of (1), the photosensitive resin composition of this invention is apply | coated on a board | substrate, and it is set as the wet film containing a solvent.

In the solvent removal process of (2), a solvent is removed from the apply | coated film | membrane by pressure reduction (backing) and / or heating, and a dry coating film is formed on a board | substrate.

In the exposure process of (3), actinic light of wavelength 300nm or more and 450nm or less is irradiated to the obtained coating film. In this step, (B) the photoacid generator decomposes and an acid is generated. By the catalysis of the generated acid, the acid-decomposable group in the monomer unit represented by formula (Ia) and / or formula (Ib) and / or formula (IIa) and / or formula (IIb) contained in the polymer (A) Decomposition results in carboxyl and / or phenolic hydroxyl groups.

In the generated region of the acid catalyst, in order to accelerate the hydrolysis reaction, after exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") can be performed. PEB can promote the generation of carboxyl groups from acid-decomposable groups.

The acid-decomposable group in the monomer unit represented by Formula (Ia) and / or Formula (Ib) in this invention has low activation energy of acid decomposition, and it decompose | disassembles easily by the acid derived from the acid generator by exposure, Since a carboxyl group is generated, a positive image can also be formed by image development without necessarily PEB. Moreover, in this invention, since the monomer unit represented by (IIa) and / or Formula (IIb) which has an acid-decomposable group with relatively high acid decomposition activation energy is used together, the photosensitive resin composition which is stable to the fluctuation | variation of exposure amount etc. is also used. Can be obtained.

Moreover, by performing PEB at a relatively low temperature, hydrolysis of the acid-decomposable group can be promoted without causing a crosslinking reaction. It is preferable that the temperature at the time of PEB is 30 degreeC or more and 130 degrees C or less, 40 degreeC or more and 110 degrees C or less are more preferable, 50 degreeC or more and 80 degrees C or less are especially preferable.

In the developing process of (4), the polymer which has a free carboxy group is developed using alkaline developing solution. A positive image is formed by removing the exposure part area | region containing the resin composition which has a carboxyl group which is easy to melt | dissolve in an alkaline developing solution.

In the post-baking process of (5), by heating the obtained positive image, the acid-decomposable groups in the monomer unit (a1) and the monomer unit (a2) are thermally decomposed to generate a carboxyl group, and crosslinked with an epoxy group and / or an oxetanyl group, A cured film can be formed. It is preferable to heat this heating at 150 degreeC or more high temperature, It is more preferable to heat at 180-250 degreeC, It is especially preferable to heat at 200-250 degreeC. Although heating time can be set suitably according to heating temperature etc., it is preferable to set it in the range of 10 to 90 minutes.

If a step of totally irradiating active light, preferably ultraviolet light, to the developing pattern before the post-baking step, a crosslinking reaction can be promoted by an acid generated by active light irradiation.

Next, the formation method of the cured film using the photosensitive resin composition of this invention is demonstrated concretely.

<The manufacturing method of the photosensitive resin composition>

The essential components of (A)-(C) are mixed by arbitrary methods at arbitrary ratios, are stirred and dissolved, and the photosensitive resin composition is manufactured. For example, after making (A) or (B) component into the solution which melt | dissolved in the (C) solvent previously, respectively, these can also be mixed in a predetermined ratio and a resin composition can also be manufactured. The composition solution prepared as described above may be used for use after filtration using a filter having a pore size of 0.2 μm or the like.

<Application process and solvent removal process>

The desired dry coating film can be formed by apply | coating a resin composition to a predetermined board | substrate and removing a solvent by pressure reduction and / or heating (prebaking). As said board | substrate, for example, in manufacture of a liquid crystal display element, the glass plate etc. which provided the black matrix layer, the color filter layer as needed, and provided the transparent conductive circuit layer can be illustrated. The coating method to a board | substrate is not specifically limited, For example, methods, such as a slit coating method, a spray 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 large substrates. A large board | substrate means here the board | substrate of the magnitude | size of 1 m or more in each side.

In addition, the heating conditions of (2) solvent removal process decompose an acid-decomposable group in the monomeric unit (a1), monomeric unit (a2), etc. in (A) component in an unexposed part, and (A) component is made to alkaline developing solution. Although it is a range which does not make it soluble and changes also with the kind and compounding ratio of each component, Preferably it is about 30 to 120 second at 80-130 degreeC.

<Exposure process and development process (pattern forming method)>

In an exposure process, actinic light is irradiated to the board | substrate which provided the coating film through the mask which has a predetermined pattern. After an exposure process, heat processing (PEB) is performed as needed, and in an image development process, an exposure part area | region is removed using alkaline developing solution, and an image pattern is formed.

Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, chemical lamps, LED light sources, excimer laser generators, and the like can be used for exposure to active light, and g-ray (436 nm), i-ray (365 nm), h-ray (405 nm), and the like can be used. An active light ray having a wavelength of 300 nm or more and a wavelength of 450 nm or less can be preferably used. Moreover, irradiation light can also be adjusted through spectroscopic filters, such as a long wavelength cut filter, a short wavelength cut filter, and a bandpass filter, as needed.

A basic compound is used for the developing solution used at a developing process. As a basic compound, For example, alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide, 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; Aqueous solutions, such as sodium silicate and sodium metasilicate, can be used. Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the aqueous solution of the said alkalis can also be used as a developing solution.

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 and a dipping method. After image development, flowing water washing is performed for 30 to 90 seconds, and a desired pattern can be formed.

<Post Baking Process (Crosslinking Process)>

About a pattern corresponding to the unexposed area | region obtained by image development, using heating apparatuses, such as a hotplate and oven, 5 to a predetermined time, for example, hotplate phase, at predetermined temperature, for example, 180-250 degreeC. If it is an oven for 60 minutes, it heat-processes for 30 to 90 minutes, decomposes the acid-decomposable group in (A) component, produces | generates a carboxyl group, and reacts with the crosslinkable group which is an epoxy group and / or oxetanyl group in (A) component. By crosslinking, a protective film or an interlayer insulating film excellent in heat resistance, hardness, and the like can be formed. In addition, when performing heat processing, transparency can also be improved by performing in nitrogen atmosphere.

In addition, prior to the heat treatment, after re-exposure to the substrate on which the pattern is formed by actinic light, post-baking (re-exposure / post-baking) generates an acid from the component (B) present in the unexposed portion. It is preferable to function as a catalyst which accelerates a crosslinking process.

That is, it is preferable that the formation method of the cured film of this invention includes the re-exposure process which re-exposes by actinic light between a developing process and a postbaking process.

Although exposure in a re-exposure process may be performed by the same means as the said exposure process, in the said re-exposure process, it is preferable to perform whole surface exposure with respect to the side in which the film | membrane was formed by the photosensitive resin composition of this invention of a board | substrate. As a preferable exposure amount of a re-exposure process, it is 100-1,000mJ / cm <^2> .

By the photosensitive resin composition of this invention, the interlayer insulation film which is excellent in insulation and has high transparency also when baked at high temperature is obtained. Since the interlayer insulation film which uses the photosensitive resin composition of this invention has high transparency and is excellent in cured film physical property, it is useful for the use of an organic electroluminescence display or a liquid crystal display device.

The organic EL display device or liquid crystal display device of the present invention is not particularly limited except having a planarization film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL displays having various structures. A device and a liquid crystal display device are mentioned.

In addition, the photosensitive resin composition of this invention and the cured film of this invention can be used for various uses, without being limited to the said use. For example, in addition to the planarization film and the interlayer insulating film, it can be suitably used as a spacer for maintaining the thickness of the liquid crystal layer in the liquid crystal display device or a microlens provided on the color filter in the solid-state image sensor.

1 shows a configuration conceptual diagram of an example of an organic EL display device. Typical sectional drawing of the board | substrate in a bottom emission type organic electroluminescence display is shown, and it has the planarization film 4.

A glass substrate 6 is over the insulating film 3 formed comprising, forming a TFT (1) of batom gate in a state covering the TFT (1) to the Si ₃ N _4. After forming a contact hole (not shown here) in the insulating film 3, a wiring 2 (1.0 μm in height) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state of filling the unevenness by the wiring 2.

On the planarization film 4, the bottom emission type organic electroluminescent element is formed. That is, on the planarization film 4, the 1st electrode 5 which consists of ITO is connected to the wiring 2 through the contact hole 7, and is formed. In addition, the 1st electrode 5 is corresponded to the anode of organic electroluminescent element.

The insulating film 8 of the shape which covers the periphery of the 1st electrode 5 is formed, By providing this insulating film 8, between the 1st electrode 5 and the 2nd electrode formed in a subsequent process is provided. Short can be prevented.

In addition, although not shown in FIG. 1, through a desired pattern mask, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited and provided, and then a second electrode made of Al is formed on the entire surface above the substrate to form a sealing glass plate. It seals by bonding together using an ultraviolet curable epoxy resin, and the active-matrix type organic electroluminescence display by which the TFT 1 for driving this is connected to each organic electroluminescent element is obtained.

2 is a conceptual cross-sectional view showing an example of the liquid crystal display device 10 of the active matrix system. This color liquid crystal display device 10 is a liquid crystal panel which has the backlight unit 12 in the back surface, and a liquid crystal panel has all arrange | positioned between two glass substrates 14 and 15 with which the polarizing film was affixed. Elements of the TFT 16 corresponding to the pixels are arranged. In each element formed on the glass substrate, the ITO transparent electrode 19 which forms a pixel electrode is wired through the contact hole 18 formed in the cured film 17. As shown in FIG. On the ITO transparent electrode 19, the RGB color filter 22 which has arrange | positioned the layer of liquid crystal 20 and a black matrix is provided.

[Example]

Next, an Example demonstrates this invention further more concretely. However, this invention is not limited by these Examples.

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

tert-BMA: tert-butyl methacrylate

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

GMA: glycidyl methacrylate

EDM: diethylene glycol ethyl methyl ether

Synthesis of Polymer A-1

0.5 parts by weight of phenothiazine was added to 144.2 parts by weight (2 molar equivalents) of ethyl vinyl ether, and 86.1 parts by weight of methacrylic acid (1 molar equivalents) was added dropwise while cooling the reaction system to 10 ° C. or lower, followed by room temperature (25 ° C.). It stirred at 4 hours. After adding 5.0 parts by weight of p-toluenesulfonic acid pyridinium, the mixture was stirred at room temperature for 2 hours and allowed to stand at room temperature overnight. 5 parts by weight of sodium hydrogen carbonate and 5 parts by weight of sodium sulfate were added to the reaction solution, the mixture was stirred at room temperature for 1 hour, the insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower, and the residue yellow oil was distilled under reduced pressure to obtain a boiling point. (bp.) 134.0 parts by weight of 1-ethoxyethyl methacrylate of 43 to 45 ° C./7 mmHg fraction was obtained as a colorless oil.

1-ethoxyethyl methacrylate (63.25 parts (0.4 molar equivalents)), tert-BMA (42.66 parts (0.3 molar equivalents)), GMA (42.65 parts (0.3 molar equivalents)) and EDM (126.6 parts) Part) was heated to 70 ° C. under a stream of nitrogen. While stirring this mixed solution, the mixed solution of radical polymerization initiator V-65 (made by Wako Pure Chemical Industries Ltd., 4 weight part) and EDM (100.0 weight part) was dripped over 2.5 hours. After completion of the dropwise addition, the mixture was reacted at 70 ° C for 4 hours to obtain an EDM solution (solid content concentration: 40% by weight) of polymer A-1. The weight average molecular weight measured by the gel permeation chromatography (GPC) of the obtained polymer A-1 was 18,000.

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

Polymer A-2 to A-14, A'-15, A'-16 and A-17 were prepared in the same manner as in the synthesis of Polymer A-1, except that each monomer used and its amount of use were changed to those shown in Table 1. Respectively synthesized.

TABLE 1

In addition, the copolymerization ratio of Table 1 is a molar ratio, and the symbol of Table 1 is as follows.

MAEVE: 1-ethoxyethyl methacrylate

t-BMA: tert-butyl methacrylate

GMA: glycidyl methacrylate

Oxe-30: methacrylic acid (3-ethyloxetan-3-yl) methyl (manufactured by Osaka Yuki Chemical Co., Ltd.)

Oxe-10: acrylic acid (3-ethyloxetane-3-yl) methyl (manufactured by Osaka Yuki Chemical Co., Ltd.)

HEMA: 2-hydroxyethyl methacrylate

M100: methacrylic acid 3,4-epoxycyclohexylmethyl (made by Daicel Chemical Co., Ltd.)

A400: 3, 4- epoxycyclohexyl methyl acrylate (made by Daicel Chemical Co., 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: Methacrylic acid tetrahydrofuran-2-yl

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

P-Ph-1: tetrahydropyranyl ether of methacrylic acid 4-hydroxyphenyl

St: Styrene

C1: Propylene Glycol Monomethyl Ether Acetate

C2: diethylene glycol ethyl methyl ether

In addition, thpMA (tetrahydro-2H-pyran-2-yl) was synthesized by the method of Synthesis Example 1 described in paragraph 0018 of JP-A-588367.

CHOEMA (1- (cyclohexyloxy) ethyl methacrylate) was also synthesized in the same manner. In addition, this other 1-ethoxyethyl ether protection and tetrahydropyranyl ether protection were also performed by the same method.

In addition, Ph-2, Ph-3, Ph-6, and Ph-3OH were synthesize | combined with the following method, respectively.

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

To 100 ml solution of 21 g of 4-hydroxybenzoic acid (2-hydroxyethyl) ester in acetonitrile, 20 ml of N, N-dimethylacetamide was added, and 20 g of methacrylic acid chloride was further added. After reacting with stirring at 35 ° C. for 8 hours, the reaction mixture was poured into ice water, and the precipitated crystals were filtered off, recrystallized from ethyl acetate / n-hexane, and 4-hydroxybenzoic acid (2-methacryl). Loyloxyethyl) ester was obtained.

Ph-3 (4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester) and Ph-6 (4-hydroxybenzoic acid (6-methacryloyloxyhexyl) ester) are the same as the above Ph-2. It synthesize | combined in the same way.

<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 the reaction mixture was stirred at 90 DEG C for 6 hours, after which the reaction mixture was water / acetic acid. Poured into ethyl mixed solvent, precipitated crystals were filtered out and recrystallized from ethyl acetate / n-hexane to give 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester.

<Synthesis of MATHF (methacrylic acid tetrahydrofuran-2-yl)>

Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C, and camphorsulfonic acid (4.6 g, 0.02 mol) was added. 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was dripped at this solution. After stirring for 1 hour, saturated aqueous sodium hydrogen carbonate solution (500 ml) was added, extracted with ethyl acetate (500 ml), dried over magnesium sulfate, and the insoluble matters were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a yellow oily residue. The resulting mixture was distilled under reduced pressure to obtain 125 g of tetrahydrofuran-2-yl methacrylate (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg fraction as a colorless oil (yield 80%).

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

(1) Preparation of Photosensitive Resin Composition Solution

Each component shown in following Table 2-Table 4 was mixed, it was made into a uniform solution, and it filtered using the polytetrafluoroethylene filter which has a pore size of 0.2 micrometer, and Examples 1-53 and The photosensitive resin composition solutions of Comparative Examples 1 and 2 were prepared, respectively.

TABLE 2

[Table 3]

[Table 4]

In addition, the symbol of Table 2-Table 4 is as follows.

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

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

B3: PAI-1001 (structure shown below, product of Midorigagaku Co., Ltd.)

B4: DBA (9,10-dibutoxy anthracene, the structure shown below, the Kawasaki Chemical Industries, Ltd. make)

<Synthesis of Photoacid Generator B5>

1-1. Synthesis of Synthetic Intermediate B5-A

2-aminobenzenethiol: 31.3 g (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in toluene: 100 mL (manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature (25 ° C). Next, phenyl acetyl chloride: 40.6g (Tokyo Kasei Kogyo Co., Ltd. product) was dripped, and it stirred for 1 hour and then made it react at 100 degreeC under room temperature for 2 hours. 500 mL of water was put into the obtained reaction liquid, the precipitated salt was dissolved, the toluene fraction was extracted, the extract was concentrated with the rotary evaporator, and the synthetic intermediate B5-A was obtained.

1-2. Synthesis of B5

2.25 g of the synthetic intermediate B5-A obtained as described above 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 ° C or lower. Next, tetramethylammonium hydroxide: 4.37g (25 weight% methanol solution, the Alfa Acer company make) was dripped, and it stirred for 0.5 hours and reacted under an ice bath. In addition, isopentyl nitrite: 7.03 g was added dropwise keeping the internal temperature at 20 ° C. or lower, and after completion of the dropwise addition, the reaction solution was heated to room temperature, followed by stirring for 1 hour.

Subsequently, after cooling the reaction liquid to 5 degrees C or less, p-toluene sulfonyl chloride (1.9 g) (made by Tokyo Kasei Kogyo Co., Ltd.) was thrown in, and it stirred for 1 hour, maintaining 10 degrees C or less. Then, 80 mL of water was thrown in and it stirred at 0 degreeC for 1 hour. After filtering the obtained precipitate, 60 mL of isopropyl alcohols (IPA) were added, it heated at 50 degreeC, stirred for 1 hour, was filtered and dried at the time, and 1.8 g (B5: said structure) was obtained.

The ¹ H-NMR spectrum (300 MHz, heavy DMSO ((D ₃ C) ₂ S═O)) of the obtained B5 is δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.00 (m, 1H), and 7.95 to 7.9 (m, 2H), 7.6-7.45 (m, 9H), and 2.45 (s, 3H).

From the said ¹ H-NMR measurement result, it is estimated that obtained B5 is a single type of geometric isomer.

<Synthesis of B6>

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixed solution was heated to 40 ° C for 2 hours to react. 4NHCl aqueous solution (60 mL) was dripped at the reaction liquid under ice cooling, ethyl acetate (50 mL) was added and liquid-separated. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C for 1 hour, followed by separating an aqueous solution of 2NHCl (60 mL), separating the organic layer, and then recrystallizing the crystal with diisopropyl ether (10 mL), Filtration and drying yielded the ketone compound (6.5 g).

Acetic acid (7.3g) and 50 weight% hydroxyamine aqueous solution (8.0g) were added and heated and refluxed to the obtained ketone compound (3.0g) and the suspension solution of methanol (30mL). 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 reaction mixture was heated to room temperature for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered off, reslurried with methanol (20 mL), filtered and dried to obtain B6 (2.3 g).

In addition, the ¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B6 is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), and 7.6 (dd). , 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d. 1H), 5.6 (q, 1H), 2.4 (s, 3H) and 1.7 (d, 3H).

C1: Propylene Glycol Monomethyl Ether Acetate

C2: diethylene glycol ethyl methyl ether

D1: Adecas Top AO-60 (made by ADEKA Co., Ltd.)

E1: JER-157S70 (polyfunctional novolak type epoxy resin (epoxy equivalent 200-220 g / eq), Japan epoxy resin Co., Ltd. product)

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

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

Surfactant 2: Compound W-3

Basic compound 1: 4-dimethylaminopyridine

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

Basic compound 3: triphenylimidazole

Close Enhancement Agent 1: KBM-403 (made by Shin-Etsu Chemical Co., Ltd.)

In addition, the composition used by the comparative example 3 is a composition as described in Example 1 of Unexamined-Japanese-Patent No. 2004-264623. That is, it is the composition manufactured as follows.

In a flask equipped with 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 ethylmethyl ether were charged. Then 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 and α-methylstyrene dimer 3 After charging by weight and nitrogen-substituting, stirring was gradually started. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer. The polystyrene reduced weight average molecular weight (Mw) of the obtained copolymer was 11,000. In addition, solid content concentration of the polymer solution obtained here was 31.6 weight%.

The solution containing the copolymer synthesize | combined above is the amount equivalent to 100 weight part (solid content) of a copolymer, and 4,7-di-n-butoxy-1- naphthyl tetrahydrothiophenium trifluoro 5 parts by weight of methanesulfonate was dissolved in diethylene glycol methylethyl ether so that the solid content concentration was 30% by weight, and then filtered through a membrane filter having a diameter of 0.2 µm to prepare the photosensitive resin composition of Comparative Example 3.

(2) Evaluation of sensitivity

After rotationally apply | coating the photosensitive resin composition solution on the silicon wafer which has a silicon oxide film, it prebaked at 95 degreeC for 90 second on the hotplate, and formed the coating film of 3 micrometers in film thickness.

Next, it exposed through the predetermined mask using the i-line stepper (FPA-3000i5 ⁺ by Canon Corporation). After exposure, after developing by the liquid method for 60 second by 23 degreeC tetramethylammonium hydroxide aqueous solution at 23 degreeC, it rinsed for 1 minute with ultrapure water. By these operations, the optimum exposure dose Eopt when resolving a 10 µm line and space in a 1: 1 ratio was set as the sensitivity. Sensitivity can be said to be high sensitivity in the case of exposure amount lower than 100 mJ / cm <^2> .

(3) Evaluation of exposure dose dependency

With respect to the optimum exposure dose (Eopt), (line width when exposed at an exposure amount of Eopt-10%) and (line width when exposed at an exposure amount of Eopt + 10%) were obtained, respectively, and {(exposure amount at 10% of Eopt-10%). The line width at the time of exposure to-) (the line width at the time of exposure with the exposure amount of Eopt + 10%)} made "1" the case of less than 1 micrometer, and made the case "1" and 1 micrometer or more. In the case of "1", it can be said that exposure dose dependency is favorable.

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

It turns out that all the photosensitive resin compositions of this invention are high in sensitivity, and light dose dependence is favorable.

TABLE 5

TABLE 6

(4) Evaluation of solvent resistance

After rotationally apply | coating the photosensitive resin composition solution on the silicon wafer which has a silicon oxide film, it prebaked at 95 degreeC for 90 second on the hotplate, and formed the coating film of 3 micrometers in film thickness. The obtained coating film was exposed so that the accumulated irradiation amount might be 200 mJ / cm ² (roughness: 20 mW / cm ² ) with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Corporation, and then the substrate was subjected to 1 at 230 ° C. in an oven. It heated for time and obtained the cured film. The film thickness (T1) of the obtained cured film was measured. Subsequently, the silicon wafer on which the cured film was formed was immersed for 30 minutes in N-methylpyrrolidone temperature-controlled at 25 ° C., and then the film thickness t1 of the cured film was measured and the film thickness change rate due to the immersion {| t1 -T1 | / T1} x100 (%) was computed. Moreover, solvent resistance can be said that a change rate is less than 3%.

Table 7 shows the evaluation results of solvent resistance.

It turns out that the photosensitive composition of this invention becomes favorable especially when the polymer containing an alicyclic epoxy group is used, and when the resin containing an oxetanyl group is used, and also when a crosslinking agent is used, all the photosensitive compositions of this invention are used.

TABLE 7

(5) Evaluation of heat resistance transparency

In the evaluation of solvent resistance (4), a cured film was produced on the 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. After heating the obtained cured film further at 230 degreeC in oven for 2 hours, the light transmittance was measured at the wavelength of 400-800 nm using the spectrophotometer "150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.). . Table 8 shows the evaluation of the minimum light transmittance (evaluation of heat resistance) at that time. If this value is 81% or more, it can be said that heat resistance transparency is favorable.

It turns out that the photosensitive composition of this invention all shows favorable heat-transparency, especially when the photo-acid generator B6 is used, and the case where antioxidant is used is especially favorable.

[Table 8]

Example 54

The evaluation similar to Example 51 was performed using the photosensitive resin composition of Example 51 using the UV-LED light source exposure machine instead of the ultrahigh pressure mercury lamp, and the result similar to Example 51 was obtained.

Example 55

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

Forming a TFT (1) of batom gate on the glass substrate 6, thereby forming the insulating film 3 made of Si ₃ N ₄ in a state covering the TFT (1). Next, a contact hole (not shown here) is formed in the insulating film 3, and then a wiring 2 (1.0 m in height) connected to the TFT 1 through the contact hole is formed on the insulating film 3. did. This wiring 2 is for connecting the TFT 1 with the organic EL element formed between the TFTs 1 or in a later step.

In addition, in order to planarize the unevenness caused by the formation of the wiring 2, the planarization layer 4 was formed on the insulating film 3 in a state of filling the unevenness by the wiring 2. Formation of the planarization film 4 on the insulating film 3 is carried out by spin-coating the photosensitive resin composition of Example 7 on a substrate, prebaking (90 占 폚 x 2 minutes) on a hot plate, and using a high pressure mercury lamp on a mask. After irradiating i line | wire (365 nm) to 45mJ / cm <^2> (roughness 20mW / cm <^2> ), it developed in alkaline aqueous solution, the pattern was formed, and it heat-processed for 60 minutes at 230 degreeC. The applicability | paintability at the time of apply | coating this photosensitive resin composition was favorable, and generation | occurrence | production of a wrinkle and a crack was not recognized by the cured film obtained after exposure, image development, and baking. In addition, the film thickness of the planarization film 4 which produced 500 nm of average level | step differences of the wiring 2 was 2,000 nm.

Next, the bottom emission type organic electroluminescent element was formed on the obtained planarization film 4. First, on the planarization film 4, the 1st electrode 5 which consists of ITO was connected to the wiring 2 through the contact hole 7, and was formed. Then, the resist was apply | coated and prebaked, and it exposed and developed through the mask of a desired pattern. Using this resist pattern as a mask, pattern processing was performed by wet etching using ITO etchant. Then, the resist pattern was stripped using the resist stripping solution (mixed liquid of monoethanolamine and dimethyl sulfoxide (DMSO)). The 1st electrode 5 obtained in this way is corresponded to the anode of organic electroluminescent element.

Next, the insulating film 8 of the shape which covers the periphery of the 1st electrode 5 was formed. It formed in the insulating film 8 by the method similar to the above using the photosensitive resin composition of Example 7. By providing this insulating film 8, the short between the 1st electrode 5 and the 2nd electrode formed in a later process can be prevented.

Moreover, the hole transport layer, the organic light emitting layer, and the electron carrying layer were sequentially deposited and provided through the desired pattern mask in the vacuum vapor deposition apparatus. Next, the 2nd electrode which consists of Al was formed in the whole surface above a board | substrate. The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the sealing glass plate and an ultraviolet curable epoxy resin.

As described above, an active matrix organic EL display device obtained by connecting the TFT 1 for driving this to each organic EL element was obtained. When voltage was applied through the drive circuit, it was found that the display was a good organic EL display device with good display characteristics.

Example 56

In Example 55, the organic EL device was similarly manufactured except having changed the photosensitive resin composition of Example 7 into the photosensitive resin composition of Example 34. It showed that it was an organic electroluminescent display apparatus which shows favorable display characteristics and is highly reliable.

(Example 57)

In Example 55, the organic EL device was produced similarly except having changed the photosensitive resin composition of Example 7 into the photosensitive resin composition of Example 51. It showed that it was an organic electroluminescent display apparatus which shows favorable display characteristics and is highly reliable.

(Example 58)

In the active matrix liquid crystal display device of FIGS. 1 and 2 of JP-A-3321003, a cured film 17 was formed as follows as an interlayer insulating film to obtain a liquid crystal display device of Example 58.

That is, using the photosensitive resin composition of Example 7, the cured film 17 was formed as an interlayer insulation film by the method similar to the formation method of the planarization film 4 of the organic electroluminescent display in Example 55.

When the drive voltage was applied to the obtained liquid crystal display device, it showed favorable display characteristics and it turned out that it is a highly reliable liquid crystal display device.

Example 59

In Example 58, the liquid crystal display device was produced similarly except having changed the photosensitive resin composition of Example 7 into the photosensitive resin composition of Example 34. It showed that favorable display characteristics were shown and it was a highly reliable liquid crystal display device.

Example 60

In Example 58, the liquid crystal display device was produced similarly except having changed the photosensitive resin composition of Example 7 into the photosensitive resin composition of Example 51. It showed that favorable display characteristics were shown and it was a highly reliable liquid crystal display device.

1: TFT (Thin Film Transistor)
2: wiring
3: insulation film
4: planarization film
5: first electrode
6: glass substrate
7: contact hole
8: insulating film
10: liquid crystal display device
12: backlight unit
14,15: glass substrate
16: TFT
17: cured film
18: contact hole
19: ITO transparent electrode
20: liquid crystal
22: color filter

Claims (14)

(A) A carboxyl group is produced | generated by the monomer unit (a1) which has a structure represented by Formula (Ia) which produces | generates a carboxyl group by acid, or a structure represented by Formula (Ib) which produces | generates a phenolic hydroxyl group by acid, and an acid. Monomer unit (a2) which has a structure represented by Formula (IIb) which produces | generates a phenolic hydroxyl group by the structure or acid represented by Formula (IIa), and the monomeric unit (a3) which has an epoxy group and / or an oxetanyl group Polymers containing
(B) a photo-acid generator, and
(C) containing a solvent, characterized by
Photosensitive resin composition.

(Wherein, R ¹ each independently represents an alkyl group or a cycloalkyl group, R ² each independently represents an alkyl group, R ³ represents a tertiary alkyl group or 2-tetrahydropyranyl group, and R ⁴ represents A tertiary alkyl group, tert-butoxycarbonyl group or 2-tetrahydropyranyl group, each of Ar ¹ and Ar ² independently represents a divalent aromatic group, and a dashed portion represents a bonding position with another structure. ¹ and R ² may be linked to each other to form a cyclic ether (except for a six-membered ring structure)) The method of claim 1,
The said photosensitive resin composition whose monomeric unit (a1) is a monomeric unit represented by Formula (III), and the said monomeric unit (a2) is a monomeric unit represented by 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) ) The method according to claim 1 or 2,
The photosensitive resin composition which is a chemically amplified positive type photosensitive resin composition. 4. The method according to any one of claims 1 to 3,
The photosensitive resin composition in which the said monomer unit (a3) is a monomer unit which has an alicyclic epoxy group, and / or a monomer unit which has an oxetanyl group. The method according to any one of claims 1 to 4,
The monomer unit (a3) in the polymer (A) is acrylic acid 3,4-epoxycyclohexylmethyl, methacrylic acid 3,4-epoxycyclohexylmethyl, acrylic acid (3-ethyloxetan-3-yl) The photosensitive resin composition which is a monomer unit derived from at least 1 sort (s) chosen from the group which consists of methyl and a methacrylic acid (3-ethyloxetan-3-yl) methyl. The method according to any one of claims 1 to 5,
The photosensitive resin composition whose said (B) photo-acid generator is a compound which has an oxime sulfonate residue. The method according to any one of claims 1 to 6,
The photosensitive resin composition whose said (B) photo-acid generator is a compound represented by a formula (OS-3), a formula (OS-4), or a formula (OS-5).

(In formula (OS-3)-Formula (OS-5), R <^1> represents an alkyl group, an aryl group, or a heteroaryl group, R <^2> respectively independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ⁶ are, each independently, a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group and represents an amino-sulfonyl group, or an alkoxy-sulfonyl, X represents O or S, n represents 1 or 2, m is 0 to 6 of Represents an integer) The method according to any one of claims 1 to 7,
(D) Photosensitive resin composition which further contains antioxidant. The method according to any one of claims 1 to 8,
(E) Photosensitive resin composition which further contains a crosslinking agent. (1) an application step of applying the photosensitive resin composition according to any one of claims 1 to 9 on a substrate;
(2) a solvent removal step of removing the solvent from the applied photosensitive resin composition,
(3) an exposure step of exposing with active light;
(4) a developing step of developing with an aqueous developer, and
(5) comprising a post-baking step of thermosetting
Formation method of a cured film. The cured film formed by the method of Claim 10. The method of claim 11,
Cured film which is an interlayer insulation film. The organic electroluminescence display provided with the cured film of Claim 11 or 12. The liquid crystal display device provided with the cured film of Claim 11 or 12.

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