KR102099092B1 - Photo-sensitive resin composition, method for manufacturing cured film by using the same, cured film, liquid crystal display and organic el device - Google Patents

Abstract

Provision of a positive photosensitive resin composition having excellent sensitivity, residual film ratio, and relative dielectric constant.
(A) (a1) a repeating unit having an acid group protected by an acid-decomposable group, (a2) an oxiranyl group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) A polymer component comprising a repeating unit having a selected group, and (a3) a repeating unit having a carboxyl group at the side chain terminal and having 4 or more atoms of a divalent linking group linking the polymer main chain and the carboxyl group in the same or different polymer, (B) It is a photosensitive resin composition containing a photoacid generator and (D) a solvent.

Description

Photosensitive resin composition, manufacturing method of cured film using the same, cured film, liquid crystal display device, and organic EL display device

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

In the electronic components such as thin film transistor (hereinafter referred to as "TFT") type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state imaging elements, an interlayer insulating film is generally formed to insulate between wirings arranged in layers. have. As a material for forming the interlayer insulating film, a photosensitive resin composition is widely used in that it is desirable to have a small number of steps for obtaining the required pattern shape and to have sufficient flatness.

Specifically, as a photosensitive resin composition, a composition comprising a resin having an acetal structure and / or a ketal structure and an epoxy structure and a photoacid generator (Japanese Patent Publication No. 2004-264623) is known. However, the composition cannot be developed without post exposure baking (PEB), so the scope of application is limited. In addition, the composition disclosed in Japanese Patent Laid-Open No. 2004-264623 has excellent heat resistance and development margin, but is low in sensitivity and has a problem with residual film properties.

Further, a composition comprising a repeating unit having a group that is decomposed by the action of an acid to generate an alkali-soluble group, and a resin having a repeating unit having a functional group that crosslinks between resins by heating, and a photoacid generator (Japanese Patent Publication 2009 -288343 publication) is known. However, the scope of application is limited because the composition is premised to be used by the double patterning method. In addition, the composition disclosed in Japanese Patent Laid-Open Publication No. 2009-288343 has problems in residual film properties and relative dielectric constant.

Moreover, a polymer (Japanese Patent Publication No. 2008-95087 publication) containing a resin containing a structural unit having a lactone skeleton or a naphthalene skeleton in a polymer is known. The polymer disclosed in Japanese Patent Laid-Open Publication No. 2008-95087 cannot exhibit high sensitivity without using an ArF laser.

An object of the present invention is to solve the above problems, and an object of the present invention is to provide a positive type photosensitive resin composition excellent in sensitivity, residual film ratio, and relative dielectric constant.

As a result of intensive investigations by the inventors of the present invention under the above-mentioned problems, it is shown that the use of a polymer having a repeating unit of a long chain carboxylic acid in combination with a specific two kinds of polymers leads to an improvement in the mobility of the acid groups and a decrease in the glass transition point (Tg) of the membrane. An improvement in sensitivity and an improvement in residual film rate were shown, and it was found that the above problem could be solved.

The means for solving the above problems are the means of the following [1], preferably the means of the following [2] to [13].

[1] (A) (a1) Recurring unit having an acid group protected by an acid-decomposable group, (a2) an oxiranyl group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) A repeating unit having a crosslinkable group selected from), and (a3) a polymer having a carboxyl group at the end of the side chain and having a repeating unit having 4 or more atoms in the divalent linking group connecting the polymer main chain and the carboxyl group in the same or different polymer ingredient,

(B) a photoacid generator, and

(D) contains a solvent,

The divalent linking group is -CR ¹ _2- (R ¹ represents a hydrogen atom or a methyl group), -O-, -O-SO _2- , -OC (O)-, -C (O) -O-,- A photosensitive resin composition characterized by S-, -C (O)-, an amino group which may have a substituent, a phenylene group which may have a substituent, or a group selected from structures of (iv) below and optionally combined.

(In formula (iv), z represents the integer of 0-5)

[2] The photosensitive resin composition according to [1], wherein the polymer component (A) has the repeating unit (a2) and a polymer containing the repeating unit (a3).

[3] The photosensitive resin composition according to [1] or [2], wherein the polymer component (A) has the repeating unit (a1), the repeating unit (a2), and a polymer comprising the repeating unit (a3). .

[4] The photosensitive resin composition according to any one of [1] to [3], which is a chemically amplified positive type photosensitive resin composition.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the repeating unit (a3) contains at least one repeating unit represented by formulas (i) to (iii).

(In the general formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. , n represents an integer from 0 to 4)

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

(In the general formula (A2 '), R ¹ and R ² each represents a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group)

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the repeating unit (a2) is a repeating unit represented by formula (2).

(In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms)

[8] The photosensitive resin composition according to any one of [1] to [7], wherein the repeating unit (a2) is a repeating unit having an oxiranyl group and / or an oxetanyl group.

[9] (1) The step of applying the photosensitive resin composition according to any one of [1] to [8] on a substrate,

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

(3) Process of exposing with active radiation,

(4) Process for developing with an aqueous developer, and

(5) A method for producing a cured film comprising a post-baking step of thermosetting.

[10] The method for forming a cured film according to [9], comprising a step of exposing the entire surface after the developing step and before the post-baking step.

[11] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [8].

[12] The cured film according to [11], which is an interlayer insulating film.

[13] A liquid crystal display device or an organic EL display device having the cured film of [11] or [12].

(Effects of the Invention)

ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition excellent in sensitivity, residual film rate, and relative dielectric constant, the manufacturing method of a pattern, the organic EL display device, the manufacturing method of a liquid crystal display device, and the cured film can be provided.

1 shows a conceptual view of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a flattening film 4 is provided.
2 shows a conceptual view of a configuration of an example of a liquid crystal display device. It shows a schematic cross section of the active matrix substrate in a liquid crystal display device, and has a cured film 17 which is an interlayer insulating film.

Hereinafter, the content of the present invention will be described in detail. The description of the constitutional requirements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, "-" is used by the meaning including the numerical value described before and after that as a lower limit and an upper limit. Note that the organic EL display device in the present invention refers to an organic electroluminescence display device (organic electroluminescence element).

In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

In addition, in the present invention, the "alkali-soluble" solution of a compound (resin) is applied on a substrate, and heated at 90 ° C for 2 minutes at 23 ° C of a film (thickness 3 µm) of the compound (resin). It means that the dissolution rate in 0.4% tetramethylammonium hydroxide aqueous solution is 0.01 µm / sec or more, and is formed by applying a solution of a compound (resin) to the substrate and heating at 90 ° C. for 2 minutes. It means that the dissolution rate of the (resin) film (thickness 3 µm) in an aqueous solution of 0.4% tetramethylammonium hydroxide at 23 ° C is less than 0.01 µm / sec.

[Photosensitive resin composition]

The photosensitive resin composition of the present invention,

(A) (a1) a repeating unit having an acid group protected by an acid-decomposable group, (a2) an oxiranyl group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) A polymer component comprising a repeating unit having a selected group and (a3) a repeating unit having a carboxyl group at the side chain terminal and having 4 or more atoms of a divalent linking group linking the polymer main chain and the carboxyl group in the same or different polymer,

(B) a photoacid generator, and

(D) It is characterized by containing a solvent.

The component (A),

(1): Formation by copolymerizing the repeating unit (a1), repeating unit (a2), and repeating unit (a3),

(2): Copolymer of repeating unit (a1) and repeating unit (a3), copolymer of repeating unit (a2) and repeating unit (a3),

(3): the form of a polymer containing a repeating unit (a1), a polymer containing a repeating unit (a2), and a polymer containing a repeating unit (a3),

(4): Copolymer of repeating unit (a1) and repeating unit (a3), form of polymer comprising repeating unit (a2),

(5): Copolymer of repeating unit (a2) and repeating unit (a3), form of polymer comprising repeating unit (a1), and

(6): Examples of the copolymer of the repeating unit (a1) and the repeating unit (a2) and the form of a polymer containing the repeating unit (a3).

Among these forms, the forms (1), (3) to (4), and (6) are preferred.

The said (A) component may contain multiple types of these forms, and may also contain another repeating unit (a4).

Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated.

<(A) component>

The photosensitive resin composition of the present invention (hereinafter also referred to as the photosensitive composition of the present invention or the composition of the present invention) is the same or different repeating unit (a1), repeating unit (a2), and repeating unit (a3) as (A) component We include in polymer.

The component (A) may contain other structural (repeating) units (a4) other than the repeating units (a1) to (a3).

[Repeat unit (a1)]

(A) When a component has a structural unit (a1), it can be set as the highly sensitive photosensitive resin composition.

In the present invention, "a residue in which the acid group is protected with an acid-decomposable group" refers to a residue in which the carboxyl group is protected with acetal, a residue in which the acid group is protected with a ketal, a residue in which the acid group is protected with a tertiary alkyl group, or a tertiary alkyl with an acid group. It is a residue protected with a carbonate group.

Examples of the acid group include a carboxyl group and a phenolic hydroxyl group.

In addition, specifically, as the residue in which the acid group is protected with an acid-decomposable group, acetal such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group of a group represented by formula (A1) described later, or And tertiary alkyl-based functional groups such as ketal-based functional groups, t-butyl ester groups, and t-butyl carbonate groups.

(a1) It is preferable that the structural unit which has the residue whose acid group was protected by the acid-decomposable group is a structural unit which has the protective carboxyl group protected by the acid-decomposable group, or the structural unit which has the protective phenolic hydroxyl group protected by the acid-decomposable group.

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

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

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

There is no restriction | limiting in particular as a structural unit which has the said carboxyl group which can be used for the structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated mono carboxylic acid, an unsaturated dicarboxylic acid, an unsaturated tricarboxylic acid, or ethylene The structural unit (a1-1-2) which has both the structure derived from an unsaturated group and an acid anhydride is mentioned.

Hereinafter, a structural unit derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the (a1-1-1) molecule used as the structural unit having the carboxyl group, and (a1-1-2) ethylenically unsaturated group and acid anhydride Structural units having all of the derived structures will be described in order, respectively.

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

As the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule and the like, the unsaturated carboxylic acid used in the present invention is used below. That is, examples of the unsaturated mono carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Moreover, as an unsaturated dicarboxylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc. are mentioned, for example. Moreover, the acidic anhydride may be sufficient as the unsaturated polycarboxylic acid used for obtaining the structural unit which has a carboxyl group. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, etc. are mentioned. Moreover, the unsaturated polyhydric carboxylic acid may be mono (2-methacryloyloxyalkyl) ester of polyhydric carboxylic acid, for example, mono succinic acid (2-acryloyloxyethyl), mono succinic acid (2-methacryl). Royloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. Moreover, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of both terminal dicarboxy polymers, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, etc. You can. Moreover, as an unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene, etc. can also be used.

Among them, in order to form a structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule from the viewpoint of developability, acrylic acid, methacrylic acid, or anhydride of an unsaturated polycarboxylic acid, etc. It is preferable to use, and it is more preferable to use acrylic acid or methacrylic acid.

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

<<<< (a1-1-2) Structural unit having both an ethylenically unsaturated group and an acid anhydride-derived structure >>>>

It is preferable that the structural unit (a1-1-2) which has both the ethylenic unsaturated group and the structure derived from an acid anhydride is a unit derived from the monomer obtained by reacting the hydroxyl group and the acid anhydride present in the structural unit having an ethylenically unsaturated group.

As the acid anhydride, a known one can be used, and specifically, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, phthalic anhydride tetrahydro, phthalic anhydride hexahydrophthalic anhydride and chlorendic anhydride; And acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Of these, phthalic anhydride, tetrahydro phthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability.

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

<<<< An acid-decomposable group that can be used in the structural unit (a1-1) >>>>

As the acid-decomposable group that can be used for the structural unit (a1-1) having a protective carboxyl group protected by the acid-decomposable group, conventionally known as the acid-decomposable groups in the positive resist for KrF and the positive resist for ArF can be used. It may, and is not particularly limited. Conventionally, as an acid-decomposable group, a group that is relatively easily decomposed by an acid (for example, an acetal-based functional group such as tetrahydropyranyl group) or a group that is relatively difficult to decompose by an acid (for example, tert-butyl ester group, tert -Tert-butyl functional groups such as butyl carbonate groups) are known.

Among these acid-decomposable groups, the basic properties of the resist, in particular, sensitivity or pattern shape, contact hole formation, photosensitive resin, is a structural unit having a protective carboxyl group protected by acetal or ketal, or a protective carboxyl group protected by ketal. It is preferable from the viewpoint of storage stability of the composition. Further, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protective carboxyl group protected by acetal or ketal represented by the following general formula (a1-1). In addition, when the carboxyl group is a protective carboxyl group protected by acetal or ketal represented by the following general formula (a1-1), the entire protective carboxyl group has a structure of-(C = O) -O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) It is done.

General formula (a1-1)

(In formula (a1-1), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether)

In the general formula (a1-1), R ¹⁰¹ to R ¹⁰³ each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be either linear, branched or cyclic. Here, in the case where both of R ¹⁰¹ and R ¹⁰² represent a hydrogen atom is not, at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

When R ¹⁰¹ , R ¹⁰² and R ^{103 in} the general formula (a1-1) represent an alkyl group, the alkyl group may be linear, branched or cyclic.

The linear or branched alkyl group is preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-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 and the like.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and even more preferably 4 to 6 carbon atoms. As said cyclic alkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group etc. are mentioned, for example.

The said alkyl group may have a substituent, and a halogen atom, an aryl group, and an alkoxy group can be illustrated as a substituent. When having a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ become a haloalkyl group, and when having aryl group as a substituent, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ become an aralkyl group.

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

Moreover, as said aryl group, a C6-C20 aryl group is preferable, More preferably, it is C6-C12, Specifically, a phenyl group, alpha-methylphenyl group, naphthyl group, etc. can be illustrated, The alkyl group substituted by the aryl group As a whole, that is, an aralkyl group, a benzyl group, an α-methylbenzyl group, a phenethyl group, a naphthylmethyl group, etc. can be illustrated.

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

Moreover, when the said alkyl group is a cycloalkyl group, the said cycloalkyl group may have a C1-C10 linear or branched alkyl group as a substituent, and when the alkyl group is a linear or branched alkyl group, it has 3 ~ You may have 12 cycloalkyl groups.

These substituents may be further substituted with the above substituents.

In the general formula (a1-1), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group is preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms can be preferably exemplified. As an aryl group, a phenyl group, a tolyl group, a silyl group, a cumenyl group, 1-naphthyl group, etc. can be illustrated, for example.

In addition, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are bonded to each other, and they may be combined with one carbon atom to which they are attached to form a ring. As the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded, for example, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, tetrahydrofuranyl group, adamantine And til groups and tetrahydropyranyl groups.

In addition, in the general formula (a1-1), it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

A commercially available radical polymerizable monomer used to form a structural unit having a protective carboxyl group represented by the general formula (a1-1) may be used, or a synthesized one by a known method may be used. For example, as shown below, (meth) acrylic acid can be synthesized by reacting with vinyl ether in the presence of an acid catalyst. This reaction may be performed in the step of a monomer, or may be carried out after forming a polymer.

In the above scheme, R ¹¹¹ represents a hydrogen atom or an alkyl group, and the alkyl group is the same as the alkyl group represented by R ¹⁰¹ to R ¹⁰³ in the general formula (a1-1). R ¹¹¹ is preferably a hydrogen atom or a methyl group.

R ¹¹² and R ¹¹³ are -CH (R ¹¹² ) (R ¹¹³ ), which is synonymous with R ¹⁰² in the general formula (a1-1), and R ¹¹⁴ is R in the general formula (a-1). and ¹⁰¹ and consent, R ¹¹⁵ is R ^103, and accept in the general formula (a1-1), also, all of which it is like a preferable range.

In the above synthesis, (meth) acrylic acid may be previously copolymerized with other monomers, and then reacted with vinyl ether in the presence of an acid catalyst.

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

Expression (A2 ')

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

When R ¹ and R ² are alkyl groups, the alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, respectively.

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

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

The second preferred form of the structural unit (a1-1) having a protective carboxyl group protected by the acid-decomposable group is a structural unit of the following general formula.

(Wherein, R ¹²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L ¹ represents a carbonyl group or a phenylene group, and R ¹²² to R ¹²⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

R ¹²¹ is preferably a hydrogen atom or a methyl group.

L ¹ is preferably a carbonyl group.

R ¹²² to R ¹²⁸ are preferably a hydrogen atom.

The following structural unit can be illustrated as a preferable specific example of the structural unit (a1-1) which has the protective carboxyl group protected by the said acid-decomposable group. In addition, R represents a hydrogen atom or a methyl group.

<<< Constituent unit having a protective phenolic hydroxyl group protected by (a1-2) acid decomposable group >>>

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

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

Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene-based structural unit and a structural unit in a novolac-based resin, among which structural units derived from hydroxystyrene or α-methylhydroxystyrene. Is preferred from the viewpoint of transparency. Among the structural units having a phenolic hydroxyl group, the structural units represented by the following general formula (a1-2) are preferred from the viewpoint of transparency and sensitivity.

General formula (a1-2)

(In the general formula (a1-2), R ²²⁰ represents a hydrogen atom or a methyl group, R ²²¹ represents a single bond or a divalent linking group, and R ²²² represents a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Represents, a represents an integer from 1 to 5, b represents an integer from 0 to 4, and a + b is 5 or less, and when R ²²² is 2 or more, these R ²²² may be different or the same)

In the general formula (a1-2), R ²²⁰ represents a hydrogen atom or a methyl group, and is preferably a methyl group.

Further, R ²²¹ represents a single bond or a divalent linking group. In the case of a single bond, it is preferable because the sensitivity can be improved and the transparency of the cured film can be improved. R may be exemplified by an alkylene group as the divalent linkage group of ^221, R ²²¹ is an alkylene group Specific examples include methylene group, ethylene group, propylene group, isopropylene group, an n- butyl group, isobutyl group, tert- butyl group, And a pentylene group, an isopentylene group, a neopentylene group, and a hexylene group. Especially, it is preferable that R ²²¹ is a single bond, a methylene group, and an ethylene group. Moreover, the said bivalent coupling group may have a substituent, and a halogen atom, a hydroxyl group, an alkoxy group, etc. are mentioned as a substituent.

In addition, a represents an integer of 1 to 5, but a is preferably 1 or 2, and more preferably a is 1 from the viewpoint of the effect of the present invention and ease of manufacture.

In addition, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4 position when the carbon atom bound to R ²²¹ is used as the reference (1 position).

R ²²² is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. You can. Especially, it is preferable that it is a chlorine atom, a bromine atom, a methyl group, or an ethyl group from the point that manufacture is easy.

In addition, b represents 0 or an integer of 1-4.

<<<< An acid-decomposable group that can be used in structural units (a1-2) >>>>

As the acid-decomposable group that can be used for the structural unit (a1-2) having a protective phenolic hydroxyl group protected by the acid-decomposable group, it can be used for the structural unit (a1-1) having a protective carboxyl group protected by the acid-decomposable group. A well-known thing can be used like an acid-decomposable group, and it is not specifically limited. Among the acid-decomposable groups, the basic physical properties of the resist, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, are the structural units having a protective phenolic hydroxyl group protected by acetal or a protective phenolic hydroxyl group protected by ketal. It is preferable from the viewpoint of formability of the contact hole. Further, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protective phenolic hydroxyl group protected by acetal or ketal represented by the general formula (a1-1). In addition, when the phenolic hydroxyl group is a protected phenolic hydroxyl group protected by acetal or ketal represented by the general formula (a1-1), the entire protective phenolic hydroxyl group is -Ar-O-CR ¹⁰¹ R ¹⁰² (OR ¹⁰³ ) It is made of a structure. In addition, AR represents an arylene group.

Preferred examples of the acetal ester structure of the phenolic hydroxyl group are R ¹⁰¹ = R ¹⁰² = R ¹⁰³ = methyl group or R ¹⁰¹ = R ¹⁰² = methyl group and R ¹⁰³ = benzyl group can be exemplified.

Moreover, as a radically polymerizable monomer used to form a structural unit having a protective phenolic hydroxyl group protected by acetal or ketal, the phenolic hydroxyl group is, for example, a 1-alkoxyalkyl protector of hydroxystyrene or hydroxystyrene. Tetrahydropyranyl protector, α-methyl-hydroxystyrene 1-alkoxyalkyl protector, α-methyl-hydroxystyrene tetrahydropyranyl protector, 4-hydroxyphenylmethacrylate 1-alkoxyalkyl Protector, tetrahydropyranyl protector of 4-hydroxyphenylmethacrylate, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (1-methacryloyloxymethyl) ester, 4-hydroxybenzoic acid (1 Tetrahydropyranyl protector of methacryloyloxymethyl) ester, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (2-methacryloyloxyethyl) ester, 4-hydroxybenzoic acid (2-metha Kryloyloxyethyl) Stear's tetrahydropyranyl protector, 1-alkoxyalkyl protector of 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester Tetrahydropyranyl protector, 4-hydroxybenzoic acid (3-methacryloyloxy-2-hydroxypropyl) ester 1-alkoxyalkyl protector, 4-hydroxybenzoic acid (3-methacryloyloxy And tetrahydropyranyl protectors of -2-hydroxypropyl) ester.

Of these, 4-hydroxyphenyl methacrylate 1-alkoxyalkyl protectors and 4-hydroxyphenylmethacrylate tetrahydropyranyl protectors are preferred from the viewpoint of transparency.

Specific examples of the acetal protecting group and ketal protecting group of the phenolic hydroxyl group include a 1-alkoxyalkyl group, for example, 1-ethoxyethyl group, 1-methoxyethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group , 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group And 1-benzyloxyethyl groups, and these can be used alone or in combination of two or more.

A commercially available radical polymerizable monomer used to form the structural unit (a1-2) having a protective phenolic hydroxyl group protected by the acid-decomposable group may be used, or a compound synthesized by a known method may also be used. For example, a compound having a phenolic hydroxyl group can be synthesized by reacting with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with other monomers, and then reacted with vinyl ether in the presence of an acid catalyst.

Although the following structural unit can be illustrated as a preferable specific example of the structural unit (a1-2) which has the protective phenolic hydroxyl group protected by the said acid-decomposable group, This invention is not limited to these.

<<< preferable form of structural unit (a1) >>>

(A) Among the structural units constituting the component, the content rate of the structural unit (a1) is preferably 1 to 95 mol%, more preferably 10 to 80 mol%, and 20 to 70, from the viewpoint of sensitivity as a whole of the polymer. Molar% is more preferable, and 20 to 50 mol% is particularly preferable. In addition, especially when the acid-decomposable group that can be used in the structural unit (a1) is a carboxyl group-protected carboxyl group protected with acetal or a carboxyl group-protected carboxyl group-protected carboxyl group, the structural unit (a1) is included. The content rate of the structural unit (a1) in the structural unit constituting the polymer is more preferably 20 to 60 mol%, and particularly preferably 20 to 50 mol%.

The structural unit (a1-1) having a protective carboxyl group protected by the acid-decomposable group has a feature that the phenomenon is faster than that of the structural unit (a1-2) having a protective phenolic hydroxyl group protected by the acid-decomposable group. Therefore, when it is desired to develop rapidly, the structural unit (a1-1) having a protective carboxyl group protected by an acid-decomposable group is preferable. Conversely, when it is desired to slow development, it is preferable to use a structural unit (a1-2) having a protective phenolic hydroxyl group protected by an acid-decomposable group.

[Repeat unit (a2)]

The repeating unit (a2) is a structural unit having a crosslinkable group selected from an oxiranyl group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). The structural unit having the crosslinkable group is preferably a compound-derived structural unit having a cyclic ether group, more preferably a structural unit derived from a compound having an oxiranyl group and / or an oxetane group, (3) to (5) ) Is more preferably a repeating unit composed of a radically polymerizable monomer. These compounds may be used alone or in combination of two or more. Moreover, the repeating unit represented by the following general formula (2) may be sufficient.

In General Formulas (3) to (5), X represents a divalent linking group, and examples thereof include organic groups such as -O-, -S-, or -COO-, -OCH ₂ COO-. X is preferably -COO-.

R ⁷ represents a hydrogen atom, a methyl group or a halogen atom, and a hydrogen atom or a methyl group is preferable.

R ⁸ to R ¹⁵ each independently represent a hydrogen atom or an alkyl group. It preferably represents a hydrogen atom or a methyl group.

n is an integer of 1-10, Preferably it is an integer of 1-3.

Specific examples of the radically polymerizable monomer used to form a structural unit containing an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, and 3,4-methacrylate. Epoxybutyl, 4,5-epoxypentyl acrylate, 4,5-epoxypentyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, (Meth) acrylates such as 3,4-epoxycyclohexyl methyl methacrylate; o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycine Vinyl benzyl glycidyl ethers such as dil ether and α-methyl-p-vinyl benzyl glycidyl ether; and vinyl phenyl glycidyl ethers such as o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, and p-vinyl phenyl glycidyl ether. Acrylic acid glycidyl, methacrylic acid glycidyl, p-vinylphenylglycidyl ether, 3,4-epoxycyclohexylmethylacrylate, 3,4-epoxycyclohexylmethylmethacrylate are preferred, and acrylic acid glycylic acid Dill and glycidyl methacrylate are particularly preferred.

As a structural unit which has the said crosslinkable group, the structural unit which consists of a radically polymerizable monomer represented by the following general formula (6) or (7) in another form is preferable, and can be used individually or in combination of 2 or more type. The molecular weight of the radically polymerizable monomer represented by the general formula (6) or (7) is preferably 100 to 500, more preferably 150 to 200.

In General Formulas (6) and (7), X represents a divalent linking group, and examples thereof include organic groups such as -O-, -S-, or -COO-, -OCH ₂ COO-. X is preferably -COO-.

R ⁷ represents a hydrogen atom, a methyl group or a halogen atom, and a hydrogen atom or a methyl group is preferable.

R ⁸ to R ¹⁵ each independently represent a hydrogen atom or an alkyl group. It preferably represents a hydrogen atom or a methyl group.

n is an integer of 1-10, Preferably it is an integer of 1-3.

Examples of the radically polymerizable monomer used to form the structural unit having such an oxetanyl group include a compound in which the oxiranyl group is substituted with an oxetanyl group in the above specific example of a radically polymerizable monomer containing an oxiranyl group, for example And (meth) acrylic acid esters having an oxetanyl group described in paragraphs 0011 to 0016 of Japanese Patent Laid-Open No. 2001-330953.

As the radically polymerizable monomer used to form a structural unit having a crosslinkable group, commercially available ones or those synthesized by a known method may be used. For example, Osaka Yuki Kagaku High School's OXE series and the like.

The following structural unit can be illustrated as a preferable specific example of the structural unit which has a functional group which can react and form a covalent bond by reacting with a carboxyl group.

The structural unit having the crosslinkable group is also preferably a structural unit (a2-2) having -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms). By having the structural unit (a2-2), a curing reaction can be caused by gentle heat treatment, and a cured film excellent in various characteristics can be obtained.

R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be either a straight chain, branched or cyclic alkyl group, and a straight chain or branched alkyl group is preferable.

Moreover, the said alkyl group may have a substituent. Examples of the substituent that the alkyl group may have include a halogen atom, an aryl group, and an alkoxy group.

As the structural unit (a2-2) having -NH-CH ₂ -OR, a structural unit having a group represented by the following general formula (2) is preferable.

General formula (2)

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

R ² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. Further, the alkyl group may be either a straight chain, branched or cyclic alkyl group, but is preferably a straight chain or branched alkyl group.

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

(A) Among the structural units constituting the component, the content rate of the structural unit (a2) is preferably 1 to 95 mol%, more preferably 5 to 70 mol%, still more preferably 10 to 50 mol%, and 20 to 50 mol% is more preferable, and 30-50 mol% is especially preferable. If it is within the range of the above values, various properties of the cured film obtained from the photosensitive resin composition will be good.

[Repeat Unit (a3)]

The photosensitive composition of the present invention contains a monomeric unit (a3) having a carboxyl group at the side chain terminal and having at least 4 atoms in a divalent linking group constituting a group connecting a polymer main chain and a side chain terminal carboxyl group, and the bivalent linking group is -CR ¹ _2- (R ¹ represents a hydrogen atom or a methyl group), -O-, -O-SO _2- , -OC (O)-, -C (O) -O-, -S-, -C (O) -, An amino group which may have a substituent, a phenylene group which may have a substituent, or a group selected from structures of (iv) below and optionally combined.

L is a divalent linking group having 4 or more atoms connecting the polymer main chain and a carboxyl group, preferably 6 to 20 atoms, and more preferably 8 to 12 atoms.

As a divalent linking group (L) having 4 or more atoms, -CR ¹ _2- (R ¹ represents a hydrogen atom or a methyl group), -O-, -O-SO _2- , -OC (O)-, -C (O ) -O-, -S-, -C (O)-, an amino group which may have a substituent, a phenylene group which may have a substituent, or a group selected from the structures of (iv) below and optionally combined.

In general formula (iv), z represents the integer of 0-5.

Z is preferably 2-3, and 3 is particularly preferable.

As the amino group, an amino group having 0 to 50 carbon atoms is preferable, for example, -NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N-sulfonylamino group, N, N-dialkylamino group, N And N-diarylamino groups, N-alkyl-N-arylamino groups, and N, N-disulfonylamino groups. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N- Octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino group, N-2-chlorophenylamino group, N-2 -Methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-sia Nophenylamino group, N-3-trifluoromethylphenylamino group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenyl Amino group, N-4-phenylsulfanylphenylamino group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-di Tylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N -(Dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, 5-dimethylmorpholino group, carbazole group, etc. are mentioned. Among these, -NH ₂ , N, N-diphenylamino group and carbazole group are preferable.

As a phenylene group, an o-phenylene group, m-phenylene group, and p-phenylene group are mentioned, for example. Among these, o-phenylene group and p-phenylene group are preferable.

A halogen atom, an aryl group, and an alkoxy group are mentioned as a substituent which the amino group and the phenylene group may have.

In addition, in this specification, the number of atoms of a divalent linking group means the number of atoms in which the number of atoms constituting the main chain connecting the polymer main chain and the carboxyl group is small. For example, the following exemplary compound (a3-1) has 8 atoms, (a3-2) has 8 atoms (the number of atoms constituting the main chain connecting the polymer main chain and the carboxyl group is 8 and 12) Is considered, but since the number of atoms constituting the main chain connecting the polymer main chain and the carboxyl group is defined as the number of atoms, the number of atoms is 8), and (a3-20) is 8 atoms (in the formula below) Numbers refer to the number of atoms).

As the component (a3), it is preferable to include at least one repeating unit represented by the following general formulas (i) to (iii).

(In formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, and L represents a divalent linking group having 4 or more atoms. In general formula (iii), R ² represents a halogen atom, a hydroxyl group, or 1 carbon atom.) Represents an alkyl group of ∼3, and n represents an integer of 0 to 4)

It is preferable that it is selected from the group of the linking group shown below as an example of L. Among the following linking groups, "*" represents the linking site of the polymer main chain and the carboxyl group.

In General Formula (iii), R ² is a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, and a chlorine atom, a bromine atom, a hydroxyl group, or a methyl group is preferable.

n is an integer of 0-4, and 0 is preferable.

It is preferable that the repeating units represented by the general formulas (i) to (iii) are repeating units represented by the following general formulas (i ') to (iii').

(Formula (i ') ~ (iii' ) of, R ¹ is formula (i) and R ~ ¹ and consent of (iii), L ¹ represents an alkylene group of a carbon number of 1 to 4.)

L ¹ represents an alkylene group having 1 to 4 carbon atoms, and an alkylene group having 2 to 3 carbon atoms is preferable.

Although the following structure is mentioned as a specific example of a repeating unit (a3), This invention is not limited to the following structure.

Among the specific examples, (a3-1) to (a3-15) are preferred, and (a3-1) to (a3-3), (a3-5), (a3-7), and (a3-9) Is more preferable, and (a3-2) is more preferable.

(A) Among the structural units constituting the component, the content rate of the repeating unit (a3) is preferably 0.1 to 50 mol%, more preferably 0.1 to 45 mol%, and 5.0 to 35 mol%, of the structural units of all resin components. Is more preferred. When the content is 0.1 mol% or more, an effect of high sensitivity and high residual film ratio is obtained, and if it is 45 mol% or less, it is preferable from the viewpoint of improving developability.

The weight average molecular weight (Mw) of the polymer having a repeating unit (a3) is preferably in the range of 3000 to 300000, more preferably 4000 to 100,000, and still more preferably 8000 to 50000. The effect of improving the residual film rate is obtained by setting it to 3000 or more, and the effect of high sensitivity is obtained by setting it to 300000 or less. Here, the weight average molecular weight is defined as the polystyrene conversion value of gel permeation chromatography.

[Repeat unit (a4)]

The said (A) component may contain the polymer which has as a repeating unit (a4) derived from another monomer other than the said repeating units (a1)-(a3). Moreover, you may copolymerize the repeating unit (a4). Other monomers include hydrogenated hydroxystyrene; Halogen, alkoxy or alkyl substituted hydroxystyrene; Styrene; Halogen, alkoxy, acyloxy or alkyl substituted styrene; Maleic anhydride; Acrylic acid derivatives; Methacrylic acid derivatives; And N-substituted maleimide, and the like, but are not limited to these.

(A) Among the structural units constituting the component, the content of the structural unit (a4) is preferably 0.01 to 50 mol%, more preferably 0.01 to 33 mol%, and even more preferably 5 to 23 mol%.

In the present invention, among the repeating units constituting the component (A), the repeating units having 3 or less atoms of "L" in the repeating units represented by the general formulas (i) to (iii) are preferably 3 mol% or less, and substantially It is more preferable not to include it. By not including substantially, it means that it does not affect the effect of this invention, for example.

[Molecular weight of component (A)]

The weight average molecular weight (Mw) of the component (A) is preferably in the range of 3000 to 300,000, more preferably 4000 to 100,000, and even more preferably 8000 to 50000. The effect of improving the residual film rate is obtained by setting it to 3000 or more, and the effect of high sensitivity is obtained by setting it to 300000 or less. Here, the weight average molecular weight is defined as the polystyrene conversion value of gel permeation chromatography.

<< (A) compounding amount >>

The photosensitive resin composition of the present invention preferably contains at least 30% by weight of the component (A), more preferably at least 40% by weight, and even more preferably at least 50% by weight. By setting it as such a range, the structural unit (a2) will remain in the composition, and the effect of this invention will be exhibited more effectively. The upper limit is not particularly limited, and may be 100% by weight.

<< (A) Method of manufacturing >>

In addition, although various methods are known for the method for synthesizing the component (A), for example, radical polymerization properties including, for example, radically polymerizable monomers used to form the structural units represented by (a1) and (a2) above The monomer mixture can be synthesized by polymerization in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction. Moreover, it is also preferable that (A) component has a carboxyl group at the terminal.

[Synthesis method of resin having a carboxyl group at the terminal]

The resin having a carboxyl group at the terminal can be produced by copolymerizing a corresponding monomer by radical polymerization, anionic polymerization, group transfer polymerization (GTP) or the like. Although the manufacturing method of the resin which has a carboxyl group at the terminal of this invention is not specifically limited, For example, the method of (a)-(h) described in paragraph of Japanese Patent Publication 2005-122035-0099 paragraph -0117 paragraph is mentioned. Among these, the methods of a and b are preferred.

(a) As a method of using a polymerization initiator having a carboxyl group, a polymerization initiator having a carboxyl group is used as an initiator during polymerization.

Although widely used as a polymerization initiator having a carboxyl group, VA-057 (manufactured by Wako Pure Chemical Industries, Ltd.) and V-501 (manufactured by Wako Pure Chemical Industries, Ltd.) are exemplified.

It is preferable that this polymerization initiator is 0.05-10 mol% with respect to 100 mol of polymerizable monomers, and it is more preferable that it is 0.1-5 mol%.

The reaction temperature of the copolymerization reaction is preferably 50 to 100 ° C, more preferably 60 to 100 ° C.

(H) In the method of using a chain transfer agent having a carboxyl group during polymerization, a thiol compound having at least one carboxyl group is used together during polymerization. The following examples are given as thiol compounds having at least one carboxyl group.

The chain transfer agent is preferably blended in a ratio of 1/100 to 2/3 mol with respect to the amount of initiator, and more preferably blended in a ratio of 1/20 to 1/3 mol.

Although the molecular weight is adjusted by the sum of the initiator amount and the chain transfer agent, it is preferably 0.05 to 10 mol%, more preferably 0.1 to 5 mol%, based on the total moles of all monomers. The reaction temperature of the copolymerization reaction is preferably 50 to 100 ° C, more preferably 60 to 95 ° C.

<(B) Photoacid generator>

The photosensitive resin composition of the present invention contains a photoacid generator (B). The photoacid generator used in the present invention is preferably a compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm, but its chemical structure is not particularly limited. In addition, for a photoacid generator that does not directly respond to actinic rays having a wavelength of 300 nm or more, any compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more by using in combination with a sensitizer can be preferably used in combination with a sensitizer. The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, and more preferably a photoacid generator that generates an acid having a pKa of 3 or less.

Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts or iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from an insulating viewpoint. These photoacid generators may be used alone or in combination of two or more.

The following can be illustrated as a specific example of these.

As trichloromethyl-s-triazine, 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-methoxynaphthyl ) -Bis (4,6-trichloromethyl) -s-triazine, etc .;

As a diaryl iodonium salt, diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium tree Fluoroacetate, phenyl, 4- (2'-hydroxy-1'-tetradecaoxy) phenyl iodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodine Niumhexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetradecaoxy) phenyl iodonium-p-toluenesulfonate, etc .;

As triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfate Phonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate;

As a quaternary ammonium salt, tetramethylammonium butyltris (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, etc .;

As a diazomethane derivative, bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, etc .;

As an imide sulfonate derivative, trifluoromethylsulfonyloxybicyclo [2.2.1] hepto-5-endicarboxyimide, succinimide trifluoromethylsulfonate, phthalimide trifluoromethylsulfonate, N- Hydroxynaphthalimidemethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyimidepropanesulfonate, etc .;

The compound shown below as an oxime sulfonate compound.

As the oxime sulfonate compound, that is, a compound having an oxime sulfonate residue, a compound containing an oxime sulfonate residue represented by the formula (b1) can be preferably exemplified.

(In formula (b1), R ⁵ represents an alkyl group or an aryl group.)

Any group may be substituted, and the alkyl group for R ⁵ may be linear or branched or cyclic. Acceptable substituents are described below.

The alkyl group of R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ^{5 preferably} contains bicyclic cycloaliphatic groups such as an aryl group having ⁶ to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group). Alkyl group, etc.).

The aryl group of R ⁵ is preferably an aryl group having ⁶ to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ⁵ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

It is preferable that it is an oxime sulfonate compound represented by Formula (OS-3), Formula (OS-4), or Formula (OS-5) as a compound containing the oxime sulfonate residue represented by said Formula (b1). .

(In formulas (OS-3) to (OS-5), R ¹ represents an alkyl group, an aryl group, or a heteroaryl group, and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ⁶ Each independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, X represents O or S, n represents 1 or 2, and m represents an integer from 0 to 6 Indicates)

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

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

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

Examples of the alkyl group for R ¹ are 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, and n-octyl group. , n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group.

Moreover, among the formulas (OS-3) to (OS-5), the aryl group for R ¹ is preferably an aryl group having 6 to 30 carbon atoms, which may have a substituent.

Examples of the substituent which the aryl 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 aminosulfonyl group. And an alkoxysulfonyl group.

Examples of the aryl group for R ¹ include a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, and p-phenoxyphenyl group.

Moreover, in the formulas (OS-3) to (OS-5), a heteroaryl group having ⁴ to 30 carbon atoms is preferable as the heteroaryl group for R ¹ .

As a substituent which the heteroaryl group in R ¹ may have, 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, an amino sulfo And a nil group and an alkoxysulfonyl group.

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

The heteroaryl group for R ¹ is selected from the group consisting of thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring, and benzoimidazole ring which may have a substituent. The group which excluded one hydrogen atom from the ring 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 two or more compounds 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 that it is, one is an alkyl group, and the rest are particularly preferably hydrogen atoms.

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

As a substituent which the alkyl group or aryl group in R ² may have, the same group as the substituent which the alkyl group or aryl group in R ¹ may have may be exemplified.

The alkyl group for R ² is preferably an alkyl group having 1 to 12 total carbons which may have a substituent, and more preferably an alkyl group having 1 to 6 total carbons which may have a substituent.

Examples of the alkyl group for R ² are 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, and bromomethyl group. , Methoxymethyl group, benzyl group is preferred, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group is preferred, methyl group, ethyl group , n-propyl group, n-butyl group, n-hexyl group is more preferable, and a methyl group is preferred.

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

As the aryl group for R ² , specifically, a phenyl group, p-methylphenyl group, o-chlorophenyl group, p-chlorophenyl group, o-methoxyphenyl group, or p-phenoxyphenyl group is preferable.

Examples of the halogen atom for R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these, chlorine atom and bromine atom are preferable.

In the formulas (OS-3) to (OS-5), X represents O or S and is preferably 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 alkyloxy group for R ⁶ may have a substituent.

Among 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.

Examples of the alkyl group for R ⁶ are 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, and n-octyl group. , n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group is preferred.

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

The alkyloxy group for R ⁶ is preferably a methyloxy group, ethyloxy group, butyloxy group, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, or ethoxyethyloxy group.

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

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

Further, in the formulas (OS-3) to (OS-5), m represents an integer from 0 to 6, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0. Do.

In addition, it is particularly preferable that the compound containing an oxime sulfonate residue represented by the formula (b1) is an oxime sulfonate compound represented by any one of the following formulas (OS-6) to (OS-11).

(In formulas (OS-6) to (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 represents a hydrogen atom, and has 1 to 8 carbon atoms. Alkyl group, halogen atom, chloromethyl group, bromomethyl group, bromoethyl group, methoxymethyl group, phenyl group or chlorophenyl group, R ⁹ represents a hydrogen atom, halogen atom, methyl group or methoxy group, R ¹⁰ hydrogen atom or methyl group Indicates)

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

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

R ⁸ in the 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 a chlorophenyl group It represents, 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 more preferable that it is a C1-C6 alkyl group, It is especially preferable that it is a methyl group.

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

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

In addition, in the oxime sulfonate compound, any one of the three-dimensional structures (E, Z) of the oxime may be a mixture.

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

It is also preferable that it is a compound represented by Formula (OS-1) as said compound containing the oxime sulfonate residue represented by Formula (b1).

(In 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 a heteroaryl group R ² represents an alkyl group or an aryl group)

X represents -O-, -S-, -NH-, -NR ^5- , -CH _2- , -CR ⁶ H-, or -CR ⁶ R ^7- , R ⁵ to R ⁷ are alkyl groups, or aryl Group.

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

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

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

It is more preferable that the compound represented by the formula (OS-1) is a compound represented by the following formula (OS-2).

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

Among these, the form in which R ^{1 in} formula (OS-1) and formula (OS-2) is a cyano group or an aryl group is more preferable, represented by formula (OS-2), and R ¹ is a cyano group, The most preferred form is a phenyl group or naphthyl group.

In addition, in the oxime sulfonate compound, any one of the three-dimensional structures (E, Z, etc.) of an oxime or a benzothiazole ring may be a mixture, respectively.

Below, although the specific example (example compounds b-1-b-34) of the compound represented by Formula (OS-1) which can be used suitably for this invention is shown, this invention is not limited to this. In addition, Me represents a methyl group, Et represents an ethyl group, Bn represents a benzyl group, and Ph represents a phenyl group.

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

The compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the following formula (b2).

(In formula (b2), R ⁵ represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m represents an integer of 0 to 3, and m is 2 or 3, a plurality of X May be the same or different)

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

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

The halogen atom as X is preferably a chlorine atom or a fluorine atom.

m is preferably 0 or 1.

In formula (b2), m is 1, X is a methyl group, the substitution position of X is an ortho position, R5 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorbornylmethyl group, Or a compound which is a p-toluyl group is particularly preferable.

The compound containing an oxime sulfonate residue represented by formula (b1) may be an oxime sulfonate compound represented by formula (b3).

(Wherein (b3) of, R ⁵ is R ⁵ as agreed in the formula (b1), X 'is an alkoxy group of the alkyl group, having 1 to 4 carbon atoms a halogen atom, a hydroxyl group, having 1 to 4 carbon atoms, a cyano group or a nitro group Group, and L represents an integer from 0 to 5)

As R ⁵ in the formula (b3), a methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group, perfluoro A ro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and n-octyl group is particularly preferred.

As X ', an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group is more preferable.

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

Specific examples of the compound represented by formula (b3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) benzylsia Need, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] aceto Nitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n- Butylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile.

The following compound (i)-(viii) etc. are mentioned as a specific example of a preferable oxime sulfonate compound, It can be used individually by 1 type, or can use 2 or more types together. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of photo-acid generator (B).

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

<(C) component>

It is preferable that the photosensitive resin composition of this invention contains the polymer (polymer) which has (C) at least a crosslinking group.

(C) It is preferable that a component is resin of an addition polymerization type, and it is more preferable that it is a polymer containing the structural unit derived from (meth) acrylic acid and / or its ester. Moreover, you may have a structural unit other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, a structural unit derived from styrene, a structural unit derived from a vinyl compound, or the like.

It is preferable that (C) component contains 50 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units in a polymer, and it is more preferable to contain 90 mol% or more, It is particularly preferable that it is a polymer composed of only structural units derived from (meth) acrylic acid and / or its esters.

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

(C) component may also contain the structural unit which the (c1) acidic radical has the residue protected by the acid-decomposable group. (C) When component (c1) contains, sensitivity improves, and by containing (c2), the permanent film characteristic improves. Further, (C) component is the side that does not include a structural unit having -NH-CH ₂ -OR (R is an alkyl group) in a substantially preferred. By setting it as such a structure, the effect of this invention tends to be exhibited more effectively. Here, substantially not included means not adding at a level that affects the effect of the present invention, for example, 3 mol% or less, and 1 mol% or less of the preceding constituent units of the component (C). Things are listed.

As the component (c1) of the component (C), a group such as the above-described << (a1) structural unit having a residue protected by an acid-decomposable group >> can be used. Among the structural units constituting the copolymer (C), the content rate of the structural unit (c1) is preferably 0 to 95 mol%, more preferably 5 to 90 mol%, and 20 to 20 mol%, with the polymer as a whole from the viewpoint of sensitivity. 70 mol% is particularly preferable.

As the component (c2) of the component (C), groups such as the above-mentioned << (a3) structural unit having a crosslinking group >> can be used. The preferred form is also the same. Among the structural units constituting the copolymer (C), the content rate of the structural unit (c2) is preferably 0 to 95 mol%, more preferably 5 to 90 mol%, and 30 to 30 mol%, with the polymer as a whole from the viewpoint of sensitivity. 70 mol% is particularly preferable.

(C) A component may have other structural units (c3) except (c1), (c2), and (a2). There is no restriction | limiting in particular as a monomer which becomes another structural unit (c3). Groups such as the above-described [repeating unit (a3)] and << (a4) other structural units >> can be preferably used. The preferred form is also the same. The preferred range is also the same.

<< (C) molecular weight of component >>

The molecular weight of the component (C) is a weight average molecular weight in terms of polystyrene, preferably 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable as long as it is within the range of the above values. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, and more preferably 1.5 to 3.5.

<< Method for producing molecular weight of component (C) >>

Although various methods are known for the method for synthesizing the component (C), for example, a radically polymerizable monomer mixture containing a radically polymerizable monomer used to form the structural units represented by (c1) and (c2) above is used. It can be synthesized by polymerization using a radical polymerization initiator in an organic solvent. It can also be synthesized by a so-called polymer reaction.

It is also preferable to have a carboxyl group at the terminal similar to the component (A).

(C) Examples of ingredients

Methacrylic acid-3,4-epoxycyclohexylmethyl / acrylic acid / hydroxystyrene / methyl methacrylate copolymer (30/40/15/15 in molar ratio, Mw 7000)

Methacrylic acid glycidyl / methacrylic acid / styrene / dicyclopentanyl methacrylate copolymer (molar ratio 70/10/10/10, Mw 15000)

p-vinylbenzylglycidyl ether / (3-ethyl-3-oxetanyl) methyl methacrylate / maleic acid / methacrylic acid cyclohexyl copolymer (25/25/30/20 in molar ratio, Mw 27000)

Methacrylic acid 1-ethoxyethyl / methacrylic acid / methacrylic acid (3-ethyloxetan-3-yl) methyl / methacrylic acid 2-hydroxyethyl / methyl methacrylate copolymer (38/7/35 / 15/5, Mw 35000),

Methacrylic acid 1-cyclohexyloxyethyl / methacrylic acid / methoxypolyethylene glycol methacrylate (Bremmer PME-400, Nichiyu Co., Ltd. (70/10/10, Mw 45000)

(3-ethyl-3-oxetanyl) methyl acrylate / methacrylic acid / N-phenylmaleimide copolymer (30/30 / in molar ratio, Mw 57000).

The content of the component (C) is preferably 0 to 80% by weight of the total polymer component, more preferably 8 to 70% by weight, even more preferably 30 to 65% by weight, and particularly preferably 30 to 50% by weight. . (C) When 2 or more types of components are included, the total amount becomes said range.

<Ratio of each constituent unit to the total polymer component>

It is preferable that 99 weight% or more of the photosensitive resin composition of this invention is (A) component or (C) component.

In the present invention, the proportion of the structural unit (a2) in the total polymer component is preferably 1 to 50 mol%, more preferably 10 to 50 mol%, and even more preferably 15 to 50 mol%. In the present invention, the proportion of the crosslinking group in the total polymer component is preferably 1 to 40 mol%, more preferably 10 to 35 mol%, and even more preferably 15 to 30 mol%.

In particular, in the present invention, 10 mol% or more of the total polymer component included in the positive photosensitive composition is a structural unit (a2) having -NH-CH ₂ -OR (R is an alkyl group), and 20 mol% or more of the total polymer component. It is preferable that it is this crosslinking group.

Moreover, in this invention, it is preferable that the ratio of the total amount of a crosslinkable group and a structural unit (a2) in a whole polymer component is 10-70 mol%, and it is more preferable that it is 40-60 mol%. By setting it as such a range, the effect of this invention tends to be exhibited more effectively.

<(D) Solvent>

The photosensitive resin composition of this invention usually contains (D) solvent. It is preferable that the photosensitive resin composition of this invention is prepared as a solution which melt | dissolved the essential component, preferable component, and arbitrary components in (D) solvent.

As the (D) solvent used in the photosensitive resin composition of the present invention, a known solvent can be used, and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ethers , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, di And propylene glycol monoalkyl ether acetates, esters, ketones, amides and lactones.

As a solvent (D) used for the photosensitive resin composition of this invention, For example,

(D-1) ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

(D-2) ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dipropyl ether;

(D-3) 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-4) Propylene glycol monoalkyl ethers, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;

(D-5) Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether;

(D-6) 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;

(D-7) diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;

(D-8) 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;

(D-9) dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether; (Co) dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;

(D-10) dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate, and other dipropylene glycol monoalkyl ether acetates;

(D-11) 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;

(D-12) 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;

(D-13) ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate , Other esters such as 3-methyl-3-methoxybutylbutylate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;

(D-14) ketones such as methyl ethyl ketone, methyl propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone;

(D-15) amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone;

And lactones such as (D-16) γ-butylolactone.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1, if necessary also for these solvents. -Solvents such as octanol, 1-nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, and propylene carbonate may also be added. These solvents can be used alone or in combination of two or more. The solvent which can be used in the present invention is preferably one type or a combination of two types, more preferably two types, and propylene glycol monoalkyl ether acetates and diethylene glycol dialkyl ethers are used in combination. It is more preferable.

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

In the positive photosensitive resin composition of the present invention, in addition to the above components, a crosslinking agent, adhesion improving agent, basic compound, surfactant, plasticizer, and thermal radical generator, antioxidant, and thermal acid generator, UV absorber, thickener, and organic or Known additives, such as inorganic precipitation inhibitors, can be added.

<(E) Adherence improving agent>

The photosensitive resin composition of this invention may contain (E) adhesion improver. (E) Adhesion improvers that can be used in the photosensitive resin composition of the present invention provide adhesion between an inorganic substance serving as a base material, for example, silicon compounds such as silicon, silicon oxide, and silicon nitride, metals such as gold, copper, and aluminum, and insulating films. It is a compound to improve. Specifically, a silane coupling agent, a thiol type compound, etc. are mentioned. The silane coupling agent used as the (E) adhesion improving agent used in the present invention is for the purpose of modifying the interface, and is not particularly limited and a known one can be used.

Preferred silane coupling agents include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropyldialkoxysilane, and γ-meta Krilloxypropyltrialkoxysilane, γ-methacryloxypropyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyl trialkoxysilane, And vinyl trialkoxysilane. Among these, γ-glycidoxypropyl trialkoxysilane or γ-methacryloxypropyl trialkoxysilane is more preferable, and γ-glycidoxypropyl trialkoxysilane is more preferable. These may be used alone or in combination of two or more. These are effective not only for improving the adhesion to the substrate but also for adjusting the taper angle with the substrate.

The content of the adhesion improving agent (E) in the photosensitive resin composition of the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin component.

<(G) basic compound>

The photosensitive resin composition of this invention may contain (G) basic compound. (G) As a basic compound, it can be used selecting arbitrarily from what is used by chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like.

Examples of the aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, And triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.

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

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-oxy Quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1 And 8-diazabicyclo [5.3.0] -7-undecene.

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

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

The basic compound that can be used in the present invention may be used singly or in combination of two or more kinds, but two or more kinds are preferably used in combination, more preferably two kinds in combination, and two kinds of heterocyclic amines. It is more preferable to use together.

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

<(H) surfactant>

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

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. In addition, the following product names are KP (made by Shin-Etsu Chemical Co., Ltd.), polyflow (made by Kyoeisha Kagaku Co., Ltd.), F-top (manufactured by JEMCO), Megapack (manufactured by DIC Co., Ltd.), Florad (Sumitomo 3M Co., Ltd.), Asahi Guard, Surfon (Asahi Garas Co., Ltd.), PolyFox (manufactured by OMNOVA) and the like.

Moreover, the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography, which includes structural unit A and structural unit B represented by the following formula (1) as a surfactant and using tetrahydrofuran (THF) as a solvent. A copolymer having (Mw) of 1,000 to 10,000 is exemplified as a preferred example.

(In formula (1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a straight-chain alkylene group having 1 to 4 carbon atoms, and R ⁴ is a hydrogen atom or 1 to 4 carbon atoms) Represents an alkyl group, L represents an alkylene group having 3 to 6 carbon atoms, p and q are weight percentages representing a polymerization ratio, p represents a value of 10% by weight or more and 80% by weight or less, and q is 20% by weight More than 90% by weight, r represents an integer of 1 to 18, and n represents an integer of 1 to 10)

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

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

These surfactants can be used alone or in combination of two or more.

The addition amount of the (H) surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by weight or less, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the resin component. Do.

<(I) Plasticizer>

The photosensitive resin composition of this invention may contain (I) plasticizer. Examples of the plasticizer (I) include dibutyl phthalate, dioctyl phthalate, didodecyl phthalate, polyethylene glycol, glycerin, dimethylglycerin phthalate, dibutyl stannate, dioctyl adipic acid, and triacetylglycerin.

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

<(J) Thermal radical generator>

The photosensitive resin composition of the present invention may include (J) a thermal radical generator, and when it contains an ethylenically unsaturated compound such as a compound having at least one ethylenically unsaturated double bond described above, (J) thermal radical generation It is preferred to contain the agent. As the thermal radical generator in the present invention, a known thermal radical generator can be used.

Thermal radical generators are compounds that generate radicals by thermal energy and initiate or accelerate the polymerization reaction of the polymerizable compound. By adding a thermal radical generator, the obtained cured film may be more robust, and heat resistance and solvent resistance may be improved.

Preferred 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, carbon halogen bonds And compounds having, azo-based compounds, and non-benzyl compounds. (J) The thermal radical generator may be used alone or in combination of two or more.

The addition amount of the thermal radical generator (J) in the photosensitive resin composition of the present invention is preferably from 0.01 to 50 parts by weight, and more preferably from 0.1 to 20 parts by weight, when the polymer (A) is 100 parts by weight from the viewpoint of improving film properties. And most preferably 0.5 to 10 parts by weight.

<(K) antioxidant>

The photosensitive resin composition of this invention may contain (K) antioxidant. (K) As an antioxidant, a well-known antioxidant can be contained. (K) By adding an antioxidant, coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and there is an advantage of excellent heat resistance and transparency.

Examples of such antioxidants include phosphorus-based antioxidants, hydrazides, hindered amine-based antioxidants, sulfur-based antioxidants, phenol-based antioxidants, ascorbic acid, zinc sulfate, sugars, nitrites, sulfites, thiosulfate, hydroxyl And amine derivatives. Among these, a phenolic antioxidant is particularly preferred from the viewpoint of coloring the cured film and reducing film thickness. These may be used alone or in combination of two or more.

Commercial products of phenolic antioxidants include, for example, Adekastab AO-60, Adekastab AO-80 (above, manufactured by ADEKA Corporation), and Irganox 1098 (manufactured by Chiba Japan Corporation). .

The content of the (K) antioxidant is preferably 0.1 to 6% by mass, more preferably 0.2 to 5% by mass, and particularly preferably 0.5 to 4% by mass, based on the total solid content of the photosensitive resin composition. By setting it as this range, sufficient transparency of the formed film is obtained and also the sensitivity at the time of pattern formation is favorable.

Further, as the additives other than the antioxidant, various ultraviolet absorbers, metal deactivators, and the like described in "Advanced Polymer Additives (Nigan Kogyo Newspaper Co., Ltd.)" may be added to the photosensitive resin composition of the present invention.

<(L) crosslinking system>

It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent (L) as needed. As the crosslinking agent (L), for example, a compound having two or more epoxy groups or oxetanyl groups, a alkoxymethyl group-containing crosslinking agent, and a compound having at least one ethylenically unsaturated double bond can be added to the molecule described below. A cured film can be made into a more robust film by adding a crosslinking agent (L). The following can be added as a crosslinking agent.

<A compound having two or more epoxy groups in a molecule>

Specific examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and aliphatic epoxy resin.

These can be obtained as a commercial item. For example, as the bisphenol A type epoxy resin, JER827, JER828, JER834, JER1001, JER1002, JER1003, JER1055, JER1007, JER1009, JER1010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 , DIC Corporation), etc., as bisphenol F-type epoxy resins JER806, JER807, JER4004, JER4005, JER4007, JER4010 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON830, EPICLON835 (above, manufactured by DIC Corporation) ), LCE-21, RE-602S (above, manufactured by Nippon Kayaku Co., Ltd.) are phenol novolac-type epoxy resins such as JER152, JER154, JER157S65, JER157S70 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, and EPICLON N-775 (above, manufactured by DIC Corporation) are examples of cresol novolac-type epoxy resins such as EPICLON N-660, EPICLON N-665, EPICLON N- 670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 (above, manufactured by Nippon Kayaku Co., Ltd.), aliphatic epoxy As resin, ADEKA RESIN EP-4080S, EP-4085S, Copper EP-4088S (above, manufactured by ADEKA Corporation), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE3150, EPOLEAD PB 3600, Copper PB 4700 (above, Daicel Kagaku High School Co., Ltd.) etc. are mentioned. In addition, ADEKA RESIN EP-4000S, copper EP-4003S, copper EP-4010S, copper EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN And -501, EPPN-502 (above, manufactured by Adeka Corporation). These may be used alone or in combination of two or more.

Among them, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, aliphatic epoxy resins, phenol novolac-type epoxy resins, and cresol novolac-type epoxy resins are preferred. In particular, bisphenol A type epoxy resin, phenol novolak type epoxy resin, and aliphatic epoxy resin are preferred.

<A compound having two or more oxetanyl groups in the molecule>

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

The addition amount of the compound having an epoxy group or an oxetanyl group to the photosensitive resin composition is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight when the total amount of the resin component is 100 parts by weight.

<Alkoxymethyl group-containing crosslinking agent>

As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea are preferable. These are each obtained by converting the methylol group of methirolated melamine, methirolated benzoguanamine, metilylated glycoluril, or methirolated urea to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxy methyl group, a propoxymethyl group, and a butoxymethyl group. desirable. Among these crosslinkable compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are mentioned as preferred crosslinkable compounds, and alkoxymethylated glycoluril is particularly preferred from the viewpoint of transparency.

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

When the alkoxymethyl group-containing crosslinking agent is used in the photosensitive resin composition of the present invention, the addition amount of the alkoxymethyl group-containing crosslinking agent is preferably 0.05 to 50 parts by weight, more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the resin component. By adding in this range, preferable alkali solubility at the time of development and excellent solvent resistance of the film after curing are obtained.

<A compound having at least one ethylenically unsaturated double bond>

As the compound having at least one ethylenically unsaturated double bond, a (meth) acrylate compound such as a monofunctional (meth) acrylate, bifunctional (meth) acrylate, or trifunctional or higher (meth) acrylate can be preferably used. .

As monofunctional (meth) acrylate, for example, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboronil (meth) acrylate, 3-methoxybutyl (meth) acrylic Rate, 2- (meth) acryloyloxyethyl-2-hydroxypropylphthalate, and the like.

As the bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, polypropylene glycoldi (Meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene diacrylate, and the like.

As trifunctional or higher (meth) acrylates, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (metha) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

Among these, compounds having at least one ethylenically unsaturated double bond are used singly or in combination of two or more.

The use ratio of the compound having at least one ethylenically unsaturated double bond in the photosensitive resin composition of the present invention is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the resin component. By containing a compound having at least one ethylenically unsaturated double bond in such a ratio, the heat resistance and surface hardness of the insulating film obtained from the photosensitive resin composition of the present invention can be improved. When adding a compound having at least one ethylenically unsaturated double bond, it is preferable to add (J) a thermal radical generator.

The positive photosensitive resin composition of the present invention contains at least the photoacid generator (B) in the range of 0.1% by mass to 10% by mass relative to the total solid content in terms of mass conversion, and further comprises 40% by mass of the resin (A). It is preferable to include in the range of 95% by mass. In addition, with respect to the total solid content, the resin (A) is included in the range of 40% by mass to 95% by mass, the photoacid generator (B) is included in the range of 0.1% by mass to 10% by mass, and the crosslinking agent (D) It is more preferable to contain 3 mass% to 40 mass%.

<Sensitizer>

It is preferable that the photosensitive resin composition of this invention contains a sensitizer in order to accelerate its decomposition in combination with the photoacid generator (B). The sensitizer absorbs actinic rays or radiation and becomes an electron excitation state. The sensitizer in the electronic excitation state comes into contact with the photoacid generator, and causes electron transfer, energy transfer, and heat generation. Thereby, the photoacid generator causes chemical changes and decomposes to produce an acid. Preferred sensitizers include compounds belonging to the following compounds and having absorption wavelengths in any one of the wavelength ranges of 350 nm to 450 nm.

Polynuclear aromatics (for example, 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, dimethylthioxanthone, diethylthioxane) Tone), cyanines (for example, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), rodacyanine, oxonol, thiazines (For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), acridones (for example, acridon, 10 -Butyl-2-chloroacridone), anthraquinones (for example, anthraquinone), squaliums (for example, squalium), styryls, base STRY Class (eg, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (eg, 7-diethylamino4-methylcoumarin, 7-hydroxy4) -Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-iｊ] quinolidine-11-non).

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

(How to form a cured film)

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

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

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

(2) Process of removing solvent from applied photosensitive resin composition

(3) Process of exposing with active light

(4) Process developed with aqueous developer

(5) Heat curing process (post baking process)

Each process is explained in order below.

In the step (1), the photosensitive resin composition of the present invention is applied (usually applied) to a substrate to obtain a wet film containing a solvent.

Addition of a step of irradiating the active light before the heating process can promote a crosslinking reaction by an acid generated by irradiation of the active light.

Next, a method of forming a cured film using the positive photosensitive resin composition of the present invention will be specifically described.

In the solvent removal step of (2), the solvent is removed from the applied film by depressurization (holding) and / or heating to form a dry film on the substrate.

In the step of exposing (3), active light having a wavelength of 300 nm or more and 450 nm or less is irradiated to the obtained coating film. In this process, (B) the photoacid generator decomposes to generate an acid. The acid-decomposable group contained in the component (A) is hydrolyzed by the catalytic action of the generated acid to generate a carboxyl group or a phenolic hydroxyl group. By irradiating the obtained film with actinic light, a photoacid generator decomposes to generate an acid. The acid-dissociable group in the structural unit represented by the general formula (A2 ') contained in the resin (A) is decomposed by a hydrolysis reaction to generate a carboxyl group by the catalytic action of the generated acid. Subsequently, by developing using an alkali developer, the exposed portion containing the resin having a carboxyl group that is easily soluble in the alkali developer is removed, and a positive image is formed.

The reaction formula of this hydrolysis reaction is shown below.

In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as "PEB") can be performed as necessary. The production of carboxyl groups or phenolic hydroxyl groups from acid-decomposable groups can be promoted by PEB.

The acid-decomposable group in the monomer unit represented by formula (1) in the present invention has low activation energy for acid decomposition, and is easily decomposed by acid derived from an acid generator by exposure to generate a carboxyl group or phenolic hydroxyl group. It is also possible to form a positive image by developing without performing PEB.

Moreover, it is also possible to promote the hydrolysis of the acid-decomposable group without causing a crosslinking reaction by performing PEB at a relatively low temperature. When PEB is performed, the temperature is preferably 30 ° C or higher and 130 ° C or lower, more preferably 40 ° C or higher and 110 ° C or lower, and particularly preferably 50 ° C or higher and 80 ° C or lower.

In the developing step (4), a copolymer having an advantageous carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing the region of the exposed portion containing the resin composition having a carboxyl group or a phenolic hydroxyl group that is easily soluble in an alkaline developer.

By heating the positive image obtained in the step of post-baking in (5), the acid decomposable group in the monomer unit (a1) is thermally decomposed to generate a carboxy group or a phenolic hydroxyl group to crosslink the crosslinking group in the monomer unit (a2) to form a cured film. have. The heating is preferably heated to a high temperature of 150 ° C or higher, more preferably 180 to 250 ° C, and particularly preferably 200 to 250 ° C. The heating time can be appropriately set depending on the heating temperature or the like, but is preferably within the range of 10 to 90 minutes.

Adding a step of irradiating the development pattern with active light, preferably ultraviolet light, before the post-baking process can promote a crosslinking reaction with an acid generated by active light irradiation.

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

<Preparation method of photosensitive resin composition>

Various components are mixed in a predetermined ratio and by any method, and the mixture is stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can also be prepared by preparing each component in a solution previously dissolved in a solvent, and then mixing them at a predetermined ratio. The composition solution prepared as described above may be provided for use after filtration using a filter having a pore diameter of 0.2 µm or the like.

<Application process and solvent removal process>

A desired dry coating film can be formed by applying a photosensitive resin composition to a predetermined substrate and removing the solvent by reducing pressure and / or heating (pre-baking). As the substrate, for example, in the manufacture of a liquid crystal display device, a polarizing plate, a black matrix layer and a color filter layer are provided as necessary, and a glass plate provided with a transparent conductive circuit layer can be exemplified. The method of application to the substrate is not particularly limited, and for example, methods such as a slit coating method, a spray method, a roll coating method, and a rotation coating method can be used. Especially, it is preferable from a viewpoint that a slit coating method is suitable for a large substrate. It is preferable to manufacture a large substrate due to high productivity. Here, a large substrate means a substrate having a size of 1 m or more on each side.

In addition, the heating condition of the (2) solvent removal step is a range in which the acid-decomposable group is decomposed in the monomer unit (a1) in the resin component in the unexposed portion so that the resin component is not soluble in the alkali developer. Although it differs depending on the mixing ratio, it is preferably about 30 to 120 seconds at 80 to 130 ° C.

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

In the exposure process, the active light is irradiated to the substrate on which the coating film is provided through a mask having a predetermined pattern. After the heat treatment (PEB) is performed as necessary after the exposure step, in the developing step, an exposed portion region is removed using an alkaline developer to form an image pattern.

For exposure by actinic light, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, such as g-ray (436nm), i-ray (365nm), h-ray (405nm), etc. Active light rays having a wavelength of 300 nm or more and 450 nm or less can be preferably used. In addition, if necessary, the irradiation light may be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter.

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

The pH of the developer 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 puddle method and a dip method. After development, water washing can be performed for 30 to 90 seconds to form a desired pattern.

<Post baking process (crosslinking process)>

For a pattern corresponding to the unexposed area obtained by development, a heating device such as a hot plate or oven is used, and at a predetermined temperature, for example, 180 to 250 ° C, for a predetermined time, for example, 5 to 5 on a hot plate phase. A protective film or interlayer insulating film having excellent heat resistance, hardness, etc., by decomposing an acid decomposable group in a resin component by heating treatment for 30 minutes to 90 minutes in an oven, generating a carboxy group or a phenolic hydroxyl group, and reacting with a crosslinking group to crosslink it. Can form. Moreover, when heat-processing, transparency can also be improved by performing under nitrogen atmosphere.

Further, prior to heat treatment, after re-exposure to the substrate on which the pattern has been formed by actinic rays, post-baking (reexposure / post-baking) generates an acid from the component (B) present in the unexposed portion and crosslinks. It is desirable to function as a catalyst to accelerate the process.

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

The preferred exposure amount of the reexposure process is 100 to 1,000 mJ / cm 2.

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

The organic EL display device or liquid crystal display device of the present invention is not particularly limited except for having a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices taking various structures And a liquid crystal display device.

Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, but can be used for various uses. For example, in addition to a planarization film or an interlayer insulating film, a protective film of a color filter, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device, a micro lens provided on a color filter in a solid-state imaging device, etc. are preferable. Can be used.

1 shows a conceptual view of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a flattening film 4 is provided.

A bottom gate TFT 1 is formed on the glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed in a state that covers the TFT 1. After forming a contact hole (not shown here) in the insulating film 3, a wiring 2 (height 1.0 µm) 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 and the organic EL element formed between the TFTs 1 or in a post process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarization layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is filled.

On the planarization film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarization film 4 by connecting it to the wiring 2 through the contact hole 7. Note that the first electrode 5 corresponds to the anode of the organic EL element.

An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed, and by installing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in a subsequent process is prevented. can do.

In addition, although not shown in FIG. 1, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second electrode made of Al is formed on the entire surface of the substrate, An active matrix type organic EL display device is obtained, which is sealed by adhering to each other using a sealing glass plate and an ultraviolet curable epoxy resin, and the TFT 1 for driving it is connected to each organic EL element.

2 is a conceptual cross-sectional view showing an example of the active matrix type liquid crystal display 10. This color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on its rear surface, and the liquid crystal panel is a TFT (corresponding to all pixels disposed between two glass substrates 14 and 15 with a polarizing film attached thereon). The elements of 16) are arranged. Each device formed on the glass substrate is wired with an ITO transparent electrode 19 forming a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a layer of the liquid crystal 20 and a black matrix are arranged is provided.

Examples of the TFT (Thin-Film Transistor) included in the organic EL display device and the liquid crystal display device of the present invention include amorphous silicon-TFT, silicon low-temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention has excellent electrical properties, it can be suitably used in combination with these TFTs.

In addition, as a method of the liquid crystal display device of the present invention, TN (TwistedNematic) method, VA (Virtical Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB And the (Optical Compensated Bend) method.

Moreover, a rubbing alignment method, a photo-alignment method, etc. are mentioned as a specific alignment method of the liquid crystal aligning film which the liquid crystal display device of this invention can take. Further, the polymer orientation may be supported by PSA (Polymer Sustained Alignment) technology described in Japanese Patent Laid-Open No. 2003-149647 or Japanese Patent Laid-Open No. 2011-257734.

Example

The present invention will be described in more detail with reference to Examples below. Materials, amounts, proportions, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Note that "parts" and "%" are based on mass unless otherwise specified.

In the following synthesis examples, the following symbols denote the following compounds, respectively.

V-65: 2,2'-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Junyaku High School)

V-601: dimethyl-2,2'-azobis (2-methylpropionate) (manufactured by Wako Junyaku High School)

MAEVE: 1-ethoxyethyl methacrylate

MATHF: Methacrylic acid tetrahydro-2H-furan-2-yl

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

NBMA: n-butoxymethylacrylamide (NBMA, manufactured by Tokyo Kasei)

GMA: glycidyl methacrylate

St: Styrene

MMA: methyl methacrylate

MAA: Methacrylic acid

EDM: Diethylene glycol ethyl methyl ether (manufactured by Toho Kagaku High School, Highsolve EDM)

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

DCPM: Methacrylic acid (tricyclo [5.2.1.02,6] decane-8-yl)

(a3-1) to (a3-3), (a3-5) to (a3-7), (a3-9), (a3-10), (a3-14), (a3-16) the following compounds

<Synthesis of Polymer C-2>

Diethylene glycol ethyl methyl ether (manufactured by Toho Kagaku Kogyo Co., Highsolve EDM, 36 g) was added to the three-neck flask as a solvent, and the temperature was elevated to 70 ° C under a nitrogen atmosphere. Glycidyl methacrylate 34.7g (244mmmol), methyl methacrylate 1.63g (16.3mmol), light acrylate HO-a-HH (Kyoeisha, 7.04g, 26.06mmmol), styrene 4.07g (39.08mmol) ) Was heated to 70 ° C under a nitrogen stream. While stirring this mixed solution, a mixed solution of a radical polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 3.64 g) and diethylene glycol ethyl methyl ether (35.6 g) was added dropwise over 2.5 hours. After the dropping was completed, the mixture was reacted at 70 ° C for 5 hours to obtain a diethylene glycol ethyl methyl ether solution (solid content concentration: 40% by weight) of binder a-1. The weight average molecular weight of the obtained binder C-2 was 9,000.

<Synthesis of MATHF>

Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C, and camphor sulfonic acid (4.6 g, 0.02 mol) was added. 2-Dihydrofuran (71 g, 1 mol, 1.0 eq) was added dropwise to the solution. After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure at 40 ° C. or lower after filtering, and the residue was yellow. The oily product was distilled under reduced pressure to obtain 125 g of methacrylic acid tetrahydro-2H-furan-2-yl (MATHF) having a boiling point (bp.) Of 54 to 56 ° C / 3.5 mmHg as a colorless oily product (yield 80%).

<Synthesis of Polymer A-1>

Diethylene glycol ethyl methyl ether (manufactured by Toho Kagaku Kogyo Co., Highsolve EDM, 43 g) was added to the three-neck flask as a solvent, and the temperature was raised to 90 ° C under a nitrogen atmosphere. As a monomer component in the solution, methacrylic acid 1-ethoxyethyl (MAEVE, 20.61 g), n-butoxymethylacrylamide (NBMA, manufactured by Tokyo Kasei, 14.58 g), light acrylate HO-a-HH (Kyoe Ishaze, 19.81 g), Styrene (St, Wako Junyaku High School, 3.39 g), and dimethyl 2,2'-azobis (2-methylpropionate) (V-601, Wako Junyaku as polymerization initiator) High school agent, 6.00 g, 8 mol% with respect to monomer) and diethylene glycol ethyl methyl ether (Toho Kagaku Kogyo company, Hisolve EDM, 43 g) were dissolved and added dropwise over 2 hours. It stirred after completion | finish of dripping for 2 hours. V-601 (1.5 g, 2 mol% based on monomer) was also added to the solution, stirred for 2 hours, and the reaction was terminated. Thereby, binder A-1 was obtained. The weight average molecular weight was 16000.

The monomer types and the like were changed as shown in the table below, and polymers A-2 to 24, A'-1 to 5, and C-1 and C-3 to 5 were synthesized similarly.

(Adjustment of photosensitive resin composition)

[Example 1]

The components were dissolved and mixed so as to have a solid secretion shown in the table, filtered through a filter made of polytetrafluoroethylene having a diameter of 0.2 µm, and the photosensitive resin composition of Example 1 was obtained. In addition, as a solvent, a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol ethyl methyl ether / 1,3-butylene glycol diacetate = 60/37/3 (weight ratio) was used, and the viscosity was 5 mPa · s. Adjusted.

[Examples 2 to 36 and Comparative Examples 1 to 5]

Each compound used in Example 1 was adjusted in the same manner as in Example 1 except that the compounds described in Tables 4 to 7 were changed.

The details of the symbol used for each compound used in Examples and Comparative Examples are as follows.

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

B-1

B-2: PAI-101 (manufactured by Chiba Specialty Chemicals)

B-3: Structure shown below (synthesis examples will be described later)

B-4: Structure shown below (synthesis example will be described later)

<Synthesis of B-3>

The compound represented by B-3 (α- (methylsulfonyloxyimino) -2-phenylacetonitrile) was synthesized as follows.

[Synthesis of α- (hydroxyimino) -2-phenylacetonitrile]

5.85 g of phenyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with tetrahydrofuran: 50 ml (manufactured by Wako Pure Chemical Industries, Ltd.) and applied to an ice bath to cool the reaction solution to 5 ° C or lower. Subsequently, 11.6 g of SM-28 (sodium methoxide 28% methanol solution, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was stirred and reacted under an ice bath for 30 minutes. Subsequently, 7.03 g of isopentyl nitrite (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining an internal temperature of 20 ° C or lower, and the reaction solution was allowed to react for 1 hour at room temperature after completion of the dropwise addition. The obtained reaction solution was poured into 150 ml of water in which 1 g of sodium hydroxide was dissolved, completely dissolved, and then 100 ml of ethyl acetate was added and separated to obtain about 180 ml of an aqueous layer having the target product. Further, 100 ml of ethyl acetate was added again, the aqueous layer was made acidic with a pH of 3 or less with concentrated hydrochloric acid, and the product was extracted and concentrated. When the obtained crude crystal was washed with hexane, 4.6 g of α- (hydroxyimino) -2-phenylacetonitrile was obtained in a yield of 63%.

[Synthesis of α- (methylsulfonyloxyimino) -2-phenylacetonitrile (Compound b-3)]

11.5 g of α- (hydroxyimino) -2-phenylacetonitrile was dissolved in 100 mL of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and applied to an ice bath to cool the reaction solution to 5 ° C or lower. Subsequently, 9.9 g of methanesulfonyl chloride (manufactured by Wako Junyakus) was added dropwise, and then, 9.55 g (manufactured by Wako Junyakus) of triethylamine was added dropwise while maintaining an internal temperature of 20 ° C. or lower, and the mixture was stirred and reacted under an ice bath for 1 hour.

The obtained reaction solution was added dropwise to 500 ml of water, and stirred at room temperature for 1 hour. When the obtained powdery precipitate was filtered and dried, 16 g of α- (methylsulfonyloxyimino) -2-phenylacetonitrile (compound b-5) was obtained in a yield of 90%. The H-NMR spectrum of this compound indicates that the product is a mixture of oxime structure isomers (syn / anti), and the abundance ratio is syn: anti = 25/75.

<Synthesis of B-4>

Α- (p-toluenesulfonyloxyimino) phenylacetonitrile (Compound b-4) was synthesized according to the method described in paragraph No. [0108] of Japanese Patent Publication No. 2002-528451.

B-5: Structure shown below (synthesis examples will be described later)

B-6: Structure shown below (synthesis examples will be described later)

B-7: Structure shown below (synthesis examples will be described later)

B-8: Structure shown below (synthesis examples will be described later)

<Synthesis of B-5>

1-1. Synthesis of Synthetic Intermediate B-5A

2-Aminobenzenethiol: 31.3 g (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was dissolved in toluene: 100 ml (manufactured by Wako Junyaku Kogyo Co., Ltd.) under room temperature (25 ° C). Subsequently, phenylacetyl chloride: 40.6 g (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise to the resulting solution, and reacted by stirring at room temperature for 1 hour and then at 100 ° C for 2 hours. 500 ml of water was added to the obtained reaction solution to dissolve the precipitated salt, toluene oil was extracted, and the extract was concentrated with a rotary evaporator to obtain a synthetic intermediate B-5A.

Synthesis of 1-2.B-5

2.25 g of the synthetic intermediate B-5A obtained as described above was mixed with 10 ml of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and then applied to an ice bath to cool the reaction solution to 5 ° C or lower. Subsequently, tetramethylammonium hydroxide: 4.37g (25 mass% methanol solution, Alfa Acer company make) was dripped at the reaction liquid, and it reacted by stirring for 0.5 hour in an ice bath. Furthermore, isopentyl nitrite: 7.03 g was added dropwise while maintaining an internal temperature of 20 ° C or lower, and after completion of the dropwise addition, the reaction solution was heated to room temperature, and then stirred for 1 hour.

Subsequently, after the reaction solution was cooled to 5 ° C or lower, p-toluenesulfonyl chloride (1.9 g) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added and stirred for 1 hour while maintaining at 10 ° C or lower. Thereafter, 80 ml of water was added, and the mixture was stirred at 0 ° C for 1 hour. After filtering the obtained precipitate, 60 ml of isopropyl alcohol (IPA) was added, heated to 50 ° C., stirred for 1 hour, filtered and dried on heat to obtain 1.8 g of B-5 (structure described above).

The obtained B-5 has ¹ H-NMR spectrum (300 MHz, heavy DMSO ((D ₃ C) ₂ S = O)) δ = 8.2 to 8.17 (m, 1H), 8.03 to 8.00 (m, 1H), 7.95 to 7.9 (m, 2H), 7.6 to 7.45 (m, 9H), 2.45 (s, 3H).

It is estimated that B-5 obtained from the results of the above ¹ H-NMR measurement is a single type isomer.

<Synthesis of B-6>

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension solution of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. and reacted for 2 hours. . Under ice-cooling, 4 NHCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added to separate the solution. Potassium carbonate (19.2 g) was added to the organic layer, and after reacting at 40 ° C. for 1 hour, a 2 NHCl aqueous solution (60 mL) was added to separate the solution, and the organic layer was concentrated, and the crystals were recovered with diisopropyl ether (10 mL). The slurry was filtered, and dried to obtain a ketone compound (6.5 g).

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

The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the mixture was heated to room temperature and reacted for 1 hour. . Water (50 ml) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 ml), filtered and dried to obtain 2.3 g of B-6 (structure described above).

In addition, ¹ H-NMR spectrum of B-6 (300MHz, CDCl ₃ ) is δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 ( dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H), 2.4 (s, 3H), 1.7 (d, 3H).

<Synthesis of B-7>

2-naphthol (20 g) was dissolved in N, N-dimethylacetamide (150 ml), potassium carbonate (28.7 g) and 2-bromooctanoate ethyl (52.2 g) were added and reacted at 100 ° C for 2 hours. Water (300 ml) and ethyl acetate (200 ml) were added to the reaction mixture, and the organic layer was concentrated, followed by addition of 48% by mass aqueous sodium hydroxide solution (23 g), ethanol (50 ml), and water (50 ml). , And reacted for 2 hours. The reaction solution was poured into a 1N HCl aqueous solution (500 mL), and the precipitated crystals were filtered and washed to obtain a carboxylic acid composition, and 30 g of polyphosphoric acid was added to react at 170 ° C for 30 minutes. The reaction solution was poured into water (300 mL), ethyl acetate (300 mL) was added and separated, and the organic layer was concentrated and purified by silica gel column chromatography to obtain a ketone compound (10 g).

Sodium acetate (30.6 g), hydroxylamine hydrochloride (25.9 g), and magnesium sulfate (4.5 g) were added to the suspension solution of the obtained ketone compound (10.0 g) and methanol (100 mL), followed by heating to reflux for 24 hours. After cooling, water (150 mL) and ethyl acetate (150 mL) were added for separation, and the organic layer was partitioned four times with 80 mL of water, concentrated and purified by silica gel column chromatography to obtain an oxime compound (5.8 g).

The obtained oxime (3.1 g) was sulfonated similarly to B-6, and 3.2 g of B-7 (structure described above) was obtained.

In addition, ¹ H-NMR spectrum of _{B-7 (300MHz, CDCl 3} ) is δ = 8.3 (d, 1H) , 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 ( dd, 1H), 7.5 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (dd, 1H), 2.4 (s, 3H), 2.2 (ddt, 1H), 1.9 (ddt, 1H), 1.4 to 1.2 (m, 8H), and 0.8 (t, 3H).

<Synthesis of B-8>

B-8 (structure described above) was synthesized in the same manner as B-6 except that benzenesulonyl chloride was used in place of p-toluenesulfonyl chloride in B-6.

In addition, the ^1-8 H-NMR spectrum of B-8 (300MHz, CDCl ₃ ) is δ = 8.3 (d, 1H), 8.1 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.7- 7.5 (m, 4H), 7.4 (dd, 1H), 7.1 (d.1H), 5.6 (q, 1H), 1.7 (d, 3H).

B-9: TPS-1000 (Midori Kagaku Corporation)

NQD: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide- Condensate of 5-sulfonic acid chloride (2.0 mol)

E-1: DBA (9,10-dibutoxyanthracene, Kawasaki Kasei high school)

E-2: NBCA (Kurogane Kasei Co., Ltd.)

F-1: JER157S65 (brand name, phenol novolac type epoxy resin, made by Japan Epoxy Resin Co., Ltd.)

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

F-3: EX-111 (manufactured by Nagase Chemtex)

F-4: EX-212L (manufactured by Nagase Chemtex)

F-5: Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.)

G-1: KBM-403 (brand name, 3-glycidoxypropyl trimethoxysilane, structure shown below, Shin-Etsu Chemical Co., Ltd. product)

G-2: KBE-403 (trade name, 3-glycidoxypropyl triethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-3: KBE-1003 (brand name, vinyl triethoxysilane, Shin-Etsu Chemical Co., Ltd. product)

G-4: KBM-502 (trade name, 3-methacryloxypropyl dimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-5: KBM-5103 (brand name, 3-acryloxypropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-6: KBM-803 (trade name, 3-mercaptopropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

G-7: KBM-903 (trade name, 3-aminopropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

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

H-2: Triphenylimidazole

H-3: The following structure

I-1: Nonionic surfactant containing perfluoroalkyl group represented by the following structural formula

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

Each evaluation shown below was performed about the photosensitive resin composition of the Example obtained by the above and the comparative example.

<Evaluation of sensitivity>

After slit-coating each photosensitive resin composition on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)), pre-baking on a hot plate at 95 ° C / 140 seconds to volatilize the solvent, the photosensitive resin composition layer having a thickness of 4.0 µm Formed.

Subsequently, the obtained photosensitive resin composition layer was exposed using a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Co., Ltd. through a predetermined mask. Then, the photosensitive composition layer after exposure was developed with an alkali developer (0.4% by weight of tetramethylammonium hydroxide aqueous solution) for 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.

The optimum i-line exposure amount (Eopt) when resolving a 9 µm line and space 1: 1 by these operations was defined as sensitivity. In addition, evaluation criteria are as follows. 3 to 5 are practically no problem levels.

Less than 5: 40mJ / ㎠

4: 40mJ / ㎠ to 60mJ / ㎠

3:60 mJ / cm2 or more and less than 80 mJ / cm2

2: 80 mJ / cm 2 or more and less than 150 mJ / cm 2

1: 150mJ / ㎠ or more

<Evaluation of residual rate>

By measuring the film thickness of the unexposed portion after development, and obtaining the ratio to the film thickness after application (film thickness after undeveloped portion ÷ film thickness after application x 100 (%)), the residual film rate during development was evaluated based on the following criteria. .

5: 98% or more

4: 95% or more but less than 98%

3: 90% or more but less than 95%

2: 80% or more and less than 90%

Less than 1: 80%

<Evaluation of relative dielectric constant>

After slit-coating a photosensitive resin composition solution on a bare wafer (N-type low resistance) (manufactured by SUMCO), it was prebaked on a hot plate at 90 degrees for 2 minutes to form a photosensitive resin composition layer having a thickness of 3.0 µm. The obtained photosensitive resin composition was exposed with a PLA-501F exposure machine (ultra high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the accumulated irradiation amount was 300 mJ / cm 2 (roughness: 20 mW / cm 2), and the substrate was heated in an oven at 220 ° C. for 1 hour. A cured film was obtained.

CVmap92A (manufactured by Four Dimensions Inc.) was used for this cured film, and the relative dielectric constant was measured at a measurement frequency of 1 MHz and evaluated according to the following criteria. When this value is small, it can be said that the relative dielectric constant of the cured film is good.

Less than 5: 3.5

4: 3.5 or more and less than 3.7

3: 3.7 or more and less than 3.9

2: 3.9 or more and less than 4.2

1: 4.2 or higher

As shown in the table, since the photosensitive resin composition of the example contains a repeating unit (a3), the photosensitive resin composition layer becomes flexible. For this reason, it became easy to dissolve in the developer, showing excellent sensitivity, excellent residual film ratio, and excellent relative dielectric constant regardless of any of the substrate and the exposure machine, and the shape of the formed pattern was also excellent. On the other hand, it can be seen that the comparative example not including the repeating unit (a3) had a lower sensitivity, residual film property, and relative dielectric constant than the example.

[Example 100]

In Example 100, the photosensitive resin composition of Example 24 was used, and the substrate was changed to a 6 inch silicon wafer from a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) to the photosensitive resin composition of Example 1 As in the case of evaluation of sensitivity, residual film properties, and relative dielectric constant, all of the evaluations were 5.

[Example 101]

For the same solid component as in Example 100, a mixed solvent of propylene glycol monomethyl ether acetate / diethylene glycol ethyl methyl ether / 1,3-butylene glycol diacetate = 60/37/3 (weight ratio) was used, and the viscosity was It adjusted to 35 mPa * s, and evaluated similarly to Example 100 except having made all the coatings into spin coat. As in the case of the photosensitive resin composition of Example 1, evaluation of sensitivity, residual film property, and relative dielectric constant was all evaluated.

[Example 102]

To the photosensitive resin composition of Example 1 except that the photosensitive resin composition of Example 100 was used and the exposure machine was changed from a PLA-501F exposure machine made by Canon Co., Ltd. to a FX-803M (gh-Line stepper) manufactured by Nikon Co., Ltd. As for the evaluation, all of the evaluations were conducted as a result of evaluating the sensitivity, residual film properties, and relative dielectric constant.

[Example 103]

Sensitivity was similar to that performed for the photosensitive resin composition of Example 1 except that the photosensitive resin composition of Example 100 was used and the exposure machine was changed from a PLA-501F exposure machine made by Canon Co., Ltd. to a 355 nm laser exposure machine to perform 355 nm laser exposure. Evaluated.

In addition, as a 355 nm laser exposure machine, "AEGIS" manufactured by V Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec). In addition, as in the case of the photosensitive resin composition of Example 1, evaluation of the residual film property and the relative dielectric constant was all evaluated.

[Example 104]

The sensitivity was evaluated in the same manner as for the photosensitive resin composition of Example 1 except that the photosensitive resin composition of Example 100 was used and the exposure machine was changed from a PLA-501F exposure machine made by Canon Corporation to a UV-LED light source exposure machine. The evaluation was 5. In addition, as in the case of the photosensitive resin composition of Example 1, evaluation of the residual film property and the relative dielectric constant was all evaluated.

[Example 200]

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

A bottom gate type TFT 1 was formed on the glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed in a state covering the TFT 1. Subsequently, after forming a contact hole not shown here in this insulating film 3, a wiring 2 (height 1.0 µm) connected to the TFT 1 through this contact hole is formed on the insulating film 3 did. This wiring 2 is for connecting the TFT 1 and the organic EL element formed between the TFTs 1 or in a post process.

Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarization film 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is filled. Formation of the planarization film 4 on the insulating film 3 is performed by spin-coating the photosensitive resin composition of Example 16 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure mercury from the mask. After irradiating 45 mJ / cm <2> (irradiance 20 mW / cm <2>) of i-line (365 nm) using, it developed with an aqueous alkali solution, formed a pattern, and heat-processed at 230 degreeC for 60 minutes.

The coatability at the time of applying the photosensitive resin composition was good, and no occurrence of wrinkles or cracks was observed in the cured film obtained after exposure, development and firing. Moreover, the average level difference of the wiring 2 was 500 nm, and the thickness of the produced flattening film 4 was 2,000 nm.

Subsequently, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, the first electrode 5 made of ITO was formed on the planarization film 4 by connecting to the wiring 2 through the contact hole 7. Thereafter, the resist was applied, prebaked, exposed through a mask of a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was peeled at 50 ° C using a resist stripper (remover 100, manufactured by AZ Electronics Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.

Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The photosensitive resin composition of Example 100 was used for the insulating film 8, and the insulating film 8 was formed in the same manner as above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in a subsequent process.

Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding to each other using a sealing glass plate and an ultraviolet curing epoxy resin.

As described above, an active matrix organic EL display device obtained by connecting TFTs 1 for driving this to each organic EL element is obtained. As a result of applying the voltage through the driving circuit, it was found that the organic EL display device exhibited good display characteristics and was highly reliable.

[Example 201]

In the active matrix type liquid crystal display device described in Fig. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, thereby obtaining a liquid crystal display device of Example 201.

That is, the photosensitive resin composition of Example 100 was used, and the cured film 17 was formed as an interlayer insulating film in the same manner as the method of forming the flattening film 4 of the organic EL display device in Example 200 above.

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

1: TFT (Thin Film Transistor) 2: Wiring
3: insulating film 4: flattened film
5: first electrode 6: glass substrate
7: Contact hole 8: Insulation film
10: liquid crystal display device 12: backlight unit
14, 15: Glass substrate 16: TFT
17: hard film 18: contact hole
19: ITO transparent electrode 20: liquid crystal
22: Color filter

Claims (18)

(A) (a1) a repeating unit having an acid group protected by an acid-decomposable group, (a2) an oxiranyl group, an oxetanyl group, or -NH-CH ₂ -OR (R is an alkyl group having 1 to 20 carbon atoms) A polymer component comprising a repeating unit having a crosslinkable group selected, and (a3) a repeating unit having a carboxyl group at the side chain end and having 6 to 20 or less atoms in the divalent linking group connecting the polymer main chain and the carboxyl group in the same or different polymer ,
(B) a photoacid generator, and
(D) contains a solvent,
The divalent linking group is -CR ¹ _2- (R ¹ represents a hydrogen atom or a methyl group), -O-, -O-SO _2- , -OC (O)-, -C (O) -O-,- A photosensitive resin composition characterized by S-, -C (O)-, an amino group which may have a substituent, a phenylene group which may have a substituent, and a group selected from structures of (iv) below and optionally combined.

[In formula (iv), z represents the integer of 0-5] According to claim 1,
The (A) polymer component is a photosensitive resin composition, characterized in that it has a polymer comprising the repeating unit (a2) and the repeating unit (a3). The method of claim 1 or 2,
The polymer component (A) has a polymer comprising the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3). The method of claim 1 or 2,
A photosensitive resin composition characterized by being a chemically amplified positive type photosensitive resin composition. The method of claim 1 or 2,
The repeating unit (a3) is a photosensitive resin composition comprising at least one repeating unit represented by formulas (i) to (iii).

[In the general formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. , n represents the integer of 0-4] The method of claim 1 or 2,
The repeating unit (a1) is a photosensitive resin composition, characterized in that the repeating unit represented by the general formula (A2 ').

[In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group] The method of claim 1 or 2,
The repeating unit (a2) is a photosensitive resin composition, characterized in that the repeating unit represented by the general formula (2).

[In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms] The method of claim 1 or 2,
The repeating unit (a2) is a photosensitive resin composition characterized in that it is a repeating unit having an oxiranyl group and / or an oxetanyl group. The method of claim 1 or 2,
The repeating unit (a1) is a repeating unit represented by the general formula (A2 '), the repeating unit (a2) is a repeating unit represented by the general formula (2), and the repeating unit (a3) is the general formula (i )-(Iii), a photosensitive resin composition comprising at least one repeating unit.

[In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group]

[In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms]

[In the general formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. , n represents the integer of 0-4] The method of claim 1 or 2,
The repeating unit (a1) is a repeating unit represented by the general formula (A2 '), the repeating unit (a2) is a repeating unit having an oxiranyl group and / or oxetanyl group, and the repeating unit (a3) is a general unit A photosensitive resin composition comprising at least one repeating unit represented by formulas (i) to (iii).

[In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group]

[In the general formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. , n represents the integer of 0-4] The method of claim 1 or 2,
The polymer component (A) has a polymer comprising the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3), and the repeating unit (a1) is represented by the general formula (A2 '). Paper is a repeating unit, and the repeating unit (a2) is a repeating unit represented by general formula (2), and the repeating unit (a3) includes one or more repeating units represented by general formulas (i) to (iii). Photosensitive resin composition, characterized in that.

[In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group]

[In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms]

[In the general formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. , n represents the integer of 0-4] The method of claim 1 or 2,
The polymer component (A) has a polymer comprising the repeating unit (a1), the repeating unit (a2), and the repeating unit (a3), and the repeating unit (a1) is represented by the general formula (A2 '). Paper is a repeating unit, and the repeating unit (a2) is a repeating unit having an oxiranyl group and / or an oxetanyl group, and the repeating unit (a3) is a repeating unit represented by general formulas (i) to (iii) 1 A photosensitive resin composition comprising at least a species.

[In the general formula (A2 '), R ¹ and R ² each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, R ¹ or R ² and R ³ may be connected to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group]

[In the general formulas (i) to (iii), R ¹ represents a hydrogen atom or a methyl group, L represents a divalent linking group having 4 or more atoms, and R ² represents a halogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms. , n represents the integer of 0-4] (1) The step of applying the photosensitive resin composition according to item 1 or 2 on a substrate,
(2) process of removing the solvent from the applied photosensitive resin composition,
(3) Process of exposing with active radiation,
(4) Process for developing with an aqueous developer, and
(5) A method for producing a cured film comprising a post-baking step of thermosetting. The method of claim 13,
After the developing step and before the post-baking step, a method of manufacturing a cured film comprising the step of exposing the entire surface. A cured film comprising curing the photosensitive resin composition according to claim 1 or 2. The method of claim 15,
A cured film, which is an interlayer insulating film. A liquid crystal display device comprising the cured film according to claim 15. An organic EL display device comprising the cured film according to claim 15.

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