KR20200067261A - Polymerizable Composition, Method for Producing Cured Film, and Cured Film - Google Patents

Abstract

The present invention relates to a photosensitive polymerizable composition, which can inhibit generation of a development residue in a non-patterned portion during the formation of a functional film patterned by a photolithographic process, even though the composition includes at least one filler (D) selected from the group consisting of an inorganic filler (D1) containing a specific element and a basic filler (D2), and a polymerizable group-containing ingredient, a method for producing a cured film by using the polymerizable composition, a cured film obtained by curing the polymerizable composition, a transparent dielectric obtained by curing the polymerizable composition containing the inorganic filler (D1), and a display device provided with the transparent dielectric. The photosensitive polymerizable composition, including at least one filler (D) selected from the group consisting of an inorganic filler (D1) containing a specific element and a basic filler (D2), and a polymerizable group-containing ingredient, further includes a specific silicon-containing resin (A).

Description

Polymerizable composition, method for producing cured film and cured film {Polymerizable Composition, Method for Producing Cured Film, and Cured Film}

The present invention relates to a method for producing a polymerizable composition and a cured film using the polymerizable composition, a display device comprising a cured film formed by curing the polymerizable composition, a transparent insulating film, and a transparent insulating film.

Various additives have been conventionally used to form a functional film. As additives for imparting a function to the membrane, for example, flame retardants such as magnesium hydroxide or aluminum hydroxide, conductive polymers such as polypyrrole, polyaniline and polyanilenvinylene are known (see Patent Documents 1 and 2). .).

In addition, in order to form a transparent insulating film having a high dielectric constant and excellent transparency, an inorganic filler containing elements such as La, Ce, Nd, Gd, Ho, Lu, Hf and Ta is formed in the film-forming material (negative photosensitive composition). Blending is also known.

Japanese Patent Publication No. 2006-43974 Japanese Patent Publication No. 2010-257981 Japanese Patent Publication No. 2016-75853

However, the basic filler or basic polymer described in Patent Documents 1 and 2 is blended into a photosensitive polymerizable composition containing a polymerization initiator and a polymerizable group-containing component, or an inorganic filler containing a specific type of element described in Patent Document 3 is blended. When forming a functional film patterned according to a photolithography method using the polymerizable composition, there is a problem that development residues tend to occur in the non-patterned portion (unexposed portion) after development.

The present invention in view of the above problems, even if it contains one or more fillers (D) and polymerizable group-containing components selected from the group consisting of inorganic fillers (D1) and basic fillers (D2) containing specific elements, the photo A photosensitive polymerizable composition capable of suppressing the occurrence of developing residues in a non-patterned portion (unexposed portion) when forming a functional film patterned according to a lithography method, a method for producing a cured film using the polymerizable composition, and polymerization It is an object of the present invention to provide a cured film formed by curing the composition, a transparent insulating film formed by curing the polymerizable composition containing the above-described inorganic filler (D1), and a display device comprising the transparent insulating film.

The present inventors have a photosensitive polymerizable composition comprising a polymerizable group-containing component and at least one filler (D) selected from the group consisting of an inorganic filler (D1) and a basic filler (D2) containing a specific element, specific silicon It has been found that the above problems can be solved by incorporating the containing resin (A), and the present invention has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention

A polymerizable composition comprising a polymerizable group-containing component,

The polymerizable composition

Silicon-containing resin (A),

A polymerization initiator (C),

Contains filler (D),

The silicon-containing resin (A) is selected from the group consisting of silsesquioxane resin (A1), polysilane-polysiloxane resin (AI), resin mixture (A-II), and polysilane structure-containing resin (A-III). Contains at least one,

The silsesquioxane resin (A1) is represented by the following formula (a1a):

[Tue 1]

(In formula (a1a), R ^a1 is the following formula (a1a-I):

-X ^a -B ^a -Y ^a -COOH… (a1a-I)

Is a group represented by

X ^a is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a group represented by -R ^a6 -NH-R ^a7 -,

R ^a6 and R ^a7 are each independently an alkylene group having 1 to 3 carbon atoms,

Y ^a is a divalent cyclic organic group or a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms,

B ^a is -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH- or -NH-CO-NH-,

X ^a and Y ^a may each independently be substituted with one or more groups selected from the group consisting of (meth)acryloyloxy groups, vinyl groups, and epoxy group-containing organic groups.)

Silsesquioxane resin having a structural unit represented by,

The polysilane-polysiloxane resin (A-I) is a polysilane-polysiloxane resin having a polysilane structure (I-1) and a polysiloxane structure (I-2),

The resin mixture (A-II) is a mixture of a resin having a polysilane structure (II-1) and a resin having a polysiloxane structure (II-2),

The polysilane structure-containing resin (A-III) is a resin having the polysilane structure (II-1),

The polymerizable group-containing components are (1) to (5) below:

(1) the expression a structural unit represented by (a1a), the formula (a1a-I) of X ^a and Y ^a of at least one (meth) acryloyloxy group of acrylic, vinyl, and epoxy-consisting of a organic in Silsesquioxane resin (A1-1) substituted with one or more groups selected from the group,

(2) The structural unit represented by the formula (a1a) and the following formula (a2a):

[Tue 2]

(In formula (a2a), R ^a2 is the following formula (a1a-II):

-Z ^a -A ^a … (a1a-Ⅱ)

Is a group represented by

Z ^a is a single bond, an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 12 carbon atoms,

A ^a is an (meth)acryloyloxy group, a vinyl group or an organic group containing an epoxy group.)

Silsesquioxane resin (A1-2) having a structural unit represented by,

(3) Silsesquioxane resin (A2) which has a structural unit represented by the formula (a2a) and does not correspond to the silsesquioxane resin (A1),

(4) a polyfunctional polymerizable monomer (B), and

(5) It has at least one group selected from the group consisting of (meth)acryloyloxy group, vinyl group and epoxy group-containing organic group, and further includes the silsesquioxane resin (A1), the silsesquioxane resin (A2) or the A polymerizable group-containing resin (B2) which does not correspond to any of the polyfunctional polymerizable monomer (B1);

At least one of the

The filler (D) includes at least one selected from the group consisting of an inorganic filler (D1) and a basic filler (D2),

The inorganic filler (D1) is a group of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf and Ta, an oxide of the aforementioned element, a chelate compound of the aforementioned element, and the aforementioned One or more selected from the group consisting of an elemental salt and an alloy of the aforementioned elements,

The basic filler (D2) is at least one polymerizable composition selected from a basic filler and a basic polymer.

The second aspect of the present invention

Forming a coating film on the substrate using the polymerizable composition according to the first aspect,

Position-selective exposure of the coating film,

Developing the exposed coating film,

It is a manufacturing method of the cured film containing.

The third aspect of the present invention is a cured film obtained by curing the polymerizable composition according to the first aspect.

The fourth aspect of the present invention is a transparent insulating film formed by curing the polymerizable composition according to the first aspect, which includes the inorganic filler (D1) as the filler (D).

The fifth aspect of the present invention is a display device including the transparent insulating film according to the fourth aspect.

Although the polymerizable composition of the present invention contains one or more fillers (D) selected from the group consisting of inorganic fillers (D1) and basic fillers (D2) containing specific elements, and polymerizable group-containing components, the photolithography method Accordingly, it is possible to suppress the occurrence of development residues in the non-patterned portion (unexposed portion) when forming the patterned functional film.

In addition, according to the present invention, a method for producing a cured film using the polymerizable composition, a cured film obtained by curing the polymerizable composition, a transparent insulating film obtained by curing the polymerizable composition containing the aforementioned inorganic filler (D1), and A display device including the transparent insulating layer can be provided.

≪Polymerizable composition≫

The polymerizable composition contains a polymerizable group-containing component. Moreover, a polymerizable composition contains silicon-containing resin (A), a polymerization initiator (C), and a filler (D).

The polymerizable composition contains a polymerizable group-containing component and a polymerization initiator (C). For this reason, the polymerizable composition has curability that is cured by exposure.

Further, the polymerizable composition contains a silicon-containing resin (A) that expresses alkali solubility as described later. Therefore, when the coating film made of the polymerizable composition is subjected to position-selective exposure, the unexposed portion that is not cured is soluble in an alkaline developer.

In addition, when a photosensitive composition containing a specific filler (D) described later is used, residues are likely to be generated in the unexposed portion during development when forming a functional film patterned according to a photolithography method.

However, when a polymerizable composition containing a combination of a silicon-containing resin (A) having a predetermined structure and a specific filler (D) is used, generation of residues in the unexposed portion during development is suppressed.

Hereinafter, essential or optional components in the polymerizable composition will be described.

<Silicone-containing resin (A)>

The polymerizable composition essentially contains the silicon-containing resin (A). Such silicon-containing resin (A) is from the group consisting of silsesquioxane resin (A1), polysilane-polysiloxane resin (AI), resin mixture (A-II), and polysilane structure-containing resin (A-III), described later. It contains at least one selected.

Silsesquioxane resin (A1)

Silsesquioxane resin (A1) is a silsesquioxane resin having a carboxyl group-containing group represented by formula (a1a-I). Silsesquioxane resin (A1) shows an action as an alkali-soluble resin in a polymerizable composition.

For this reason, the polymerizable composition is insoluble in an alkaline developer by polymerization reaction of a polymerizable group-containing component when exposed, while being soluble in an alkaline developer in an unexposed state.

When the silicon-containing resin (A) contains silsesquioxane resin (A1), the content of silsesquioxane resin (A1) in the silicon-containing resin (A) is within a range that does not impair the object of the present invention. Although not particularly limited, from the viewpoint of developability of the polymerizable composition, 50 mass% or more is preferable, 70 mass% or more is more preferable, 80 mass% or more is more preferable, 90 mass% or more is particularly preferable, and 100 mass% % Is most preferred.

As a general structure of silsesquioxane compound, basket type, incomplete basket type, ladder type, random type, etc. are well known. The structure of the silsesquioxane resin (A1) is not particularly limited, and any conventionally known structure such as a basket type, an incomplete basket type, a ladder type, or a random type may be used.

Silsesquioxane resin (A1) has the following formula (a1a):

[Tue 3]

(In formula (a1a), R ^a1 is the following formula (a1a-I):

-X ^a -B ^a -Y ^a -COOH… (a1a-I)

Is a group represented by

X ^a is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a group represented by -R ^a6 -NH-R ^a7 -,

R ^a6 and R ^a7 are each independently an alkylene group having 1 to 3 carbon atoms,

Y ^a is a divalent cyclic organic group or a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms,

B ^a is -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH- or -NH-CO-NH-,

X ^a and Y ^a may each independently be substituted with one or more groups selected from the group consisting of (meth)acryloyloxy groups, vinyl groups, and epoxy group-containing organic groups.)

It has a structural unit represented by.

For example, the silsesquioxane resin (A1) may contain a structural unit represented by the following formula (a1a-1) or (a1a-2) in addition to the structural unit represented by formula (a1a).

In the structural unit represented by the following formula (a1a-1) or (a1a-2), when R ^a0 is an organic group, the organic group may contain at least one selected from aromatic groups, amide bonds and urethane bonds. .

[Tue 4]

(In formulas (a1a-1) and (a1a-2), R ^a0 is each independently a hydrogen atom or a monovalent organic group.)

When R ^a0 in formulas (a1a-1) and (a1a-2) is an organic group, the number of carbon atoms is not particularly limited, but is preferably 1 to 50, for example 1 to 30, more preferably 1 to 20 is particularly preferred. The structure of the organic group may be linear, branched, or cyclic, or a combination of these structures. The organic group may have one or more unsaturated bonds. The organic group may contain a hetero atom. Examples of the hetero atom include a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom.

Suitable examples of organic groups include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, saturated aliphatic acyloxy groups, alkoxycarbonyl groups, phenyl groups which may have substituents, phenoxy groups which may have substituents, and substituents Benzoyl group optionally, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthoxy group which may have a substituent, substituent A naphthoyl group which may have, a naphthoxycarbonyl group which may have a substituent, a naphthoyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocyclyl group which may have a substituent, or organic of 1 or 2 And amino groups substituted with groups.

Substituents which these groups may have include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, and a carbon atom. Saturated aliphatic acyl group having 2 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, saturated aliphatic acyloxy group having 2 to 20 carbon atoms, phenyl group, phenoxy group, phenylthio group, benzoyl group, phenoxycarbonyl group, benzoyl Oxy group, phenyl alkyl group having 7 to 20 carbon atoms, naphthyl group, naphthoxy group, naphthoyl group, naphthoxycarbonyl group, naphthoyloxy group, naphthyl alkyl group having 11 to 20 carbon atoms, heterocyclyl group, hetero A cycloalkyl group, an amino group, an amino group substituted with 1 or 2 organic groups having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, a halogen atom, a cyano group, or a carboxy group.

In the formula (a1a), R ^a1 is the following formula (a1a-I):

-X ^a -B ^a -Y ^a -COOH… (a1a-I)

It is a group represented by.

In the formula (a1a-I), X ^a is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a group represented by -R ^a6 -NH-R ^a7 -.

R ^a6 and R ^a7 are each independently an alkylene group having 1 to 3 carbon atoms.

Y ^a is a divalent cyclic organic group or a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms.

B ^a is -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH- or -NH-CO-NH-.

X ^a and Y ^a may each independently be substituted with one or more groups selected from the group consisting of (meth)acryloyloxy groups, vinyl groups and epoxy group-containing organic groups.

Specifically as the alkylene group having 1 to 6 carbon atoms in X ^a , for example, methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3- And diyl groups, propane-1,2-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, and hexane-1,6-diyl groups.

The number of carbon atoms in the arylene group in X ^a is 6 to 12, and 6 to 10 is preferable.

Suitable specific examples of the arylene group include o-phenylene group, m-phenylene group, p-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group, And biphenyl-4,4'-diyl group.

-R ^a6 -NH-R ^a7 -specifically, for example, -CH ₂ -NH-CH ₂ -, -(CH ₂ ) ₂ -NH-(CH ₂ ) ₂ -, -(CH ₂ ) _3- NH-(CH ₂ ) ₃ -, -CH ₂ -NH-(CH ₂ ) ₂ -, -(CH ₂ ) ₂ -NH-CH ₂ -, -(CH ₂ ) ₂ -NH-(CH ₂ ) _3- , -(CH ₂ ) ₃ -NH-(CH ₂ ) ₂ -, -CH ₂ -NH-(CH ₂ ) ₃ -, -(CH ₂ ) ₃ -NH-CH ₂ -.

The divalent cyclic organic group in Y ^a may be a contribution excluding two hydrogen atoms from an aromatic ring, or a contribution excluding two hydrogen atoms from an aliphatic ring.

When Y ^a is a divalent group containing an aromatic ring, a group in which two hydrogen atoms are removed from an aromatic ring having 6 to 10 carbon atoms which may have a substituent having 1 or 2 carbon atoms is preferable as a divalent cyclic organic group. . Suitable examples of the aromatic ring having 6 to 10 carbon atoms include a benzene ring, a naphthalene ring, a methylbenzene ring, and a dimethylbenzene ring.

When Y ^a is ^a divalent group containing an aliphatic ring, a group obtained by removing two hydrogen atoms from an aliphatic ring having 5 to 16 carbon atoms is preferable as the divalent cyclic organic group. Suitable examples of the aliphatic ring having 5 to 16 carbon atoms include cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, dicyclopentadiene ring, norbornane ring, norbornene ring, and cuban (cubane) ring, Basketane ring, etc. are mentioned.

When Y ^a is a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, the chain aliphatic hydrocarbon group may be linear or branched, or may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

Suitable examples of the chain aliphatic hydrocarbon group having 1 to 20 carbon atoms are methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane-1,3-diyl group, propane-1,2 -Diyl group, propane-1,3-diyl group, propane-1,2-diyl group, vinylene group, (2-octenyl)ethylene group, (2,4,6-trimethyl-2-nonenyl)ethylene group And an alkylene group having a double bond, or an alkylene group having a branched chain having 1 to 9 carbon atoms.

In the formula (a1a-I), X ^a and Y ^a may each independently be substituted with one or more groups selected from the group consisting of (meth)acryloyloxy groups, vinyl groups and epoxy group-containing organic groups.

Moreover, the silsesquioxane resin (A1) is silsesquioxane in which at least one of X ^a and Y ^a is substituted with one or more groups selected from the group consisting of (meth)acryloyloxy groups, vinyl groups and epoxy group-containing organic groups. It is preferable that it is resin (A1-1). In this case, the silsesquioxane resin (A1-1) acts as both the silsesquioxane resin (A1) and the polymerizable group-containing component, thereby achieving desired performance without excessively increasing the types of constituents of the polymerizable composition. It can be provided to a polymerizable composition.

Silsesquioxane resin (A1-1) may contain other structural units other than the structural unit represented by Formula (a1a).

The other structural units are not particularly limited, but the following structural units (a2b):

[Tue 5]

(In the formula (a2b), R ^a3 represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms.)

The structural unit represented by is preferable.

When R ^a3 is an alkyl group, for example, a methyl group, an ethyl group and an n-propyl group are preferable. When R ^a3 is an aryl group or an aralkyl group, for example, a phenyl group, a benzyl group, a tolyl group, a xylyl group, and a naphthyl group are preferable.

In the silsesquioxane resin (A1-1), at least one of X ^a and Y ^a is substituted with one or more groups selected from the group consisting of (meth)acryloyloxy groups, vinyl groups and epoxy group-containing organic groups, Moreover, the ratio of the structural unit represented by Formula (a1a) is not specifically limited, It is 10-100 mol%, and 30-70 mol% is preferable.

Silsesquioxane resin (A1) is a structural unit represented by formula (a1a), and the following formula (a2a):

[Tue 6]

(In formula (a2a), R ^a2 is the following formula (a1a-II):

-Z ^a -A ^a … (a1a-Ⅱ)

Is a group represented by

Z ^a is a single bond, an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 12 carbon atoms,

A ^a is an (meth)acryloyloxy group, a vinyl group or an organic group containing an epoxy group.)

It is also preferable that it is silsesquioxane resin (A1-2) which has a structural unit represented by. While such silsesquioxane resin (A1-2) also acts as an alkali-soluble resin, it can be preferably used as a polymerizable group-containing component.

In formula (a1a-II), suitable examples in the case where Z ^a is an alkylene group having 1 to 6 carbon atoms are methylene group, ethane-1,2-diyl group, ethane-1,1-diyl group, propane- And 1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-1,6-diyl group.

The number of carbon atoms in the arylene group in Z ^a is 6 to 12, and 6 to 10 is preferable.

Suitable specific examples of the arylene group include o-phenylene group, m-phenylene group, p-phenylene group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-2,6-diyl group, And biphenyl-4,4'-diyl group.

In formula (a1a-II), A ^a is a (meth)acryloyloxy group, a vinyl group, or an epoxy group-containing organic group. Although it does not specifically limit as an organic group containing an epoxy group, For example, an oxiranyl group, a glycidyl group, a glycidyloxy group, etc. are mentioned.

Silsesquioxane resin (A1-2) contains the structural unit represented by Formula (a2a) which has a polymerizable group. For this reason, in the structural unit represented by the formula (a1a) in the silsesquioxane resin (A1-2), X ^a and Y ^a are necessarily (meth)acryloyloxy groups, vinyl groups, and organic groups containing an epoxy group. It need not be substituted with one or more groups selected from the group consisting of. It is preferable that X ^a and Y ^a in Formula (a1a) are not substituted with such a polymerizable group from the viewpoint of easy synthesis and availability of a compound that gives the structural unit represented by Formula (a1a).

As a specific example of the group represented by Formula (a1a-I) in the structural unit represented by Formula (a1a) contained in silsesquioxane resin (A1-2), X ^a , B ^a And ^a group in which Y ^a is a combination shown in Table 1 below. Y ^a in Table 1 has two binding hands, but one of them binds to a carboxy group and the other to B ^a . B ^a in Table 1 is similarly combined with X ^a and Y ^a .

As a specific example of the group represented by Formula (a2a-II) in the structural unit represented by Formula (a2a) contained in silsesquioxane resin (A1-2), Z ^a and A ^a are, for example. The group which is a combination shown in Table 2 below is mentioned.

Silsesquioxane resin (A1-2) may contain other structural units other than the structural unit represented by Formula (a1a) and the structural unit represented by Formula (a2a).

Although it does not specifically limit as another structural unit, The structural unit represented by Formula (a2b) mentioned above is preferable.

The proportion of the structural unit represented by formula (a2a) in silsesquioxane resin (A1-2) is not particularly limited, but is 5 to 90 mol%, preferably 10 mol% to 70 mol%, and 20 Molar% to 60 mol% is preferred.

Moreover, in the silsesquioxane resin (A1-2), the proportion of the structural unit represented by the formula (a1a) is not particularly limited, but is 5 mol% to 90 mol%, and 10 mol% to 70 mol% Preferably, 20 mol% to 60 mol% is preferable.

The silicon-containing resin (A) may include a silsesquioxane resin (A2) having a structural unit represented by the formula (a2a) and not corresponding to the silsesquioxane resin (A1). Silsesquioxane resin (A2) contains a polymerizable group because it has a structural unit represented by formula (a2a). For this reason, silsesquioxane resin (A2) can be suitably used as a polymerizable group-containing component.

Silsesquioxane resin (A2) may consist only of the structural unit represented by Formula (a2a), or may consist of a structural unit represented by Formula (a2a) and other structural units. The other structural unit is not particularly limited, but a structural unit represented by the formula (a2b) described above is preferable.

The proportion of the structural unit represented by formula (a2a) in silsesquioxane resin (A2) is not particularly limited, but is 5 to 100 mol%, preferably 10 mol% to 70 mol%, and 20 mol% ~60 mol% is preferred. 30 mol% or more is preferable, 40 mol% or more is more preferable, and 50 mol% or more is particularly preferable.

When the silicon-containing resin (A) becomes silsesquioxane resin (A1) or silsesquioxane resin (A2), the weight average molecular weight Mw is a range in which 1000 to 100,000 is usually obtained, preferably 1000 to 50000, More preferably, it is 1500-20000.

Next, the polysilane-polysiloxane resin (A-I), the resin mixture (A-II), and the polysilane structure-containing resin (A-III) will be described.

The polysilane-polysiloxane resin (A-I) is a polysilane-polysiloxane resin having a polysilane structure (I-1) and a polysiloxane structure (I-2).

The resin mixture (A-II) is a mixture of a resin having a polysilane structure (II-1) and a resin having a polysiloxane structure (II-2).

The polysilane structure-containing resin (A-III) is a resin having a polysilane structure (II-1).

The polysiloxane structures (I-2) and (II-2) are each independently selected from the group consisting of silicon compounds represented by the following formulas (A-1-1) to (A-1-4): It is preferred to include a hydrolysis condensation structure of the silicon compound.

R ¹ R ² R ³ SiX ¹ (A-1-1)

R ⁴ R ⁵ SiX ² ₂ (A-1-2)

R ⁶ SiX ³ ₃ (A-1-3)

SiX ⁴ ₄ (A-1-4)

(In the above formula, X ¹ ~ X ⁴ are each independently a hydrolyzable group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an organic group, and this organic group The hydrogen atom in the above may be substituted with a halogen atom.)

Examples of the hydrolyzable group represented by X ¹ to X ⁴ include an alkoxy group, a halogen atom or an isocyanate group (NCO), and is preferably an alkoxy group.

Examples of the alkoxy group include an alkoxy group having 1 to 6 carbon atoms, specifically methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group, pentoxy group And the like.

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

The organic group represented by R ¹ to R ⁶ includes an organic group having 1 to 30 carbon atoms, and the number of carbon atoms such as an alkyl group [methyl, ethyl, n-propyl, i-propyl, n-butyl group and t-butyl group] 1-10 alkyl groups (preferably alkyl groups having 1 to 6 carbon atoms, especially alkyl groups having 1 to 4 carbon atoms, etc.), cycloalkyl groups (cycloalkyl groups having 5 to 8 carbon atoms such as cyclohexyl groups, especially carbon atoms) Number 5 to 6 cycloalkyl group), alkenyl group (ethenyl group, propenyl group, butenyl group, etc., alkenyl group having 2 to 10 carbon atoms (preferably alkenyl group having 2 to 6 carbon atoms, especially 2 to 4 carbon atoms) Alkenyl group, etc.)], cycloalkenyl group [1-cyclopentenyl group, 1-cyclohexenyl group, cycloalkenyl group having 5 to 10 carbon atoms (preferably cycloalkenyl group having 5 to 8 carbon atoms, In particular, a cycloalkenyl group having 5 to 7 carbon atoms)], an aryl group (an aryl group having 6 to 10 carbon atoms such as phenyl or naphthyl group), an aralkyl group [C _6-10 aryl-C ₁ such as benzyl or phenethyl group] _-6 alkyl group (C _6-10 aryl-C _1-4 alkyl group, etc.)], amino group, N-substituted amino group (N-mono or di substituted substituted with the above alkyl group, cycloalkyl group, aryl group, aralkyl group, acyl group, etc.) Amino groups, etc.). The alkyl group, cycloalkyl group, aryl group, or aryl group constituting an aralkyl group may have one or more substituents. As such a substituent, the alkyl group of the said example (especially the alkyl group of 1-6 carbon atoms, etc.), the alkoxy group of the said example, etc. are mentioned. The organic group having such a substituent is, for example, a C _1-6 alkyl-C _6-10 aryl group such as tolyl, xylenyl, ethylphenyl, or methylnaphthyl group (preferably mono, di or tri C _1-4) Alkyl-C _6-10 aryl groups, especially mono or di C _1-4 alkylphenyl groups, etc.); C _1-10 alkoxy C _6-10 aryl groups such as methoxyphenyl, ethoxyphenyl, methoxy naphthyl groups (preferably Is C _1-6 alkoxy C _6-10 aryl group, in particular C _1-4 alkoxyphenyl group, etc.).

The silicon compounds represented by the formulas (A-1-1) to (A-1-4) include trihalosilanes such as trichlorosilane, tribromosilane, and trifluorosilane; tetrachlorosilane and tetrabromosilane And tetrahalosilanes such as tetrafluorosilane; methyltrichlorosilane, methyltribromosilane, methyltrifluorosilane, ethyltrichlorosilane, ethyltribromosilane, ethyltrifluorosilane, and n-propyltrichlorosilane , n-propyltribromosilane, n-propyltrifluorosilane, isopropyltrichlorosilane, isopropyltribromosilane, isopropyltrifluorosilane, n-butyltrichlorosilane, n-butyltribromosilane, n -Butyl trifluorosilane, isobutyl trichlorosilane, isobutyl tribromosilane, isobutyl trifluorosilane, sec-butyl trichlorosilane, sec-butyl tribromosilane, sec-butyl trifluorosilane, tert-butyl Alkyl trihalosilanes such as trichlorosilane, tert-butyl tribromosilane and tert-butyl trifluorosilane; phenyl trihalosilanes such as phenyl trichlorosilane, phenyl tribromosilane and phenyl trifluorosilane; dichloro Dimethylsilane, dibromodimethylsilane, difluorodimethylsilane, dichlorodiethylsilane, dibromodiethylsilane, difluorodiethylsilane, dichlorodi-n-propylsilane, dibromodi-n-propylsilane, di Fluorodi-n-propylsilane, dichlorodiisopropylsilane, dibromodiisopropylsilane, difluorodiisopropylsilane, dichlorodi-n-butylsilane, dibromodi-n-butylsilane, difluorodi-n -Butylsilane, dichlorodi-n-butylsilane, dibromodi-n-butylsilane, difluorodi-n-butylsilane, dichlorodiisobutylsilane, dibromodiisobutylsilane, difluorodiisobutylsilane, Dichlorodi-sec-butylsilane, dibromodi-sec-butylsilane, difluorodi-sec-butylsilane, dichlorodi-tert-butylsilane, dichlorodi-tert-butylsilane and dichlorodi-tert-butylsilane, etc. Dialkyldihalosilanes; diphenyldihalosilanes such as dichlorodiphenylsilane, dibromodiphenylsilane and difluorodiphenylsilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyl Triethoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyl Triethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane , Cyclohexyltriethoxysilane, cyclohexenyltrimethoxysilane, cyclohexenyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, tolyltri Methoxysilane, tolyl triethoxysilane, anisiltrimethoxysilane, anisiltriethoxysilane, phenethyltrimethoxysilane, phenethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxy Silane, diethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, dipropyldimethoxysilane, dibutyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, trimethylmethoxysilane, dimethylethylmeth Methoxysilane, dimethylphenylmethoxysilane, dimethylbenzylmethoxysilane, dimethylphenethylmethoxysilane, tetraisocyanatesilane, methyltriisocyanatesilane, ethyltriisocyanatesilane, propyltriisocyanatesilane, butyltriisocyanatesilane, dimethyldiisocyanatesilane And diethyl diisocyanate silane, dipropyl diisocyanate silane, dibutyl diisocyanate silane, trimethyl isocyanate silane, triethyl isocyanate silane, tripropyl isocyanate silane, and tributyl isocyanate silane.

Further, the silicon compound represented by the formula (A-1-3) may be a silicon compound that induces the structural unit represented by the formula (a1a) or (a2a), but in this case, in the resin mixture (A-II) The resin having the polysiloxane structure (II-2) of is the same as the silsesquioxane resin (A1) or silsesquioxane resin (A2).

The hydrolysis-condensation reaction proceeds as a condition of the hydrolysis-condensation reaction of at least one silicon compound selected from the group consisting of silicon compounds represented by the formulas (A-1-1) to (A-1-4). As long as there is no particular limitation, known conditions may be used, and a catalyst may be used at this time. Examples of the catalyst include tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, and tetramethyl And ammonium hydroxide, tetrabutylammonium hydroxide, hydrochloric acid, sulfuric acid, formic acid, and oxalic acid. Moreover, as reaction conditions, for example, 1 to 10 hours, and 25 to 100°C can be used.

The polysilane structures (I-1) and (II-1) are each independently selected from the group consisting of polysilane compounds represented by the following formulas (A-2-1) and (A-2-2): It is preferred to include structures derived from species.

(R ⁷ R ⁸ R ⁹ Si) _a1 (R ¹⁰ R ¹¹ Si) _a2 (R ¹² Si) _a3 (Si) _a4 … (A-2-1)

(In the above formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, a hydroxyl group or an organic group. a1, a2, a3 and a4 are each independently a molar fraction, a1+a2+a3+a4=1, 0≤a1≤1, 0≤a2≤1, 0≤a3≤1 and 0≤a4≤1.)

[Tue 7]

(In the formula (A-2-2), R ^a1 and R ^a2 each independently represent a hydrogen atom, a hydroxyl group, or an organic group. n represents an integer of 3 to 20.)

As the organic group represented by R ⁷ to R ⁶ , R ^a1 and R ^a2 , the organic group represented by R ¹ to R ⁶ is the same as the specific examples and preferred examples.

As the organic groups represented by R ⁷ to R ¹² , R ^a1 and R ^a2 , any organic group can be introduced by, for example, the method described in Japanese Patent Application Laid-Open No. 2003-261681, paragraph 0031.

(Polysilane-polysiloxane resin (A-I))

The polysilane-polysiloxane resin (A-I) has a polysilane structure (I-1) and a polysiloxane structure (I-2).

The polysilane-polysiloxane resin (AI) is preferably a polysilane-polysiloxane resin in which the polysilane structure (I-1) and the polysiloxane structure (I-2) are connected through an oxygen atom (ether bond (-O-)). .

In the polysilane-polysiloxane resin (AI), the bonding of the connecting portion (for example, an ether bond) with the polysiloxane structure of the polysilane structure is relatively relative to the Si-Si bond in the polysilane structure and the Si-O bond in the polysiloxane structure. It is unstable and easy to decompose under the action of an alkali developer. Thereby, when a polymerizable composition contains polysilane-polysiloxane resin (A-I), alkali developability is excellent.

The polysilane-polysiloxane resin (A-I) preferably contains at least one member selected from the group consisting of structures represented by the following formulas (H1) and (H2).

[Tue 8]

(In the formulas (H1) and (H2), A ¹ each independently represents a polysiloxane structure comprising at least one of the structures represented by the following formula (HA1), and also including at least one leftmost structure. .

-A ² O- each independently represents a linking group which is any one of the structures represented by the following formula (HA2). In addition, in the formula (H1), -OA ² -represents a -OSi-structure in which the bonding sequence of the main chain -SiO- in the following formula (HA1) is reversed.

Psi represents the polysilane structure (I-1).)

[Tue 9]

[Tue 10]

(In the formulas (HA1) and (HA2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or an organic group, and the hydrogen atom in the organic group is replaced by a halogen atom May be)

Specific examples and preferred examples of the organic group represented by R ¹ to R ⁶ are as described above.

The polysilane structure (I-1) represented by Psi includes a polysilane structure having 3 to 40 Si atoms, and is preferably a polysilane structure having 5 to 30 Si atoms.

It is preferable that the polysilane structure (I-1) represented by Psi contains one or more of the polysilane structures represented by the following formula (HB1).

[Tue 11]

(In the formula (HB1), R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, a hydroxyl group, or an organic group. * represents a bond.)

The polysilane structure (I-1) represented by Psi makes it easy to remove the polymerizable composition film when the polymerizable composition film is removed at the time of processing in the manufacturing process or when the polymerizable composition is subjected to lithography performance. In view of this, it is more preferable to include a polysilane structure represented by the following formula (HB1-1).

[Tue 12]

(In the formula (HB1-1), *, R ¹⁰ and R ¹¹ have the same meanings as in the formula (HB1).)

Specific examples and preferred examples of the organic group represented by R ¹⁰ to R ¹² are the same as those described above as specific examples and preferred examples of the organic group represented by R ¹ to R ⁶ .

One specific example of the structure represented by the formula (H1) includes a structure represented by the following formula (H3).

[Tue 13]

(In the formula (H3), A ¹ , -A ² O-, -OA ² -, and Psi have the same meanings as in the formula (H1).)

The mass average molecular weight (Mw) of the polysilane-polysiloxane resin (AI) is not particularly limited as long as it does not impair the object of the present invention, but 500-20000 is preferable, 1000-10000 is more preferable, and 2000-8000 is It is more preferable.

In this specification, the mass average molecular weight (Mw) is a measured value by gel permeation chromatography (GPC) in terms of polystyrene.

(Method for producing polysilane-polysiloxane resin (A-I))

At least one silicon compound selected from the group consisting of silicon compounds represented by the formulas (A-1-1) to (A-1-4) and hydrolyzates, condensates and hydrolysis condensates of the silicon compounds. A polysilane-polysiloxane resin (AI) can be produced by subjecting at least one member selected from the group consisting of a resin having a polysilane structure to a hydrolysis-condensation reaction.

The resin having the polysilane structure used for production is preferably at least one member selected from the group consisting of polysilane compounds represented by the formulas (A-2-1) and (A-2-2).

The hydrolysis-condensation reaction conditions are not particularly limited as long as the hydrolysis-condensation reaction proceeds. For example, one or more compounds selected from inorganic acids, aliphatic sulfonic acids and aromatic sulfonic acids can be used as the acid catalyst. . At this time, examples of the acid catalyst used include hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. The catalyst is used in an amount of 10 ^-6 to 10 mol, more preferably 10 ^-5 to 5 mol, based on 1 mol of the silicon compounds represented by the formulas (A-1-1) to (A-1-4) above, More preferably, it is 10 ^-4 to 1 mol.

The amount of water during hydrolysis condensation of the silicon compounds represented by the formulas (A-1-1) to (A-1-4) is represented by the formulas (A-1-1) to (A-1-4). 0.01-100 mol is preferable per mol of the hydrolyzable group which the silicon compound has, and more preferably 0.05-50 mol, more preferably 0.1-30 mol is added.

The reaction temperature is preferably 0 to 100°C, more preferably 5 to 80°C.

Organic solvents that can be added to the aqueous catalyst solution include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, acetone, acetonitrile, tetrahydrofuran, toluene, and hexane , Ethyl acetate, cyclohexanone, methyl amyl ketone, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether , Diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate , Propylene glycol mono t-butyl ether acetate, γ-butyrolactone and mixtures thereof are preferred.

Among these solvents, more preferable ones are water-soluble. For example, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, polyhydric alcohols such as ethylene glycol and propylene glycol, butanediol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butanediol monoethyl Polyhydric alcohol condensate derivatives such as ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, butanediol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monopropyl ether, acetone, acetonitrile, tetrahydrofuran, and the like. have. Particularly preferred among these are those having a boiling point of 100°C or lower.

Further, as the organic solvent, at least one selected from the group consisting of a terpene compound having at least one group selected from the group consisting of hydroxy groups and acetoxy groups to be described later and an acetate compound containing a cyclic skeleton (excluding the terpene compounds). Dog solvents can be preferably used.

Moreover, 0-1,000 ml is preferable with respect to 1 mol of silicon compounds represented by said Formula (A-1-1)-(A-1-4), and, as for the usage-amount of an organic solvent, 0-500 ml is especially preferable.

Thereafter, if necessary, a neutralization reaction of the catalyst is carried out, and alcohol generated by the hydrolysis condensation reaction may be removed under reduced pressure to obtain an aqueous reaction mixture solution.

The polysilane compound represented by the formula (A-2-1) or (A-2-2) can be prepared by applying or applying various production methods of polysilane.

For example, (a) a method for dehalogen polycondensation reaction of halosilanes with magnesium as a reducing agent ("magnesium reduction method", WO 98/29476 publication, Japanese Patent Publication No. 2003-277507, etc.), ( b) A method of vigorously stirring a dialkyldihalosilane or dihalotetraalkyldisilane in a toluene solvent using an alkali metal such as sodium metal at a temperature of 100° C. or higher and reductively coupling [J. Am. Chem. Soc., 103(1981) 7352], (c) a method of anionic polymerization of disylene masked with biphenyl (Japanese Patent Application Publication No. Hei 1-23063), (d) a method of ring-opening polymerization of cyclic silanes (Japan Patent Publication No. Hei 5-170913), (e) Hydrogenation of a polyhydrogen condensation reaction with a transition metal complex catalyst (Japanese Patent Publication No. Hei 7-17753), (f) dihalosilanes at room temperature or lower And a method for producing polysilane by electrode reduction at a temperature (Japanese Patent Application Laid-open No. Hei 7-309953) and the like, and the magnesium reduction method is preferred.

As the polysilane compound represented by the formula (A-2-1) or (A-2-2), Ogsol SI-10-10 (polymethylphenylsilane) manufactured by Osaka Gas Chemical, SI-10-20 (poly Commercial products such as methylphenylsilane), SI-20-10 (polyphenylsilane), SI-20-10 (open) (polyphenylsilane), and SI-30-10 (cyclic polydiphenylsilane) can also be used. have. Moreover, you may use what reacted these under the following basic conditions, and made low molecular weight.

(Resin mixture (A-II))

As described above, the resin mixture (A-II) is a mixture of a resin having a polysilane structure (II-1) and a resin having a polysiloxane structure (II-2). Hereinafter, the resin having a polysilane structure (II-1) and the resin having a polysiloxane structure (II-2) will be described.

((Resin with polysilane structure (II-1)))

Examples of the resin having a polysilane structure (II-1) include a resin having a polysilane structure having 3 to 40 Si atoms, and a resin having a polysilane structure having 5 to 30 Si atoms.

The resin having a polysilane structure (II-1) preferably contains at least one of the polysilane structures represented by the formula (HB1), and includes a polysilane structure represented by the formula (HB1-1). It is more preferable to do.

It is preferable that the resin having a polysilane structure (II-1) is at least one selected from the group consisting of polysilane compounds represented by the formulas (A-2-1) and (A-2-2).

When a resin having a polysilane structure (II-1) has a substituent represented by the formula (a1a-II), a resin having a polysilane structure (II-1) containing a polymerizable group (described later (5) It can be suitably used as) in the case of a polymerizable group-containing resin.

The mass average molecular weight (Mw) of the resin having the polysilane structure (II-1) is not particularly limited as long as the object of the present invention is not impaired, but 500 to 20,000 is preferable, 1000 to 10000 is more preferable, and 2000 ~5000 is more preferable.

((Resin having polysiloxane structure (II-2)))

The resin having a polysiloxane structure (II-2) is hydrolyzed and condensed of a mixture containing at least one member selected from the group consisting of silicon compounds represented by the formulas (A-1-1) to (A-1-4). It is preferable to have a structure, and it is more preferable to include at least one of the polysiloxane structures represented by the formula (HA1).

The resin having a polysiloxane structure (II-2) is hydrolyzed and condensed of a mixture containing at least one member selected from the group consisting of silicon compounds represented by the formulas (A-1-1) to (A-1-4). It can be prepared by reaction.

The mass average molecular weight (Mw) of the resin having the polysiloxane structure (II-2) is not particularly limited as long as the object of the present invention is not impaired, but 500 to 20,000 is preferable, and 1000 to 10000 is more preferable.

When the silicon-containing resin (A) is a resin mixture (A-II), the mixing ratio of the resin having the polysilane structure (II-1) to the resin having the polysiloxane structure (II-2) impairs the effect of the present invention. There are no particular limitations as long as it does so, but 0.01 to 5 times the mass is preferred, and 0.05 to 1 times the mass.

(Polysilane structure-containing resin (A-III))

The polysilane structure-containing resin (A-III) is a resin having a polysilane structure (II-1) and is the same as the resin having a polysilane structure (II-1) in the resin mixture (A-II).

When the silicon-containing resin (A) is a polysilane structure-containing resin (A-III), the resin having a polysilane structure (II-1) has a polysilane structure treated under basic conditions (for example, purification treatment). It is preferable that it is a resin or has a substituent represented by the formula (a1a-I).

For treatment under basic conditions, various basic compounds can be used as the base to be used. For example, sodium hydroxide, potassium hydroxide, barium hydroxide, ammonia, tetramethylammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, carbonic acid Inorganic bases such as potassium, lithium hydride, sodium hydride, potassium hydride, calcium hydride, alkyl metals such as methyllithium, n-butyllithium, methylmagnesium chloride, ethylmagnesium bromide, Cr, Ga, Fe(Fe(II), Fe (III)), metal halides composed of metals (or metal ions) such as Cd, Co, Ni, Sn, Pb, Cu (Cu(II), Cu(I)), Ag, Pd, Pt, Au, etc., Alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, triethylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, diazabicycloundecene ( Organic bases such as DBU) can be used. The reaction temperature is preferably about -50°C to the boiling point of the solvent, and more preferably room temperature to 100°C.

Further, when the silicon-containing resin (A) contains a polysilane structure-containing resin (A-III), as the silicon-containing resin (A), silsesquioxane resin (A1) and/or polysilane-polysiloxane resin It is preferable to combine (AI).

Moreover, when silicon-containing resin (A) contains polysilane structure containing resin (A-III), it is preferable to use it in combination with (4) polyfunctional polymerizable monomer (B) as a polymerization component.

The content of the silicon-containing resin (A) in the polymerizable composition is preferably 20 to 97% by mass, more preferably 30 to 90% by mass, and 40 to 80% by mass relative to the total solid content in the polymerizable composition. It is more preferable.

By using the silicon-containing resin (A) in an amount in this range, it is easy to suppress generation of residues in the unexposed portion, and it is easy to ensure good developability.

<Polyfunctional polymerizable monomer (B1)>

The polymerizable composition may contain a polyfunctional polymerizable monomer (B1) as a polymerizable group-containing component. The polyfunctional polymerizable monomer is a compound having a (meth)acryloyloxy group, a vinyl group or an epoxy group-containing organic group as a polymerizable group.

Suitable examples of the polyfunctional polymerizable monomer (B1) include an unsaturated compound (B1-1) having a (meth)acryloyloxy group or a vinyl group and an epoxy compound (B1-2) having an epoxy group-containing organic group.

Among these polyfunctional polymerizable monomers (B1), a polyfunctional polymerizable monomer having a trifunctional or higher functionality is preferable, and a polyfunctional polymerizable monomer having a trifunctional or higher functionality is preferred because it tends to increase the adhesiveness of the polymerizable composition to the substrate and the strength after curing of the polymerizable composition. A polyfunctional polymerizable monomer is more preferable, and a polyfunctional polymerizable monomer having 5 or more functionalities is more preferable.

As the unsaturated compound (B1-1), ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di (Meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin Di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol Tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritolpenta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, 2,2-bis(4-(meth)) Acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene Glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycylate Diethyl ether (meth)acrylate, urethane (meth)acrylate (i.e., reactants of 2-hydroxyethyl (meth)acrylate with tolylene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate), methylene bis( And polyfunctional monomers such as meta)acrylamide, (meth)acrylamide methylene ether, and condensates of polyhydric alcohols and N-methylol (meth)acrylamide, triacrylic formal, and the like. These polyfunctional monomers can be used alone or in combination of two or more.

Among these unsaturated compounds (B1-1) having an ethylenically unsaturated group, a trifunctional or higher unsaturated compound is preferred, and a trifunctional or higher functional compound is preferable because it tends to increase the adhesion of the polymerizable composition to the substrate and the strength after curing of the polymerizable composition. The above unsaturated compound is more preferable, and the 5-functional or higher unsaturated compound is more preferable.

As a specific example of the epoxy compound (B1-2), bifunctional, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin. Epoxy resins; glycidyl ester type epoxy resins such as dimer acid glycidyl ester and triglycidyl ester; tetraglycidyl amino diphenylmethane, triglycidyl-p-aminophenol, tetraglycidyl metaxylylene Glycidylamine type epoxy resins such as diamine and tetraglycidylbisaminomethylcyclohexane; heterocyclic epoxy resins such as triglycidyl isocyanurate; fluoroglycinol triglycidyl ether, and trihydroxybiphenyl Triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerin triglycidyl ether, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[ 4-(2,3-epoxypropoxy)phenyl]ethyl]phenyl]propane and 1,3-bis[4-[1-[4-(2,3-epoxypropoxy)phenyl]-1-[4- Trifunctional epoxy resins such as [1-[4-(2,3-epoxypropoxy)phenyl]-1-methylethyl]phenyl]ethyl]phenoxy]-2-propanol; tetrahydroxyphenylethane tetraglycine And tetrafunctional epoxy resins such as diether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, and tetraglycidoxybiphenyl.

When the polymerizable composition contains the polyfunctional polymerizable monomer (B1), the content of the polyfunctional polymerizable monomer (B1) is preferably 1 to 80% by mass relative to the total mass of the solid content of the polymerizable composition, and 5 to 5 40 mass% is more preferable. Moreover, it is preferable to make 10-200 mass parts of polyfunctional polymerizable monomers (B1) with respect to 100 mass parts of silicon-containing resins (A), and the range of 20-120 mass parts is more preferable. By setting it as the said range, there exists a tendency for balance of sensitivity, developability, and resolution to be easy to take.

<Polymerizable group-containing resin (B2)>

The polymerizable composition has at least one group selected from the group consisting of a (meth)acryloyloxy group, a vinyl group, and an epoxy group-containing organic group as a polymerizable group-containing component, and further includes silsesquioxane resin (A1), silsesquioxane resin ( The polymerizable group-containing resin (B2) which does not correspond to any of A2) and the polyfunctional polymerizable monomer (B1) may be included.

Further, the polymerizable group-containing resin (B2) may be used in combination with the polyfunctional polymerizable monomer (B1).

Suitable examples of the polymerizable group-containing resin (B2) include (meth)acryloyloxy groups or unsaturated resins having a vinyl group (B2-1) and epoxy group-containing resins having an epoxy group-containing organic group (B2-2).

Hereinafter, the unsaturated resin (B2-1) and the epoxy group-containing resin (B2-2) will be described.

[Unsaturated resin (B2-1)]

The unsaturated resin (B2-1) is not particularly limited as long as it is a resin having a (meth)acryloyloxy group or a vinyl group. Suitable examples of the unsaturated resin (B2-1) include a resin in which an unsaturated carboxylic acid is reacted with at least a part of the epoxy group of the epoxy group-containing resin (B2-2) described later.

Examples of the unsaturated carboxylic acid include (meth)acrylic acid; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.

Moreover, the resin (also referred to as a cardo resin) having a cardo structure represented by the following formula (b-1) is also preferable as the unsaturated resin (B2-1).

[Tue 14]

In the formula (b-1), X ^b represents a group represented by the following formula (b-2). m1 represents the integer of 0-20.

[Tue 15]

In the formula (b-2), R ^b1 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a halogen atom, R ^b2 each independently represents a hydrogen atom or a methyl group, and R ^b3 each It independently represents a linear or branched alkylene group, m2 represents 0 or 1, and W ^b represents a group represented by the following formula (b-3).

[Tue 16]

In formula (b-2), R ^b3 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and particularly preferably an alkylene group having 1 to 6 carbon atoms. And ethane-1,2-diyl group, propane-1,2-diyl group and propane 1,3-diyl group are most preferred.

Ring A ^b in Formula (b-3) represents an aliphatic ring which may be condensed with an aromatic ring or may have a substituent. The aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocycle.

Examples of the aliphatic ring include monocycloalkane, bicycloalkane, tricycloalkane, and tetracycloalkane.

Specifically, monocycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are mentioned.

The aromatic ring which may be condensed on the aliphatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle, and an aromatic hydrocarbon ring is preferable. Specifically, a benzene ring and a naphthalene ring are preferable.

Suitable examples of the divalent group represented by formula (b-3) include the following groups.

[Tue 17]

The divalent group X ^b in the formula (b-1) is introduced into the cardo resin by reacting the tetracarboxylic acid anhydride giving the residue Z ^b with the diol compound represented by the formula (b-2a) below.

[Tue 18]

In formula (b-2a), R ^b1 , R ^b2 , R ^b3 and m2 are as described for formula (b-2). The ring A ^b in Formula (b-2a) is as having described for Formula (b-3).

The diol compound represented by formula (b-2a) can be produced, for example, by the following method.

First, after replacing the hydrogen atom in the phenolic hydroxyl group of the diol compound represented by the following formula (b-2b) with a group represented by -R ^b3 -OH according to a conventional method, if necessary, epichlorohydrin, etc. It is glycidylated to obtain an epoxy compound represented by the following formula (b-2c).

Then, the diol compound represented by formula (b-2a) is obtained by reacting the epoxy compound represented by formula (b-2c) with acrylic acid or methacrylic acid.

In formulas (b-2b) and (b-2c), R ^b1 , R ^b3 and m2 are as described for formula (b-2). The ring A ^b in Formulas (b-2b) and (b-2c) is as described for Formula (b-3).

In addition, the manufacturing method of the diol compound represented by Formula (b-2a) is not limited to the above method.

[Tue 19]

The following diol compound is mentioned as a suitable example of a diol compound represented by Formula (b-2b).

[Tue 20]

In the formula (b-1), R ^b0 is a hydrogen atom or a group represented by -CO-Y ^b -COOH. Here, Y ^b represents the residue excluding the acid anhydride group (-CO-O-CO-) from dicarboxylic acid anhydride. Examples of dicarboxylic acid anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendmethylene anhydride tetrahydrophthalic acid, chlorendic anhydride, methyltetrahydro phthalic anhydride, anhydride And glutaric acid.

Moreover, in said Formula (b-1), Z ^b represents the residue which remove|excluding two acid anhydride groups from tetracarboxylic acid anhydride. Examples of the tetracarboxylic acid anhydride include pyromellitic acid anhydride, benzophenone tetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, biphenyl ether tetracarboxylic acid anhydride, and other alicyclic skeleton-containing tetracarboxylic acid anhydride.

Moreover, in said Formula (b-1), m1 represents the integer of 0-20.

The weight average molecular weight of the cardo resin is preferably 1000 to 40000, more preferably 1500 to 30000, and even more preferably 2000 to 10,000. By setting it as the said range, sufficient heat resistance and film strength can be obtained, obtaining favorable developability.

[Epoxy group-containing resin (B2-2)]

The epoxy group-containing resin (B2-2) may be a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group. The epoxy group-containing resin may be a polymer having a functional group having a reactivity such as a hydroxyl group, a carboxyl group, or an amino group, for example, an epoxy group may be introduced using a compound having an epoxy group such as epichlorhydrin. A polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing an epoxy group is preferable as the polymer having an epoxy group from the viewpoint of easy availability, preparation, adjustment of the amount of the epoxy group in the polymer, and the like.

Preferred examples of the epoxy group-containing resin (B2-2) are phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, bisphenol A novolac type epoxy resins and bisphenol AD novolac type epoxy And aromatic epoxy resins such as novolac epoxy resins such as resins; cyclic aliphatic epoxy resins such as epoxides of dicyclopentadiene type phenol resins and epoxides of naphthalene type phenol resins.

Moreover, in the epoxy group-containing resin (B2-2), it is either a homopolymer of the (meth)acrylic acid ester having an epoxy group or a (meth)acrylic acid ester having an epoxy group from the viewpoint of easy preparation or adjustment of physical properties of the formed film. And other monomers are preferred.

The (meth)acrylic acid ester having an epoxy group may be a (meth)acrylic acid ester having a chain aliphatic epoxy group or a (meth)acrylic acid ester having an alicyclic epoxy group described later. Moreover, (meth)acrylic acid ester which has an epoxy group may contain the aromatic group. Among the (meth)acrylic acid esters having an epoxy group, aliphatic (meth)acrylic acid esters having a chain aliphatic epoxy group or aliphatic (meth)acrylic acid esters having an alicyclic epoxy group are preferred, and aliphatic (meth)acrylic acid esters having an alicyclic epoxy group are It is more preferable.

Examples of the (meth)acrylic acid ester containing an aromatic group and having an epoxy group are 4-glycidyloxyphenyl (meth)acrylate, 3-glycidyloxyphenyl (meth)acrylate, 2-glycidyloxyphenyl ( Meth)acrylate, 4-glycidyloxyphenylmethyl (meth)acrylate, 3-glycidyloxyphenylmethyl (meth)acrylate, and 2-glycidyloxyphenylmethyl (meth)acrylate. have.

Examples of the aliphatic (meth)acrylic acid ester having a chain aliphatic epoxy group include oxy groups (-O-) in ester groups (-O-CO-), such as epoxyalkyl (meth)acrylate and epoxyalkyloxyalkyl (meth)acrylate. (Meth)acrylic acid ester to which a chain aliphatic epoxy group bonds. The chain aliphatic epoxy group of the (meth)acrylic acid ester may contain one or a plurality of oxy groups (-O-) in the chain. Although the number of carbon atoms of a chain aliphatic epoxy group is not specifically limited, 3-20 are preferable, 3-15 are more preferable, and 3-10 are especially preferable.

Specific examples of the aliphatic (meth)acrylic acid ester having a chain aliphatic epoxy group include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 3,4-epoxy butyl (meth)acrylate, 6 Epoxy alkyl (meth)acrylates such as ,7-epoxyheptyl (meth)acrylate; 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxy-n-propyl (meth)acrylate, 4 Epoxy alkyl such as glycidyloxy-n-butyl (meth)acrylate, 5-glycidyloxy-n-hexyl (meth)acrylate, and 6-glycidyloxy-n-hexyl (meth)acrylate And oxyalkyl (meth)acrylates.

Specific examples of the aliphatic (meth)acrylic acid ester having an alicyclic epoxy group include compounds represented by the following formulas (b1-1) to (b1-15). Among these, compounds represented by the following formulas (b1-1) to (b1-5) are preferable, and compounds represented by the following formulas (a1-1) to (a1-3) are more preferable. Moreover, about each of these compounds, the bonding site of the oxygen atom of the ester group to an alicyclic is not limited to what is shown here, and may contain some positional isomers.

[Tue 21]

[Tue 22]

[Tue 23]

In the above formula, R ^b7 represents a hydrogen atom or a methyl group, R ^b8 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^b9 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and t ⁰ Represents an integer from 0 to 10. R ^b8 is preferably a straight or branched alkylene group such as a methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group or hexamethylene group. R ^b9 is preferably a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, or a cyclohexylene group, for example.

As a polymer having an epoxy group, both a homopolymer of an (meth)acrylic acid ester having an epoxy group and a copolymer of an (meth)acrylic acid ester having an epoxy group and other monomers can be used, but (meth)acrylic acid having an epoxy group in the polymer having an epoxy group The content of the structural unit derived from the ester is preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, and most preferably 100% by mass.

When the polymer having an epoxy group is a copolymer of an (meth)acrylic acid ester having an epoxy group and other monomers, the other monomers include unsaturated carboxylic acid, (meth)acrylic acid ester having no epoxy group, (meth)acrylamides, allyl compound, vinyl ether And vinyl esters and styrenes. These compounds may be used alone or in combination of two or more. In view of the storage stability of the polymerizable composition or the chemical resistance to the alkali of the film formed using the polymerizable composition, the copolymer of the (meth)acrylic acid ester having an epoxy group and other monomers does not contain a structural unit derived from an unsaturated carboxylic acid. It is preferred.

Examples of the unsaturated carboxylic acid include (meth)acrylic acid; (meth)acrylic acid amide; crotonic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and anhydrides of these dicarboxylic acids.

Examples of the (meth)acrylic acid ester having no epoxy group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, amyl (meth)acrylate, t-octyl (meth)acrylate, and the like. Straight or branched chain alkyl (meth)acrylate; chloroethyl (meth)acrylate, 2,2-dimethylhydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, trimethylolpropane mono (Meth)acrylate, benzyl (meth)acrylate, perfuryl (meth)acrylate; (meth)acrylic acid ester having a group having an alicyclic skeleton. Among the (meth)acrylic acid esters that do not have an epoxy group, (meth)acrylic acid esters having a group having an alicyclic skeleton are preferred.

In the (meth)acrylic acid ester having a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic alicyclic group. Moreover, as a polycyclic alicyclic group, a norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, tetracyclododecyl group etc. are mentioned.

Examples of the (meth)acrylic acid ester having a group having an alicyclic skeleton include compounds represented by the following formulas (b2-1) to (b2-8). Among these, compounds represented by the following formulas (b2-3) to (b2-8) are preferable, and compounds represented by the following formulas (b2-3) or (b2-4) are more preferable.

[Tue 24]

[Tue 25]

In the above formula, R ^b10 represents a hydrogen atom or a methyl group, R ^b11 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^b12 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Shows. R ^b11 is preferably a single bond, straight or branched alkylene group, for example, a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^b12 , a methyl group and an ethyl group are preferable.

Examples of (meth)acrylamides include (meth)acrylamide, N-alkyl(meth)acrylamide, N-aryl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, N,N-aryl (Meth)acrylamide, N-methyl-N-phenyl (meth)acrylamide, N-hydroxyethyl-N-methyl (meth)acrylamide, and the like.

Examples of allyl compounds include allyl esters such as allyl acetate, allyl capric acid, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, and allyl lactic acid; allyloxyethanol; And the like.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl Vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl And aliphatic vinyl ethers such as ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl aryl ethers such as vinyl anthranyl ether; and the like. .

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, vinyl chloro acetate, vinyl dichloro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl phenyl And acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, and vinyl naphthoate.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, and trifluoro Alkyl styrene such as methyl styrene, ethoxy methyl styrene and acetoxy methyl styrene; Alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; Chloro styrene, dichloro styrene, trichloro styrene, tetra Chlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodinestyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoro Halostyrenes such as romethylstyrene; and the like.

The molecular weight of the epoxy group-containing resin (B2-2) is not particularly limited within a range that does not impair the object of the present invention, but as a weight average molecular weight in terms of polystyrene, 3,000 to 30,000 is preferable, and 5,000 to 15,000 is more preferable.

When the polymerizable composition contains a polymerizable group-containing resin (B2), the content of the polymerizable group-containing resin (B2) is preferably 1 to 50% by mass, and 5 to 40% by mass relative to the total mass of the solid content of the polymerizable composition. % Is more preferred. By setting it as the said range, there exists a tendency for balance of sensitivity, developability, and resolution to be easy to take.

Moreover, when using together the polyfunctional polymerizable monomer (B1) and the polymerizable group-containing resin (B2), the sum of both contents is preferably 1 to 50% by mass relative to the total mass of the solid content of the polymerizable composition, and 5 to 5 40 mass% is more preferable.

<Polymerization initiator (C)>

The polymerization initiator (C) is not particularly limited as long as the polymerization reaction of the polymerizable group-containing component in the polymerizable composition can proceed. Typically, a compound used as a photopolymerization initiator in various photosensitive compositions can be used without particular limitation.

Specifically as the polymerization initiator (C), 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl ]-2-hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecyl Phenyl)-2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis(4-dimethylaminophenyl)ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, O -Acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitro-9H-carbazol-3-yl) [4-(2-methoxy-1-methylethoxy)-2-methylphenyl]methanone O-acetyloxime, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octa Paddy, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid butyl, 4-dimethylamino-2-ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyl dimethyl ketal, 1-phenyl-1,2-propanedione -2-(O-ethoxycarbonyl)oxime, methyl o-benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4 -Propoxytoxyoxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octa Methylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, 2-mercaptobenzoimidazole, 2-mercaptobenzo Oxazole, 2-mercaptobenzothiazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)-imidazolyl dimer, benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl , Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxyacetophenone , p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p -tert-butyldichloroacetophenone, α,α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethyl Aminobenzoate, 9-phenylacridine, 1,7-bis-(9-acridinyl)heptane, 1,5-bis-(9-acridinyl)pentane, 1,3-bis-(9- Acridinyl)propane, p-methoxytriazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine , 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl ]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s -Triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4, 6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-n-butoxy Phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2 ,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-me Ethoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, and the like. These polymerization initiators may be used alone or in combination of two or more.

Among these, it is particularly preferable from the viewpoint of sensitivity to use an oxime-based polymerization initiator. Among the oxime-based polymerization initiators, particularly preferred are O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, ethanone,1-[ 9-ethyl-6-(pyrrole-2-ylcarbonyl)-9H-carbazol-3-yl],1-(O-acetyloxime) and 2-(benzoyloxyimino)-1-[4-(phenyl Thio)phenyl]-1-octanone.

Moreover, when the polymerizable group is an epoxy group-containing organic group, a photosensitive cationic polymerization initiator such as an iodonium salt or a sulfonium salt can also be used as the polymerization initiator (C).

It is also preferable to use an oxime-based compound represented by the following formula (c1) as the polymerization initiator (C).

[Tue 26]

(R ^c1 is a group selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups and cyano groups,

n1 is an integer from 0 to 4,

n2 is 0 or 1,

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent,

R ^c3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In the formula (c1), R ^c1 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Suitable examples when R ^c1 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, and a phenoxy group which may have a substituent. , Benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthock which may have a substituent Timing, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, amino group , Amino group substituted with 1 or 2 organic groups, morpholine-1-yl and piperazin-1-yl groups, halogen, nitro and cyano groups. When n1 is an integer of 2 to 4, R ^c1 may be the same or different. In addition, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the substituent.

When R ^c1 is an alkyl group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Moreover, when R ^c1 is an alkyl group, it may be linear or branched. Specific examples when R ^c1 is an alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isophene Tyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n -Decyl group and isodecyl group. Moreover, when R ^c1 is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When R ^c1 is an alkoxy group, 1 to 20 carbon atoms are preferable, and 1 to 6 carbon atoms are more preferable. Moreover, when R ^c1 is an alkoxy group, it may be linear or branched. Specific examples when R ^c1 is an alkoxy group are methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy Group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group. Moreover, when R ^c1 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group and methoxy And propyloxy groups.

When R ^c1 is a cycloalkyl group or a cycloalkoxy group, 3 to 10 carbon atoms are preferable, and 3 to 6 carbon atoms are more preferable. Specific examples when R ^c1 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ^c1 is a cycloalkoxy group include cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, and cyclooctyloxy group.

When R ^c1 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c1 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, and n-hexanoyl group , n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n -Pentadecanoyl group and n-hexadecanoyl group. Specific examples when R ^c1 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropano Iloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, and n-tridecanoyloxy groups, n-tetradecanoyloxy groups, n-pentadecanoyloxy groups, and n-hexadecanoyloxy groups.

When R ^c1 is an alkoxycarbonyl group, 2 to 20 carbon atoms are preferable, and 2 to 7 carbon atoms are more preferable. Specific examples when R ^c1 is an alkoxycarbonyl group are methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert- Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, and sec-octyloxycarbonyl groups, tert-octyloxycarbonyl groups, n-nonyloxycarbonyl groups, isononyloxycarbonyl groups, n-decyloxycarbonyl groups, and isodecyloxycarbonyl groups.

When R ^c1 is a phenylalkyl group, 7 to 20 carbon atoms are preferable, and 7 to 10 carbon atoms are more preferable. Moreover, when R ^c1 is a naphthyl alkyl group, 11-20 carbon atoms are preferable, and 11-14 carbon atoms are more preferable. Specific examples when R ^c1 is a phenylalkyl group include a benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. Specific examples when R ^c1 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. When R ^c1 is a phenylalkyl group or a naphthylalkyl group, R ^c1 may further have a substituent on the phenyl group or the naphthyl group.

When R ^c1 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, and O, or a heterocyclyl group condensed between these monocyclic groups or such a monocyclic ring and a benzene ring. . When the heterocyclyl group is a condensed ring, it is assumed to have up to 3 rings. The heterocycles constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyri Midine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, prof Thalazine, synnoline, and quinoxaline. When R ^c1 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c1 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic group having 2 to 20 carbon atoms. Actual group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent And a naphthyl alkyl group having 11 to 20 carbon atoms and a heterocyclyl group. Specific examples of these suitable organic ^groups are the same as R ^c1 . Specific examples of the amino group substituted with the organic group of 1 or 2 are methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta Noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group and β-naphthoylamino group. Can.

As a substituent when the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 7 carbon atoms Saturated aliphatic acyl group, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, alkyl group having 1 to 6 carbon atoms Dialkylamino group, morpholine-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, etc. are mentioned. When the phenyl group, the naphthyl group, and the heterocyclyl group included in R ^c1 further have a substituent, the number of the substituents is not limited within the range not impairing the object of the present invention, but 1 to 4 is preferred. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c1 have a plurality of substituents, the plurality of substituents may be the same or different.

In R ^c1 , from the point of chemical stability, little steric hindrance, and easy synthesis of an oxime ester compound, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a number of carbon atoms A group selected from the group consisting of 2 to 7 saturated aliphatic acyl groups is preferable, alkyl having 1 to 6 carbon atoms is more preferable, and a methyl group is particularly preferable.

R ^c1 is a position bonded to the phenyl group with respect to the group which the R ^c1 bond, a phenyl group and the oxime if over the position of the coupling hand of the main skeleton of the ester compound No. 1 and 2 the position of the methyl group, and 4 above, or 5 The stomach is preferred, and the fifth is more preferred. Moreover, n1 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and 0 or 1 is particularly preferable.

R ^c2 is a phenyl group which may have a substituent or a carbazolyl group which may have a substituent. Moreover, when R ^c2 is a carbazolyl group which may have a substituent, the nitrogen atom on the carbazolyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

In R ^c2 , the substituent group of the phenyl group or carbazolyl group is not particularly limited within a range not impairing the object of the present invention. Examples of suitable substituents that the phenyl group or carbazolyl group may have on the carbon atom include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a number of carbon atoms. 3 to 10 cycloalkoxy group, 2 to 20 carbon atoms saturated aliphatic acyl group, 2 to 20 carbon atoms alkoxycarbonyl group, 2 to 20 carbon atoms saturated aliphatic acyloxy group, a phenyl group which may have a substituent, A phenoxy group which may have a substituent, a phenylthio group which may have a substituent, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a benzoyloxy group which may have a substituent, and a carbon atom which may have a substituent The number 7-20 phenylalkyl group, the naphthyl group which may have a substituent, the naphthoxy group which may have a substituent, the naphthoyl group which may have a substituent, the naphthoxycarbonyl group which may have a substituent, and naphtho which may have a substituent Iloxy group, a naphthyl alkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, a heterocyclylcarbonyl group which may have a substituent, an amino group, or an amino group substituted with an organic group of 1 or 2 , Morpholine-1-yl group and piperazin-1-yl group, halogen, nitro group and cyano group.

When R ^c2 is a carbazolyl group, examples of suitable substituents that the carbazolyl group may have on the nitrogen atom include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and 2 to 20 carbon atoms. Of saturated aliphatic acyl groups, alkoxycarbonyl groups having 2 to 20 carbon atoms, phenyl groups which may have substituents, benzoyl groups which may have substituents, phenoxycarbonyl groups which may have substituents, and 7 to 7 carbon atoms which may have substituents. 20 phenylalkyl group, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a substituent The heterocyclyl group which may have, and the heterocyclylcarbonyl group which may have a substituent are mentioned. Among these substituents, an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

Regarding specific examples of the substituent which the phenyl group or carbazolyl group may have, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, an alkoxycarbonyl group, a saturated aliphatic acyloxy group, a phenylalkyl group which may have a substituent, The naphthylalkyl group which may have a substituent, the heterocyclyl group which may have a substituent, and the amino group substituted with the organic group of 1 or 2 are the same as R ^c1 .

In R ^c2 , examples of the substituent when the phenyl group, the naphthyl group, and the heterocyclyl group included in the substituent having the phenyl group or carbazolyl group further have a substituent include an alkyl group having 1 to 6 carbon atoms; Alkoxy group of 6; saturated aliphatic acyl group having 2 to 7 carbon atoms; alkoxycarbonyl group having 2 to 7 carbon atoms; saturated aliphatic acyloxy group having 2 to 7 carbon atoms; phenyl group; naphthyl group; benzoyl group; naphtho Diary; benzoyl group substituted by a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; mono having an alkyl group having 1 to 6 carbon atoms Alkylamino groups; dialkylamino groups having an alkyl group having 1 to 6 carbon atoms; morpholine-1-yl group; piperazin-1-yl group; halogen; nitro group; cyano group. When a phenyl group, a naphthyl group, and a heterocyclyl group included in a substituent having a phenyl group or a carbazolyl group further has a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but 1-4 desirable. When a phenyl group, a naphthyl group, and a heterocyclyl group have a plurality of substituents, the plurality of substituents may be the same or different.

From R ^c2 , since it is easy to obtain a polymerization initiator excellent in sensitivity, the group represented by the following formula (c2) or (c3) is preferable, and the group represented by the following formula (c2) is more preferable, and the following formula (c2) As the group represented by, a group in which A is S is particularly preferable.

[Tue 27]

(R ^c4 is a group selected from the group consisting of monovalent organic groups, amino groups, halogens, nitro groups and cyano groups, A is S or O, and n3 is an integer from 0 to 4.)

[Tue 28]

(R ^c5 and R ^c6 are each a monovalent organic group.)

When R ^c4 in the formula (c2) is an organic group, it can be selected from various organic groups within a range that does not impair the object of the present invention. Suitable examples when R ^c4 is an organic group in the formula (c2) include an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a saturated aliphatic acyl group having 2 to 7 carbon atoms; and a number of carbon atoms. 2 to 7 alkoxycarbonyl groups; 2 to 7 saturated aliphatic acyloxy groups with carbon atoms; phenyl groups; naphthyl groups; benzoyl groups; naphthoyl groups; alkyl groups with 1 to 6 carbon atoms, morpholine-1-yl groups, piperazine A benzoyl group substituted by a group selected from the group consisting of -1-yl groups and phenyl groups; monoalkylamino groups having an alkyl group having 1 to 6 carbon atoms; dialkylamino groups having an alkyl group having 1 to 6 carbon atoms; morpholine- 1-diary; piperazine-1-diary; halogen; nitro group; cyano group.

Among R ^c4 , a benzoyl group substituted with a group selected from the group consisting of a benzoyl group; a naphthoyl group; an alkyl group having 1 to 6 carbon atoms, a morpholine-1-yl group, a piperazin-1-yl group, and a phenyl group; a nitro group The benzoyl group; naphthoyl group; 2-methylphenylcarbonyl group; 4-(piperazin-1-yl)phenylcarbonyl group; 4-(phenyl)phenylcarbonyl group is more preferable.

Moreover, in Formula (c2), n3 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and particularly preferably 0 or 1. if n3 is 1, the binding position of R ^c4 are for the combined hand a phenyl group that is R ^c4 bond with oxygen atom or sulfur atom, preferably in the para position.

R ^c5 in the formula (c3) can be selected from various organic groups within a range that does not impair the object of the present invention. Suitable examples of R ^c5 include alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, saturated aliphatic acyl groups having 2 to 20 carbon atoms, alkoxycarbonyl groups having 2 to 20 carbon atoms, and substituents A phenyl group which may be substituted, a benzoyl group which may have a substituent, a phenoxycarbonyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, and a naph which may have a substituent A soil group, a naphthoxycarbonyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, a heterocyclyl group which may have a substituent, and a heterocyclylcarbonyl group which may have a substituent. Can be.

Among R ^c5 , an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an ethyl group is particularly preferable.

R ^c6 in the formula (c3) is not particularly limited within a range that does not impair the object of the present invention, and can be selected from various organic groups. Specific examples of the group suitable as R ^c6 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. As R ^c6 , among these groups, a phenyl group which may have a substituent is more preferable, and a 2-methylphenyl group is particularly preferable.

As a substituent when the phenyl group, naphthyl group, and heterocyclyl group included in R ^c4 , R ^c5 or R ^c6 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon Monoalkylamino group having a saturated aliphatic acyl group having 2 to 7 atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and a carbon atom And dialkylamino groups having an alkyl group having 1 to 6, morpholine-1-yl, piperazin-1-yl, halogen, nitro and cyano groups. When a phenyl group, a naphthyl group, and a heterocyclyl group included in R ^c4 , R ^c5 or R ^c6 further has a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but 1 to 4 is desirable. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c4 , R ^c5 or R ^c6 have a plurality of substituents, the plurality of substituents may be the same or different.

R ^c3 in Formula (c1) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. As R ^c3 , a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

Among the oxime ester compounds represented by the formula (c1), the following PI-1 to PI-42 are particularly preferable compounds.

[Tue 29]

[Tue 30]

[Tue 31]

[Tue 32]

[Tue 33]

[Tue 34]

Moreover, the oxime ester compound represented by following formula (c4) is also preferable as a polymerization initiator (C).

[Tue 35]

(R ^c7 is a hydrogen atom, a nitro group or a monovalent organic group, R ^c8 and R ^c9 are each a linear alkyl group which may have a substituent, a cyclic organic group or a hydrogen atom which may have a substituent, and R ^c8 and R ^c9 are They may combine with each other to form a ring, R ^c10 is a monovalent organic group, R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent or an aryl group which may have a substituent, and n4 is 0 It is an integer of ~4, and n5 is 0 or 1.)

Here, a compound represented by the following formula (c5) is suitable as the oxime compound for preparing the oxime ester compound of formula (c4).

[Tue 36]

(R ^c7 , R ^c8 , R ^c9 , R ^c10 , n4 and n5 are the same as in formula (c4).)

In formulas (c4) and (c5), R ^c7 is a hydrogen atom, a nitro group, or a monovalent organic group. R ^c7 is bonded to a 6-membered aromatic ring different from a 6-membered aromatic ring which is bonded to a group represented by -(CO) _n5 -on the fluorene ring in formula (c4). In the formula (c4), the binding position of R ^{c7 to} the fluorene ring is not particularly limited. When the compound represented by the formula (c4) has one or more R ^c7 , the synthesis of the compound represented by the formula (c4) is easy, such that one of the one or more R ^c7 is bonded to the second position in the fluorene ring. desirable. When R ^c7 is plural, plural R ^c7 may be the same or different.

When R ^c7 is an organic group, R ^c7 is not particularly limited as long as it does not impair the object of the present invention, and is appropriately selected from various organic groups. Suitable examples when R ^c7 is an organic group include an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkoxy group, a saturated aliphatic acyl group, a saturated aliphatic acyloxy group, an alkoxycarbonyl group, a phenyl group which may have a substituent, and a phenoxy group which may have a substituent. , Benzoyl group which may have a substituent, phenoxycarbonyl group which may have a substituent, benzoyloxy group which may have a substituent, phenylalkyl group which may have a substituent, naphthyl group which may have a substituent, naphthock which may have a substituent Timing, naphthoyl group which may have a substituent, naphthoxycarbonyl group which may have a substituent, naphthyloxy group which may have a substituent, naphthylalkyl group which may have a substituent, heterocyclyl group which may have a substituent, substituent And an amino group substituted with an organic group of 1 or 2, a morpholine-1-yl group, and a piperazin-1-yl group.

When R ^c7 is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1-20, and more preferably 1-6. Moreover, when R ^c7 is an alkyl group, it may be linear or branched. Specific examples when R ^c7 is an alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isophene Tyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n -Decyl group and isodecyl group. Moreover, when R ^c7 is an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When R ^c7 is an alkoxy group, the number of carbon atoms in the alkoxy group is preferably 1-20, more preferably 1-6. Moreover, when R ^c7 is an alkoxy group, it may be linear or branched. Specific examples when R ^c7 is an alkoxy group are methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group , n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octyloxy Group, tert-octyloxy group, n-nonyloxy group, isononyloxy group, n-decyloxy group and isodecyloxy group. Moreover, when R ^c7 is an alkoxy group, the alkoxy group may contain the ether bond (-O-) in a carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, propyloxyethoxyethoxy group and methoxy And propyloxy groups.

When R ^c7 is a cycloalkyl group or a cycloalkoxy group, the number of carbon atoms in the cycloalkyl group or cycloalkoxy group is preferably 3 to 10, and more preferably 3 to 6. Specific examples when R ^c7 is a cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples when R ^c7 is a cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

When R ^c7 is a saturated aliphatic acyl group or a saturated aliphatic acyloxy group, the number of carbon atoms in the saturated aliphatic acyl group or saturated aliphatic acyloxy group is preferably 2 to 21, and more preferably 2 to 7. Specific examples when R ^c7 is a saturated aliphatic acyl group include an acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, and n-hexanoyl group , n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n -Pentadecanoyl group and n-hexadecanoyl group. Specific examples when R ^c7 is a saturated aliphatic acyloxy group include acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropano Iloxy group, n-hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, and n-tridecanoyloxy groups, n-tetradecanoyloxy groups, n-pentadecanoyloxy groups, and n-hexadecanoyloxy groups.

When R ^c7 is an alkoxycarbonyl group, the number of carbon atoms in the alkoxycarbonyl group is preferably 2-20, and more preferably 2-7. Specific examples when R ^c7 is an alkoxycarbonyl group are methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert- Butyloxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, and sec-octyloxycarbonyl groups, tert-octyloxycarbonyl groups, n-nonyloxycarbonyl groups, isononyloxycarbonyl groups, n-decyloxycarbonyl groups, and isodecyloxycarbonyl groups.

When R ^c7 is a phenylalkyl group, the number of carbon atoms in the phenylalkyl group is preferably 7 to 20, and more preferably 7 to 10. Moreover, when R ^c7 is a naphthyl alkyl group, ^11-20 are preferable and, as for the carbon atom number of a naphthyl alkyl group, 11-14 are more preferable. Specific examples when R ^c7 is a phenylalkyl group include a benzyl group, 2-phenylethyl group, 3-phenylpropyl group, and 4-phenylbutyl group. Specific examples when R ^c7 is a naphthylalkyl group include α-naphthylmethyl group, β-naphthylmethyl group, 2-(α-naphthyl)ethyl group, and 2-(β-naphthyl)ethyl group. When R ^c7 is a phenylalkyl group or a naphthylalkyl group, R ^c7 may further have a substituent on the phenyl group or a naphthyl group.

When R ^c7 is a heterocyclyl group, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing 1 or more N, S, O, or a heterocyclyl group condensed between these monocyclic groups or such a monocyclic ring and a benzene ring. . When the heterocyclyl group is a condensed ring, it is assumed to have up to 3 rings. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. The heterocycles constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyri Midine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, prof Thalazine, cynolin, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran and tetrahydrofuran. When R ^c7 is a heterocyclyl group, the heterocyclyl group may further have a substituent.

When R ^c7 is a heterocyclylcarbonyl group, the heterocyclyl group included in the heterocyclylcarbonyl group is the same as when R ^c7 is a heterocyclyl group.

When R ^c7 is an amino group substituted with an organic group of 1 or 2, suitable examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a saturated aliphatic group having 2 to 21 carbon atoms. Actual group, a phenyl group which may have a substituent, a benzoyl group which may have a substituent, a phenylalkyl group having 7 to 20 carbon atoms which may have a substituent, a naphthyl group which may have a substituent, a naphthoyl group which may have a substituent, and a substituent And a naphthyl alkyl group having 11 to 20 carbon atoms and a heterocyclyl group. Specific examples of these suitable organic ^groups are the same as R ^c7 . Specific examples of the amino group substituted with the organic group of 1 or 2 are methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, n-butylamino group, di-n-butyl Amino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthylamino group, acetylamino group, propanoylamino group, n-buta Noylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-decanoylamino group, benzoylamino group, α-naphthoylamino group and β-naphthoylamino group. Can.

When a phenyl group, a naphthyl group, or a heterocyclyl group included in R ^c7 further has a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 7 carbon atoms Saturated aliphatic acyl group, alkoxycarbonyl group having 2 to 7 carbon atoms, saturated aliphatic acyloxy group having 2 to 7 carbon atoms, monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, alkyl group having 1 to 6 carbon atoms Dialkylamino group, morpholine-1-yl group, piperazin-1-yl group, halogen, nitro group, cyano group, etc. are mentioned. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c7 further has a substituent, the number of the substituents is not limited within a range that does not impair the object of the present invention, but 1 to 4 is preferred. When the phenyl group, naphthyl group, and heterocyclyl group included in R ^c7 have a plurality of substituents, the plurality of substituents may be the same or different.

Among the groups described above, R ^c7 is preferably a nitro group or a group represented by R ^c12 -CO-, which tends to improve sensitivity and is preferable. R ^c12 is not particularly limited as long as it does not impair the object of the present invention, and can be selected from various organic groups. Examples of suitable groups as R ^c12 include an alkyl group having 1 to 20 carbon atoms, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, and a heterocyclyl group which may have a substituent. Among these groups, R ^c12 is particularly preferably a 2-methylphenyl group, a thiophen-2-yl group, or an α-naphthyl group.

Moreover, when R ^c7 is a hydrogen atom, transparency tends to be good and is preferable. Moreover, when R ^c7 is a hydrogen atom and R ^c10 is a group represented by the following formula (c4a) or (c4b), transparency tends to be better.

In formula (c4), R ^c8 and R ^c9 are each a chain alkyl group which may have a substituent, a cyclic organic group which may have a substituent, or a hydrogen atom. R ^c8 and R ^c9 may combine with each other to form a ring. Among these groups, a chain alkyl group which may have a substituent as R ^c8 and R ^c9 is preferable. When R ^c8 and R ^c9 are a chain alkyl group which may have a substituent, the chain alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

When R ^c8 and R ^c9 are a chain alkyl group having no substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Specific examples when R ^c8 and R ^c9 are a chain alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pen Tyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, iso And nonyl groups, n-decyl groups, and isodecyl groups. Moreover, when R ^c8 and R ^c9 are an alkyl group, the alkyl group may contain the ether bond (-O-) in a carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propyloxyethoxyethyl group and methoxypropyl group.

When R ^c8 and R ^c9 are a chain alkyl group having a substituent, the number of carbon atoms in the chain alkyl group is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. In this case, the number of carbon atoms in the substituent is not included in the number of carbon atoms in the chain alkyl group. It is preferable that the chain alkyl group which has a substituent is linear.

The substituent which an alkyl group may have is not specifically limited in the range which does not inhibit the objective of this invention. Suitable examples of substituents include cyano groups, halogen atoms, cyclic organic groups and alkoxycarbonyl groups. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, fluorine atom, chlorine atom and bromine atom are preferable. Cycloalkyl group, aromatic hydrocarbon group, heterocyclyl group is mentioned as a cyclic organic group. The specific example of a cycloalkyl group is the same as a suitable example when R ^c7 is a cycloalkyl group. Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, anthryl group, and phenanthryl group. Specific examples of the heterocyclyl group are the same as suitable examples when R ^c7 is a heterocyclyl group. When R ^c7 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and linear is preferable. The number of carbon atoms in the alkoxy group contained in the alkoxycarbonyl group is preferably 1 to 10, and more preferably 1 to 6.

When a chain alkyl group has a substituent, the number of substituents is not specifically limited. The preferred number of substituents varies depending on the number of carbon atoms in the chain alkyl group. The number of substituents is typically 1 to 20, preferably 1 to 10, and more preferably 1 to 6.

When R ^c8 and R ^c9 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group. Examples of the cyclic organic group include aliphatic cyclic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclyl groups. When R ^c8 and R ^c9 are cyclic organic groups, the substituents which the cyclic organic group may have are the same as those of R ^c8 and R ^c9 chain alkyl groups.

When R ^c8 and R ^c9 are aromatic hydrocarbon groups, the aromatic hydrocarbon group is preferably a phenyl group, a group formed by bonding a plurality of benzene rings through a carbon-carbon bond, or a group formed by condensation of a plurality of benzene rings. When the aromatic hydrocarbon group is a phenyl group or a group formed by bonding or condensation of a plurality of benzene rings, the number of rings of the benzene ring contained in the aromatic hydrocarbon group is not particularly limited, 3 or less is preferable, 2 or less is more preferable, and 1 is particularly desirable. Preferred specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, anthryl group and phenanthryl group.

When R ^c8 and R ^c9 are aliphatic cyclic hydrocarbon groups, the aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. Although the number of carbon atoms of an aliphatic cyclic hydrocarbon group is not specifically limited, 3-20 are preferable and 3-10 are more preferable. Examples of the monocyclic cyclic hydrocarbon group are cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group , Tetracyclododecyl group and adamantyl group.

When R ^c8 and R ^c9 are heterocyclyl groups, the heterocyclyl group is a 5-membered or 6-membered monocyclic ring containing one or more N, S, O, or heterocycles condensed between these monocyclic groups or such a monocyclic ring and a benzene ring. It is a krill group. When the heterocyclyl group is a condensed ring, it is assumed to have up to 3 rings. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group. The heterocycles constituting such heterocyclyl groups include furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyri Midine, pyridazine, benzofuran, benzothiophene, indole, isoindole, indolizine, benzoimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, prof Thalazine, cynolin, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran and tetrahydrofuran.

R ^c8 and R ^c9 may combine with each other to form a ring. The group consisting of rings formed by R ^c8 and R ^c9 is preferably a cycloalkylidene group. When R ^c8 and R ^c9 are combined to form a cycloalkylidene group, the ring constituting the cycloalkylidene group is preferably a 5- to 6-membered ring, and more preferably a 5-membered ring.

When the group formed by bonding of R ^c8 and R ^c9 is a cycloalkylidene group, the cycloalkylidene group may be condensed with one or more other rings. Examples of the ring which may be condensed with a cycloalkylidene group include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a furan ring, a thiophene ring, a pyrrole ring, and a pyridine ring , Pyrazine ring and pyrimidine ring.

Examples of suitable groups among R ^c8 and R ^c9 described above include groups represented by formula -A ¹ -A ² . In the formula, A ¹ is a straight chain alkylene group, and A ² is an alkoxy group, cyano group, halogen atom, halogenated alkyl group, cyclic organic group or alkoxycarbonyl group.

The number of carbon atoms in the straight-chain alkylene group of A ¹ is preferably 1 to 10, and more preferably 1 to 6. When A ² is an alkoxy group, the alkoxy group may be linear or branched, and linear is preferable. The number of carbon atoms in the alkoxy group is preferably 1 to 10, and more preferably 1 to 6. When A ² is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable, and a fluorine atom, a chlorine atom, and a bromine atom are more preferable. When A ² is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom, a chlorine atom or a bromine atom. The halogenated alkyl group may be linear or branched, and linear is preferred. When A ² is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ^c8 and R ^c9 have as a substituent. When A ² is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups R ^c8 and R ^c9 have as substituents.

Suitable examples of R ^c8 and R ^c9 include alkyl groups such as ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-heptyl group and n-octyl group; 2-methoxyethyl group, 3-methy Methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group, 8-methoxy Methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n- Alkoxyalkyl groups such as hexyl group, 7-ethoxy-n-heptyl group and 8-ethoxy-n-octyl group; 2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n- Cyanoalkyl groups such as butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group and 8-cyano-n-octyl group;2- Phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group and 8- Phenylalkyl groups such as phenyl-n-octyl group; 2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclo Hexyl-n-hexyl group, 7-cyclohexyl-n-heptyl group, 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n- Cycloalkyl alkyl groups such as butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl-n-hexyl group, 7-cyclopentyl-n-heptyl group and 8-cyclopentyl-n-octyl group;2- Methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n -Hexyl group, 7-methoxycarbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4- Ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n-pentyl group, 6-ethoxycarbonyl-n-hexyl group, 7-ethoxycarbonyl-n-heptyl group and 8-ethoxy Alkoxycarbonylalkyl groups such as carbonyl-n-octyl group; 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro- n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n- Octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7 -Bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5-heptafluoro-n And halogenated alkyl groups such as -pentyl group.

Among R ^c8 and R ^c9 , suitable groups among the above are ethyl group, n-propyl group, n-butyl group, n-pentyl group, 2-methoxyethyl group, 2-cyanoethyl group, 2-phenylethyl group, 2-cyclohexylethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group and 3,3,4,4,5,5,5-heptafluoro-n -It is a pentyl group.

Examples of suitable organic groups for R ^c10 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, phenyl groups which may have substituents, and substituents, similar to R ^c7 Phenoxy group which may be substituted, benzoyl group which may have substituent, phenoxycarbonyl group which may have substituent, benzoyloxy group which may have substituent, phenylalkyl group which may have substituent, naphthyl group which may have substituent, and substituent A naphthoxy group which may be used, a naphthyl group which may have a substituent, a naphthoxycarbonyl group which may have a substituent, a naphthyloxy group which may have a substituent, a naphthylalkyl group which may have a substituent, a heterocy which may have a substituent And a krill group, a heterocyclylcarbonyl group which may have a substituent, an amino group substituted with an organic group of 1 or 2, a morpholine-1-yl group, and a piperazin-1-yl group. Specific examples of these groups are the same as those described for R ^c7 . Moreover, as R ^c10 , a cycloalkyl alkyl group, a phenoxyalkyl group which may have a substituent on the aromatic ring, and a phenylthioalkyl group which may have a substituent on the aromatic ring are also preferable. The substituent which the phenoxyalkyl group and the phenylthioalkyl group may have is the same as the substituent which the phenyl group contained in R ^c7 may have.

Among organic groups, R ^c10 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, or a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group. Among the phenyl groups which may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable. The number of carbon atoms in the cycloalkyl group included in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and particularly preferably 5 or 6. 1-8 are preferable, as for the carbon atom number of the alkylene group contained in a cycloalkyl alkyl group, 1-4 are more preferable, and 2 is especially preferable. Among the cycloalkyl alkyl groups, a cyclopentyl ethyl group is preferable. As for the number of carbon atoms of the alkylene group contained in the phenylthioalkyl group which may have a substituent on the aromatic ring, 1-8 are preferable, 1-4 are more preferable, and 2 is especially preferable. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2-(4-chlorophenylthio)ethyl group is preferable.

Moreover, the group represented by -A ³ -CO-OA ⁴ is also preferable as R ^c10 . A ³ is a divalent organic group, preferably a divalent hydrocarbon group, and preferably an alkylene group. A ⁴ is a monovalent organic group, and is preferably a monovalent hydrocarbon group.

When A ³ is an alkylene group, the alkylene group may be linear or branched, and linear is preferable. When A ³ is an alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.

Suitable examples of A ⁴ include alkyl groups having 1 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. Suitable examples of A ⁴ are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, And phenyl groups, naphthyl groups, benzyl groups, phenethyl groups, α-naphthylmethyl groups, and β-naphthylmethyl groups.

Suitable examples of the group represented by -A ³ -CO-OA ⁴ include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n-butyloxy Carbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n- Propyl group, 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycar And a carbonyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl-n-propyl group, and 3-phenoxycarbonyl-n-propyl group. .

As mentioned above, although R ^c10 has been described, a group represented by the following formula (c4a) or (c4b) is preferable as R ^c10 .

[Tue 37]

(In the formulas (c4a) and (c4b), R ^c13 and R ^c14 are each an organic group, n6 is an integer from 0 to 4, and when R ^c13 and R ⁸ are in adjacent positions on the benzene ring, R ^c13 And R ^c14 may combine with each other to form a ring, n7 is an integer from 1 to 8, n8 is an integer from 1 to 5, n9 is an integer from 0 to (n8+3), and R ^c15 is an organic group.)

^Examples of the organic ^group for R ^c13 and R ^c14 in the formula (c4a) are the same as R ^c7 . As R ^{c13, an} alkyl group or a phenyl group is preferable. When R ^c13 is an alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, 1 to 3 is particularly preferred, and 1 is most preferred. That is, R ^c13 is most preferably a methyl group. When R ^c13 and R ^c14 combine to form a ring, the ring may be an aromatic ring or an aliphatic ring. As a group represented by formula (c4a), suitable examples of the group in which R ^c13 and R ^c14 form a ring include a naphthalen-1-yl group, 1,2,3,4-tetrahydronaphthalen-5-yl group, and the like. Can be. In the formula (c4a), n6 is an integer from 0 to 4, preferably 0 or 1, and more preferably 0.

In the formula (c4b), R ^c15 is an organic group. ^Examples of the organic group include the same groups as the organic group described for R ^c7 . Among organic groups, alkyl groups are preferred. The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. As R ^c15 , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and the like are preferably exemplified, and among these, a methyl group is more preferable.

In the formula (c4b), n8 is an integer from 1 to 5, an integer from 1 to 3 is preferable, and 1 or 2 is more preferable. In said formula (c4b), n9 is 0-(n8+3), the integer of 0-3 is preferable, the integer of 0-2 is more preferable, and 0 is especially preferable. In said formula (c4b), n7 is an integer of 1-8, the integer of 1-5 is preferable, the integer of 1-3 is more preferable, and 1 or 2 is especially preferable.

In the formula (c4), R ^c11 is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms which may have a substituent, or an aryl group which may have a substituent. As a substituent which may be taken when R ^c11 is an alkyl group, a phenyl group, a naphthyl group, or the like is preferably exemplified. Moreover, as a substituent which may be taken when R ^c7 is an aryl group, a C1-C5 alkyl group, an alkoxy group, a halogen atom, etc. are illustrated preferably.

In the formula (c4), R ^c11 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, or a naphthyl group, and among them, a methyl group Or a phenyl group is more preferable.

The compound represented by the formula (c4) is a step of converting the oxime group (>C=N-OH) contained in the compound represented by the formula (c5) described above into an oxime ester group represented by >C=NO-COR ^c11 . It is manufactured by a method including. R ^c11 and R ^c11 are the same as in the formula (c4).

The conversion of the oxime group (>C=N-OH) to the oxime ester group represented by >C=NO-COR ^c11 is performed by reacting the compound represented by the formula (c5) with an acylating agent.

Examples of the acylating agent that provides an acyl group represented by -COR ^c11 include an acid anhydride represented by (R ^c11 CO) ₂ O, or an acid halide represented by R ^c11 COHal (Hal is a halogen atom).

The following specific examples of the compound represented by the formula (c4) include PI-43 to PI-83.

[Tue 38]

[Tue 39]

It is preferable that content of a polymerization initiator (C) is 0.5-30 mass% with respect to the mass of the whole solid content of a polymerizable composition, and it is more preferable that it is 1-20 mass %. When the content of the polymerization initiator (C) is within the above range, a polymerizable composition in which pattern-like defects are unlikely to be produced can be obtained.

Moreover, you may combine a photoinitiator with the polymerization initiator (C). As a photoinitiator, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, benzoic acid 2-dimethylaminoethyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10 -Diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxy And thiol compounds such as benzothiazole, 3-mercaptopropionic acid, methyl 3-mercaptopropionic acid, pentaerythritol tetramercaptoacetate, and 3-mercaptopropionate. These photoinitiators may be used alone or in combination of two or more.

<pillar (D)>

The polymerizable composition includes a filler (D). The filler (D) includes at least one selected from the group consisting of an inorganic filler (D1) and a basic filler (D2). The inorganic filler (D1) and the basic filler (D2) will be described later in detail.

Since the polymerizable composition contains a silsesquioxane resin (A) that satisfies the above-mentioned predetermined requirements, even after containing an inorganic filler (D1) or a basic filler (D2), after development during patterning according to the photolithography method Therefore, generation of residues in the unexposed portion is suppressed.

[Weapon Filler (D1)]

The inorganic filler (D1) is a group of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf and Ta, an oxide of the aforementioned element, a chelate compound of the aforementioned element, and the aforementioned It is one or more selected from the group consisting of salts of elements and alloys of the aforementioned elements.

The above elements have high electron density. For this reason, the single element, the oxide of the element, the chelate compound of the element, the salt of the element, and the alloy of the element have a high dielectric constant. Further, the simple substance of the element, the oxide of the element, the chelate compound of the element, the salt of the element, and the alloy of the element, in a film formed using a polymerizable composition, dispersed in a matrix constituting the film, visible light It is difficult to inhibit the transmission.

For this reason, the film formed using the polymerizable composition containing the above-described inorganic filler (D1) has a high dielectric constant and tends to be excellent in transparency, and can be suitably used as a transparent insulating film. Each of the simple substance of the element, the oxide of the element, the chelate compound of the element, the salt of the element and the alloy of the element can be used alone or in combination of two or more.

The valence of the element contained in the oxide of the element is not particularly limited.

In the chelating compound of the element, pyridine, triphenylphosphine, carbon monoxide, ethylenediamine, bipyridine, catechol, ethylenediamine tetraacetic acid (EDTA) and the like are mentioned as ligands for forming the element and chelate.

The salt of the element may be a salt of an inorganic acid or a salt of an organic acid. Preferred salts include halides, sulfates, nitrates, phosphates, acetates, formates, propionates and benzoates. The valence of the said element constituting the salt is not particularly limited.

The combination of metals (elements) contained in the alloy of the above elements is not particularly limited. Moreover, the mixing ratio of the some metal (element) contained in an alloy is also not specifically limited.

Of the simple substance of the element, the oxide of the element, the chelating compound of the element, the salt of the element, and the alloy of the element, the oxide is stable because it is stable in the composition, or because it is easy to form a film excellent in transparency using the polymerizable composition desirable. Suitable examples of the oxide of the element include La ₂ O ₃ , CeO ₂ , Nd ₂ O ₃ , Gd ₂ O ₃ , Ho ₂ O ₃ , Lu ₂ O ₃ , HfO ₂ and Ta ₂ O ₅ .

The shape of the inorganic filler D1 is not particularly limited. The average particle diameter of the inorganic filler (D1) is preferably 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less. When the average particle diameter of the inorganic filler (D1) is 200 nm or less, the inorganic filler (D1) is less likely to precipitate in the dispersion, and it is easy to obtain a polymerizable composition in a liquid form. Moreover, the lower limit of the average particle diameter of the inorganic filler (D1) is not particularly limited, and is preferably 40 nm or more, and more preferably 45 nm or more. When the lower limit of the average particle diameter of the inorganic filler (D1) is 40 nm or more, the surface of the inorganic filler (D1) becomes easy to coat, and the film obtained using the polymerizable composition is unlikely to lower the dielectric constant, and it is difficult to generate a leak current. Moreover, the inorganic filler (D1) is hard to aggregate.

In addition, in this specification, an average particle diameter means the volume average particle diameter measured by the dynamic light scattering measurement method (DLS).

Content of the inorganic filler (D1) in a polymerizable composition is not specifically limited in the range which does not inhibit the objective of this invention. The content of the inorganic filler (D1) in the polymerizable composition is typically 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 15 to 40 parts by mass relative to 100 parts by mass of the silicon-containing resin (A). Do.

[Basic filler (D2)]

The basic filler (D2) is at least one selected from basic fillers and basic polymers.

Hereinafter, a basic filler and a basic polymer are demonstrated in order.

(Basic filler)

The basic filler is a powdery, plate-like or short-fiber filler made of a material whose surface is basic. The basic filler may be an organic filler or an inorganic filler. The shape of the basic filler is not particularly limited, and may be in the form of a powder, a plate, or a short fiber.

The size of the basic filler is not particularly limited within a range that does not impair the object of the present invention, and may be appropriately selected in accordance with the desired pattern size or the like. The size of the basic filler is preferably 1 nm to 1500 nm, more preferably 2 to 800 nm, and even more preferably 10 nm to 100 nm as the average diameter in the case of a spherical shape. In the case of a plate shape or a short fiber shape, 5 nm to 1500 nm is preferable as the average length, and 10 nm to 100 nm is more preferable. Moreover, in the case of a fibrous form, the average aspect ratio (L1/L2) which is the ratio of the average length of the filler (L1) and the average cross-sectional diameter (L2) of the filler is not particularly limited, and 1.5 to 1000 is preferable, It is more preferable.

Examples of the base filler include basic metal carbonate, basic metal hydroxide, talc, mica, cement powder, basic active alumina, hydrotalcite, and a powder of a basic polymer described later. Examples of the basic metal carbonate include calcium carbonate and magnesium carbonate. Examples of the basic metal hydroxide include aluminum hydroxide and magnesium hydroxide.

Moreover, as a base filler, the filler whose surface was covered with the basic material, or the filler which attached the basic material to the surface may be sufficient. The property of the surface of the filler treated with a basic material is not particularly limited, and may be acidic, basic or neutral.

Examples of fillers treated with a basic material include powders of metal oxides such as silica, alumina, zirconia, mullite, spinel, and zinc oxide; powders of metal hydroxides such as aluminum hydroxide and magnesium hydroxide; calcium carbonate and carbonic acid Powders of metal carbonates such as magnesium; mica, talc, short glass fibers, short carbon fibers, potassium titanate whiskey, barium titanate whiskey, aluminum borate whiskey, titanium oxide whiskey, calcium carbonate whiskey, etc. And fillers; powders of organic resins; powders of metal particles such as iron, cobalt, nickel, copper, palladium, silver, tin, platinum, and gold.

Examples of the basic material used for the surface treatment of the filler include ammonia, an organic amine, a silane coupling agent containing a nitrogen-containing basic group, and a basic nitrogen-containing cyclic compound. Among these, a silane coupling agent containing a nitrogen-containing basic group is preferable from the viewpoint of chemically bonding to the surface of the inorganic filler. Suitable examples of such silane coupling agents include N-phenyl-γ-aminopropyltrimethoxysilane or γ-aminopropyltriethoxysilane.

Further, the treatment of the filler with a basic material may be a coating treatment with a basic polymer described later, a resin mixture containing a basic polymer, or the like. For example, after synthesizing metal particles stabilized to some extent by a lower ammonium ligand, a method of exchanging the ligand with a basic polymer or by directly reducing the metal ion of the metal in a solution of a basic polymer having an ammonium group A complex in which a basic polymer is attached or coordinated may be formed. Moreover, the powder which made the uniform composition containing a basic polymer and a filler micronized by methods, such as grinding, can also be used as a basic filler.

(Basic polymer)

As the basic polymer, various basic polymers known in the art can be used. Suitable examples of the basic polymer include polypyrrole, polyaniline and polyanilenvinylene, and derivatives of these resins.

(Meth)acrylate, vinylpyridine, vinylpyrrolidine, vinylpiperid having basic functional groups such as dimethylaminoethyl group, diethylaminoethyl group, di-n-butylaminoethyl group and N-ethyl-N-phenylaminoethyl group Having a structural bond derived from a basic unsaturated monomer such as dine, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinyllactam (N-vinylpyrrolidone, etc.) Homopolymers or copolymers of monomers are also preferred as basic polymers.

As such a basic homopolymer or copolymer, acrylic resin and styrene acrylic resin are preferable.

Resin having a carboxylic acid base exhibiting basicity such as an alkali metal salt of carboxylic acid is also mentioned as a basic polymer. Examples of the resin include resins containing structural units derived from unsaturated carboxylic acids such as (meth)acrylic acid, and resins in which the carboxyl groups of the side chains of resins containing vinyl acetic acid units are converted to basic carboxylic acid bases. have.

Moreover, the basic polymer is not limited to a polymer having a straight chain main chain. As the basic polymer, a polymer having a so-called dendrimer structure branched into a network or a water phase may also be used. When the basic polymer has a dendrimer structure, the basic functional group is preferably present in the outermost layer of the polymer.

A suitable example of a polymer having a dendrimer structure is a polymer represented by the following formula (d1).

[Tue 40]

In the formula, R ^d1 each independently represents a hydrogen atom or a methyl group. R ^d2 and R ^d3 are each independently an organic group having a basic group or a basic group at the terminal. t is an integer from 2 to 100,000.

In formula (d1), A ^d1 is a divalent group represented by the following formula (d2).

[Tue 41]

In formula (d2), A ^d2 represents an alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond. In addition, Y ^d1 , Y ^d2 , Y ^d3 and Y ^d4 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxyl group, an amino group, a carboxy group, or a cyano group. Indicates.

In the formula (d1), examples of the basic group included in R ^d2 and R ^d3 include a basic heterocyclic group such as an ammonium base and a pyridinyl group, an amino group substituted with an organic group of 1 or 2, and the like.

Ammonium salt group include ^{-N + R d4 R d5 R d6} · Z - is preferably a group represented by. R ^d4 , R ^d5 and R ^d6 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a group represented by -(CH ₂ CH ₂ O) _u -R ^d7 to be. Moreover, u is an integer of ^2-100 , and R ^d7 is a hydrogen atom or a methyl group. Any two of R ^d4 , R ^d5 and R ^d6 may combine with each other to form a ring.

Z ^- is an anion, and a halogen atom, PF ₆ ^-, BF ₄ ^- or an alkane sulphonate is preferably a perfluoroalkyl.

The amino group substituted with the organic group of 1 or 2 is preferably an alkylamino group or a dialkylamino group. The alkyl group included in the alkylamino group or dialkylamino group is preferably an alkyl group having 1 to 10 carbon atoms and a hydroxyalkyl group having 1 to 10 carbon atoms.

The group connecting the carbon atom or A ^d1 and the basic group included in R ^d2 or R ^d3 is an alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond, -O-CO-*, -S -CO-*, -S-CS-*, and the like. In addition, the bonding hand with * is a bonding hand which bonds with the basic group contained in R ^d2 or R ^d3 .

As A ^d1 in the formula (d1), a divalent group having the following structure is preferable.

[Tue 42]

That is, the compound represented by the following formula (d3) is preferable as the compound represented by the formula (d1).

[Tue 43]

In the formula (d3), R ^d1 , R ^d2 , R ^d3 and t are the same as in the formula (d1).

The basic polymer may be uniformly dissolved in the polymerizable composition, or may be uniformly dispersed in the polymerizable composition.

Content of the basic filler (D2) in a polymerizable composition is not specifically limited in the range which does not inhibit the objective of this invention. The content of the basic filler (D2) in the polymerizable composition is typically 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass, relative to 100 parts by mass of the silicon-containing resin (A). Do. Moreover, it is preferable that it is 1-30 mass% with respect to the whole solid content in a polymerizable composition, and 1.5-25 mass% is more preferable.

<Organic solvent (S)>

It is preferable that the polymerizable composition usually contains the (S) organic solvent for the purpose of adjusting coating properties and dispersing the filler (D). As such an organic solvent (S), an organic solvent conventionally blended with various photosensitive compositions can be used without particular limitation.

Suitable examples of the organic solvent (S) are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether (Poly)alkylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, di (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, Other ethers such as diethylene glycol diethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionic acid, ethyl 2-hydroxypropionic acid Lactic acid alkyl esters such as 2-hydroxy-2-methylpropionic acid ethyl, 3-methoxypropionic acid methyl, 3-methoxypropionic acid ethyl, 3-ethoxypropionic acid methyl, 3-ethoxypropionic acid ethyl, ethyl ethoxyacetic acid , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, acetic acid Ethyl, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, part Other esters, such as n-butyl tirrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-iodobutanoate; aromatic hydrocarbons such as toluene and xylene; .

Moreover, the organic solvent (S) may contain the nitrogen-containing organic solvent. In particular, when the polymerizable composition contains a basic filler (D2), it is preferable to include a nitrogen-containing organic solvent as the organic solvent (S).

In this case, aggregation or dispersion failure of the basic filler and/or the basic polymer in the polymerizable composition can be suppressed, whereby a film having a smooth cross-section or surface is easily formed using the polymerizable composition.

As long as the nitrogen-containing organic solvent contains nitrogen atoms, it may be a polar solvent or a non-polar solvent. As the nitrogen-containing organic solvent, a nitrogen-containing polar organic solvent is preferable.

Examples of the nitrogen-containing polar organic solvent include amides such as N,N-dimethylacetamide, N,N-dimethylformamide, N,N-diethylacetamide, and N,N-diethylformamide; 1,3- And heterocyclic polar organic solvents such as dimethyl-2-imidazolidinone, N-methylpyrrolidone, N-ethylpyrrolidone, and γ-butyrolactone. In addition, the nitrogen-containing organic solvent and the nitrogen-containing polar organic solvent are not limited to these examples. Further, the nitrogen-containing organic solvent may be used in combination of two or more.

The nitrogen-containing polar organic solvent is preferably a compound represented by the following formula (S1).

[Tue 44]

(In formula (S1), R ^s1 and R ^s2 are each independently an alkyl group having 1 to 3 carbon atoms, and R ^s3 is a formula (S1-1) or a formula (S1-2) below:

[Tue 45]

It is a group represented by. In formula (S1-1), R ^s4 is a hydrogen atom or a hydroxyl group, and R ^s5 and R ^s6 are each independently an alkyl group having 1 to 3 carbon atoms. In the formula (S1-2), R ^s7 and R ^s8 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

Among the compounds represented by formula (S1), specific examples when R ^s3 is a group represented by formula (S1-1) are N,N,2-trimethylpropionamide, N-ethyl,N,2-dimethylpropionamide , N,N-diethyl-2-methylpropionamide, N,N,2-trimethyl-2-hydroxypropionamide, N-ethyl-N,2-dimethyl-2-hydroxypropionamide and N,N- And diethyl-2-hydroxy-2-methylpropionamide.

Among the compounds represented by formula (S1), specific examples when R ^s3 is a group represented by formula (S1-2) are N,N,N',N'-tetramethylurea, N,N,N', And N'-tetraethylurea.

Among the compounds represented by the formula (S1), N,N is particularly preferred from the viewpoint of easily dissolving various materials and easily suppressing aggregation of the basic filler and/or basic polymer in the polymerizable composition. And 2-trimethylpropionamide and N,N,N',N'-tetramethylurea.

The content of the nitrogen-containing organic solvent in the organic solvent (S) is, for example, 5 to 100 mass%, and when the filler (D) contains a basic filler (D2), 50 to 100 mass% is preferable, and 60 to 90 mass% is more preferable.

In addition, as a solvent, at least one solvent selected from the group consisting of a terpene compound having at least one group selected from the group consisting of hydroxy groups and acetoxy groups and an acetate compound containing a cyclic skeleton (excluding the terpene compounds) is used. May be

(Terpene compound having at least one group selected from the group consisting of hydroxy groups and acetoxy groups)

Terpene compounds having at least one group selected from the group consisting of a hydroxy group and acetoxy group include tapineol, dihydrotapineol, 4-(acetyloxy)-α,α, 4-trimethylcyclohexanemethanol acetate, 2 -[1-methyl-1-(4-methyl-3-cyclohexen-1-yl) ethoxy]ethanol, etc. are mentioned preferably.

The following isomers of α-, β-, and γ- are present in tapineol, and are sold by Japan Perfume Pharmaceutical Co., Ltd., or Terpen Chemical Co., Ltd. of Japan.

[Tue 46]

In addition, the following two compounds (1-hydroxy-p-mentan and 8-hydroxy-p-mentan) exist in dihydrotapineol, and dihydrotapineol and tersolve from Japan Terpene Chemical Co., Ltd. It is sold as DTO-210.

[Tue 47]

4-(acetyloxy)-α,α,4-trimethylcyclohexanemethanol acetate is a compound represented by the following formula C-3, but as a mixture of a compound represented by formula C-1 and a compound represented by formula C-2 , For example, it is marketed as Tersolve THA-90 and Tersolve THA-70 from Terpen Chemical Co., Ltd. of Japan.

[Tue 48]

2-[1-methyl-1-(4-methyl-3-cyclohexen-1-yl)ethoxy]ethanol is a compound represented by the following formula, for example, Tersolve TOE from Terpen Chemical Co., Ltd. of Japan It is sold as -100.

[Tue 49]

Among these, tapineol, dihydrotapineol, tersolve THA-90, tersolve THA-70, and tersolve TOE-100 are preferable, and dihydrotapineol, tersolve THA-90, tersolve THA- 70 is more preferable, and tersolve THA-90 and tersolve THA-70 are more preferable.

The terpene compounds may be used alone or in combination of two or more.

(Acyclic skeletal-containing acetate compound)

The cyclic skeleton-containing acetate compound (except the terpene compound) is not particularly limited as long as it is an acetate-based solvent having a cyclic skeleton that does not impair the effects of the present invention, but is a cycloalkyl acetate represented by the following formula (S1) desirable.

[Tue 50]

(In formula (S1), R ^s1 are each independently an alkyl group, p is an integer from 1 to 6, and q is an integer from 0 to (p+1).)

^Examples of the alkyl group represented by R ^s1 include an alkyl group having 1 to 3 carbon atoms, and a methyl group, ethyl group, n-propyl group, and i-propyl group.

Specific examples of the cycloalkyl acetate represented by formula (S1) include cyclopropyl acetate, cyclobutyl acetate, cyclopentyl acetate, cyclohexyl acetate, cycloheptyl acetate and cyclooctyl acetate.

Among these, cyclooctyl acetate is preferred from the viewpoint of availability and the like.

The cyclic skeleton-containing acetate compound may be used alone or in combination of two or more.

The content of the organic solvent (S) is not particularly limited, and is appropriately set depending on the film thickness or the like of the film formed of the polymerizable composition. The organic solvent (S) is typically used in an amount of 1 to 50% by mass, preferably 5 to 30% by mass, of the solid content concentration of the polymerizable composition.

<other ingredients>

In addition to the components described above, the polymerizable composition may contain additives such as surfactants, photobase generators, photoacid generators, adhesion improvers, colorants, thermal polymerization inhibitors, antifoaming agents, and curing accelerators, if necessary. Any additive can be used conventionally known. Examples of the surfactant include compounds such as anionic, cationic, and nonionic. Examples of the thermal polymerization inhibitor include hydroquinone and hydroquinone monoethyl ether. Antifoaming agents include silicone-based and fluorine-based compounds.

<Preparation method of polymerizable composition>

The method for preparing the polymerizable composition is not particularly limited as long as it is a method capable of uniformly mixing predetermined components. For example, the polymerizable composition can be prepared by mixing (dispersing and kneading) the above components with a stirrer such as a three-roll mill, a ball mill, or a sand mill, and filtering them with a filter such as a 5 µm membrane filter, if necessary.

≪Production method of cured film≫

The method for producing the cured film is not particularly limited as long as it is a method capable of curing the film made of the polymerizable composition described above. Typically, it is desirable to produce a patterned cured film.

Examples of suitable methods

Forming a coating film on the substrate using the polymerizable composition described above,

Position-selective exposure of the coating film,

Developing the exposed coating film,

And a method comprising a.

The substrate is not particularly limited, and various substrates such as a glass substrate and a silicon substrate can be used without particular limitation.

For example, when the polymerizable composition contains the inorganic filler (D1) described above, a transparent conductive film substrate such as an ITO film substrate is preferably used as the substrate.

As a method of applying the polymerizable composition on the substrate, for example, a contact transfer type coating device such as a roll coater, a reverse coater, a bar coater, a slit coater, or a non-contact type coating such as a spinner (rotary coating device) or curtain flow coater And a method of using the device.

The applied polymerizable composition is dried as necessary to form a coating film. The drying method is not particularly limited, and for example, (1) a method of drying for 60 to 120 seconds at a temperature of 80 to 120°C, preferably 90 to 100°C in a hot plate, (2) several hours to several hours at room temperature. And a method of removing the solvent by putting it in a hot air heater or an infrared heater for several minutes to several hours for a day or a day.

Then, the coating film is exposed. Exposure is performed by irradiating active energy rays such as ultraviolet rays and excimer laser light. The exposure is performed position-selectively, for example, by a method of performing exposure through a negative mask. The energy dose to be irradiated also varies depending on the composition of the polymerizable composition, but, for example, about 40 to 300 mJ/cm 2 is preferable.

After the coating film is subjected to position-selective exposure, it is patterned into a desired shape by developing with a developer. The developing method is not particularly limited, and for example, an immersion method, a spray method, or the like can be used. The developer is appropriately selected depending on the composition of the polymerizable composition. An alkaline aqueous solution is preferably used as the developer. The aqueous alkali solution may be an aqueous solution of an inorganic base or an aqueous solution of an organic base. Suitable developing solutions include, for example, basic aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts, and aqueous solutions of tetramethylammonium hydroxide are particularly preferred.

It is preferable to heat (bake) the patterned cured film after development. The baking temperature is not particularly limited as long as thermal decomposition or excessive deformation does not occur in the patterned cured film, but 180-280°C is preferable, and 190-260°C is more preferable.

Through the above operation, a cured film of a polymerizable composition patterned in a desired shape is obtained.

Since the above-mentioned polymerizable composition is used in the cured film according to the above method, residues are unlikely to occur in the unexposed portion during development with an aqueous alkali solution.

≪Transparent insulating film and display device≫

In particular, when a polymerizable composition containing an inorganic filler (D1) is used, a transparent insulating film can be formed by the above method. Further, the transparent insulating film formed in this way is excellent in transparency and has a high dielectric constant, and therefore is suitably used in manufacturing various types of display devices. From these advantages, the transparent insulating film formed in this way is expected as a substitute material for the transparent insulating film made of silicon nitride, which is conventionally used in display devices such as liquid crystal displays.

[Example]

Hereinafter, the present invention will be described in more detail by examples, but the present invention is not limited to these examples.

[Preparation Example 1]

First, 235 g of bisphenol fluorene-type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid were added to a 500 mL four-necked flask. The mixture was heated and dissolved at 90°C to 100°C while blowing air at a rate of 25 mL/minute. Subsequently, the solution was gradually heated while being cloudy, and heated to 120°C to dissolve completely. Here, the solution gradually became a transparent consistency, but stirring was continued as it was. In the meantime, the acid value was measured and heating and stirring was continued until it was less than 1.0 mgKOH/g. It took 12 hours to reach the goal. Then, it was cooled to room temperature to obtain a bisphenol fluorene-type epoxy acrylate.

Then, 600 g of 3-methoxy butyl acetate was added and dissolved in 307.0 g of the bisphenol fluorene-type epoxy acrylate obtained as described above, and then 80.5 g of benzophenone tetracarboxylic acid anhydride and 1 g of tetraethylammonium bromide were mixed, The temperature was gradually increased and reacted at 110°C to 115°C for 4 hours. After confirming the disappearance of the acid anhydride, 38.0 g of 1,2,3,6-tetrahydro phthalic anhydride were mixed and reacted at 90°C for 6 hours to obtain Resin 4 (mass average molecular weight: 3400) having a cardo structure. The disappearance of the acid anhydride was confirmed by IR spectrum.

[Examples 1 to 4 and Comparative Examples 1 to 5]

In Examples 1-4, the following silsesquioxane resin 1 was used as alkali-soluble resin.

Silsesquioxane resin 1: 2-(3-(triethoxysilylpropyl)carbamoyl)cyclohexanecarboxylic acid (40 mol%), methacrylic acid 3-(trimethoxysilyl)propyl (40) as monomer composition Mole%) and phenyltrimethoxysilane (20 mol%).

In Comparative Examples 1 to 4, Resin 2, which is an acrylic resin composed of structural units I to IV represented by the following formula, and whose amount of each structural unit is the lower right value (mass %) of parentheses for each unit is alkali. It was used as a soluble resin.

In Comparative Example 5, resin 4, which is a resin having a cardo structure obtained in Preparation Example 1, was used as an alkali-soluble resin.

[Tue 51]

In Examples 1 to 3 and Comparative Examples 1 to 3, CeO ₂ (average particle diameter 50 nm) was used as the inorganic filler.

In addition, in Example 4, Comparative Example 4 and Comparative Example 5, basic alumina fine particles (average particle diameter 700 nm) were used as the basic filler.

In Examples and Comparative Examples, dipentaerythritol hexaacrylate (DPHA) was used as a polyfunctional polymerizable monomer.

In Examples and Comparative Examples, the following compounds were used as polymerization initiators.

[Tue 52]

Each of the materials in the amounts listed in Table 3 was used in Examples 1 to 3 and Comparative Examples 1 to 3 so that the solid content concentration in PGMEA was 12% by mass, and in Examples 4, Comparative Examples 4 and 5, N Polymerization of Examples 1 to 4 and Comparative Examples 1 to 5 by uniformly mixing the solid content concentration in the mixed solvent (mass ratio 80:20) of ,N,N',N'-tetramethylurea and PGMEA to be 16% by mass. A sex composition was obtained.

The following evaluation was performed using the obtained polymerizable composition. Table 3 shows the evaluation results.

[Evaluation of unexposed residue and leakage current]

After applying the polymerizable compositions of each of Examples and Comparative Examples onto a glass substrate using a spin coater, baking at 90°C for 120 seconds was performed to obtain a coated film having a film thickness of 1 µm.

With respect to the obtained coating film, the exposure amount was 30 mJ/cm 2 in Examples 1 to 3 and Comparative Examples 1 to 3 through a mask capable of forming a line pattern having a line width of 3 μm, Example 4, Comparative Example 4 and Comparative Example 5 In, exposure was performed at an exposure amount of 300 mJ/cm 2.

The coating film after exposure was developed using an aqueous solution of tetramethylammonium hydroxide having a concentration of 2.38% by mass at a temperature of 23°C.

The coated film after development was baked at 230°C for 20 minutes to obtain a cured film patterned in a line.

The unexposed portion (non-patterned portion) was observed under a microscope to evaluate the unexposed portion residue. The case where the residue after development was hardly confirmed was judged as ○, and the case where the residue after development was confirmed as ×.

Moreover, the leak current was measured with the dielectric constant measuring device SSM495 (made by SSM Japan). When the value of the leakage current was 1.0 × E-8 or less, it was judged as ○, and when it was 1.0 × E-9 or less, it was determined as ◎. The case where the leakage current value was over 1.0×E-8 was judged as ×.

In addition, residues derived from inorganic fillers or basic fillers are one factor in increasing the leakage current value.

<gas generation evaluation>

After the polymerizable composition was applied onto a 10 cm×10 cm glass substrate, it was dried at 90° C. for 120 seconds to form a coating film.

Subsequently, full exposure was performed with an exposure amount of 50 mJ/cm 2 using an exposure machine using a high pressure mercury lamp as the coating film.

The exposed coating film was post-baked at 230°C for 30 minutes to obtain a cured film having a film thickness of 2 µm.

The formed cured film was used as a sample, and the amount of generated gas was evaluated by gas chromatography mass spectrometry (P&T-GC/MS) equipped with a purge & trap sampler (heat desorption device). Measurement and gas determination were carried out in the order of (i) to (i) below.

(Iv) Gas generation and capture into secondary adsorption tubes

A 1 mg cured film was placed in the primary trap tube, and heated at 230° C. for 10 minutes using a desorption device (manufactured by Perkin Elmer: Tarbo Matrix ATD) to adsorb the desorbed gas to the secondary trap tube.

(Ii) GC/MS analysis

The secondary trap tube was heated at 250°C for 1 minute, and the released gas was analyzed by GC/MS (Agilent Technologies Inc.: 7790B (GC), 5977AMSD (MS)).

(Ⅲ) Quantitative analysis

Quantification was performed from each peak area of the chart obtained by PT-GC/MS analysis of the resin composition. Specifically, the total area% of the peak of the detected outgas was determined as an evaluation value.

Based on the obtained evaluation value (% of total area), the amount of generated gas was evaluated in accordance with the following criteria.

○: The value of evaluation values less than 5.0 E ^9.

×: The value of the evaluation value was 5.0 E ⁹ or higher.

From Table 3, if the polymerizable composition of the example containing the silicon-containing resin (A) of a predetermined structure, the polymerizable composition is developed by an aqueous alkali solution even if it contains a specific type of inorganic filler (D1) or basic filler (D2) It turns out that generation|occurrence|production of the poetry residue is suppressed.

In particular, it can be seen that the outgas is less generated in the cured film formed using the polymerizable composition containing the silicon-containing resin (A) having a predetermined structure.

On the other hand, when a silicon-containing resin having a predetermined structure is used, and a polymerizable composition containing an alkali-soluble resin having a different structure is used, residues are easily generated during development by an aqueous alkali solution, and outgass are easily generated from the cured film. You can see that

Claims (7)

A polymerizable composition comprising a polymerizable group-containing component,
The polymerizable composition comprises a silicon-containing resin (A), a polymerization initiator (C) and a filler (D),
The silicon-containing resin (A) is selected from the group consisting of silsesquioxane resin (A1), polysilane-polysiloxane resin (AI), resin mixture (A-II), and polysilane structure-containing resin (A-III). Contains at least one,
The silsesquioxane resin (A1) is a silsesquioxane resin having a structural unit represented by the following formula (a1a),
[Tue 1]

(In formula (a1a), R ^a1 is a group represented by the following formula (a1a-I),
-X ^a -B ^a -Y ^a -COOH… (a1a-I)
X ^a is a single bond, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a group represented by -R ^a6 -NH-R ^a7 -,
R ^a6 and R ^a7 are each independently an alkylene group having 1 to 3 carbon atoms,
Y ^a is a divalent cyclic organic group or a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms,
B ^a is -NH-CO-, -CO-NH-, -NH-CO-O-, -O-CO-NH- or -NH-CO-NH-,
X ^a and Y ^a may each independently be substituted with one or more groups selected from the group consisting of (meth)acryloyloxy groups, vinyl groups, and epoxy group-containing organic groups.)
The polysilane-polysiloxane resin (AI) is a polysilane-polysiloxane resin having a polysilane structure (I-1) and a polysiloxane structure (I-2),
The resin mixture (A-II) is a mixture of a resin having a polysilane structure (II-1) and a resin having a polysiloxane structure (II-2),
The polysilane structure-containing resin (A-III) is a resin having the polysilane structure (II-1),
The polymerizable group-containing component includes at least one of the following (1) to (5),
(1) the expression a structural unit represented by (a1a), the formula (a1a-I) of X ^a and Y ^a of at least one (meth) acryloyloxy group of acrylic, vinyl, and epoxy-consisting of a organic in Silsesquioxane resin (A1-1) substituted with one or more groups selected from the group,
(2) Silsesquioxane resin (A1-2) having a structural unit represented by the formula (a1a) and a structural unit represented by the following formula (a2a),
[Tue 2]

(In formula (a2a), R ^a2 is a group represented by the following formula (a1a-II),
-Z ^a -A ^a … (a1a-Ⅱ)
Z ^a is a single bond, an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 12 carbon atoms, and A ^a is an (meth)acryloyloxy group, a vinyl group, or an organic group containing an epoxy group.)
(3) Silsesquioxane resin (A2) which has a structural unit represented by the formula (a2a) and does not correspond to the silsesquioxane resin (A1),
(4) a polyfunctional polymerizable monomer (B) and
(5) It has at least one group selected from the group consisting of (meth)acryloyloxy group, vinyl group and epoxy group-containing organic group, and further includes the silsesquioxane resin (A1), the silsesquioxane resin (A2) or the A polymerizable group-containing resin which does not correspond to any of the polyfunctional polymerizable monomers (B);
The filler (D) includes at least one selected from the group consisting of inorganic fillers (D1) and basic fillers (D2),
The inorganic filler (D1) is a group of at least one element selected from the group consisting of La, Ce, Nd, Gd, Ho, Lu, Hf and Ta, the oxide of the element, the chelate compound of the element, the element One or more selected from the group consisting of salts and alloys of the above elements,
The basic filler (D2) is at least one polymerizable composition selected from a basic filler and a basic polymer. The method according to claim 1,
The polymerizable composition wherein the polyfunctional polymerizable monomer (B) is a polyfunctional monomer having 5 or more functionalities. Forming a coating film on a substrate using the polymerizable composition according to claim 1 or claim 2,
Position-selective exposure of the coating film,
Developing the exposed coating film,
Method for producing a cured film comprising a. The method according to claim 3,
The manufacturing method of the cured film which develops using the exposed said coating film using alkaline aqueous solution as a developing solution. A cured film obtained by curing the polymerizable composition according to claim 1 or 2. A transparent insulating film formed by curing the polymerizable composition according to claim 1 or 2, comprising the inorganic filler (D1) as the filler (D). A display device comprising the transparent insulating film according to claim 6.