JP2017014418A - Radical-polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radical-polymerizable composition that can form cured products with high sensitivity, the obtained cured products being excellent in transparency, chemical resistance and insulation.SOLUTION: As essential components of the radical-polymerizable composition, the following components are combined: a polymer (A) having at least one backbone selected from the group consisting of (Ia) and (Ib), and preferably further having a backbone represented by (Ic) and/or (Id); a radical polymerization initiator (B) represented by the general formula (II); and an ethylenically unsaturated compound (C) excluding the polymer (A).SELECTED DRAWING: None

Description

  The present invention relates to a radical polymerizable composition containing a polymer having a tetrahydropyran skeleton or a dihydromaleimide skeleton, a radical polymerization initiator having an oxime ester group, and a compound having an ethylenically unsaturated bond.

  Since the radically polymerizable composition can be rapidly polymerized and cured by performing irradiation with ultraviolet rays, electron beams, heating, or the like, it is useful in various applications.

  The above radical polymerizable composition may be used when forming a transparent insulating film in a liquid crystal display or a touch panel sensor. The transparent insulating film is required to have high transparency in the visible region, high insulating property, and high chemical resistance, but it is difficult to satisfy these characteristics at the same time, which is a problem in the transparent insulating film.

  The following Patent Document 1 discloses a curable composition containing a polymer having a tetrahydropyran skeleton in the main chain, and the following Patent Document 2 contains a negative type containing a polymer having a dihydromaleimide skeleton in the main chain. A resist composition is disclosed. Patent Document 3 listed below discloses a highly sensitive photopolymerization initiator containing an oxime ester group and having a high visible light region transmittance. Patent Document 4 listed below discloses a dihydromaleimide skeleton. A photosensitive transparent insulating film forming material containing a polymer having a main chain as a main chain is disclosed. However, a radically polymerizable composition that can form a cured product with high sensitivity and the obtained cured product is excellent in transparency, chemical resistance, and insulation has not been obtained.

JP 2009-067826 A JP 2013-061599 A JP 2011-132215 A JP 2002-365800 A

  Therefore, the problem to be solved by the present invention is to provide a radical polymerization composition that can form a cured product with high sensitivity, and the obtained cured product is excellent in transparency, chemical resistance, and insulation.

（式中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数３〜２０のシクロアルキル基又は炭素原子数７〜２０のアリールアルキル基を表し、
上記炭素原子数１〜２０のアルキル基及び炭素原子数７〜２０のアリールアルキル基のアルキレン部分は更に置換基を有する場合があり、
上記炭素原子数１〜２０のアルキル基及び炭素原子数７〜２０のアリールアルキル基中のメチレン基は−Ｏ−、−Ｓ−、−ＮＨＣＯ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、−ＣＯ−又はＯＣＯ−で置換される場合もあり、
ポリマー（Ａ）中に複数のＲ¹及びＲ²が存在する場合、それぞれ同一の場合も異なる場合もある。）

（式中、Ｒ³及びＲ⁴は、それぞれ独立に水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、
Ｒ³及びＲ⁴で表される炭素原子数１〜２０のアルキル基の末端は炭素原子数４〜１０のシクロアルキル基である場合もあり、
Ｒ³及びＲ⁴で表される炭素原子数６〜２０のアリール基は、炭素原子数１〜２０のアルキル基又はＯＲで置換される場合もあり、
Ｒは炭素原子数１〜２０のアルキル基を表し、
Ｒで表される炭素原子数１〜２０のアルキル基は、ハロゲン原子で置換される場合もあり、
Ｒで表される炭素原子数１〜２０のアルキル基中のメチレン基は、−Ｏ−で置換される場合もあり、
Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²及びＲ¹³（以下、Ｒ⁵〜Ｒ¹³とも記載）は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ¹⁴、ＯＲ¹⁵、ＳＲ¹⁶、ＮＲ¹⁷Ｒ¹⁸、ＣＯＲ¹⁹、ＳＯＲ²⁰、ＳＯ₂Ｒ²¹又はＣＯＮＲ²²Ｒ²³を表し、
Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸、Ｒ¹⁹、Ｒ²⁰、Ｒ²¹、Ｒ²²及びＲ²³は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、
Ｒ¹⁵で表される炭素原子数１〜２０のアルキル基は、ハロゲン原子、ニトロ基、シアノ基、水酸基又はカルボキシル基で置換される場合もあり、
Ｒ¹⁹で表される炭素原子数６〜２０のアリール基は、ニトロ基、ＯＲ'、炭素原子数１〜２０のアルキル基又は炭素原子数２〜２０の複素環含有基で置換される場合もあり、
Ｒ'は、炭素原子数１〜２０のアルキル基を表し、
Ｒ'で表される炭素原子数１〜２０のアルキル基は、その末端が、炭素原子数３〜１０の複素環含有基である場合もあり、
Ｘ¹は、酸素原子、硫黄原子、セレン原子、ＣＲ²⁴Ｒ²⁵、ＣＯ、ＮＲ²⁶又はＰＲ²⁷を表し、
Ｒ²⁴、Ｒ²⁵、Ｒ²⁶及びＲ²⁷は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環含有基を表し、
Ｒ²⁶で表される炭素原子数６〜２０のアリール基は、−Ｃ（Ｒ³）＝Ｎ−Ｏ−Ｃ（＝Ｏ）Ｒ⁴で置換される場合もあり、
Ｘ²は、単結合又はＣＯを表し、
Ｒ⁵とＲ⁶、Ｒ⁵とＲ²⁴、Ｒ⁵とＲ²⁵、Ｒ⁵とＲ²⁶、Ｒ⁵とＲ²⁷、Ｒ⁷とＲ⁸、Ｒ⁸とＲ⁹、Ｒ⁸とＲ²⁴、Ｒ⁸とＲ²⁵、Ｒ⁸とＲ²⁶、Ｒ⁸とＲ²⁷、Ｒ⁹とＲ¹⁰、Ｒ⁹とＲ²⁴、Ｒ⁹とＲ²⁵、Ｒ⁹とＲ²⁶、Ｒ⁹とＲ²⁷、Ｒ¹⁰とＲ¹¹、Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ²⁴、Ｒ¹³とＲ²⁵、Ｒ¹³とＲ²⁶及びＲ¹³とＲ²⁷は結合して環を形成する場合もある。） The present inventor has found that the above problem can be solved by using a polymer having a tetrahydropyran skeleton or a dihydromaleimide skeleton, a radical polymerization initiator having an oxime ester group, and a compound having an ethylenically unsaturated bond, The present invention has been completed.
That is, the present invention is represented by a polymer (A) having at least one skeleton selected from the group consisting of the following (Ia) and (Ib) (hereinafter also referred to as polymer (A)) and the following general formula (II). Radical polymerization initiator (B) (hereinafter also referred to as radical polymerization initiator (B)) and ethylenically unsaturated compound (C) excluding polymer (A) (hereinafter also referred to as ethylenically unsaturated compound (C)) The radically polymerizable composition containing this is provided.

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or carbon. Represents an arylalkyl group having 7 to 20 atoms,
The alkylene part of the alkyl group having 1 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms may further have a substituent,
The methylene group in the alkyl group having 1 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms is —O—, —S—, —NHCO—, —SO ₂ —, —SS—, —SO—. , -CO- or OCO-,
When a plurality of R ¹ and R ² are present in the polymer (A), they may be the same or different. )

Wherein R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents an arylalkyl group of ˜20 or a heterocyclic-containing group of 2 to 20 carbon atoms,
The terminal of the alkyl group having 1 to 20 carbon atoms represented by R ³ and R ⁴ may be a cycloalkyl group having 4 to 10 carbon atoms,
The aryl group having 6 to 20 carbon atoms represented by R ³ and R ⁴ may be substituted with an alkyl group having 1 to 20 carbon atoms or OR,
R represents an alkyl group having 1 to 20 carbon atoms,
The alkyl group having 1 to 20 carbon atoms represented by R may be substituted with a halogen atom,
The methylene group in the alkyl group having 1 to 20 carbon atoms represented by R may be substituted with -O-,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ (hereinafter also referred to as R ^{5 to} R ¹³ ) are each independently a hydrogen atom, halogen atom, nitro Represents a group, a cyano group, a hydroxyl group, a carboxyl group, R ¹⁴ , OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ , COR ¹⁹ , SOR ²⁰ , SO ₂ R ²¹ or CONR ²² R ²³ ;
R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each independently an alkyl group having 1 to 20 carbon atoms or 6 to 6 carbon atoms. 20 represents an aryl group, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms,
The alkyl group having 1 to 20 carbon atoms represented by R ¹⁵ may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group or a carboxyl group,
The aryl group having 6 to 20 carbon atoms represented by R ¹⁹ may be substituted with a nitro group, OR ′, an alkyl group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Yes,
R ′ represents an alkyl group having 1 to 20 carbon atoms,
The terminal of the alkyl group having 1 to 20 carbon atoms represented by R ′ may be a heterocyclic ring-containing group having 3 to 10 carbon atoms,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ²⁴ R ²⁵ , CO, NR ²⁶ or PR ²⁷ ,
R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a carbon atom. Represents a heterocyclic group containing 2 to 20,
The aryl group having 6 to 20 carbon atoms represented by R ²⁶ may be substituted with —C (R ³ ) ═N—O—C (═O) R ⁴ ,
X ² represents a single bond or CO,
R ⁵ and R ⁶ , R ⁵ and R ²⁴ , R ⁵ and R ²⁵ , R ⁵ and R ²⁶ , R ⁵ and R ²⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁸ and R ²⁴ , R ⁸ And R ²⁵ , R ⁸ and R ²⁶ , R ⁸ and R ²⁷ , R ⁹ and R ¹⁰ , R ⁹ and R ²⁴ , R ⁹ and R ²⁵ , R ⁹ and R ²⁶ , R ⁹ and R ²⁷ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ²⁴ , R ¹³ and R ²⁵ , R ¹³ and R ^26, and R ¹³ and R ²⁷ may combine to form a ring. )

  Moreover, this invention provides the hardened | cured material obtained using the manufacturing method of the hardened | cured material using the said radically polymerizable composition, and the said radically polymerized composition.

  According to the present invention, a highly sensitive radically polymerizable composition can be provided. Moreover, the hardened | cured material excellent in transparency, chemical-resistance, and insulation can be provided by using this radically polymerizable composition.

  Hereinafter, the radically polymerizable composition of the present invention will be described based on preferred embodiments.

  The radical polysynthetic composition of the present invention contains a polymer (A), a radical polymerization initiator (B), and an ethylenically unsaturated compound (C). Hereinafter, each component will be described in order.

（式中、Ｒ²⁸及びＲ³⁰は、それぞれ独立に水素原子及び炭素原子数１〜５のアルキル基を表し、
Ｒ²⁹は、炭素原子数１〜２０のアルカンジイル基を表し、
上記アルカンジイル基は更に置換基を有する場合があり、
上記アルカンジイル基中のメチレン基は-Ｏ-、-Ｓ−、−ＮＨＣＯ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、−ＣＯ−又はＯＣＯ−で置換される場合もあり、
ポリマー（Ａ）中に複数のＲ²⁸、Ｒ²⁹及びＲ³⁰が存在する場合、それぞれ同一の場合も異なる場合もある。）
また、下記（Iｄ）に示す骨格を主鎖に有すると上記ラジカル重合性組成物にアルカリ現像性を付与できる。

（式中、Ｒ³¹は、水素原子及び炭素原子数１〜５のアルキル基を表し、
ポリマー（Ａ）中に複数のＲ³¹が存在する場合、それぞれ同一の場合も異なる場合もある。） <Polymer (A)>
The polymer (A) used in the curable composition of the present invention is a polymer having at least one skeleton selected from the group consisting of (Ia) and (Ib).
When having at least one skeleton represented by (Ia) or (Ib) in the polymer main chain, radical polymerizability containing polymer (A), radical polymerization initiator (B) and ethylenically unsaturated compound (C) The heat resistance of the cured product obtained from the composition is improved. Further, when the main chain further has a skeleton shown in (Ic) below, the hardness and chemical resistance of the cured product are improved.

(Wherein R ²⁸ and R ³⁰ each independently represent a hydrogen atom and an alkyl group having 1 to 5 carbon atoms,
R ²⁹ represents an alkanediyl group having 1 to 20 carbon atoms,
The alkanediyl group may further have a substituent,
The methylene group in the alkanediyl group may be substituted with —O—, —S—, —NHCO—, —SO ₂ —, —SS—, —SO—, —CO— or OCO—.
When a plurality of R ²⁸ , R ²⁹ and R ³⁰ are present in the polymer (A), they may be the same or different. )
Moreover, when the skeleton shown in the following (Id) is included in the main chain, alkali developability can be imparted to the radical polymerizable composition.

(In the formula, R ³¹ represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms;
When a plurality of R ³¹ are present in the polymer (A), they may be the same or different. )

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ² in the skeletons (Ia) and (Ib) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, Undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl and heptafluoropropyl, etc.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹ and R ² in the skeletons (Ia) and (Ib) include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, o-tolyl, m-tolyl, p-tolyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4 -Cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4- Dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylphenyl, 2,5-di-t-butylphenyl Enyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di-t-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4 -Chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-trifluorophenyl, perfluorophenyl, etc.
The cycloalkyl group having 3 to 20 carbon atoms represented by R ¹ and R ² in the skeletons (Ia) and (Ib) is a saturated monocyclic or saturated polycyclic ring having 3 to 20 carbon atoms. Meaning an alkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1.1 .1] pentanyl group and the like.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ and R ² in the skeletons (Ia) and (Ib) include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, and styryl. , Cinnamyl and 4-chlorophenylmethyl, etc.
Examples of the substituent on the alkylene moiety of the alkyl group having 1 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms represented by R ¹ and R ² in the skeletons (Ia) and (Ib) include , (Meth) acryloyl group, vinyl group, allyl group, epoxy group, amino group, isocyanate group, carboxyl group, hydroxy group, aryl group, heterocyclic ring-containing group, alicyclic hydrocarbon group, halogen atom and MgX group (here X is a halogen atom, preferably a bromine atom or a chlorine atom).
As R ¹ in the skeleton (Ia), it is more preferable that the α-position is interrupted by —CO— and the β-position is interrupted by —O— because the reactivity of the monomer forming the skeleton (Ia) is good. For example, a methyl acetate group can be mentioned,
R ² in the skeleton (Ib) is preferably an arylalkyl group because of good heat resistance, and examples thereof include a benzyl group.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ²⁸ and R ³⁰ in the skeleton (Ic) and R ³¹ in the skeleton (Id) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl amyl, iso-amyl, tert-amyl and the like,
R ²⁸ and R ³¹ are preferably a hydrogen atom or methyl since the reactivity of the monomer forming the polymer is good, and R ³⁰ has a good reactivity of the unsaturated double bond present in the side chain of the polymer. Therefore, a hydrogen atom or a methyl group is preferable.
Examples of the alkanediyl group having 1 to 20 carbon atoms represented by R ²⁹ in the skeleton (Ic) include methanediyl, ethanediyl, propanediyl, iso-propanediyl, butanediyl, sec-butanediyl, tert-butanediyl, iso-butanediyl, pentanediyl, iso-pentanediyl, tert-pentanediyl, hexanediyl, heptanediyl, isoheptanediyl, t-heptanediyl, n-octanediyl, isooctanediyl, t-octanediyl, 2-ethylhexanediyl, n-nonanediyl, n-decanediyl, undecanediyl, dodecanediyl, tridecanediyl, isotridecanediyl, tetracandedyl, hexadecanediyl, octadecanediyl, trifluoromethanediyl and difluoro Such as lomethanediyl,
Examples of the substituent of the alkanediyl group having 1 to 20 carbon atoms represented by R ²⁹ in the skeleton (Ic) include (meth) acryloyl group, vinyl group, allyl group, epoxy group, amino group, and isocyanate. Group, carboxyl group, hydroxy group, aryl group, heterocycle-containing group, alicyclic hydrocarbon group, halogen atom and MgX group (where X is a halogen atom, preferably bromine atom or chlorine atom).
Since the alkanediyl group having 1 to 20 carbon atoms represented by R ²⁹ in the skeleton (Ic) is easily available, the α-position methylene group is substituted with —O—, and the γ-position is a hydroxyl group. More preferred is butanediyl having

  The ratio of the skeleton (Ia) is not particularly limited, but when the skeleton (Ib) is not included, the mass derived from the skeleton (Ia) is 2 to 60% by mass with respect to the mass of the polymer (A), more preferably, It is 5-50 mass%. When the mass derived from the skeleton (Ia) is larger than 60% by mass, it may be difficult to control the polymerization reaction. When the mass is smaller than 2% by mass, the heat resistance of the cured product obtained from the radical polymerizable composition is low. It may be insufficient.

  The ratio of the skeleton (Ib) is not particularly limited, but when the skeleton (Ia) is not included, the mass derived from the skeleton (Ib) is 50% by mass or more, more preferably 70% by mass with respect to the mass of the polymer (A). It is at least 90% by mass, more preferably at least 90% by mass. If the mass derived from the skeleton (Ib) is less than 50% by mass, the heat resistance of the cured product obtained from the radically polymerizable composition may be insufficient.

  When the polymer (A) includes both the skeleton (Ia) and the skeleton (Ib), the sum of masses derived from the skeleton (Ia) and the skeleton (Ib) is 5 to 80 mass with respect to the mass of the polymer (A). %, More preferably 10 to 70% by mass. If the sum of the mass derived from the skeleton (Ia) and the skeleton (Ia) constituting the skeleton (Ia) and the skeleton (Ib) is more than 80% by mass, it may be difficult to control the polymerization reaction. If it is less than mass%, the heat resistance of the cured product obtained from the radical polymerizable composition may be insufficient.

The ratio of the skeleton (Ic) is not particularly limited, but the mass derived from the skeleton (Ic) is 0 to 70% by mass, more preferably 5 to 70% by mass with respect to the mass of the polymer (A). Preferably it is 10-60 mass%. If the mass derived from the skeleton (Ic) constituting the skeleton (Ic) is greater than 70% by mass, the heat resistance of the cured product obtained from the radical polymerizable composition may be insufficient, and is less than 5% by mass. In some cases, the sensitivity of the radical polymerizable composition is lowered, and the chemical resistance of the cured product obtained from the radical polymerizable composition is insufficient.

  The ratio of the skeleton (Id) is not particularly limited, but the mass derived from the skeleton (Id) is 0 to 70% by mass, more preferably 5 to 70% by mass with respect to the mass of the polymer (A). Preferably it is 10-60 mass%. If the mass derived from the skeleton (Id) constituting the skeleton (Id) is greater than 70% by mass, the heat resistance of the cured product obtained from the radical polymerizable composition may be insufficient, and is less than 5% by mass. And the radically polymerizable composition may not be imparted with alkali developability.

  The molecular weight of the polymer (A) is not particularly limited, but the weight average molecular weight is preferably 2000 to 50000, more preferably 5000 to 20000. When the weight average molecular weight is less than 2000, the heat resistance of the cured product may be lowered, and when the weight average molecular weight is more than 50000, the alkali developability may be lowered.

In the curable composition used in the method for producing a cured product of the present invention, the content of the polymer (A) is the sum of the masses of the polymer (A), the radical polymerization initiator (B), and the ethylenically unsaturated compound (C). Preferably it is 20-80 mass parts with respect to 100 mass parts, More preferably, it is 30-60 mass parts. If the content of the polymer (A) is less than 20 parts by mass, the volume resistivity of the cured product may be reduced, and if it is greater than 80 parts by mass, the chemical resistance of the cured product may be reduced.
For example, when forming a cured product having a film thickness of 1 to 100 μm, the content of the polymer (A) is the sum of the masses of the polymer (A), the radical polymerization initiator (B) and the ethylenically unsaturated compound (C). Preferably it is 20-80 mass parts with respect to 100 mass parts. More preferably, it is 30-60 mass parts.
If the content of the polymer (A) is less than 20 parts by mass, the volume resistivity of the cured product may be reduced, and if it is greater than 80 parts by mass, the chemical resistance of the cured product may be reduced.

<Radical polymerization initiator (B)>
As the radical polymerization initiator (B) used in the curable composition of the present invention, the sensitivity of the radical polymerizable composition and the heat resistance and chemical resistance of the cured product obtained from the radical polymerizable composition are good. A compound represented by the general formula (II) is used.

The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms and the aryl group having 7 to 20 carbon atoms represented by R ³ , R ⁴ and R ^{14 to} R ²⁷ in the general formula (II). Examples of the alkyl group and the alkyl group having 1 to 20 carbon atoms represented by R and R ′ are the same as those exemplified for R ¹ and R ² above.
Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R ³ , R ⁴ , R ^{14 to} R ²⁷ in the general formula (II) include, for example, pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, pyridadyl, piperazyl. , Piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoyl Oxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazo 3-yl and 2,4-dioxy-oxazolidinedione-3-yl, and the like.
Examples of the case where the terminal of the alkyl group having 1 to 20 carbon atoms represented by R ³ and R ⁴ is a cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl , Cyclooctyl, cyclononyl, cyclodecyl and the like.
Examples of the case where the terminal of the alkyl group having 1 to 20 carbon atoms represented by R ′ is a heterocyclic group containing 3 to 10 carbon atoms include the heterocyclic group represented by R ^{3 and the} like In addition to those satisfying a predetermined number of carbon atoms, 1,3-dioxolane and the like can be mentioned.

R ^{5 to} R ¹³ may be bonded to each other to form a ring, and R ⁵ and R ⁶ , R ⁵ and R ²⁴ , R ⁵ and R ²⁵ , R ⁵ and R ²⁶ , R ⁵ and R ²⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁸ and R ²⁴ , R ⁸ and R ²⁵ , R ⁸ and R ²⁶ , R ⁸ and R ²⁷ , R ⁹ and R ¹⁰ , R ⁹ and R ²⁴ , R ⁹ And R ²⁵ , R ⁹ and R ²⁶ , R ⁹ and R ²⁷ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ²⁴ , R ¹³ and R ²⁵ , R ¹³ and R ²⁶ and R ¹³ and R ²⁷ may combine to form a ring.
Examples of such rings include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, pyrrolidine ring, pyrrole ring, piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, tetrahydropyridine ring, lactone ring, and lactam ring. Examples thereof include 5- to 7-membered rings and condensed rings such as naphthalene ring, anthracene ring, and carbazole ring.

  Of the oxime ester compounds represented by the general formula (II), structures represented by the following general formulas (IIa) to (IId) are preferable from the viewpoints of sensitivity and transparency.

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²⁴、Ｒ²⁵及びＸ²は、上記一般式（II）と同じである。）

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ²⁴ , R ²⁵ and X ² are the same as those in the general formula (II)). is there.)

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²⁶及びＸ²は、上記一般式（II）と同じである。）

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ²⁶ and X ² are the above-mentioned general formula (II) Is the same.)

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²⁶及びＸ²は、上記一般式（II）と同じである。）

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ²⁶ and X ² are the same as those in the general formula (II).)

（式中、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³及びＸ²は、上記一般式（II）と同じである。）

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and X ² are the same as in the general formula (II)). is there.)

  Preferable specific examples of the oxime ester compound represented by the general formula (II) include the following compound Nos. B1-No. B26 may be mentioned. However, the present invention is not limited by the following compounds.

Among the compounds represented by the general formula (IIa), the following are preferable.
R ³ and R ⁴ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms (particularly one substituted with an alkyl group having 1 to 6 carbon atoms). Any of R ^{10 to} R ¹³ , particularly R ¹² is a nitro group or COR ¹⁹ [R ¹⁹ is an aryl group having 6 to 10 carbon atoms (particularly unsubstituted, an alkyl group having 1 to 6 carbon atoms or a nitro group) A benzene ring substituted with a group or an unsubstituted naphthalene ring) or a heterocyclic-containing group having 3 to 10 carbon atoms (particularly a thiophene ring)] R ²⁴ and / or R ²⁵ is a carbon atom What is a C1-C10 alkyl group (especially C3-C6 alkyl group) Moreover, among the compounds represented by the said general formula (IIb), the following are preferable.
-R ³ or R ⁴ is an alkyl group having 1 to 6 carbon atoms-Any of R ^{9 to} R ¹³ , especially R ¹¹ is COR ¹⁹ [R ¹⁹ is aryl having 6 to 10 carbon atoms A group (particularly an unsubstituted or substituted benzene ring or unsubstituted naphthalene ring substituted with an alkyl group having 1 to 6 carbon atoms) or a heterocyclic group containing 3 to 10 carbon atoms (particularly a thiophene ring)] Some where R ²⁶ is an aryl group having 6 to 10 carbon atoms and substituted with —C (R ³ ) ═N—O—C (═O) R ⁴ Among the compounds represented by the formula (IIc), the following are preferable.
R ³ or R ⁴ is an alkyl group having 1 to 20 carbon atoms (including a terminal having a cycloalkyl group having 4 to 6 carbon atoms), an aryl group having 6 to 20 carbon atoms [carbon atom An alkyl group of 1 to 6 or OR (R is an alkyl group of 1 to 6 carbon atoms, provided that it may be substituted with a halogen atom, and methylene in the middle may be substituted with -O- Any one of R ^{10 to} R ¹³ , particularly R ¹¹ is a nitro group, COR ¹⁹ [R ¹⁹ is an aryl group having 6 to 10 carbon atoms [particularly unsubstituted] , An alkyl group having 1 to 6 carbon atoms, a heterocycle-containing group having 3 to 20 carbon atoms, OR ′ (where R ′ is an alkyl group having 1 to 6 carbon atoms, and the terminal thereof is carbon. Including those that are heterocycle-containing groups having 3 to 10 atoms (especially 1,3-dioxolane)] Those · R ²⁶ is those substituted] is an alkyl group or an aryl group having 6 to 10 carbon atoms of 1 to 6 carbon atoms, and, -C (R) = N- O-C ( = O) Those substituted with R 'Further, among the compounds represented by the general formula (IId), the following are preferable.
R ³ or R ⁴ is an alkyl group having 1 to 20 carbon atoms (including a terminal having a cycloalkyl group having 4 to 6 carbon atoms), an aryl group having 6 to 20 carbon atoms (carbon atom) Any one of R ^{9 to} R ¹³ , especially R ¹¹ is OR ¹⁵ (R ¹⁵ is an alkyl group having 1 to 6 carbon atoms, May be substituted with a hydroxyl group), COR ¹⁹ (R ¹⁹ is an aryl group having 6 to 10 carbon atoms) R ²⁶ is an alkyl group having 1 to 6 carbon atoms or 6 carbon atoms To 10 aryl groups and substituted with —C (R ³ ) ═N—O—C (═O) R ⁴

  Commercially available products can also be used as the radical polymerizable compound represented by the general formula (II). For example, DFI-091, DFI-120 (manufactured by Daito Chemix), SOX-337 (manufactured by Suntype), TR -PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-314, TR-PBG-327 (manufactured by TRONLY), Adekaoptomer N-1919, Adeka Arcles NCI-831, Adeka Arc Ruse NCI-930 (manufactured by ADEKA), IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04 (manufactured by BASF) and the like.

  These radical polymerization initiators can be used alone or in combination according to the desired performance.

In the curable composition used in the method for producing a cured product of the present invention, the content of the polymer (A) is the sum of the masses of the polymer (A), the radical polymerization initiator (B), and the ethylenically unsaturated compound (C). Preferably it is 2.0-60 mass parts with respect to 100 mass parts. More preferably, it is 10-40 mass parts. When the content of the radical polymerization initiator (B) is less than 2.0 parts by mass, the sensitivity of the radical polymerizable composition may be reduced. When the content is more than 60 parts by mass, the chemical resistance of the cured product is reduced. There is a case.
For example, when forming a cured product having a film thickness of 1 to 100 μm, the content of the radical polymerization initiator (B) is such that the polymer (A), the radical polymerization initiator (B), and the ethylenically unsaturated compound (C). Preferably it is 2.0-60 mass parts with respect to 100 mass parts of sum of mass. More preferably, it is 10-40 mass parts. When the content of the radical polymerization initiator (B) is less than 2.0 parts by mass, the sensitivity of the radical polymerizable composition may be reduced. When the content is more than 60 parts by mass, the chemical resistance of the cured product is reduced. There is a case.

<Ethylenic unsaturated compound (C)>
The ethylenically unsaturated compound (C) used in the radically polymerizable composition of the present invention is not particularly limited as long as it is a compound having a carbon-carbon double bond in the compound, and is already used. Things can be used.

  Examples of the ethylenically unsaturated compound (C) include unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, and tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, monosuccinic acid [2- (meta ) Acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate, etc., polymer mono (meth) having a carboxy group and a hydroxyl group at both ends Acrylate; hydroxyethyl (meth) acrylate malate, H Unsaturated monobasic acids such as roxypropyl (meth) acrylate malate, dicyclopentadiene malate and polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups; (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following compound No. C1-No. C4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate and tri [(meth) acryloylethyl] isocyanurate and polyester (meth) acrylate oligomers; Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride Hydrous maleic acid adduct, acid anhydrides of unsaturated polybasic acids such as dodecenyl succinic anhydride and methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meta ) Unsaturated monobasic acids and amides of polyvalent amines such as acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; Unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene chloride and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinyl Unsaturated aromatic compounds such as perfume acid, vinylphenol, vinylsulfonic acid, 4-vinylbenzenesulfonic acid, vinylbenzyl methyl ether and vinylbenzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinylamine, allylamine, N-vinyl Unsaturated amine compounds such as pyrrolidone and vinylpiperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether and allyl glycidyl ether; maleimide, N-phenyl Unsaturated imides such as maleimide and N-cyclohexylmaleimide; indenes such as indene and 1-methylindene; 1,3-butadiene, isoprene and chloroprene Aliphatic monomers such as polystyrene; macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane; Vinyl chloride, vinylidene chloride, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer, poly Examples thereof include vinyl urethane compounds of isocyanate compounds, vinyl monomers containing hydroxyl groups, and vinyl epoxy compounds of polyepoxy compounds.

Among the ethylenically unsaturated compounds (C), when a compound having an acidic group is used, alkali developability can be imparted to the radically polymerizable composition of the present invention. When using the compound which has the said acidic group, it is preferable to make the usage-amount become 50-99 mass% of the said ethylenically unsaturated compound (C) whole.
The compound having an acidic group can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound. By adjusting the acid value of the compound having an acidic group, the alkali developability of the radical polymerizable composition can be improved. The compound having an acidic group (that is, the ethylenically unsaturated compound (C) imparting alkali developability) preferably has a solid acid value in the range of 5 to 120 mgKOH / g, and is a monofunctional or polyfunctional epoxy compound. Is preferably selected so as to satisfy the acid value.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the above-mentioned compound no. C2 and No. C3 etc. are mentioned.

  A commercial item can be used as said ethylenically unsaturated compound (C), for example, Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30 (made by Nippon Kayaku Co., Ltd.), SPC -3000 (made by Showa Denko), Aronix M-140, M-215, M-350 (made by Toagosei), NK ester A-DPHA-TMPT, A-DCP, A-HD-N, A-9300, TMPT , DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).

In the curable composition used in the method for producing a cured product of the present invention, the content of the ethylenically unsaturated compound (C) is the polymer (A), the radical polymerization initiator (B), and the ethylenically unsaturated compound (C). Preferably it is 5.0-70 mass parts with respect to 100 mass parts of sum of mass. More preferably, it is 10-50 mass parts. If the content of the ethylenically unsaturated compound (C) is less than 5.0 parts by mass, the chemical resistance of the cured product made of the radical polymerizable composition may be lowered. If the content is more than 70 parts by mass, the cured product is obtained. The volume resistivity may decrease.
For example, when forming a cured product having a film thickness of 1 to 100 μm, the content of the ethylenically unsaturated compound (C) is such that the polymer (A), the radical polymerization initiator (B), and the ethylenically unsaturated compound (C). Preferably it is 5.0-70 mass parts with respect to 100 mass parts of sum of mass. More preferably, it is 10-50 mass parts. If the content of the ethylenically unsaturated compound (C) is less than 5.0 parts by mass, the chemical resistance of the cured product made of the radical polymerizable composition may be lowered. If the content is more than 70 parts by mass, the cured product is obtained. The volume resistivity may decrease.

  The radically polymerizable composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability. As such a compound, an acidic aqueous solution can be obtained by having an acidic group. Although it will not specifically limit if it is a soluble compound, Alkali-soluble novolak resin (henceforth "novolak resin" only) is mentioned as a typical thing. The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5- Shirenoru, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferred. These phenols are used alone or in combination of two or more.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde and p N-butylbenzaldehyde and the like are used, and among these compounds, formaldehyde Rudehydr, acetaldehyde and benzaldehyde are preferred. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acid catalysts used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mol of phenols. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, or cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. Although the reaction temperature of a condensation reaction can be suitably adjusted according to the reactivity of a reaction raw material, it is 10-200 degreeC normally, Preferably it is 70-150 degreeC. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally raised to 130 to 230 ° C., and volatile components are distilled off under reduced pressure. The molten novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane and n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.

  Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, and polyvinylhydroxybenzoate.

  The curable composition contains a solvent capable of dissolving or dispersing each of the above components (polymer (A), radical polymerization initiator (B) and ethylenically unsaturated compound (C)) as necessary. Can be added. For example, ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-di Ether solvents such as ethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate and texanol; Cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol, ethanol, iso- or n-propanol, iso- or n-butanol And alcohol solvents such as amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl Ether ester solvents such as propionate; BTX solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; Terpene carbonization such as turpentine oil, D-limonene and pinene Hydrogen oil; paraffinic solvents such as mineral spirits, Swazol # 310 (manufactured by Cosmo Matsuyama Oil Co., Ltd.) and Solvesso # 100 (manufactured by Exxon Chemical); carbon tetrachloride, chloroform Halogenated aliphatic hydrocarbon solvents such as trichloroethylene, methylene chloride and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, Examples thereof include carbon sulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and water, and these solvents can be used as one kind or a mixture of two or more kinds. . Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate (PGMEA) and cyclohexanone are preferable because they are compatible with the above-described components.

  In the radically polymerizable composition of the present invention, the content of the solvent is not particularly limited, but since the handling becomes good, the concentration of the composition other than the solvent (hereinafter also referred to as solid content) is 5 to 5. The amount is preferably 50% by mass, more preferably 10 to 30% by mass. When the amount is less than 5% by mass, a cured product having a sufficient film thickness may not be obtained. When the amount is more than 50% by mass, the radical polymerizable composition may increase in viscosity, and good handling may not be obtained. For example, when a transparent insulating film is formed, the content of the solvent (D) is preferably 5 to 50% by mass, more preferably 10 to 30% by mass of the composition other than the solvent. . When the amount is less than 5% by mass, a cured product having a sufficient film thickness may not be obtained. When the amount is more than 50% by mass, the radical polymerizable composition may increase in viscosity, and good handling may not be obtained.

  In the radically polymerizable composition of the present invention, if necessary, an initiator other than the radical polymerization initiator represented by the general formula (II); p-anisole, hydroquinone, pyrocatechol, t-butylcatechol and phenothiazine A thermal polymerization inhibitor such as a plasticizer; an adhesion promoter; a filler; an antifoaming agent; a coupling agent; a leveling agent; a surface conditioner; an antioxidant; an ultraviolet absorber; a dispersion aid; Effect promoters: Conventional additives such as crosslinking agents and thickeners can be added.

  It is preferable to add the coupling agent because the adhesion between the cured product and the substrate is improved. For example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, and other alkyl functional alkoxysilanes, vinyl Alkenyl functional alkoxysilanes such as trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldi (Meth) acrylic acid ester functionality such as ethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane Alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyl Amino functionality such as epoxy-functional alkoxysilanes such as trimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane -Functional alkoxysilanes, mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, isocyanate-functional alkoxysilanes such as 3-isocyanatopropyltriethoxysilane, and urethanes such as 3-ureidopropyltrialkoxysilane Functional alkoxysilanes, isocyanurate functional alkoxysilanes such as tris- (trimethoxysilylpropyl) isocyanurate, titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium dioctyloxybis (octyleneglycol) Rate), titanium chelates such as titanium diisopropoxybis (ethyl acetoacetate), zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, and zirconium acylates such as zirconium tributoxymonostearate Isocyanate silanes such as methyl triisocyanate silane can be used.

  A commercial item can be used as said coupling agent, for example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM- 502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-903, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE- 103, HMDS-3, KBM-3063, KBM-3103C, KPN 3504 and KF-99 (manufactured by Shin-Etsu Silicone), and the like.

  In the radically polymerizable composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, melamine, and the like can be further used in combination.

  As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate); iodo such as disulfide compounds obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4 Dimethyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. D1, Showa Denko Co., Ltd. Karenz PE1 and NR1 etc. are mentioned.

  Specific examples of the sensitizer include benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine. , Benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butyl Nthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5,7 -Dimethoxycarbonylcoumarin) and coronene.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants and silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, and they may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril, and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

  In the radically polymerizable composition of the present invention, the content of optional components other than the polymer (A), the radical polymerization initiator (B), and the ethylenically unsaturated compound (C) is appropriately selected according to the purpose of use. Although it does not restrict | limit in particular, Preferably, it is 20 mass parts or less in total with respect to 100 mass parts of solid content of a radically polymerizable composition. When content of an arbitrary component exceeds 20 mass parts, the effect of this invention may not fully be expressed.

  The radically polymerizable composition of the present invention is a curable paint or varnish, adhesive, printing ink, gel coat, electronic photoresist, electroplating resist, etching resist, both liquid and dry film, solder resist, LCD Resists for forming structures in the manufacturing process, compositions for encapsulating electrical and electronic components, solder resists, glass fiber cable coatings, materials for producing three-dimensional objects by stereolithography, holographic recording materials, Image recording materials, fine electronic circuits, bleaching materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and visible lasers for direct imaging systems Induction in sequential lamination of photoresist materials and printed circuit boards. Can be used in various applications of the photoresist material and the like used in the body layer forming, there is no particular limitation on the application.

  About the manufacturing method of the hardened | cured material of this invention, a preferable coating method, a hardening method, and hardening conditions are shown below.

  The radical polymerizable composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, Cellulose esters such as butyrylcellulose, acetylpropionylcellulose, nitrocellulose; polyamides; polycarbonates; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane Polyester such as -4,4'-dicarboxylate, polybutylene terephthalate, etc .; polystyrene; poly, such as polyethylene, polypropylene, polymethylpentene Olefin; Acrylic resin such as polymethyl methacrylate; Polycarbonate; Polysulfone; Polyethersulfone; Polyetherketone; Polyetherimide; Plastic such as polyoxyethylene and norbornene resin; Glass such as soda glass and quartz glass; Semiconductor substrate; Metal And can be applied on a supporting substrate such as paper. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  Moreover, as the light source of the active light used when curing the colored composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, carbon arc. And a xenon arc etc. can be used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

Hereinafter, although a specific example is given about the manufacturing method of hardened | cured material, this invention is not limited to the following manufacturing method.
For example, a glass plate is spin-coated so as to have a film thickness of 2 μm, baked at 110 ° C. for 2 minutes as a pre-bake, exposed to 100 mJ / cm ² with a high-pressure mercury lamp, and baked at 230 ° C. for 20 minutes as a post-bake. Created.

  Cured products using the radically polymerizable composition of the present invention include color filters in color display liquid crystal display panels such as printed boards, color televisions, PC monitors, personal digital assistants, digital cameras, color filters of CCD image sensors, and touch panels. , Electrode materials for plasma display panels, powder coatings, printing plates, highly transparent insulating films, electroluminescent display devices, magnetic recording materials, micro mechanical parts, waveguides, optical switches, plating masks, etching masks, glass fiber cables It can be used for various applications such as coating, stencil for screen printing, and protective film, and the application is not particularly limited.

  The cured product using the radically polymerizable composition of the present invention is used mainly for the purpose of forming a transparent insulating film among the above-mentioned uses, and the transparent insulating film is particularly transparent insulating for image display devices such as touch panels. Useful as a membrane.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Production Example 1] Polymer (A) No. Preparation of 1 20 parts by mass of dimethyl-2,2 ′-[oxybis (methylene)] diacrylate, 50 parts by mass of methyl methacrylate, 65 parts by mass of methacrylic acid, t-butylperoxy-2-ethylhexanoate 4 parts by mass and 100 parts by mass of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMEA) were mixed until uniform and filled in the monomer dropping layer. On the other hand, 130 parts by mass of PGMEA was charged into a reaction vessel consisting of a separable flask equipped with a cooling tube, purged with nitrogen, heated with an oil bath while stirring, and the temperature of the reaction vessel was raised to 90 ° C. to the same temperature. And stabilized. And the monomer dropping liquid was dripped from the monomer dripping tank over 120 minutes, keeping temperature at 90 degreeC. Sixty minutes after the completion of dropping, the reaction vessel was heated to 110 ° C. and maintained in that state for 3 hours. Further, while bubbling a mixed gas of oxygen / nitrogen = 5/95 (v / v) through the gas introduction pipe into the reaction tank, 30 parts by mass of glycidyl methacrylate, 2,2′-methylenebis (4 -Methyl-6-tert-butylphenol) 0.2 parts by mass, tetraphenylphosphonium bromide 0.35 parts by mass, reacted as it is at 110 ° C. for 12 hours, cooled to room temperature, and obtained polymer After reprecipitating the solution with n-hexane, n-hexane was removed under reduced pressure to obtain a polymer. Thereafter, it was dissolved in PGMEA and adjusted so that the polymer component was 40 wt%. It was set to 1.
The obtained polymer (A) No. The weight average molecular weight of 1 was 12000, and the acid value was 70 mgKOH / g.

[Production Example 2] Polymer (A) No. Preparation of 2 In a polymerization tank, 40.0 parts by mass of PGMEA as a solvent was charged, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Then, 7 parts by mass of benzylmaleimide, 15 parts by mass of PGMEA, 25 parts by mass of methyl methacrylate, methacrylic Acid (MAA) 12.55 parts by mass, dropping system 2 as perbutyl O (manufactured by NOF Corporation) 0.6 parts, dropping system 3 as n-dodecyl mercaptan (n-DM) 1.2 parts by mass for 3 hours each Over time. Then, after maintaining 90 degreeC for 30 minutes, temperature was heated up to 105 degreeC and superposition | polymerization was continued for 3 hours.
Subsequently, 13 parts by mass of glycidyl methacrylate, 0.1 part by mass of triethylamine as a catalyst, and 0.1 part by mass of Antage W400 (manufactured by Kawaguchi Chemical Industry) as a polymerization inhibitor were added, and air and nitrogen mixed to adjust to 5% oxygen concentration The reaction was continued for 8 hours while bubbling gas at a flow rate of 200 ml / min. After allowing to cool to room temperature, PGMEA was added so that the solid content was 40 wt%.
Polymer (A) No. The average molecular weight of 2 was 7500, and the acid value was 70 mgKOH / g.

[Production Example 3] Polymer (A) No. Preparation of 3 20 parts by mass of dimethyl-2,2 ′-[oxybis (methylene)] diacrylate, 50 parts by mass of methyl methacrylate, 20 parts by mass of methacrylic acid, t-butylperoxy-2-ethylhexanoate 4 parts by mass and 80 parts by mass of PGMEA were mixed until uniform, and filled in the monomer dropping layer.
On the other hand, 130 parts by mass of PGMEA was charged into a reaction vessel consisting of a separable flask equipped with a cooling tube, purged with nitrogen, heated with an oil bath while stirring, and the temperature of the reaction vessel was raised to 90 ° C. to the same temperature. And stabilized. And the monomer dropping liquid was dripped from the monomer dripping tank over 120 minutes, keeping temperature at 90 degreeC. Sixty minutes after the completion of dropping, the reaction vessel was heated to 110 ° C. and maintained in that state for 3 hours. Further, while bubbling a mixed gas of oxygen / nitrogen = 5/95 (v / v) through the gas introduction pipe into the reaction tank, 30 parts by mass of glycidyl methacrylate, 2,2′-methylenebis (4 -Methyl-6-tert-butylphenol) 0.2 parts by mass, tetraphenylphosphonium bromide 0.35 parts by mass, reacted as it is at 110 ° C. for 12 hours, cooled to room temperature, and obtained polymer After reprecipitating the solution with n-hexane, n-hexane was removed under reduced pressure to obtain a polymer. Thereafter, it was dissolved in PGMEA and adjusted so that the polymer component was 40 wt%. It was set to 3.
The obtained polymer (A) No. 3 had a weight average molecular weight of 18,000 and an acid value of 2 mgKOH / g.

[Comparative Production Example 1] Ethylenically unsaturated compound No. 1 Production of 1 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g And PGMEA 65.9 g, and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. After cooling to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Furthermore, 9,9-bis (4
-Glycidyloxyphenyl) fluorene 30.0 g, 2,6-di-t-butyl-p-cresol 0.269 g, and PGMEA 1.50 g were added, and after stirring at 90 ° C. for 90 minutes and 120 ° C. for 4 hours, PGMEA 122 .2 g is added, and the ethylenically unsaturated compound No. 1 as the target product as a PGMEA solution is added. 1 (Mw = 4190, Mn = 2170, acid value (solid content) 52 mg · KOH / g)

[Examples 1 to 8 and Comparative Examples 1 to 6] Preparation of radical polymerization composition
Each component was prepared according to the mixing | blending of [Table 1] and [Table 2], and the radically polymerizable composition (Examples 1-8 and Comparative Examples 1-6) was obtained. In addition, the number in a table | surface represents a mass part. Moreover, the code | symbol of each component in a table | surface represents the following component.
A-1 Polymer (A) No. 1 (Solid content 40 wt% PGMEA solution)
A-2 Polymer (A) No. 2 (Solid content 40 wt% PGMEA solution)
A-3 Polymer (A) No. 3 (Solid content 40 wt% PGMEA solution)
B-1 Adeka Arcles NCI-930
(Oxime ester radical polymerization initiator; manufactured by ADEKA)
B-2 IRGACURE OXE01
(Oxime ester radical polymerization initiator; manufactured by BASF)
C-1 Kayalad DPHA (polyfunctional acrylate; manufactured by Nippon Kayaku)
C-2 SPC-3000 (polyfunctional acrylate; Showa Denko)
C-3 ethylenically unsaturated compound No. 1 1
(Polyfunctional acrylate; solid content 55 wt% PGMEA solution)
D-1 KBM-403 (silane coupling agent; manufactured by Shin-Etsu Chemical)
D-2 PGMEA
D-3 Irg-369
(Α-aminoalkylphenone radical polymerization initiator; manufactured by BASF)
D-4 Irg-907
(Α-aminoalkylphenone radical polymerization initiator; manufactured by BASF)

[Evaluation Examples 1 to 8 and Comparative Evaluation Examples 1 to 6]
Each cured product was obtained under the following curing conditions. The resulting cured product was evaluated for transparency, chemical resistance test, volume resistivity and sensitivity. The results are shown in [Table 1] and [Table 2].

(sensitivity)
When the exposure amount is 30 mJ / cm ² and the pattern is fixed well after development, A is assumed. After the development when the exposure amount is 40 mJ / cm ² and the pattern after development is poorly fixed and the exposure amount is 80 mJ / cm ² . B was obtained when the pattern was fixed well.

(transparency)
Spin-coated so that the cured product has a thickness of 2 μm, baked at 110 ° C. for 2 minutes as a pre-bake, exposed to 100 mJ / cm ² with a high-pressure mercury lamp, and baked at 230 ° C. for 20 minutes as a post-bake to produce a cured product did. The obtained cured product having a 400 nm transmittance of 95% or more was rated as “◯”, and the cured product having a transmittance of less than 95% as “×”.

(Chemical resistance test)
The cured product was spin-coated so as to have a thickness of 2 μm, fired at 110 ° C. for 2 minutes as a pre-baking, exposed to 100 mJ / cm ² with a high-pressure mercury lamp, and fired at 230 ° C. for 20 minutes as a post-baking to produce a cured product. The chemical resistance test of the produced cured product was performed by the following method.
According to the test method of JIS D 0202, the cured product was cross-cut into a base shape. Next, the cured product thus prepared was placed in 50 ° C. aqua regia for 5 minutes, 40 ° C. in KOH for 5 minutes, 45 ° C. in an Al acid aqueous solution (phosphoric acid, nitric acid aqueous solution) in 5 minutes, and 80 ° C. resist stripping solution N-300 (Nagase Chem) Tex) It was immersed in order for 20 minutes (5 minutes × 4 times) and washed with water. Next, a peeling test was performed with a cellophane tape, and the peeled state of the base was visually evaluated. A sample in which no peeling was observed was marked with ○, and a sample in which peeling was observed was marked with ×.

(Volume resistivity)
A clear film is spin-coated on a chromium substrate to a thickness of 2 μm, fired at 110 ° C. for 2 minutes as a pre-bake, exposed with a high-pressure mercury lamp at 100 mJ / cm ² , and fired at 230 ° C. for 180 minutes as a post-bake. The clear film was allowed to stand in a high-temperature and high-humidity device at 85 ° C. and 85% RH for 100 hours, and then volume resistivity was measured. The unit is Ω · cm.

  From the above results, it is clear that the curable composition of the present invention can form a cured product with high sensitivity, and the obtained cured product is excellent in transparency, chemical resistance and insulation. Therefore, the radically polymerizable composition of the present invention is particularly useful for an insulating film having transparency.

Claims (5)

Polymer (A) having at least one skeleton selected from the group consisting of the following (Ia) and (Ib) (hereinafter also referred to as polymer (A)) and a radical polymerization initiator represented by the following general formula (II) ( B) radical polymerizability containing an ethylenically unsaturated compound (C) (hereinafter also referred to as ethylenically unsaturated compound (C)) excluding polymer (A) (hereinafter also referred to as radical polymerization initiator (B)). Composition.

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or carbon. Represents an arylalkyl group having 7 to 20 atoms,
The alkylene part of the alkyl group having 1 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms may further have a substituent,
The methylene group in the alkyl group having 1 to 20 carbon atoms and the arylalkyl group having 7 to 20 carbon atoms is —O—, —S—, —NHCO—, —SO ₂ —, —SS—, —SO—. , -CO- or OCO-,
When a plurality of R ¹ and R ² are present in the polymer (A), they may be the same or different. )

Wherein R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 carbon atoms. Represents an arylalkyl group of ˜20 or a heterocyclic-containing group of 2 to 20 carbon atoms,
The terminal of the alkyl group having 1 to 20 carbon atoms represented by R ³ and R ⁴ may be a cycloalkyl group having 4 to 10 carbon atoms,
The aryl group having 6 to 20 carbon atoms represented by R ³ and R ⁴ may be substituted with an alkyl group having 1 to 20 carbon atoms or OR,
R represents an alkyl group having 1 to 20 carbon atoms,
The alkyl group having 1 to 20 carbon atoms represented by R may be substituted with a halogen atom,
The methylene group in the alkyl group having 1 to 20 carbon atoms represented by R may be substituted with -O-,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ (hereinafter also referred to as R ^{5 to} R ¹³ ) are each independently a hydrogen atom, halogen atom, nitro Represents a group, a cyano group, a hydroxyl group, a carboxyl group, R ¹⁴ , OR ¹⁵ , SR ¹⁶ , NR ¹⁷ R ¹⁸ , COR ¹⁹ , SOR ²⁰ , SO ₂ R ²¹ or CONR ²² R ²³ ;
R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are each independently an alkyl group having 1 to 20 carbon atoms or 6 to 6 carbon atoms. 20 represents an aryl group, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms,
The alkyl group having 1 to 20 carbon atoms represented by R ¹⁵ may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group or a carboxyl group,
The aryl group having 6 to 20 carbon atoms represented by R ¹⁹ may be substituted with a nitro group, OR ′, an alkyl group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. Yes,
R ′ represents an alkyl group having 1 to 20 carbon atoms,
The terminal of the alkyl group having 1 to 20 carbon atoms represented by R ′ may be a heterocyclic ring-containing group having 3 to 10 carbon atoms,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ²⁴ R ²⁵ , CO, NR ²⁶ or PR ²⁷ ,
R ²⁴ , R ²⁵ , R ²⁶ and R ²⁷ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a carbon atom. Represents a heterocyclic group containing 2 to 20,
The aryl group having 6 to 20 carbon atoms represented by R ²⁶ may be substituted with —C (R ³ ) ═N—O—C (═O) R ⁴ ,
X ² represents a single bond or CO,
R ⁵ and R ⁶ , R ⁵ and R ²⁴ , R ⁵ and R ²⁵ , R ⁵ and R ²⁶ , R ⁵ and R ²⁷ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , R ⁸ and R ²⁴ , R ⁸ And R ²⁵ , R ⁸ and R ²⁶ , R ⁸ and R ²⁷ , R ⁹ and R ¹⁰ , R ⁹ and R ²⁴ , R ⁹ and R ²⁵ , R ⁹ and R ²⁶ , R ⁹ and R ²⁷ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ²⁴ , R ¹³ and R ²⁵ , R ¹³ and R ^26, and R ¹³ and R ²⁷ may combine to form a ring. ) The radically polymerizable composition according to claim 1, wherein the polymer (A) further has a skeleton represented by the following (Ic).

(Wherein R ²⁸ and R ³⁰ each independently represent a hydrogen atom and an alkyl group having 1 to 5 carbon atoms,
R ²⁹ represents an alkanediyl group having 1 to 20 carbon atoms,
The alkanediyl group may further have a substituent,
The methylene group in the alkanediyl group may be substituted with —O—, —S—, —NHCO—, —SO ₂ —, —SS—, —SO—, —CO— or OCO—.
When a plurality of R ²⁸ , R ²⁹ and R ³⁰ are present in the polymer (A), they may be the same or different. ) The radically polymerizable composition according to claim 1, wherein the polymer (A) further has a skeleton represented by (Id) below.

(In the formula, R ³¹ represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms;
When a plurality of R ³¹ are present in the polymer (A), they may be the same or different. )   The manufacturing method of the hardened | cured material using the radically polymerizable composition as described in any one of Claims 1-3.   Hardened | cured material obtained using the radically polymerizable composition as described in any one of Claims 1-3.