JP2009040762A - Oxime ester photo-initiator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an initiator excellent in photopolymerization reaction. <P>SOLUTION: This oxime ester compound is expressed by formula I [wherein, R<SB>1</SB>is an alkenyl, a heteroarylalkyl, an alkoxycarbonylalkyl, a phenoxycarbonylalkyl, a heteroaryloxycarbonylalkyl, a heteroarylthioalkyl, or an alkyl substituted by an amino, an aminoalkyl or an -N(R<SB>4</SB>)(OR<SB>5</SB>) group; R<SB>2</SB>is an alkyl; R<SB>4</SB>, R<SB>5</SB>are each independently H or an alkylcarbonyl; and Ar is a naphthyl, thienyl or furyl group which may be substituted as desired]. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to certain oxime ester compounds comprising acrylated N-alkylcarbazoles and their use as photoinitiators in photopolymerizable compositions.

Common oxime ester compounds and their use as photoinitiators are, for example, WO 02/100903, WO 04/050653, WO 06/018405, WO 07 / No. 062963 pamphlet, WO 07/071797 pamphlet or WO 05/080337 pamphlet.
International Publication No. 02/100903 Pamphlet International Publication No. 04/050653 Pamphlet International Publication No. 06/018405 Pamphlet International Publication No. 07/062963 Pamphlet International Publication No. 07/071797 Pamphlet International Publication No. 05/080337 Pamphlet

  In photopolymerization technology, there remains a need for photoinitiators that are extremely reactive, easy to manufacture, and easy to handle. For example, in color filter resist applications, advanced color resists are required for advanced color quality characteristics. As the pigment content increases, curing of the color resist becomes more difficult. For this reason, photoinitiators that are extremely reactive compared to current initiators are required. In addition, such novel photoinitiators must meet high industry requirements with respect to properties such as high solubility, thermal stability and storage stability.

（式中、
Ｒ₁は、いずれも非置換の又は置換された、炭素原子数２乃至２５のアルケニル基、炭素
原子数１乃至２０のヘテロアリールアルキル基、炭素原子数３乃至２０のアルコキシカルボニルアルキル基、炭素原子数８乃至２０のフェノキシカルボニルアルキル基、炭素原子数１乃至２０のヘテロアリールオキシカルボニルアルキル基、炭素原子数１乃至２０のヘテロアリールチオアルキル基、炭素原子数０乃至２０のアミノ基または炭素原子数１乃至２０のアミノアルキル基を表し；又はＲ₁は

及び所望によりさらなる基によって置換された炭素原子数１乃至２０のアルキル基を表し
；
又はＲ₁は
連結基として、所望により置換された炭素原子数１乃至１０のアルキレン基、−（ＣＨ＝ＣＨ）ｎ−基、−（Ｃ≡Ｃ）ｎ−基、又はそれらの組み合わせを介してカルバゾール環と一緒になって環を形成し、前記形成された環は非置換であるかまたは置換されており；
ｎは０乃至３の整数を表し；
Ｒ₂は炭素原子数１乃至２０のアルキル基を表し；
Ｒ₄及びＲ₅は互いに独立して水素原子又は炭素原子数１乃至２０のアルキルカルボニル基を表し；
Ａｒは所望により置換されたナフチル基、チエニル基又はフリル基を表す。）で表される化合物が上記要求を特に満たすことを見出した。 Surprisingly, the formula (I)

(Where
R ₁ is an unsubstituted or substituted alkenyl group having 2 to 25 carbon atoms, heteroarylalkyl group having 1 to 20 carbon atoms, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, carbon atom A phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, a heteroarylthioalkyl group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, or the number of carbon atoms Represents 1 to 20 aminoalkyl groups; or R ₁ is

And optionally represents an alkyl group of 1 to 20 carbon atoms substituted by a further group;
Or R ₁ as a linking group via an optionally substituted alkylene group of 1 to 10 carbon atoms, — (CH═CH) n— group, — (C≡C) n— group, or a combination thereof. Taken together with a carbazole ring to form a ring, said formed ring being unsubstituted or substituted;
n represents an integer of 0 to 3;
R ₂ represents an alkyl group having 1 to 20 carbon atoms;
R ₄ and R ₅ each independently represent a hydrogen atom or an alkylcarbonyl group having 1 to 20 carbon atoms;
Ar represents an optionally substituted naphthyl group, thienyl group or furyl group. It was found that the compound represented by

  According to the invention, the compounds of the formula (I) are used as photoinitiators for the photopolymerization of ethylenically unsaturated compounds or mixtures containing these compounds.

  The alkyl group having 1 to 20 carbon atoms is linear, branched or cyclic, for example, a carbon atom having 1 to 18 carbon atoms, 1 to 14 carbon atoms, and 1 to 12 carbon atoms. An alkyl group having 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Pentyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group, icosyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl A group, an ethylcyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a norbornyl group, or a 2-norbornenemethyl group.

  An alkenyl group having 2 to 25 carbon atoms is mono-unsaturated or poly-unsaturated, linear, branched or cyclic, for example, having 2 to 20 carbon atoms and having 2 to 16 carbon atoms. An alkenyl group having 2 to 10 carbon atoms, 2 to 8 carbon atoms, 2 to 6 carbon atoms, 2 to 5 carbon atoms, or 2 to 4 carbon atoms. For example, allyl group, methallyl group, vinyl group, 1,1-dimethylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 1-cyclohexenyl group, 5-hexenyl Or a 7-octenyl group, in particular an allyl group or a vinyl group.

  The alkoxycarbonylalkyl group having 3 to 20 carbon atoms is linear, branched or cyclic, for example, methoxycarbonylmethyl group, methoxycarbonylbutyl group, ethoxycarbonylmethyl group, ethoxycarbonyloctyl group, methoxycarbonylethyl group, Ethoxycarbonylethyl group, propoxycarbonylethyl group, n-butylcarbonylethyl group, propoxycarbonylmethyl group, n-butyloxycarbonylmethyl group, isobutyloxycarbonylmethyl group, 1,1-dimethylpropoxycarbonylethyl group, pentyloxycarbonylethyl Group, hexyloxycarbonylmethyl group, heptyloxycarbonylethyl group, octyloxycarbonylethyl group, nonyloxycarbonylethyl group, decyloxycarbonylethyl group Dodecyloxycarbonyl methyl group, tetrahydrofurfuryl carbonyl methyl group, and the like tetrahydrofurfuryl methylcarbonyl ethyl, in particular, methoxycarbonylmethyl, methoxycarbonylethyl group, ethoxycarbonylmethyl group, an ethoxycarbonylethyl group.

であり、式中、炭素原子数１乃至１３のアルキル基は、しかるべき炭素原子数まで、上記炭素原子数１乃至２０のアルキル基で示した意味のうちの一つである。 The phenoxycarbonylalkyl group having 8 to 20 carbon atoms is

In the formula, an alkyl group having 1 to 13 carbon atoms is one of the meanings represented by the alkyl group having 1 to 20 carbon atoms up to the appropriate number of carbon atoms.

  The substituted phenoxycarbonylalkyl group having 8 to 20 carbon atoms is substituted, for example, at 1 to 4 positions, for example, 1, 2 or 3 positions, particularly 2 or 3 positions. The substituent in the phenyl ring is preferably in the 4-position of the phenyl ring or in the 3,4-, 3,4,5-, 2,6-, 2,4- or 2,4,6-position, in particular Located in the 4-position or 3,4-position.

  The alkylene group having 1 to 10 carbon atoms is a linear or branched alkylene group such as methylene group, ethylene group, propylene group, 1-methylethylene group, 1,1-dimethylethylene group, butylene group. 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group and the like.

A heteroarylalkyl group having 1 to 20 carbon atoms, such as a heteroarylalkyl group having 2 to 20 carbon atoms, 5 to 20 carbon atoms, and 6 to 20 carbon atoms, is bonded via an alkyl group. A heteroaryl group. Corresponding alkyl groups are as described above. In the context of this invention, a heteroaryl group is meant to include any single ring system or multiple ring systems, eg, linked ring systems. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, dibenzofuryl group, chromenyl group, xanthenyl group, thioxanthyl group, phenoxatinyl group, pyrrolyl group, imidazolyl group, Pyrazolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, indolyl group, indazolyl group, purinyl group, quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group Pteridinyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, isothiazolyl group, phenothiazinyl group, isoxaxin group A lyl group, a furazanyl group, a phenoxazinyl group, a 7-phenanthryl group, an anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl) group, a 3-benzo [b] thienyl group, 5 -Benzo [b] thienyl group, 2-benzo [b] thienyl group, 4-dibenzofuryl group, 4,7-dibenzofuryl group, 4-methyl-7-dibenzofuryl group, 2-xanthenyl group, 8-methyl- 2-xanthenyl group, 3-xanthenyl group, 2-phenoxyacetylinyl group, 2,7-phenoxyacetylinyl group, 2-pyrrolyl group, 3-pyrrolyl group, 5-methyl-3-pyrrolyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 2-methyl-4-imidazolyl group, 2-ethyl-4-imidazolyl group, 2-ethyl-5-imidazolyl Group, 1H-tetrazol-5-yl group, 3-pyrazolyl group, 1-methyl-3-pyrazolyl group, 1-propyl-4-pyrazolyl group, 2-pyrazinyl group, 5,6-dimethyl-2-pyrazinyl group 2-indolidinyl group, 2-methyl-3-isoindolyl group, 2-methyl-1-isoindolyl group, 1-methyl-2-indolyl group, 1-methyl-3-indolyl group, 1,5-dimethyl-2- Indolyl group, 1-methyl-3-indazolyl group, 2,7-dimethyl-8-purinyl group, 2-methoxy-7-methyl-8-purinyl group, 2-quinolidinyl group, 3-isoquinolyl group, 6-isoquinolyl group 7-isoquinolyl group, 3-methoxy-6-isoquinolyl group, 2-quinolyl group, 6-quinolyl group, 7-quinolyl group, 2-methoxy-3-quinolyl group, 2-methoyl group Ci-6-quinolyl group, 6-phthalazinyl group, 7-phthalazinyl group, 1-methoxy-6-phthalazinyl group, 1,4-dimethoxy-6-phthalazinyl group, 1,8-naphthridin-2-yl group, 2- Quinoxalinyl group, 6-quinoxalinyl group, 2,3-dimethyl-6-quinoxalinyl group, 2,3-dimethoxy-6-quinoxalinyl group, 2-quinazolinyl group, 7-quinazolinyl group, 2-dimethylamino-6-quinazolinyl group, 3-cinnolinyl group, 6-cinnolinyl group, 7-cinnolinyl group, 3-methoxy 7-cinnolinyl group, 2-pteridinyl group, 6-pteridinyl group, 7-pteridinyl group, 6,7-dimethoxy-2-pteridinyl group, 2 -Carbazolyl group, 3-carbazolyl group, 9-methyl-2-carbazolyl group, 9-methyl-3-carbazolyl Group, β-carbolin-3-yl group, 1-methyl-β-carbolin-3-yl group, 1-methyl-β-carbolin-6-yl group, 3-phenanthridinyl group, 2-acridinyl group, 3-acridinyl group, 2-perimidinyl group, 1-methyl-5-perimidinyl group, 5-phenanthrolinyl group, 6-phenanthrolinyl group, 1-phenazinyl group, 2-phenazinyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 10-methyl-3-phenothiazinyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 4-methyl -3-furazanyl group, 2-phenoxazinyl group, 10-methyl-2-phenoxazinyl group and the like.

  A heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms, such as a heteroaryloxycarbonylalkyl group having 3 to 20 carbon atoms, 5 to 20 carbon atoms, and 6 to 20 carbon atoms, is used as a bonding group. Means a heteroaryl group as described above further comprising an OCO-alkyl group, the alkyl group being as defined above until the appropriate number of carbon atoms. Specific examples include a thienyl-CO-alkyl group and a furyl-CO-alkyl group.

  A heteroarylthioalkyl group having 1 to 20 carbon atoms, for example, a heteroarylthioalkyl group having 2 to 20 carbon atoms, 5 to 20 carbon atoms, and 6 to 20 carbon atoms, is Means a heteroarylalkyl group as described above further having an alkyl group, the alkyl group being as defined above until the appropriate number of carbon atoms. Specific examples include a thienyl-S-alkyl group and a furyl-S-alkyl group.

An amino group having 0 to 20 carbon atoms means an amino group —NRxRy, wherein Rx and R are independently of each other a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (wherein the alkyl group is As defined in the above). Specific examples are -NH ₂ group, methylamino group, ethylamino group, propylamino group, butylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, methylethylamino group, methylpropylamino group. And ethylpropylamino group.

  The aminoalkyl group having 1 to 20 carbon atoms is the above alkyl group having 1 to 20 carbon atoms substituted with the above amino group having 0 to 20 carbon atoms (the alkyl group having 1 to 20 carbon atoms). NRxRy group).

Suitable substituents for alkyl groups having 1 to 20 carbon atoms include, for example, one or more halogens, acyl groups having 1 to 20 carbon atoms, hydroxy groups, alkoxy groups having 1 to 20 carbon atoms, and 6 carbon atoms. Aryloxy group having 1 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms Di (alkyl having 1 to 20 carbon atoms) amino group, arylamino group having 6 to 20 carbon atoms, di (aryl having 6 to 20 carbon atoms) amino group, aryl group having 6 to 20 carbon atoms, Heteroaryl group having 5 to 20 carbon atoms, heteroaryl- (CO) O group having 5 to 20 carbon atoms, heteroaryl having 5 to 20 carbon atoms S group, CN groups, NO ₂ groups, alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having 6 to 20 carbon atoms, alkylaminocarbonyl group having 1 to 20 carbon atoms, di (C 1 -C An alkyl) aminocarbonyl group having 20 to 20 carbon atoms, an arylaminocarbonyl group having 6 to 20 carbon atoms, and di (6 to 2 carbon atoms).
0 aryl) aminocarbonyl group, acyl group having 1 to 20 carbon atoms- (acyloxy group having 1 to 20 carbon atoms) -amino group, alkylthio group having 1 to 20 carbon atoms, and 6 to 20 noarylthio group. is there.

An alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 6 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, and 6 carbon atoms Suitable substituents for the heteroaryloxycarbonylalkyl group having 20 to 20 carbon atoms, the heteroarylthioalkyl group having 6 to 20 carbon atoms and the amino group having 0 to 20 carbon atoms are, for example, one or more halogen atoms and carbon atoms. An alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, an acyl group having 1 to 20 carbon atoms, a hydroxy group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy having 6 to 20 carbon atoms A group, an acyloxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, Aryloxycarbonyl group having 7 to 20 carbon atoms, alkylamino group having 1 to 20 carbon atoms, di (alkyl having 1 to 20 carbon atoms) amino group, arylamino group having 6 to 20 carbon atoms, di ( Aryl having 6 to 20 carbon atoms) amino group, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, heteroaryl- (CO) O group having 5 to 20 carbon atoms, carbon Heteroaryl-S group having 5 to 20 atoms, CN group, NO ₂ group, alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 20 carbon atoms, alkylamino having 1 to 20 carbon atoms Carbonyl group, di (alkyl having 1 to 20 carbon atoms) aminocarbonyl group, arylaminocarbonyl group having 6 to 20 carbon atoms, di (number of carbon atoms) 6-20 aryl) aminocarbonyl group, acyl group having 1 to 20 carbon atoms- (acyloxy group having 1 to 20 carbon atoms) -amino group, alkylthio group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. An arylthio group.

基に対応し、式中Ｒｘ及びＲｙは上記に定義したとおりの炭素原子数１乃至２０のアシル基を表す。
炭素原子数６乃至２０のアリール基は、例えば、フェニル基、ナフチル基、アントリル基またはフェナントリル基であり、特にフェニル基又はナフチル基であり、好ましくはフェニル基である。
炭素原子数１乃至２０のヘテロアリール基の例は、炭素原子数１乃至２０のヘテロアリールアルキル基の定義に関連して上記に与えられている。
炭素原子数１乃至２０のヘテロアリール−（ＣＯ）Ｏ基及び炭素原子数１乃至２０のヘテロアリール−Ｓ基の定義は、ヘテロアリール基で為された定義を考慮に入れれば自明である。
炭素原子数１乃至２０のアルキルスルホニル基は、例えば炭素原子数１乃至１８の、炭素原子数１乃至１２の、炭素原子数１乃至１０の、炭素原子数１乃至８の、炭素原子数１乃至７の、炭素原子数１乃至６の、炭素原子数１乃至４のアルキルスルホニル基である。それは炭素原子数１乃至２０のアルキル−ＳＯ₃−基であり、ここで、アルキル部分は上
記に定義されたとおりである。具体例は、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、イソプロピルスルホニル基、ｎ−ブチルスルホニル基、第二−ブチルスルホニル基、イソブチルスルホニル基、第三−ブチルスルホニル基、デシルスルホニル基、ドデシルスルホニル基、イコシルスルホニル基などである。
炭素原子数６乃至２０のアリールスルホニル基は、炭素原子数６乃至２０のアリール−ＳＯ₃基であり、ここで、アリール部分は上記に定義されたとおりである。
炭素原子数１乃至２０のアルキルチオ基は、直鎖または分枝鎖状であり、例えば炭素原子数１乃至１０の、炭素原子数１乃至８の、炭素原子数１乃至６の、または炭素原子数１乃至４のアルキルチオ基である。具体例は、メチルチオ基、エチルチオ基、プロピルチオ基、イソプロピルチオ基、ｎ−ブチルチオ基、第二−ブチルチオ基、イソ−ブチルチオ基、第三−ブチルチオ基、ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基、２，４，４−トリメチルペンチルチオ基、２−エチルヘキシルチオ基、オクチルチオ基、ノニルチオ基、デシルチオ基、又はドデシルチオ基であり、特にメチルチオ基、エチルチオ基、プロピルチオ基、イソプロピルチオ基、ｎ−ブチルチオ基、第二−ブチルチオ基、イソ−ブチルチオ基、第三−ブチルチオ基であり、好ましくはメチルチオ基である。
炭素原子数１乃至２０のアリールチオ基 The halogen atom is a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, for example, a chlorine atom, a fluorine atom and a bromine atom, and particularly a chlorine atom and a fluorine atom.
A haloalkyl group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms as defined above substituted with a halogen atom as defined above. Alkyl groups are, for example, mono- or poly-halogenated and at most all H-atoms are replaced by halogen atoms. For example, CnHxHally, where x + y = 2n + 1, Hal represents a halogen atom, preferably F. Specific examples are a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, or a 2-bromopropyl group, particularly a trifluoromethyl group or a trichloromethyl group.
The acyl group having 1 to 20 carbon atoms corresponds to an alkanoyl group having 1 to 20 carbon atoms, an arylcarbonyl group having 6 to 20 carbon atoms, or a heteroarylcarbonyl group having 1 to 20 carbon atoms, Branched or cyclic, for example, having 1 to 18 carbon atoms, 1 to 14 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, Or an acyl group having 1 to 4 carbon atoms, or an acyl group having 4 to 12 carbon atoms, or 4 to 8 carbon atoms. Specific examples are formyl group, acetyl group, propionyl group, butanoyl group, isobutanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, dodecanoyl group, tetradecanoyl group, pentadecanoyl group, Hexadecanoyl group, octadecanoyl group, icosanoyl group, benzoyl group, 2-toluoyl group, 4-toluoyl group, 4-methoxybenzoyl group, 2-chlorobenzoyl group, 2,4-dichlorobenzoyl group, 1-naphthoyl group 2-naphthoyl group, 2-furanylcarbonyl group and 2-thiophenylcarbonyl group, preferably acetyl group.
The alkoxy group having 1 to 20 carbon atoms is linear, branched or cyclic, for example, a carbon atom having 1 to 18 carbon atoms, 1 to 16 carbon atoms, and 1 to 12 carbon atoms. An alkoxy group having 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Specific examples are methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butyloxy group, sec-butyloxy group, iso-butyloxy group, tert-butyloxy group, pentyloxy group, hexyloxy group, heptyloxy group. 2,4,4-trimethylpentyloxy group, 2-ethylhexyloxy group, tetrahydrofurfuryloxy group, tetrahydrofurfurylmethyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, hexadecyloxy group, Octadecyloxy or icosyloxy groups, especially groups, methoxy groups, ethoxy groups, propoxyisopropoxy groups, n-butyloxy groups, sec-butyloxy groups, iso-butyloxy groups, tert-butyloxy groups, especially methoxy groups is there.
An aryloxy group having 6 to 20 carbon atoms means an aryl-O— group having 1 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms is as defined below. Specific examples are a phenyloxy group, a 1-naphthyloxy group or a 2-naphthyloxy group, particularly a phenyloxy group.
An acyloxy group having 1 to 20 carbon atoms means an acyl-O— group having 1 to 20 carbon atoms, and the acyl group having 1 to 20 carbon atoms is as defined above.
The alkoxycarbonyl group having 2 to 20 carbon atoms is linear, branched or cyclic and includes, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, tetrahydro Furfuryloxycarbonyl group, tetrahydrofurfurylmethyloxycarbonyl group, 1,1-dimethylpropoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxy A carbonyl group or a dodecyloxycarbonyl group, particularly a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butyloxycarbonyl group or an iso-butyloxy group. An aryloxycarbonyl group, preferably a methoxycarbonyl group.
An aryloxycarbonyl group having 7 to 20 carbon atoms means an aryl-O- (CO)-group having 6 to 20 carbon atoms, and the aryl group having 6 to 20 carbon atoms is defined below. It is as follows.
The meaning of an arylamino group having 6 to 20 carbon atoms and a di (aryl having 6 to 20 carbon atoms) amino group corresponds to those represented as an amino group -NRxRy having 0 to 20 carbon atoms, provided that In this group, the alkyl group is substituted with an aryl group as defined below. An alkylaminocarbonyl group having 1 to 20 carbon atoms, a di (alkyl having 1 to 20 carbon atoms) aminocarbonyl group, an arylaminocarbonyl group having 1 to 20 carbon atoms, and di (aryl having 1 to 20 carbon atoms). An aminocarbonyl group corresponds to the group defined above attached to the —CO— group.
C1-C20 acyl- (C1-C20 acyloxy) -amino group is:

In the formula, Rx and Ry represent an acyl group having 1 to 20 carbon atoms as defined above.
The aryl group having 6 to 20 carbon atoms is, for example, a phenyl group, a naphthyl group, an anthryl group or a phenanthryl group, particularly a phenyl group or a naphthyl group, preferably a phenyl group.
Examples of heteroaryl groups having 1 to 20 carbon atoms are given above in connection with the definition of heteroarylalkyl groups having 1 to 20 carbon atoms.
The definition of a heteroaryl- (CO) O group having 1 to 20 carbon atoms and a heteroaryl-S group having 1 to 20 carbon atoms is self-evident when the definition made for a heteroaryl group is taken into consideration.
The alkylsulfonyl group having 1 to 20 carbon atoms is, for example, 1 to 18 carbon atoms, 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 1 carbon atoms. 7 is an alkylsulfonyl group having 1 to 6 carbon atoms and 1 to 4 carbon atoms. It is a C 1-20 alkyl-SO ₃ — group, wherein the alkyl moiety is as defined above. Specific examples are methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, secondary-butylsulfonyl group, isobutylsulfonyl group, tertiary-butylsulfonyl group, decylsulfonyl group, dodecylsulfonyl. Group, icosylsulfonyl group and the like.
An arylsulfonyl group having 6 to 20 carbon atoms is an aryl-SO ₃ group having 6 to 20 carbon atoms, wherein the aryl moiety is as defined above.
The alkylthio group having 1 to 20 carbon atoms is linear or branched, for example, having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, or the number of carbon atoms 1 to 4 alkylthio groups. Specific examples are methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, second-butylthio group, iso-butylthio group, tert-butylthio group, pentylthio group, hexylthio group, heptylthio group, 2, 4,4-trimethylpentylthio group, 2-ethylhexylthio group, octylthio group, nonylthio group, decylthio group, or dodecylthio group, especially methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, A 2-butylthio group, an iso-butylthio group and a tert-butylthio group are preferred, and a methylthio group is preferred.
Arylthio group having 1 to 20 carbon atoms

When R ₁ forms a ring together with the carbazole ring, the linking group is optionally substituted alkylene group having 1 to 10 carbon atoms,-(CH = CH) n- group,-(C≡C) n-groups or combinations thereof.

The optional substituents in the linking group are one or more halogen, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 12 carbon atoms, an acyl group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. 20 alkoxy groups, aryloxy groups having 1 to 20 carbon atoms, acyloxy groups having 1 to 20 carbon atoms, alkoxycarbonyl groups having 1 to 20 carbon atoms, aryloxycarbonyl groups having 1 to 20 carbon atoms, carbon An alkylamino group having 1 to 20 atoms, a di (alkyl having 1 to 20 carbon atoms) amino group, an arylamino group having 1 to 20 carbon atoms, a di (aryl having 1 to 20 carbon atoms) amino group, carbon Aryl group having 1 to 20 atoms, heteroaryl group having 1 to 20 carbon atoms, heteroaryl- (CO) O group having 1 to 20 carbon atoms, carbon Heteroaryl -S group child having 1 to 20, CN groups, NO ₂ groups, alkylsulfonyl group having 1 to 20 carbon atoms, an arylsulfonyl group having a carbon number of 1 to 20, alkylamino of 1 to 20 carbon atoms Carbonyl group, di (alkyl having 1 to 20 carbon atoms) aminocarbonyl group, arylaminocarbonyl group having 1 to 20 carbon atoms, di (aryl having 1 to 20 carbon atoms) aminocarbonyl group, 1 to carbon atoms 20 acyl- (acyloxy having 1 to 20 carbon atoms) -amino group, alkylthio group having 1 to 20 carbon atoms, and arylthio group having 1 to 20 carbon atoms.

である。 Specific examples of the corresponding structure in the case where “R ₁ forms a ring together with a carbazole ring”

It is.

  The ring formed may be, for example, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or 8 to 8 carbon atoms. 20 phenoxycarbonylalkyl groups, heteroaryloxycarbonylalkyl groups having 1 to 20 carbon atoms, heteroarylthioalkyl groups having 1 to 20 carbon atoms, amino groups having 0 to 20 carbon atoms, and 1 to 20 carbon atoms Of the aminoalkyl groups are substituted by the substituents given above.

The naphthyl group represents a 1-naphthyl group or a 2-naphthyl group, and is preferably a 1-naphthyl group.
The thienyl group represents a 2-thienyl group or a 3-thienyl group, preferably a 2-thienyl group.
A furyl group represents a 2-furyl group or a 3-furyl group, preferably a 2-furyl group.

In this document, the term “and / or” or “or / and” means that not only one of the defined options (substituents) may be present, but also some of the defined options (substituents). Are meant to indicate that a mixture of different options (substituents) may exist together.
The term “at least” is meant to define one or more than one, eg one or two or three, preferably one or two.
The term “optionally substituted” means that the group referred to is either unsubstituted or substituted.
Unless the context requires otherwise, throughout this specification and the claims, the terms “include” or “include” (variations such as “comprise” or “comprises” or “comprising”) are defined. It is understood that a given integer, or process, or group of integers, or process groups, is not intended to exclude other integers or processes, or groups of integers, or process groups.

基で置換された炭素原子数１乃至２０のアルキル基である。
炭素原子数１乃至２０のアルキル基としてのＲ₂は、好ましくは炭素原子数１乃至８の
アルキル基、特に炭素原子数１乃至４のアルキル基、すなわち、メチル基又はエチル基、特にエチル基である。

基で置換された炭素原子数１乃至２０のアルキル基中のＲ₄及びＲ₅は、好ましくは同一であり、炭素原子数１乃至８のアルキルカルボニル基、特に炭素原子数１乃至４のアルキルカルボニル基、すなわち、アセチル基、プロピオニル基、特にアセチル基である。 Ar preferably represents a naphthyl group or a thienyl group, particularly a 1-naphthyl group or a 2-thienyl group.
R ₁ is, for example, in particular an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or

And an alkyl group having 1 to 20 carbon atoms substituted with a group.
R ₂ as an alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, particularly an alkyl group having 1 to 4 carbon atoms, that is, a methyl group or an ethyl group, particularly an ethyl group. is there.

R ₄ and R _{5 in} the alkyl group having 1 to 20 carbon atoms substituted with a group are preferably the same, and are an alkylcarbonyl group having 1 to 8 carbon atoms, particularly an alkylcarbonyl having 1 to 4 carbon atoms. A group, ie an acetyl group, a propionyl group, in particular an acetyl group.

で置換された炭素原子数１乃至２０のアルキル基を表し；
Ｒ₂は炭素原子数1乃至２０のアルキル基を表し；
Ｒ₄及びＲ₅は互いに独立して水素原子又は炭素原子数１乃至２０のアルキルカルボニル基を表し；そして
Ａｒは所望により置換されたナフチル基又はチエニル基を表す。 Of further interest are compounds of the formula (I), wherein
R ₁ is an optionally substituted alkoxycarbonylalkyl group having 3 to 20 carbon atoms,
An aminoalkyl group having 1 to 20 carbon atoms, or

Represents an alkyl group having 1 to 20 carbon atoms substituted with
R ₂ represents an alkyl group having 1 to 20 carbon atoms;
R ₄ and R ₅ each independently represent a hydrogen atom or an alkylcarbonyl group having 1 to 20 carbon atoms; and Ar represents an optionally substituted naphthyl group or thienyl group.

で置換された炭素原子数１乃至２０のアルキル基を表し；
Ｒ₂はエチル基を表し；
Ｒ₄及びＲ₅は互いに独立してアセチル基を表し；そして
Ａｒは所望により置換されたナフチル基又はチエニル基を表すものである。 Other preferred compounds of the formula (I) are
R ₁ is an alkoxycarbonylalkyl group having 3 to 20 carbon atoms or

Represents an alkyl group having 1 to 20 carbon atoms substituted with
R ₂ represents an ethyl group;
R ₄ and R ₅ independently of one another represent an acetyl group; and Ar represents an optionally substituted naphthyl or thienyl group.

Specific examples of compounds according to the invention are

Ｒ₁、Ｒ₂及びＡｒは上記に定義したとおりであり、Ｈａｌはハロゲン原子、特にＣｌを意味する。 The oxime ester represented by the formula (I) can be prepared by methods described in the literature, for example, diethyl ether, t-butyl methyl ether, tetrahydrofuran (THF), ethyl acetate, toluene, xylene, acetone, methyl ethyl ketone, dichloromethane, chloroform, chlorobenzene. In the presence of a base such as triethylamine, diisopropylethylamine, potassium hydroxide, sodium hydroxide, sodium hydride, 2,6-lutidine or pyridine in an inert solvent such as dimethylacetamide or dimethylformamide, or pyridine From the corresponding oximes by reacting the corresponding oxime with an acyl halide, especially chloride, or anhydride in a basic solvent such as For example

R ₁ , R ₂ and Ar are as defined above, Hal means a halogen atom, in particular Cl.

  Said reaction is known to those skilled in the art and is generally carried out at temperatures of -15 to + 50 ° C, preferably at temperatures of 0 to 25 ° C.

（式中、Ｒ₁、Ｒ₂及びＡｒは上述に示したとおりである。）
で表されるオキシム化合物を式（Ｖ）又は（ＶＩ）で表されるアシルハライド又は無水物

（式中Ｈａｌはハロゲン原子を意味する。）
と塩基又は塩基混合物の存在下で反応させることによる、上述の式（Ｉ）で表される化合物の製造方法である。 The subject of the present invention is therefore of the formula (Ia)

(Wherein R ₁ , R ₂ and Ar are as described above.)
An oxime compound represented by formula (V) or (VI):

(In the formula, Hal means a halogen atom.)
Is a method for producing a compound represented by the above formula (I) by reacting with a base or a base mixture.

  Furthermore, the subject of the present invention is a compound of the formula (Ia) as defined above.

Another object of the present invention is the above-described method, wherein R ₁ in the formula (Ia) is an alkyl group having 1 to 20 carbon atoms substituted with a —NHOH group.

The oximes required as starting materials are standard chemistry textbooks (eg J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992), or specialized monographs such as SR Sandler & W. Karo, It can be obtained by various methods described in Organic functional group preparations, Vol. 3, Academic Press. One of the most convenient methods is, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidinone (NMP), dimethylsulfoxide (DMSO) of aldehyde or ketone and hydroxylamine or a salt thereof. , Methanol, ethanol, isopropanol, ethylene glycol, ethyl acetate, tert-butyl methyl ether, diethylene glycol dimethyl ether, toluene, chlorobenzene, dichlorobenzene and the like. Mixtures of these solvents are also suitable for the reaction. A base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent, and the base can be added at the start or continuously during the reaction. Water can also be added to the reaction mixture for dissolution of the inorganic solvent. Basic solvents such as pyridine can also be used as base and / or solvent or cosolvent. The reaction temperature is generally from room temperature to the reflux temperature of the mixture, usually about 20-120 ° C. The carbonyl group is selectively converted to an oxime by adjusting the reaction temperature and selecting a solvent (since the reaction rate depends on them). In general, anhydrides are the most reactive, followed by dialkyl ketones, alkyl aryl ketones and diaryl ketones with less reactivity.

は、例えば、ヒドロキシルアミン基をアシルクロリド［ＲＣＯＣｌ］又は無水物［（ＲＣＯ）₂Ｏ］と上述の塩基条件下で反応させることによって、製造可能である。 When reacting an α, β-unsaturated carbonyl group with hydroxylamine or a salt thereof under the conditions described above, the hydroxylamino group can be derivatized at the β-position of the carbonyl group. Bulltein des
As described in Societes Chimiques Belges (1987), 96 (4), 293-301 and Acta Chimica Hungarica (1989), 126 (6), 813-20, β-hydroxyamino-oximes have the corresponding α, It can be synthesized from a β-unsaturated ketone using hydroxylamine or a salt thereof. Adjustment of the reaction conditions is essential for the selective conversion of the carbonyl group to the oxime. Base

Can be prepared, for example, by reacting a hydroxylamine group with an acyl chloride [RCOCl] or an anhydride [(RCO) ₂ O] under the basic conditions described above.

（式中、Ｒ₁は非置換の又は置換された炭素原子数２乃至２５のアルケニル基、
Ｒ₂及びＡｒは上記に定義されたとおりである。）
をヒドロキシルアミン又はその塩と反応させることによる、上述の式（Ｉａ）で表される化合物（式中、Ｒ₁は−ＮＨＯＨ基で置換された炭素原子数１乃至２０のアルキル基を表
す。）の製造方法である。 Therefore, the subject of the present invention is also a ketone compound represented by the formula (Ib)

Wherein R ₁ is an unsubstituted or substituted alkenyl group having 2 to 25 carbon atoms,
R ₂ and Ar are as defined above. )
Is a compound represented by the above formula (Ia) by reacting with hydroxylamine or a salt thereof (wherein R ₁ represents an alkyl group having 1 to 20 carbon atoms substituted with —NHOH group). It is a manufacturing method.

を与える

である上述の方法が好ましい。Ａｒ及びＲ₂は上記に定義されたとおりである。 In particular, in the formula, the compound represented by the formula (Ib) reacts with hydroxylamine or a salt thereof to form a compound

give

The above method is preferred. Ar and R ₂ are as defined above.

  The corresponding ketone intermediate is produced, for example, by the method described in the literature, for example, WO 2005-080337. Such reactions are known to those skilled in the art.

Another convenient synthesis of oximes is the nitrosation of “active” methylene groups using nitrous acid or alkyl nitrites. Vol. VI (J. Wiley & Sons, New York, 1988), pp 199 and 840, and alkaline conditions such as those described in Organic Synthesis coll. Vol V, pp32 and 373, coll. Vol. Any of the acidic conditions such as those described in III, pp191 and 513, coll. Voll. Nitrous acid is usually produced from sodium nitrite. The alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, or isoamyl nitrite.

  All oxime ester groups can exist in two configurations (Z) or (E). Isomers can be separated by conventional methods, but isomer mixtures can also be used as photoinitiating species. Accordingly, the present invention also relates to a mixture of configurational isomers of the compound represented by formula (I).

The compounds of the formula (I) are suitable as radical photoinitiators.
Thus, another subject of the present invention is
(A) at least one ethylenically unsaturated photopolymerizable compound, and (b) at least one compound represented by the above formula (I) as a photoinitiator, or represented by the above formula (I). A photopolymerizable composition comprising a mixture of compounds to be prepared.

  In addition to the photoinitiator (b), the composition may comprise at least one further photoinitiator (c) and / or other additives (d).

  The unsaturated compound (a) can have one or more olefinic double bonds. They can be low molecular weight (monomeric) or high molecular weight (oligomeric). Examples of monomers having a double bond are alkyl, hydroxyalkyl, cycloalkyl (optionally interrupted by O) or aminoacrylate, or alkyl, hydroxyalkyl, cycloalkyl (optionally interrupted by O) or Amino methacrylates such as methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, tetrahydrofurryl acrylate, isobornyl acrylate, methyl methacrylate, cyclohexyl methacrylate or ethyl methacrylate. Silicone acrylates are also convenient. Other examples include acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl- and halo-styrenes, N-vinyl pyrrolidone, vinyl chloride, Or vinylidene chloride.

  Examples of monomers having two or more double bonds are ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or diacrylate of bisphenol A, and 4,4′-bis (2-acryloyloxyethoxy) diphenyl. With propane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, or tris (2-acryloylethyl) isocyanurate is there.

Examples of polyunsaturated compounds (oligomers) that are relatively high in molecular weight are acrylated epoxy resins, polyesters containing acrylate groups, vinyl ether groups or epoxy groups, polyurethanes, and polyethers. A further example of an unsaturated oligomer is an unsaturated polyester resin, usually made from maleic acid, phthalic acid, and one or more diols, having a molecular weight of about 500 to about 3,000. In addition, vinyl ether monomers and oligomers, and maleic acid terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxy backbones can also be used. Particularly suitable are combinations of oligomers having vinyl ether groups with polymers as described in WO 90/01512. However, copolymers of vinyl ether and maleic acid functionalized monomers are also suitable. This type of unsaturated oligomer may also be referred to as a prepolymer.

  Particularly suitable examples are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the chain or in side groups, such as unsaturated polyesters, polyamides and polyurethanes, and their Copolymers, polymers and copolymers having (meth) acrylic groups in the side chain, and mixtures of one or more such polymers.

  Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic acid and methacrylic acid are preferred.

  Suitable polyols are aromatic and in particular aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-hydroxydiphenyl, 2,2-di (4-hydroxyphenyl) -propane, and novolaks and resoles. Examples of polyepoxides are based on the above polyols, in particular aromatic polyols, and epichlorohydrin. Other suitable polyols are polymers and copolymers having hydroxy groups in the polymer chain or side groups, such as polyvinyl alcohol and copolymers thereof, or polyhydroxyalkyl methacrylates or copolymers thereof. Other suitable polyols are oligoesters having hydroxy end groups.

  Examples of aliphatic and cycloaliphatic polyols are preferably alkylene diols having 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3. -Or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, preferably polyethylene glycol having a molecular weight of 200 to 1,500, 1,3-cyclopentanediol, 1 , 2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol Over a Le and sorbitol.

  Polyols can be partially or fully esterified with one carboxylic acid or a different unsaturated carboxylic acid, in which the free hydroxy groups are modified, for example etherified or esterified with other carboxylic acids. Can be done.

Examples of esters are:
Trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Acrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol diacrylate Tacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pen titaconate, dipentaerythritol hexaitaco Acrylate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol Tetramethacrylate, sorbitol pentaacrylate Sorbitol hexaacrylate, acrylic acid and methacrylic acid oligoesters, diacrylic acid and glycerol triacrylate, 1,4-cyclohexanediacrylate, bisacrylic acid and bismethacrylic acid esters of polyethylene glycol having a molecular weight of 200 to 1,500, or It is a mixture of these.

  Likewise suitable as component (a) are aromatic, alicyclic and aliphatic, preferably having 2 to 6, in particular 2 to 4 amino groups of the same or different unsaturated carboxylic acids. Amide with polyamine. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6 -Hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di (β- Aminoethoxy)-or di (β-aminopropoxy) -ethane. Suitable other polyamines are preferably polymers and copolymers having additional amino groups in the side chain, and oligoamides having amino end groups. Examples of such unsaturated amides are methylene bisacrylamide, 1,6-hexamethylene bisacrylamide, diethylenetriamine trismethacrylamide, bis (methacrylamidepropoxy) ethane, β-methacrylamide ethyl methacrylate and N [(β-hydroxyethoxy ) Ethyl] acrylamide.

  Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines. Some of the maleic acid can be replaced with other dicarboxylic acids. They can be used with ethylenically unsaturated comonomers such as styrene. The polyesters and polyamides can be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, in particular those having a relatively long chain, for example of 6 to 20 carbon atoms. Examples of polyurethanes are those composed of saturated or unsaturated diisocyanates and unsaturated or saturated diols respectively.

  Polymers having (meth) acrylate groups in the side chain are likewise known. They can be, for example, reaction products of novolak-based epoxy resins with (meth) acrylic acid, or homopolymers or copolymers of vinyl alcohol or their hydroxyalkyl derivatives esterified with (meth) acrylic acid Or can be homopolymers and copolymers of (meth) acrylate esters esterified with hydroxyalkyl (meth) acrylates.

  Other suitable polymers having acrylate or methacrylate groups in the side chain are, for example, solvent-soluble or alkali-soluble polyimide precursors, such as photopolymerizable side chains attached to either the backbone or ester groups in the molecule. It is a poly (amic acid ester) compound having a group, ie described in EP 624826. Such oligomers or polymers can be formulated using this novel photoinitiator, and optionally a reactive diluent, such as a multifunctional (meth) acrylate, to produce a highly sensitive polyimide precursor resist. Can do.

The present photopolymerizable compounds can be used alone or in any desired mixture. Preference is given to using a mixture of polyol (meth) acrylates.

Examples of component (a) are also polymers or oligomers having at least two ethylenically unsaturated groups and at least one carboxyl functional group in the molecular structure, for example saturated or unsaturated polybasic acid anhydrides and , A resin obtained by reacting an epoxy compound with an unsaturated monocarboxylic acid reaction product, for example, a commercially available product such as EB9696 (UCB Chemicals), KAYARAD TCR1025 (Nippon Kayaku Co., Ltd.), or a carboxyl group-containing resin , An addition product formed between an unsaturated compound having an α, β-unsaturated double bond and an epoxy group (for example, ACA200M (Daicel Chemical Industries, Ltd.)).

  The subject of the present invention is also the photopolymerizable composition described above, wherein the component (a) is a reaction of a saturated or unsaturated polybasic acid anhydride with a reaction product of an epoxy resin and an unsaturated carboxylic acid. It is resin obtained by. Such compounds include, for example, JP-A-6-1638, JP-A-6-1938, JP-A-8-278629, JP-A-8-278630, JP-A-10-301276, and JP-A-10-301276. No. 2001-40022, JP-A-10-221843, JP-A-11-231523, JP-A-2002-206014, or JP-A-2006-53569, the disclosure of which is incorporated herein by reference. Incorporated.

  The unsaturated compound (a) can also be used as a mixture with a film-forming component that is not photopolymerizable. These can be, for example, physically drying polymers or their solutions in organic solvents, such as nitrocellulose or cellulose acetobutyrate. However, it may also be a chemically and / or thermally curable (thermosetting) resin, for example polyisocyanates, polyepoxides and melamine resins, and polyimide precursors. The simultaneous use of thermosetting resins is important for use in systems known as hybrid systems, which are photopolymerized in the first step and crosslinked by thermal aftertreatment in the second step.

The present invention also provides a composition comprising as component (a) at least one ethylenically unsaturated photopolymerizable compound emulsified or dissolved in water. Many variations of such radiation curable aqueous prepolymer dispersions are commercially available. A dispersion of prepolymer is understood to be a dispersion of water and at least one prepolymer dispersed therein. The concentration of water in these systems is, for example, 5 to 80% by weight, in particular 30 to 60% by weight. The concentration of the radiation curable prepolymer or prepolymer mixture is, for example, 95 to 20% by weight, in particular 70 to 40% by weight. In these compositions, the sum of percentages shown for water and prepolymer is 100 in each case, and auxiliaries and additives are added in amounts that vary depending on the intended use.
A radiation-curable film-forming prepolymer that is dispersed in water and often dissolved is an aqueous prepolymer dispersion of monofunctional or polyfunctional ethylenically unsaturated prepolymers known per se. For example, having a polymerizable double bond content of 0.01 to 1.0 mole per 100 g of prepolymer, and for example having an average molecular weight of at least 400, in particular 500 to 10,000. . However, higher molecular weight prepolymers can also be considered depending on the intended use. For example, a polyester having a polymerizable C—C double bond and having an acid value of 10 or less, a polyether having a polymerizable C—C double bond, and at least two epoxide groups per molecule are used. A hydroxyl-containing reaction product of a polyepoxide having a hydroxyl group with at least one α, β-ethylenically unsaturated carboxylic acid, a polyurethane (meth) acrylate, and an acrylic copolymer having an α, β-ethylenically unsaturated acryl group. A polymer, as described in EP 12339. Mixtures of these prepolymers can be used as well. Also suitable are polymerizable prepolymers described in EP 33896, having an average molecular weight of at least 600, a carboxyl group content of 0.2 to 15%, and 0.01 to 100 g per 100 g of prepolymer. It is a thioether adduct of a polymerizable prepolymer having 0.8 mol of a polymerizable C—C double bond. Other suitable aqueous dispersions based on specific alkyl (meth) acrylate polymers are described in EP 41125, and suitable water dispersible, radiation curable prepolymers of urethane acrylates are described in German patents. No. 2936039.
Further additives that may be included in these radiation curable aqueous prepolymer dispersions are dispersion aids, emulsifiers, antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol) or 2 1,6-di-t-butylphenol, light stabilizers, dyes, pigments, fillers such as glass or alumina, such as talc, gypsum, silicic acid, rutile, carbon black, zinc oxide, iron oxide, reaction accelerators Leveling agents, lubricants, wetting agents, thickeners, matting agents, antifoaming agents, and other aids commonly used in paint technology. Suitable dispersing aids are high molecular weight substances and water-soluble organic compounds having polar groups, such as polyvinyl alcohol, polyvinyl pyrrolidone or cellulose ether. The emulsifiers that can be used are nonionic emulsifiers and, if desired, ionic emulsifiers can also be used.

In some cases it may be advantageous to use a mixture of two or more of the novel photoinitiators. Of course, mixtures with known photoinitiators (c), such as camphorquinone; benzophenones, such as 2,4,6-trimethylbenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-methoxycarbonyl Benzophenone, 4,4′-bis (chloromethyl) benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxy-benzophenone, [4- (4-methylphenylthio) phenyl]- Phenylmethanone, methyl-2-benzoylbenzoate, 3-methyl-4′-phenylbenzophenone, 2,4,6-trimethyl-4′-phenylbenzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4 '-Bis (diethylamino) benzofe Benzophenone derivatives such as benzoyl; benzyl ketals such as benzoyl alkyl ethers such as benzyldimethyl ketal (IRGACURE® 651); acetophenones, dialkoxyacetophenones such as 2-hydroxy-2-methyl-1-phenyl-propanone (DARUCUR ( 1173), 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACUR® 184), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one (IRGACURE® 2959), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane-1 -ON (IRGAC RE (registered trademark) 127), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -phenoxy] -phenyl} -2-methyl-propan-1-one and the like -Hydroxyacetophenone; for example, (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane (IRUGACURE® 907), (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (IRGACURE®) 369), (4-morpholinobenzoyl) -1- (4-methylbenzyl) 1-dimethylaminopropane (IRGACURE® 379), (4- (2-hydroxyethyl) aminobenzoyl) -1-benzyl- 1-dimethylaminopropane), 2-benzyl-2-dimethylamino- Α-aminoacetophenones such as-(3,4-dimethoxyphenyl) butan-1-one; 4-aroyl 1,3-dioxane, benzoin alkyl ethers, phenylglyoxalates and their derivatives such as oxo-phenyl- Oxyl-phenyl-acetic acid-1-methyl-2- [2- (2), such as dimethyl phenylglyoxalate, such as benzoin alkyl ester acetate, for example, phenylglyoxalic acid methyl ester (DAROCUR® MBF) -Oxo-2-phenyl-acetoxy) -propoxy] -ethyl ester (IRGACURE® 754); further oxime esters such as 1,2-octane-dione 1- [4- (phenylthio) phenyl] 2- ( O-Benzoyloxime) (IRG CURE® OXE01), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9Hcarbazol-3-yl] -1- (O-acetyloxime (IRGACURE® OXE02), 9H -Thio-xanthene-2-carboxaldehyde 9-oxo-2- (O-acetyloxime), described in International Publication No. 07/062963, International Publication No. 07/071797 and International Publication No. 05/080337 Peresters such as benzophenone tetracarboxylic acid peresters described in European Patent 126541, monoacylphosphine oxides such as (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (DAROCUR®) TPO), bisacylphosphine oxide, for example, bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE® 819), bis (2,4,6-trimethylbenzoyl) -2,4-dipentoxyphenylphosphine oxide, trisacylphosphine oxide, halomethyltriazine, such as 2- [2- (4- Methoxyphenyl) -vinyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- (4-methoxy-phenyl) -4,6-bis-trichloromethyl- [1,3,5 ] Triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trick Romethyl- [1,3,5] triazine, 2-methyl-4,6-bis-trichloromethyl- [1,3,5] triazine, hexaarylbisimidazole / co-initiator system such as 2-mercaptobenzthiazole And 4,4′-bis (diethylamino) benzophenone, a ferrocenium compound, or bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium (IRGACURE® 784), etc. Mixtures of ortho-chlorohexaphenyl-bisimidazole in combination with other titanocenes can also be used. Furthermore, boron compounds can also be used as auxiliary initiators.

When the novel photoinitiator system is used in a hybrid system, in addition to the new free radical curing agent, a cationic photoinitiator, a peroxide compound such as benzoyl peroxide (other suitable peroxides are U.S. Pat. No. 4,950,581, column 19, lines 17 to 25), for example, an aromatic sulfonium salt, phosphonium, described in U.S. Pat. No. 4,950,581, column 18, lines 60 to 19, line 10. Salts or iodonium salts, or cyclopentadienyl-arene-iron (II) complex salts such as (η ⁶ -isopropylbenzene) (η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate, and oxime sulfonic acid Esters, for example those described in EP 780729. Pyridinium and (iso) quinolinium salts, as described, for example, in EP 497531 and EP 441232 may also be used in combination with the novel photoinitiators.

  The novel photoinitiator, whether alone or in a mixture with other known photoinitiators and sensitizers, can be used in the form of a dispersion or emulsion in water or an aqueous solution. When the compound is conveniently used in an emulsion or dispersion, conventional dispersants and emulsifiers are added to form a stable emulsion or dispersion. Corresponding suitable additives are known to the person skilled in the art.

  The photopolymerizable composition generally comprises from 0.05 to 25% by weight, preferably from 0.01 to 10% by weight, in particular from 0.01 to 8% by weight of photoinitiator, based on the solid composition. When using a mixture of initiators, this amount means the sum of all the photoinitiators added. Therefore, this amount means either photoinitiator (b) or photoinitiator (b) + (c).

In addition to the photoinitiator, the photopolymerizable mixture may contain various additives (d). These examples are thermal inhibitors intended to prevent premature polymerization, examples of which are hydroquinone, hydroquinone derivatives, p-methoxyphenol, β-naphthol or sterically hindered phenols such as 2,6-di- Tertiary-butyl-p-cresol. To increase storage stability in the dark, for example, copper compounds such as naphthenic acid, stearic acid or copper octylate, phosphorus compounds such as triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite Alternatively, tribenzyl phosphite, quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives such as N-diethylhydroxylamine can be used. Paraffin or similar waxy substances can be added to eliminate atmospheric oxygen during polymerization, and these are poorly soluble in the polymer, so they move to the surface early in the polymerization and prevent air entry. A transparent surface layer is formed. An oxygen-impermeable layer such as poly (vinyl alcohol-co-vinyl acetate) can also be applied over the coating. Light stabilizers that can be added in small amounts are UV absorbers, for example of the hydroxyphenylbenzotriazole, hydroxyphenylbenzophenone, oxalamide or hydroxyphenyl-s-triazine type. These compounds can be used individually or as a mixture in the presence or absence of sterically hindered amines (HALS).

Examples of such UV absorbers and light stabilizers are
1. 2- (2′-hydroxyphenyl) benzotriazole ,
For example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) benzotriazole, 2- (5′- Tert-butyl-2′-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5 ′-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ′, 5 '-Di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole 2- (3′-secondary-butyl-5′-tert-butyl-2′-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- ( 3 ', 5'-Di-tertiary-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-Tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-[2- (2 -Ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl)- 5-chlorobenzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5 ′-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3′-tert. Butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'-[2- (2-ethylhexyloxy) carbonylethyl]- 2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5'- (2-Isooctyloxycarbonylethyl) phenyl) benzotriazole, 2,2′-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol] Mixture; 2- [3′-tert-butyl-5 ′-(2-methoxycarbonylethyl) -2′-hydroxyphenyl] benzotriazole and polyethylene Transesterification products of glycol _{300; [R-CH 2 CH} 2 -COOCH 2] 3] 2 - ( wherein, R = 3'tert - butyl-4'-hydroxy-5'-2H-benzo Triazol-2-ylphenyl).

2. 2-hydroxybenzophenone ,
For example, 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-,
4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy-derivatives.

3. Esters of substituted or unsubstituted benzoic acid ,
For example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, and 2 Methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

4). Acrylate ,
For example, isooctyl or ethyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, butyl or methyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carboxymethoxy-p-methoxy Cinnamate, and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

5). A sterically hindered amine ,
For example, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6,6-sebacate) Pentamethylpiperidyl), bis (1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1-hydroxyethyl-2, Condensation product of 2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N′-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4 -Condensation products with tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris- (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetra Kis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetraoate, 1,1 ′-(1,2-ethanediyl) bis (3,3, 5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) 2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9 , 9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, succinic acid Bis (1-octyloxy-2,2,6, 6-tetramethylpiperidyl), N, N′-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5- Condensation product with triazine, 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2- Condensation product with bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1, Condensation product of 3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8- Triazospiro [4.5] decane-2,4-dione, 3- Dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, and 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4- Piperidyl) pyrrolidine-2,5-dione.

6). Oxalamide ,
For example, 4,4′-dioctyloxy oxanilide, 2,2′-diethoxy oxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butyl oxanilide, 2,2 '-Didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2- Ethoxy-5-tert-butyl-2'-ethyloxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, o- and p- Methoxy- and a mixture of o- and p-ethoxy-disubstituted oxanilides.

7. 2- (2-hydroxyphenyl) -1,3,5-triazine ,
For example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2 , 4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2, 4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3 5-triazine 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2 -Hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyl / tri Decyloxy- (2-hydroxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

8). Phosphites and phosphonites ,
For example, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl phosphite), trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl diphosphite, tris- (2,4 -Di-tert-butylphenyl) phosphite, diisodecylpentaerythrityl diphosphite, bis- (2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, bis- (2,6-di -Tert-butyl-4-methylphenyl) pentaerythrityl diphosphite, bis-isodecyloxypentaerythrityl diphosphite, bis- (2,4-di-tert-butyl-6-methylphenyl) penta Erythrityl diphosphite, bis (2,4,6 Tri-tert-butylphenyl) pentaerythrityl diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylenediphosphonite, 6-isooctyl Oxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra- Tert-butyl-12-methyldibenzo [d, g] -1,3,2-dioxaphosphocin,
Bis- (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

To promote photopolymerization, as component (d), an amine such as triethanolamine, N-methyldiethanolamine, ethyl-p-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, 2-ethylhexyl-p- Dimethylaminobenzoate, octyl-pN, N-dimethylaminobenzoate, N- (2-hydroxyethyl) -N-methyl-p-toluidine or Michler's ketone can be added. The action of amines is enhanced by the addition of benzophenone type aromatic ketones. Examples of amines that can be used as oxygen scavengers are substituted N, N-dialkylanilines as described in EP 339841. Other promoters, co-initiators, and autoxidizers are thiols, thioethers, disulfides, phosphonium salts, phosphine oxides or phosphines, such as, for example, EP 438123, British Patent 2180358, And as described in JP-A-6-68309.

  In addition, chain transfer agents customary in the art can also be added to the compositions of the present invention as component (d). Examples are mercaptans, amines and benzothiazoles.

  Photopolymerization can also be accelerated by further adding (as component (d)) a photosensitizer or co-initiator that shifts or broadens the spectral sensitivity. These are in particular aromatic compounds such as benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its derivatives, coumarin and phenothiazine and its derivatives, and also 3- (aroylmethylene) thiazoline, rhodanine, camphorquinone, but also Eosin, rhodamine, erythrosine, xanthene, thioxanthene, acridine such as 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, cyanine, and merocyanine dyes .

Specific examples of such compounds are
1. Thioxanthone Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone 2-ethoxycarbonylthioxanthone, 3- (2-methoxyethoxycarbonyl) thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3- Chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phen Rusulfurylthioxanthone, 3,4-di- [2- (2-methoxyethoxy) ethoxycarbonyl] thioxanthone, 1,3-dimethyl-2-hydroxy-9H-thioxanthen-9-one 2-ethylhexyl ether, 1-ethoxy Carbonyl-3- (1-methyl-1-morpholinoethyl) thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6- (1,1-dimethoxybenzyl) thioxanthone, 2-morpholinomethylthioxanthone, 2- Methyl-6-morpholinomethylthioxanthone, N-allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N- (1,1,3,3-tetramethylbutyl) thioxanthone -3,4-dicarboxyimi 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-carboxylic acid polyethylene glycol ester, 2-hydroxy-3- (3,4-dimethyl-9 -Oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride;

2. Benzophenone Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis (dimethylamino) ) Benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (methylethylamino) benzophenone, 4,4′-bis (p-isopropylphenoxy) benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, 4- (4-methylthiophenyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate, 4- (2-hydroxyethylthio) benzophenone, 4- (4- Tolylthio) benzofe 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (toluene-4-sulfonyl) propan-1-one, 4-benzoyl-N, N, N-trimethylbenzenemethanami Nium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propanaminium chloride monohydrate, 4- (13-acryloyl-1,4,7,10, 13-pentaoxatridecyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) oxy] ethylbenzenemethananium chloride;

3. Coumarin Coumarin 1, Coumarin 2, Coumarin 6, Coumarin 7, Coumarin 30, Coumarin 102, Coumarin 106, Coumarin 138, Coumarin 152, Coumarin 153, Coumarin 307, Coumarin 314, Coumarin 314T, Coumarin 334, Coumarin 337, Coumarin 500, 3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-dipropoxycoumarin, 3-benzoyl-6,8-dichlorocoumarin 3-benzoyl-6-chlorocoumarin, 3,3′-carbonyl-bis [5,7-di (propoxy) coumarin], 3,3′-carbonyl-bis (7-methoxycoumarin), 3,3′- Carbonyl-bis (7-diethylaminocoumarin), 3-isobutyro Lukumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-di (methoxyethoxy) Coumarin, 3-benzoyl-5,7-di (allyloxy) coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy -3- (1-naphthoyl) coumarin, 5,7-diethoxy-3- (1-naphthoyl) coumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-thienoylcoumarin, 3- (4-cyano Benzoyl) -5,7-dimethoxycoumarin, 3- (4-cyanobenzoyl) -5, -Dipropoxycoumarin, 7-dimethylamino-3-phenylcoumarin, 7-diethylamino-3-phenylcoumarin, coumarin derivatives disclosed in JP-A Nos. 09-179299 and 09-325209, such as 7-[{ 4-chloro-6- (diethylamino) -S-triazin-2-yl} amino] -3-phenylcoumarin;

4. 3- (Aroylmethylene) thiazoline 3-methyl-2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline;

5). Rhodanine 4-dimethylaminobenzalrhodanine, 4-diethylaminobenzalrhodanine, 3-ethyl-5- (3-octyl-2-benzothiazolinylidene) rhodanine, disclosed in JP-A-08-305019 A rhodanine derivative of the formulas [1], [2], [7];

6). Other compounds Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 4,4'-bis (dimethylamino) benzyl, 2-acetylnaphthalene, 2-naphthaldehyde, dansylic acid derivative, 9,10 Anthraquinone, anthracene, pyrene, aminopyrene, perylene, phenatrene, phentolenquinone, 9-fluorenone, dibenzosuberone, curcumin, xanthone, thiomichlerketone, α- (4-dimethylaminobenzylidene) ketone, for example 2,5- Bis (4-diethylaminobenzylidenecyclopentanone, 2- (4-dimethylaminobenzylidene) indan-1-one, 3- (4-dimethylaminophenyl) -1-indan-5-ylpropenone, 3-phenylthiophthalimide, N − Chill-3,5-di (ethylthio) phthalimide, N- methyl-3,5-di (
Ethylthio) phthalimide, phenothiazine, methylphenothiazine, amine such as N-phenylglycine, ethyl 4-dimethylaminobenzoate, butoxyethyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, triethanolamine, methyldiethanolamine, dimethylaminoethanol 2- (dimethylamino) ethyl benzoate, poly (propylene glycol) -4- (dimethylamino) benzoate.

  A photopolymerizable composition comprising a photosensitizer compound selected from the group consisting of benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, or coumarin derivatives as a further additive (d) is preferred.

  The curing process is carried out by adding photosensitizers, in particular as colored compositions (for example with titanium dioxide) and free radicals under thermal conditions, as described in EP 245639. Components to form, eg azo or peroxy compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), triazene, diazo sulfide, pentaazadiene, eg hydroperoxide or peroxycarbonate It can also be assisted, for example, by adding tert-butyl hydroperoxide.

  The composition according to the invention comprises as further additives (d) photoreducible dyes such as xanthene-, benzoxanthene-, benzothioxanthene-, thiazine-, pyronin-, porphyrin- or acridine-dyes, and / or It may contain a trihalogen methyl compound that can be cleaved by irradiation. Similar compositions are described, for example, in EP 445624.

  Further additives known to the person skilled in the art can be used as component (d), for example vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy. Silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane , It may be added as wearing accelerator. Surfactants, optical brighteners, pigments, dyes, wetting agents, leveling aids, dispersants, anti-agglomeration agents, antioxidants or fillers are further examples of additives (d). In order to cure thick and colored coatings, it is appropriate to add glass microspheres or finely divided glass fibers, for example as described in US Pat. No. 5,013,768.

  As already mentioned above, further suitable components (d) include surfactants and dispersants and other components, particularly to support the application of pigments or colorants in the formulation.

  It is desirable to apply a surface treatment to the pigment in order to disperse the pigment easily and to stabilize the resulting pigment dispersion. The surface treatment agent is, for example, a surfactant, a polymer dispersant, a general texture improver, a pigment derivative, and a mixture thereof. It is particularly preferred that the colorant composition of the present invention comprises at least one polymer dispersant and / or at least a pigment derivative.

Suitable surfactants are anionic surfactants such as alkylbenzene-alkylnaphthalene-sulfonates, alkylsulfosuccinates or naphthalene formaldehyde sulfonates; cationic surfactants such as quaternary salts such as benidyltributylammonium chloride, respectively. Nonionic or amphoteric surfactants such as polyoxyethylene surfactants and alkyl or amidopropyl betaines.

  Specific examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Oxyethylene alkyl phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes, polyethylene amines; KP (Shin-Etsu Chemical Co., Ltd.) Products), Polyflow (Kyoeisha Chemical Co., Ltd.), F Top (Tochem Products Co., Ltd.), Mega Fuck (Large) This Ink and Chemicals Industry Co., Ltd. products), Fluorad (Sumitomo 3M products), those available under the trade name of Asahi guard and Sarfron (Asahi Glass Co., Ltd. products); the other, and the like.

  These surfactants can be used alone or in admixture of two or more. The surfactant is generally used in an amount of 50 parts by mass or less, preferably 0 to 30 parts by mass, based on the mass of the colorant composition.

  Examples of the polymer dispersant include a high molecular weight polymer having a pigment affinity group. Specific examples are: statistical copolymers composed of, for example, styrene derivatives, (meth) acrylates and (meth) acrylamides, and the statistical copolymers modified by subsequent modification; for example, styrene derivatives, (meth) Block copolymers and / or comb polymers composed of acrylates and (meth) acrylamides, and the block copolymers and / or comb polymers modified by subsequent modification; eg polyethyleneamines made of polyesters Polyamines made of polyesters, for example; and many types of (modified) polyurethanes.

  Polymeric dispersants can also be used. Suitable polymeric dispersants are, for example, BYK's DISPERBYK® 101, 115, 130, 140, 160, 161, 162, 163, 164, 166, 168, 169, 170, 171, 180, 182, 2000, 2001, 2020, 2050, 2090, 2091, 2095, 2096, 2150, Ciba Specialty Chemicals' Ciba® EFKA® 4008, 4009, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4406, 4500, 4510, 4520, 4530, 4540, 4550, 4560, Ajinomoto Fine Techno PB (registered trademark) 711, 821, 22, 823, 824, 827, SOLSPERSE 1320, 13940, 17000, 20000, 21000, 24000, 26000, 27000, 28000, 32845, 32500, 32550, 32600, 33500, 34750, 36000, 36600, Lubrizol, 37500, 39000, 41090, 44000, 53095, and combinations thereof.

As a dispersant, Ciba (registered trademark) EFKA (registered trademark) 4067, 4047, 4060, 4300, 4330, 4340, DISPERBYK (registered trademark) 161, 162, 163, 164, 165, 166, 168, 169, 170, 2000 2001, 2020, 2050, 2090, 2091, 2095, 2096, 2105, 2150, PB (registered trademark) 711, 821, 822, 823, 824, 827, SOLPERSE (registered trademark) 24000, 31845, 32500, 32550, 32600 , 33500, 34750, 36000, 36600, 37500, 39000, 41090, 44
000, 53095 and combinations thereof are preferred.

  Suitable texture improvers are, for example, fatty acids such as stearyl acid or behenic acid, and fatty amines such as laurylamine and stearylamine. In addition, fatty alcohols such as aliphatic 1,2-diols or ethoxylated fatty alcohol polyols, or epoxidized soybean oil, waxes, resin acids and resin acid salts can be used for this purpose.

  Suitable pigment dispersants include, for example, copper phthalocyanine derivatives such as Ciba (R) EFKA (R) 6745 from Ciba Specialty Chemicals, SOLPERSE (R) 5000, 12000 from Lubrizol, SYNERGIST 2100 from BYK, and Ciba Azo derivatives such as (registered trademark) EFKA (registered trademark) 6750, SOLSPERSE (registered trademark) 22000, and SYNERGIST 2105.

  The dispersants and surfactants for the pigments described above are used, for example, in the compositions of the invention used as resist formulations, in particular in color filter formulations.

  The subject of the invention is also the above-mentioned photopolymerizable composition comprising a dispersant or dispersant mixture as further additive (d), and the above-mentioned photopolymerizable composition comprising a pigment or pigment mixture as further additive (d). It is a thing.

  The choice of additive (s) (d) is made according to the field of application and the properties required for that field. The above additives are customary for those skilled in the art and are therefore added in amounts commonly used in each application.

  A binder (e) can also be added to the new composition. This is particularly advantageous when the photopolymerizable compound is a liquid or a viscous material. The amount of binder can be, for example, 2-98% by weight, preferably 5-95% by weight, in particular 20-90% by weight, based on the total solids content. The choice of binder is made depending on the field of application and the properties required for that field, such as development capacity in aqueous and organic solvent systems, adhesion to substrates, and sensitivity to oxygen.

Examples of suitable binders are polymers having a molecular weight of about 2,000 to 2,000,000, preferably 3,000 to 1,000,000. Examples of the alkali-developing binder include acrylic polymers having a carboxylic acid functional group as a pendant group, such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylic acid, 2-carboxypropyl (meth) acrylic acid, and itacon. An ethylenically unsaturated carboxylic acid, such as acid, crotonic acid, maleic acid, fumaric acid and mono (meth) acrylic acid ω-carboxypolycaprolactone, and an ester of (meth) acrylic acid, such as methyl (meth) acrylate, (Meth) ethyl acrylate, (meth) propyl acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, (meth) acrylic acid Hydroxypropyl, glycerol mono (meth) acrylate, ( Data) acrylic acid tricyclo [5.2.1.0 ^2,6] decan-8-yl, (meth) acrylate, glycidyl (meth) 2-methyl glycidyl acrylate, (meth) acrylic acid 3,4-epoxy Butyl, (meth) acrylic acid 6,7-epoxyheptyl; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, vinylbenzylglycidyl ether; amide type unsaturated compounds, (meth) acrylamide Diacetone acrylamide, N-methylol acrylamide, N-butoxy methacrylamide; and polyolefin type compounds such as butadiene, isoprene, chloroprene, etc .; methacrylonitrile, methyl isopropenyl ketone, mono-2-[(meth) acryloyloxy] succinate Ethyl, N-fu Obtained by copolymerizing with one or more monomers selected from nilmaleimide, maleic anhydride, vinyl acetate, vinyl propionate, vinyl pivalate, polystyrene macromonomer, or polymethyl (meth) acrylate methyl macromonomer And conventionally known copolymers. Examples of copolymers include copolymers of acrylates and methacrylates with acrylic acid or methacrylic acid, and styrene or substituted styrenes, phenolic resins such as novolac, (poly) hydroxystyrene, and hydroxystyrene with alkyl acrylates, acrylic acid and / or Or a copolymer with methacrylic acid. Preferred examples of the copolymer include methyl methacrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid copolymer, methyl methacrylate / ethyl acrylate / methacrylic acid copolymer, benzyl methacrylate / methacrylic acid / styrene copolymer, benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, Methyl methacrylate / butyl methacrylate / methacrylic acid / styrene copolymer, methyl methacrylate / benzyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate copolymer. Examples of solvent developable binder polymers are poly (alkyl methacrylate), poly (alkyl acrylate), poly (benzyl methacrylate-co-hydroxyethyl methacrylate-co-methacrylic acid), poly (benzyl methacrylate-co-methacrylic acid; cellulose ester And cellulose ethers such as cellulose acetate, cellulose acetobutyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal, cyclized rubber, polyethers such as polyethylene oxide, polypropylene oxide and polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefin, poly Vinyl chloride, vinyl chloride / vinylidene copolymer, vinylidene chloride and acrylonitrile, methyl methacrylate And copolymers with vinyl acetate, polyvinyl acetate, ethylene / vinyl acetate copolymers, polymers such as polycaprolactam and poly (hexamethylene adipamide), and poly (ethylene glycol terephthalate) and poly (hexamethylene glycol succinate) Such as polyester and polyimide binder resins.
The polyimide binder resin in the present invention can be either a solvent-soluble polyimide or a polyimide precursor, such as polyamic acid.

Preferable is a photopolymerizable composition containing a copolymer of methacrylate and methacrylic acid as the binder polymer (e).
Of further interest are polymeric binder components, for example as described in JP-A-10-171119, especially for use in color filters.

The present photopolymerizable compositions are used for various purposes, for example as printing inks, for example screen printing inks, offset or flexographic inks, as transparent finishes, for example as white or colored finishes on wood or metal, especially as powder coatings. As coating materials for paper, wood, metal or plastic, building markings and road markings, photo reproduction techniques, holographic recording materials, image recording techniques, or production of printing masters that can be developed with organic solvents or aqueous alkalis, screen printing masks As a sun curable coating for manufacturing, as a dental filling composition, as an adhesive, as a pressure sensitive adhesive, as a laminating resin, as an etching resist, solder resist, electroplating of both liquid film and dry film As a resist or permanent resist, for printed circuit boards and electronic circuits, as an optically configurable dielectric, for various display applications, or for the formation of structures in the manufacturing process of plasma display panels and electroluminescent display devices For producing color filters (for example, US Pat. No. 5,853,446, European Patent 863,534, JP-A-9-244230, JP-A-10-62980, JP-A-8-171863, US Pat. No. 5840465, European Patent No. 855731, JP-A-5-271576, JP-A-5-67405, etc.), for the production of holographic data storage (HDS) materials, optical For the manufacture of switches, optical gratings (interference gratings), and optical circuits, mass curing (UV hardening with transparent molds) ) Or stereolithographic techniques (eg, as described in US Pat. No. 4,575,330), composite materials (eg, glass and / or other fibers and other if desired) For the production of coatings or sealing of electronic components and integrated circuits, or for optical fibers, or for optical lenses, eg contacts It can be used as a coating for the production of lenses or Fresnel lenses. The composition of the invention is further suitable for the production of medical devices, aids or implants. Furthermore, the compositions according to the invention are suitable for the production of gels having thermotropic properties, as described, for example, in German Patent No. 19700064 and European Patent No. 678534.

  The novel photoinitiator is used as an initiator for emulsion polymerization, pearl polymerization or suspension polymerization, as a polymerization initiator for fixing the regular state of liquid crystal monomers and oligomers, or for fixing a dye to an organic material. It can be used additionally as an initiator.

Often the coating material uses a prepolymer mixture with a polyunsaturated monomer, which may additionally contain a monounsaturated monomer. Here, it is this prepolymer that primarily determines the properties of the coating film, and by altering it, one skilled in the art can influence the properties of the cured film. The polyunsaturated monomer functions as a crosslinker that renders the film insoluble. Monounsaturated monomers function as reactive diluents and are used to reduce viscosity without the use of solvents.
Unsaturated polyester resins are usually used in a two-component system together with a monounsaturated monomer, preferably styrene. For photoresists, a specific one-component system such as polymaleimide, polychalcone or polyimide as described in DE 2308830 is often used.

The novel photoinitiator can also be used for the polymerization of radiation curable powder coatings. Powder coatings can be based on solid resins and monomers having reactive double bonds such as malates, vinyl ethers, acrylates, acrylamides, and mixtures thereof. Free radical UV curable powder coatings can be formulated by mixing an unsaturated polyester resin with solid acrylamide (eg methyl methyl acrylamide glycolate) and a new free radical photoinitiator, such formulation For example, M. Wittigand and Th. The paper "Radiation Cur" by Gohmann
ing of Powder Coatings ", Conference Process
edings, Radtech Europe 1993. The powder coating can also comprise a binder, as described, for example, in DE 4228514 and EP 636669. UV-curable powder coatings with free radicals can also be formulated by mixing unsaturated polyester resins with solid acrylates, methacrylates or vinyl ethers, and novel photoinitiators (or photoinitiator mixtures). The powder coating may also comprise a binder, as described for example in DE 4228514 and EP 636669. This UV curable powder coating may additionally contain white or colored pigments. For example, to give a hardened powder coating with good hiding power, preferably rutile titanium dioxide can be used at a concentration of 50% by weight or less. The procedure usually involves spraying powder or static electricity on a substrate, such as metal or wood, melting the powder by heat, and forming a smooth film, for example a medium pressure mercury lamp, a metal halide lamp. Or radiation curing of the coating with ultraviolet and / or visible light using a xenon lamp. A special advantage of radiation curable powder coatings over their corresponding thermosetting ones is that they can slow the flow time after melting the powder particles and ensure the formation of a smooth, excellent glossy coating. . In contrast to thermoset systems, radiation curable powder coatings can be formulated to melt at lower temperatures without the undesirable effect of shortening their lifetime. Therefore, it is also suitable as a coating on heat sensitive substrates such as wood or plastic. In addition to the novel photoinitiator system, the powder coating formulation may also include a UV absorber. Suitable examples are listed above in paragraphs 1-8.

The novel photocurable compositions can be of all kinds, for example wood, fiber, paper, ceramic, glass, plastic (polyester), which are intended to produce an image, for example by applying a protective layer or by exposure to the image. , Polyethylene terephthalate, polyolefin or cellulose acetate etc.), especially in film form, and of metals such as Al, Cu, Ni, Fe, Zn, Mg or Co, and of GaAs, Si or SiO ₂ substrates Suitable as a coating material for.

  The novel radiation-sensitive composition further has application as a negative resist that has a very high sensitivity to light and can be developed without swelling in an aqueous alkaline medium. They are used for the production of relief and lithographic printing paper, gravure or screen printing paper, for the production of relief copies, for example for the production of text in braille, for the production of stamps, for chemical polishing. Suitable for use in crushing or as a microresist in the manufacture of integrated circuits. The composition may further be used as a photodrawable dielectric layer or coating, an encapsulating material, and an insulating coating in the manufacture of computer chips, printed boards and other electrical or electronic components. The possible layer supports and the processing conditions of the coated substrate are varied.

  The novel composition also relates to a photosensitive thermosetting resin composition and a method for forming a solder resist pattern by use of the composition, and more particularly to the manufacture of printed circuit boards, precision work of metal products, glass and stone. Novel photosensitive thermosetting resin compositions useful as materials for product etching, plastic product relief, and printing master production, and particularly useful as solder resists for printed circuit boards, and The present invention relates to a method of forming a solder resist pattern by selectively exposing a layer to actinic radiation through a photomask having a pattern and developing an unexposed portion of the layer.

  Solder resist is a material used when soldering a given part to a printed circuit board in order to prevent molten solder from adhering to inappropriate parts and protective circuits. Therefore, it is necessary to possess properties such as high adhesion, insulation resistance, resistance to soldering temperature, solvent resistance, alkali resistance, acid resistance, and plating resistance.

  Since the photocurable compositions of the present invention have excellent thermal stability and are sufficiently resistant to inhibition by oxygen, they are color filters or color mosaics, as described, for example, in EP 320264. Particularly suitable for the formation of systems. Color filters are typically flat panel displays such as LCDs, PDPs (plasma panel displays), EL (electroluminescent) displays, and projection systems for scanners, digital cameras and video cameras, image sensors, CCDs (charge coupled devices) and Used in the manufacture of CMOS (complementary metal oxide semiconductor) sensors.

Color filters are typically manufactured by forming red, green and blue pixels and a black matrix on a glass substrate. In these steps, the photocurable composition of the present invention can be used. A particularly preferred method of use is to add red, green and blue coloring substances, dyes and pigments to the photosensitive resin composition of the present invention, coat the substrate with the composition, and dry the coating with a short heat treatment. The coating is exposed to actinic radiation, and then the pattern is developed in an aqueous alkaline developer solution and optionally heat treated. In this way, a color filter layer having red, green and blue pixels can be produced by sequentially superimposing the red, green and blue colored coatings on each other in this manner in any desired order. .

  Development is carried out by washing away areas not polymerized with a suitable alkaline developer. This process is repeated to form an image having a plurality of colors.

  In the photosensitive resin composition of the present invention, at least one or more pixels are formed on a transparent substrate, and then exposed from the side of the transparent substrate where the above pixels are not formed, The above pixel can be used as a light shielding mask. In this case, for example, when the overall exposure is given, the position adjustment of the mask becomes unnecessary, and the concern about the positional deviation is eliminated. Then, it is possible to cure all the portions where the pixels are not formed. Furthermore, in this case, by partially using a light shielding mask, it is possible to develop and remove a part of the portion where the pixel is not formed.

  In any case, since no gap is formed between the pixel formed first and the pixel formed later, the composition of the present invention is suitable for a color filter forming material, for example. Specifically, red, green and blue coloring substances, dyes and pigments are added to the photosensitive resin composition of the present invention, and the process of forming an image is repeated to form red, green and blue pixels. To do. Thus, for example, a photosensitive resin composition to which a black coloring material, a dye and a pigment are added is applied to the entire surface. An overall exposure (or partial exposure through a shading mask) is applied over it, and black pixels are placed in the entire space between red, green and blue pixels (or the whole area other than the partial area of the shading mask). Can be formed.

  In addition to the process of applying the photosensitive resin composition to the substrate and drying, the photosensitive resin composition of the present invention can also be used for a layer transfer material. That is, the photosensitive resin composition is directly provided in a layer form on a temporary support, preferably a polyethylene terephthalate film, or on a polyethylene terephthalate film provided with an oxygen barrier layer and a release layer, or a release layer and an oxygen barrier layer. . Usually, a removable cover sheet made of synthetic resin is laminated to it for protection during handling. Furthermore, a layer structure in which an alkali-soluble thermoplastic resin layer and an intermediate layer are provided on a temporary support and a photosensitive resin composition layer is further provided thereon can be applied (special feature). (Kaihei 5-173320).

  The above cover sheet is removed at the time of use, and the photosensitive resin composition layer is laminated on the permanent support. Next, when an oxygen barrier layer and a release layer are provided, between the layer and the temporary support, when a release layer and an oxygen barrier layer are provided, between the release layer and the oxygen barrier layer, and a release layer. Alternatively, when any of the oxygen blocking layers is not provided, peeling is performed between the temporary support and the layer of the photosensitive resin composition, and the temporary support is removed.

  Metal supports, glass, ceramics and synthetic resin films can be used as the support for the color filter. Glass and synthetic resin films that are transparent and have excellent dimensional stability are particularly preferred.

  The layer thickness of the photosensitive resin composition is usually 0.1 to 50 μm, particularly 0.5 to 5 μm.

A diluted aqueous solution of an alkaline substance can be used as a developer of the composition if the photosensitive resin composition of the present invention contains an alkali-soluble resin or an alkali-soluble monomer or oligomer, and a small amount of water. Also included is a developer solution prepared by adding a miscible organic solvent thereto.

  Examples of suitable alkaline substances include alkali metal hydroxides (eg, sodium hydroxide and potassium hydroxide), alkali metal carbonates (eg, sodium carbonate and potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate) And potassium bicarbonate), alkali metal silicates (eg, sodium silicate and potassium silicate), alkali metal metasilicates (eg, sodium metasilicate and potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, Examples include morpholine, tetraalkylammonium hydroxide (eg, tetraalkylammonium hydroxide), or trisodium phosphate. The concentration of the alkaline substance is 0.01 to 30% by mass, and the pH is preferably 8 to 14.

  Suitable water miscible organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, Propylene glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, n-butyl acetate, benzyl alcohol, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 2-pentanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, lactic acid Mention may be made of methyl, ε-caprolactam and N-methylpyrrolidinone. The concentration of the water-miscible organic solvent is 0.1 to 30% by mass.

  Furthermore, a known surfactant can be added. The concentration of the surfactant is preferably 0.001 to 10% by mass.

  The photosensitive resin composition of the present invention can also be developed with an organic solvent containing a mixture of two or more solvents not containing an alkaline compound. Suitable solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate Ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, n-butyl acetate, benzyl alcohol, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 2-pentanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε- Caprolactam and N- methylpyrrolidinone, and the like. If desired, water can be added to these solvents to a level where a clear solution is still obtained and sufficient solubility of the unexposed areas of the photosensitive composition is maintained.

  The developer solution can be used in all forms known to those skilled in the art, for example in the form of a bath, paddle or spray solution. In order to remove the uncured portion of the layer of the photosensitive resin composition, methods such as friction using a rotating brush and friction using a wet sponge can be combined. Usually, the temperature of the developer is preferably about room temperature to 40 ° C. The development time is variable depending on the specific type of the photosensitive resin composition, the alkalinity and temperature of the developer, and the type and concentration of the organic solvent when added. Usually it is 10 seconds to 2 minutes. A washing step can be placed after the development step.

The final heat treatment is preferably performed after the development step. Therefore, a support having a layer photopolymerized by exposure (hereinafter referred to as a photocured layer) is heated in an electric furnace and dryer, or the photocured layer is irradiated with an infrared lamp, or on a hot plate. Heat with. The heating temperature and time depend on the composition used and the thickness of the formed layer. In general, heating is preferably performed at about 120 to about 250 ° C. for about 5 to about 60 minutes.

  The pigments that can be included in the compositions according to the invention, including colored color filter resist compositions, are preferably processed pigments such as acrylic resins, vinyl chloride-vinyl acetate copolymers, maleic acid A powdery or pasty product produced by finely dispersing a pigment in at least one resin selected from the group consisting of a resin and an ethylcellulose resin.

The red pigment is, for example, an anthraquinone type pigment alone, a diketopyrrolopyrrole type pigment alone, a mixture thereof, or a mixture of at least one of them and a diazo type yellow pigment or an isoindoline type yellow pigment, particularly C.I. I. Pigment Red 177 alone, C.I. I. Pigment Red 254 alone, or C.I. I. Pigment red 177 and C.I. I. Pigment red 254 mixture, or C.I. I. Pigment red 177 and C.I. I. Pigment Red 254 and C.I. I. Pigment yellow 83 or C.I. I. A mixture of CI Pigment Yellow 139 ("CI" means a color index known to the person skilled in the art and publicly available).
Further suitable examples of pigments include C.I. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 168, 176, 179, 180, 185, 202, 207, 209, 214, 222, 242, 244, 255, 264, 272, and C.I. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 31, 53, 55, 93, 95, 109, 110, 128, 129, 138, 39, 150, 153, 154, 155, 166, 168, 185, 199, 213, and C.I. I. Pigment Orange 43.
Examples of red dyes are C.I. I. Solvent Red 25, 27, 30, 35, 49, 83, 89, 100, 122, 138, 149, 150, 160, 179, 218, 230, C.I. I. Direct Red 20, 37, 39, 44, and C.I. I. Acid Red 6, 8, 9, 13, 14, 18, 26, 27, 51, 52, 87, 88, 89, 92, 94, 97, 111, 114, 115, 134, 145, 151, 154, 180, 183, 184, 186, 198, C.I. I. Basic Red 12, 13, C.I. I. Disperse threads 5, 7, 13, 17, and 58. Red dyes can be used in combination with yellow and / or orange dyes.

The green pigment is, for example, a halogenated phthalocyanine type pigment alone or a mixture of the pigment with a diazo type yellow pigment, a quinophthalone type yellow pigment or a metal complex, particularly C.I. I. Pigment Green 7 alone, C.I. I. Pigment Green 36 alone or C.I. I. Pigment green 7, C.I. I. Pigment Green 36 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138 or C.I. I. A mixture of CI pigment yellow 150 is included. Other suitable green pigments are C.I. I. Pigment Greens 15, 25, and 37.
Examples of suitable green dyes are C.I. I. Acid Green 3, 9, 16, C.I. I. Basic green 1 and 4.

Examples of suitable blue pigments are phthalocyanine type pigments used either alone or in combination with dioxazine type violet pigments such as C.I. I. Pigment Blue 15: 6 alone, C.I. I. Pigment blue 15: 6 and C.I. I. This is a combination of pigment violet 23. Further examples for blue pigments include C.I. I. Blue 15: 3, 15: 4, 16, 22, 28 and 60. Other suitable pigments include C.I. I. Pigment violet 14, 19, 23, 29, 32, 37, 177, and C.I. I. Orange 73.
Examples of suitable blue dyes are C.I. I. Solvent Blue 25, 49, 68, 78, 94, C.I.
I. Direct Blue 25, 86, 90, 108, C.I. I. Acid Blue 1, 7, 9, 15, 103, 104, 158, 161, C.I. I. Basic Blue 1, 3, 9, 25 and C.I. I. Disperse Blue 198.

  The pigment of the photopolymer composition for the black matrix preferably comprises at least one selected from the group consisting of carbon black, titanium black and iron oxide. However, other pigment mixtures that give an overall black appearance can also be used. For example, C.I. I. Pigment Blacks 1, 7, and 31 can be used alone or in combination.

  Other examples of dyes used in the color filter include C.I. I. Solvent Yellow 2, 5, 14, 15, 16, 19, 21, 33, 56, 62, 77, 83, 93, 162, 104, 105, 114, 129, 130, 162, C.I. I. Disperse yellow 3, 4, 7, 31, 54, 61, 201, C.I. I. Direct Yellow 1, 11, 12, 28, C.I. I. Acid Yellow 1, 3, 11, 17, 23, 38, 40, 42, 76, 98, C.I. I. Basic Yellow 1, C.I. I. Solvent Violet 13, 33, 45, 46, C.I. I. Disperse violet 22, 24, 26, 28, C.I. I. Acid Violet 49, C.I. I. Basic violet 2, 7, 10, C.I. I. Solvent Orange 1, 2, 5, 6, 37, 45, 62, 99, C.I. I. Acid Orange 1, 7, 8, 10, 20, 24, 28, 33, 56, 74, C.I. I. Direct Orange 1, C.I. I. Disperse Orange 5, C.I. I. Direct Brown 6, 58, 95, 101, 173, C.I. I. Acid Brown 14, C.I. I. Solvent Black 3, 5, 7, 27, 28, 29, 35, 45 and 46.

  In some cases of color filter manufacture, catching color, yellow, magenta, cyan and optionally green are used instead of red, green and blue. As yellow for this type of color filter, the yellow pigments and dyes described above can be used. Suitable examples of colorants for magenta color are C.I. I. Pigment red 122, 144, 146, 169, 177, C.I. I. Pigment Violet 19 and 23. Examples of cyan colors are aluminum phthalocyanine pigments, thianium phthalocyanine pigments, cobalt phthalocyanine pigments and tin phthalocyanine pigments.

  For any color, combinations of two or more pigments can also be used. Particularly suitable for color filter applications are powder processed pigments produced by finely dispersing pigments in the above-described resins.

  The concentration of the pigment in all solid components (pigments and resins of various colors) is, for example, in the range of 5 to 80% by weight, in particular in the range of 20 to 45% by weight.

  The pigment in the color filter resist composition preferably has an average particle size smaller than the wavelength of visible light (400 to 700 nm). Particularly preferred is an average pigment diameter of <100 nm.

  If necessary, the pigment can be stabilized in the photosensitive composition by pretreating the pigment with a dispersant to improve the dispersion stability of the pigment in the liquid formulation. Suitable additives are those indicated above.

  Preferably, the color filter resist composition of the present invention further contains at least one addition polymerizable monomer compound as component (a).

The ethylenically unsaturated compound (s) (a) contain one or more olefinic double bonds. These can be low (monomeric) or high (oligomeric) molecular weight. Examples of compounds containing double bonds are (meth) acrylic acid, alkyl, hydroxyalkyl or aminoalkyl (meth) acrylates such as methyl, ethyl, n-butyl, isobutyl, tert-butyl, n-propyl, isopropyl N-hexyl, cyclohexyl, 2-ethylhexyl, isobornyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, methoxyethyl, ethoxyethyl, glycerol, phenoxyethyl methoxydiethylene glycol, ethoxydiethylene glycol, pyropyrene glycol, polypropylene glycol, glycidyl, N, N-dimethylaminoethyl and N, N-diethylaminoethyl (meth) acrylate. Other examples include (meth) acrylonitrile, (meth) acrylamide, N-substituted (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N- Dibutyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide and N- (meth) acryloylmorpholine, vinyl esters such as vinyl acetate, isobutyl vinyl ether, etc. Vinyl ethers, styrene, alkyl-, hydroxy- and halostyrenes, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylacetamide, N-vinylformamide, vinyl chloride and vinylidene chloride.

  Examples of relatively high molecular weight (oligomer) polyunsaturated compounds are polyesters, polyurethanes, polyethers and polyamides, including ethylenically unsaturated carboxylates.

  Particularly suitable examples are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides.

  Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, transdermal acid, and unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic and methacrylic acid are preferred.

Suitable polyols are aromatic, in particular aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4′-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, novolaks and resoles. Examples of aliphatic and alicyclic polyols are preferably alkylene diols having 2 to 12 C atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- Or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, preferably polyethylene glycols having a molecular weight of 200 to 1500, 1,3-cyclopentanediol, 1,2 -, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, triethanolamine, trimethylolethane, trimethylolpropane, pentaerythritol, pentaerythritol monooxalate, dipep Taerythritol, ethers of pentaerythritol and ethylene glycol or propylene glycol, ethers of dipentaerythritol and ethylene glycol or propylene glycol, sorbitol, 2,2-bis [4- (2-hydroxyethoxy) phenyl] methane, 2 , 2-bis [4- (2-hydroxyethoxy) phenyl] propane and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene. Other suitable polyols are polymers or copolymers containing hydroxy groups in the polymer chain or side chain, for example homopolymers or copolymers containing vinyl alcohol or hydroxyalkyl (meth) acrylates. Further suitable polyols are hydroxyl-terminated esters and urethanes.

  The polyols can be partially or completely esterified with one unsaturated carboxylic acid or with different unsaturated carboxylic acids, in which the free hydroxy groups are etherified or esterified with other carboxylic acids, for example. It can be denatured, for example.

Examples of polyol-based esters are trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate monooxy Dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol Penta (meth) acrylate mono (2-hydroxyethyl) ether, tripentaerythritol octa (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol diitaconate, hexanediol di (meta) ) Acrylate, 1,4-cyclohexanediol di (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (Meth) acrylate, sorbitol hexa (meth) acrylate, oligoester (meth) acrylates, glycerol di (meth) acrylate and tri (meth) acrylate, di (meth) acrylate of polyethylene glycol having a molecular weight of 200 to 1500, pentaerythritol diitaco Dipentaerythritol trisitaconate, dipentaerythritol pen titaconate, dipentaerythritol hexaitaconate, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4- Butanediol diitaconate, tetramethylene glycol diitaconate, sorbitol tetritaconate, ethylene glycol dicrotonate, tetramethylene Glycol dicrotonate, pentaerythritol dicrotonate, ethylene glycol dimaleate, thiethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate or mixtures thereof.

（式中、Ｍ₁は−ＣＨ₂ＣＨ₂Ｏ−又は−［ＣＨ₂ＣＨ（ＣＨ₃）Ｏ］−を表し、
Ｒ₁₀₀は−ＣＯＣＨ＝ＣＨ₂又は−ＣＯＣ（ＣＨ₃）＝ＣＨ₂を表し、
ｐは０乃至６（ｐ総数：３−２４）を表し、並びにｑは０乃至６（ｑ総数：２−１６）を表す。） Other examples are pentaerythritol and dipentaerythritol derivatives represented by the following formulas (XII) and (XIII):

(Wherein M ₁ represents —CH ₂ CH ₂ O— or — [CH ₂ CH (CH ₃ ) O] —,
R ₁₀₀ represents —COCH═CH ₂ or —COC (CH ₃ ) ═CH ₂ ,
p represents 0 to 6 (p total number: 3-24), and q represents 0 to 6 (q total number: 2-16). )

  Examples of polyepoxides are those based on the aforementioned polyols as well as epichlorohydrin. Representative examples are bis (4-glycidyloxyphenyl) methane, 2,2-bis (4-glycidyloxyphenyl) propane, 2,2-bis (4-glycidyloxyphenyl) hexafluoropropane, 9,9- Bis (4-glycidyloxyphenyl) fluorene, bis [4- (2-glycidyloxyethoxy) phenyl] methane, 2,2-bis [4- (2-glycidyloxyethoxy) phenyl] propane, 2,2-bis [ 4- (2-glycidyloxyethoxy) phenyl] hexafluoropropane, 9,9-bis [4- (2-glycidyloxyethoxy) phenyl] fluorene, bis [4- (2-glycidyloxypropropoxy) phenyl] methane 2,2-bis [4- (2-glycidyloxypropoxy) phenyl] propane, 2,2 Bis [4- (2-glycidyl) phenyl] hexafluoropropane is 9,9-bis [4- (2-glycidyloxypropoxy) phenyl] fluorene and glycidyl ethers of phenol and cresol novolacs.

  Representative examples of component (a) based on polyepoxides are 2,2-bis [4-{(2-hydroxy-3-acryloxy) propoxy} phenyl] propane, 2,2-bis [4- {(2-hydroxy-3-acryloxy) propoxyethoxy} phenyl] propane, 9,9-bis [4-{(2-hydroxy-3-acryloxy) propoxy} phenyl] fluorene, 9,9-bis [4 -{(2-Hydroxy-3-acryloxy) propoxyethoxy} phenyl] fluorine and a reaction product of an epoxy resin based on novolaks and (meth) acrylic acid.

  Polyethers obtained by reacting the aforementioned polyols or polyepoxides with unsaturated compounds having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and vinyl alcohol can also be used as component (a).

  Further suitable as component (a) are amides of the same or different unsaturated carboxylic acids and preferably aromatic, cycloaliphatic and aliphatic polyamines having 2 to 6, in particular 2 to 4, amino groups. It is. Examples of the polyamines include ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6- Hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di (β-amino) Ethoxy)-or di (β-aminopropoxy) ethane. Other suitable polyamines are preferably polymers and copolymers having additional amino groups in the side chain and oligoamides having amino end groups. Examples of the unsaturated amides include methylene bisacrylamide, 1,6-hexamethylene bisacrylamide, diethylenetriamine tris methacrylamide, bis (methacrylamide propoxy) ethane, β-methacrylamide ethyl methacrylate and N [(β-hydroxyethoxy). Ethyl] acrylamide.

  Other examples are unsaturated urethanes derived from polyisocyanates and unsaturated compounds having hydroxy groups or from polyisocyanates, polyols and unsaturated compounds having hydroxy groups.

Other examples are polyesters, polyamides or polyurethanes having an ethylenically unsaturated group in the chain. Suitable unsaturated polyesters and polyamides are also derived, for example, from maleic acid and diols or diamines. Some of the maleic acid can be replaced by other carboxylic acids. Polyesters and polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, particularly those having relatively long chains, for example, 6 to 20 carbon atoms. Examples of polyurethanes are those consisting of saturated or unsaturated diisocyanates, as well as unsaturated or, respectively, saturated diols.

  Other suitable polymers having acrylate or methacrylate groups in the side chain are, for example, solvent-soluble or alkali-soluble polyimide precursors such as ester groups in the backbone or molecule as shown in EP 624826. Poly (amidate esters) compounds having photopolymerizable side chains attached. The oligomers or polymers are optionally blended with reactive diluents such as multifunctional (meth) acrylates to produce high sensitivity polyimide precursor resists.

Further examples of component (a) are also resins obtained by reaction of saturated or unsaturated polybasic acid anhydrides with the reaction products of phenol or cresol novolac epoxy resins indicated above and unsaturated monocarboxylic acids. Polymers or oligomers having at least one carboxyl functional group and at least two ethylenically unsaturated groups in the molecular structure. Examples of polybasic acid anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Glutaric anhydride, glutaconic anhydride, sitaraconic anhydride, diglycolic anhydride, iminodiacetic anhydride, 1,1-cyclopentanediacetic anhydride, 3,3-dimethylglutaric anhydride, 3-ethyl -3-Methylglutaric anhydride, 2-phenylglutaric anhydride, homophthalic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic acid Dianhydrides and biphenyl ether tetracarboxylic dianhydrides. Suitable epoxy compounds are novolak epoxy resins, bisphenol fluorenediglycidyl ether, bisphenol propane diglycidyl ether, and the like. Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linolenic acid and oleic acid. Acrylic acid and methacrylic acid are preferred.

（式中、Ｙ₁は

を表し、
Ｒ₂₀₀は水素原子又はメチル基を表し、
Ｒ₃₀₀及びＲ₄₀₀はそれぞれ独立して水素原子、メチル基、Ｃｌ又はＢｒを表し、Ｍ₂は１
乃至１０の炭素原子数を有する置換又は非置換のアルキレン基を表し、ｘは０乃至５を表し、ｙは１乃至１０を表す。）成分（ａ）としてのそのような化合物の例は、特開２００２−２０６０１４号公報、特開２００４−６９７５４号公報、特開２００４−３０２２４５号公報、特開２００５−７７４５１号公報、特開２００５−３１６４４９号公報、特開２００５−３３８３２８号公報及び特許第３７５４０６５号明細書に記載される。 Another example is a product obtained by polycondensation reaction and / or addition reaction between the compound represented by the formula (XIV) and one or more polybasic acid anhydrides.

(Where Y ₁ is

Represents
R ₂₀₀ represents a hydrogen atom or a methyl group,
R ₃₀₀ and R ₄₀₀ each independently represent a hydrogen atom, a methyl group, Cl or Br, and M ₂ is 1
Represents a substituted or unsubstituted alkylene group having from 10 to 10 carbon atoms, x represents 0 to 5 and y represents 1 to 10; ) Examples of such compounds as component (a) are JP-A No. 2002-206014, JP-A No. 2004-69754, JP-A No. 2004-302245, JP-A No. 2005-77451, JP-A No. 2005. -316449, JP-A-2005-338328, and Japanese Patent No. 3754065.

  The aforementioned polymers and oligomers have a molecular weight of, for example, about 1,000 to 1,000,000, preferably 2,000 to 200,000, and about 10 to 200 mg KOH / g, preferably 20 to 180 mg KOH / g. g acid value.

  A preferred photopolymerizable compound is a compound having at least two ethylenically unsaturated bonds and at least one carboxylic acid group in the molecule as component (a), and in particular, an epoxy group-containing unsaturated compound is converted to a carboxylic acid group. It is a reaction product obtained by adding to a part of the carboxyl group of the containing polymer, or a reaction product of a compound shown below and one or more polybasic acid anhydrides. Further preferred components (a) include compounds obtained by reacting a compound represented by formula XIV with one or more polybasic acid anhydrides.

  A further example is a reaction product obtained by adding an epoxy group-containing unsaturated compound to a part of the carboxyl group of a carboxylic acid group-containing polymer. Examples of the carboxylic acid-containing polymer include the above-described binder polymers obtained from a reaction between an unsaturated carboxylic acid compound and one or more polymerizable compounds, such as (meth) acrylic acid, benzyl (meth) acrylate, styrene, and 2-hydroxy. Copolymer of ethyl (meth) acrylate, copolymer of (meth) acrylic acid, styrene and α-methystyrene, copolymer of (meth) acrylic acid, N-phenylmaleimide, styrene and benzyl (meth) acrylate, (meth) acrylic acid and styrene Copolymers of (meth) acrylic acid and benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, styrene and (meth) acrylic acid.

（式中、Ｒ₅₀は水素原子又はメチル基を表し、Ｍ_３は１乃至１０の炭素原子数を有する置換または非置換のアルキレン基を表す。） The example of the unsaturated compound which has an epoxy group is shown by the following formula | equation (V-1)-(V-15).

(Wherein R ₅₀ represents a hydrogen atom or a methyl group, and M ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.)

Among these compounds, a compound having an alicyclic epoxy group is particularly preferred because it has high reactivity with a carboxyl group-containing resin and can therefore shorten the reaction time. Furthermore, these compounds do not cause gelation in the reaction process, and the reaction can be carried out stably. On the other hand, glycidyl acrylate and glycidyl methacrylate are advantageous from the viewpoint of sensitivity and heat resistance because they have a low molecular weight and can give a high conversion rate of esterification.

  Specific examples of the above compound are, for example, a reaction product of a copolymer of styrene, α-methylstyrene and acrylic acid or a copolymer of methyl methacrylate and acrylic acid, and 3,4-epoxycyclohexylmethyl (meth) acrylate.

  For example, unsaturated compounds having hydroxy groups such as 2-hydroxyethyl (meth) acrylate and glycerol mono (meth) acrylate can be used as reactants for carboxylic acid group-containing polymers in place of the epoxy group-containing unsaturated compounds. It can be used.

  Other examples include half esters of anhydride-containing polymers, such as copolymers of maleic anhydride and one or more polymerizable compounds, and alcoholic hydroxy groups such as 2-hydroxyethyl (meth) acrylate ( It is a reaction product with (meth) acrylates or (meth) acrylates having an epoxy group such as compounds described in formulas (V-1)-(V-15).

  Reaction products of alcoholic hydroxy group-containing polymers such as copolymers of 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, benzyl methacrylate and styrene with (meth) acrylic acid or (meth) acrylic chloride are also components. It can be used as (a).

  Other examples include polyesters and terminal unsaturated groups obtained by reaction of a dibasic acid anhydride with a compound having at least two epoxy groups followed by a reaction with an unsaturated compound. It is a reaction product with a basic acid anhydride.

  A further example is the reaction of a saturated or unsaturated polybasic acid anhydride with a reaction product obtained by adding an epoxy group-containing (meth) acrylic compound to all the carboxyl groups of the carboxylic acid-containing polymer described above. It is resin obtained by.

  The polymerizable compounds can be used alone or in any desired mixture.

  In the color filter resist composition, the total amount of monomers contained in the photopolymerizable composition is preferably 5 to 5 with respect to the total solid content of the composition, that is, the amount of all components excluding the solvent (s). 80% by weight, in particular 10 to 70% by weight.

The binder used in the color filter resist composition and soluble in an alkaline aqueous solution and insoluble in water includes, for example, polymerization having one or more acid groups and one or more polymerizable unsaturated bonds in the molecule. A homopolymer of a polymerizable compound, or a copolymer of two or more thereof, and a copolymer of one or more polymerizable compounds having one or more unsaturated bonds that can be copolymerized with these compounds and not containing an acid group Can be used. Such compounds include one or more low molecular weight compounds having one or more acid groups and one or more polymerizable unsaturated bonds in the molecule, and one or more unsaturated compounds copolymerizable with these compounds. It is obtained by copolymerizing one or more polymerizable compounds having a bond and not containing an acid group. Examples of acid groups are —COOH group, —SO ₃ H group, —SO ₂ NHCO— group, phenolic hydroxy group, —SO ₂ NH— group and CO—NH—CO— group. Among these, a polymer compound having a —COOH group is particularly preferable.

Preferably, the organic polymer binder in the color filter resist composition includes an alkali-soluble copolymer containing at least one unsaturated organic acid compound such as acrylic acid or methacrylic acid as an addition polymerizable monomer unit. As further comonomers for polymer binders, unsaturated organic acid ester compounds such as methyl acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, styrene etc. are used, alkali solubility, adhesion hardness, chemical resistance, etc. It is preferable to balance these characteristics.
The organic polymer binder can be either a random copolymer or a block copolymer as described, for example, in US Pat. No. 5,368,976.

  Examples of polymerizable compounds having one or more acid groups and one or more polymerizable unsaturated bonds in the molecule include the following compounds:

  Examples of the polymerizable compound having one or more —COOH groups and one or more polymerizable unsaturated bonds in the molecule include (meth) acrylic acid, 2-carboxyethyl (meth) acrylic acid, 2-carboxypropyl ( (Meth) acrylic acid, crotonic acid, cinnamic acid, mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] adipate, mono [2- (meth) acryloyloxyethyl] phthalate, Mono [2- (meth) acryloyloxyethyl] hexahydrophthalate, mono [2- (meth) acryloyloxyethyl] malate, mono [2- (meth) acryloyloxypropyl] succinate, mono [2- (meth) acryloyloxy Propyl] adipate, mono [2- (meth) acryloyloxypropyl] Talate, mono [2- (meth) acryloyloxypropyl] hexahydrophthalate, mono [2- (meth) acryloyloxypropyl] malate, mono [2- (meth) acryloyloxybutyl] succinate, mono [2- (meth) [Acryloyloxybutyl] adipate, mono [2- (meth) acryloyloxybutyl] phthalate, mono [2- (meth) acryloyloxybutyl] hexahydrophthalate, mono [2- (meth) acryloyloxybutyl] malate, 3- ( Alkylcarbamoyl) acrylic acid, α-chloroacrylic acid, maleic acid, monoesterified maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride and ω-carboxypolycaprolactone mono (meth) acrylate .

Vinylbenzenesulfonic acid and 2- (meth) acrylamido-2-methylpropanesulfonic acid have one or more —SO ₃ H groups and one or more polymerizable unsaturated bonds.
It is an example of a polymeric compound.
N-methylsulfonyl (meth) acrylamide, N-ethylsulfonyl (meth) acrylamide, N-phenylsulfonyl (meth) acrylamide, and N- (p-methylphenylsulfonyl) (meth) acrylamide are one or more —SO _2. An example of a polymerizable compound having an NHCO- group and one or more polymerizable unsaturated bonds.

  Examples of polymerizable compounds having one or more phenolic hydroxyl groups and one or more polymerizable unsaturated bonds in the molecule include hydroxyphenyl (meth) acrylamide, dihydroxyphenyl (meth) acrylamide, and hydroxyphenyl-carbonyloxy. Ethyl (meth) acrylate, hydroxyphenyloxyethyl (meth) acrylate, hydroxyphenylthioethyl (meth) acrylate, dihydroxyphenylcarbonyloxyethyl (meth) acrylate, dihydroxyphenyloxyethyl (meth) acrylate, and dihydroxy-phenylthioethyl ( And (meth) acrylate.

In a molecule having one or more -SO ₂ NH- groups and one or more polymerizable unsaturated bond, examples of the polymerizable compounds, formula (a) or (b):
_{CH 2 = CHA 1 -Y 1 -A} 2 -SO 2 -NH-A 3 (a)
_{CH 2 = CHA 4 -Y 2 -A} 5 -NH-SO 2 -A 6 (b)
(Wherein, Y ₁ and Y ₂ are each -COO- group,-ConA ₇ - group or a single bond,; A ₁ and A ₄ each represents H or CH ₃ group; A ₂ and A ₅ is an optionally substituted cycloalkylene group, arylene group or aralkylene group having 1 to 12 carbon atoms, or an alkyl group having 2 to 12 carbon atoms into which an ether group and a thioether group are inserted. Each represents an alkylene group, a cycloalkylene group, an arylene group or an aralkylene group; A ₃ and A ₆ each represent 1 to 12 carbon atoms having H, optionally a cycloalkyl group, an aryl group or an aralkyl group as a substituent. It represents an alkyl group; a ₇ has H, an optionally substituted group, a cycloalkyl group, an aryl group or aralkyl group Compounds represented by the representative.) The alkyl atom having 1 to 12 can be mentioned.

  Examples of the polymerizable compound having one or more —CO—NH—CO— groups and one or more polymerizable unsaturated bonds include maleimide and N-acryloyl-acrylamide. These polymerizable compounds are polymerized into a polymer compound containing a —CO—NH—CO— group in which a ring is formed together with the main chain. Furthermore, a methacrylic acid derivative and an acrylic acid derivative each having a —CO—NH—CO— group can also be used. Examples of such methacrylic acid derivatives and acrylic acid derivatives include N-acetylmethacrylamide, N-propionylmethacrylamide, N-butanoylmethacrylamide, N-pentanoylmethacrylamide, N-decanoylmethacrylamide, N-dodeca. Noyl methacrylamide, N-benzoyl methacrylamide, N- (p-methylbenzoyl) methacrylamide, N- (p-chlorobenzoyl) methacrylamide, N- (naphthylcarbonyl) methacrylamide, N- (phenylacetyl) methacrylamide, And methacrylamide derivatives such as 4-methacryloylaminophthalimide, and acrylamide derivatives having the same substituents. These polymerizable compounds are polymerized into compounds having —CO—NH—CO— groups in the side chains.

Examples of polymerizable compounds having one or more polymerizable unsaturated bonds and containing no acid groups include esters of (meth) acrylic acid, such as methyl (meth) acrylate, ethyl (meth) acrylate , Propyl (meth) acrylate, butyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy Butyl (meth) acrylate, glycerol mono (meth) acrylate, dihydroxypropyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, methoxyphenyl (meth) Acrylate, methoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropyl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl ( (Meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, Aminoethyl (meth) acrylate, N, N-diemethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, glycy Zyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene , Vinyl toluene, p-chlorostyrene, polychlorostyrene, fluorostyrene, bromostyrene, ethoxymethyl styrene, methoxy styrene, 4-methoxy-3-methystyrene, dimethoxy styrene, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether, indene, 1 -Methylindene; vinyl or allyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl benzoate, vinyl trimethyl acetate, vinyl diethyl Acetate, vinyl valerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxy acetate, vinyl phenyl acetate, vinyl acetate, vinyl acetoacetate, vinyl lactate, vinyl phenyl butyrate, vinyl cyclohexyl carboxylate, Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, allyl acetate, allyl propionate, allyl butyrate, allyl pivalate, allyl benzoate, allyl caproate, allyl stearate, allyl acetoacetate, allyl lactate; vinyl Or allyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl hex Sil ether, vinyl octyl ether, vinyl ethyl hexyl ether, vinyl methoxy ethyl ether, vinyl ethoxy ethyl ether, vinyl chloro ethyl ether, vinyl hydroxy ethyl ether, vinyl ethyl butyl ether, vinyl hydroxy ethoxy ethyl ether, vinyl dimethyl amino ethyl ether, vinyl diethyl amino Ethyl ether, vinyl butyl amino ethyl ether, vinyl benzyl ether, vinyl tetrahydrofurfuryl ether, vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl chloroethyl ether, vinyl dichlorophenyl ether, vinyl naphthyl ether, vinyl anthryl ether, allyl glycidyl Ethers; amide type unsaturated compounds, for example (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dibutyl (meth) acrylamide, N, N-diethylhexyl (meth) acrylamide, N, N-dicyclohexyl (Meth) acrylamide, N, N-diphenyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide, N-methyl (meth) acrylamide, N- Ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-heptyl (meth) acrylamide, N-octyl (meth) acrylamide, N-ethylhexyl (Meta) Kurylamide, N-hydroxyethyl (meth) acrylamide cyclohexyl, N-benzyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-tolyl (meth) acrylamide, N-hydroxyphenyl (meth) acrylamide, N-naphthyl (meth) ) Acrylamide, N-phenylsulfonyl (meth) acrylamide, N-methylphenylsulfonyl (meth) acrylamide and N- (meth) acryloylmorpholine, diacetone acrylamide, N-methylol acrylamide, N-butoxyacrylamide; polyolefin type compounds such as Butadiene, isoprene, chloroprene, etc .; (meth) acrylonitrile, methyl isopropyl ketone, maleimide, N-phenylmaleimide, N-methylphenylmale Imide, N-methoxyphenylmaleimide, N-cyclohexylmaleimide, N-alkylmaleimide, maleic anhydride, polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, polybutyl (meth) acrylate macromonomer; crotonates such as butyl croto And itaconates, such as dimethyl itaconate, diethyl itaconate, dibutyl itaconate; and polymerizations selected from malates and fumarates, such as dimethyl malate, dibutyl fumarate And compounds having an unsaturated group.

Preferred examples of copolymers include methyl (meth) acrylate and (meth) acrylic acid copolymers, benzyl (meth) acrylate and (meth) acrylic acid copolymers, methyl (meth) acrylate /, ethyl (meth) acrylate and Copolymers of (meth) acrylic acid, copolymers of benzyl (meth) acrylate, copolymers of (meth) acrylic acid and styrene, copolymers of benzyl (meth) acrylate, (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate, Methyl (meth) acrylate, butyl (meth) acrylate, copolymers of (meth) acrylic acid and styrene, methyl (meth) acrylate, benzyl (meth) acrylate, copolymers of (meth) acrylic acid and hydroxyphenyl (meth) acrylate Copolymers of methyl (meth) acrylate, (meth) acrylic acid and polymethyl (meth) acrylate macromonomer, copolymers of benzyl (meth) acrylate, (meth) acrylic acid and polymethyl (meth) acrylate macromonomer, tetrahydrofurfuryl ( Of (meth) acrylate, copolymers of styrene and (meth) acrylic acid, copolymers of methyl (meth) acrylate, (meth) acrylic acid and polystyrene macromonomer, benzyl (meth) acrylate, (meth) acrylic acid and polystyrene macromonomer Copolymers, copolymers of benzyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and polystyrene macromonomer, benzyl (meth) acrylate, Copolymers of meth) acrylic acid, 2-hydroxypropyl (meth) acrylate and polystyrene macromonomer, benzyl (meth) acrylate, (meth) acrylic acid, 2-hydroxy-3-phenoxypropyl (meth) acrylate and polymethyl (meth) Copolymers of acrylate macromonomers, methyl (meth) acrylate, (meth) acrylic acid, copolymers of 2-hydroxyethyl (meth) acrylate and polystyrene macromonomer, benzyl (meth) acrylate, (meth) acrylic acid, 2-hydroxy Copolymers of ethyl (meth) acrylate and polymethyl (meth) acrylate macromonomers, copolymers of N-phenylmaleimide, benzyl (meth) acrylate, (meth) acrylic acid and styrene, Copolymers of benzyl (meth) acrylate, (meth) acrylic acid, N-phenylmaleimide, mono- [2- (meth) acryloyloxyethyl] succinate and styrene, allyl (meth) acrylate, (meth) acrylic acid, N- Copolymers of phenylmaleimide, mono [2- (meth) acryloyloxyethyl] succinate and styrene, copolymers of benzyl (meth) acrylate, (meth) acrylic acid, N-phenylmaleimide, glycerol mono (meth) acrylate and styrene, Benzyl (meth) acrylate, ω-carboxypolycaprolactone mono (meth) acrylate, (meth) acrylic acid, N-phenylmaleimide, copolymers of glycerol mono (meth) acrylate and styrene, and benzyl ( Data) acrylate, (meth) acrylic acid, N- cyclohexyl maleimide and copolymers of styrene.
As used herein, the term “(meth) acrylate” refers to acrylate and the corresponding methacrylate.

  Hydroxystyrene homopolymers or copolymers, or novolac type phenolic resins such as poly (hydroxystyrene) and poly (hydroxystyrene-co-vinylcyclohexanol), novolac resins, cresol novolac resins, and halogenated phenol novolac resins can also be used. . More specifically, for example, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic anhydride copolymers, such as those with styrene as a copolymer, and maleic acid copolymers , As well as partially esterified maleic acid copolymers, for example, Japanese Patent Publication No. 59-44615 (the term “special publication” as used herein means a patent publication that has been examined). ), JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048, JP-A-60- 159743, JP-A-60-258539, JP-A-1-152449, JP-A-2- No. 99403 and JP-A-2-199404, for example, as shown in US Pat. No. 5,650,263, these copolymers are further capable of reacting with amines, and further carboxyl groups in the side chain. The cellulose derivative can be used, and particularly preferably described in, for example, U.S. Pat. No. 4,139,391, JP-B-59-44615, JP-A-60-159743, and JP-A-60-258539. As well as copolymers of benzyl (meth) acrylate and (meth) acrylic acid and copolymers of benzyl (meth) acrylate, meth (acrylic acid) and other monomers.

Among the above organic binder polymers, for those having a carboxylic acid group, some or all of the carboxylic acid groups are reacted with glycidyl (meth) acrylate or epoxy (meth) acrylate to obtain photosensitivity, coating film strength, Photopolymerizable organic binder polymers can be obtained for the purpose of improving the coating solvent, chemical resistance, and adhesion to the substrate. Examples are disclosed in JP-B-50-34443 and JP-B-50-34,444, US Pat. Kudo et al. Appl. Phys. 37 (1998), 3594-3603, US Pat. No. 5,677,385 and US Pat. No. 5,650,233.

  The weight average molecular weight of the binder is preferably 500 to 1,000,000, such as 3,000 to 1,000,000, more preferably 5,000 to 400,000.

  These compounds may be used alone or as a mixture of two or more. The binder content in the photosensitive resin composition is preferably 10 to 95% by mass, more preferably 15 to 90% by mass, based on the total solids.

Furthermore, in the color filter, all solid components of each color may contain an ionic impurity scavenger, for example, an organic compound having an epoxy group. The concentration of the ionic impurity scavenger in the total solid component is generally in the range of 0.1 to 10% by mass.
An example of a color filter, in particular the above combination of pigment and ionic impurity scavenger, is given in EP 320264. It is understood that the photoinitiators according to the invention, ie the compounds of the formulas I and II in the color filter formulation described in EP 320624, can replace the triazine initiator compounds.

The composition according to the present invention further comprises, for example, a cross-linking agent activated by an acid and a compound which generates an acid thermally or by actinic radiation and activates a cross-linking reaction, as described in JP-A-10-221843. Can be included.
The composition according to the invention can also comprise a latent pigment which is converted into a finely dispersed pigment during the heat treatment of the latent pigment containing a photosensitive pattern or coating. The heat treatment can be performed after exposure or development of the photoimageable layer containing the latent pigment. Such latent pigments can be converted to insoluble pigments using chemical, thermal, photolytic or radiation-induced methods, for example as described in US Pat. No. 5,879,855. It is a soluble pigment precursor. This conversion of such latent pigments can be enhanced by adding to the composition a compound that generates an acid upon actinic exposure or by adding an acidic compound. Therefore, it is also possible to produce color filter resists that contain latent pigments in the composition according to the invention.

Examples of color filter resists, compositions of such resists and processing conditions are described in T.W. Kudo et al., Jpn. J. et al. Appl. Phys. 37 (1998) 3594; Kudo et al. Photopolym. Sci. Technol. 9 (1996) 109
K. Kobayashi, Solid State Technol. November 1992, p. S15-S18; US Pat. No. 5,368,976; US Pat.
No. 52; U.S. Pat. No. 5,882,843; U.S. Pat. No. 5,889,855; U.S. Pat. No. 5,866,298; U.S. Pat. No. 5,863,678; Description: JP-A-9-269410; JP-A-10-221843; JP-A-1-090516; JP-A-10-171119; US Pat. No. 5,821,016; US Pat. No. 5,874,015 U.S. Pat. No. 5,882,843; U.S. Pat. No. 5,719,008; EP 881541 or EP 902327.
The photoinitiators of the present invention can be used in color filter resists such as those described in the above examples, or known photoinitiators can be partially or completely replaced in such resists. The use of the novel photoinitiators of the present invention is limited to specific binder resins, crosslinkers and color filter resist formulation examples described herein to form photosensitive color filter inks or color filter resists. It will be appreciated by those skilled in the art that any radically polymerizable component can be used in combination with dyes or color pigments or latent pigments.

The subject of the present invention is therefore also provided with red, green and blue (RGB) color elements—pixels—and optionally a black matrix (all comprising a photosensitive resin and pigment on a transparent substrate) and a substrate A color filter manufactured by providing a transparent electrode on either the surface of the color filter layer or the surface of the color filter layer, wherein the photosensitive resin is represented by a polyfunctional acrylate monomer, an organic polymer binder, and the above formula I A color filter containing a photopolymerization initiator. Monomer and binder components and suitable pigments are described above. In the production of the color filter, the transparent electrode layer can be applied on the surface of the transparent substrate or can be applied to the surface of the red, green and blue pixels and the black matrix. A transparent substrate is a glass substrate which can have an electrode layer further on the surface, for example.
In order to improve the contrast of the color filter, it is preferable to apply a black matrix between the color areas of different colors.

As already mentioned, the photosensitive composition of the present invention is also suitable for producing a black matrix of a color filter. For example, the black matrix composition is a photoinitiator compound of formula I of the present invention or a compound of formula I of the present invention as described above,
An organic binder, specifically, an organic binder that is an epoxy acrylate resin having a carboxyl group,
-Black coloring material,
-Polymer dispersants, specifically polymer dispersants containing basic functional groups.
Those skilled in the art are familiar with such formulations. Suitable black matrix compositions described above and their components (other than photoinitiators) are given in Japanese Patent No. 375065, the disclosure of which is incorporated herein by reference.

  To form a black pattern that separates red, green, and blue regions on a transparent substrate, a black matrix is formed using the photosensitive composition, and the black photosensitive composition is exposed photolithographically in a pattern (ie, Instead of (through a suitable mask), it is possible to use an inorganic black matrix. Such an inorganic black matrix is suitable for image processing, for example, photolithographic patterning with an etching resist by etching the inorganic layer in areas not protected by the etching resist and then removing the residual etching resist. By utilizing, it can be formed from a deposited (ie, sputtered) metal (ie, chromium) film on a transparent substrate.

  There are various known methods for how and in which steps the black matrix can be applied in the color filter manufacturing process. Prior to the formation of the already described red, green and blue (RGB) color filters, they can be applied directly on the transparent substrate or can be applied after the RGB color filters are formed on the substrate. it can.

In a different embodiment of a color filter for a liquid crystal display device according to US Pat. No. 6,267,796, a black matrix can be applied on the substrate opposite the RGB color filter element-holding substrate, which is due to the liquid crystal layer. Separated from the former.

  If the transparent electrode layer is deposited after applying the RGB color filter element and -optionally-black matrix, a further overcoat film as a protective layer, for example as described in US Pat. No. 5,650,263 Can be applied onto the color filter layer prior to the deposition of the electrode layer.

  In order to form the overcoat layer of the color filter, a photosensitive resin or a thermosetting resin composition is used. The cured film of the composition of the present invention forms flatness, hardness, chemical resistance, heat resistance, especially transparency in the visible region, adhesion to the substrate, and transparent conductive film such as ITO film thereon The photosensitive composition can also be used to form such an overcoat layer because of its excellent suitability to do so. In the production of the protective layer, as described in JP-A-57-42009, JP-A-1-130103 and JP-A-1-134306, for example, on a scribing line for cutting a substrate and solid There is a requirement that unnecessary portions of the protective layer on the bonding pads of the image sensor should be removed from the substrate. In this regard, it is difficult to selectively form a protective layer with good accuracy using the above thermosetting resin. However, the photosensitive composition makes it possible to easily remove unnecessary portions of the protective layer by photolithography.

  The photosensitive composition of the present invention is suitable for the production of color filters regardless of the above differences in processing, regardless of the additional layers that can be applied, and the differences in color filter design. It will be apparent to those skilled in the art that it can be used to form blue pixels and black matrices. The use of the composition according to the invention for forming the coloring elements should not be considered limited by the different designs and production methods of such color filters.

  Although the photosensitive composition of this invention can be used suitably for forming a color filter, it is not limited to this use. It is equally useful for recording materials, resist materials, protective layers, dielectric layers, paints, and printing inks in display applications and display elements.

The photosensitive composition according to the present invention includes a liquid crystal display device, and more particularly, a reflective liquid crystal display device including an active matrix type having a thin film transistor (TFT) as a switching device and a passive matrix type display device without a switching device. It is also suitable for manufacturing an interlayer insulating layer or a dielectric layer.
In recent years, liquid crystal display devices have been widely used, for example, in portable television sets and communication terminal devices because of their thin thickness and light weight.
Reflective liquid crystal devices that do not require the use of a backlight are particularly in demand because they are extremely thin, lightweight, and can significantly reduce power consumption. However, even if the backlight is removed from the currently available transmissive color liquid crystal display device and a light reflection plate is added to the lower surface of the display device, the light use efficiency is low, so that it cannot have practical brightness. This causes a problem.
As a solution to this problem, various reflective liquid crystal display devices have been proposed in order to enhance the light utilization efficiency. For example, some types of reflective liquid crystal display devices are designed to include pixel electrodes having a reflective function.
The reflective liquid crystal display device includes an insulating substrate and a substrate facing the insulating substrate with a space therebetween. The space between the substrates is filled with liquid crystal. A gate electrode is formed on an insulating substrate, and both the gate electrode and the insulating substrate are covered with a gate insulating film. Next, a semiconductor layer is formed on the gate insulating film over the gate electrode. A source electrode and a drain electrode are also formed on the gate insulating film in contact with the semiconductor layer. The source electrode, the drain electrode, the semiconductor layer, and the gate electrode cooperate with each other, thereby forming a bottom gate type TFT as a switching device.
An interlayer insulating film is formed so as to cover the source electrode, the drain electrode, the semiconductor layer, and the gate insulating film. A contact hole is formed through the interlayer insulating film on the drain electrode. Aluminum pixel electrodes are formed on both the interlayer insulating film and the inner wall of the contact hole. As a result, the drain electrode of the TFT is in contact with the pixel electrode through the interlayer insulating film. The interlayer insulating layer generally has a roughened surface, whereby the pixel electrode is designed to act as a reflector that diffuses light to obtain a wider viewing angle (visible angle).
The reflection type liquid crystal display device remarkably enhances the efficiency of using light by the pixel electrode acting as a light reflector.
In the above reflective liquid crystal display device, the interlayer insulating film is designed to have irregularities by a photolithography method. Photolithography using positive and negative photoresists is used to roughen the surface by forming and controlling fine shapes in the micrometer dimension of irregularities and to form contact holes. For these resists, the compositions according to the invention are particularly suitable.

The photosensitive composition according to the present invention can also be used for the production of a spacer for controlling the cell gap of the liquid crystal portion in the liquid crystal display panel. Since the characteristics of the light transmitted or reflected through the liquid crystal layer in the liquid crystal display device depend on the cell gap, the accuracy and uniformity of the thickness of the entire pixel array is critical for the performance of the liquid crystal display unit. Parameter. In a liquid crystal cell, the spacing between the substrates in the cell is kept constant by sparsely distributing glass or polymer spheres with a diameter of several micrometers as spacers between the substrates. Therefore, these spacers are held between the substrates so as to keep the distance between the substrates constant. This distance is determined by the spacer diameter. The spacer ensures a minimum spacing between the substrates, i.e. prevents a decrease in the distance between the substrates. However, they cannot prevent the substrates from being spaced apart from each other, i.e. increasing the distance between the substrates. In addition, this method using spacer beads has the problem of non-uniform orientation and spacer alignment in the pixel array region, as well as the problem of spacer bead diameter uniformity and the difficulty of uniform dispersibility on the spacer bead panel. It has the problem of reduced brightness and / or optical aperture depending on the position. In recent years, a liquid crystal display device having a large image display area has attracted much interest. However, an increase in the area of the liquid crystal cell generally causes distortion of the substrate constituting the cell. The layer structure of the liquid crystal tends to be destroyed due to the deformation of the substrate. Therefore, even when a spacer is used to keep the distance between the substrates constant, a liquid crystal display device having a large image display area cannot be realized because the display device is disturbed.
Instead of the spacer sphere dispersion method described above, a method of forming column pillars as spacers in the cell gap has been proposed. In this method, a predetermined cell gap is formed by forming a resin column as a spacer in a region between a pixel array region and a counter electrode. A photosensitive material having adhesive properties is generally used, for example, in a photolithography method in a color filter manufacturing process. This method is advantageous in that the position, number and height of the spacer can be freely controlled as compared with the conventional method using spacer beads. In a color liquid crystal display panel, such a spacer is formed in a non-imaging region under a black matrix of color filter elements. Therefore, the spacer formed using the photosensitive composition does not decrease the luminance and the optical aperture.
A photosensitive composition for forming a protective layer having a color filter spacer is disclosed in JP-A No. 2000-81701, and a dry film type photoresist for a spacer material is also disclosed in JP-A Nos. 11-174259 and It is disclosed in Japanese Patent Application Laid-Open No. 11-174464. As described in these documents, photosensitive compositions, liquid and dry film photoresists include at least an alkali or acid soluble binder polymer, a radical polymerizable monomer, and a radical initiator. In some cases, thermally crosslinkable components such as epoxides and carboxylic acids may additionally be included.
The process of forming a spacer using the photosensitive composition is as follows:
The photosensitive composition is applied to a substrate, such as a color filter panel, and the substrate is pre-baked and then exposed through a mask. The substrate is then developed with a developer and patterned to form the desired spacer. When the composition contains any thermosetting component, a post bake is usually performed to heat cure the composition.
The photocurable composition according to the present invention is suitable for producing a spacer for a liquid crystal display device (as described above) because of its high sensitivity.

The photosensitive composition according to the present invention is also suitable for producing microlens arrays used for liquid crystal display panels, image sensors and the like.
Microlenses are fine passive optical devices that are compatible with active optoelectronic devices such as detectors, displays, and light emitting devices (light emitting diodes, horizontal and vertical hole lasers) to improve their optical input and output quality. It is a part. The field of application is wide and covers fields such as telecommunications, information technology, audiovisual services, solar cells, detectors, solid state light sources, and optical interconnects.
Current optical systems use various techniques to achieve efficient coupling between microlenses and microoptical devices.
A microlens array is used to collect illumination light in a pixel area of a non-luminous display device, for example a liquid crystal display device, to increase the brightness of the display device, to collect incident light, or for example a facsimile As a means to improve the sensitivity of these devices by forming an image in the photoelectric conversion region of a line image sensor used in the process, and for printing with photosensitive means used in liquid crystal printers or light emitting diode (LED) printers Used to form an image.

The most common application is their use to improve the efficiency of light detection arrays in solid state imaging devices such as charge coupled devices (CCDs). In a detector array, as much light collection as possible is required at each detector element or pixel. When a microlens is attached to the top of each pixel, the lens collects incoming light and focuses on a radiation surface that is smaller than the lens size.
According to the prior art, microlens arrays can be produced in various ways; for each of them, the composition of the invention can be used.
(1) A planar lens pattern is drawn on a thermoplastic resin by a conventional photolithographic technique, and then the thermoplastic resin is heated to a temperature exceeding the softening point of the resin so as to have fluidity. Then, a method of obtaining a convex lens (for example, Japanese Patent Application Laid-Open Nos. 60-38989, 60-165623, and Japanese Patent Application Laid-Open No. 60-165623, which causes a sag in the pattern edge (so-called “reflowing”). (See Sho 61-67003 and JP-A 2000-39,503). In this method, when the thermoplastic resin used is photosensitive, a lens pattern can be obtained by exposure of this resin.
(2) A method of molding a plastic or glass material by using a mold or a stamper. In this method, a photocurable resin and a thermosetting resin can be used as the lens material (see, for example, pamphlet of International Publication No. 99/38035).
(3) Based on the phenomenon that when the photosensitive resin is exposed to a desired pattern by using an aligner (exposure device), the unreacted monomer moves from the non-exposed area to the exposed area, and as a result, the exposed area expands. And a method of forming a convex lens (see, for example, Journal of the Research Group in Microelectronics Japan Society of Applied Physics, Colloquimin in Optics, Vol. .2, pp. 87-92 (1988)).
A photosensitive resin layer is formed on the upper surface of the support substrate. Thereafter, the upper surface of the photosensitive resin layer is illuminated with light such as a mercury lamp using a separate light shielding mask to expose the photosensitive resin layer. as a result,
The exposed portion of the photosensitive resin layer expands into the shape of a convex lens to form a condensing layer having a plurality of microlenses.
(4) Convex surface that causes clouding on the pattern edge and distributes the amount of photochemical reaction product according to the degree of cloudiness on the pattern edge, and exposes the photosensitive resin by a proximity exposure method that does not contact the resin with the photomask. A method for obtaining a lens (see, for example, JP-A-61-153602).
(5) A method of generating a lens effect by exposing a photosensitive resin with a specific intensity distribution to form a refractive index having a distribution pattern according to the intensity of light (for example, JP-A-60-72927 and (See JP-A-60-166946).
The photosensitive composition of the present invention can be used to form a microlens array using a photocurable resin composition in any one of the above methods.

A particular class of techniques concentrates on forming microlenses in thermoplastic resins such as photoresist. An example is described by Popovic et al. In the reference SPIE 898, pp. 23-25 (1988). The technique, termed the reflow technique, defines the lens footprint in a thermoplastic resin, for example by photolithography in a photosensitive resin such as a photoresist, and then heats the material beyond its reflow temperature. Process. The surface tension draws the photoresist islands into a spherical cap having a volume equal to the first island before reflow.
This cap is a plano-convex microlens. The advantages of this approach are, inter alia, simplicity, replicability, and the possibility of being directly integrated into the top of an optoelectronic device for luminescent or photodetection.
In some cases, prior to reflow, an overcoat layer is formed on the rectangular patterned lens unit to avoid sagging in the center of the resin island without reflow to the spherical cap in the reflow process. The overcoat serves as a permanent protective layer. The coating layer is also formed from the photosensitive composition.
The microlens array can also be made by use of a mold or a stamper, as disclosed for example in EP0932256. The method for producing a planar microlens array is as follows:
A mold release agent is coated on the molding surface of the stamper in which the convex portions are densely arranged, and a photocurable synthetic resin material having a high refractive index is set on the molding surface of the stamper. Next, the glass substrate is pressed against the synthetic resin material, whereby the synthetic resin material is stretched, and the synthetic resin material is cured by irradiation with ultraviolet rays or heating to form a convex microlens. Then remove the stamper. Next, a photocurable synthetic resin material having a low refractive index is further coated on the convex microlens as an adhesive layer, and the glass substrate formed on the cover glass plate is pressed against the synthetic resin material, thereby extending it. Next, the synthetic resin material is cured, and finally, a planar microlens array is formed.
As disclosed in US Pat. No. 5,969,867, a similar method using a mold is applied to the manufacture of prism sheets, which enhances brightness as part of a backlight unit for a color liquid crystal display panel. Used to do. The prism sheet forming the prism row on one side is attached to the light emitting surface of the backlight. In order to manufacture a prism sheet, the active energy ray-curable composition is cast into a metal, glass, or resin lens mold and extended to form a lens shape such as a prism array, and then a transparent substrate sheet. Is placed on it, and active energy rays from an active energy ray emission source are irradiated through the sheet for curing. Next, the manufactured lens sheet is released from the lens molding die to obtain a lens sheet.
The active energy ray curable composition used to form the lens portion must possess various properties, including adhesion to a transparent substrate and appropriate optical properties.
At least some prior art photoresist lenses are undesirable for some applications due to poor optical transmission at the blue end of the optical spectrum.
Since the photocurable composition of the present invention has low yellowing property both thermally and photochemically, it is suitable for the production of the microlens array.

The novel radiation-sensitive compositions are also suitable for photolithography processes used in plasma display panel (PDP) manufacturing processes, particularly barrier ribs, phosphor layers and electrode imaging processes.
The PDP is a flat display device for displaying images and information by light emission by gas discharge. Depending on the configuration of the panel and the method of operation, two types are known: a DC (direct current) type and an AC (alternating current) type.
For illustrative purposes, the principle of the DC color PDP will be briefly described. In the DC type color PDP, a space interposed between two transparent substrates (generally glass plates) is divided into a large number of fine cells by lattice-like barrier ribs inserted between the transparent substrates. The In the individual cells, a discharge gas, for example He or Xe, is sealed. On the rear wall of each cell, there is a fluorescent layer that emits three primary colors of visible light when excited by ultraviolet light generated by the discharge of the discharge gas. Electrodes are arranged on the inner surfaces of the two substrates so as to face each other through the associated cells. In general, the cathode is formed of a transparent conductive material film such as NESA glass. When a high voltage is applied between these electrodes formed on the front and back walls, the discharge gas sealed in the cell induces a plasma discharge, resulting in red, blue and red by the emitted ultraviolet light. The green fluorescent element is excited to emit light and display an image. In the full-color display system, each of the three primary colors of red, blue, and green is joined together to form one pixel.
The cells in the DC type PDP are divided by the barrier ribs constituting the lattice, whereas those in the AC type PDP are divided by barrier ribs arranged parallel to each other on the substrate surface. In either case, the cells are divided by barrier ribs. The purpose of these barrier ribs is to confine the light-emitting discharge in a fixed region, eliminate erroneous discharge or crosstalk between adjacent discharge cells, and ensure an ideal display.

  The compositions of the present invention also find use for the production of one or more layered materials for image recording or image reproduction (copying, copying), which can be monochromatic or multicolored. Furthermore, the material is suitable for color test systems. In this technique, a formulation comprising microcapsules can be applied and a heat treatment can be performed after radiation curing for image generation. Such systems and techniques and their applications are disclosed, for example, in US Pat. No. 5,376,459.

The compounds of formula I are also suitable as photoinitiators in holographic data storage applications. The photoinitiator generates radicals and initiates monomer polymerization upon irradiation with blue laser radiation suitable for holographic data storage. The wavelength range of the blue laser is 390-420 nm, preferably 400-410 nm, in particular 405 nm. A holographic storage system (holographic recording medium) is used, for example, for recording and reading a large amount of data with a quick access time. The photoinitiators according to the invention are particularly suitable, for example, for the system described in WO 03/021358 pan frets.
The holographic data storage system preferably consists of a matrix network of low refractive index matrix precursors and a high refractive index photopolymerizable monomer.
The matrix precursor and the photoactive monomer are: (a) the reaction in which the matrix precursor polymerizes during curing is independent of the reaction in which the photoactive monomer polymerizes during the recording of the pattern, eg data, and ( b) The matrix polymer and the polymer obtained by polymerization of the photoactive monomer (photosensitive resin) are selected so that they can be mixed with each other. When the optical recording material (ie, the matrix material plus photoactive monomer, photoinitiator and / or additive) exhibits an elastic modulus of at least about 10 ⁵ Pa, generally from about 10 ^{5 to} 10 ⁹ Pa, the matrix Is determined to be formed.
The media matrix is formed by in situ polymerization, obtained as a crosslinked network, in the presence of photopolymerizable monomers that are “dissolved” and remain unreacted. The matrix containing unreacted photopolymerizable monomer can also be formed by other means, for example by using a solid-resin matrix material in which the photoactive liquid monomer is uniformly dispersed. Monochromatic irradiation then produces a holographic pattern that follows the light intensity distribution and polymerizes the photoreactive monomer in a solid preformed matrix. Unreacted monomer (if the light intensity is minimal) diffuses into the matrix, producing a refractive index modulation, calculated by the difference between the refractive index of the monomer and the matrix, as well as by the volume fraction of the monomer. The thickness of the recording layer ranges from a few micrometers up to 1 millimeter. Because it is such a thick holographic data storage layer, the photoinitiator has high photoreactivity and is made transparent at the laser wavelength and the photopolymerization range is as independent as possible from the exposure depth in the recording layer. It is required to have a low absorbance.
It has been found that the photoinitiators of the present invention combine high reactivity at 405 nm with low absorbance and are suitable for this application. Dyes and sensitizers can also be added to the formulation. Dyes and sensitizers suitable for blue laser irradiation are, for example, coumarin, xanthone, thioxanthone (see list above).
In particular, the items 1. 2. And 3. Thioxanthone, coumarin and benzophenone described in 1).
It has been found that the photoinitiator enables high-sensitivity and photopolymerization of monomers in a thick layer as required for holographic data storage, and obtains a recording layer highly sensitive to blue laser irradiation. When used at a concentration of 2-8% by weight in a 20 μ thick photosensitive layer, the photoinitiator absorbs less than 0.4, preferably less than 0.2, of the layer containing the photoinitiator at the laser wavelength. Get.
Photoinitiators include in particular optical articles (eg optical waveguides) or the above-mentioned polymers and organic photoinitiators, have maximum absorption at UV wavelengths in the range of 340-450 nm and have a refractive index contrast adapted to sensitivity of 3 ×. It is particularly suitable for the production of a holographic recording medium that is 10 ⁻⁶ Δn / (mJ / cm ² ). For example, the polymer is formed by polymerizing a material comprising component 1 and component 2 (component 1 includes an NCO-terminated prepolymer and component 2 includes a polyol). Component 1 is, for example, diphenylmethane diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate derivative, methylene biscyclohexyl isocyanate, methylene biscyclohexyl isocyanate derivative. Component 2 is, for example, a polypropylene oxide polyol. Preferably, the photoactive monomer is an acrylate monomer. In the medium, the shrinkage caused by writing is usually less than 0.25%.

  In addition, photocuring is very important for printing because the ink drying time is an important factor for the production rate of the drawing product and should be on the order of a fraction of a second. UV curable inks are particularly important for screen printing and offset inks.

As already mentioned, the new mixture is also very suitable for the production of printing plates. This use can be made, for example, with soluble linear polyamides or styrene / butadiene and / or styrene / isoprene rubbers, polyacrylates or polymethylmethacrylates with carboxyl groups, polyvinyl alcohol or urethane acrylates and photopolymerizable monomers, for example Acrylamide and / or methacrylamide, or a mixture with acrylate and / or methacrylate, and a photoinitiator are used. These (dry or wet) system films and plates are exposed over the negative (or positive) of the printed original, and then the uncured part is washed off with a suitable solvent or aqueous solution.
Another area in which light curing is used is, for example, metal coatings in the case of metal plates and tubes, cans or bottle cap coatings, and, for example, PVC-based floor or wall coverings Photocuring of polymer coatings such as
Examples of photocuring of paper coatings are colorless varnishing of labels, record jackets and book covers.

Of further interest is the use of this novel photoinitiator to cure molded articles made from composite compositions. The composite compound comprises a self-supporting matrix material, such as a glass fiber fabric, or a plant fiber, for example [K.-P. Mieck, T. Reu.
ssmann in Kunststoff 85 (1995), 366-370], which is impregnated with a photocured formulation. Molded parts containing composite compounds obtain a high level of mechanical stability and resistance when manufactured with the new compounds. The novel compounds can also be used as photocuring agents in molding, impregnation and coating compositions, as described for example in EP 7086. Examples of such compositions are gel coat resins subject to stringent requirements with regard to curing activity and yellowing resistance, and fiber reinforced molded articles, for example light diffusions that are flat or have a corrugation in the longitudinal or transverse direction It is a panel. Techniques for producing such molded articles, such as hand layup, spray layup, centrifugal casting, or filament winding, are described in, for example, P.I. H. “Glass” by Selden
faserverstarkte Kunststoff ", p.610, Spri
nger Verlag Berlin-Heidelberg-New York 1967. Examples of articles that can be produced by these techniques are boats, fiberboard or chipboard panels, pipes, containers, etc. with double-sided coatings of glass fiber reinforced plastic. Further examples of molding, impregnation and coating compositions are UP resin gel coats for molded articles containing glass fibers (GRP), such as corrugated sheets and paper laminates. The paper laminate can be based on urea resin or melamine resin. Prior to production of the laminate, a gel coat is formed on a support (eg a film). The novel photocurable composition can also be used for resin casting or for embedding articles such as electronic components.

  The compositions and compounds according to the present invention can be used in the manufacture of holography, waveguides, and optical switches that take advantage of the difference in refractive index between irradiated and non-irradiated regions.

  The use of photocurable compositions for imaging techniques and optical formation of information carriers is also important. In such applications, as already mentioned, the layer (wet or dry) applied to the support is imagewise irradiated with UV or visible light, for example through a photomask, and the unirradiated areas of the layer are developed. Removed by treatment with agent. Application of the photocured layer to the metal can also be carried out by electrodeposition. The exposed area becomes a polymer by cross-linking and therefore becomes insoluble and remains on the support. Appropriate coloring produces a visible image. When the support is a metallized layer, the metal can be reinforced by etching away the unexposed areas or electroplating after exposure and development. In this way, electronic circuits and photoresists can be manufactured. When used in imaging materials, this novel photoinitiator produces a so-called printout image, thereby giving excellent performance in which a color change is induced due to irradiation. Different dyes and / or leuco forms thereof are used to form such a printout image, examples for such a printout image system are for example WO 96/41240, European patent No. 706091, EP 511403, US Pat. No. 3,579,339 and US Pat. No. 4,622,286.

  The novel photoinitiators are also suitable for photopatternable compositions for forming dielectric layers of multilayer circuit boards that are produced by a sequential lamination process.

As described above, the present invention includes colored and non-colored paints and varnishes, powder coatings, printing inks, printing plates, adhesives, pressure-sensitive adhesives, dental compositions, gel coats, photoresists for electronics, and electroplating resists. Etching resists for both liquid and dry film, solder resists, resists for producing color filters for various display applications, plasma-display panels (eg barrier ribs, phosphor layers, electrodes), electroluminescent displays and LCDs (eg Magnetic recording materials, micromachines as compositions for encapsulating electrical and electronic components for holographic data storage (HDS) to form structures in the manufacturing process of interlayer insulation layers, spacers, microlens arrays) Components, waveguides, optical switches, plating masks, edges Image recording materials, microelectronic circuits, decoloring materials, for manufacturing stereo masks, color test systems, glass fiber cable coatings, and stencils for screen printing, for producing three-dimensional objects by stereolithography, and for holographic recording, The present invention provides a composition as a decolorizing material for image recording material, a photoresist material used for forming a dielectric layer in sequential lamination of printed circuit boards, for image recording material using microcapsules .

  Substrates used for recording photographic information include, for example, polyester and cellulose acetate films, or polymer-coated paper; the substrate for offset printing paper is specially treated aluminum and printed circuit manufacture The substrate for is a copper clad laminate and the substrate for the manufacture of integrated circuits is, for example, a silicon wafer. The layer thickness of the photosensitive layer for photographic materials and offset printing paper is generally about 0.5 to 10 μm, but for printed circuits it is 0.1 to about 100 μm. After painting the substrate (base material), the solvent is removed, typically by drying, leaving a photoresist coat on the substrate.

The coating of the substrate is performed by applying a liquid composition, solution or suspension to the substrate. The choice of solvent and concentration mainly depends on the type of composition and the coating technique. The solvent must be inert, i.e. not cause a chemical reaction with the components, and must be removable again upon drying after coating. Examples of suitable solvents are ketones, ethers and esters such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2. -Propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate, ethyl 3-ethoxypropionate, 2-methoxypropyl acetate, methyl-3-methoxypropionate, 2-heptanone, 2-pentanone and ethyl lactate It is.
The solution is uniformly applied to the substrate by known coating techniques such as spin coating, dip coating, knife coating, curtain coating, brushing, spraying, especially electrostatic spraying and reverse roll coating, or also by electrophoretic deposition To do. The photosensitive layer can also be coated onto a final substrate, such as a copper-clad circuit board or glass substrate, by applying it to a temporary flexible support and then moving the layers by lamination.
The amount applied (coat thickness) and the nature of the substrate (layer support) depend on the required field of application. The range of the coating thickness generally includes a value of about 0.1 to 100 μm or more, for example, 0.1 μm to 1 cm, preferably 0.5 to 1,000 μm.

  After coating the substrate, the solvent is generally removed by drying, leaving a basically dry resist film of photoresist on the substrate.

The photosensitivity of the new composition can generally range from about 150 to 600 nm, such as 190 to 600 nm (UV to visible region). Suitable radiation is present, for example, in sunlight or light from artificial light sources. As a result, a great many very different types of light sources are used. Both point sources and arrays (“lamp carpets”) are suitable. Examples are carbon arc lamps, xenon arc lamps, low pressure, medium pressure, high pressure and ultra high pressure mercury lamps (metal halide lamps) that may have metal halide dopes, microwave-excited metal vapor lamps, excimer lamps, super Actinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, electronic flashes, photographic flood lamps, light emitting diodes (LEDs), electron beams and X-rays. The distance between the lamp and the substrate to be exposed according to the invention can vary depending on the intended application and the type and output of the lamp, for example 2 to 150 cm. Also suitable are laser light sources, such as excimer lasers, for example F ₂ excimer lasers at 157 nm exposure, KrF excimer lasers for exposure at 248 nm, and ArF excimer lasers for exposure at 193 nm. Lasers in the visible region can also be used.

The term “imagewise” exposure includes exposure through a photomask containing a predetermined pattern, such as a slide, chrome mask, stencil mask or reticle, and under computer control over the surface of a coated substrate, for example. It includes both exposure with a laser or light beam that moves and thus produces an image. A UV laser exposure system suitable for this purpose is provided, for example, by Etec and Orbotech (DP-100® DIRECT IMAGEING SYSTEM). Other examples of laser light sources are, for example, excimer lasers, such as the F ₂ excimer laser at 157 nm exposure, the KrF excimer laser for exposure at 248 nm, and the ArF excimer laser for exposure at 193 nm. Further suitable are solid-state UV lasers (eg Gemini (Mania Barco), DI-2050 (Pentax)) and 405 nm output violet laser diodes (DI-2080, DI-PDP (Pentax)). Lasers in the visible region can also be used. And computer controlled illumination is also achieved by the electron beam. For example, A.I. Bertsch, J .; Y. Jezequel, J. et al. C. Andre, Journal of Photochemistry and Photobiology A: Chemistry 1997, 107, p. 271-181 and K.K. -P. Nicolay in Offset Printing 1997, 6, p. As described in 34-37, it is also possible to use a mask made of liquid crystal that can be handled pixel by pixel to generate a digital image.
It may be advantageous to perform a short heat treatment after the imagewise exposure of the material and before development. After development, a thermal post-bake can be performed to harden the composition and remove all traces of solvent. The temperature used is generally from 50 to 250 ° C., preferably from 80 to 220 ° C .; the duration of the heat treatment is generally from 0.25 to 60 minutes.

  The photocurable composition may additionally be used in a method for producing a printing plate or a photoresist, for example as described in DE 4013358. In such a method, the composition is exposed to visible light having a wavelength of at least 400 nm for a short time without a mask, before, simultaneously with, or after image-wise irradiation.

  After exposure and, if implemented, heat treatment, the unexposed areas of the photosensitive coating are removed in a manner known per se with a developer.

As already mentioned, the new composition can be developed with aqueous alkali or organic solvents. Particularly suitable aqueous alkaline developer solutions are tetraalkyl ammonium hydroxides or aqueous solutions of alkali metal silicates, phosphates, hydroxides and carbonates. Small amounts of wetting agents and / or organic solvents may also be added to these solutions if desired. Examples of typical organic solvents that can be added in small amounts to the developer are cyclohexanone, 2-ethoxyethanol, toluene, acetone, and mixtures of these solvents. Depending on the substrate, a solvent, for example an organic solvent, or, as described above, a mixture of an aqueous alkaline solution with such a solvent can also be used as a developer. Particularly useful solvents for solvent development include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, propylene Glycol monomethyl ether acetate, ethyl-3-ethoxypropionate, methyl-3-methoxypropionate, n-butyl acetate, benzyl alcohol, acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, 2-pentanone, ε -Caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, lactic acid Mention may be made of methyl, ε-caprolactam and N-methylpyrrolidone. If desired, water can be added to these solvents to a level where still clear solutions are obtained and sufficient solubility of the unexposed areas of the photosensitive composition is maintained.

Accordingly, the present invention provides a method for photopolymerization of a compound having an ethylenically unsaturated double bond, that is, a monomer, oligomer or polymer compound having at least one ethylenically unsaturated double bond. And at least one photoinitiator of the formula I above is added to the compound, and the resulting composition is subjected to electromagnetic radiation, in particular light having a wavelength of 150 to 600 nm, in particular 190 to 600 nm, electron beam or X-ray. A method comprising irradiating with is also provided.
In other words, to the compound having an ethylenically unsaturated double bond, at least one photoinitiator represented by the above formula I is added, and the resulting composition is subjected to electromagnetic radiation, in particular a wavelength of 150 to 600 nm, in particular Irradiation with light of 190 to 600 nm, electron beam or X-ray.

  The present invention further provides a coated substrate having at least one surface coated with the above composition, and subjecting the coated substrate to imagewise exposure, and then removing unexposed portions with a developer. A method for photographic production of relief images is described. Imagewise exposure can be accomplished by irradiation through a mask or by the laser or electron beam described above. Particularly advantageous in this situation is the laser beam exposure described above.

  The compounds of the present invention have good thermal stability, low volatility, excellent storage stability and high solubility, and are also suitable for photopolymerization in the presence of air (oxygen). Furthermore, they cause only a slight yellowing in the composition after photopolymerization.

  The following examples illustrate the invention in more detail. Parts and percentages are by weight unless otherwise stated, as in the remainder of the specification and claims. Where an alkyl group having 3 or more carbon atoms is mentioned without any mention of a particular isomer, it means the n-isomer in each case.

Example 1 Synthesis of 4- [9-ethyl-6- (naphthalene-1-carbonyl) -9H-carbozol-3-yl] -4-acetoxyimino-butyric acid ethyl ester

1a. 4- [9-Ethyl-6- (naphthalene-1-carbonyl) -9H-carbazol-3-yl-4-oxo-butyric acid ethyl ester N-ethylcarbazole (5.00 g) in CH ₂ Cl ₂ (100 mL) 1-naphthoyl chloride (4.88 g) and AlCl ₃ (3.52 g) were added at 0 ° C.
After stirring overnight at room temperature, ethyl succinyl chloride (4.34 g) and AlCl ₃ (
Further 7.17 g) was added and the mixture was stirred at room temperature overnight. The reaction mixture was poured into cold water and the crude product was extracted with CH ₂ Cl ₂ . The organic layer was washed twice with H ₂ O and MgS
Dry over O ₄ and concentrate to product 1. a. Got. The structure of the product obtained as a beige solid was confirmed by 1H-NMR (CDCl ₃ ).
δ [ppm]: 1.27 (t, 3H), 1.49 (t, 3H), 2.79 (t, 2H), 3.41 (t, 2H), 4.16 (q, 2H), 4.43 (q, 2H), 7.44-7.50 (m, 3H), 7.54 (t, 1H), 7.59 (d, 1H), 7.65 (d, 1H), 7 .96 (d, 1H), 8.05 (d, 2H), 8.18 (d, 2H), 8.60 (s, 1H), 8.66 (s, 1H).

1. b. 4- [9-ethyl-6- (naphthalene-1-carbonyl) -9H-carbazol-3-yl] -4-hydroxyimino-butyric acid ethyl ester 4- [9-ethyl- suspended in ethanol (50 ml) 6- (Naphthalene-1-carbonyl) -9H-carbazol-3-yl] -4-oxo-butyric acid ethyl ester (5.00 g) was charged with hydroxylamine hydrochloride (1.09 g) and sodium acetate (1.46 g). added. After stirring for 2 hours under reflux, the reaction mixture was poured into water. The crude product was extracted with ethyl acetate. The organic layer is washed 3 times with H ₂ O, dried over MgSO ₄ and concentrated to product 1. b. Got. The structure of the product obtained as a beige solid was confirmed by 1H-NMR spectrum (CDCl ₃ ).
δ [ppm]: 1.19 (t, 3H), 1.46 (t, 3H), 2.63 (t, 2H), 3.20 (t, 2H), 4.09 (q, 2H), 4.40 (q, 2H), 7.40-7.58 (m, 5H), 7.63 (d, 1H), 7.79 (d, 1H), 7.94 (d, 1H), 8 0.02 (d, 1H), 8.05 (d, 1H) 8.10 (d, 1H), 8.24 (s, 1H), 8.62 (s, 1H).

1. c. 4- [9-Ethyl-6- (naphthalene-1-carbonyl) -9H-carbazol-3-yl] -4-acetoxyimino-butyric acid ethyl ester In acetone (30 ml) 4- [9-ethyl-6- ( Naphthalene-1-carbonyl) -9H-carbazol-3-yl] -4-hydroxyimino-butyric acid ethyl ester (4.76 g) was added dropwise with triethylamine (1.47 g) and acetic chloride (1.14 g) at 0 ° C. Added. After stirring at 0 ° C. for 2 hours, the reaction mixture was poured into water. The product was extracted with ethyl acetate and the organic layer was washed twice with H ₂ O, dried over MgSO ₄ and concentrated to give a residue, which was eluted with hexane / ethyl acetate = 9/1 by column chromatography. Purified on silica gel using ~ 4/6. The product obtained as a pale yellowish solid 1. c. Was confirmed by 1H-NMR spectrum (CDCl ₃ ).
δ [ppm]: 1.21 (t, 3H), 1.48 (t, 3H), 2.28 (s, 3H), 2.60 (t, 2H), 3.26 (t, 2H), 4.12 (q, 2H), 4.42 (q, 2H), 7.43-7.49 (m, 2H), 7.51 (d, 1H), 7.55 (d, 1H), 7 .58 (d, 1H), 7.64 (d, 1H), 7.92 (d, 1H), 7.95 (d, 1H), 8.04 (t, 2H), 8.15 (d, 1H), 8.36 (s, 1H), 8.61 (s, 1H).

本化合物を実施例１に記載された手順に従って、１−ナフトイルクロリドの代わりに２−チオフェンカルボニルクロリドを用いて合成した。構造を１Ｈ−ＮＭＲスペクトル（Ｃ
ＤＣｌ₃）で確認した。
δ［ｐｐｍ］：１．２４（ｔ，３Ｈ）、１．５０（ｔ，３Ｈ）、２．３０（ｓ，３Ｈ）、２．６４（ｔ，２Ｈ）、３．３１（ｔ，２Ｈ）、４．１４（ｑ，２Ｈ）、４．４４（ｑ，２Ｈ）、７．２３（ｔ，１Ｈ）、７．４８（ｄ，１Ｈ）、７．５１（ｄ，１Ｈ）、７．７４（ｄ，１Ｈ）、７．７５（ｄ，１Ｈ）、７．９５（ｄ，１Ｈ）、８．１２（ｄ，１Ｈ）、８．５０（ｓ，１Ｈ）、８．７３（ｓ，１Ｈ）。 Example 2 : Synthesis of 4- [9-ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl] -4-acetoxyimino-butyric acid ethyl ester

This compound was synthesized according to the procedure described in Example 1, using 2-thiophenecarbonyl chloride instead of 1-naphthoyl chloride. The structure was analyzed by 1H-NMR spectrum
DCl ₃ ).
δ [ppm]: 1.24 (t, 3H), 1.50 (t, 3H), 2.30 (s, 3H), 2.64 (t, 2H), 3.31 (t, 2H), 4.14 (q, 2H), 4.44 (q, 2H), 7.23 (t, 1H), 7.48 (d, 1H), 7.51 (d, 1H), 7.74 (d , 1H), 7.75 (d, 1H), 7.95 (d, 1H), 8.12 (d, 1H), 8.50 (s, 1H), 8.73 (s, 1H).

Example 3 : N-acetoxy-N- {3- [9-ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl] -1-methyl-3-acetoxyimino-propyl} acetamide Composition

3. a. (E) -1- [9-Ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl] -but-2-en-1-one in CH ₂ Cl ₂ (200 ml), N— To ethylcarbazole (5.00 g), 2-thiophenecarbonyl chloride (3.75 g) and AlCl ₃ (3.52 g) were added at 0 ° C.
After stirring overnight at room temperature, trans-crotonyl chloride (2.76 g) and AlCl ₃ (3.
76 g) was added at 0 ° C. and the mixture was stirred at room temperature overnight. The reaction mixture was poured into cold water and the crude product was extracted with CH ₂ Cl ₂ . The organic layer was washed twice with H ₂ O, dried over MgSO ₄ and concentrated to give a residue, which was purified by column chromatography using hexane / ethyl acetate = 9/1 to 5/5 as eluent. Purified on silica gel. The product was further purified by recrystallization from hexane-ethyl acetate. 2. Product obtained as a beige solid . a. Was confirmed by 1H-NMR spectrum (CDCl ₃ ).
δ [ppm]: 1.51 (t, 3H), 2.06 (d, 3H), 4.46 (q, 2H), 7.12-7.17 (m, 2H), 7.23 (t , 1H), 7.50 (d, 1H), 7.53 (d, 1H), 7.73-7.78 (m, 2H), 8.14 (d, 1H), 8.20 (d, 1H), 8.76 (s, 1H), 8.78 (s, 1H).

3. b. 1- [9-Ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl] -3-hydroxyamino-butan-1-one oxime (E) -1- [ 9-Ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl] -but-2-en-1-one (2.00 g) to hydroxylamine hydrochloride (0.82 g) and sodium acetate (0.97 g) was added. After stirring under reflux for 1 hour, the reaction mixture was poured into water, a precipitate was obtained and isolated by filtration. The crude product thus obtained was dissolved in ethyl acetate. The solution is MgSO ₄
Dried over and concentrated to product 3. b. Got. The structure of the product obtained as a pale yellowish solid was confirmed by 1H-NMR spectrum (CDCl ₃ ).
δ [ppm]: 1.20 (d, 3H), 1.41 (t, 3H), 3.01 (dd, 1H), 3.34 (dd, 1H), 3.47 (dd, 1H), 4.32 (q, 2H), 5.50 (bs, 1H), 7.16 (t, 1H), 7.35 (d, 1H), 7.40 (d, 1H), 7.63-7 .71 (m, 2H), 7.78 (d, 1H), 8.04 (d, 1H), 8.35 (s, 1H), 8.59 (s, 1H).

3. c. N-acetoxy-N- {3- [9-ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl] -1-methyl-3-acetoxyimino-propyl} -acetamide THF (15 ml) 1- [9-Ethyl-6- (thiophen-2-carbonyl) -9H-carbazol-3-yl] -3-hydroxyamino-butan-1-one oxime (1.52 g) to triethylamine (2.06 g) ) And acetic chloride (1.60 g) were added dropwise at 0 ° C. After stirring at room temperature overnight, the reaction mixture was poured into water. The product was extracted with ethyl acetate and the organic layer was washed twice with H ₂ O, dried over MgSO ₄ and concentrated to give a residue, which was eluted with hexane / ethyl acetate = 8/2 by column chromatography. Purified on silica gel using ~ 1/9. The resulting product 3 as a pale yellowish solid. c. Was confirmed by 1H-NMR spectrum (CDCl ₃ ).
δ [ppm]: 1.21 (bd, 3H), 1.50 (t, 3H), 1.87 (s, 3H), 2.24 (s, 3H), 2.33 (s, 3H), 3.18-3.41 (m, 2H), 4.44 (q, 2H), 4.92 (bs, 1H), 7.22 (t, 1H), 7.49 (d, 1H), 7 .51 (d, 1H), 7.73 (d, 1H), 7.78 (d, 1H), 7.99 (d, 1H), 8.13 (d, 1H), 8.58 (s, 1H), 8.77 (s, 1H).

本化合物は実施例３に記載された手順に従って、２−チオフェンカルボニルクロリドの代わりに１−ナフトイルクロリドを用いて合成した。構造を１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ₃）で確認した。
δ［ｐｐｍ］：１．１７（ｂｄ，３Ｈ）、１．４８（ｔ，３Ｈ）、１．８２（ｓ，３Ｈ）、２．１７（ｓ，３Ｈ）、２．３１（ｓ，３Ｈ）、３．１２−３．３８（ｍ，２Ｈ）、４．４２（ｑ，２Ｈ）、４．８７（ｂｓ，１Ｈ）、７．４３−７．６１（ｍ，５Ｈ）、７．６５（ｄ，１Ｈ）、７．９５（ｄ，１Ｈ）、７．９７（ｄ，１Ｈ）、８．０３（ｄ，１Ｈ）、８．０６（ｄ，１Ｈ）、８．１５（ｄ，１Ｈ）、８．４３（ｓ，１Ｈ）、８．６４（ｓ，１Ｈ）。 Example 4 : N-acetoxy-N- {3- [9-ethyl-6- (naphthalene-1-carbonyl) -9H-carbazol-3-yl] -1-methyl-3-acetoxyimino-propyl} -acetamide Synthesis of

This compound was synthesized according to the procedure described in Example 3, using 1-naphthoyl chloride instead of 2-thiophenecarbonyl chloride. The structure was confirmed by 1H-NMR spectrum (CDCl ₃ ).
δ [ppm]: 1.17 (bd, 3H), 1.48 (t, 3H), 1.82 (s, 3H), 2.17 (s, 3H), 2.31 (s, 3H), 3.12-3.38 (m, 2H), 4.42 (q, 2H), 4.87 (bs, 1H), 7.43-7.61 (m, 5H), 7.65 (d, 1H), 7.95 (d, 1H), 7.97 (d, 1H), 8.03 (d, 1H), 8.06 (d, 1H), 8.15 (d, 1H), 8. 43 (s, 1H), 8.64 (s, 1H).

本化合物は実施例１に記載された手順に従って、１−ナフトイルクロリドの代わりに２−トルオイルクロリドを用いて合成した。構造を１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ₃）
で確認した。
δ［ｐｐｍ］：１．２３（ｔ，３Ｈ）、１．４８（ｔ，３Ｈ）、２．２９（ｓ，３Ｈ）、２．３６（ｓ，３Ｈ）、２．６２（ｔ，２Ｈ）、３．２８（ｔ，２Ｈ）、４．１３（ｑ，２Ｈ）、４．４２（ｑ，２Ｈ）、７．２８−７．４９（ｍ，６Ｈ）、７．９２（ｄ，１Ｈ）、８．１０（ｄ，１Ｈ）、８．４１（ｓ，１Ｈ）、８．５２（ｓ，１Ｈ）。 Reference Example 1 : Synthesis of 4- [9-ethyl-6- (2-toluoyl) -9H-carbazol-3-yl] -4-acetoxyimino-butyric acid ethyl ester

This compound was synthesized according to the procedure described in Example 1 using 2-toluoyl chloride instead of 1-naphthoyl chloride. 1H-NMR spectrum (CDCl ₃ ) of the structure
Confirmed with.
δ [ppm]: 1.23 (t, 3H), 1.48 (t, 3H), 2.29 (s, 3H), 2.36 (s, 3H), 2.62 (t, 2H), 3.28 (t, 2H), 4.13 (q, 2H), 4.42 (q, 2H), 7.28-7.49 (m, 6H), 7.92 (d, 1H), 8 .10 (d, 1H), 8.41 (s, 1H), 8.52 (s, 1H).

本化合物は実施例３に記載された手順に従って、２−チオフェンカルボニルクロリドの代わりに２−トルオイルクロリドを用いて合成した。構造を１Ｈ−ＮＭＲスペクトル（ＣＤＣｌ₃）で確認した。
δ［ｐｐｍ］：１．１９（ｂｄ，３Ｈ）、１．４８（ｔ，３Ｈ）、１．８５（ｓ，３Ｈ）、２．２３（ｓ，３Ｈ）、２．３２（ｓ，３Ｈ）、２．３６（ｓ，３Ｈ）、３．１８−３．３７（ｍ，２Ｈ）、４．４２（ｑ，２Ｈ）、４．８１（ｂｓ，１Ｈ）、７．２８−７．５０（ｍ，６Ｈ）、７．９６（ｄ，１Ｈ）、８．０９（ｄ，１Ｈ）、８．４８（ｓ，１Ｈ）、８．５６（ｓ，１Ｈ）。 Reference Example 2 : Synthesis of N-acetoxy-N- {3- [9-ethyl-6- (2-toluoyl) -9H-carbazol-3-yl] -1-methyl-3-acetoxyimino-propyl} -acetamide

This compound was synthesized according to the procedure described in Example 3 using 2-toluoyl chloride instead of 2-thiophenecarbonyl chloride. The structure was confirmed by 1H-NMR spectrum (CDCl ₃ ).
δ [ppm]: 1.19 (bd, 3H), 1.48 (t, 3H), 1.85 (s, 3H), 2.23 (s, 3H), 2.32 (s, 3H), 2.36 (s, 3H), 3.18-3.37 (m, 2H), 4.42 (q, 2H), 4.81 (bs, 1H), 7.28-7.50 (m, 6H), 7.96 (d, 1H), 8.09 (d, 1H), 8.48 (s, 1H), 8.56 (s, 1H).

Application Examples A photocured formulation for sensitivity testing was prepared by mixing the following ingredients [quantities given in parts by weight].
200.0 parts acrylated alkyl copolymer (ACA200M, provided by Daicel Chemical Industries, Ltd., solid content 50% by mass)
15.0 parts Dipentaerythritol hexaacrylate ((DPHA), provided by UCB Chemicals)
100.0 parts methanol

To this formulation, 4.6 parts or 8.0 parts by weight of the photoinitiator to be tested was added and stirred. All operations were performed under yellow light. The composition was applied to an aluminum plate using an electric applicator with a wound bar. The solvent was removed by heating at 80 ° C. for 10 minutes in a convection oven. The thickness of the dry film was about 5 μm. A 21-step standard test negative film (Staufer-step optical wedge) consisting of different optical densities was placed between the film and the resist with a gap of about 100 μm. A glass filter (L-39) was placed on the negative film. The exposure was performed at a distance of 15 cm using a 250 W ultra-high pressure mercury lamp (USHIO Inc., USH-250BY). The total exposure on the glass filter as measured by an optical power meter (ORC UV light major model UV-M02 with UV-35 detector) was 2000 mJ / cm ² . After exposure, the exposed film is sprayed with a 5% alkaline aqueous solution (Yokohama Yushi Kogyo Co., Ltd., Semi-clean DL-A4) at 28 ° C. for 2 minutes using a spray type developing device (Takizawa Sangyo Co., Ltd., AD-1200). Developed. The sensitivity of the initiator used was revealed by an indication of the highest number of steps remaining (ie polymerized) after development. The higher the number of steps, the more sensitive the system tested. The results are summarized in Table 1 below.

Claims (18)

Compound represented by formula (I)

(Where
R ₁ is an unsubstituted or substituted alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, or the number of carbon atoms 8 to 20 phenoxycarbonylalkyl group, 1 to 20 carbon atoms heteroaryloxycarbonylalkyl group, 1 to 20 carbon atoms heteroarylthioalkyl group, 0 to 20 carbon atoms amino group, or 1 carbon atom Represents 20 to 20 aminoalkyl groups;
Or R ₁ is

Represents an alkyl group of 1 to 20 carbon atoms substituted by a group and optionally further groups;
Or R ₁ is carbazole as an linking group via an optionally substituted alkylene group having 1 to 10 carbon atoms, — (CH═CH) n— group, — (C≡C) n— group or a combination thereof. Taken together with a ring to form a ring, said formed ring being unsubstituted or substituted;
n represents an integer of 0 to 3;
R ₂ represents an alkyl group having 1 to 20 carbon atoms;
R ₄ and R ₅ each independently represent a hydrogen atom or an alkylcarbonyl group having 1 to 20 carbon atoms;
Ar represents an optionally substituted naphthyl group, thienyl group or furyl group. ). In the above formula,
R ₁ is an alkoxycarbonylalkyl group having 3 to 20 carbon atoms or

Represents an alkyl group having 1 to 20 carbon atoms substituted with
R ₂ represents an ethyl group;
R ₄ and R ₅ independently of one another represent an acetyl group; and
The compound represented by the formula (I) according to claim 1, wherein Ar represents an optionally substituted naphthyl group or thienyl group. (A) at least one ethylenically unsaturated photopolymerizable compound, and (b) at least one compound represented by formula (I) according to claim 1 as a photoinitiator,
A photopolymerizable composition comprising: The photopolymerizable composition according to claim 3, wherein the compound (a) is a resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with a reaction product of an epoxy resin and an unsaturated monocarboxylic acid. The photopolymerizable composition according to claim 3 or 4, further comprising a binder polymer (e), in particular a copolymer of methacrylate and methacrylic acid. Photopolymerizability according to any one of claims 3 to 5, comprising in addition to the photoinitiator (b) at least one further photoinitiator (c) and / or other additives (d). Composition. 7. Light according to any one of claims 3 to 6, comprising from 0.05 to 25% by weight of photoinitiator (b) or photoinitiators (b) and (c), based on the solid composition. Polymerizable composition. 7. Photopolymerizable composition according to claim 6, comprising a pigment or a pigment mixture as further additive (d). 9. The photopolymerizable composition according to claim 8, comprising a dispersant or dispersant mixture as further additive (d). Formula (Ia)

(Wherein R ₁ , R ₂ and Ar are as defined in claim 1).
An oxime compound represented by the formula:

(In the formula, Hal means a halogen atom.)
The manufacturing method of the compound represented by Formula (I) of Claim 1 by making it react with the halide or anhydride represented by these in presence of a base or a base mixture. The method according to claim 10, wherein in formula (Ia), R ₁ represents an alkyl group having 1 to 20 carbon atoms substituted with -NHOH group. Formula (Ib)

(Where
R ₁ represents an unsubstituted or substituted alkenyl group having 2 to 25 carbon atoms,
R ₂ and Ar are as defined in claim 1. )
In accordance represented by ketone compound to be reacted with hydroxylamine or a salt thereof, in formula (Ia), R ₁ represents an alkyl group having carbon atom number of 1 to 20 substituted by -NHOH group, according to claim 10 A process for producing a compound represented by the formula (Ia): A method for photopolymerization of a compound containing an ethylenically unsaturated double bond, wherein the composition according to any one of claims 3 to 9 is subjected to electromagnetic radiation in the range of 150 to 600 nm, or an electron beam or X Irradiating with a line. Etching both colored and non-colored paints and varnishes, powder coatings, printing inks, printing plates, adhesives, pressure sensitive adhesives, dental compositions, gel coats, electronic photoresists, electroplating resists, liquids and dry films Resist,
Electrical for holographic data storage (HDS) to form structures in the manufacturing process of plasma-display panels, electroluminescent displays and LCDs as resists for producing solder resists, color filters for various display applications And as a composition for encapsulating electronic components, manufacturing magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, and stencils for screen printing For manufacturing a three-dimensional object by stereolithography, for image recording material for holographic recording, fine electronic circuit, decoloring material, and decoloring material for image recording material, for image recording material using microcapsules , UV and visible laser direct imaging As a photoresist material for the stem, as a photoresist material used for forming dielectric layers in a sequential lamination of printed circuit board, the composition according to any one of claims 3 to 9. A coated substrate coated on at least one surface with the composition of claim 3. A method for producing a relief image, wherein the coated substrate according to claim 15 is subjected to imagewise exposure, and then the non-exposed portion is removed with a developer. Providing red, green and blue pixels and a black matrix (all containing photosensitive resin and pigment) on a transparent substrate, and providing a transparent electrode on either the surface of the substrate or the surface of the color filter layer A color filter, wherein the photosensitive resin contains a polyfunctional acrylate monomer, an organic polymer binder, and a photopolymerization initiator represented by the formula (I) according to claim 1. Formula (Ia)

(Wherein Ar, R ₁ and R ₂ are as defined in claim 1).
(Corresponding free oxime).