CN101341172A - Oxime ester photoinitiators - Google Patents

Oxime ester photoinitiators Download PDF

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CN101341172A
CN101341172A CNA2006800480657A CN200680048065A CN101341172A CN 101341172 A CN101341172 A CN 101341172A CN A2006800480657 A CNA2006800480657 A CN A2006800480657A CN 200680048065 A CN200680048065 A CN 200680048065A CN 101341172 A CN101341172 A CN 101341172A
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alkyl
phenyl
group
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methyl
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CN101341172B (en
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A·马特素莫托
J·塔纳比
H·库拉
M·奥瓦
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BASF Schweiz AG
Ciba SC Holding AG
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Ciba SC Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings

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Abstract

Compounds of the Formula (I) and (II) wherein M1, M2 and M3 independently of one another are no bond, a direct bond, CO, O, S, SO, SO2 or NR14; provided that at least one of M1, M2 or M3 is a direct bond, CO, O, S, SO, SO2 or NR14; M4 is a direct bond, CR''3R''4, CS, O, S, SO, or SO2; Y is S or NR18; R1 for example is hydrogen, C3-C8cycloalkyl, phenyl or naphthyl, both of which are optionally substituted; R2 for example is C1-C20alkyl; R''2 has one of the meanings given for R2; R3 and R4 are for example hydrogen, halogen, C1-C20alkyl; R'3, R'4, R''3 and R''4 indepedently of one another have one of the meanings given for R3 and R4; and R5 is for example hydrogen, halogen, C1-C20alkyl; provided that in the compounds of the Formula (I) at least two oxime ester groups are present; exhibit an unexpectedly good performance in photopolymerization reactions.

Description

Oxime ester photoinitiator
The present invention relates to have at least two oxime ester bases groups as the substituent specific oxime ester compound that comprises on the many aromatic systems of heterocyclic, and as the purposes of the light trigger in the photopolymerisable compositions.
Know that from U.S. Pat 3558309 some oxime ester (oxime ester) derivative is a light trigger.Oxime ester compound is disclosed in US 4255513.US 6596445 has described some and has had the oxime ester compound of electron-donating group.US 4202697 discloses the amino oxime ester that replaces of acryl.At JP 7-140658A (=Derwent No.95-234519/31), Bull.Chem.Soc.Jpn.1969,42 (10), 2981-3, Bull.Chem.Soc.Jpn.1975,48 (8), 2393-4, Han ' guk Somyu Konghakhoechi 1990,27 (9), 672-85 (=Chem.Abstr.No.115:115174), Macromolecules, 1991,24 (15), 4322-7 and European Polymer Journal, 1970, some aldoxime ester cpds have been described among the 933-943.Several benzophenone oxime ester compounds are disclosed in US 4590145 and JP 61-24558-A (=Derwent No.86-073545/11).At Glas.Hem.Drus.Beograd, 1981,46 (6), 215-30, J.Chem.Eng.Data 9 (3), 403-4 (1964), J.Chin.Chem.Soc. (Taipei) 41 (5) 573-8, (1994), JP 62-273259-A (=Chemical Abstract109:83463w), JP 62-286961-A (=Derwent No.88-025703/04), JP62-201859-A (=Derwent No.87-288481/41), JP 62-184056-A (=Derwent No.87-266739/38), US 5019482 and J.of Photochemistry and Photobiology A 107 have described some to the phenalkyloxy-oxime ester compound among the 261-269 (1997).In addition, in WO 02/100903, WO 04/050653, WO 06/018405 and european patent application No.2005/05111539.2 oxime ester compound is disclosed.
In the photopolymerization technology, still need high activity, be easy to the preparation and easy-to-handle light trigger.For example, in colour filter resist Application Areas, high color quality character needs highly colored resist.Along with the raising of pigment content, the curing of colored resist becomes more difficult.Therefore, need susceptibility to be higher than the light trigger of existing initiator system.In addition, this type of novel photoinitiator also must meet high industrial requirements in the properties as thermostability and stability in storage and so on.
Find that surprisingly the compound of formula I and II especially meets above-mentioned requirements,
Figure A20068004806500161
Wherein
M 1, M 2And M 3Be no key (no bond), direct key, CO, O, S, SO, SO independently of one another 2Or NR 14Condition is M 1, M 2Or M 3At least one be direct key, CO, O, S, SO, SO 2Or NR 14
M 4Be direct key, CR " 3R " 4, CO, CS, O, S, SO or SO 2
Y is direct key, S or NR 18
R 1Be hydrogen, C 3-C 8Cycloalkyl, C 2-C 5Alkenyl, C 1-C 20Alkoxyl group, unsubstituted C 1-C 20Alkyl or by one or more halogens, phenyl, C 1-C 20The C that alkyl phenyl and/or CN replace 1-C 20Alkyl;
Or R 1Be phenyl or naphthyl, both all are unsubstituted or by one or more C 1-C 6Alkyl, C 1-C 4Haloalkyl, halogen, CN, OR 11, SR 10And/or NR 12R 13Replace;
Or R 1Be benzyloxy or phenoxy group, both all are unsubstituted or by one or more C 1-C 6Alkyl, C 1-C 4Haloalkyl and/or halogen replace;
R 2Be hydrogen, C 1-C 20Alkyl or C 3-C 10Cycloalkyl, it is optional by O, CO or NR 14Insert;
Or R 2Be optional by one or more halogens, OR 11, COOR 11, CONR 12R 13, phenyl or by halogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11Or NR 12R 13The C that the phenyl that replaces replaces 1-C 20Alkyl;
Or R 2Inserted by one or more O and/or choose wantonly by one or more halogens, OR 11, COOR 11, CONR 12R 13, phenyl or by SR 10, OR 11Or NR 12R 13The C that the phenyl that replaces replaces 2-C 20Alkyl;
Or R 2Be phenyl, naphthyl, tonka bean camphor base (coumarinyl) or heteroaryl, optional separately by one or more C 1-C 12Alkyl, phenyl, halogen, C 1-C 4Haloalkyl, CN, NO 2, SR 10, OR 11, NR 12R 13Replace, or chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
Or R 2Be C 2-C 20Alkyloyl or do not replace or by one or more C 1-C 6Alkyl, halogen, phenyl, SR 10, OR 11Or NR 12R 13The benzoyl that replaces;
Or R 2Be optional the insertion by one or more O and/or the optional C that is replaced by one or more OH 2-C 12Alkoxy carbonyl;
Or R 2Be unsubstituted or by one or more C 1-C 6Alkyl, C 1-C 4Haloalkyl, halogen, phenyl, SR 10, OR 11Or NR 12R 13The phenyloxycarbonyl that replaces;
R " 2Have R 2One of implication that provides; Or be
Figure A20068004806500171
Or
Figure A20068004806500172
M 5Be no key, direct key, CO, O, S, SO, SO 2Or NR 14
R 3And R 4Be hydrogen, halogen, C independently of one another 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or be C 4-C 8Cycloalkenyl group, C 2-C 12Alkynyl group, phenyl-C 1-C 4Alkyl, CN, NO 2,
Figure A20068004806500173
, or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 3And R 4Be not replace or by one or more SR 10, OR 11Or NR 12R 13The phenyl that replaces;
Or R 3And R 4Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring;
Or R 3And R 4Be C together 1-C 6Alkylidene group or C 2-C 6Inferior alkene chain base, thus dicyclo formed with the phenyl that links to each other with them, and wherein said dicyclo is optional by one or more C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11, NR 12R 13, halogen, phenyl, COOR 11, CONR 12R 13, CN, NO 2Replace, or chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted, or quilt is by O, CO or NR 14The C that inserts 2-C 20Alkyl replaces, and wherein said dicyclo is optional condenses with other aromatic ring and/or hetero-aromatic ring;
R ' 1Have R 1One of implication that provides;
R ' 2Have R 2One of implication that provides;
R ' 3, R ' 4, R " 3And R " 4Have R independently of one another 3And R 4One of implication that provides;
R 5Be hydrogen, halogen, C 1-C 4Haloalkyl, C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or be C 4-C 8Cycloalkenyl group, C 2-C 12Alkynyl group, phenyl-C 1-C 4Alkyl, CN, NO 2,
Figure A20068004806500181
, or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 5Be not replace or by one or more halogens, C 1-C 4Haloalkyl, C 1-C 20Alkyl, SR 10, OR 11, NR 12R 13, or by O, CO or NR 14The C that inserts 2-C 20The phenyl that alkyl replaces;
Or R 5Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring;
Or R 5Be Or
Figure A20068004806500183
R 6And R ' 6Be hydrogen, halogen, C independently of one another 1-C 4Haloalkyl, C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or be C 4-C 8Cycloalkenyl group, C 2-C 12Alkynyl group, phenyl-C 1-C 4Alkyl, CN, NO 2,
Figure A20068004806500184
Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 6And R ' 6Be not replace or by one or more halogens, C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11Or NR 12R 13The phenyl that replaces;
Or R 6And R ' 6Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring;
Or R 6And R ' 6Be C together 1-C 6Alkylidene group or C 2-C 6Inferior alkene chain base, thus dicyclo formed with the phenyl that links to each other with them, and wherein said dicyclo is optional by one or more C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl replaces, by C 1-C 4Haloalkyl, SR 10, OR 11, NR 12R 13, halogen, phenyl, COOR 11, CONR 12R 13, CN, NO 2, or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted, and wherein said dicyclo is optional condenses with other aromatic ring and/or hetero-aromatic ring; Condition is
Group
Figure A20068004806500191
Or
Figure A20068004806500192
Be connected on arbitrary ring of described dicyclo;
R 7, R ' 7, R 8And R ' 8Have R independently of one another 3And R 4One of implication that provides;
R 9And R ' 9Be hydrogen, halogen, C independently of one another 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl or optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or C 4-C 8Cycloalkenyl group, C 2-C 12Alkynyl group, phenyl-C 1-C 4Alkyl, CN, NO 2, Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 9And R ' 9Be not replace or by one or more halogens, C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11Or NR 12R 13The phenyl that replaces;
Or R 9And R ' 9Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring;
R 10Be hydrogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, C 2-C 12Alkenyl, optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl,
Or R 10Be phenyl-C 1-C 4Alkyl; By OH, SH, CN, C 3-C 6Alkenyloxy ,-OCH 2CH 2CN ,-OCH 2CH 2(CO) O (C 1-C 4Alkyl) ,-O (CO)-(C 1-C 4Alkyl) ,-O (CO)-phenyl ,-(CO) OH or-(CO) O (C 1-C 4Alkyl) C of Qu Daiing 1-C 8Alkyl;
Or R 10By the C of one or more O or S insertion 2-C 20Alkyl;
Or R 10Be-(CH 2CH 2O) nH ,-(CH 2CH 2O) n(CO)-(C 1-C 8Alkyl), C 2-C 8Alkyloyl, benzoyl, C 3-C 6Alkenoyl;
Or R 10Be phenyl or naphthyl, respectively do for oneself unsubstituted or by one or more halogens, C 1-C 12Alkyl, C 1-C 4Haloalkyl, C 1-C 12Alkoxyl group,
Figure A20068004806500201
Phenyl-C 1-C 3Alkoxyl group, phenoxy group, C 1-C 12Alkyl alkylthio base, phenyl sulfane base ,-N (C 1-C 12Alkyl) 2, diphenyl amino ,-(CO) O (C 1-C 8Alkyl) or (CO) N (C 1-C 8Alkyl) 2Replace;
Or R 10Be phenyl or naphthyl, they are via direct key, C 1-C 4Alkylidene group, O, S, NR 14Or CO and and SR 10The benzyl ring that links to each other forms 5-or 6-unit ring together, and wherein said phenyl or naphthyl is unsubstituted or by one or more C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl replaces, or is chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted or by halogen,
Figure A20068004806500202
C 1-C 20Alkoxyl group, C 1-C 20Alkyl-carbonyl or phenylcarbonyl group replace;
N is the integer of 1-12;
R " 1Have R 1And R ' 1One of implication that provides;
R " ' 2Have R 2And R ' 2One of implication that provides;
R 11Be hydrogen, the optional C that is replaced by one or more halogens 1-C 20Alkyl; Or be-(CH 2CH 2O) nH ,-(CH 2CH 2O) n(CO)-(C 1-C 8Alkyl), C 1-C 8Alkyloyl, C 2-C 12Alkenyl, C 3-C 6Alkenoyl, phenyl-C 1-C 4Alkyl; The C that is inserted by one or more O 2-C 20Alkyl; Optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 11By OH, SH, CN, C 3-C 6Alkenyloxy ,-OCH 2CH 2CN ,-OCH 2CH 2(CO) O (C 1-C 4Alkyl) ,-O (CO)-(C 1-C 4Alkyl) ,-O (CO)-phenyl ,-(CO) OH or-(CO) O (C 1-C 4Alkyl) C of Qu Daiing 1-C 8Alkyl;
Or R 11Be unsubstituted or by one or more C 1-C 6Alkyl, halogen, C 1-C 4Haloalkyl, OH or C 1-C 4The benzoyl that alkoxyl group replaces;
Or R 11Be phenyl or naphthyl, respectively do for oneself unsubstituted or by one or more halogens, OH, C 1-C 12Alkyl, C 3-C 10Cycloalkyl or C 1-C 12Alkoxyl group replaces;
R 12And R 13Be hydrogen, C independently of one another 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, C 2-C 4Hydroxyalkyl, C 1-C 12Alkoxyl group, phenyl-C 1-C 4Alkyl, (CO) R 15, C 2-C 10Alkoxyalkyl, C 3-C 5Alkenyl or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 12And R 13Be phenyl or naphthyl, respectively do for oneself unsubstituted or by one or more halogens, C 1-C 4Haloalkyl, C 1-C 20Alkoxyl group, (CO) R 15, phenyl, NR 16R 17, SR 10, OR 11,
Figure A20068004806500211
C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl replaces, or is chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
Or R 12And R 13Be C independently of one another 2-C 5Alkylidene group or C 2-C 5Alkylene group, it is connected to and NR 12R 13On one of C-atom of the phenyl or naphthyl ring that links to each other, wherein said C 2-C 5Alkylidene group or C 2-C 5Alkylene group is optional by O, CO or NR 14Insert; Or
R 12And R 13Be phenyl independently of one another, it is connected to NR via direct key 12R 13On the benzyl ring thereon of position; Or
R 12And R 13Form the saturated or unsaturated ring of 5-or 6-unit with the N-atom that links to each other with them, it is optional by O, N or NR 14Insert, and this ring is unsubstituted or by one or more C 1-C 20Alkyl, C 1-C 20Alkoxyl group ,=O, SR 10, OR 11Or NR 16R 17, (CO) R 15, NO 2, halogen, C 1-C 4Haloalkyl, CN, phenyl,
Figure A20068004806500212
Replace, or chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted; Or
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them, this hetero-aromatic ring system is unsubstituted or by one or more C 1-C 20Alkyl, C 1-C 4Haloalkyl, C 1-C 20Alkoxyl group ,=O, SR 10, OR 11, NR 16R 17, (CO) R 15,
Figure A20068004806500213
Halogen, NO 2, CN, phenyl replace, or by optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
R 14Be hydrogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, the C that is inserted by O or CO 2-C 20Alkyl, or be phenyl-C 1-C 4Alkyl, optional by the C of O or CO insertion 3-C 8Cycloalkyl, or be (CO) R 15Or phenyl, this phenyl is unsubstituted or by one or more C 1-C 20Alkyl, halogen, C 1-C 4Haloalkyl, SR 10, OR 11, NR 12R 13Or
Figure A20068004806500214
Replace;
R 15Be hydrogen, OH, C 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl, or be phenyl-C 1-C 4Alkyl, SR 10, OR 11Or NR 12R 13
Or R 15Be phenyl, naphthyl, tonka bean camphor base or heteroaryl, respectively do for oneself unsubstituted or by one or more SR 10, OR 11, NR 12R 13,
Figure A20068004806500215
CN, NO 2, halogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
R 16And R 17Be hydrogen, C independently of one another 1-C 20Alkyl, C 1-C 4Haloalkyl, C 3-C 10Cycloalkyl or phenyl; Or
R 16And R 17Form the saturated or unsaturated ring of 5-or 6-unit with the N-atom that links to each other with them, it is optional by O, S or NR 14Insert;
Or R 16 and R 17Be C independently of one another 2-C 5Alkylidene group or C 2-C 5Alkylene group, it is connected to and NR 16R 17On one of the benzyl ring that links to each other or C-atom of naphthyl ring, wherein said C 2-C 5Alkylidene group or C 2-C 5Alkylene group is optional by O, CO or NR 15Insert, and choose wantonly at this C 2-C 5Alkylidene group or C 2-C 5Fused benzene rings on the alkylene group;
R 18Be hydrogen, (CO) R " 2, C 1-C 20Alkoxy carbonyl, phenyl-C 1-C 4Alkyl, optional by one or more halogens, COOR 11Or CONR 12R 13The C that replaces 1-C 20Alkyl;
Or R 18By O, CO or NR 14The C that inserts 2-C 20Alkyl; Optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or be C 4-C 8Cycloalkenyl group or C 2-C 12Alkynyl group;
Or R 18Be benzoyl, naphthoyl, phenyloxycarbonyl or naphthyloxy carbonyl, optional separately by one or more C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11, NR 12R 13, halogen, phenyl, COOR 11, CONR 12R 13, CN, NO 2Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
Or R 18Be optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl, or optional by O, CO or NR 14The C that inserts 3-C 10Naphthene base carbonyl, or optional by O, CO or NR 14The C that inserts 3-C 10Cyclo alkoxy carbonyl;
Or R 18Be phenyl or naphthyl, both are all optional by one or more SR 10, OR 11, NR 12R 13, CN, NO 2, halogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20 alkyl or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
Condition is to have at least two oxime ester base groups in molecule.
According to the present invention, the compound of formula I and II can be used as olefinic (replace in full) unsaturated compound or comprise the light trigger of photopolymerization reaction usefulness of the mixture of this compounds.
C 1-C 20Alkyl is a straight or branched, and is C for example 1-C 18-, C 1-C 14-, C 1-C 12-, C 1-C 8-, C 1-C 6-or C 1-C 4Alkyl.Example is methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl, 2,4,4-tri-methyl-amyl, 2-ethylhexyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and eicosyl.C 1-C 18Alkyl, C 1-C 14Alkyl, C 1-C 12Alkyl, C 1-C 8Alkyl, C 1-C 6Alkyl and C 1-C 4Alkyl has above to C 1-C 20The implication of the corresponding carbonatoms of as many as that alkyl provides.
By O, CO or NR 14The C that inserts 2-C 20Alkyl is for example respectively by O, CO or NR 14Insert one or many, for example 1-9,1-7 or once or twice.Under the situation that the group quilt inserts more than an O, described O-atom is separated each other by at least one methylene radical, and promptly the O-atom is discontinuous.Example is following structural unit-CH 2-O-CH 3,-CH 2CH 2-O-CH 2CH 3, y=1-9-[CH 2CH 2O] y-CH 3,-(CH 2CH 2O) 7CH 2CH 3,-CH 2-CH (CH 3)-O-CH 2-CH 2CH 3Or-CH 2-CH (CH 3)-O-CH 2CH 3C 1-C 4Haloalkyl is by halogen list or polysubstituted C 1-C 4-alkyl, C 1-C 4-alkyl is as above definition for example.Alkyl is coverlet halogenation or many halogenations for example, are replaced by halogen up to all H atoms.Example is chloromethyl, trichloromethyl, methyl fluoride, difluoromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.
C 3-C 12Cycloalkyl is for example cyclopropyl, cyclopentyl, cyclohexyl, ring octyl group, cyclo-dodecyl, especially cyclopentyl and cyclohexyl, is preferably cyclohexyl.
C in the application's text 3-C 12It is the alkyl that comprises a ring at least that cycloalkyl is interpreted as.For example also being meant cyclopropyl, methyl-cyclopentyl, cyclopentyl, cyclohexyl, methyl-or Dimethylcyclohexyl, ring octyl group, is cyclopentyl and cyclohexyl especially, is preferably cyclohexyl.Further example be as
Figure A20068004806500231
Structure, and bridging or condensed member ring systems, for example
Figure A20068004806500232
Be considered to be covered Deng also by this term.
By O, CO or NR 14The C that inserts 3-C 12Cycloalkyl has the implication that above provides, wherein at least one CH of this alkyl 2-group is by O, CO or NR 14Replace.Example is following structure
Figure A20068004806500233
Or the like.
Phenyl-C 1-C 4Alkyl is for example benzyl, styroyl, α-Jia Jibianji, phenyl butyl, phenyl-propyl group or α, and α-Er Jiajibianji especially is a benzyl.Phenyl-the C that replaces 1-C 4Alkyl preferably is substituted on benzyl ring one to four time, for example once, twice or three times, especially is twice or three times.
C 2-C 12Alkenyl is monounsaturated or polyunsaturated, straight or branched, and for example is C 2-C 8-, C 2-C 6-, C 2-C 5-or C 2-C 4Alkenyl.Example is allyl group, methylallyl, vinyl, 1,1-dimethyl-allyl, 1-butylene base, 3-butenyl, crotyl, 1,3-pentadiene base, 5-hexenyl or 7-octenyl, especially allyl group or vinyl.
C 4-C 8Cycloalkenyl group has one or more pairs of keys, and is C for example 4-C 6Cycloalkenyl group or C 6-C 8Cycloalkenyl group.Example is cyclobutene base, cyclopentenyl, cyclohexenyl or cyclooctene base, is cyclopentenyl and cyclohexenyl especially, is preferably cyclohexenyl.
C 2-C 12Alkynyl group is monounsaturated or polyunsaturated, straight or branched, and for example is C 2-C 8-, C 2-C 6-or C 2-C 4Alkynyl group.Example is ethynyl, propargyl (=proyl), butynyl, ethyl acetylene base, 3-butynyl, 2-butyne base, pentynyl hexin base, 2-hexin base, 5-hexin base, octyne base etc.
C 1-C 20Alkyl phenyl is equivalent on benzyl ring to be replaced by alkyl the phenyl of one or many, and is C for example 1-C 12Alkyl-, C 1-C 8Alkyl-or C 1-C 4Alkyl phenyl, wherein the alkyl number is corresponding to the sum of all C-atoms in all alkyl substituents on the benzyl ring.Example is tolyl, xylyl, trimethylphenyl, ethylphenyl, diethyl phenyl, particularly tolyl and trimethylphenyl.
C 1-C 20Alkoxyl group is a straight or branched, and is C for example 1-C 18-, C 1-C 16-, C 1-C 12-, C 1-C 8-, C 1-C 6-or C 1-C 4-alkoxyl group.Example be methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, heptan the oxygen base, 2,4,4-trimethylpentyloxy, 2-ethyl hexyl oxy, octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, dodecyloxy, n-Hexadecane oxygen base, octadecane oxygen base or eicosane oxygen base, particularly methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert.-butoxy, especially methoxyl group.
C 1-C 12Alkyl alkylthio base is the C that has a S-atom in " yl " part 1-C 12Alkyl.C 1-C 12Alkyl has above to C 1-C 20The implication of the corresponding carbonatoms of as many as that alkyl provides.C 1-C 12Alkyl alkylthio base is a straight or branched, for example methyl sulfane base, ethyl sulfane base, propylthio alkyl, sec.-propyl sulfane base, normal-butyl sulfane base, sec-butyl sulfane base, isobutyl-sulfane base, tertiary butyl sulfane base.
C 3-C 6Alkenyloxy is monounsaturated or polyunsaturated, and is for example allyloxy, methyl allyloxy, butenyloxy, amylene oxygen base, 1,3-pentadiene oxygen base, 5-hexene oxygen base.
C 1-C 20Alkyl-carbonyl is equivalent to C 1-C 20Alkyloyl, and be straight or branched, and be C for example 1-C 18-, C 1-C 14-, C 1-C 12-, C 1-C 8-, C 2-C 8-, C 1-C 6-or C 1-C 4Alkyloyl or C 4-C 12-or C 4-C 8Alkyloyl.Example is formyl radical, ethanoyl, propionyl, butyryl radicals, isobutyryl, pentanoyl, caproyl, oenanthyl, capryloyl, nonanoyl, decanoyl, lauroyl, myristoyl, pentadecanoyl, palmitoyl, stearoyl, 20 acyl groups, preferred ethanoyl.C 2-C 8Alkyloyl, C 2-C 6Alkyloyl and C 2-C 4Alkyloyl has above to C 2-C 20The implication of the corresponding carbonatoms of as many as that alkyloyl provides.
C 3-C 6Alkenoyl is monounsaturated or polyunsaturated, and is for example acryl, 2-methyl-acryl, crotonoyl, pentenoyl, 1,3-pentadiene acyl group, 5-hexenoyl.
C 3-C 10Naphthene base carbonyl wherein should " base " be connected on the CO part corresponding to cycloalkyl as defined above.Example be cyclohexyl-carbonyl, cyclopentylcarbonyl, And bridging or condensed member ring systems, for example
Figure A20068004806500252
Deng, in being also contemplated as falling with.
By O or NR 14The C that inserts 3-C 10Naphthene base carbonyl is corresponding to C as defined above 3-C 10Naphthene base carbonyl, wherein at least one CH of this alkyl 2-group is by O or NR 14Substitute.Example is
Figure A20068004806500253
Deng.
C 2-C 12Alkoxy carbonyl is a straight or branched, and be for example methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, n-butoxy carbonyl, isobutoxy carbonyl, 1,1-dimethyl propoxycarbonyl, pentyloxy carbonyl, hexyloxy carbonyl, heptan oxygen base carbonyl, carbonyl octyloxy, the ninth of the ten Heavenly Stems oxygen base carbonyl, the last of the ten Heavenly stems oxygen base carbonyl or dodecyloxy carbonyl, especially be methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, n-butoxy carbonyl or isobutoxy carbonyl, be preferably methoxycarbonyl.C 2-C 6Alkoxy carbonyl and C 2-C 4Alkoxy carbonyl has above to C 2-C 12The implication of the corresponding carbonatoms of as many as that alkoxy carbonyl provides.
By the C of one or more-O-insertion 2-C 12Alkoxy carbonyl is a straight or branched.Atomicity is 1 to 5, for example 1 to 4,1 to 3,1 or 2.Two O-atoms are by at least two methylene radical, and promptly ethylidene separates.
Phenyloxycarbonyl is
Figure A20068004806500261
The naphthyloxy carbonyl is equivalent to
Figure A20068004806500262
The phenyloxycarbonyl and the naphthyloxy carbonyl group that replace are substituted one to four time, for example once, twice or three times, especially are twice or three times.Substituting group on the benzyl ring is preferably in the position on benzyl ring 4, or 3,4-, 3,4,5-, 2,6-, 2,4-or 2,4, the 6-configuration is especially in 4-or 3, in the 4-configuration.
C 3-C 10Cyclo alkoxy carbonyl is corresponding to cycloalkyl as defined above, wherein should " base " be connected to-O (CO)-part on.Example be cyclohexyloxy carbonyl, cyclopentyloxy carbonyl,
Figure A20068004806500263
And bridging or condensed member ring systems, for example
Figure A20068004806500264
Deng, in being also contemplated as falling with.
By O or NR 14The C that inserts 3-C 10Cyclo alkoxy carbonyl is corresponding to group, wherein at least one CH of this alkyl as defined above 2-group is by O or NR 14Substitute.Example is
Figure A20068004806500265
Deng.
C 1-C 6Alkylidene group is the straight or branched alkylidene group, for example methylene radical, ethylidene, propylidene, 1-methyl ethylidene, 1,1-dimethyl ethylidene, butylidene, 1-methyl propylidene, 2-methyl-propylidene, pentylidene or hexylidene.
C 2-C 6Alkylene group is monounsaturated or polyunsaturated, and is for example vinylidene, 1-propenylidene, 1-crotonylidene, 3-crotonylidene, 2-crotonylidene, 1, inferior pentadienyl of 3-or the inferior hexenyl of 5-.
Halogen is fluorine, chlorine, bromine and iodine, is fluorine, chlorine and bromine especially, is preferably fluorine and chlorine.The tonka bean camphor base is
Figure A20068004806500266
Be preferably 1-tonka bean camphor base, skimmetine base or 5-tonka bean camphor base.
Term " and/or " or " or/and " be intended in this article represent not only to have one of defined option (substituting group), also may there be defined several option (substituting group) together, i.e. the mixing of different options (substituting group).
Term " at least " is meant one or surpass one, for example one or two or three, preferably one or two.
Term " optional substituted " is meant that the indication group is not replace or substituted.
In specification sheets below and claims full text, unless requirement separately in the literary composition, term " comprise " or variant as " comprising " or " containing ", be interpreted as meaning and comprise described integer or step, or the set of integer or step, but do not get rid of any other integer or step, or the set of integer or step.
If as (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13R 3, R 4, R 5, R 6, R ' 6, R 9Or R ' 9Via radicals R 10, R 11, R 12, R 13Or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with the C-atom of benzyl ring, then comprise for example following array structure of following kind Deng.
If M 1Be no key, substituent R 3, R 4, R ' 3, R ' 4, R 5Or
Figure A20068004806500272
One or two can occupy the corresponding benzyl ring of N-atom adjacent position, i.e. M among the formula I 1Residing position.
If M 2And/or M 3Be no key, this is equally applicable to corresponding substituting group.At M 2Under the situation for no key, this means substituent R 3, R 4, R 5, R " 3, R " 4Or
Figure A20068004806500273
One or two can occupy the corresponding benzyl ring of N-atom adjacent position, i.e. M among the formula I 2Residing position; At M 3Under the situation for no key, substituent R ' 3, R ' 4, R " 3, R " 4, Or
Figure A20068004806500275
One or two can occupy the corresponding benzyl ring of N-atom adjacent position, i.e. M among the formula I 3Residing position.
If R 3And R 4, R ' 3And R ' 4, R " 3And R " 4Or R 6And R ' 6Be C together 1-C 6Alkylidene group or C 2-C 6Alkylene group is so that form dicyclo with the phenyl that links to each other with them, and wherein said dicyclo is optional to be substituted, and then this oximido group for example is connected on arbitrary ring, for example
Figure A20068004806500276
Or
Figure A20068004806500277
Deng, wherein this bicyclic system is optional has as defined above further substituting group, or wherein said bicyclic system for example condenses with other aromatic ring or hetero-aromatic ring, for example:
Or
Figure A20068004806500282
If R " 3And R " 4Be C together 1-C 6Alkylidene group or C 2-C 6Alkylene group is so that form dicyclo with phenyl, and this is equally applicable to the R of group-(CO) " 2
At M 1Under the situation for no key, R ' 3And R ' 4Can be for example by using M on the benzyl ring 1Position (as mentioned above) form dicyclo, for example produce
Figure A20068004806500283
Structure.Work as M 1, M 2, M 3, M 4And/or M 5When being defined as " no key ", this is equally applicable to R 3And R 4, R ' 3And R ' 4, R " 3And R " 4, R 6And R ' 6
If R 10Be via direct key, C 1-C 4Alkylidene group, O, S, NR 14Or CO and and SR 10The benzyl ring that links to each other forms the phenyl or naphthyl of 5-or 6-unit ring, and wherein said phenyl or naphthyl is unsubstituted or replaces, for example, defined the compound of the structure with following type Deng, wherein phenyl or naphthyl is optional further is substituted.
If R 12And R 13Independently of one another for being connected to and NR 12R 13C on one of the benzyl ring that links to each other or C-atom of naphthyl ring 2-C 5Alkylidene group or C 2-C 5Alkylene group, for example, definition has the structure of following type down
Figure A20068004806500286
Deng, wherein said C 2-C 5Alkylidene group or C 2-C 5Alkylene group is optional by O or NR 14Insert:
Figure A20068004806500291
Deng.
If R 12And R 13Independently of one another for to be connected to and NR via direct key 12R 13Phenyl on the benzyl ring that links to each other for example, has defined the compound of array structure under comprising
Figure A20068004806500292
If R 12And R 13Form optional with the N-atom that links to each other with them by O, N or NR 14Saturated or the unsaturated ring of 5-that inserts or 6-unit then forms saturated or unsaturated ring, for example aziridine, pyrroles, tetramethyleneimine, imidazoles, triazole, oxazole, pyridine, 1,3-diazines, 1,2-diazine, piperidines or morpholine.
If R 12And R 13The N-atom that links to each other with their forms the hetero-aromatic ring system, and then described member ring systems means to comprise and surpass a ring, two or three rings for example, and one or surpass the heteroatoms of an identical or different type.Suitable heteroatoms is for example N, S, O or P, particularly N, S or O.Example is carbazole, indoles, isoindole, indazole, purine, isoquinoline 99.9, quinoline, carboline, thiodiphenylamine etc.
If R 16And R 17Form optional with the N-atom that links to each other with them by O, S or NR 14Saturated or the unsaturated ring of 5-that inserts or 6-unit then forms saturated or unsaturated ring, for example aziridine, pyrroles, thiazole, tetramethyleneimine, oxazole, pyridine, 1,3-diazines, 1,2-diazine, piperidines or morpholine.
If R 16And R 17Independently of one another for being connected to and NR 16R 17C on one of the benzyl ring that links to each other or C-atom of naphthyl ring 2-C 5Alkylidene group or C 2-C 5Alkylene group, wherein said C 2-C 5Alkylidene group or C 2-C 5Alkylene group is optional by O or NR 15Insert, and choose wantonly at this C 2-C 5Alkylidene group or C 2-C 5Fused benzene rings on the alkylene group then is meant the structure of following type: Deng.
If R 12And R 13Or R 2, R ' 2, R " 2, R " ' 2Or other " R "-substituting group is used in reference to for the group that surpasses in the same molecular of formula I or II, and then for each described group, their implication can be different, but obviously only give difference in the scope that defines in institute.
In the compound of formula I, oximido is preferably placed at the contraposition of N-atom:
Figure A20068004806500301
This is equally applicable to the R of group-(CO) " 2
Figure A20068004806500302
Therefore special wherein oximido and the R of group-(CO) meaningfully " 2All
Compound in the N-atom contraposition of benzyl ring separately:
Figure A20068004806500303
In the compound of formula II, oximido is preferably placed at M 4Or the contraposition of Y:
Figure A20068004806500304
Particularly in the contraposition of Y.
Work as R 5For
Figure A20068004806500305
The time, the compound of formula II meaningfully, wherein two oximidos all are positioned at M 4Or the contraposition of Y, particularly wherein two oximidos all are positioned at the compound of Y contraposition.
Meaningfully wherein Y is the compound of the formula II of S.
M 4Be for example direct key, CR " 3R " 4, CS, O, S, SO or SO 2
Or M 4Be direct key, CR " 3R " 4, O, S, SO or SO 2Or be direct key, CR " 3R " 4, O or S; Or be CO, O or directly key, particularly CO or directly key.
The compound of formula I preferably.
In the compound of formula I, M 2Be for example direct key, CO, O, S, SO, SO 2Or NR 14, particularly direct key, and M 1With M 3Be no key.
In other significant compound, M 1Be for example direct key, CO, O, S, SO, SO 2Or NR 14, particularly direct key, and M 2With M 3Be no key.
M wherein preferably 1, M 2Or M 3In to have only one be not the compound of the formula I of " no key ".
Especially preferred is the compound of formula I, wherein R 5For
Figure A20068004806500306
Especially with the benzyl ring position of N-atom contraposition; R particularly 3And R 4This compounds for hydrogen.
R wherein further preferably " 2For phenyl or by C 1-C 6Alkyl and/or NR 12R 13Those compounds of formula I during the phenyl that replaces.In described compound, R 12And R 13Preferably form the heterocyclic system that does not replace or replace together with coupled N-atom.Described member ring systems is in particular carbazole.
In a preferred embodiment of the invention, the compound of formula I has following array structure (Ix)
Figure A20068004806500311
R wherein 1, R ' 1, R 2, R ' 2, R 3, R ' 3, R " 3, R 4, R ' 4, R " 4As above definition, and R xBe one or more hydrogen, C 1-C 12Alkyl, phenyl, halogen, CN, NO 2, SR 10, OR 11, NR 12R 13Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl, and R 10, R 11, R 12And R 13As above definition.
In another embodiment of the present invention, R 5For
Figure A20068004806500312
And R " 2Be phenyl, optional being substituted is particularly by C 1-C 20Alkyl or NR 12R 13Replace.
The special meaningfully compound of formula I, wherein M 3Be for example direct key, and M 1And M 2Be no key, and R 5
Figure A20068004806500313
, and R " 2Be phenyl, optional being substituted is particularly by C 1-C 20Alkyl or NR 12R 13Replace, for example have structure (Iy)
Figure A20068004806500314
R wherein 1, R ' 1, R 2, R ' 2, R 3, R ' 3, R " 3, R 4, R ' 4, R " 4As above definition, and R xBe one or more hydrogen, C 1-C 12Alkyl, phenyl, halogen, CN, NO 2, SR 10, OR 11, NR 12R 13Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl; And R 10, R 11, R 12And R 13As above definition.
Another embodiment of the present invention comprises the compound of formula I, wherein M 1Be direct key, M 2And M 3Be no key, and R 5For
Figure A20068004806500315
And R " 2Be phenyl, optional being substituted is particularly by C 1-C 20Alkyl or NR 12R 13Replace, for example, have structure (IZ)
Figure A20068004806500321
R wherein 1, R ' 1, R 2, R ' 2, R 3, R ' 3, R " 3, R 4, R ' 4, R " 4As above definition, and R xBe one or more hydrogen, C 1-C 12Alkyl, phenyl, halogen, CN, NO 2, SR 10, OR 11, NR 12R 13Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl; And R 10, R 11, R 12And R 13As above definition.
The significant especially compound that also has formula I, wherein R " 2Be the heteroaryl that do not replace or replace, for example thienyl or furyl, both are all unsubstituted or by for example C 1-C 20Alkyl, for example methyl or ethyl replace.
R 1, R ' 1And R " 1Be for example hydrogen, C independently of one another 3-C 8Cycloalkyl, C 2-C 5Alkenyl, C 1-C 20Alkoxyl group, C 1-C 20Alkyl, phenyl, naphthyl, benzyloxy or phenoxy group; C particularly 1-C 20Alkyl.
R 2, R ' 2And R " ' 2For example independently of one another for choosing wantonly by O, CO or NR 14The C that inserts 1-C 20Alkyl or C 3-C 10Cycloalkyl;
Or R 2And R ' 2By halogen, OR 11COOR 11, CONR 12R 13Or the C of phenyl replacement 1-C 20Alkyl;
Or R 2And R ' 2Be unsubstituted phenyl or naphthyl, particularly phenyl, or by one or more C 1-C 12Alkyl, phenyl, halogen, SR 10, OR 11Or NR 12R 13The phenyl or naphthyl, particularly phenyl that replace.
Or R 2And R ' 2Be C 2-C 20Alkyloyl, benzoyl, C 2-C 12Alkoxy carbonyl or phenyloxycarbonyl.
R 2, R ' 2, R " 2And R " ' 2Preferably be C independently of one another 1-C 20Alkyl, unsubstituted phenyl or by one or more C 1-C 12Alkyl, SR 10, OR 11Or NR 12R 13The phenyl that replaces.R " 2Be in addition in all cases
Figure A20068004806500322
Or
R 3, R 4, R ' 3, R ' 4, R " 3And R " 4(with therefore R 7, R ' 7, R 8And R ' 8) for example be hydrogen, C independently of one another 1-C 20Alkyl, halogen, C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, phenyl-C 1-C 4Alkyl or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 3, R 4, R ' 3, R ' 4, R " 3And R " 4(with therefore R 7, R ' 7, R 8And R ' 8) be unsubstituted or by one or more SR 10, OR 11Or NR 12R 13The phenyl that replaces; Or R 3, R 4, R ' 3, R ' 4, R " 3And R " 4Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13
R 3, R 4, R ' 3, R ' 4, R " 3And R " 4(with therefore R 7, R ' 7, R 8And R ' 8) preference is as being hydrogen, C independently of one another 1-C 20Alkyl, (CO) R 15, SR 10, OR 11Or NR 12R 13
R 5For example be hydrogen, C 1-C 20Alkyl,
Figure A20068004806500331
Unsubstituted or by one or more C 1-C 20Alkyl, SR 10, OR 11, NR 12R 13The phenyl that replaces; Or R 5Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring; Or R 5For Or
Figure A20068004806500333
Be preferably hydrogen,
Figure A20068004806500334
Or
Figure A20068004806500335
R 6And R ' 6For example be hydrogen or C independently of one another 1-C 20Alkyl, particularly hydrogen; Or R 6And R ' 6Be C together 1-C 6Alkylidene group or C 2-C 6Alkylene group is so that form dicyclo with the phenyl that links to each other with them; Condition is a group
Figure A20068004806500336
Or
Figure A20068004806500337
Be connected on arbitrary ring of described dicyclo.R 6And R ' 6Preference is as being hydrogen or C independently of one another 1-C 20Alkyl.
R 9And R ' 9Be for example hydrogen, C 1-C 20Alkyl or phenyl, be preferably hydrogen,
Figure A20068004806500342
Or C 1-C 20Alkyl, particularly hydrogen or
Figure A20068004806500343
R 10Be preferably phenyl, or via direct key, C 1-C 4Alkylidene group, O, S, NR 14Or CO, especially via CO and and SR 10The benzyl ring that links to each other forms the phenyl of 5-or 6-unit ring, and wherein said phenyl is unsubstituted or by one or more C 1-C 20Alkyl replaces.
If R 10Be via CO and and SR 10The benzyl ring that links to each other forms the phenyl of 5-or 6-unit ring, then forms sulfo-xanthenyl (thioxanthyl).
R 11Be C for example 1-C 20Alkyl, phenyl-C 1-C 4Alkyl; The C that is inserted by one or more O 2-C 20Alkyl; Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl; Be preferably C 1-C 20Alkyl or the optional C that is inserted by O 3-C 10Cycloalkyl.
R 12And R 13For example be hydrogen, C 1-C 20Alkyl, by O or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 12And R 13Be phenyl or naphthyl, phenyl particularly, it replaces separately, or by one or more (CO) R 15, NR 16R 17, SR 10, OR 11Or C 1-C 20Alkyl replaces;
Or R 12And R 13Independently of one another for being connected to and NR 12R 13C on one of the benzyl ring that links to each other or carbon atom of naphthyl ring 2-C 5Alkylidene group, wherein said C 2-C 5Alkylidene group or C 2-C 5Alkylene group is optional by O or NR 14Insert; Or
R 12And R 13Independently of one another for to be connected to NR via direct key 12R 13Phenyl on the benzyl ring thereon of position; Or
R 12And R 13Form optional with the N-atom that links to each other with them by O, N or NR 14, the saturated or unsaturated ring of 5-that is inserted by O or 6-unit, and this ring especially is unsubstituted or by one or more C 1-C 20Alkyl, SR 10, OR 11, NR 16R 17Or (CO) R 15Replace; Or
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them, this hetero-aromatic ring system is unsubstituted or by one or more C 1-C 20Alkyl, SR 10, OR 11, NR 16R 17Or (CO) R 15Replace.
This hetero-aromatic ring system preference unsubstituted or that replace is a carbazole unsubstituted or that replace, or indoles unsubstituted or that replace.
R 14For example hydrogen or C 1-C 20Alkyl.
R 15For example be C 1-C 20Alkyl, by O or NR 14The C that inserts 2-C 20Alkyl, or be phenyl or the optional C that is inserted by O 3-C 10Cycloalkyl; C particularly 1-C 20Alkyl.
R 16And R 17Be for example hydrogen, C independently of one another 1-C 20Alkyl, C 3-C 10Cycloalkyl or phenyl; Or
R 16And R 17Form the saturated or unsaturated ring of 5-or 6-unit with the N-atom that links to each other with them, it is optional by O, S or NR 14Insert;
Or R 16And R 17Independently of one another for being connected to and NR 16R 17C on one of the benzyl ring that links to each other or carbon atom of naphthyl ring 2-C 5Alkylidene group, wherein said C 2-C 5Alkylidene group or C 2-C 5Alkylene group is optional by O or NR 14Insert, and choose wantonly at this C 2-C 5Alkylidene group or C 2-C 5Fused benzene rings on the alkylene group; R 16And R 17Be preferably C 1-C 20Alkyl or for being connected to and NR 16R 17C on one of the benzyl ring that links to each other or carbon atom of naphthyl ring 2-C 5Alkylidene group, and choose wantonly at this C 2-C 5Fused benzene rings on the alkylidene group.
The compound of formula I and II preferably, wherein
M 1, M 2And M 3Be no key or direct key independently of one another; Condition is M 1, M 2Or M 3At least one be direct key;
M 4Be direct key, CO or O;
Y is S or NR 18
R 1And R ' 1Be C 1-C 20Alkyl;
R 2And R ' 2Be C 1-C 20Alkyl, C 1-C 4Haloalkyl or optional by one or more C 1-C 20Alkyl, halogen, C 1-C 4Haloalkyl or NR 12R 13The phenyl that replaces;
R " 2Be phenyl, it is optional by one or more C 1-C 12Alkyl, halogen, C 1-C 4Haloalkyl replaces; Or be
Figure A20068004806500351
Or
Figure A20068004806500352
M 5It is direct key;
R 3, R 4, R ' 3, R ' 4, R " 3, R " 4, R 6, R ' 6, R 8, R ' 8, R 9And R ' 9Be hydrogen;
R 5Be hydrogen, Or
Figure A20068004806500354
R 7And R ' 7Be hydrogen or
Figure A20068004806500355
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them;
R 14Be C 1-C 20Alkyl; And
R 1The 8th, C 1-C 20Alkyl, C 1-C 4Haloalkyl or optional by one or more C 1-C 20Alkyl, halogen or C 1-C 4The phenyl that haloalkyl replaces; And
Condition is to have at least two oxime ester base groups in this molecule.
Other compounds of formula I meaningfully, wherein
M 1, M 2And M 3Be no key or direct key independently of one another; Condition is M 1, M 2Or M 3At least one be direct key;
R 1And R ' 1Be C 1-C 20Alkyl;
R 2And R ' 2Be C 1-C 20Alkyl or by NR 12R 13The phenyl that replaces;
R " 2Be optional by C 1-C 12The phenyl that alkyl replaces;
R 3, R 4, R ' 3, R ' 4, R " 3, R " 4Be hydrogen;
R 5Be hydrogen or And
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them, particularly the carbazole member ring systems; With
Condition is to have at least two oxime ester base groups in this molecule.
The further compound of formula I and II meaningfully, wherein
M 1, M 2And M 3Be no key or direct key independently of one another; Condition is M 1, M 2Or M 3At least one be direct key;
M 4Be direct key or CO;
Y is S or NR 18
R 1And R ' 1Be C 1-C 20Alkyl; C 1-C 20Alkoxyl group or phenyl;
R 2And R ' 2Be unsubstituted C independently of one another 1-C 20Alkyl, by COOR 11Or CONR 12R 13The C that replaces 1-C 20Alkyl; Unsubstituted or by OR 11The C that replaces 2-C 20Alkyloyl; Or by NR 12R 13The phenyl that replaces;
R " 2It is phenyl; By one or more NR 12R 13, halogen, C 1-C 20Alkyl replaces, or by the optional C that is inserted by O 3-C 10The phenyl of cycloalkyl substituted;
Or R " 2Be heteroaryl, particularly thienyl and furyl, it is chosen wantonly and is replaced by alkyl;
Or
Figure A20068004806500371
Or
Figure A20068004806500372
M 5It is direct key;
R 3, R 4, R ' 3, R ' 4, R " 3And R " 4Be independently of one another hydrogen, halogen,
Figure A20068004806500373
(CO) R 15
Or R 3And R 4Be C together 2-C 6Thereby alkylene group and coupled phenyl form dicyclo together;
R 5Be hydrogen,
Figure A20068004806500374
Or
Figure A20068004806500375
R 6, R ' 6, R 8And R ' 8Be hydrogen;
R 7And R ' 7Be independently of one another hydrogen or
Figure A20068004806500376
R 9And R ' 9Be hydrogen, (CO) R independently of one another 15Or
Figure A20068004806500377
R 11Be C 1-C 20Alkyl;
R 12And R 13Be C independently of one another 1-C 20Alkyl; Or
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them, this hetero-aromatic ring system is unsubstituted, or quilt
Figure A20068004806500378
Replace;
R 14Be C 1-C 20Alkyl;
R 15Be phenyl or heteroaryl, optional separately by NR 12R 13Or C 1-C 20Alkyl replaces;
R 18Be C 1-C 20Alkyl; Optional by C 1-C 20Alkyl or NR 12R 13The benzoyl that replaces; Or phenyl or naphthyl, both all optional by one or more halogens or
Figure A20068004806500379
Replace; And
Condition is to have at least two oxime ester base groups in this molecule.
By the method preparation formula I that describes in the document or the oxime ester of II; for example by corresponding oxime and acyl halide; particularly chloride of acid or acid anhydrides are at inert solvent; for example in t-butyl methyl ether, tetrahydrofuran (THF) (THF) or the dimethyl formamide at alkali; for example triethylamine or pyridine exist down, or react in the basic solvent as pyridine.For example:
Figure A20068004806500381
R 1, R ' 1, R 2, R " 2, R 3, R ' 3, R " 3, R 4, R ' 4, R " 4, R 5, Y, M 1, M 2, M 3And M 4As above definition, Hal is meant halogen atom, particularly Cl.
R 1Be preferably methyl.
This type of reaction is that those skilled in the art are known, and usually at-15 to+50 ℃, carries out under preferred 0-25 ℃ the temperature.
(pass through R if obtain the mixture of the compound of formula I or II 1And R ' 1Difference), described mixture can be used for the light trigger purposes like this, maybe can pass through the known common methods of chemical field, for example crystallization, chromatography etc. are separated to obtain pure compound.
Therefore theme of the present invention is the method that is used for the compound of preparation formula I or II, by making the oxime compound of formula Ia or IIa
Figure A20068004806500382
Wherein
R 2, R " 2, Y, M 1, M 2, M 3And M 4As above definition;
R 3, R ' 3, R " 3, R 4, R ' 4, R " 4And R 5As above definition, wherein group as defined above
Figure A20068004806500391
And/or Can by
Figure A20068004806500393
And/or
Figure A20068004806500394
Substitute;
R ' 2And R " ' 2As above definition;
Z is hydrogen, COR 1, COR ' 1Or COR " 1
Condition is that at least one group Z is a hydrogen in the compound of formula Ia and IIa;
Acyl halide or acid anhydrides with formula V or VI
Figure A20068004806500395
Or formula V and (Va) or (VI) and the mixture of acyl halide (VIa)
Figure A20068004806500396
Wherein Hal is meant halogen atom, and R 1And R ' 1As claim 1 definition,
Reaction in the presence of the mixture of alkali or alkali.
Can pass through standard chemical textbook (for example, J.March, Advanced Organic Chemistry, the 4th edition, Wiley Interscience, 1992) or monograph, for example S.R.Sandler﹠amp as the required oxime of starting raw material; W.Karo, Organic functional group preparations, the 3rd volume, the whole bag of tricks described in the Academic Press obtains.
One of method of most convenient is that for example aldehydes or ketones and azanol or its salt react in the solvent of picture dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMA), N-Methyl pyrrolidone (NMP), methyl-sulphoxide (DMSO), methyl alcohol, ethanol, Virahol, ethylene glycol, ethyl acetate, t-butyl methyl ether, diethylene glycol dimethyl ether, toluene, chlorobenzene, dichlorobenzene etc.The mixture of these solvents also is applicable to this reaction.Add as the alkali of sodium acetate or pyridine to control the pH value of reaction mixture.Be well known that speed of reaction depends on the pH value, and alkali can add when beginning or add continuously in reaction process.Water can be added in the reaction mixture with the dissolving inorganic reagent.Also can use basic solvent as pyridine as alkali and/or solvent or cosolvent.Temperature of reaction is generally the reflux temperature of room temperature to mixture, about 20-120 ℃ usually.Because speed of reaction depends on this, can this carbonyl optionally be converted into oxime by control reaction temperature or selective solvent.Usually the reactivity of aldehyde is the highest, is dialkyl ketone secondly, and the reactivity of alkylaryl ketone and diaryl ketone is lower.
Another of oxime synthesis method easily be, with nitrous acid or alkyl nitrite with the nitrosification of " activity " methylene group.Organic Syntheses coll.Vol.VI (J.Wiley ﹠amp for example; Sons, New York, 1988), alkaline condition described in the 199th and 840 page, and Organic Syntheses coll. volume V for example, the 32nd and 373 page, Coll. are rolled up III, and the 191st and 513 page, Coll. are rolled up II, 202nd, the acidic conditions described in 204 and 363 pages all is applicable to the oxime of preparation as starting raw material of the present invention.Nitrous acid is generally produced by Sodium Nitrite.Alkyl nitrite can be for example methyl nitrite, ethyl nitrite, nitrous acid isopropyl ester, butyl nitrite and Isopentyl nitrite.
Meaningfully be prepared as follows the method for the compound of formula I or II:
By traditional method with the ketone of formula Ib or IIb or the one or more ketone groups or the aldehyde group of aldehyde cpd:
Wherein
R 2, R " 2, Y, M 1, M 2, M 3And M 4As above definition;
R 3, R ' 3, R " 3, R 4, R ' 4, R " 4And R 5As above definition, wherein group as defined above
Figure A20068004806500402
And/or
Figure A20068004806500403
Can by
Figure A20068004806500404
And/or
Figure A20068004806500405
Substitute;
R ' 2And R " ' 2As above definition;
Transform the corresponding oxime of accepted way of doing sth Ia or IIa
Figure A20068004806500406
Wherein
R 2, R " 2, Y, M 1, M 2, M 3And M 4As above definition;
R 3, R ' 3, R " 3, R 4, R ' 4, R " 4And R 5As above definition, wherein group as defined above
Figure A20068004806500407
And/or
Figure A20068004806500408
Can by And/or
Figure A200680048065004010
Substitute;
R ' 2And R " ' 2As above definition;
Z is hydrogen, COR 1, COR ' 1Or COR " 1
Condition is that at least one group Z is a hydrogen in the compound of formula Ia and IIa;
In the presence of alkali or alkali mixture, make the oxime compound of described formula Ia or IIa and acyl halide or the anhydride reaction of formula V or VI
Figure A20068004806500411
Or with formula V and (Va) or (VI) and acyl halide mixture reaction (VIa),
Figure A20068004806500412
Wherein Hal is meant halogen atom, and R 1And R ' 1As definition in the claim 1.
Each oxime ester base group can (Z) or (E) exist with two kinds of configurations.Can pass through traditional method separating isomerism body, but also can use isomer mixture like this as light-initiated thing class.Therefore, the invention still further relates to the mixture of configurational isomer of the compound of formula I and II.
The present invention relates on many aromatic ring systems, have the specific oxime ester compound of at least two oxime ester base groups.This precursor usually can be the polyketide with corresponding many aromatic ring systems.Ketone can carry out in a selective manner to the conversion of oxime, or carries out with moderate selectivity.Under one situation of back, final oxime ester product can be the mixture that surpasses a kind of compound.Therefore, the invention still further relates to this type of mixture, condition is at least a compound that also comprises in formula I or II scope except that aforesaid configurational isomer.
Another theme of the present invention is the compound of formula Ia or IIa
Figure A20068004806500413
Wherein
R 2, R " 2, Y, M 1, M 2, M 3And M 4As above definition;
R 3, R ' 3, R " 3, R 4, R ' 4, R " 4And R 5As above definition, wherein group as defined above
Figure A20068004806500421
And/or
Figure A20068004806500422
Can by
Figure A20068004806500423
And/or
Figure A20068004806500424
Substitute;
R ' 2And R " ' 2As above definition;
Z is hydrogen, COR 1, COR ' 1Or COR " 1
Condition is that at least one group Z is a hydrogen in the compound of formula Ia and IIa, and condition is to have at least two groups that contain group Z in this molecule.
Another object of the present invention is a kind of photoinitiator mixtures, and it comprises
(A) compound of at least a I of formula as defined above or II, with
(B) compound of at least a formula I ' or II '
Wherein
A is a group
Figure A20068004806500426
M 1, M 2, M 3, M 4, Y, R 1And R 2As above definition;
R 3, R 4, R 5, R ' 3, R ' 4, R " 2, R " 3And R " 4As above definition, wherein group as defined above
Figure A20068004806500427
And/or
Figure A20068004806500428
Can by
Figure A20068004806500429
And/or
Figure A200680048065004210
Substitute;
Z is hydrogen, COR 1, COR ' 1Or COR " 1
R ' 1, R " 1, R ' 2And R " ' 2As above definition;
Condition is to have at least two oxime ester base groups in this molecule.
Especially meaningfully aforesaid photoinitiator mixtures, it comprises the compound of formula I and the compound of formula I ', wherein
M 1And M 2Be no key;
M 3Be direct key;
R 1, R ' 1, R " 1, R 2And R ' 2As above definition;
R 3, R ' 3, R " 3, R 4, R ' 4And R " 4Be hydrogen;
R 5For
Figure A20068004806500431
R " 2By NR 12R 13The phenyl that replaces; And
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them, or comprise the compound of formula II and the compound of formula II ', wherein M 4Be direct key;
R 1, R ' 1, R " 1, R " ' 2And R ' 2As above definition;
Y is NR 18
R 18By
Figure A20068004806500432
The phenyl that replaces;
R 2By NR 12R 13The phenyl that replaces; With
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them.
Further meaningfully aforesaid photoinitiator mixtures also comprises other oxime ester photoinitiator except that the compound of formula I or II and formula I ' or II '.
The ratio of the compound of mixture Chinese style I and I ' or formula II and II ' is unimportant in principle.The example of the suitable ratio of these compounds is 90-98%/10-2% or 50-90%/50-10%.
Aforesaid this class mixture can comprise in addition with of the present invention similar but only have the oxime ester compound of oxime ester base group.This compounds for example is disclosed among the EP patent application No.05111539.2 that submitted on December 1st, 2005, and it is incorporated herein by this reference.
The mixture of described oxime ester compound is to be used as light trigger with the identical mode of one-component.
The compound of formula I and II is suitable as free radical photo-initiation.
Therefore another theme of the present invention is a kind of photopolymerizable composition, and it comprises
(a) the undersaturated photopolymerization compound of at least a olefinic and
(b) as at least a I of formula as defined above of light trigger or the compound of II, or the mixture of the compound of aforesaid formula I or II.
Except that light trigger or photoinitiator mixtures (b), said composition can also comprise at least a other light trigger (c) and/or other additive (d) in addition.
Unsaturated compound (a) can comprise one or more olefinic double bonds.They can have low (monomer) or high (oligomeric) molecular weight.The monomeric example that contains two keys is acrylic acid alkyl ester, hydroxy alkyl ester, cycloalkyl ester (it is chosen wantonly and is inserted by O) or amino ester, or the alkyl ester of methacrylic acid, hydroxy alkyl ester, cycloalkyl ester (it is chosen wantonly and is inserted by O) or amino ester, for example methyl acrylate, ethyl ester, butyl ester, 2-ethylhexyl or 2-hydroxy methacrylate, vinylformic acid tetrahydrofurfuryl ester, isobornyl acrylate, methyl methacrylate, cyclohexyl methacrylate or Jia Jibingxisuanyizhi.Silicone (silicone) acrylate also is favourable.Other example is (methyl) acrylamide, vinyl ester such as the vinyl-acetic ester of vinyl cyanide, acrylamide, Methacrylamide, N-replacement, vinyl ether such as IVE, vinylbenzene, alkyl-and halogenated styrenes, N-vinyl pyrrolidone, vinylchlorid or vinylidene chloride.
The monomeric example that contains two or more pairs key is the diacrylate and 4 of ethylene glycol, propylene glycol, neopentyl glycol, hexylene glycol or dihydroxyphenyl propane, 4 '-two (2-acryloyl-oxy base oxethyl) diphenyl propane, Viscoat 295, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, Vinylstyrene, succsinic acid divinyl ester, Phthalic acid, diallyl ester, triallyl phosphate, triallyl isocyanurate or three (2-acryloxy ethyl) isocyanuric acid ester.
Relatively the example of high-molecular weight polyunsaturated compounds (oligopolymer) be acrylated Resins, epoxy, contain the propylene acid group-, vinyl ether-or polyester and the urethane and the polyethers of epoxy-group.Other example of unsaturated oligomer is a unsaturated polyester resin, and it is usually by toxilic acid, phthalic acid with one or more glycol are made and molecular weight is about 500-3000.In addition, the maleic acid ester end-blocking oligopolymer that can also use vinyl ether monomers and oligopolymer and have polyester, urethane, polyethers, polyvingl ether and epoxy main chain.Particularly suitable be have the oligopolymer of vinyl ether group with as WO 90/01512 described mixture of polymers.But vinyl ether and toxilic acid functionalized monomer's multipolymer also is suitable.Such unsaturated oligomer is also referred to as prepolymer.
Specially suitable example is the ester of ethylenically unsaturated carboxylic acids and polyvalent alcohol or polyepoxide and the polymkeric substance that has ethylenically unsaturated group in main chain or side group, for example unsaturated polyester, polymeric amide and urethane and multipolymer thereof, in side chain, contain the polymkeric substance and the multipolymer of (methyl) acrylic acid groups and one or more these type of mixture of polymers.
The example of unsaturated carboxylic acid is vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, styracin and unsaturated fatty acids, as linolic acid or oleic acid.Vinylformic acid and methacrylic acid are preferred.
Suitable polyvalent alcohol is aromatics and is aliphatic series or alicyclic polyol especially.The example of aromatic polyol is a quinhydrones, 4,4 '-dihydroxybiphenyl, 2,2-two (4-hydroxy phenyl) propane and phenolic novolac and resol.The example of polyepoxide is based on above-mentioned polyvalent alcohol, especially those of aromatic polyol and Epicholorohydrin.Other suitable polyvalent alcohol is for containing the polymkeric substance and the multipolymer of hydroxyl at polymer chain or in side group, the example is polyvinyl alcohol and multipolymer or polymethyl acrylic acid hydroxy alkyl ester or its multipolymer.Other suitable polyvalent alcohol is the oligomer ester that contains terminal hydroxy group.
The example of aliphatic series and alicyclic polyol is for preferably having the alkylene glycol of 2-12 carbon atom, ethylene glycol for example, 1,2-or 1, ammediol, 1,2-, 1,3-or 1, the 4-butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, dodecanediol, glycol ether, triglycol, the polyoxyethylene glycol of the preferred 200-1500 of molecular weight, 1,3-encircles pentanediol, 1,2-, 1,3-or 1, the 4-cyclohexanediol, 1,4-dihydroxyl methylcyclohexane, glycerine, three (beta-hydroxy ethyl) amine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol and Sorbitol Powder.
Polyvalent alcohol can be with a kind of carboxylic acid or with the partially or completely esterification of different unsaturated carboxylic acids, and in the part ester, free hydroxyl group can be modified, for example by other carboxylic acid etherificate or esterification.
The example of ester is:
Viscoat 295, the trimethylolethane trimethacrylate acrylate, trimethylolpropane trimethacrylate, the trimethylolethane trimethacrylate methacrylic ester, butylene glycol dimethacrylate, triethylene glycol dimethacrylate, Viscoat 335HP, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the Dipentaerythritol diacrylate, the Dipentaerythritol triacrylate, the Dipentaerythritol tetraacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate, tripentaerythritol eight acrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, the Dipentaerythritol dimethacrylate, Dipentaerythritol tetramethyl-acrylate, tripentaerythritol prestox acrylate, the tetramethylolmethane diitaconate, Dipentaerythritol three itaconic esters, Dipentaerythritol five itaconic esters, Dipentaerythritol six itaconic esters, glycol diacrylate, 1, the 3-butylene glycol diacrylate, 1, the 3-butylene glycol dimethacrylate, 1,4-butyleneglycol diitaconate, the sorbyl alcohol triacrylate, the sorbyl alcohol tetraacrylate, the triacrylate of tetramethylolmethane modification, sorbyl alcohol tetramethyl-acrylate, sorbyl alcohol five acrylate, sorbyl alcohol six acrylate, oligomer ester acrylate and methacrylic ester, glycerine diacrylate and triacrylate, 1,4-hexanaphthene diacrylate, molecular weight is the diacrylate and the dimethacrylate of the polyoxyethylene glycol of 200-1500, or its mixture.
Same suitable component (a) is identical or different unsaturated carboxylic acid and preferably have 2 to 6, especially the acid amides of the aromatics of 2 to 4 amino, alicyclic and aliphatic polyamines.The example of this type of polyamines is a quadrol, 1,2-or 1,3-propylene diamine, 1,2-, 1,3-or 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine, octamethylenediamine, dodecane diamines, 1,4-diamino-cyclohexane, isophorone diamine, phenylenediamine, benzidine, two-beta-aminoethyl ether, diethylenetriamine, Triethylenetetramine (TETA), two (beta-amino oxyethyl group)-or two (beta-amino propoxy-) ethane.Other suitable polyamines is for preferably having additional amino polymkeric substance and multipolymer and the oligoamide with amino end group in side chain.The example of this type of unsaturated amides is a methylene-bisacrylamide, 1, the own diacrylamine of 6-, diethylenetriamine trimethylammonium acrylamide, two (methacrylamido propoxy-) ethane, methacrylic acid Beta-methyl acrylamido ethyl ester and N-[(beta-hydroxy oxyethyl group) ethyl] acrylamide.
Suitable unsaturated polyester and polymeric amide are derived from for example toxilic acid with derived from glycol or diamines.Some toxilic acids can change other dicarboxylic acid into.They can with the olefinic unsaturated comonomer, for example vinylbenzene uses together.Polyester and polymeric amide also can be derived from dicarboxylic acid with derived from olefinic unsaturated diol or diamines, especially derived from having long relatively chain, for example those of 6-20 carbon atom.The example of urethane is those that constitute by saturated or unsaturated vulcabond with by unsaturated or saturated respectively glycol.
The polymkeric substance that has (methyl) acrylate group in side chain is known equally.They can for example be based on the Resins, epoxy and (methyl) acrylic acid reaction product of phenolic novolac, maybe can be with the vinyl alcohol of (methyl) acroleic acid esterification or the homopolymer or the multipolymer of its hydroxyalkyl derivant, maybe can be (methyl) acrylic acid homopolymer and the multipolymer with the esterification of (methyl) acrylic acid hydroxy alkyl ester.
Other suitable polymers that has acrylate or methacrylate based group in side chain for example is, have and be connected on the skeleton or be connected to photopolymerizable side group on the ester group in the molecule, promptly the solvable or soluble polyimide precursor of alkali according to the solvent of EP 624826 for example gathers (amic acid esters) compound.This quasi-oligomer or polymkeric substance can with novel photoinitiator and optional reactive diluent, for example multifunctional (methyl) acrylate is prepared together to prepare extremely sensitive polyimide precursor resist.
Photopolymerizable compound can use separately or use in any required mixture.The preferred mixture that uses (methyl) acrylic acid multielement alcohol ester.
The example of component (a) also can be polymkeric substance or the oligopolymer that has at least two ethylenically unsaturated groups and at least one carboxyl-functional in molecular structure, the resin that obtains as the reaction by saturated or unsaturated polyprotonic acid acid anhydrides and epoxy compounds and unsaturated monocarboxylic reaction product, for example, light-sensitive compound described in JP 6-1638 and JP 10301276 and as EB9696, UCB Chemcials; KAYARAD TCR1025, Nippon Kayaku Co., the commodity of LTD, or carboxylic resin with have a α, the adduct that generates between the unsaturated compound of β-unsaturated double-bond and epoxide group (for example, ACA200M, Daicel Industries, Ltd.).
As thinner, can comprise the list that accounts for the maximum 70 weight % of described composition solid part-or the mixture of multifunctional alefinically unsaturated compounds or several described compounds in the above-mentioned composition.
Unsaturated compound (a) also can be used as the mixture use with not photopolymerizable film-forming components.They can be the polymkeric substance of for example physical dryness or its at organic solvent, the solution in Nitrocellulose or the cellulose acetobutyrate for example.But they also can be the resin of chemistry and/or heat solidifiable (thermal curable), for example polymeric polyisocyanate, polyepoxide and melamine resin and polyimide precursor.Using the thermal curable resin simultaneously is important for the application in the system that is known as heterozygosis (hybrid) system, and this system is carried out photopolymerization in the fs, carries out crosslinked in the logical superheated aftertreatment of subordinate phase then.
The present invention also provide comprise at least a in water emulsification or the undersaturated photopolymerizable compound of dissolved olefinic as the composition of component (a).Many forms of the prepolymer water dispersion of this type of radiation-hardenable can be buied.Prepolymer dispersions is understood that it is water and at least a dispersion that is dispersed in prepolymer wherein.The concentration of water in these systems is for example 5-80 weight %, particularly 30-60 weight %.The prepolymer of radiation-hardenable or the concentration of pre-polymer mixture are for example 95-20 weight %, particularly 70-40 weight %.In these compositions, the summation of the percentage ratio that water and prepolymer are provided is being 100 under the situation separately, and adds auxiliary agent and additive according to desired use with the difference amount.
Be dispersed in the water and usually also dissolved radiation curable film-forming prepolymer be that itself is known, can cause by free radical, polymerizable double bond content for for example 0.01-1.0 mole/100 restrain prepolymers and molecular-weight average for for example at least 400,500 to 10,000 list-or the prepolymer water dispersion of the unsaturated prepolymer of multifunctional olefinic particularly.But also can consider to have more high-molecular weight prepolymer according to desired use.Described in EP12339, for example use contains the two keys of polymerizable C-C and acid number is no more than 10 polyester, the polyethers that contains the two keys of polymerizable C-C, polyepoxide and at least a α that per molecule contains at least two epoxide groups, the reaction product of the hydroxyl of β-ethylenically unsaturated carboxylic acids, urethane (methyl) acrylate and contain α, the acrylic copolymer of the unsaturated acrylic acid groups of β-olefinic.Can use the mixture of these prepolymers equally.Same suitable is the polymerizable prepolymer described in the EP33896, and it is that molecular-weight average at least 600, carboxyl-content are that 0.2-15% and polymerizable C-C double bond content are the thioether affixture of the polymerizable prepolymer of 0.01-0.8 mole/100 gram prepolymers.Other suitable water dispersion based on specific (methyl) acrylic acid alkyl ester polymer has been described in EP41125, and, the prepolymer of suitable water dispersible, the radiation-hardenable of urethanum acrylate can in DE2936039, be found.
Other additive that can comprise in the prepolymer water dispersion of these radiation-hardenables is dispersing auxiliary, emulsifying agent, antioxidant, for example 2,2-thiobis (4-methyl-6-tert butyl phenol) or 2, the 6-di-tert-butylphenol, photostabilizer, dyestuff, pigment, filler, as glass or aluminum oxide, for example talcum, gypsum, silicic acid, rutile, carbon black, zinc oxide, ferric oxide, reaction promotor, even flat (levelling) agent, lubricant, wetting agent, thickening material, matting agent, defoamer and conventional other auxiliary agent in technical field of coatings.Suitable dispersing auxiliary is the water-soluble organic compounds that has high molecular and contain polar group, for example polyvinyl alcohol, Polyvinylpyrolidone (PVP) or ether of cellulose.Operable emulsifying agent is a nonionic emulsifying agent, also can use ionic emulsifying agent if desired.
In some cases, it may be favourable using the mixture of two or more novel photoinitiators.Certainly, also can use mixture with known light trigger (c), for example with the mixture of following material: camphorquinone, benzophenone, benzophenone derivates, as 2,4, the 6-tri-methyl benzophenone, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-methoxycarbonyl benzophenone, 4,4 '-two (chloromethyl) benzophenone, the 4-chlorobenzophenone, the 4-phenyl benzophenone, 3,3 '-dimethyl-4-methoxyl group-benzophenone, [4-(4-aminomethyl phenyl sulfo-) phenyl]-phenyl ketone, methyl-2-benzoyl benzoic ether, 3-methyl-4 '-phenyl benzophenone, 2,4,6-trimethylammonium-4 '-phenyl benzophenone, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone; Ketal compound, for example benzil dimethyl ketal (IRGACURE
Figure A20068004806500481
651); Methyl phenyl ketone, acetophenone derivs, for example Alpha-hydroxy cycloalkyl phenyl ketone, for example 2-hydroxy-2-methyl-1-phenyl-acetone (DAROCUR
Figure A20068004806500482
1173), 1-hydroxyl-cyclohexyl-phenyl-ketone (IRGACURE
Figure A20068004806500483
184); 1-[4-(2-hydroxyl-oxethyl)-phenyl]-2-hydroxy-2-methyl-1-third-1-ketone (IRGACURE
Figure A20068004806500484
2959); 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl }-2-methyl-third-1-ketone (IRGACURE
Figure A20068004806500485
127); 2-hydroxyl-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-phenoxy group]-phenyl }-2-methyl-third-1-ketone; Dialkoxy methyl phenyl ketone, Alpha-hydroxy-or alpha-aminoacetophenone, for example (4-methyl thiobenzoyl)-1-methyl isophthalic acid-morpholino ethane (IRGACURE
Figure A20068004806500486
907), (4-morpholino benzoyl)-1-benzyl-1-dimethylaminopropanecompounds (IRGACURE
Figure A20068004806500491
369), (4-morpholino benzoyl)-1-(4-methyl-benzyl)-1-dimethylaminopropanecompounds (IRGACURE
Figure A20068004806500492
379) 2-benzyl-2-dimethylamino-1-(3, the 4-Dimethoxyphenyl) fourth-1-ketone, (4-(2-hydroxyethyl) amino benzoyl)-1-benzyl-1-dimethylaminopropanecompounds); 4-aroyl 1; the 3-dioxolane; benzoin alkylether and benzil ketals; phenyl glyoxylic acid ester and derivative thereof; oxo-phenyl-acetic acid 2-(2-hydroxyl-oxyethyl group)-ethyl ester for example; the phenyl glyoxylic acid ester of dimerization, for example oxo-phenyl-acetic acid 1-methyl-2-[2-(2-oxo-2-phenyl-acetoxyl group)-propoxy-]-ethyl ester (IRGACURE
Figure A20068004806500493
754); Other oxime ester, for example 1,2-acetyl caproyl 1-[4-(phenyl sulfo-) phenyl]-2-(o-benzoyl base oxime) (IRGACURE
Figure A20068004806500494
OXE01), ethyl ketone 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(adjacent ethanoyl oxime) (IRGACURE
Figure A20068004806500495
OXE02), 9H-thioxanthene-2-formaldehyde 9-oxo-2-(adjacent ethanoyl oxime); oxime ester described in the european patent application No.05111539.2 that submitted on December 1st, 2005; peresters; the benzophenone tetracarboxylic peresters described in the EP126541 for example; the monoacyl phosphine oxide; (2,4,6-trimethylammonium-benzoyl) diphenyl phosphine oxide (DAROCUR for example
Figure A20068004806500496
TPO), diacyl phosphine oxide, for example two-(2,6-dimethoxy-benzoyl)-(2,4,4-trimethylammonium-amyl group) phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenyl phosphine oxide (IRGACURE
Figure A20068004806500497
819); two (2,4, the 6-trimethylbenzoyl)-2; 4-two pentyloxy phenyl-phosphine oxides, three acyl group phosphine oxides, halogenated methyl triazine; 2-[2-(4-methoxyl group-phenyl)-vinyl for example]-4; 6-pair-trichloromethyl-[1,3,5] triazine; 2-(4-methoxyl group-phenyl)-4; two-three chloro-methyl-[1 of 6-; 3,5] triazine; 2-(3,4-dimethoxy-phenyl)-4; 6-pair-trichloromethyl-[1; 3,5] triazine; 2-methyl-4,6-pair-trichloromethyl-[1; 3; 5] triazine; hexa-aryl bi-imidazole/coinitiator system is for example with the adjacent chlorine hexaphenyl of 2-mercaptobenzothiazole bonded-two imidazoles and 4; 4 '-two-(diethylamino) benzophenone ferrocene (ferrocenium) compound; or two luxuriant titaniums, for example two (cyclopentadienyl)-two (2,6-two fluoro-3-pyrryl-phenyl) titanium (IRGACURE
Figure A20068004806500498
784).In addition, borate compound can be used as coinitiator.
If this novel photoinitiator system is used in the heterozygosis system, except this new free-radical stiffening agent, also can use cation light initiator, superoxide, as benzoyl peroxide (it is capable that other suitable superoxide is described in United States Patent (USP) 4950581 the 19th hurdle 17-25), walk to the aromatic sulfonium-, Phosphonium described in the 19th hurdle 10 row-or salt compounded of iodine as United States Patent (USP) 4950581 the 18th hurdle 60, or cyclopentadienyl-aromatic hydrocarbons-iron (II) complex salt, for example (η 6-isopropyl benzene) (η 5-cyclopentadienyl)-iron (II) hexafluorophosphate, and the oxime sulfonates described in for example EP780729.Pyridine described in for example EP497531 and EP441232 and (different) quinolinium also can be used in combination with this novel photoinitiator.
Also can use separately or with other known light trigger and this novel photoinitiator of photosensitizers blended with the form of the dispersion in the water or the emulsion or the aqueous solution.
Meaningfully except that the compound of formula I or II, also comprise at least a alpha-amino group ketone, particularly the composition of (4-methyl thiobenzoyl)-1-methyl isophthalic acid-morpholino ethane or (4-morpholino benzoyl)-1-(4-methyl-benzyl)-1-dimethylaminopropanecompounds.
This photopolymerizable composition comprises the 0.05-25 weight % of solids composition usually, preferred 0.01-10 weight %, the particularly light trigger of 0.01-5 weight %.If adopt the mixture of initiator, this amount is meant the summation of the light trigger of all interpolations.Therefore, this amount is meant this light trigger or photoinitiator mixtures (b) or light trigger (b)+(c).
Except light trigger, this photopolymerizable mixture can also comprise various additives (d).The example of these additives is the hot inhibitor that are used to prevent the premature polymerization reaction, and for example quinhydrones, hydroquinone derivatives, right-methoxyl group phenol, 2-Naphthol or sterically hindered phenol are as 2,6 ditertiary butyl p cresol.In order to improve the lucifuge stability in storage, can use for example copper compound, as copper naphthenate, copper stearate or cupric octoate, phosphorus compound, for example triphenylphosphine, tributylphosphine, triethyl-phosphite, triphenyl phosphite or Tribenzyl Phosphite, quaternary ammonium compound, for example Tetramethylammonium chloride or Variquat B 200, or hydroxylamine derivative, for example N-diethyl hydroxylamine.In order in polymerization process, to get rid of atmosphericoxygen, can add paraffin or similar waxy substance, their solubleness in polymkeric substance is not enough, moves to the surface and form the transparent surface layer that prevents air admission when polymerization begins.Also can on the coating top, spread the not layer of oxygen flow, for example poly-(vinyl alcohol-altogether-vinyl-acetic ester).The photostabilizer that can add on a small quantity is the UV absorption agent, for example those of hydroxy phenyl benzotriazole, hydroxy phenyl-benzophenone, oxamide or hydroxy phenyl-s-triazine type.These compounds can use separately, or use with form of mixtures, can contain or not contain bulky amine (HALS).
The example of this type of UV absorption agent and photostabilizer is
(1.2-2 '-hydroxy phenyl) benzotriazole2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole for example, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethyl butyl) benzotriazole phenyl), 2-(3 ', 5 '-di-t-butyl-2 '-hydroxy phenyl)-the 5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(3 '-sec-butyl-the 5 '-tertiary butyl-2 '-hydroxy phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxy phenyl) benzotriazole, 2-(3 ', 5 '-two-(α, α-Er Jiajibianji)-2 '-hydroxy phenyl) benzotriazole, the mixture of following material: 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen carbonyl of 2-ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl)-5-chlorobenzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxycarbonyl ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-carbonyl octyloxy ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) carbonyl ethyl]-2 '-hydroxy phenyl) benzotriazole, 2-(3 '-dodecyl-2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole and 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the different hot oxygen carbonyl ethyl of 2-) phenyl) benzotriazole; 2,2 '-methylene radical-two [4-(1,1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-base-phenol]; The 2-[3 '-tertiary butyl-5 '-(2-methoxycarbonyl ethyl)-2 '-hydroxy phenyl] product of transesterification reaction of benzotriazole and Liquid Macrogol; [R-CH 2CH 2-COO (CH 2) 3] 2-, R=3 '-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-base-phenyl wherein.
2.2-dihydroxy benaophenonel, for example the 4-hydroxyl-, the 4-methoxyl group-, the 4-octyloxy-, 4-oxygen in last of the ten Heavenly stems base-, the 4-dodecyloxy-, the 4-benzyloxy-, 4,2 ', 4 '-trihydroxy--and 2 '-hydroxyl-4,4 '-dimethoxy derivative.
3. replace or the ester of unsubstituting phenenyl formic acidFor example Whitfield's ointment 4-tert-butyl-phenyl ester, salol, Whitfield's ointment octyl octylphenyl, dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol, benzoyl Resorcinol, 3; 5-di-tert-butyl-4-hydroxybenzoic acid 2; 4-di-tert-butyl-phenyl ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid stearyl and 3,5-di-tert-butyl-4-hydroxybenzoic acid 2-methyl-4,6-di-tert-butyl-phenyl ester.
4. acrylateAlpha-cyano-β for example, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester or ethyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl-p-methoxycinnamic acid butyl ester or methyl esters, α-carboxyl methoxyl group-p-methoxycinnamic acid methyl esters and N-(beta-carbomethoxy-3-beta-cyano vinyl)-2-methyl indoline.
5. bulky amine, for example sebacic acid two (2,2; 6, the 6-tetramethyl piperidine) ester; succsinic acid two (2,2; 6, the 6-tetramethyl piperidine) ester; sebacic acid two (1,2; 2,6,6-pentamethyl-piperidines) ester; normal-butyl-3; 5-di-tert-butyl-4-hydroxyl benzyl propanedioic acid two (1,2,2; 6,6-pentamethyl-piperidines) ester; 1-hydroxyethyl-2,2; 6, the condensation product of 6-tetramethyl--4-hydroxy piperidine and succsinic acid; N, N '-two (2; 2,6, the 6-tetramethyl-piperidyl) hexamethylene-diamine and uncle's 4-octyl group amino-2; 6-two chloro-1,3, the condensation product of 5-s-triazine; nitrilotriacetic acid(NTA) three-(2; 2,6,6-tetramethyl--4-piperidines) ester; 1; 2,3,4-butane tetracid four-(2; 2; 6,6-tetramethyl--4-piperidines) ester; 1,1 '-(1; 2-second two bases)-two (3; 3,5,5-tetramethyl--piperazine ketone); 4-benzoyl-2; 2; 6, the 6-tetramethyl piperidine; 4-stearoyl-oxy-2,2; 6; the 6-tetramethyl piperidine; 2-normal-butyl-2-(2-hydroxyl-3,5-di-t-butyl benzyl) propanedioic acid two-(1,2; 2; 6,6-pentamethyl-piperidines) ester; 3-n-octyl-7,7; 9; 9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2; the 4-diketone; sebacic acid is two-(1-octyloxy-2; 2,6, the 6-tetramethyl piperidine) ester; succsinic acid is two-(1-octyloxy-2; 2; 6, the 6-tetramethyl piperidine) ester; N, N '-two-(2; 2; 6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and 4-Lin Dai-2,6-two chloro-1; 3; the condensation product of 5-triazine; 2-chloro-4,6-two (4-normal-butyl amino-2,2; 6; the 6-tetramethyl-piperidyl)-1,3,5-triazines and 1; the condensation product of 2-pair-(3-amino propyl amino) ethane; 2-chloro-4; 6-two (4-normal-butyl amino-1,2,2; 6; 6-pentamethyl-piperidyl)-1,3,5-triazines and 1; the condensation product of 2-two (3-amino propyl amino) ethane; 8-ethanoyl-3-dodecyl-7; 7,9,9-tetramethyl--1; 3; 8-thriazaspiro [4.5] decane-2, the 4-diketone; 3-dodecyl-1-(2,2; 6; 6-tetramethyl--4-piperidyl) tetramethyleneimine-2,5-diketone and 3-dodecyl-1-(1,2; 2; 6,6-pentamethyl--4-piperidyl) tetramethyleneimine-2, the 5-diketone.
6. oxamideFor example 4,4 '-two octyloxy N, N '-oxalyl pentanoic, 2,2 '-diethoxy N, N '-oxalyl pentanoic, 2,2 '-two octyloxies-5,5 '-di-t-butyl N, N '-oxalyl pentanoic, 2,2 '-two (dodecyl oxygen bases)-5,5 '-di-t-butyl N, N '-oxalyl pentanoic, 2-oxyethyl group-2 '-ethyl-N, N '-oxalyl pentanoic, N, N '-two (3-dimethylamino-propyl) oxamide, 2-oxyethyl group-5-the tertiary butyl-2 '-ethyl n, N '-oxalyl pentanoic, and with 2-oxyethyl group-2 '-ethyl-5,4 '-di-t-butyl N, the mixture of N '-oxalyl pentanoic, adjacent-and right-methoxyl group-and adjacent-and right-oxyethyl group-disubstituted N, the mixture of N '-oxalyl pentanoic.
(7.2-2-hydroxyphenyl)-1,3,5-triazines, for example 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3,5-triazines, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-pair-(2, the 4-3,5-dimethylphenyl)-1,3, the 5-triazine, 2-(2, the 4-dihydroxyphenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2, two (2-hydroxyl-4-propoxy--phenyl)-6-(2, the 4-3,5-dimethylphenyl)-1,3 of 4-, the 5-triazine, 2-(2-hydroxyl-4-octyloxyphenyl)-4, two (the 4-aminomethyl phenyls)-1,3 of 6-, the 5-triazine, 2-(2-hydroxyl-4-dodecyloxy phenyl)-4, two (2, the 4-3,5-dimethylphenyl)-1 of 6-, 3, the 5-triazine, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy-propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy-propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines, 2-[4-dodecyl/tridecyl-oxygen base-(2-hydroxypropyl) oxygen base-2-hydroxyl-phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5-triazines.
8. phosphorous acid ester and phosphinateTriphenyl phosphite for example, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl phenyl) ester, the tricresyl phosphite Lauryl Ester, tricresyl phosphite (octadecyl) ester, diphosphorous acid distearyl pentaerythritol ester, tricresyl phosphite-(2, the 4-di-tert-butyl-phenyl) ester, diphosphorous acid diiso decyl pentaerythritol ester, diphosphorous acid two-(2, the 4-di-tert-butyl-phenyl) pentaerythritol ester, diphosphorous acid two-(2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol ester, two isodecyl oxygen base season of diphosphorous acid the eleventh of the twelve Earthly Branches tetrol ester, diphosphorous acid two-(2,4-di-t-butyl-6-aminomethyl phenyl) pentaerythritol ester, diphosphorous acid two-(2,4,6-tri-tert phenyl) pentaerythritol ester, three tricresyl phosphite stearyl sorbitol esters, two phosphonous acid four (2, the 4-di-tert-butyl-phenyl)-4,4 '-Ya biphenyl ester, 6-iso-octyl oxygen base-2,4,8,10-tetra-tert-12H-dibenzo [d, g]-1,3,2-dioxy phospha eight rings (dioxaphosphocine), 6-fluoro-2,4,8,10-tetra-tert-12-methyl-dibenzo [d, g]-1,3,2-dioxy phospha eight rings, phosphorous acid two-(2,4-di-t-butyl-6-aminomethyl phenyl) methyl ester, with two (2, the 4-di-t-butyl-6-aminomethyl phenyl) ethyl esters of phosphorous acid.
In order to quicken the photopolymerization reaction, can add amine as component (d), for example trolamine, N methyldiethanol amine, right-the dimethylaminobenzoic acid ethyl ester, phenylformic acid 2-(dimethylamino) ethyl ester, right-dimethylaminobenzoic acid 2-ethylhexyl, right-N, N-dimethylaminobenzoic acid monooctyl ester, N-(2-hydroxyethyl)-N-methyl-para-totuidine or Michler's keton.The effect of amine can be strengthened by the aromatic ketone that adds the benzophenone type.Described in EP339841, can be used as the N of example for replacing of the amine of oxygen remover, the N-dialkyl aniline.Described in EP438123, GB2180358 and JP Kokai Hei 6-68309, other promotor, coinitiator and autoxidator are mercaptan, thioether, disulphide, microcosmic salt, phosphine oxide or phosphine.
Can also in composition of the present invention, add this area chain-transfer agent commonly used as component (d).Example is mercaptan, amine and benzothiazole.
The photopolymerization reaction can also be quickened by adding other photosensitizers that can move or widen spectrum sensitivity or coinitiator (as component (d)).These materials are aromatic substance particularly; for example benzophenone and derivative thereof, thioxanthone and derivative thereof, anthraquinone and derivative thereof, tonka bean camphor and thiodiphenylamine and derivative thereof and 3-(aroyl methylene radical) thiazoline, rhodanine, camphorquinone; and eosin, rhodamine, tetraiodofluorescein, xanthene, thioxanthene, acridine; as 9-phenylacridine, 1; two (9-acridyl) heptane, 1 of 7-, two (9-acridyl) pentanes of 5-, cyanine and merocyanine dyes.
The specific examples of these compounds is
1. thioxanthone
Thioxanthone, the 2-isopropyl thioxanthone, the 2-clopenthixal ketone, 1-chloro-4-propoxy-thioxanthone, 2-dodecyl thioxanthone, 2, the 4-diethyl thioxanthone, 2,4-dimethyl thioxanthone, 1-methoxycarbonyl thioxanthone, 2-ethoxy carbonyl thioxanthone, 3-(2-methoxy ethoxy carbonyl)-thioxanthone, 4-butoxy carbonyl thioxanthone, 3-butoxy carbonyl-7-methyl thioxanthone, 1-cyano group-3-clopenthixal ketone, 1-ethoxy carbonyl-3-clopenthixal ketone, 1-ethoxy carbonyl-3-oxyethyl group thioxanthone, the amino thioxanthone of 1-ethoxy carbonyl-3-, 1-ethoxy carbonyl-3-phenyl sulfonyl thioxanthone, 3,4-two-[2-(2-methoxy ethoxy) ethoxy carbonyl]-thioxanthone, 1,3-dimethyl-2-hydroxyl-9H-thioxanthene-9-one, 2-ethylhexyl ether, 1-ethoxy carbonyl-3-(1-methyl isophthalic acid-morpholino ethyl) thioxanthone, 2-methyl-6-dimethoxy-methyl-thioxanthone, 2-methyl-6-(1, the 1-dimethoxy-benzyl)-thioxanthone, 2-morpholino methyl thioxanthone, 2-methyl-6-morpholino methyl thioxanthone, N-allyl group thioxanthone-3, the 4-dicarboximide, N-octyl group thioxanthone-3, the 4-dicarboximide, N-(1,1,3, the 3-tetramethyl butyl) thioxanthone-3, the 4-dicarboximide, 1-propoxy-thioxanthone, 6-ethoxy carbonyl-2-methoxyl group thioxanthone, 6-ethoxy carbonyl-2-methyl thioxanthone, thioxanthone-2-formic acid macrogol ester, 2-hydroxyl-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-base oxygen base)-N, N, N-trimethylammonium-1-chlorination propylamine;
2. benzophenone
Benzophenone, the 4-phenyl benzophenone, the 4-methoxy benzophenone, 4,4 '-dimethoxy-benzophenone, 4,4 '-dimethyl benzophenone, 4,4 '-dichloro benzophenone, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (methylethyl amino) benzophenone, 4,4 '-two (right-the sec.-propyl phenoxy group) benzophenone, 4-methyldiphenyl ketone, 2,4, the 6-tri-methyl benzophenone, 4-(4-methyl thio-phenyl) benzophenone, 3,3 '-dimethyl-4-methoxy benzophenone, 2-benzoyl methyl benzoate, 4-(2-hydroxyethyl sulfo-) benzophenone, 4-(the 4-tolyl is dredged generation) benzophenone, 1-[4-(4-benzoyl phenyl sulfo-)-phenyl]-2-methyl-2-(toluene-4-alkylsulfonyl)-third-1-ketone, the 4-benzoyl-N, N, N-Three methyl Benzene methylamine muriate, 2-hydroxyl-3-(4-benzoyl phenoxy group)-N, N, N-trimethylammonium-1-propylamine muriate-hydrate, 4-(13-acryl-1,4,7,10,13-five oxa-tridecyls)-benzophenone, the 4-benzoyl-N, N-dimethyl-N-[2-(1-oxo-2-propenyl) oxygen base] ethyl-benzene methanamine muriate;
3. tonka bean camphor
Tonka bean camphor 1, tonka bean camphor 2, coumarin 6, tonka bean camphor 7, tonka bean camphor 30, tonka bean camphor 102, Coumarin 106, tonka bean camphor 138, tonka bean camphor 152, tonka bean camphor 153, tonka bean camphor 307, tonka bean camphor 314, tonka bean camphor 314T, tonka bean camphor 334, tonka bean camphor 337, tonka bean camphor 500,3-benzoyl tonka bean camphor, 3-benzoyl-ayapanin, 3-benzoyl-5, the 7-escoparone, 3-benzoyl-5,7-dipropoxy tonka bean camphor, 3-benzoyl-6,8-two Clocoumarol, 3-benzoyl-6-Clocoumarol, 3,3 '-carbonyl-two [5,7-two (propoxy-)-tonka bean camphor], 3,3 '-carbonyl-two (ayapanin), 3,3 '-carbonyl-two (7-diethyl amino coumarin), 3-isobutyryl tonka bean camphor, 3-benzoyl-5,7-dimethoxy-tonka bean camphor, 3-benzoyl-5,7-diethoxy-tonka bean camphor, 3-benzoyl-5,7-dibutoxy-tonka bean camphor, 3-benzoyl-5,7-two (methoxy ethoxy)-tonka bean camphor, 3-benzoyl-5,7-two (allyl group oxygen base)-tonka bean camphor, 3-benzoyl-7-dimethylamino-tonka bean camphor, 3-benzoyl-7-diethyl amino coumarin, 3-isobutyryl-7-dimethylamino tonka bean camphor, 5,7-dimethoxy-3-(1-naphthoyl base) tonka bean camphor, 5,7-diethoxy-3-(1-naphthoyl base) tonka bean camphor, 3-benzoyl benzo [f] tonka bean camphor, 7-diethylamino-3-thiophene acyl group tonka bean camphor, 3-(4-cyano group benzoyl)-5, the 7-escoparone, 3-(4-cyano group benzoyl)-5,7-dipropoxy tonka bean camphor, 7-dimethylamino-3-phenyl tonka bean camphor, 7-diethylamino-3-phenyl tonka bean camphor, disclosed coumarin derivatives among JP 09-179299-A and the JP09-325209-A, for example 7[{4-chloro-6-(diethylamino)-S-triazine-2-yl } amino] 3-phenyl tonka bean camphor;
(4.3-aroyl methylene radical) thiazoline
3-methyl-2-benzoyl methylene radical-β-aphthothiazoles quinoline, 3-methyl-2-benzoyl methylene radical benzo thiazoline, 3-ethyl-2-propionyl methylene radical-β-aphthothiazoles quinoline;
5. rhodanine
The Rhodanine derivant of disclosed formula [1], [2], [7] among 4-dimethylamino benzylidene rhodanine, 4-diethylamino benzylidene rhodanine, 3-ethyl-5-(3-octyl group-2-[4-morpholinodithio quinoline base)-rhodanine, the JP 08-305019A;
6. other compound
Methyl phenyl ketone; the 3-methoxyacetophenone; 4-phenyl methyl phenyl ketone; benzil; 4; 4 '-two (dimethylamino) benzil; 2 acetyl naphthalene; the 2-naphthaldehyde; red sulfonic acid; 9; the 10-anthraquinone; anthracene; pyrene; amino pyrene perylene; luxuriant and rich with fragrance; phenanthrenequione; the 9-Fluorenone; dibenzosuberone; turmeric; xanthone; the sulfo-Michler's keton; α-(4-dimethylamino benzylidene) ketone; as 2; two (the 4-diethylamino benzylidene) cyclopentanone of 5-; 2-(4-dimethylamino benzylidene)-1-Indanone; 3-(4-dimethylaminophenyl)-1-indenes-5-base-acetone; 3-thiophenyl phthalic imidine; N-methyl-3; 5-two (ethyl sulfenyl)-phthalic imidine; N-methyl-3; 5-two (ethyl sulfenyl)-phthalic imidine; thiodiphenylamine; the methyl thiodiphenylamine; amine, for example N-phenylglycine; 4-dimethylaminobenzoic acid ethyl ester; 4-dimethylaminobenzoic acid butoxy ethyl ester; 4-dimethylamino benzoylformaldoxime; trolamine; methyldiethanolamine; dimethylaminoethanol; phenylformic acid 2-(dimethylamino) ethyl ester; poly-(propylene glycol)-4-(dimethylamino) benzoic ether.
The photopolymerizable composition that also comprises the further additive (d) of photosensitizers conduct that is selected from benzophenone and derivative, thioxanthone and derivative thereof, anthraquinone and derivative thereof or coumarin derivatives is preferred.
By adding photosensitizers, particularly in the composition of painted (for example use titanium dioxide painted), and by being added under the heat condition component that forms free radical, azo-compound for example is as 2, two (the 4-methoxyl groups-2 of 2 '-azo, the 4-methyl pentane nitrile), triazene, diazonium sulphur, pentazdiene or peralcohol, for example hydroperoxide or percarbonate, for example the tertbutyl peroxide described in EP245639 can be assisted solidification process.
Composition of the present invention can comprise the light curable dyestuff, for example xanthene-, benzodiphenylene oxide-, benzothioxanthene, thiazine-, pyronine-, tetrazaporphin-or acridine dye, and/or trihalogenmethyl compound that can be by radiation cleavage is as further additive (d).For example among the EP445624 similar compositions is being described.
Other additive known in the art can be used as component (d) and adds, FLOW IMPROVERS for example, tackifier, as vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane and 3-sulfydryl propyl trimethoxy silicane.Tensio-active agent, white dyes, pigment, dyestuff, wetting agent, even flat auxiliary agent, dispersion agent, aggregation-preventing agent, antioxidant or filler are other examples of additive (d).
Described in for example US 5013768,, can suitably add glass microsphere or powdered glass fiber in order to solidify thick and painted coating.
That has mentioned as mentioned is such, and other suitable component (d) is tensio-active agent and dispersion agent and other component, to support the application in this prescription of pigment or tinting material especially.
Preferably pigment is imposed surface treatment so that make pigment be easy to disperse, and make gained pigment dispersion stabilization.Surface treatment agent is for example tensio-active agent, polymeric dispersant, common quality improving agent, pigment derivative and composition thereof.When dye compositions of the present invention comprises at least a polymeric dispersant and/or at least during pigment derivative, this is especially preferred.
Suitable tensio-active agent comprises anion surfactant, as alkylbenzene-or alkylnaphthalene-sulphonate, alkylthio succinate or naphthaldehyde sulphonate; Cats product comprises for example quaternary ammonium salt, as benzyl tributyl ammonium chloride; Or non-ionic type or amphoterics, respectively as polyoxyethylene surfactant and alkyl-or amido propyl betaine.
The illustrative examples of tensio-active agent comprises Voranol EP 2001, as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ether is as polyoxyethylene octyl phenyl ether and polyoxyethylene nonylplenyl ether; Polyethylene glycol di is as polyethylene glycol dilaurate and polyglycol distearate; Sorbitan aliphatic ester; Fatty acid modified polyester; The tertiary amine modified polyurethane; Polymine; Can be with KP (Shin-EtsuChemical Co., the product of Ltd), Polyflow (KYOEISHA CHEMICAL Co., the product of Ltd), F-Top (Tochem Products Co., the product of Ltd), MEGAFAC (Dainippon Ink ﹠amp; Chemicals, the product of Inc.), Fluorad (product of Sumitomo 3M Ltd), Asahi Guard and Surflon (Asahi Glass Co., the product of Ltd) obtain for trade(brand)name those; And analogue.
These tensio-active agents can use separately, or use with two or more mixture.
Usually, per 100 weight part dye compositions use 50 weight parts or still less, the tensio-active agent of preferred 0 to 30 weight part.
Polymeric dispersant comprises the high-molecular weight polymer with pigment affinity (affinic) group.Example is: by for example statistical copolymer of styrene derivatives, (methyl) acrylate and (methyl) acrylamide formation, and this type of statistical copolymer that passes through the modification of post-modification method; By for example segmented copolymer and/or the comb-shaped copolymer of styrene derivatives, (methyl) acrylate and (methyl) acrylamide formation, and this based block copolymer and/or the comb shaped polymer that pass through the modification of post-modification method; Polymine, it for example uses the polyester grafting; Polyamine, it for example uses the polyester grafting; With polytype (modification) urethane.
Also can use polymeric dispersant.Suitable polymeric dispersant is BYK ' s DISPERBYK for example
Figure A20068004806500571
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 SpecialtyChemicals ' Ciba
Figure A20068004806500572
EFKA
Figure A20068004806500573
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 ' s PB
Figure A20068004806500574
711,821,822,823,824,827, Lubrizol ' s SOLSPERSE
Figure A20068004806500575
1320,13940,17000,20000,21000,24000,26000,27000,28000,31845,32500,32550,32600,33500,34750,36000,36600,37500,39000,41090,44000,53095 and the combination.
Preferred Ciba
Figure A20068004806500576
EFKA
Figure A20068004806500577
4046,4047,4060,4300,4330,4340, DISPERBYK
Figure A20068004806500578
161162,163,164,165,166,168,169,170,2000,2001,2020,2050,2090,2091,2095,2096,2105,2150, PB
Figure A20068004806500579
711,821,822,823,824,827, SOLSPERSE
Figure A200680048065005710
24000,31845,32500,32550,32600,33500,34750,36000,36600,37500,39000,41090,44000,53095 and the combination use as dispersion agent.
Suitable quality improving agent is a lipid acid for example, as stearic acid or docosoic acid, and aliphatic amide, as lauryl amine and stearylamine.In addition, can use the Fatty Alcohol(C12-C14 and C12-C18) polyvalent alcohol of Fatty Alcohol(C12-C14 and C12-C18) or ethoxylation for this purpose, for example aliphatics 1,2-glycol or epoxidised soybean oil, wax, resinous acid and resinate.
Suitable pigment derivative is a copper phthalocyanine derivative thing for example, as CibaSpecialty Chemicals ' Ciba
Figure A20068004806500581
EFKA
Figure A20068004806500582
6745, Lubrizol ' s SOLSPERSE
Figure A20068004806500583
5000,12000, BYK ' sSYNERGIST 2100 and azo derivative are as Ciba
Figure A20068004806500584
EFKA
Figure A20068004806500585
6750, SOLSPERSE
Figure A20068004806500586
22000 and SYNERGIST2105.
In composition of the present invention, particularly in the colour filter prescription, for example use above-mentioned pigment dispersant and tensio-active agent as the resist prescription.
Application Areas and the required performance in this field are depended in the selection of additive (d).Above-mentioned additive is this area routine, therefore adds with amount common in each self-application.
Also can in this novel compositions, add tackiness agent (e).When photopolymerizable compound is liquid or viscous substance, this particularly advantageous.With respect to total solid content, the amount of tackiness agent can be 2-98 weight % for example, preferred 5-95 weight %, especially 20-90 weight %.The required performance of Application Areas and this field is depended in the selection of tackiness agent, for example the development capability in water-based and organic solvent system, with the binding property of substrate with to the susceptibility of oxygen.
The example of suitable binder is that molecular weight is about 2000 to 2000000, preferred 3000 to 1000000 polymkeric substance.The example of alkali developable tackiness agent is to have the acrylic polymers of carboxylic acid functional as side group, for example by for example making (methyl) vinylformic acid, 2-carboxy ethyl (methyl) vinylformic acid, 2-carboxyl propyl group (methyl) vinylformic acid, methylene-succinic acid, Ba Dousuan, toxilic acid, the ethylenically unsaturated carboxylic acids of fumaric acid and ω-carboxyl polycaprolactone list (methyl) acrylate and one or more are selected from following monomer copolymerization and the conventional known multipolymer that obtains: (methyl) acrylic acid ester, as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) benzyl acrylate, (methyl) 2-EHA, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, single (methyl) vinylformic acid glyceryl ester, (methyl) vinylformic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid 2-methyl glycidyl ester, (methyl) vinylformic acid 3,4-epoxy butyl ester, (methyl) vinylformic acid 6,7-epoxy heptyl ester; Vinyl aromatic compounds is as vinylbenzene, alpha-methyl styrene, Vinyl toluene, right-chloro-styrene, vinyl benzyl glycidyl ether; The acid amide type unsaturated compound, (methyl) acrylamide diacetone acrylamide, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide; With the polyolefin-type compound, as divinyl, isoprene, chloroprene and analogue; Methacrylonitrile, methyl isopropenyl ketone, mono succinate-2-[(methyl) acryloxy] ethyl ester, N-phenylmaleimide, maleic anhydride, vinyl-acetic ester, propionate, new vinyl acetate acid, the big monomer of polystyrene or the poly-big monomer of (methyl) methyl acrylate.The example of multipolymer be acrylate and methacrylic ester and acrylic or methacrylic acid and with multipolymer, the resol of vinylbenzene or substituted phenylethylene, for example multipolymer of lacquer resins, (gathering) hydroxy styrenes and hydroxy styrenes and alkyl acrylate, vinylformic acid and/or methacrylic acid.The preferred embodiment of multipolymer is the multipolymer of methyl methacrylate/methacrylic acid, the multipolymer of methacrylic acid benzyl ester/methacrylic acid, the multipolymer of methyl methacrylate/ethyl acrylate/methacrylic acid, methacrylic acid benzyl ester/methacrylic acid/cinnamic multipolymer, the multipolymer of methacrylic acid benzyl ester/methacrylic acid/methacrylic acid hydroxyethyl ester, methyl methacrylate/butyl methacrylate/methacrylic acid/cinnamic multipolymer, the multipolymer of methyl methacrylate/methacrylic acid benzyl ester/methacrylic acid/methacrylic acid hydroxyl phenylester.Can the develop example of binder polymer of solvent is poly-(alkyl methacrylate), poly-(alkyl acrylate), poly-(methacrylic acid benzyl ester-altogether-methacrylic acid hydroxyethyl ester-altogether-methacrylic acid), poly-(methacrylic acid benzyl ester-altogether-methacrylic acid); Cellulose ester and ether of cellulose are as rhodia, acetobutyric acid Mierocrystalline cellulose, methylcellulose gum, ethyl cellulose; Polyvinyl butyral, polyvinyl methylal, cyclisation rubber amine, polyethers are as polyethylene oxide, poly(propylene oxide) and polytetrahydrofuran; The multipolymer of polystyrene, polycarbonate, urethane, chlorinatedpolyolefins, polyvinyl chloride, vinylchlorid/vinylidene chloride copolymer, vinylidene chloride and vinyl cyanide, methyl methacrylate and vinyl-acetic ester, polyvinyl acetate, copolymerization (Ethylene/vinyl acetate), polymkeric substance, as polycaprolactam and poly-(hexa-methylene hexanamide) and polyester, as poly-(ethylene glycol terephthalate) and poly-(succsinic acid hexylene glycol ester) and polyimide adhesive resin.
Polyimide adhesive resin among the present invention can be solvent soluble polyimide or polyimide precursor, for example poly-(amido acid).
The multipolymer that comprises methacrylic ester and methacrylic acid is preferred as the photopolymerizable composition of binder polymer (e).
Further meaningfully described in JP 10-171119-A, be used in the polymeric binder component in the colour filter especially.
This photopolymerizable composition can be used for various uses, for example as printing-ink, as screen printing ink, be used for hectograph-or the printing ink of flexographic printing, as clear finish (finish), as white or colored final lacquer, for example be used for timber or metal, as powder coating, as coating material, in particular for paper, timber, metal or plastics, as buildings mark or pavement marker use can day photo-cured coating, be used for the photocopying technology, be used for hologram recording material, the printing plate that is used for the image recording technology or is used to produce available organic solvent or develops with alkali aqueous solution, be used to make the silk screen printing mask, as the dentistry filling components, as tackiness agent, as pressure sensitive adhesive, as laminating resin, as anti-etching dose, solder resist, platedresist, or permanent resist, liquid and desciccator diaphragm, as can photic structurized dielectric medium, be used for printed circuit board (PCB) and electronic circuit, as making the resist that the colour filter be used for various demonstration purposes uses or being used to produce the resist that the structure of plasma display panel and electroluminescent display is used, (as for example US5853446, EP863534, JP09-244230-A, JP 10-62980-A, JP08-171863-A, US5840465, EP 855731, JP 05-271576-A, described in the JP 05-67405-A), be used to make holographic data storage (HDS) material, be used to make optical switch, grating (interference grating), optical circuit, be used for making three-dimensional article by integrally curing (solidifying) or by stereolithography techniques at transparent mould UV, for example described in the US4575330, be used to make matrix material (polystyrene polyester for example, if desired, it can contain glass fibre and/or other fiber and other auxiliary agent) and other thick layered composition, be used for coating or seal electronic element and unicircuit, or as fibre-optic coating, or be used to make optical lens, as contact lens or Fresnel lens.Composition of the present invention also is applicable to the manufacturing of medical facilities, auxiliary material or implant.In addition.Composition of the present invention also is applicable to the preparation of the gel with thermotropic denaturalization matter, for example described in DE19700064 and the EP678534.
This novel photoinitiator can be used as the initiator of letex polymerization, pearl polymerization or suspension polymerization in addition, the polymerization starter of using as the order state of fixing liquid crystal monomer and oligopolymer or be used as the initiator that dyestuff fixing is used on organic materials.
In coating material, often use the mixture of prepolymer and many unsaturated monomers, it can also comprise single insatiable hunger monomer in addition.The performance that prepolymer is filmed in this major decision, and by changing prepolymer, the technician can influence the performance of cured film.Many unsaturated monomers serve as makes the insoluble linking agent of film.Single unsaturated monomer serves as the reactive diluent that is used to reduce viscosity and need not to use solvent.
Common and the single unsaturated monomer of unsaturated polyester resin preferably is used in the bicomponent system with vinylbenzene.For photo-resist, use specific single-component system usually, for example the poly maleimide described in DE2308830, poly-phenyl styryl ketone or polyimide.
This novel photoinitiator and composition thereof also can be used for the polymerization of the powder coating of radiation-hardenable.Powder coating can be based on solid resin that contains reactive double bond and monomer, for example maleic acid ester, vinyl ether, acrylate, acrylamide and composition thereof.The curable powder coating of free radical UV can be prepared by unsaturated polyester resin is mixed with solid acrylamide (for example methacrylamido methyl glycolate) and new free-radical light trigger, these Formulation Examples are as being described in the paper " Radiation Curing of Powder Coating (radiation curing of powder coating) " (Conference Proceedings, Radtech Europe 1993 (M.Wittig and Th.Gohmann)).Powder coating can also contain just like the tackiness agent described in DE4228514 and the EP636669.The powder coating of free radical UV-curable also can be prepared by unsaturated polyester resin is mixed with solid propenoic acid ester, methacrylic ester or vinyl ester and with novel photoinitiator (or photoinitiator mixtures).This powder coating also can comprise the tackiness agent described in for example DE4228514 and EP636669.The curable powder coating of UV can comprise white or coloured pigment in addition.For example, rutile titanium dioxide can preferably use with the concentration of maximum 50% weight, thereby produces the curing powder coating with good opacifying power.Its program generally includes electrostatic powder spraying or friction electrostatic painting is arrived substrate, for example on metal or the timber,, and after forming smooth film, coating is solidified with ultraviolet ray and/or visible radiation powder smelting by heating, for example use medium pressure mercury lamp, metal halide lamp or xenon lamp.The powder coating of radiation-hardenable is that with the certain benefits that its heat-setting homologue is compared the flowing time behind the melting powder particle can postpone to guarantee to form level and smooth high-gloss coating.Be different from heat-curable systems, the powder coating of radiation-hardenable can be mixed with fusing at a lower temperature, and does not shorten the not desirable influence in its life-span.For this reason, they also are suitable as the coating of temperature-sensitive substrate (for example timber or plastics).Except this novel photoinitiator system, the powder coating prescription can also contain the UV absorption agent.Suitable example is listed in the above-mentioned 1-8 joint.
This novel photocurable composition for example is suitable as all types of substrates (will apply protective layer thereon; or by producing image according to pattern exposure) coating; for example timber, textiles, paper, pottery, glass, plastics are (as polyester, polyethylene terephthalate, polyolefine or rhodia; especially be the plastics of form of film); and metal, as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO 2
This novel radiation sensitive composition further finds can be used as negative resist, and it has high photosensitivity and can develop in the buck medium and can swelling.They are suitable for making the press plate or the screen printing plate that are used for letterpress, lithography, rotogravure, are used to make the relief printing plate copy, for example be used for making the braille French this, little resist of being used for making stamp, being used in chemical grinding or making as unicircuit.But said composition also can be used as the dielectric layer of light drawing or coating, encapsulating material and insulating coating, printing plate and other electric or electronic component in computer chip is made.The possible layer carrier and the processing conditions of coat substrates can reasonable change.
Novel compositions also relates to photosensitive thermosetting resin composition and forms the method for soldering-resistant pattern with it, relate more specifically to novel photosensitive thermosetting resin composition, the material that it can be used as the preparation usefulness of the embossment of etching, plastics of precision manufacturing, glass and the stone goods of printed circuit board (PCB) manufacturing, metal products and printing plate can be used as the solder resist of printed circuit board (PCB) especially; And relate to the method that forms soldering-resistant pattern by following steps: with actinic rays selectivity exposure resin combination layer, the unexposed portion of this layer is developed via photomask with pattern.
Solder resist is to prevent being used to of using in the time will being welded on the printed circuit board (PCB) to limiting-members that melt flux from adhering on the irrelevant part and the material of holding circuit.Therefore, need have following character: high-adhesiveness, insulation resistance, anti-welding temperature, solvent resistance, alkali resistance, acid resistance and anti-plating.
Because Photocurable composition of the present invention has good thermostability and is enough to prevent that by oxygen quenching they are specially adapted to make colour filter or colored mosaic system described in for example EP320264.Colour filter is usually used in making LCD, optical projection system and image sensor.Colour filter can for example be used for television receiver indicating meter and image reading apparatus, video monitor or computer, be used for flat panel display etc.
Colour filter is made by formation redness, green and blue pixel and black matix on substrate of glass usually.In these methods, can adopt Photocurable composition of the present invention.Particularly preferred using method comprises: add coloring material in photosensitive resin composition of the present invention, redness, green and blue dyes and pigment, use the said composition coat substrates, by short period of time thermal treatment with the coating drying, coating is exposed in the actinic radiation according to pattern, subsequently pattern is developed in alkaline developer solution and optional thermal treatment.Thus, by on each layer, applying redness, green and blue-colored coating with this method, can make colour filter with redness, green and blue pixel by any desired sequence.
By not developing the zone of convergency with appropriate base developing solution flush away.Repeat this process to form multicolor image.
In photosensitive resin composition of the present invention,, can use above-mentioned pixel as shadow mask by at first never forming the method for exposing on the transparent substrates one side of above-mentioned pixel then at the one or more at least pixels of formation on the transparent substrates.In this case, for example when carrying out overall exposing, mask need not to carry out position adjustments, also need not consider its position slippage.And, can solidify all parts that do not form above-mentioned pixel on it.In addition, in this case, a part that does not form the position of above-mentioned pixel owing to using the part shadow mask thereon can also be developed and removes.
Because in either case, the pixel that forms before and after do not form the gap between the pixel of formation, composition of the present invention for example is applicable to the formed material of colour filter.Particularly, in photosensitive resin composition of the present invention, add coloring material, redness, green and blue dyes and pigment, the complex of laying equal stress on becomes the process of image to form redness, green and blue pixel.Then, on whole, provide the photosensitive resin composition that has wherein added black colorant material, dyestuff and pigment.(or except the regional area of shadow mask everywhere) the formation black pixel that can provide overall exposing (or via shadow mask part exposure) thereon so that in the whole space between red, green and blue pixel.
Except coating photosensitive resin composition and exsiccant method in substrate, can also use photosensitive resin composition of the present invention as layer transferred material.That is to say that photosensitive resin composition preferably on polyethylene terephthalate thin film, or has on the polyethylene terephthalate thin film of oxygen barrier layer and peel ply or peel ply and oxygen barrier layer and successively provides directly on interim carrier thereon.Usually, will press thereon so that protection to be provided when operating by the removable cover layer that synthetic resins is made.In addition, also can the applied layer structure---solvable thermoplastic resin of alkali and middle layer wherein are being provided on interim carrier and photosensitive resin composition layer (JP 5-173320-A) further is being provided thereon.
Remove above-mentioned cover plate in use and photosensitive resin composition is pressed on the permanent carrier layer by layer.Subsequently, when oxygen barrier layer and peel ply are provided between these layers and interim carrier, when peel ply and oxygen barrier layer are provided between peel ply and oxygen barrier layer, and when peel ply or oxygen barrier layer are provided temporarily between carrier and the photosensitive resin composition, peel off, and remove interim carrier.
Metallic carrier, glass, pottery and synthetic resin film can be used as the carrier of colour filter.Transparent and to have the glass and a synthetic resin film of excellent size stability preferred especially.
The thickness of photosensitive resin composition layer is generally 0.1 to 50 micron, particularly 0.5 to 5 micron.
If said composition contains alkali soluble resins or caustic solubility monomer or oligopolymer, the developing solution that can use the dilute aqueous solution of alkaline matter to use as photosensitive resin composition of the present invention, and also can further comprise by adding the developer solution that a spot of water miscibility organic solvent is made therein.
The example of suitable basic material comprises alkali metal hydroxide (for example sodium hydroxide and potassium hydroxide), alkaline carbonate (for example yellow soda ash and salt of wormwood), alkali metal hydrocarbonate (for example sodium bicarbonate and saleratus), alkalimetal silicate (for example water glass and potassium silicate), alkalimetal silicate (for example water glass and potassium silicate), trolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxide (for example tetramethyl ammonium hydroxide) or tertiary sodium phosphate.The concentration of alkaline matter is 0.01 to 30 weight %, and the pH value is preferably 8 to 14.
The appropriate organic solvent miscible with water comprises methyl alcohol, ethanol, the 2-propyl alcohol, the 1-propyl alcohol, butanols, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, ethyl-3-ethoxy-c acid esters, methyl-3-methoxyl group-propionic ester, n-butyl acetate, benzylalcohol, acetone, methylethylketone, cyclopentanone, pimelinketone, 2-heptanone, 2 pentanone, 6-caprolactone, gamma-butyrolactone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-Ji Neixianan and N-methyl-pyrrolidone.With the concentration of the miscible organic solvent of water be 0.1 to 30 weight %.
In addition, can add known tensio-active agent.Surfactant concentrations is preferably 0.001 to 10 weight %.
Photosensitive resin composition of the present invention can also comprise that the mixture of two or more solvents develops with the organic solvent of alkali-free compound.Suitable solvent comprises methyl alcohol, ethanol, the 2-propyl alcohol, the 1-propyl alcohol, butanols, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, the glycol monomethyl n-butyl ether, diglyme, propylene glycol monomethyl ether, ethyl-3-ethoxy-c acid esters, methyl-3-methoxy propyl acid esters, n-butyl acetate, benzylalcohol, acetone, methylethylketone, cyclopentanone, pimelinketone, 2-heptanone, 2 pentanone, 6-caprolactone, gamma-butyrolactone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-Ji Neixianan, and N-Methyl pyrrolidone.Randomly, can in these solvents, add entry, need only the enough solubleness that still obtains clear solution and keep the unexposed area of photosensitive composition.
Developing solution can use with any form well known by persons skilled in the art, for example the form of tank liquor (bath solution), mud or spray solution.In order to remove the uncured portion of photosensitive resin composition layer, can merge method as rotating brush friction and wet sponge friction and so on.Usually, the temperature of developing solution preferably or near about room temperature to 40 ℃.Development time can according to the alkalescence of the concrete kind of photosensitive resin composition, developing solution and temperature and under the situation that adds organic solvent the kind and the concentration of this organic solvent become.Usually, it is 10 seconds to 2 minutes.Can after development treatment, carry out rinse step.
Final thermal treatment is preferably carried out after development treatment.Therefore, the carrier that will have by exposure polymeric layer (below be called photocurable layers) heats in electric furnace and moisture eliminator, or with photocurable layers with infrared lamp irradiation or on hot plate, heat.Heating temperature and time are depended on the thickness of compositions for use and formed layer.In general, heating was preferably carried out under about 120 to about 250 ℃ about 5 to about 60 minutes.
The pigment optimization that can be included in the present composition (the colour filter corrosion-resistant composition that comprises pigment coloring) is finished pigment, for example by pigment being finely dispersed at least a powdery or the paste product of making in the resin of acrylic resin, vinyl chloride vinyl acetate copolymer, maleic acid resin and ethyl cellulose resin that be selected from.
Red pigment comprises for example independent anthraquinone type pigment, independent diketopyrrolo-pyrrole type pigment, their mixture or the mixture that constitutes by at least a and tetrazo type yellow ultramarine in them or isoindoline type yellow ultramarine, particularly independent C.I. Pigment red 177, independent C.I. Pigment red 254, C.I. the mixture of Pigment red 177 and C.I. Pigment red 254, or the mixture that constitutes by at least a and C.I. pigment yellow 83 or the C.I. pigment yellow 13 9 of C.I. Pigment red 177 and C.I. Pigment red 254 (" C.I. " represents colour index, and this is that those skilled in the art are known and can openly obtain).
The example that other of pigment is suitable is a C.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. pigment Yellow 12,13,14,17,20,24,31,53,55,93,95,109,110,128,129,138,139,150,153,154,155,166,168,185,199,213 and C.I pigment orange 43.
The example of orchil is a C.I. solvent red 25,27,30,35,49,83,89,100,122,138,149,150,160,179,218,230, C.I. directly red 20,37,39,44, with C.I. Xylene 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. alkali red 1:1 2,13, C.I. Disperse Red 5,7,13,17 and 58.Orchil can be used in combination with yellow and/or orange dye.
Veridian comprises the mixture of for example independent halogenated phthalocyanines type pigment or itself and tetrazo type yellow ultramarine, quinophthalone (quinophthalone) type yellow ultramarine or metal complex, the mixture that at least a and C.I. pigment yellow 83 of particularly independent C.I. pigment Green 7, independent C.I. pigment green 36 or C.I. pigment Green 7, C.I. pigment green 36, C.I. pigment yellow 13 8 or C.I. Pigment Yellow 73 150 constitute.Other suitable veridian is a C.I. Pigment green 15,25 and 37.
The example of suitable green colouring material is a C.I. acid green 3,9,16, C.I. alkali green 1 and 4.
The example of suitable blue pigments is a phthalocyanine type pigment, can be used in combination for example independent C.I. pigment Blue 15 separately or Yu dioxazine type violet pigment: 6, and C.I. pigment Blue 15: 6 and the combination of C.I. pigment Violet 23.Other example of blue pigments is the C.I. pigment Blue 15: 3,15:4,16,22,28 and 60.Other suitable pigment is C.I. pigment violet 14,19,23,29,32,37,177 and C.I. orange 73.
The example of suitable blue dyes is a C.I. solvent blue 25,49,68,78,94, C.I. sun blue 25,86,90,108, C.I. Blue VRS, 7,9,15,103,104,158,161, C.I. alkali blue 1,3,9,25 and C.I. disperse Blue 19 8.
The pigment optimization of the photopolymerizable composition that black matix is used comprises and is selected from least a of the black and ferric oxide of carbon black, titanium.But also can use the common generation black mixture of other existing pigment outward.For example, also can separately or be used in combination C.I. Pigment black 1,7 and 31.
Other example of the dyestuff that colour filter is used is the C.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. DISPERSE YELLOW 3,4,7,31,54,61,201, C.I. direct yellow 1,11,12,28, C.I. turmeric yellow 1,3,11,17,23,38,40,42,76,98, C.I. basic yellow 1, C.I. solvent violet 13,33,45,46, C.I. 63 ,DIS,PER,SE ,Vio,let, 63 22,24,26,28, C.I. acid violet 49, C.I. alkalescence purple 2,7,10, C.I. the solvent orange 1,2,5,6,37,45,62,99, C.I. von Muller's indicator 1,7,8,10,20,24,28,33,56,74, C.I. direct orange 1, C.I. DISPERSE ORANGE 30 200 5, C.I. direct brown 6,58,95,101,173, C.I. ACID BROWN 14, C.I. solvent black 3,5,7,27,28,29,35,45 and 46.
Under some particular cases of making colour filter, use the complementarity color, yellow, magenta, cyan and optional green replacement are red, green and blue.As the yellow that such colour filter is used, can use above-mentioned yellow ultramarine and dyestuff.The example that is fit to the colorant of magenta is a C.I. pigment red 122,144,146,169,177, C.I. pigment violet 19 and 23.The example of cyan is aluminum phthalocyanine pigment, phthalocyanine titanium pigment, phthalocyanine cobalt pigment and phthalocyanine tin pigment.
For any color, also can use the combination of two or more pigment.What be particularly useful for the colour filter purposes is by with the finely divided powdery processed pigment of making in the resin of above-mentioned pigment.
The concentration of pigment in total solids component (versicolor pigment and resin) for example is 5 weight % to 80 weight %, particularly 20 weight % to 45 weight %.
Pigment optimization in the colour filter resist composition has the median size less than visible wavelength (400 nanometer to 700 nanometer).Particularly preferred average pigment particle size is less than 100 nanometers.
If desired, by using dispersion agent pre-treatment pigment, can make pigment stabilization in photosensitive composition to improve the dispersion stabilization of pigment in this liquid preparation.Suitable additive has been described above.
Preferably, but colour filter resist composition of the present invention contains the monomeric compound of at least a addition polymerization in addition as component (a).
Ethylenically unsaturated compounds (a) comprises one or more olefinic double bonds, and they can have low (monomer) or high (oligomeric) molecular weight.Double bond containing examples for compounds is (methyl) vinylformic acid, (methyl) acrylic acid alkyl ester, hydroxy alkyl ester or aminoalkyl ester, (methyl) acrylic acid methyl esters for example, ethyl ester, positive butyl ester, isobutyl ester, the tert-butyl ester, n-propyl, isopropyl ester, just own ester, cyclohexyl, the 2-ethylhexyl, isobornyl thiocyanoacetate, the benzyl ester, the 2-hydroxy methacrylate, the 2-hydroxy propyl ester, the methoxyl group ethyl ester, ethoxy ethyl ester, glyceryl ester, phenoxy ethyl, the methoxyl group binaryglycol ester, the oxyethyl group binaryglycol ester, macrogol ester, the polypropylene glycol ester, glycidyl ester, N, the N-dimethylamino ethyl ester, N, N-diethylamino ethyl ester.Other example is (methyl) vinyl cyanide; (methyl) acrylamide; N-replaces (methyl) acrylamide; N for example; N-dimethyl (methyl) acrylamide; N; N-diethyl (methyl) acrylamide; N; N-dibutyl (methyl) acrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-butyl (methyl) acrylamide and N-(methyl) acryloyl morpholine; vinyl ester such as vinyl-acetic ester; vinyl ether such as IVE, vinylbenzene; alkyl-; hydroxyl-and halogenated styrenes; the N-vinyl pyrrolidone; the N-caprolactam; the N-vinyl acetamide; N-vinyl-methane amide; vinylchlorid or vinylidene chloride.
The example of high-molecular weight polyunsaturated compounds (oligopolymer) is polyester, urethane, polyethers and the polymeric amide that contains the ethylenically-unsaturated carboxylic acid ester relatively.
Specially suitable example is the ester of ethylenic unsaturated carboxylic acid and polyvalent alcohol or polyepoxide.
The example of unsaturated carboxylic acid is vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, styracin and unsaturated fatty acids, as linolic acid or oleic acid.Vinylformic acid and methacrylic acid are preferred.
Suitable polyvalent alcohol is an aromatics, is in particular aliphatic series or alicyclic polyol.The example of aromatic polyol is a quinhydrones, 4,4 '-dihydroxybiphenyl, 2, two (4-hydroxy phenyl) methane, 2 of 2-, two (4-hydroxy phenyl) propane, 2 of 2-, two (4-hydroxy phenyl) HFC-236fa, 9 of 2-, two (4-hydroxy phenyl) fluorenes of 9-, phenolic novolac and resol.The example of aliphatic series and alicyclic polyol is for preferably having the alkylene glycol of 2-12 carbon atom, ethylene glycol for example, 1,2-or 1, ammediol, 1,2-, 1,3-or 1, the 4-butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, dodecanediol, glycol ether, triglycol, preferred 200 to 1500 the polyoxyethylene glycol of molecular weight, 1,3-encircles pentanediol, 1,2-, 1,3-or 1, the 4-cyclohexanediol, 1,4-dihydroxyl methylcyclohexane, glycerine, trolamine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, tetramethylolmethane list oxalate, Dipentaerythritol, the ether of tetramethylolmethane and ethylene glycol or propylene glycol, the ether of Dipentaerythritol and ethylene glycol or propylene glycol, Sorbitol Powder, 2, two [4-(2-hydroxyl-oxethyl) phenyl] methane of 2-, 2, two [4-(2-hydroxyl-oxethyl) phenyl] propane and 9 of 2-, two [4-(2-hydroxyl-oxethyl) phenyl] fluorenes of 9-.Other suitable polyvalent alcohol is polymkeric substance and the multipolymer that contains hydroxyl at polymer chain or in side chain, for example comprises vinyl alcohol or comprises the homopolymer or the multipolymer of (methyl) acrylic acid hydroxy alkyl ester.Other suitable polyvalent alcohol is ester and the urethane with hydroxyl end groups.
Polyvalent alcohol can be with a kind of unsaturated carboxylic acid carboxylic acid or with the partially or completely esterification of different unsaturated carboxylic acids, and in the part ester, free hydroxyl group can be modified, for example by other carboxylic acid etherificate or esterification.
Example based on the ester of polyvalent alcohol is trimethylolpropane tris (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triglycol two (methyl) acrylate, Tetraglycol 99 two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate list barkite, Dipentaerythritol two (methyl) acrylate, Dipentaerythritol three (methyl) acrylate, Dipentaerythritol four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate list (2-hydroxyethyl) ether, tripentaerythritol eight (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, 1,4-butyleneglycol diitaconate, hexylene glycol two (methyl) acrylate, 1,4-cyclohexanediol two (methyl) acrylate, Sorbitol Powder three (methyl) acrylate, Sorbitol Powder four (methyl) acrylate, Sorbitol Powder five (methyl) acrylate, Sorbitol Powder six (methyl) acrylate, oligomer ester (methyl) acrylate, two (methyl) vinylformic acid glyceryl ester and three (methyl) vinylformic acid glyceryl ester, molecular weight is two (methyl) acrylate of 200 to 1500 polyoxyethylene glycol, the tetramethylolmethane diitaconate, Dipentaerythritol three itaconic esters, Dipentaerythritol five itaconic esters, Dipentaerythritol six itaconic esters, the ethylene glycol bisthioglycolate itaconic ester, the propylene glycol diitaconate, 1,3-butyleneglycol diitaconate, 1,4-butyleneglycol diitaconate, 1,4-butyleneglycol diitaconate, Sorbitol Powder four itaconic esters, the ethylene glycol bisthioglycolate crotonate, 1,4-butyleneglycol two crotonates, tetramethylolmethane two crotonates, the ethylene glycol bisthioglycolate maleic acid ester, ti-ethylene glycol bisthioglycolate maleic acid ester, the tetramethylolmethane dimaleate, Sorbitol Powder four maleic acid esters or their mixture.
Other example be following formula (XII) and (XIII) shown in tetramethylolmethane and Dipentaerythritol derivative:
Figure A20068004806500691
Wherein
M 1Be-(CH 2CH 2O)-or-[CH 2CH (CH 3) O]-,
R 100Be-COCH=CH 2Or-COC (CH 3)=CH 2,
P is that 0 to 6 (summation of p: 3-24), and q is 0 to the 6 (summation of q: 2-16).
The example of polyepoxide is based on those of above-mentioned polyvalent alcohol and Epicholorohydrin.Representative instance is two (4-glycidoxy phenyl) methane, 2, two (the 4-glycidoxy phenyl) propane of 2-, 2, two (the 4-glycidoxy phenyl) HFC-236fa of 2-, 9, two (4-glycidoxy the phenyl)-fluorenes of 9-, two [4-(2-glycidoxy oxyethyl group) phenyl] methane, 2, two [4-(the 2-glycidoxy oxyethyl group) phenyl] propane of 2-, 2, two [4-(the 2-glycidoxy oxyethyl group) phenyl] HFC-236fa of 2-, 9, two [4-(the 2-glycidoxy oxyethyl group) phenyl] fluorenes of 9-, two [4-(2-glycidoxy propoxy-) phenyl] methane, 2, two [4-(the 2-glycidoxy propoxy-) phenyl] propane of 2-, 2, two [4-(the 2-glycidoxy propoxy-) phenyl] HFC-236fa of 2-, 9, the glycidyl ether of two [4-(the 2-glycidoxy propoxy-) phenyl] fluorenes of 9-and phenol and cresols novolac resin.
Representative instance based on the component (a) of polyepoxide is 2,2-pair [4-{ (2-hydroxyl-3-acryloxy) propoxy-} phenyl] propane, 2,2-pair [4-{ (2-hydroxyl-3-acryloxy) propoxy-oxyethyl group } phenyl] propane, 9,9-pair [4-{ (2-hydroxyl-3-acryloxy) propoxy-} phenyl] fluorenes, 9,9-two [4-{ (2-hydroxyl-3-acryloxy) propoxy-oxyethyl group } phenyl] fluorenes (fluorine) and based on the Resins, epoxy and (methyl) acrylic acid reaction product of novolac resin.
By above-mentioned polyvalent alcohol or polyepoxide and have the unsaturated compound of hydroxyl, for example the polyethers that obtains of the reaction of (methyl) vinylformic acid 2-hydroxyl ethyl ester, vinyl alcohol also can be used as component (a).
What be suitable as component (a) equally is identical or different unsaturated carboxylic acid and have preferred 2 to 6, especially the acid amides of the aromatics of 2 to 4 amino, alicyclic and aliphatic poly-amine.The example of this class polyamine is a quadrol, 1,2-or 1,3-propylene diamine, 1,2-, 1,3-or 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine, octamethylenediamine, dodecane diamines, 1,4-diamino-cyclohexane, isophorone diamine, phenylenediamine, two phenylenediamine, two-beta-aminoethyl ether, diethylenetriamine, Triethylenetetramine (TETA), two (beta-amino oxyethyl group) or two (beta-amino propoxy-) ethane.Other suitable polyamine is the oligoamide that preferably has the polymkeric substance and the multipolymer of additional amino and have amino end group in side chain.The example of this class unsaturated amides is a methylene-bisacrylamide, 1, oneself two bisacrylamides of 6-, diethylenetriamine trimethylammonium acrylamide, two (methacrylamido propoxy-) ethane, methacrylic acid Beta-methyl acrylamido ethyl ester and N[(beta-hydroxy oxyethyl group) ethyl] acrylamide.
Other example is derived from polymeric polyisocyanate and has the unsaturated compound of hydroxyl or derived from polymeric polyisocyanate, polyvalent alcohol with have the unsaturated urethane of the unsaturated compound of hydroxyl.
Other example is polyester, polymeric amide or the urethane that has the ethylenic unsaturated group in chain.Suitable unsaturated polyester and polymeric amide are also derived from for example toxilic acid and glycol or diamines.Some toxilic acids can be substituted by other dicarboxylic acid.Polyester and polymeric amide also can be derived from dicarboxylic acid and ethylenic unsaturated diol or diamines, especially derived from those of the relative long-chain with 6 to 20 C atoms for example.The example of urethane is those that are made of saturated or unsaturated vulcabond and saturated diols unsaturated or separately.
Other suitable polymers that has acrylate or methacrylate based group in side chain for example is, have and be connected on the skeleton or be connected to photopolymerizable side group on the ester group in the molecule, promptly the solvable or soluble polyimide precursor of alkali according to the solvent of EP 624826 for example gathers (amic acid esters) compound.This quasi-oligomer or polymkeric substance can be chosen wantonly and reactive diluent, and for example multifunctional (methyl) acrylate is prepared together to prepare extremely sensitive polyimide precursor resist.
Component other example a) also can be polymkeric substance or the oligopolymer that has at least one carboxyl functional group and at least two ethylenic unsaturated groups in molecular structure, the resin that obtains of the reaction by saturated or unsaturated multi-anhydride and phenol or cresols novolak Resins, epoxy and unsaturated monocarboxylic reaction product for example, for example, as EB9696, UCB Chemcials; KAYARAD TCR1025, Nippon Kayaku Co., the commodity of LTD.The example of multi-anhydride is a maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, tetrahydronaphthalic anhydride, hexahydro phthalic anhydride, the methyltetrahydro Tetra hydro Phthalic anhydride, Pyroglutaric acid, glutaconic anhydride, citraconic anhydride, the di-alcohol acid anhydrides, the iminodiacetic acid (salt) acid anhydrides, 1,1-pentamethylene diethyl acid anhydrides, 3,3-dimethylated pentanedioic acid acid anhydride, 3-ethyl-3-methylglutaric acid acid anhydride, 2-phenyl Pyroglutaric acid, the homopolymerization Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, with biphenyl ether tetracarboxylic dianhydride.
Other example be the compound of formula (XIV) and one or more above-mentioned multi-anhydrides polycondensation and/product of addition reaction.
Y wherein 1Be
Figure A20068004806500712
Or
Figure A20068004806500713
R 200Be hydrogen or methyl,
R 300And R 400Be hydrogen, methyl, Cl or Br independently of one another, M 2Be replacement or the unsubstituting alkylidene with 1 to 10 carbon atom, x is 0 to 5, and y is 1 to 10.As the case description of this compounds of component (a) in JP2002-206014A, JP2004-69754A, JP2004-302245A, JP2005-77451A, JP2005-316449A, JP2005-338328A and JP3754065B2.
It is for example about 1000 to 1,000,000 that aforesaid polymkeric substance or oligopolymer have, preferred 2000 to 200,000 molecular weight and about 10 to 200mg KOH/g, the acid number of preferred 20 to 180mg KOH/g.
Preferred photopolymerizable composition be included in have at least two ethylenic unsaturated link(age)s and at least one hydroxy-acid group in the molecule compound as component (a), particularly add the reaction product that obtains on a part of carboxyl of polymkeric substance of carboxy-containing acid group to by the unsaturated compound that will contain epoxy group(ing), or the reaction product of the compound shown in following and one or more multi-anhydrides.Other preferred ingredient (a) comprises the compound by the reaction acquisition of the compound of formula XIV and one or more multi-anhydrides.
Other example is to add the reaction product that obtains on a part of carboxyl of polymkeric substance of carboxy-containing acid group to by the unsaturated compound that will contain epoxy group(ing).As the polymkeric substance that contains carboxylic acid, the above-mentioned binder polymer of making by the reaction of unsaturated carboxylic acid compounds and one or more polymerizable compounds, for example, (methyl) vinylformic acid, (methyl) benzyl acrylate, the multipolymer of vinylbenzene and (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid, the multipolymer of vinylbenzene and alpha-methyl styrene, (methyl) vinylformic acid, N-phenylmaleimide, the multipolymer of vinylbenzene and (methyl) benzyl acrylate, (methyl) vinylformic acid and cinnamic multipolymer, the multipolymer of (methyl) vinylformic acid and (methyl) benzyl acrylate, (methyl) vinylformic acid tetrahydrofurfuryl ester, vinylbenzene and (methyl) acrylic acid multipolymer, and analogue.
In formula (V-1) to (V-15), provide the example of unsaturated compound below with epoxy group(ing):
Figure A20068004806500721
R wherein 50Be hydrogen or methyl, M 3Be replacement or unsubstituting alkylidene with 1 to 10 carbon atom.
In these compounds, the compound with alicyclic epoxy base is preferred especially, because these compounds and carboxylic resin have hyperergy, can correspondingly shorten the reaction times.These compounds further can not cause the gelling in the reaction process, and can stably react.On the other hand, from susceptibility and stable on heating angle, glycidyl acrylate and glycidyl methacrylate are favourable, because they have lower molecular weight and can produce high conversion rate of esterification.
The specific examples of above-claimed cpd is, for example, and vinylbenzene, alpha-methyl styrene and acrylic acid multipolymer or methyl methacrylate and acrylic acid multipolymer and (methyl) vinylformic acid 3, the reaction product of 4-epoxy group(ing) cyclohexyl methyl esters.
Can use the unsaturated compound with hydroxyl, for example (methyl) vinylformic acid 2-hydroxyl ethyl ester and single (methyl) vinylformic acid glyceryl ester replace the above-mentioned reactant that contains the unsaturated compound of epoxy group(ing) as carboxy-containing acid group's polymkeric substance.
Other example is the half ester that contains the polymkeric substance of acid anhydride, the for example multipolymer of maleic anhydride and one or more other polymerizable compounds and (methyl) acrylate with alcoholic hydroxyl, for example (methyl) vinylformic acid 2-hydroxyl ethyl ester or (methyl) acrylate, for example reaction product of the compound described in the formula (V-1) to (V-15) with epoxy group(ing).
Have the polymkeric substance (for example (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid, benzyl methacrylate and cinnamic multipolymer) of alcoholic hydroxyl and the reaction product of (methyl) vinylformic acid or (methyl) acrylate chloride and also can be used as component (a).
Other example is a polyester with terminal unsaturation group (it is further reacted with unsaturated compound then by dibasic acid anhydride and reaction with compound of at least two epoxy group(ing) and obtains) and the reaction product of multi-anhydride.
Other example is by saturated or unsaturated multi-anhydride and the resin that obtains by the reaction of adding the reaction product that (methyl) acrylic compound contain epoxy group(ing) obtains on all carboxyls of the polymkeric substance that contains carboxylic acid as mentioned above.
Photopolymerizable compound can use separately or use with any desired mixt.
In colour filter resist composition, contained monomer total amount preferably accounts for 5 to the 80 weight %, particularly 10 to 70 weight % of total solid content in the said composition (promptly not solvent-laden other all components amount) in the photopolymerizable composition.
Dissolve in the alkaline aqueous solution but water-fast tackiness agent as being used in the colour filter resist composition, for example, can use the homopolymer of the polymerizable compound that one or more acidic groups and one or more polymerizable unsaturated bonds are arranged in the molecule or wherein two or more multipolymer and one or more have and one or morely can and not contain the multipolymer of the polymerizable compound of acidic group with the unsaturated link(age) of these compound copolymerization.These compounds can have one or more can the acquisition with the unsaturated link(age) of these compound copolymerization and the polymerizable compound copolymerization that does not contain acidic group by making one or more low molecular compounds that have one or more acidic groups and one or more polymerizable unsaturated bonds in molecule and one or more.The example of acidic group is-the COOH group ,-SO 3The H group ,-SO 2NHCO-group, phenolic hydroxyl ,-SO 2The NH-group and-the CO-NH-CO-group.Wherein, have-macromolecular compound of COOH is particularly preferred.
Preferably, the organic polymer binder in the colour filter resist composition comprises alkali-soluble copolymer, and it comprises unsaturated organic acid compound at least, but as vinylformic acid, methacrylic acid and the analogue monomeric unit as addition polymerization.The preferred unsaturated organic acid ester cpds that uses, as methyl acrylate, (methyl) ethyl propenoate, (methyl) benzyl acrylate, vinylbenzene and analogue further comonomer as polymer binder, with the various performances of balance, as caustic solubility, adhesion stability, chemical resistant properties etc.
Organic polymer binder can be random copolymers or the segmented copolymer described in US 5368976.
The example that has the polymerizable compound of one or more acidic groups and one or more polymerizable unsaturated bonds in the molecule comprises following compounds:
The example that has the polymerizable compound of one or more-COOH group and one or more polymerizable unsaturated bonds in the molecule is (methyl) vinylformic acid; 2-propyloic (methyl) vinylformic acid; 2-carboxylic propyl group (methyl) vinylformic acid; Ba Dousuan; styracin; single [2-(methyl) acryloxy ethyl] succinate; single [2-(methyl) acryloxy ethyl] adipic acid ester; single [2-(methyl) acryloxy ethyl] phthalic ester; single [2-(methyl) acryloxy ethyl] hexahydro-phthalic acid ester; single [2-(methyl) acryloxy ethyl] maleic acid ester; single [2-(methyl) acryloxy propyl group] succinate; single [2-(methyl) acryloxy propyl group] adipic acid ester; single [2-(methyl) acryloxy propyl group] phthalic ester; single [2-(methyl) acryloxy propyl group] hexahydro-phthalic acid ester; single [2-(methyl) acryloxy propyl group] maleic acid ester; single [2-(methyl) acryloxy butyl] succinate; single [2-(methyl) acryloxy butyl] adipic acid ester; single [2-(methyl) acryloxy butyl] phthalic ester; single [2-(methyl) acryloxy butyl] hexahydro-phthalic acid ester; single [2-(methyl) acryloxy butyl] maleic acid ester; 3-(alkyl-carbamoyl) vinylformic acid; α-chloro-vinylformic acid; toxilic acid; the mono-esterification toxilic acid; fumaric acid; methylene-succinic acid; citraconic acid; methylfumaric acid; maleic anhydride and ω-carboxyl polycaprolactone list (methyl) acrylate.
Vinylbenzenesulfonic acid and 2-(methyl) acrylamide-2-methyl propane sulfonic acid is to have one or more-SO 3The example of the polymerizable compound of H group and one or more polymerizable unsaturated bonds.
N-methyl sulphonyl (methyl) acrylamide, N-ethylsulfonyl (methyl) acrylamide, N-phenyl sulfonyl (methyl) acrylamide and N-(right-the aminomethyl phenyl alkylsulfonyl) (methyl) acrylamide are to have one or more-SO 2The example of the polymerizable compound of NHCO-group and one or more polymerizable unsaturated bonds.
The example that has the polymerizable compound of one or more phenolic hydroxyls and one or more polymerizable unsaturated bonds in the molecule comprises hydroxyphenyl (methyl) acrylamide, dihydroxyphenyl (methyl) acrylamide, (methyl) vinylformic acid hydroxyphenyl-carbonyl oxygen base ethyl ester, (methyl) vinylformic acid hydroxyl phenoxy group ethyl ester, (methyl) vinylformic acid hydroxyphenyl sulphur ethyl ester, (methyl) vinylformic acid dihydroxyphenyl carbonyl oxygen base ethyl ester, (methyl) vinylformic acid dihydroxy phenoxy group ethyl ester, (methyl) vinylformic acid dihydroxyphenyl sulphur ethyl ester.
Has one or more-SO in the molecule 2The example of the polymerizable compound of NH-group and one or more polymerizable unsaturated bonds comprise formula (a) or (b) shown in compound:
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)
Y wherein 1And Y 2Separately representative-COO-,-CONA 7-or singly-bound; A 1And A 4Represent H or CH separately 3A 2And A 5Representative is chosen wantonly and is had substituent C separately 1-C 12Alkylidene group, ring alkylidene group, arylidene or inferior aralkyl or wherein insert the C of ether and thioether group 2-C 12Alkylidene group, ring alkylidene group, arylidene or inferior aralkyl; A 3And A 6Representative is chosen wantonly and is had substituent C separately 1-C 12Alkyl, cycloalkyl, aryl or aralkyl; And A 7Represent H, optional have a substituent C 1-C 12Alkylidene group, cycloalkyl, aryl or aralkyl.
Example with polymerizable compound of one or more-CO-NH-CO-group and one or more polymerizable unsaturated bonds comprises maleimide and N-acryl-acrylamide.These polymerizable compounds become by polymerization and comprise-macromolecular compound of CO-NH-CO-group, wherein form ring with main chain.In addition, also can use separately and have-methacrylic acid derivative and the acrylic acid derivative of CO-NH-CO-group.These methacrylic acid derivatives and acrylic acid derivative comprise; methacrylamide derivatives for example is as N-ethanoyl Methacrylamide; N-propionyl Methacrylamide; N-butyryl radicals Methacrylamide; N-pentanoyl Methacrylamide; N-decanoyl Methacrylamide; N-lauroyl Methacrylamide; N-benzoyl Methacrylamide; N-(right-methyl benzoyl) Methacrylamide; N-(right-chlorobenzene formacyl) ammonium methacrylate; N-(naphthyl carbonyl) Methacrylamide; N-(phenyl acetyl) Methacrylamide and 4-methacrylamido phthalic imidine; and have a substituent acrylamide derivative identical with these.These polymerizable compounds aggregate in the side chain to have-compound of CO-NH-CO-group.
The example that has one or more polymerizable unsaturated bonds and do not contain the polymerizable compound of acidic group comprises and is selected from the following compound with polymerizable unsaturated bond: (methyl) acrylic acid ester, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) benzyl acrylate, (methyl) 2-EHA, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) vinylformic acid hydroxy butyl ester, single (methyl) vinylformic acid glyceryl ester, (methyl) vinylformic acid two hydroxypropyl acrylates, (methyl) allyl acrylate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid methoxyl group phenyl ester, (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid methoxyl group binaryglycol ester, (methyl) vinylformic acid methoxyl group triglycol ester, (methyl) vinylformic acid methoxyl group propyl ester, (methyl) vinylformic acid methoxyl group dipropylene glycol ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclopentadienyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid three ring [5.2.1.0 2.5]-last of the ten Heavenly stems-8-base ester, (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) acrylic-amino propyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid 2-methyl glycidyl ester, (methyl) vinylformic acid 3,4-epoxy group(ing) butyl ester, (methyl) vinylformic acid 6,7-epoxy group(ing) heptyl ester; Vinyl aromatic compounds, for example vinylbenzene, alpha-methyl styrene, Vinyl toluene, to chloro-styrene, polychlorostyrene, fluorobenzene ethene, bromstyrol, ethoxyl methyl vinylbenzene, methoxy styrene, 4-methoxyl group-3-vinyl toluene, dimethoxy styrene, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether, indenes, 1-methyl indenes; Vinyl or allyl ester, for example vinyl-acetic ester, propionate, vinyl butyrate, the trimethylacetic acid vinyl acetate, vinyl benzoate, the trimethylacetic acid vinyl acetate, the diethylacetic acid vinyl acetate, vinyl barate, vinyl caproate, vinyl chloroacetate, the dichloro acetic acid vinyl acetate, the methoxyacetic acid vinyl acetate, the butoxy acetic acid vinyl acetate, the phenylacetic acid vinyl acetate, vinyl-acetic ester, the etheric acid vinyl acetate, the lactic acid vinyl acetate, the phenylbutyric acid vinyl acetate, the cyclohexane carboxylic acid vinyl acetate, vinyl salicylate, the chloro-benzoic acid vinyl acetate, the tetrachloro-benzoic acid vinyl acetate, the naphthoic acid vinyl acetate, allyl acetate, allyl propionate, allyl butyrate, the trimethylacetic acid allyl ester, the phenylformic acid allyl ester, pineapple aldehyde, the stearic acid allyl ester, acetoacetic acid allyl ester, the lactic acid allyl ester; Vinyl or allyl ethers, for example methoxy ethylene, ethyl vinyl ether, vinyl hexyl ether, vinyl octyl ether, vinyl ethylhexyl ether, vinyl methyl ethyl ether, vinyl ethoxyethyl group, vinyl chloride ether, vinyl hydroxyethyl ether, vinyl ethyl butyl ether, vinyl hydroxy ethoxyethylether, the amino ether of vinyl-dimethyl base, vinyl diethylamino ether, the amino ether of vinyl butyl, vinyl benzyl ether, vinyl tetrahydrofurfuryl ether, vinyl phenyl ether, vinyl naphthyl ether, vinyl anthryl ether, vinyl glycidyl ether; The acid amide type unsaturated compound, (methyl) acrylamide for example, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dibutyl (methyl) acrylamide, N, N-diethylhexyl (methyl) acrylamide, N, N-dicyclohexyl (methyl) acrylamide, N, N-phenylbenzene (methyl) acrylamide, N-methyl-N-phenyl (methyl) acrylamide, N-hydroxyethyl-N-methyl (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-propyl group (methyl) acrylamide, N-butyl (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide, N-heptyl (methyl) acrylamide, N-octyl group (methyl) acrylamide, N-ethylhexyl (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide cyclohexyl, N-benzyl (methyl) acrylamide, N-phenyl (methyl) acrylamide, N-tolyl (methyl) acrylamide, N-hydroxy phenyl (methyl) acrylamide, N-naphthyl (methyl) acrylamide, N-phenyl sulfonyl (methyl) acrylamide, N-aminomethyl phenyl alkylsulfonyl (methyl) acrylamide and N-(methyl) acryloyl morpholine, diacetone-acryloamide(DAA), N hydroxymethyl acrylamide, N-butoxy acrylamide; Polyolefin-type compound, for example divinyl, isoprene, chloroprene and analogue; (methyl) vinyl cyanide, methyl isopropenyl ketone, maleimide, N-phenylmaleimide, N-aminomethyl phenyl maleimide, N-p-methoxy-phenyl maleimide, N-cyclohexyl-maleimide, N-alkyl maleimide, maleic anhydride, the big monomer of polystyrene, the poly-big monomer of (methyl) methyl acrylate, the poly-big monomer of (methyl) butyl acrylate; Crotonate, for example butyl crotonate, the own ester of Ba Dousuan, single Ba Dousuan glyceryl ester; And itaconic ester, for example dimethyl itaconate, diethyl itaconate, dibutyl itaconate; With maleic acid ester or fumarate, for example dimethyl maleate, dibutyl fumarate.
The preferred embodiment of multipolymer is (methyl) methyl acrylate and (methyl) acrylic acid multipolymer, (methyl) benzyl acrylate and (methyl) acrylic acid multipolymer, (methyl) methyl acrylate, (methyl) ethyl propenoate and (methyl) acrylic acid multipolymer, (methyl) benzyl acrylate, (methyl) vinylformic acid and cinnamic multipolymer, (methyl) benzyl acrylate, the multipolymer of (methyl) vinylformic acid and (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid and cinnamic multipolymer, (methyl) methyl acrylate, (methyl) benzyl acrylate, the multipolymer of (methyl) vinylformic acid and (methyl) vinylformic acid oxybenzene ester, (methyl) methyl acrylate, (methyl) vinylformic acid and the poly-big monomeric multipolymer of (methyl) methyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid and the poly-big monomeric multipolymer of (methyl) methyl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, vinylbenzene and (methyl) acrylic acid multipolymer, (methyl) methyl acrylate, the big monomeric multipolymer of (methyl) vinylformic acid and polystyrene, (methyl) benzyl acrylate, the big monomeric multipolymer of (methyl) vinylformic acid and polystyrene, (methyl) benzyl acrylate, (methyl) vinylformic acid, (methyl) vinylformic acid 2-hydroxyl ethyl ester and the big monomeric multipolymer of polystyrene, (methyl) benzyl acrylate, (methyl) vinylformic acid, the big monomeric multipolymer of (methyl) vinylformic acid 2-hydroxypropyl acrylate and polystyrene, (methyl) benzyl acrylate, (methyl) vinylformic acid, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester and the poly-big monomeric multipolymer of (methyl) methyl acrylate, (methyl) methyl acrylate, (methyl) vinylformic acid, (methyl) vinylformic acid 2-hydroxyl ethyl ester and the big monomeric multipolymer of polystyrene, (methyl) benzyl acrylate, (methyl) vinylformic acid, (methyl) vinylformic acid 2-hydroxyl ethyl ester and the poly-big monomeric multipolymer of (methyl) methyl acrylate, N-phenylmaleimide, (methyl) benzyl acrylate, (methyl) vinylformic acid and cinnamic multipolymer, (methyl) benzyl acrylate, (methyl) vinylformic acid, N-phenylmaleimide, list-[2-(methyl) acryloxy ethyl] succinate and cinnamic multipolymer, (methyl) allyl acrylate, (methyl) vinylformic acid, N-phenylmaleimide, list-[2-(methyl) acryloxy ethyl] succinate and cinnamic multipolymer, (methyl) benzyl acrylate, (methyl) vinylformic acid, N-phenylmaleimide, single (methyl) vinylformic acid glyceryl ester and cinnamic multipolymer, (methyl) benzyl acrylate, ω-carboxyl polycaprolactone list (methyl) acrylate, (methyl) vinylformic acid, N-phenylmaleimide, single (methyl) vinylformic acid glyceryl ester and cinnamic multipolymer and (methyl) benzyl acrylate, (methyl) vinylformic acid, N-cyclohexyl maleimide and cinnamic multipolymer.
Term " (methyl) acrylate " is meant acrylate and corresponding methacrylic ester in this application.
Also can use hydroxy styrenes all-or altogether-polymkeric substance or novolac-type resol, for example poly-(hydroxy styrenes) and poly-(hydroxy styrenes-be total to-the vinyl hexalin), phenolic novolac, cresols phenolic novolac and halogenated phenol phenolic novolac.More specifically comprise for example Sipacril 2739OF, acrylic copolymer, itaconic acid copolymer, the Ba Dousuan multipolymer, copolymer-maleic anhydride (for example with vinylbenzene as comonomer), and maleic acid, and the maleic acid of partial esterification, be described in for example JP59-44615-B4 (term used herein " JP-B4 " is meant and examines Japanese patent application) separately, JP54-34327-B4, JP 58-12577-B4 and JP 54-25957-B4, JP 59-53836-A, JP59-71048-A, JP 60-159743-A, JP 60-258539-A, JP 1-152449-A, JP2-199403-A, with JP 2-199404-A, and these multipolymers can further react with amine as disclosed in the U.S. Pat 5650263; In addition, can use the derivatived cellulose that has carboxyl on the side chain, particularly preferably be (methyl) benzyl acrylate and (methyl) acrylic acid multipolymer, and (methyl) benzyl acrylate, (methyl) vinylformic acid and other monomeric multipolymer, for example described in US4139391, JP 59-44615-B4, JP 60-159743-A and the JP 60-258539-A.
For having those of hydroxy-acid group in the above-mentioned organic binder bond polymkeric substance, can make some or all hydroxy-acid groups and (methyl) glycidyl acrylate or the reaction of (methyl) acrylic acid epoxy ester obtaining photopolymerizable organic binder bond polymkeric substance, with improve photosensitivity, coating strength, to the tolerance of paint solvent and chemical and with the binding property of substrate.The example is disclosed in JP 50-34443-B4 and people's such as JP 50-34444-B4, US5153095, T.Kudo J.Appl.Phy.s, among volume 37 (1998), the 3594-3603 page or leaf, US5677385 and the US5650233.
The weight-average molecular weight of tackiness agent is preferably 500-1, and 000,000,3000-1 for example, 000,000, more preferably 5000-400,000.
These compounds can use separately or use as two or more mixture.The content of tackiness agent in photosensitive resin composition is preferably the 10-95 weight % of total solids material, more preferably 15 to 90 weight %.
In addition, in colour filter, the total solids component of each pigment can contain the ionic impurity scavenging agent, as has the organic compound of epoxy group(ing).The concentration of ionic impurity scavenging agent in the total solids component is generally 0.1 weight % to 10 weight %.
Provide the example of colour filter among the EP320264, related in particular to the aforesaid combination of pigment and ionic impurity scavenging agent.It being understood that light trigger of the present invention, promptly the compound of formula I and II can substitute the triazine initiator compounds in the prescription of the colour filter described in the EP320264.
Composition of the present invention can also comprise the linking agent of the acid activation described in JP 10221843-A in addition and produce acid and activate the compound of crosslinking reaction by heat or by actinic radiation.
Composition of the present invention also can comprise latent (latent) pigment, and it changes into finely divided pigment in the heat treatment process of photosensitive pattern that contains the pigment of diving or coating.Thermal treatment can be after exposure or containing the photoimaging layer development of the pigment of diving after carry out.This latent pigment is the solubility pigment precursors, and it can change into insoluble pigment by the chemistry described in US5879855, heat, photodissociation or radiation-induced method.This class dive this conversion of pigment can be when in said composition, being added in photochemical exposure acidic compound or promote by the adding acidic cpd.Therefore, can also prepare the colour filter resist that in the present composition, comprises the pigment of diving.
The example of colour filter resist, the composition of these resists and processing conditions are provided by following document: " Jpn.J.Appl.Phys. " volume 37 (1998) 3594 of people such as T.Kudo; People's such as T.Kudo J.Photopolym.Sci.Technol. (photopolymerization science and technology magazine), volume 9 (1996) 109; The Solid StateTechnol. (solid state technology) of K.Kobayashi, in November, 1992, S15-S18 page or leaf; US5368976; US5800952; US5882843; US5879855; US5866298; US5863678; JP 06-230212-A; EP 320264; JP09-269410-A; JP 10-221843-A; JP 01-090516-A; JP 10-171119-A, US5821016, US5847015, US5882843, US5719008, EP 881541 or EP 902327.Light trigger of the present invention can be used in the colour filter resist, those that provide as an example more than for example, or can partially or completely substitute known light trigger in this class resist.Those skilled in the art should understand that, the special adhesive resin that the application of novel photoinitiator of the present invention is not limited to above provide, linking agent and colour filter resist prescription, but can use with any free redical polymerization component and dyestuff or coloured pigment or latent pigment, to form photosensitive colour filter printing ink or colour filter resist.
Correspondingly, theme of the present invention is the colour filter by providing redness, green and blue (RGB) pixel and optional black matix to make still, all these are all comprising photosensitive resin and pigment and are providing transparency electrode on the substrate surface or on the colour filter surface on the transparent substrates, wherein said photosensitive resin comprises the Photoepolymerizationinitiater initiater of multi-functional acrylate's monomer, organic polymer binder and aforesaid formula III.Monomer and binder ingredients and suitable pigment are as mentioned above.In colour filter was made, transparent electrode layer can be applied on the surface that maybe can be provided at redness, green and blue pixel and black matix on the transparent substrates surface.Transparent substrates for example is a substrate of glass, can have electrode layer in addition on its surface.
Preferably between the look district of different colours, apply black matix to improve the contrast gradient of colour filter.
Except using photosensitive composition to form black matix and, also alternatively using inorganic black matix by the photoetching of black light sensitive composition being charted to form the black pattern of isolating red, green and blue look zone on transparent substrates according to image exposure (promptly via suitable mask).This inorganic black matix can be formed by sedimentary on the transparent substrates (being sputter) metal (being chromium) film by suitable formation method; for example utilize the photoetching chartography by anti-etching dose, the etching inorganic layer is removed all the other anti-etching dose then in not with the zone of anti-etching dose of protection.
About how applying in the colour filter manufacturing process and what stage to apply black matix in, known have a diverse ways.It can be as mentioned above be applied directly on the transparent substrates before forming red, green and blue (RGB) colour filter, or it applies after can forming the RGB colour filter in substrate.
In the different embodiments of liquid-crystal display colour filter, according to US 626796, black matix also can be applied in the substrate relative with the substrate of carrying RGB colour filter pixel, and this supporting substrate separates with the latter by liquid crystal layer.
If transparent electrode layer apply RGB colour filter pixel and optional apply black matix after deposition, can described in US5650263, before electrode layer deposits, on color filter layer, apply additional cover tunic as protective layer.
In order to form the finish coat of colour filter, use photosensitive resin or compositions of thermosetting resin.Photosensitive composition of the present invention also can be used for forming this protective layer; because the cured film of said composition have excellent planeness, hardness, chemical resistant properties and thermotolerance, transparency (especially at visible region), with the binding property of substrate; form nesa coating thereon, as the adaptability of ITO film.In the manufacturing of protective layer; requirement is removed protective layer from substrate described in JP 57-42009-A, JP 1-130103-A and JP 1-134306-A unnecessary part; for example in the line that is used to cut substrate, and on the welding zone of solid state image sensor.In this, use above-mentioned thermosetting resin to be difficult to form protective layer with good tolerance range selectivity.But photosensitive composition is removed the unnecessary part of protective layer easily by photoetching technique.
Those skilled in the art it is evident that, photosensitive composition of the present invention can be used for generating redness, green and blue pixel and black matix, be used to make colour filter, the difference of itself and above-mentioned processing aspect is irrelevant, irrelevant with the extra play that can apply, also irrelevant with the difference of color filter design aspect.The application that the present composition is used to form color component is considered to not be subjected to the different designs of this class colour filter and manufacturing process to limit.
Photosensitive composition of the present invention can suitably be used to form colour filter, but is not limited to this purposes.It also can be used for recording materials, anticorrosive additive material, protective layer, dielectric layer, is used in demonstration field and display element, paint and the printing-ink.
Photosensitive composition of the present invention also is applicable to is making liquid-crystal display, interlayer insulating film or the dielectric layer in the reflection LCD more especially, these indicating meters comprise have thin film transistor (TFT) as opening the light the active array display unit of device and the passive matrix escope that does not have switching arrangement.In recent years, liquid-crystal display owing to its thickness pocket televisor and the communication terminating unit of being widely used in little and in light weight.Need not to use reflection LCD backlight especially to meet the requirements,, and can obviously reduce watt consumption because it is ultra-thin and in light weight.Even but from the transmission type colour liquid crystal indicating meter that can get at present, remove backlightly, and and on the lower surface of indicating meter, adding reflector, also can have problems, promptly the utilising efficiency of light is low and can not have practical brightness.
As the solution of this problem, various reflection LCDs have been proposed to strengthen the utilising efficiency of light.For example, some reflection LCD is designed to comprise the pixel electrode with reflection function.
Reflection LCD comprises insulated substrate and the relative substrate that separates with insulated substrate.Space between substrate is filled with liquid crystal.On insulated substrate, form gate electrode, and gate electrode and insulated substrate are covered by gate insulation film all.Semiconductor layer forms on the gate insulation film on the gate electrode subsequently.Source electrode and drain electrode also form contact partly to lead on the gate insulation film of doing layer.Source electrode, drain electrode, semiconductor layer and gate electrode are cooperated each other, constitute the bottom door type TFT as switching arrangement thus.
Form the interlayer dielectric of covering source electrode, drain electrode, semiconductor layer and gate insulation film.On the interlayer dielectric in the whole drain electrode, form contact hole.On interlayer dielectric and contact hole inner side-wall, all form pixel electrode made of aluminum.The drain electrode of TFT finally contacts with pixel electrode by interlayer dielectric.Interlayer insulating film is usually designed to has uneven surface, and pixel electrode serves as reflector thus, its with light diffusion to produce wideer visual angle (angle of visibility).
Reflection LCD obviously strengthens the utilising efficiency of light because pixel electrode serves as reflector.
In above-mentioned reflection LCD, interlayer dielectric is designed to have projection and recessed by photolithography.In order to form and to control protruding and recessed precise shape with the micron order surfaceness and in order to form contact hole, using photolithography, it adopts positivity and negative photoresist.For these resists, the present composition is especially suitable.
Photosensitive composition of the present invention also can be used for making spacer (spacer), is used for controlling liquid crystal cell (cell gap) gap of LCD panel Liquid crystal component.Depend on cel-gap owing to see through the performance of the light of liquid crystal layer transmission and reflection in the liquid-crystal display, thickness accuracy on the pel array and homogeneity are key parameters for the performance of liquid crystal display.In liquid crystal cell, several microns glass or polymer drops keep constant in box as substrate distance thing sparse distribution the spacing in the liquid crystal cell between substrate approximately by making diameter.Spacer is fixed between the substrate thus so that the distance between substrate remains steady state value.This distance is by the diameter decision of spacer.Spacer is guaranteed the minimum spacing between substrate, and promptly they prevent reducing of distance between substrate.But they can not prevent that substrate is separated from each other, i.e. the increase of substrate spacing.In addition, use this method of spacer to have spacer diameter homogeneity question, be difficult to onboard, and have inhomogeneous orientation and brightness and/or optical aperture and descend according to the position of spacer on pixel array region with the spacer homodisperse.Liquid-crystal display with big image display area causes a large amount of concerns recently.But the increase of liquid crystal cell area causes the distortion of the substrate that constitutes liquid crystal cell usually.The deformation of substrate causes the layer structure deteriorate of liquid crystal easily.Therefore, even use spacer to make the spacing between substrate keep constant, but has the liquid-crystal display of big image display area because indicating meter is disturbed and infeasible.Be used to replace above-mentioned spacer dispersion method, proposed in cel-gap, to form the method for post as spacer.In the method, form resin column in the zone between pixel array region and counter electrode as spacer, thereby form predetermined cel-gap.Usually for example in the colour filter manufacturing process, use photochromics with photoetching bond properties.Aspect position, number and height that can free control interval thing, it be favourable that this method is compared with the ordinary method of using spacer.In color LCD board, form in the non-imaging area of this spacer under the black matix of color filter element.Therefore, the spacer that uses photosensitive composition to form can not reduce brightness and optical aperture.
Disclose among the JP 2000-81701-A and made the protective layer used photosensitive composition that has spacer that spectral filter is used, and also disclose the dry-film type photo-resist that is used for interval insulant among JP 11-174459-A and the JP 11-174464-A.As described in these files, photosensitive composition, liquid and dry film photo-resist comprise alkali or acid-solubility binder polymer, free radical polymerizable monomer and radical initiator at least.In some cases, can also comprise the thermally cross-linkable component, as epoxide and carboxylic acid.
The step that the use photosensitive composition forms spacer is as follows:
Photosensitive composition is applied to substrate, for example on the colour filter plate, after with the substrate prebake conditions, it is seen through mask exposure.Then, substrate is developed with photographic developer, patterning is to form required spacer.If said composition contains some heat-curable component, carry out back baking usually with the said composition thermofixation.
Photocurable composition of the present invention is made liquid-crystal display spacer (as mentioned above) owing to its hypersensitivity is applicable to.
Photosensitive composition of the present invention also is applicable to makes the microlens array that is used in LCD panel, the image sensor etc.
Microlens is mounted in active photoelectric device, goes up the micro-passive optical component that inputs or outputs quality with the optics that improves them as detector, indicating meter and luminescent device (photodiode, horizontal and vertical cavity laser apparatus).Application Areas extensively and contain as telecommunication, information technology, audio frequency-video unit, solar cell, detector, solid state light emitter and optical interconnects etc.
Present optical system is used the effective coupling between various technology acquisition microlenses and the microoptic device.
Microlens array is used for illumination light is converged to non-display appliance with audio processing circuit, as on the pixel area of LCD device to improve the brightness of this indicating meter, be used to assemble incident light or (for example be used at the line image sensor, be used for facsimile recorder etc.) the photoelectricity zone of transformation on form image with the sensitivity that improves these devices be used on the used light-sensitive unit of liquid crystal printer or photodiode (LED) printer, forming image to be printed.
Modal purposes is, they can be used for improving solid-state image sensing device, as the validity of the photodetector array of charge-coupled device (CCD).In detector array, need in each detector element or pixel, collect light as much as possible.If microlens is placed on each pixel, these lens are just collected incident light and it are converged on the active zone less than lens sizes.
According to prior art, microlens array can be by the whole bag of tricks manufacturing:
(1) a kind of method that obtains convex lens, wherein on thermoplastic resin, draw lens pattern with plane configuration by conventional lithographic techniques or similar techniques, the temperature that then thermoplastic resin is heated above resin softening point is to produce flowability, thus pattern edge produce sagging (so-called " backflow ") (referring to, for example JP 60-38989-A, JP 60-165623-A, JP61-67003-A and JP 2000-39503-A).In the method, if used thermoplastic resin is a photosensitivity, can expose by this resin obtains lens pattern.
(2) a kind of method of utilizing mould or pressing mold to form plastics or glass material.As lens material, can use light-curable resin and thermosetting resin (referring to, WO99/38035 for example) in this method.
(3) a kind of method that forms convex lens based on following phenomenon, wherein, when using calibrator with photosensitive resin during with required pattern exposure, unreacted monomer is shifted to exposure region from the unexposed area, cause exposure region expansion (referring to, for example " Journal of the Research Group inMicrooptics Japanese Society of Applied Physics (Japanese Applied Physics association microscopic study group magazine) ", Colloquium in Optics, the 5th volume, No.2,118-123 page or leaf (1987) and the 6th volume, No.2,87-92 page or leaf (1988)).
On the upper surface of support base, form photosensitive resin layer.Then,, use upper surface, make the photosensitive resin layer exposure thus from the rayed photosensitive resin layer of mercury lamp or analogue by independent mask.As a result, the exposure region of photosensitive resin layer just expand into convex lens shape, thereby forms the optical convergence layer with a plurality of microlenses.
(4) a kind of method that obtains convex lens, wherein by the low coverage exposure technique photosensitive resin is exposed, wherein photomask does not contact with resin, causes pattern edge fuzzy, the amount of photochemical reaction product is just disperseed (referring to, JP61-153602-A for example) according to the blur level of pattern edge like this.
(5) a kind of method that produces lens effect is wherein exposed photosensitive resin with the light with specific intensity distribution, with formation have the refractive index that depends on light intensity distribution patterns (referring to, for example JP60-72927-A and JP 60-166946-A).
Photosensitive composition of the present invention can be used for any in the aforesaid method so that use Photocurable resin composition to form microlens array.
A kind of technology of particular type concentrates on and form microlens in thermoplastic resin (as photo-resist).People such as Popovic disclose an example in reference SPIE 898, the 23-25 pages or leaves (1988).This technology that is known as technique of backflow comprises the following steps: for example to delimit the trace of lens in thermoplastic resin by photolithography in as the photosensitive resin of photo-resist, subsequently this material is heated on its reflux temperature.Surface tension pulls into the bubble cap that the original island shape thing before having volume and refluxing equates with the island shape thing of photo-resist.This lid is a kind of plano-convex microlens.The advantage of this technology especially is, directly detects on the photoelectric device at luminous or light and carries out integrated simplicity, reproducibility and possibility.
In some cases, before refluxing, on rectangular patterning lens unit, forming cover (overcoat) layer and hanging with the islands of resin shape logistics of avoiding the middle part, and backflow glomeration lid in reflow step not.This finish coat serves as permanent protective layer.Coating is also made by photosensitive composition.
Microlens array also can utilize as disclosed mould or pressing mold among the EP0932256 and make.A kind of method of making the plane microlens array is as follows: releasing agent is coated on the molded surface (convex portion is being arranged in densification on it) of pressing mold, and on the moulded section surface photocurable synthetic resins material with high refractive index is set.Then, the substrate glasses plate is shifted onto on the synthetic resins material, spread out the synthetic resins material thus, by solidifying this synthetic resins material and moulding to form the convex surface microlens with uviolizing or by heating.After this peel off pressing mold.Then, the photocurable synthetic resins material that will have low refractive index again is applied on the convex surface microlens as binder layer, and the glass substrate that will make glass cover-plate shifts onto on the synthetic resins material, thus it is spread out.Subsequently with synthetic resins material cured and the final plane microlens array that forms.
Described in US5969867, use the similar approach of mould to be applicable to the manufacturing prismatic lens, its as the part of the back lighting device of color LCD board to improve brightness.To be installed on the light-emitting area of backlight at the prismatic lens that forms the prism row on the one side.In order to make prismatic lens, the active energy beam curable compositions is poured into a mould and is layered in the lens die of being made by metal, glass or resin, and the lens shape of formation prism row, or the like, after this transparency carrier is put thereon and will be seen through the sheet material irradiation to solidify from the active energy beam of active energy beam emissive source.Then the lens of making is deviate from from lens die to obtain lens.
The active energy beam curable compositions that is used to form lenticular unit must have various character, comprises and the binding property of transparency carrier and suitable optical characteristics.
At least use the lens of some photo-resist of the prior art and be not suitable for some purposes, because the light transmission rate variance in the spectrum blue end.
Because Photocurable composition of the present invention has low yellow (hot mode and photochemistry mode), they are applicable to makes microlens array as mentioned above.
This novel radiation-sensitive composition also is applicable to used lithography step in plasma display panel (PDP) manufacturing process, is specially adapted to the imaging process of parting bead, phosphorescent layer and electrode.
PDP is a luminous flat-panel screens of coming display image and information of utilizing that geseous discharge produces.About the structure and the working method of panel, known have two types, i.e. DC (direct current) type and AC (interchange) type.
For example, the principle of brief explanation DC type color PDP.In DC type color PDP, the space between two transparency carriers (being generally sheet glass) is divided into many little unit with the trellis parting bead that is placed between transparency carrier.Sealing discharge gas in each unit, as He or Xe.On each unitary rear wall a phosphor layer is arranged, it is sending the three primary colors visible light by by the ultraviolet excitation of the discharge generation of discharge gas the time.On the internal surface of two substrates, that electrode is staggered relatively mutually across correlation unit.Generally speaking, negative electrode is by transparent conductive material, as the film formation of NESA glass.If apply high pressure between these electrodes that are formed on antetheca and the rear wall, the discharge gas that is sealed in the unit can discharge by induced plasma, and utilizes the luminous and realization pictorial display of the uv light induction redness, blueness and the green fluorescence element that therefore send.In full color display system, the above-mentioned three kinds of fluorescent elements that have three primary colors (red, blue and green) separately are in conjunction with forming a pixel.
Unit among the DC type PDP is divided with reticulation assembly parting bead, and the unit among the AC type PDP is then divided with the parting bead that is arranged in parallel with each other on real estate.In either case, the unit is all divided with parting bead.These parting beads are used for light emitting discharge is limited in the FX with crosstalking and guarantee desirable demonstration the between debug discharge or neighboring discharge cells.
Composition of the present invention also can be used for making possible monochrome or the pleochroic single or multiple lift material that is used for picture record or copying image (duplicating, reprography).In addition, these materials are applicable to colored gluing system.In this technology, can apply the preparation that comprises micro-capsule, and, can behind radiation curing, heat-treat for the image manufacturing.These systems and technology and uses thereof for example are disclosed among the US5376459.
The compound of formula I and II also is suitable as the light trigger in the holographic data storage purposes.Described light trigger produces free radical and trigger monomer polymerization when shining with the blue laser radiation that is applicable to holographic data storage.The wavelength region of blue laser is the 390-420 nanometer, preferred 400-410 nanometer, particularly 405 nanometers.Hologram Storage system (holographic recording medium) for example is used for the fast access time record or gives mass data for change.Light trigger of the present invention for example is particularly suitable for the system described in WO 03/021358.
The holographic data storage system preference is made of the matrix network of low refractive index matrix precursor and high refractive index photopolymerizable monomer.
Can select matrix precursor and photoactive monomer consequently (a) make matrix precursor in solidification process polymeric reaction and photoactive monomer at pattern, for example polymeric reaction is irrelevant in the data writing process, and (b) matrix polymer and the polymerization (photopolymer) that produced by the polymkeric substance of photoactive monomer are compatible with each other.At optical recording material, promptly substrate material+photoactive monomer, light trigger and/or additive show about at least 10 5Pa, common about 10 5Pa is to about 10 9During the Young's modulus of Pa, be considered to form matrix.
Dielectric matrix forms by in-situ polymerization, and it is producing as cross-linked network in the presence of " dissolving " and the unreacted photopolymerizable monomer as keeping.The matrix that contains unreacted photopolymerizable monomer also can form by alternate manner, for example by using solid-resin matrix material, wherein is uniform-distribution with the photoreactivity liquid monomer.Then, monochromatic exposure produces hologram pattern, and it makes the polymerization in solid premolding matrix of photoreactivity monomer according to light intensity distributions.Unreacted monomer (wherein light intensity is in minimum level) diffusion sees through matrix, thus modulation by monomer with the matrix refractive index difference with by the definite refractive index of monomeric relative volume ratio.The thickness of recording layer is the several microns extremely thickness up to 1 millimeter.Because this thick holographic data storage layer, require light trigger in conjunction with having high photoreactivity and low absorbancy, thereby make this layer transparent in to guarantee that the photopolymerization degree is according to the exposure depth that enters recording layer and low as far as possible under optical maser wavelength.
It is found that light trigger of the present invention has the high reactive and low absorbance under 405 nanometers and is applicable to this purposes.Also can in prescription, add dyestuff and sensitizing agent.For blue laser radiation, suitable dyestuff and sensitizing agent are for example tonka bean camphor, xanthone, thioxanthone, and it is listed to see above.
Relevant especially is the project 1,2 of tabulation as mentioned and thioxanthone, the tonka bean camphor that 3 times are mentioned.
It is found that, light trigger can make monomer such as holographic data storage desired in thick-layer with the highly sensitive photopolymerization, and produce recording layer to the blue laser radiation sensitivity.When this light trigger is applied in the photoactive layer of 20 micron thickness in the concentration with 2-8 weight %, make the absorbancy of this layer of comprising light trigger under optical maser wavelength less than 0.4, preferably less than 0.2.
This light trigger is particularly useful for making optical goods (for example optical waveguides) or holographic recording medium, for example comprise aforesaid polymkeric substance and organic light trigger, maximum absorption with 340-450 nanometer under the UV wavelength, wherein the sensitivity of refractive index contrast adjusting is greater than 3 * 10 -6Δ n/ (mJ/cm 2).For example, this polymkeric substance forms by making the material polymerization that comprises component 1 and component 2, and wherein component 1 comprises the end capped prepolymer of NCO, and component 2 comprises polyvalent alcohol.Component 1 is derivative, the methylene-bis cyclohexyl isocyanate of for example diphenylmethanediisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate, the derivative of methylene-bis cyclohexyl isocyanate.Component 2 is polyvalent alcohols of propylene oxide for example.Preferably, photoactive monomer is an acrylate monomer.In this class medium, write the shrinking percentage that caused usually less than 0.25%.
Photocuring is also very important to printing, because be a key factor for the productivity of image product the time of drying of printing ink, and should be about part second (fractions ofseconds).The UV curable ink is to silk screen printing and flexographic ink particularly important.
As mentioned above, this model mixture also is highly suitable for making printing plate.Solvable linear polyamide or phenylethylene/butadiene and/or synthetic polyisoprene, the polyacrylic ester that contains carboxyl or polymethylmethacrylate, polyvinyl alcohol or urethane acrylate and photopolymerizable monomer are for example used in this field, as the mixture of acrylamide and/or Methacrylamide or acrylate and/or methacrylic ester and light trigger.Suitable solvent or aqueous solution eccysis uncured portion are used in the film of these systems (wet or dried) and plate exposure on the negative film (or positive) of former of printing subsequently.
Using another field of photocuring is the coating of metal, and in this case, the photocuring of the coating of metal sheet and pipe, jar or bottle cap and polymer coating for example is for example based on floor or the wall covering of PVC.
The example of paper and coating photocuring is the colourless varnish treated of label, record big envelope and cover.
Relevant equally is that this novel photoinitiator is used to solidify the moulded products of being made by composite composition.This complex chemical compound is by the self-supporting substrate material, for example glasscloth or for example vegetable fibre [referring to K.-P.Mieck, T.Reussmann in Kunststoffe 85 (1995), 366-370] form, its is with light cure formulations dipping.If use novel cpd to make, the moulded products that comprises complex chemical compound keeps high mechanical stability and tolerance.This new compound also can be used as the light curing agent in molding, dipping and the coating composition described in EP7086.The example of these compositions is at gel coat resin that has strict demand aspect curing activity and the resisting etiolation and fiber strengthened moulded product, for example planar or have the light diffusing board of vertical or horizontal ripple.Make the technology of these moulded products,, rotational casting stranded or winding filament as manual stranded (lay-up), spraying, for example by P.H.Selden be described in "
Figure A20068004806500881
Kunststoffe ", in the 610th page, Springer VerlagBerlin-Heidelberg-New York 1967.The examples of articles that can be made by these technology is ship, have the fiberboard of double-sided glass fiber-reinforced plastic coating or shaving board, pipe, container etc.Other example of molding, dipping and coating composition is the moulded work (GPR) that is used to the contain glass fibre UP resin gel coating as corrugated sheet and ply of paper casting die.The ply of paper casting die can be based on urea-formaldehyde resin or melamine resin.Before making laminate, gel coating is made on carrier (as film).This novel Photocurable composition also can be used for casting resin or is used for the embedding goods, for example electronic component etc.
Composition of the present invention and compound can be used for making holography, waveguide, optical switch, have wherein utilized irradiation and this advantage of formation of the difference of the refractive index between the irradiated region not.
The optics manufacturing that Photocurable composition is used for imaging technique and information carrier also is important.In these purposes, as mentioned above, be applied to layer on the carrier (wet or do) and, for example see through photomask, with UV or radiation of visible light, then by handle the unexposed area of taking out this layer with photographic developer according to image.Also can photocurable layer be applied on the metal by electrodip process.Exposure region is by crosslinked and polymerization, and therefore soluble and stay on the carrier.Suitable painted generation visual picture.When carrier was metal layer, metal can be after exposure and developing, and is etched or strengthen by electroplating in the unexposed area.So can produce electronic circuit and photo-resist.In the time of in being used in the material that forms image, this novel photoinitiator provides excellent properties aspect the image producing so-called printing off, thereby owing to radiation causes colour-change.In order to form this image that prints off, use different dyestuffs and/or its leuco compound, this example that prints off the image system for example is found among WO96/41240, EP706091, EP511403, US3579339 and the US46222286.
But this novel photoinitiator also is applicable to the composition of photo-patterned, is used to form the dielectric layer of the multilayer circuit board of being made by continuous method of piling.
As mentioned above, the invention provides composition, it is used to make painted and paint and varnish non-staining, powder coating, printing-ink, printing plate, tackiness agent, pressure sensitive adhesive, dental composition, gel coating, the photo-resist that electronics is used, platedresist, anti-etching dose, liquid membrane and dry film, solder resist, be used for the resist that the colour filter of various demonstration purposes is used as manufacturing, at plasma display panel (parting bead for example, phosphor layer, electrode), electroluminescent display and LCD (interlayer insulating film for example, spacer, fibrous lens array) produces structure in, be used for holographic data storage (HDS), as the composition of sealing electricity and electronic component, be used to make magnetic recording material, micromechanical component, waveguide, optical switch, electroplate mask, etching mask, color gluing (colour proofing) system, glass fiber cable coating, the silk screen printing template, be used for making three-dimensional article by stereolithography techniques, as image recording material, be used for holographic recording, microelectronic circuit, decoloring material, the decoloring material that image recording material is used, be used to use the image recording material of microcapsule, as the used photo anti-corrosion agent material of dielectric layer in the continuous accumulation layer that forms printed circuit board (PCB).
The substrate that is used for photoetching information record comprises, for example, and polyester film, cellulose acetate membrane or polymer-coated paper film; The substrate that is used for the offset printing version is the aluminium that special disposal is crossed; The substrate that is used to make printed wiring is the laminating material that covers copper; And the substrate that is used to make unicircuit is, for example silicon chip.The layer thickness that is used for the photoactive layer of photoetching material and offset printing version is generally about 0.5 micron to 10 microns, and the layer thickness that is used for the photoactive layer of printed wiring is 0.1 micron to about 100 microns.After the substrate coating, generally remove and desolvate, thereby in substrate, stay the photo-resist coating by drying.
The coating of substrate can be undertaken by liquid composition, solution or suspension are applied in the substrate.The kind and the coating technique that depend on composition on the selection principle of solvent and concentration.Solvent should be an inert, promptly it should be unable to each component generation chemical reaction, and should be able to the coating after in drying process once more the removal.The example of suitable solvent is ketone, ether and ester, as methylethylketone, isobutyl methyl ketone, cyclopentanone, pimelinketone, N-Methyl pyrrolidone, diox, tetrahydrofuran (THF), 2-methyl cellosolve, cellosolvo, 1-methoxyl group-2-propyl alcohol, 1,2-glycol dimethyl ether, ethyl acetate, ro-butyl acetate, 3-ethoxyl ethyl propionate, 2-methoxy propyl yl acetate, methyl-3-methoxy propyl acid esters, 2-heptanone, 2 pentanone and ethyl lactate.
Use known coating technique,,, and, solution is uniformly applied in the substrate by electrophoretic deposition especially by electrostatic spraying and reverse roll coating for example by spin coating, dip-coating, scraper coating, curtain coating, brushing, spraying.Also photoactive layer can be applied on the interim flex substrate,, and be applied in the final substrate (for example covering copper circuit board or glass substrate) then by this layer of lamination transfer.
The character of glue spread (coat-thickness) and substrate (layer carrier) depends on required Application Areas.The coat-thickness scope be generally about 0.1 micron to greater than 100 microns, for example 0.1 micron to 1 centimetre, preferred 0.5 micron to 1000 microns.
After substrate coating, remove by drying usually and desolvate, thereby in substrate, stay the etchant resist of the photo-resist of substantially dry.
The photosensitivity of this novel compositions generally extends to 600 nanometers by about 150 nanometers, for example 190-600 nanometer (UV-visible region).Having suitable radiation, for example is daylight or from the light of artificial light.Therefore, can adopt many obvious different types of light sources.Point source and array (" lamp blanket ") are all suitable.The example be carbon arc lamp, xenon arc lamp, low-, in-, high-and superelevation-pressure mercury lamp, may have the lamp (metal-halogen lamp) of metal halide hotchpotch, metallic vapor lamp, excited quasi-molecular lampbulb, ultraphotic fluorescent tube, luminescent lamp, argon gas incandescent light, X-flash, photoflood, photodiode (LED), electron beam and the X-ray of microwave-excitation.Lamp and will can becoming according to the kind and the output of desired use and lamp according to the distance between the substrate of the present invention exposure, and can be for example 2 centimetres to 150 centimetres.LASER Light Source, excimer laser for example is as the F in the exposure of 157 nanometers 2Excimer laser, also be suitable at the KrF excimer laser of 248 nanometers exposures with at the ArF excimer laser of 193 nanometers exposure.Also can use laser at visible region.
Term " according to image (imagewise) " exposure comprises by having the photomask of predetermined pattern; for example lantern slide, chrome mask, die board mask or reticle expose; and by exposing by laser or light beam, this light beam for example moves and produces thus image on the surface of coat substrates under computer control.The UV laser exposure system that is fit to this purposes for example provides (DP-100 by Etec andOrbotech TMDIRECT IMAGING SYSTEM).Other example of LASER Light Source is an excimer laser for example, as the F in the exposure of 157 nanometers 2Excimer laser, at the KrF excimer laser of 248 nanometers exposures with at the ArF excimer laser of 193 nanometers exposure.Further suitable is solid-state UV laser (for example from the Gemini of ManiaBarco, from the DI-2050 of PENTAX) and have the ultraviolet laser diode (from DI-2080, the DI-PDP of PENTAX) that 405 nanometers are exported.Also can use laser at visible region.Also can realize computer-controlled radiation by electron beam.Also can use the mask of making by liquid crystal, its can one pixel then a pixel carry out addressing to produce digital picture, A.Bertsch for example, J.Y.Jezequel, J.C.Andre Journal of Photochemistry and Photobiology A:Chemistry (photochemistry and photobiology magazine A: chemistry) 1997,107,275-281 page or leaf and K.-P.Nicolay are at Offset Printing (offset printing) 1997, described in 6, the 34-37 pages or leaves.
After material is according to image exposure and before developing, short period of time thermal treatment may be favourable.After the development, can carry out after heat baking with the sclerosis said composition and remove all trace solvent.Used temperature is generally 50-250 ℃, preferred 80-220 ℃; The heat treated time length was generally 0.25 to 60 minute.
Photo curable composition also can be used in the method for manufacturing printing plate described in DE4013358 or photo-resist.In these class methods, before according to image radiation, simultaneously or afterwards, under maskless situation, said composition is in the exposure of the following short period of time of visible light of wavelength at least 400 nanometers.
After exposure and afterwards, according to known mode itself, with the unexposed area of photographic developer removal photosensitive coating in thermal treatment (if implement thermal treatment).
As mentioned above, this novel compositions can develop with alkaline solution or organic solvent.Specially suitable aqueous alkaline developer is the aqueous solution of tetra-alkyl ammonium hydroxide or alkalimetal silicate, phosphoric acid salt, oxyhydroxide and carbonate.If desired, also can in these solution, add a small amount of wetting agent and/or organic solvent.The example that can add the typical organic solvent in the developing solution on a small quantity is the mixture of pimelinketone, cellosolvo, toluene, acetone and these solvents.According to substrate, also can use solvent, as photographic developer, or use the mixture of buck and these solvents as mentioned above as organic solvent.The solvent that is particularly useful for solvent develop comprises methyl alcohol, ethanol, the 2-propyl alcohol, the 1-propyl alcohol, butanols, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, the glycol monomethyl n-butyl ether, diglyme, propylene glycol monomethyl ether, ethyl-3-ethoxy-c acid esters, methyl-3-methoxy propyl acid esters, n-butylacrylate, benzylalcohol, acetone, methylethylketone, cyclopentanone, pimelinketone, 2-heptanone, 2 pentanone, 6-caprolactone, gamma-butyrolactone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-Ji Neixianan, and N-Methyl pyrrolidone.Randomly, can in these solvents, add entry, still can obtain clear solution and keep the enough solubleness of the unexposed area of photosensitive composition until its amount.
Therefore, the present invention also provides the compound that is used to contain the ethylenic unsaturated double-bond, the method that promptly contains the photopolymerization of the haplotype of at least one ethylenic unsaturated double-bond, oligomeric or polymeric compounds, comprise the light trigger that in these compounds, adds at least a aforesaid formula I or II, and use electromagnetic radiation, particularly wavelength 150 to 600 nanometers, the particularly light of 190-600 nanometer, use electron beam, or use the x-ray irradiation resulting composition.
The present invention also is provided at least one surface and goes up the lining substrate that is coated with above-mentioned composition, and has described the photoetching manufacturing method of camegraph, and the substrate that wherein will be covered is removed unexposed portion with photographic developer then according to image exposure.Can be according to image exposure as mentioned above by seeing through the mask irradiation or being undertaken by laser or electron beam.Particularly advantageous in this article is aforesaid laser beam lithography.
Compound of the present invention has good thermostability and low volatility, and also is suitable for the photopolymerization under air (oxygen) existence.In addition, only cause low yellow in their compositions after photopolymerization.
The more detailed illustration the present invention of the following example.Unless indicate separately, umber and per-cent as in specification sheets rest part and the claim by weight.Having when not mentioning concrete isomer more than the alkyl of three carbon atoms when mentioning in the following example, all is the isomer of making a comment or criticism in each case.
Embodiment 1: 1-{9-[4-(1-acetoxyl group imino-ethyl)-phenyl]-6-(4-carbazole-9-base-benzoyl)-carbazole-3-yl }-ethyl ketone oxime O-acetic ester synthetic
1.a1-(4-carbazole-9-base-phenyl)-ethyl ketone
In the carbazole in DMSO (50 milliliters) (5.02 gram), add 4-fluoro acetophenone (3.45 gram) and K 2CO 3(10.4 gram), and mixture stirred down at 135 ℃ spend the night.This mixture is poured in the water so that throw out to be provided, with its filtering separation and wash with water.Thus obtained thick product is further purified by recrystallization from TBME (t-butyl methyl ether), produces the product of light brown solid state.By 1H-NMR composes (CDCl 3) the confirmation structure.
δ[ppm]：2.71(s，3H)，7.32(ddd，2H)，7.41-7.50(m，4H)，7.72(d，2H)，8.15(d，2H)，8.21(d，2H)。
1.b1-{4-[3-ethanoyl-6-(4-fluoro-benzoyl)-carbazole-9-yl]-phenyl }-ethyl ketone
Under 0 ℃ at CH 2Cl 2Add fluorobenzoyl chloride (3.17 gram) and AlCl among the 1-in (150 milliliters) (4-carbazole-9-base-phenyl)-ethyl ketone (5.71 gram) 3(5.41 gram).After at room temperature stirring is spent the night, further add Acetyl Chloride 98Min. (1.73 gram) and AlCl down at 0 ℃ 3(2.93 gram), and this mixture at room temperature stirred spend the night.Reaction mixture is poured in the frozen water, and with thick product CH 2Cl 2Extracting twice.With the organic layer H that merges 2O and salt water washing are at MgSO 4Last dry, and concentrate the generation residue, it is purified with hot TBME washing.By 1H-NMR composes (CDCl 3) confirm the structure of the product that obtains as white solid.
δ[ppm]：2.73(s，3H)，2.75(s，3H)，7.23(t，2H)，7.48(d，1H)，7.51(d，1H)，7.72(d，2H)，7.91(dd，2H)，7.99(d，1H)，8.14(d，1H)，8.28(d，2H)，8.66(s，1H)，8.80(s，1H).。
1.c1-{4-[3-ethanoyl-6-(4-carbazole-9-base-benzoyl)-carbazole-9-yl]-phenyl }-ethyl ketone
To the 1-{4-[3-ethanoyl-6-in DMSO (40 milliliters) (4-fluoro-benzoyl)-carbazole-9-yl]-phenyl }-add carbazole (1.79 restrain) and K in the ethyl ketone (4.0 gram) 2CO 3(3.69 gram), and this mixture stirred down at 140 ℃ spend the night.This mixture is poured in the water, and with thick product CH 2Cl 2Extracting twice.With the organic layer H that merges 2O and salt water washing are at MgSO 4Last dry, and concentrate the generation residue, it is purified with hot TBME washing.By 1H-NMR composes (CDCl 3) confirm the structure of the product that obtains as yellow solid.δ[ppm]：2.74(s，3H)，2.76(s，3H)，7.34(t，2H)，7.45-7.51(m，3H)，7.57(d，1H)，7.59(d，2H)，7.75(d，2H)，7.80(d，2H)，8.10-8.19(m，6H)，8.29(d，2H)，8.81(s，1H)，8.87(s，1H)。
1.d1-{9-[4-(1-oxyimino ethyl)-phenyl]-6-(4-carbazole-9-base-benzoyl)-carbazole-3-yl } the ethyl ketone oxime
To the 1-{4-[3-ethanoyl-6-in DMA (30 milliliters) (4-carbazole-9-base-benzoyl)-carbazole-9-yl]-phenyl }-add hydroxylamine hydrochloride (0.702 gram) and the sodium acetate (0.984 restrains) that is dissolved in the water (4 milliliters) in the ethyl ketone (2.75 gram).After stirring 3 hours under 100 ℃, reaction mixture is poured in the water to produce throw out, with its filtering separation.Thus obtained thick product promptly is used for next reaction without further purification.By 1H-NMR composes (CDCl 3) confirm the structure of main products (1.d).
δ[ppm]：2.39(s，3H)，2.43(s，3H)，7.33(t，2H)，7.42-7.52(m，4H)，7.58(d，2H)，7.61(d，2H)，7.76-7.82(m，3H)，7.93(d，2H)，8.07(d，1H)，8.12(d，2H)，8.17(d，2H)，8.47(s，1H)，8.76(s，1H)。
1.e1-{9-[4-(1-acetoxyl group imino-ethyl)-phenyl]-6-(4-carbazole-9-base-benzoyl)-carbazole-3-yl } ethyl ketone oxime O-acetic ester
Under 0 ℃ to the 1-{9-[4-in THF (30 milliliters) (1-oxyimino ethyl)-phenyl]-6-(4-carbazole-9-base-benzoyl)-carbazole-3-yl-the ethyl ketone oxime dropwise adds triethylamine (1.81 milliliters) and Acetyl Chloride 98Min. (0.92 milliliter) in (2.72 gram).After stirring 3 hours under 0 ℃, reaction mixture is poured in the water.Product is with ethyl acetate extraction twice, with the organic layer H that merges 2The O washing is at MgSO 4Last dry, and concentrate the generation residue, it is by using hexane/ethyl acetate/CH on silica gel 2Cl 2=4/3/3 to 2/5/3 column chromatography purification as eluent.By 1H-NMR composes (CDCl 3) confirm the structure of the product (1.e) that obtains as yellow solid.
δ[ppm]：2.30(s，3H)，2.32(s，3H)，2.52(s，3H)，2.54(s，3H)，7.33(t，2H)，7.43-7.49(m，3H)，7.52(d，1H)，7.59(d，2H)，7.67(d，2H)，7.79(d，2H)，7.93(d，1H)，8.04-8.18(m，7H)，8.61(s，1H)，8.78(s，1H)
Embodiment 2-4:
According to method as described in example 1 above, use corresponding reagent, the compound of preparation embodiment 2-4.Compound and property description thereof are in table 1.
Figure A20068004806500951
Table 1
Embodiment R 2And R ' 2 Outward appearance/ 1H-NMR(CDCl 3)；δ[ppm]
2 R 2＝CH 3 R’ 2＝n-C 7H 15 Yellow solid/0.90 (t, 3H), 1.24-1.50 (m, 8H), 1.63-1.73 (m, 2H), 2.30 (s, 3H), 2.32 (s, 3H), 2.54 (s, 3H), 2.94 (t, 2H), 7.34 (t, 2H), 7.44-7.49 (m, 3H), 7.53 (d, 1H), 7.59 (d, 2H), 7.66 (d, 2H), 7.79 (d, 2H), 7.93 (dd, 1H), 8.03 (d, 2H), 8.08-8.18 (m, 5H), 8.61 (s, 1H), 8.78 (s, 1H).
3 R 2＝n-C 7H 15 R’ 2＝CH 3 Yellow solid/0.85 (t, 3H), 1.20-1.47 (m, 8H), 1.58-1.68 (m, 2H), 2.29 (s, 3H), 2.32 (s, 3H), 2.52 (s, 3H), 2.99 (t, 2H), 7.34 (t, 2H), 7.43-7.49 (m, 3H), 7.52 (d, 1H), 7.59 (d, 2H), 7.67 (d, 2H), 7.79 (d, 2H), 7.87 (d, 1H), 8.04-8.19 (m, 7H), 8.58 (s, 1H), 8.79 (s, 1H).
4 R 2＝n-C 7H 15 R’ 2＝n-C 7H 15 Yellow solid/0.85 (t, 3H), 0.91 (t, 3H), 1.20-1.50 (m, 16H), 1.59-1.62 (m, 4H), 2.29 (s, 3H), 2.31 (s, 3H), 2.93-3.02 (m, 4H), 7.34 (t, 2H), 7.44-7.49 (m, 3H), 7.50 (d, 1H), 7.59 (d, 2H), 7.67 (d, 2H), 7.79 (d, 2H), 7.86 (d, 1H), 8.03 (d, 2H), 8.08 (d, 1H), 8.13 (d, 2H), 8.17 (d, 2H), 8.58 (s, 1H), 8.79 (s, 1H).
Embodiment 5-22:
According to the program described in embodiment 1 and/or the embodiment 8 (following), use corresponding reagent, the compound of preparation embodiment 5-22.Oximation reaction can be chosen wantonly at pyridine but not carry out in the presence of the sodium acetate.Compound and property description thereof are in table 2.
Embodiment 8:
8a.6-capryloyl-3-(2-thienyl)-9H-carbazole
(it is according to Bulletin of theChemical Society of Japan (1981) to use capryl(yl)chloride, 2-thiophene carbonyl chlorine and 9-benzyl carbazole; 54 (6); the 1897-8 acquisition) is created in the product that does not have benzyl protection on the nitrogen-atoms as raw-material reaction described in embodiment 1b, i.e. 6-capryloyl-3-(2-thienyl)-9H-carbazole.By 1H-NMR composes (CDCl 3) the confirmation structure.δ [ppm]: 0.88 (t, 3H), 1.22-1.44 (m, 8H), 1.82 (quintet, 2H), 3.10 (t, 2H), 7.23 (t, 1H), 7.51 (d, 1H), 7.55 (d, 1H), 7.76 (d, 2H), 8.07 (d, 1H), 8.14 (d, 1H), 8.72 (s, 1H), 8.76 (s, 1H), 9.04 (bs, 1H).
8b.1-{4-[6-capryloyl-3-(2-thienyl-)-carbazole-9-yl]-phenyl }-ethyl ketone
This conversion with similarly carry out under the condition described in the embodiment 1c.By 1H-NMR composes (CDCl 3) the confirmation structure.δ [ppm]: 0.86 (t, 3H), 1.23-1.47 (m, 8H), 1.82 (quintets, 2H), 2.73 (s, 3H), 3.15 (t, 2H), 7.24 (dd, 1H), 7.47 (d, 1H), 7.51 (d, 1H), 7.72 (d, 2H), 7.75-7.77 (m, 2H), 8.06 (d, 1H), 8.14 (d, 1H), 8.27 (d, 2H), 8.79 (s, 1H), 8.83 (s, 1H).
8c.1-{4-[6-acetoxyl group imino--octyl group-3-(2-thienyl-)-carbazole-9-yl]-phenyl }-ethyl ketone oxime O-acetic ester
Ketone carries out described in the conversion of acetate oxime such as embodiment 1d and 1e.Data rows is in table 2.
Figure A20068004806500971
Table 2
Embodiment R 2，R’ 2And R " 2 Outward appearance/ 1H-NMR(CDCl 3)；δ[ppm]
5 R 1＝CH 3 R 2＝CH 3 R’ 2＝CH 3 R” 2=2-furyl Beige solid/2.31 (s, 3H), 2.32 (s, 3H), 2.51 (s, 3H), 2.55 (s, 3H), 6.64 (m, 1H), 7.35 (d, 1H), 7.42 (d, 1H), 7.47 (d, 1H), 7.64 (d, 2H), 7.77 (m, 1H), 7.92 (d, 1H), 8.04 (d, 2H), 8.18 (d, 1H), 8.60 (s, 1H), 8.92 (s, 1H)
6 R 1＝CH 3 R 2＝CH 2CH 2CO 2C 2H 5 R’ 2＝CH 3 R” 2=2-furyl Beige solid/1.24 (t, 3H), 2.31 (s, 3H), 2.32 (s, 3H), 2.51 (s, 3H), 2.65 (t, 2H), 3.35 (t, 2H), 4.17 (q, 2H), 6.65 (m, 1H), 7.35 (d, 1H), 7.43 (d, 1H), 7.47 (d, 1H), 7.64 (d, 2H), 7.77 (m, 1H), 7.88 (d, 1H), 8.05 (d, 2H), 8.18 (d, 1H), 8.58 (s, 1H), 8.91 (s, 1H)
7 R 1＝CH 3 R 2＝CH 3 R’ 2＝CH 3 R” 2=2-thienyl Beige solid/2.30 (s, 3H), 2.32 (s, 3H), 2.51 (s, 3H), 2.54 (s, 3H), 7.23 (dd, 1H), 7.43 (d, 1H), 7.48 (d, 1H), 7.65 (d, 2H), 7.75 (m, 2H), 7.93 (d, 1H), 8.05 (m, 3H), 8.57 (s, 1H), 8.77 (s, 1H)
8 R 1＝CH 3 R 2＝n-C 7H 15 R’ 2＝CH 3 R” 2=2-thienyl Beige solid/0.84 (t, 3H), 1.20-1.48 (m, 8H), 1.60-1.68 (m, 2H), 2.29 (s, 3H), 2.32 (s, 3H), 2.51 (s, 3H), 2.96 (t, 2H), 7.28 (dd, 1H), 7.43 (d, 1H), 7.48 (d, 1H), 7.65 (d, 2H), 7.75 (m, 2H), 7.87 (d, 1H), 8.05 (m, 3H), 8.54 (s, 1H), 8.77 (s, 1H)
9 R 1＝CH 3 R 2＝CH 3 R’ 2＝iso-C 4H 9 R” 2=2-thienyl Beige solid/1.05 (d, 6H), 2.03 (m, 1H), 2.30 (s, 6H), 2.54 (s, 3H), 2.89 (d, 2H), 7.23 (dd, 1H), 7.44 (d, 1H), 7.50 (d, 1H), 7.64 (d, 2H), 7.75 (m, 2H), 7.92 (d, 1H), 7.95-8.07 (m, 3H), 8.58 (s, 1H), 8.77 (s, 1H)
Embodiment R 2，R’ 2And R " 2 Outward appearance/ 1H-NMR(CDCl 3)；δ[ppm]
10 R 1＝CH 3 R 2＝CH 2CH 2CO 2C 2H 5 R’ 2＝CH 3 R” 2=2-thienyl Beige solid/1.21 (t, 3H), 2.28 (s, 3H), 2.29 (s, 3H), 2.48 (s, 3H), 2.63 (t, 2H), 3.28 (t, 2H), 4.16 (q, 2H), 7.21 (dd, 1H), 7.41 (d, 1H), 7.45 (d, 1H), 7.62 (d, 2H), 7.73 (m, 2H), 7.85 (d, 1H), 8.03 (m, 3H), 8.52 (s, 1H), 8.74 (s, 1H)
11 R 1＝CH 3 R 2＝CH 2CH 2CO 2C 2H 5 R’ 2＝CH 3 R” 2=3-thienyl White solid/1.24 (t, 3H), 2.31 (s, 3H), 2.32 (s, 3H), 2.51 (s, 3H), 2.63 (t, 2H), 3.32 (t, 2H), 4.16 (q, 2H), 7.42-7.48 (m, 3H), 7.63-7.67 (m, 3H), 7.88 (d, 1H), 8.00 (m, 1H), 8.05 (m, 3H), 8.54 (s, 1H), 8.73 (s, 1H)
12 R 1＝OC 2H 5 R 2＝CH 2CH 2CO 2C 2H 5 R’ 2＝CH 3 R” 2=2-thienyl Yellow solid/1.24 (t, 3H), 1.39-1.44 (m, 6H), 2.52 (s, 3H), 2.66 (t, 2H), 3.31 (t, 2H), 4.13 (q, 2H), 4.35-4.43 (m, 4H), 7.24 (dd, 1H), 7.44 (d, 1H), 7.48 (d, 1H), 7.65 (d, 2H), 7.74-7.77 (m, 2H), 7.88 (dd, 1H), 8.03-8.08 (m, 3H), 8.56 (s, 1H), 8.77 (s, 1H).
13 R 1＝phenyl R 2＝CH 2CH 2CO 2C 2H 5 R’ 2＝CH 3 R” 2=2-thienyl Beige solid/1.24 (t, 3H), 2.66 (s, 3H), 2.75 (t, 2H), 3.47 (t, 2H), 4.16 (q, 2H), 7.24 (dd, 1H), 7.48-7.56 (m, 6H), 7.62-7.68 (m, 2H), 7.70 (d, 2H), 7.76 (d, 1H), 7.78 (d, 1H), 7.98 (dd, 1H), 8.08 (dd, 1H), 8.13-8.20 (m, 6H), 8.66 (s, 1H), 8.80 (s, 1H)
14 R 1＝CH 3 R 2＝CH 2CH 2CO 2C 2H 5 R’ 2＝CH 3 R” 2=3 methyl thiophene-2-base White solid/1.23 (t, 3H), 2.31 (s, 3H), 2.32 (s, 3H), 2.51 (s, 6H), 2.64 (t, 2H), 3.30 (t, 2H), 4.15 (q, 2H), 7.05 (d, 1H), 7.43 (d, 1H), 7.45 (d, 1H), 7.52 (d, 1H), 7.64 (d, 2H), 7.88 (d, 1H), 8.01 (d, 1H), 8.05 (d, 2H), 8.52 (s, 1H), 8.71 (s, 1H)
15 R 1＝CH 3 R 2＝CH 3 R’ 2＝CH 3 R” 2=4-fluorophenyl White solid/2.30 (s, 3H), 2.32 (s, 3H), 2.51 (s, 3H), 2.53 (s, 3H), 7.22 (t, 2H), 7.43 (d, 1H), 7.47 (d, 1H), 7.64 (d, 2H), 7.87-7.94 (m, 3H), 7.98 (d, 1H), 8.05 (d, 2H), 8.55 (s, 1H), 8.62 (s, 1H)
16 R 1＝CH 3 R 2＝CH 3 R’ 2＝CH 3 R” 2=2,4 dichloro benzene base Yellow solid/2.29 (s, 3H), 2.32 (s, 3H), 2.51 (s, 3H), 2.52 (s, 3H), 7.38-7.45 (m, 4H), 7.55 (s, 1H), 7.62 (d, 2H), 7.89 (d, 1H), 8.01-8.06 (m, 3H), 8.53 (s, 2H)
17 R 1＝CH 3 R 2＝CH 3 R’ 2＝CH 3 R” 2=2-tolyl White solid/2.29 (s, 3H), 2.32 (s, 3H), 2.37 (s, 3H), 2.50 (s, 3H), 2.51 (s, 3H), 7.29-7.46 (m, 6H), 7.62 (d, 2H), 7.90 (d, 1H), 8.02-8.06 (m, 3H), 8.49 (s, 1H), 8.58 (s, 1H)
18 R 1＝CH 3 R 2＝CH 3 R’ 2＝CH 3 R” 2=4-(tetrahydrofurfuryl oxygen base)-phenyl White solid/1.81 (m, 1H), 1.99 (m, 2H), 2.14 (m, 1H), 2.30 (s, 3H), 2.32 (s, 3H), 2.51 (s, 3H), 2.53 (s, 3H), 3.87 (q, 1H), 3.97 (q, 1H), 4.09 (d, 2H), 4.34 (m, 1H), 7.05 (d, 2H), 7.42 (d, 1H), 7.46 (d, 1H), 7.65 (d, 2H), 7.87 (d, 2H), 7.92 (dd, 1H), 7.97 (dd, 1H), 8.05 (d, 2H), 8.53 (s, 1H), 8.61 (s, 1H)
19 R 1＝CH 3 R 2＝CH 3 R’ 2＝n-C 3H 7 R” 2=4-(carbazole-9-yl) phenyl Yellow solid/1.05 (t, 3H), 1.70-1.76 (m, 2H), 2.30 (s, 3H), 2.32 (s, 3H), 2.54 (s, 3H), 2.94 (t, 2H), 7.34 (t, 2H), 7.44-7.49 (m, 3H), 7.53 (d, 1H), 7.59 (d, 2H), 7.66 (d, 2H), 7.79 (d, 2H), 7.93 (dd, 1H), 8.03 (d, 2H), 8.08-8.18 (m, 5H), 8.61 (s, 1H), 8.78 (s, 1H)
Embodiment R 2，R’ 2And R " 2 Outward appearance/ 1H-NMR(CDCl 3)；δ[ppm]
20 R 1＝CH 3 R 2＝n-C 3H 7 R’ 2＝n-C 3H 7 R” 2=4-(carbazole-9-yl) phenyl Yellow solid/1.02-1.10 (m, 6H), 1.64-1.77 (m, 4H), 2.29 (s, 3H), 2.31 (s, 3H), 2.92-3.02 (m, 4H), 7.33 (t, 2H), 7.44-7.49 (m, 3H), 7.53 (d, 1H), 7.58 (d, 2H), 7.66 (d, 2H), 7.78 (d, 2H), 7.91 (d, 1H), 8.02 (d, 2H), 8.07-8.18 (m, 5H), 8.58 (s, 1H), 8.79 (s, 1H).
21 R 1＝CH 3 R 2＝CH 3 R’ 2＝iso-C 4H 9 R” 2=4-(carbazole-9-yl) phenyl Yellow solid/1.05 (d, 6H), 2.02-2.26 (m, 1H), 2.30 (s, 3H), 2.31 (s, 3H), 2.54 (s, 3H), 2.90 (d, 2H), 7.34 (t, 2H), 7.44-7.49 (m, 3H), 7.53 (d, 1H), 7.59 (d, 2H), 7.66 (d, 2H), 7.79 (d, 2H), 7.93 (dd, 1H), 8.03 (d, 2H), 8.08-8.18 (m, 5H), 8.61 (s, 1H), 8.78 (s, 1H)
22 R 1＝CH 3 R 2＝n-C 3H 7 R’ 2＝CH 3 R” 2=4-(carbazole-9-yl) phenyl Yellow solid/1.03 (t, 3H), 1.70 (m, 2H), 2.30 (s, 3H), 2.32 (s, 3H), 2.52 (s, 3H), 2.99 (t, 2H), 7.33 (t, 2H), 7.44-7.49 (m, 3H), 7.53 (d, 1H), 7.59 (d, 2H), 7.67 (d, 2H), 7.79 (d, 2H), 7.88 (dd, 1H), 8.06 (d, 2H), 8.08-8.18 (m, 5H), 8.58 (s, 1H), 8.78 (s, 1H)
Embodiment 23-37:
The compound of preparation embodiment 23-37 will be combined with reagent corresponding with similar reaction described in embodiment 1, embodiment 8 and/or the embodiment 34.If necessary, oximation reaction is chosen wantonly at pyridine but not is carried out in the presence of the sodium acetate.Compound and property description thereof are in table 3, table 4 and table 5.
Embodiment 33
According to Tetrahedron, 1989,45, the program described in the 5059-5064; use corresponding chloride of acid and as J.Org.Chem., 1999,64; synthetic described in the 3671-3678 3,6-diacetyl carbazole preparation 3,6-diacetyl-N-(4-diethylamino phenyl-carbonyl)-carbazole.By 1H-NMR composes (CDCl 3) the confirmation structure.δ[ppm]：1.25(t，6H)，2.74(s，6H)，3.47(q，4H)，6.66(d，2H)，7.65-7.68(m，4H)，8.04(d，2H)，8.74(s，2H)。Ketone carries out as mentioned above to the conversion of acetate oxime.Data rows is in table 4.
Embodiment 34
34a.2,7-two (isobutyryl) thioxanthene
Use the reaction described in embodiment 1b of thioxanthene, isobutyryl chloride and aluminum chloride to produce product.By mass spectrum [M=366] and 1H-NMR composes (CDCl 3) the confirmation structure.δ [ppm]: 0.99 (d, 12H), 2.29 (septet, 2H), 2.82 (d, 4H), 4.00 (s, 2H), 7.50 (d, 2H), 7.79 (d, 2H), 7.92 (s, 2H).
34b.2,7-two (isobutyryl) thioxanthene-9-one
Under the room temperature (rt) in being dissolved in methylene dichloride (24 milliliters) 2; add four-normal-butyl bromination aqueous ammonium (1.76 grams are in 24 ml waters) and bromine (1.17 milliliters) in 7-two (isobutyryl) thioxanthene (4.0 gram) in succession, and mixture was at room temperature stirred 2 hours.The extractibility aftertreatment and from methyl alcohol recrystallization produce product.By mass spectrum [M=380] and 1H-NMR composes (CDCl 3) the confirmation structure.δ [ppm]: 1.05 (d, 12H), 2.36 (septet, 2H), 2.99 (d, 4H), 7.70 (d, 2H), 8.26 (d, 2H), 9.15 (s, 2H).
34c.2,7-pair-{ 1-(acetoxyl group imino-)-3-methyl-butyl }-thioxanthene-9-one
Ketone carries out as mentioned above to the conversion of acetate oxime.Data rows is in table 4.
Figure A20068004806501001
Table 3
Figure A20068004806501002
Figure A20068004806501011
Table 4
Figure A20068004806501012
Figure A20068004806501013
Figure A20068004806501021
Table 5
Figure A20068004806501022
Figure A20068004806501023
Figure A20068004806501031
Embodiment 38
Make the reaction mixture of making according to the program among the embodiment (1.e) by on silica gel, using CH 2Cl 2/ CH 3COOC 2H 5=4/1 short column as eluent.Thus obtained product is dry in a vacuum.Analysis revealed, the product that obtains as light yellow solid mainly are 7/3 mixtures of the compound of the compound of embodiment 1 and embodiment 32.
Application Example:
The preparation of poly-(benzyl methacrylate-be total to-methacrylic acid)
24 gram benzyl methacrylates, 6 gram methacrylic acids and 0.525 gram azobis isobutyronitrile (AIBN) are dissolved in 90 milliliters of propylene glycol 1-monomethyl ether 2-acetic ester (PGMEA).The gained reaction mixture is contained in 80 ℃ the pre-hot oil bath.Under 80 ℃ after stirring 5 hours under the nitrogen, the gained viscous soln be cooled to room temperature and be used without further purification.Solid content is about 25%.
Embodiment A l: the susceptibility test
Prepare the photo curable composition that is used for the susceptibility test by mixing following component:
200.0 the multipolymer (first of weight part benzyl methacrylate and methacrylic acid
The base benzyl acrylate: methacrylic acid=80: 20 by weight
Meter) 25% propylene glycol 1-monomethyl ether 2-acetic ester (PGMEA)
Solution, preparation in the above-described embodiments
50.0 the weight part dipentaerythritol acrylate ((DPHA),
Provide by UCB Chemicals)
2.0 weight part light trigger (or photoinitiator mixtures) and
150.0 weight part PGMEA
All operations all carries out under gold-tinted.The electric applicator that use has the coiling rod is applied to composition on the aluminium sheet.By in convection furnace, heating down to come except that desolvating in 2 minutes at 100 ℃.The thickness of dry film is about 2 microns.The stdn test negative film (Stouffer discontinuous wedge (step sedge)) that will have 21 different optical density(OD) stages (step) places between this film and the resist layer with about 100 microns clearances.(USHIO USH-250BY) exposes with 15 cm distance to use the 250W ultrahigh pressure mercury lamp.The total exposure dosage that records by light power meter (the ORC UV Light Measure Model UV-M02 with UV-35 detector) on the test negative film is 250mJ/cm 2After exposure, use spray-type photographic developer (WalterLemmen, model T21) that the film of exposure was developed 100 seconds down at 30 ℃ with 1% aqueous sodium carbonate.The susceptibility of used initiator system characterizes by the acme number that the back of pointing out to develop keeps (being polymerization).Number of stages is high more, is subjected to the examination system sensitive more.The results are shown in the table 6.
Table 6: discontinuous wedge susceptibility
Figure A20068004806501041
Figure A20068004806501051
# by Ciba Specialty Chemicals provide=
Figure A20068004806501052

Claims (18)

1. the compound of formula I or II
Figure A2006800480650002C1
Wherein
M 1, M 2And M 3Be no key, direct key, CO, O, S, SO, SO independently of one another 2Or NR 14Condition is M 1, M 2Or M 3At least one be direct key, CO, O, S, SO, SO 2Or NR 14
M 4Be direct key, CR " 3R " 4, CO, CS, O, S, SO or SO 2
Y is direct key, S or NR 18
R 1Be hydrogen, C 3-C 8Cycloalkyl, C 2-C 5Alkenyl, C 1-C 20Alkoxyl group, unsubstituted C 1-C 20Alkyl or by one or more halogens, phenyl, C 1-C 20The C that alkyl phenyl and/or CN replace 1-C 20Alkyl;
Or R 1Be phenyl or naphthyl, both all are unsubstituted or by one or more C 1-C 6Alkyl, C 1-C 4Haloalkyl, halogen, CN, OR 11, SR 10And/or NR 12R 13Replace;
Or R 1Be benzyloxy or phenoxy group, both all are unsubstituted or by one or more C 1-C 6Alkyl, C 1-C 4Haloalkyl and/or halogen replace;
R 2Be hydrogen, C 1-C 20Alkyl or C 3-C 10Cycloalkyl, it is optional by O, CO or NR 14Insert;
Or R 2Be optional by one or more halogens, OR 11, COOR 11, CONR 12R 13, phenyl or by halogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11Or NR 12R 13The C that the phenyl that replaces replaces 1-C 20Alkyl;
Or R 2Inserted by one or more O and/or choose wantonly by one or more halogens, OR 11, COOR 11, CONR 12R 13, phenyl or by SR 10, OR 11Or NR 12R 13The C that the phenyl that replaces replaces 2-C 20Alkyl;
Or R 2Be phenyl, naphthyl, tonka bean camphor base or heteroaryl, it is optional separately by one or more C 1-C 12Alkyl, phenyl, halogen, C 1-C 4Haloalkyl, CN, NO 2, SR 10, OR 11, NR 12R 13Replace, or chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
Or R 2Be C 2-C 20Alkyloyl or do not replace or by one or more C 1-C 6Alkyl, halogen, phenyl, SR 10, OR 11Or NR 12R 13The benzoyl that replaces;
Or R 2Be optional the insertion by one or more O and/or the optional C that is replaced by one or more OH 2-C 12Alkoxy carbonyl;
Or R 2Be unsubstituted or by one or more C 1-C 6Alkyl, C 1-C 4Haloalkyl, halogen, phenyl, SR 10, OR 11Or NR 12R 13The phenyloxycarbonyl that replaces;
R " 2Have R 2One of implication that provides; Or be Or
Figure A2006800480650003C2
M 5Be no key, direct key, CO, O, S, SO, SO 2Or NR 14
R 3And R 4Be hydrogen, halogen, C independently of one another 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or be C 4-C 8Cycloalkenyl group, C 2-C 12Alkynyl group, phenyl-C 1-C 4Alkyl, CN, NO 2,
Figure A2006800480650003C3
Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 3And R 4Be not replace or by one or more SR 10, OR 11Or NR 12R 13The phenyl that replaces;
Or R 3And R 4Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring;
Or R 3And R 4Be C together 1-C 6Alkylidene group or C 2-C 6Alkylene group, thus dicyclo formed with the phenyl that links to each other with them, and wherein said dicyclo is optional by one or more C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11, NR 12R 13, halogen, phenyl, COOR 11, CONR 12R 13, CN, NO 2Replace, or chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted, or quilt is by O, CO or NR 14The C that inserts 2-C 20Alkyl replaces, and wherein said dicyclo is optional condenses with other aromatic ring and/or hetero-aromatic ring;
R ' 1Have R 1One of implication that provides;
R ' 2Have R 2One of implication that provides;
R ' 3, R ' 4, R " 3And R " 4Have R independently of one another 3And R 4One of implication that provides;
R 5Be hydrogen, halogen, C 1-C 4Haloalkyl, C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or be C 4-C 8Cycloalkenyl group, C 2-C 12Alkynyl group, phenyl-C 1-C 4Alkyl, CN, NO 2, Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 5Be not replace or by one or more halogens, C 1-C 4Haloalkyl, C 1-C 20Alkyl, SR 10, OR 11, NR 12R 13, or by O, CO or NR 14The C that inserts 2-C 20The phenyl that alkyl replaces;
Or R 5Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring;
Or R 5Be
Figure A2006800480650004C2
Or
Figure A2006800480650004C3
R 6And R ' 6Be hydrogen, halogen, C independently of one another 1-C 4Haloalkyl, C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or be C 4-C 8Cycloalkenyl group, C 2-C 12Alkynyl group, phenyl-C 1-C 4Alkyl, CN, NO 2,
Figure A2006800480650004C4
, or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 6And R ' 6Be unsubstituted or by one or more halogens, C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11Or NR 12R 13The phenyl that replaces;
Or R 6And R ' 6Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring;
Or R 6And R ' 6Be C together 1-C 6Alkylidene group or C 2-C 6Alkylene group, thus dicyclo formed with the phenyl that links to each other with them, and wherein said dicyclo is optional by one or more C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl replaces, by C 1-C 4Haloalkyl, SR 10, OR 11, NR 12R 13, halogen, phenyl, COOR 11, CONR 12R 13, CN, NO 2, or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted, and wherein said dicyclo is optional condenses with other aromatic ring and/or hetero-aromatic ring; Condition is a group
Figure A2006800480650005C1
Or
Figure A2006800480650005C2
Be connected on arbitrary ring of described dicyclo;
R 7, R ' 7, R 8And R ' 8Have R independently of one another 3And R 4One of implication that provides;
R 9And R ' 9Be hydrogen, halogen, C independently of one another 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl or optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or C 4-C 8Cycloalkenyl group, C 2-C 12Alkynyl group, phenyl-C 1-C 4Alkyl, CN, NO 2,
Figure A2006800480650005C3
Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 9And R ' 9Be unsubstituted or by one or more halogens, C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11Or NR 12R 13The phenyl that replaces;
Or R 9And R ' 9Be (CO) R 15, SR 10, OR 11, SOR 10, SO 2R 10Or NR 12R 13, substituting group (CO) R wherein 15, OR 11, SR 10And NR 12R 13Optional via radicals R 10, R 11, R 12R 13And/or R 15Form 5-or 6-unit ring with further substituting group on the benzyl ring or with one of carbon atom of benzyl ring;
R 10Be hydrogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, C 2-C 12Alkenyl, optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl,
Or R 10Be phenyl-C 1-C 4Alkyl; By OH, SH, CN, C 3-C 6Alkenyloxy ,-OCH 2CH 2CN ,-OCH 2CH 2(CO) O (C 1-C 4Alkyl) ,-O (CO)-(C 1-C 4Alkyl) ,-O (CO)-phenyl ,-(CO) OH or-(CO) O (C 1-C 4Alkyl) C of Qu Daiing 1-C 8Alkyl;
Or R 10By the C of one or more O or S insertion 2-C 20Alkyl;
Or R 10Be-(CH 2CH 2O) nH ,-(CH 2CH 2O) n(CO)-(C 1-C 8Alkyl), C 2-C 8Alkyloyl, benzoyl, C 3-C 6Alkenoyl;
Or R 10Be phenyl or naphthyl, it respectively does for oneself unsubstituted or by one or more halogens, C 1-C 12Alkyl, C 1-C 4Haloalkyl, C 1-C 12Alkoxyl group,
Figure A2006800480650006C1
Phenyl-C 1-C 3Alkoxyl group, phenoxy group, C 1-C 12Alkyl alkylthio base, phenyl sulfane base ,-N (C 1-C 12Alkyl) 2, diphenyl amino ,-(CO) O (C 1-C 8Alkyl) or (CO) N (C 1-C 8Alkyl) 2Replace;
Or R 10Be phenyl or naphthyl, they are via direct key, C 1-C 4Alkylidene group, O, S, NR 14Or CO and and SR 10The benzyl ring that links to each other forms 5-or 6-unit ring together, and wherein said phenyl or naphthyl is unsubstituted or by one or more C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl replaces, or is chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted or by halogen,
Figure A2006800480650006C2
C 1-C 20Alkoxyl group, C 1-C 20Alkyl-carbonyl or phenylcarbonyl group replace;
N is the integer of 1-12;
R " 1Have R 1And R ' 1One of implication that provides;
R ' " 2Have R 2And R ' 2One of implication that provides;
R 11Be hydrogen, the optional C that is replaced by one or more halogens 1-C 20Alkyl; Or be-(CH 2CH 2O) nH ,-(CH 2CH 2O) n(CO)-(C 1-C 8Alkyl), C 1-C 8Alkyloyl, C 2-C 12Alkenyl, C 3-C 6Alkenoyl, phenyl-C 1-C 4Alkyl; The C that is inserted by one or more O 2-C 20Alkyl; Optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 11By OH, SH, CN, C 3-C 6Alkenyloxy ,-OCH 2CH 2CN ,-OCH 2CH 2(CO) O (C 1-C 4Alkyl) ,-O (CO)-(C 1-C 4Alkyl) ,-O (CO)-phenyl ,-(CO) OH or-(CO) O (C 1-C 4Alkyl) C of Qu Daiing 1-C 8Alkyl;
Or R 11Be unsubstituted or by one or more C 1-C 6Alkyl, halogen, C 1-C 4Haloalkyl, OH or C 1-C 4The benzoyl that alkoxyl group replaces;
Or R 11Be phenyl or naphthyl, its respectively do for oneself unsubstituted or by one or more halogens, OH,
Figure A2006800480650006C3
C 1-C 12Alkyl, C 3-C 10Cycloalkyl or C 1-C 12Alkoxyl group replaces;
R 12And R 13Be hydrogen, C independently of one another 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, C 2-C 4Hydroxyalkyl, C 1-C 12Alkoxyl group, phenyl-C 1-C 4Alkyl, (CO) R 15, C 2-C 10Alkoxyalkyl, C 3-C 5Alkenyl or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl;
Or R 12And R 13Be phenyl or naphthyl, it respectively does for oneself unsubstituted or by one or more halogens, C 1-C 4Haloalkyl, C 1-C 20Alkoxyl group, (CO) R 15, phenyl, NR 16R 17, SR 10, OR 11,
Figure A2006800480650007C1
C 1-C 20Alkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl replaces, or is chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
Or R 12And R 13Be C independently of one another 2-C 5Alkylidene group or C 2-C 5Alkylene group, it is connected to and NR 12R 13On one of C-atom of the phenyl or naphthyl ring that links to each other, wherein said C 2-C 5Alkylidene group or C 2-C 5Alkylene group is optional by O, CO or NR 14Insert; Or
R 12And R 13Be phenyl independently of one another, it is connected to NR via direct key 12R 13On the benzyl ring thereon of position; Or
R 12And R 13Form the saturated or unsaturated ring of 5-or 6-unit with the N-atom that links to each other with them, it is optional by O, N or NR 14Insert, and this ring is unsubstituted or by one or more C 1-C 20Alkyl, C 1-C 20Alkoxyl group ,=O, SR 10, OR 11Or NR 16R 17, (CO) R 15, NO 2, halogen, C 1-C 4Haloalkyl, CN, phenyl,
Figure A2006800480650007C2
Replace, or chosen wantonly by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted; Or
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them, this hetero-aromatic ring system is unsubstituted or by one or more C 1-C 20Alkyl, C 1-C 4Haloalkyl, C 1-C 20Alkoxyl group ,=O, SR 10, OR 11, NR 16R 17, (CO) R 15,
Figure A2006800480650007C3
Halogen, NO 2, CN, phenyl replace, or by optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
R 14Be hydrogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, the C that is inserted by O or CO 2-C 20Alkyl, or be phenyl-C 1-C 4Alkyl, optional by the C of O or CO insertion 3-C 8Cycloalkyl, or be (CO) R 15Or phenyl, this phenyl is unsubstituted or by one or more C 1-C 20Alkyl, halogen, C 1-C 4Haloalkyl, SR 10, OR 11, NR 12R 13Or
Figure A2006800480650007C4
Replace;
R 15Be hydrogen, OH, C 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl, optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl, or be phenyl-C 1-C 4Alkyl, SR 10, OR 11Or NR 12R 13
Or R 15Be phenyl, naphthyl, tonka bean camphor base or heteroaryl, it respectively does for oneself unsubstituted or by one or more SR 10, OR 11, NR 12R 13,
Figure A2006800480650008C1
CN, NO 2, halogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
R 16And R 17Be hydrogen, C independently of one another 1-C 20Alkyl, C 1-C 4Haloalkyl, C 3-C 10Cycloalkyl or phenyl; Or
R 16And R 17Form the saturated or unsaturated ring of 5-or 6-unit with the N-atom that links to each other with them, it is optional by O, S or NR 14Insert;
Or R 16And R 17Be C independently of one another 2-C 5Alkylidene group or C 2-C 5Alkylene group, it is connected to and NR 16R 17On one of the benzyl ring that links to each other or C-atom of naphthyl ring, wherein said C 2-C 5Alkylidene group or C 2-C 5Alkylene group is optional by O, CO or NR 15Insert, and choose wantonly at this C 2-C 5Alkylidene group or C 2-C 5Fused benzene rings on the alkylene group;
R 18Be hydrogen, (CO) R " 2, C 1-C 20Alkoxy carbonyl, phenyl-C 1-C 4Alkyl, optional by one or more halogens, COOR 11Or CONR 12R 13The C that replaces 1-C 20Alkyl;
Or R 18By O, CO or NR 14The C that inserts 2-C 20Alkyl; Optional by O, CO or NR 14The C that inserts 2-C 12Alkenyl, or be C 4-C 8Cycloalkenyl group or C 2-C 12Alkynyl group;
Or R 18Be benzoyl, naphthoyl, phenyloxycarbonyl or naphthyloxy carbonyl, it is optional separately by one or more C 1-C 20Alkyl, C 1-C 4Haloalkyl, SR 10, OR 11, NR 12R 13, halogen, phenyl, COOR 11, CONR 12R 13, CN, NO 2Or it is optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
Or R 18Be optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl, or optional by O, CO or NR 14The C that inserts 3-C 10Naphthene base carbonyl, or optional by O, CO or NR 14The C that inserts 3-C 10Cyclo alkoxy carbonyl;
Or R 18Be phenyl or naphthyl, both are all optional by one or more SR 10, OR 11, NR 12R 13,
Figure A2006800480650008C2
CN, NO 2, halogen, C 1-C 20Alkyl, C 1-C 4Haloalkyl, by O, CO or NR 14The C that inserts 2-C 20Alkyl or optional by O, CO or NR 14The C that inserts 3-C 10Cycloalkyl substituted;
Condition is to have at least two oxime ester base groups in molecule.
2. according to the formula I of claim 1 or the compound of II, wherein
M 1, M 2And M 3Be no key or direct key independently of one another; Condition is M 1, M 2Or M 3At least one be direct key;
M 4Be direct key or CO;
Y is S or NR 18
R 1And R ' 1Be C 1-C 20Alkyl; C 1-C 20Alkoxyl group or phenyl;
R 2And R ' 2Be unsubstituted C independently of one another 1-C 20Alkyl, by COOR 11Or CONR 12R 13The C that replaces 1-C 20Alkyl; Unsubstituted or by OR 11The C that replaces 2-C 20Alkyloyl; Or by NR 12R 13The phenyl that replaces;
R " 2It is phenyl; By one or more NR 12R 13, halogen, C 1-C 20Alkyl replaces or the optional C that is inserted by O of quilt 3-C 10The phenyl of cycloalkyl substituted;
Or R " 2Be heteroaryl, particularly thienyl and furyl, it is optional to be replaced by alkyl; Or
Figure A2006800480650009C1
Or
Figure A2006800480650009C2
M 5It is direct key;
R 3, R 4, R ' 3, R ' 4, R " 3And R " 4Be independently of one another hydrogen, halogen,
Figure A2006800480650009C3
(CO) R 15
Or R 3And R 4Be C together 2-C 6Thereby alkylene group forms dicyclo with the phenyl that links to each other with them;
R 5Be hydrogen,
Figure A2006800480650009C4
Or
Figure A2006800480650009C5
R 6, R ' 6, R 8And R ' 8Be hydrogen;
R 7And R ' 7Be independently of one another hydrogen or
Figure A2006800480650009C6
R 9And R ' 9Be hydrogen, (CO) R independently of one another 15Or
Figure A2006800480650009C7
R 11Be C 1-C 20Alkyl;
R 12And R 13Be C independently of one another 1-C 20Alkyl; Or
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them, this hetero-aromatic ring system is unsubstituted or quilt Replace;
R 14Be C 1-C 20Alkyl;
R 15Be phenyl or heteroaryl, it is optional separately by NR 12R 13Or C 1-C 20Alkyl replaces;
R 18Be C 1-C 20Alkyl; Optional by C 1-C 20Alkyl or NR 12R 13The benzoyl that replaces; Or phenyl or naphthyl, both all optional by one or more halogens or
Figure A2006800480650010C2
Replace; And
Condition is to have at least two oxime ester base groups in this molecule.
3. photoinitiator mixtures comprises
(A) compound of at least a formula I as claimed in claim 1 or II and
(B) compound of at least a formula I ' or II '
Figure A2006800480650010C3
Wherein
A is a group
Figure A2006800480650010C4
M 1, M 2, M 3, M 4, Y, R 1And R 2As definition in the claim 1;
R 3, R 4, R 5, R ' 3, R ' 4, R " 2, R " 3And R " 4As definition in the claim 1, wherein group as defining in the claim 1
Figure A2006800480650010C5
And/or
Figure A2006800480650010C6
Can by
Figure A2006800480650010C7
And/or Substitute;
Z is hydrogen, COR 1, COR ' 1Or COR " 1
R ' 1, R " 1, R ' 2And R ' " 2As definition in the claim 1;
Condition is to have at least two oxime ester base groups in this molecule.
4. according to the photoinitiator mixtures of claim 3, comprise the compound of formula I at least and the compound of formula I ' at least, wherein
M 1And M 2Be no key;
M 3Be direct key;
R 1, R ' 1, R " 1, R 2And R ' 2As definition in the claim 1;
R 3, R ' 3, R " 3, R 4, R ' 4And R " 4Be hydrogen;
R 5For
Figure A2006800480650011C1
R " 2By NR 12R 13The phenyl that replaces; And
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them, or comprise the compound of formula II at least and the compound of formula II ' at least, wherein
M 4Be direct key;
R 1, R ' 1, R " 1, R ' " 2And R ' 2As definition in the claim 1;
Y is NR 18
R 18By
Figure A2006800480650011C2
The phenyl that replaces;
R 2By NR 12R 13The phenyl that replaces; With
R 12And R 13Form the hetero-aromatic ring system with the N-atom that links to each other with them.
5. according to the photoinitiator mixtures of claim 3 or 4, it also comprises other oxime ester photoinitiator except the compound of formula I or II and formula I ' or II '.
6. a photopolymerizable composition comprises
(a) the undersaturated photopolymerization compound of at least a olefinic and
(b) as light trigger, at least a as the formula I of definition in the claim 1 or the compound of II, or as the mixture of the compound of the formula I that defines in the claim 3 or II.
7. according to the photopolymerizable composition of claim 6, it also comprises at least a other light trigger (c) and/or other additive (d) except that light trigger or photoinitiator mixtures (b).
8. according to each photopolymerizable composition of claim 6-7, comprise the light trigger (b) of 0.05 to the 25 weight % that accounts for composition, or light trigger (b) and (c).
9. according to each photopolymerizable composition of claim 6-8, comprise photosensitizers, particularly be selected from the compound of benzophenone and derivative thereof, thioxanthone and derivative thereof, anthraquinone and derivative thereof or tonka bean camphor and derivative thereof as further additive (d).
10. according to each photopolymerizable composition of claim 6-9, comprise the multipolymer of binder polymer (e), particularly methacrylic ester and methacrylic acid in addition.
11. contain the photopolymerization method of the compound of ethylenical unsaturated double bonds, it comprises the electromagnetic radiation with 150 to 600 nanometers, or with electron beam or with x-ray irradiation according to each composition of claim 6-10.
12. the preparation method of the compound of formula I as claimed in claim 1 or II comprises the oxime compound that makes formula Ia or IIa
Figure A2006800480650012C1
Wherein
R 2, R " 2, Y, M 1, M 2, M 3And M 4As definition in the claim 1;
R 3, R ' 3, R " 3, R 4, R ' 4, R " 4And R 5As definition in the claim 1, wherein group as defining in the claim 1 And/or
Figure A2006800480650012C3
Can by
Figure A2006800480650012C4
And/or
Figure A2006800480650012C5
Substitute;
R ' 2And R ' " 2As definition in the claim 1;
Z is hydrogen, COR 1, COR ' 1Or COR " 1
Condition is that at least one the group Z in the compound of formula Ia and IIa is a hydrogen;
Acyl halide or acid anhydrides with formula V or VI
Figure A2006800480650012C6
Figure A2006800480650012C7
Or formula V and (Va) or (VI) and the mixture of acyl halide (VIa)
Figure A2006800480650012C8
Wherein Hal is meant halogen atom, and R 1And R ' 1As definition in the claim 1,
Reaction in the presence of the mixture of alkali or alkali.
13. according to each the purposes of composition of claim 6-10, be used to make painted and uncoloured paint and varnish, powder coating, printing-ink, printing plate, tackiness agent, pressure sensitive adhesive, dental composition, gel coating, the electronics photo-resist, platedresist, anti-etching dose, liquid and desciccator diaphragm, solder resist, manufacturing is used for the resist that the colour filter of various demonstration purposes is used, produce plasma display panel, the resist that structure in the manufacturing processed of electroluminescent display and LCD is used, the spacer of LCD, be used for holographic data storage (HDS), as the composition of sealing electricity and electronic component, be used to make magnetic recording material, micromechanical component, waveguide, optical switch, electroplate mask, etching mask, color gluing system, glass fiber cable coating, the silk screen printing template, be used for making three-dimensional article by stereolithography techniques, as image recording material, be used for holographic recording, microelectronic circuit, decoloring material, the decoloring material that image recording material is used, be used to use the image recording material of microcapsule, the photo anti-corrosion agent material of using as UV and visible laser direct imaging optics is as the used photo anti-corrosion agent material of dielectric layer in the continuous accumulation layer that forms printed circuit board (PCB).
14. method according to claim 11, it is used to make painted and uncoloured paint and varnish, powder coating, printing-ink, printing plate, tackiness agent, pressure sensitive adhesive, dental composition, gel coating, the electronics photo-resist, platedresist, anti-etching dose, liquid and desciccator diaphragm, solder resist, manufacturing is used for the resist that the colour filter of various demonstration purposes is used, produce plasma display panel, the resist that structure in the manufacturing processed of electroluminescent display and LCD is used, the spacer of LCD, be used for holographic data storage (HDS), as the composition of sealing electricity and electronic component, be used to make magnetic recording material, micromechanical component, waveguide, optical switch, electroplate mask, etching mask, color gluing system, glass fiber cable coating, the silk screen printing template, be used for making three-dimensional article by stereolithography techniques, as image recording material, be used for holographic recording, microelectronic circuit, decoloring material, the decoloring material that image recording material is used, be used to use the image recording material of microcapsule, the photo anti-corrosion agent material of using as UV and visible laser direct imaging optics is as the used photo anti-corrosion agent material of dielectric layer in the continuous accumulation layer that forms printed circuit board (PCB).
15. at least one surface, use coat substrates according to the composition coating of claim 6.
16. be used for the method that the photograph of camegraph is made, wherein make coat substrates according to claim 15 according to image exposure, remove unexposed part with photographic developer then.
17. by providing the redness, green and the blue pixel that all comprise photosensitive resin and pigment and black matix on the transparent substrates and on the substrate surface or the colour filter that provides transparency electrode to make on the colour filter surface, wherein said photosensitive resin comprises polyfunctional acrylic ester monomer, organic polymer binder and according to the formula I of claim 1 or the photo-induced polymerization initiator of II.
18. the compound of formula Ia or IIa
Wherein
R 2, R " 2, Y, M 1, M 2, M 3And M 4As definition in the claim 1;
R 3, R ' 3, R " 3, R 4, R ' 4, R " 4And R 5As definition in the claim 1, wherein group as defining in the claim 1
Figure A2006800480650014C2
And/or
Figure A2006800480650014C3
Can by
Figure A2006800480650014C4
And/or
Figure A2006800480650014C5
Substitute;
R ' 2And R ' " 2As definition in the claim 1;
Z is hydrogen, COR 1, COR ' 1Or COR " 1
Condition is that at least one the group Z in the compound of formula Ia and IIa is a hydrogen;
And condition is to have at least two groups that comprise group Z in this molecule.
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