CN101048372A - Thiol compound, and photosensitive composition and black matrix resist composition using the compound - Google Patents

Thiol compound, and photosensitive composition and black matrix resist composition using the compound Download PDF

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CN101048372A
CN101048372A CNA2005800364238A CN200580036423A CN101048372A CN 101048372 A CN101048372 A CN 101048372A CN A2005800364238 A CNA2005800364238 A CN A2005800364238A CN 200580036423 A CN200580036423 A CN 200580036423A CN 101048372 A CN101048372 A CN 101048372A
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methyl
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CN101048372B (en
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镰田博稔
大西美奈
室伏克己
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Resonac Holdings Corp
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Showa Denko KK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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Abstract

The invention is related to a thiol compound represented by formula (1), production method thereof, and a photosensitive composition and a resist composition for black matrix for color filters which use the thiol compound and are excellent in sensitivity and can keep the line width in patterns unchanged, i. e. attain an excellent developing latitude. (All the symbols have the same meanings as defined in the Description.

Description

The photosensitive composition and the black matix resist composition of mercaptan compound and this compound of use
The cross reference of related application
The application is the application of submitting to according to 35U.S.C. the 111st (a) part, it is according to 35U.S.C. the 119th (e) (1) part, U.S. Provisional Application sequence number 60/624,530 that requirement is submitted on November 4th, 2004 according to the clause of 35U.S.C.111 (b) part and 60/624,531 rights and interests.
Technical field
The present invention relates to the new mercaptan compound with bis-phenol skeleton, its preparation method, and relate to alkali developable type photosensitive composition that uses this compound and the black matix resist composition that is used for colour filter.More particularly, the present invention relates to the new mercaptan compound with bis-phenol skeleton, relate to the photosensitive composition that uses this compound and be used for the black matix resist composition of colour filter, said composition contains: the Photoepolymerizationinitiater initiater system that (A) comprises this compound; (B) has the adhesive resin of carboxyl; (C) have the compound of ethylenically unsaturated group, and said composition has hypersensitivity when alkaline development and the characteristic of excellent maintenance live width in thread pattern.
Background technology
Photosensitive composition is used for various fields, comprises press plate, color proofing, colour filter, solder resist and light-curable ink.Especially in recent years, the character of the tool feature of Photocurable composition such as the concern that room temperature operability, rapidly-curable and solvent-free property have been subjected to each field, comprise those from the environment aspect, the application considered such as energy-conservation, work safety, production cost, and photosensitive composition has been carried out many research and development.
Compound and various additive that photosensitive composition mainly solidifies, has ethylenic unsaturated bond by Photoepolymerizationinitiater initiater, adhesive resin, by polyreaction are formed, and the kind of these components depends on the purposes of photosensitive composition.
Photoepolymerizationinitiater initiater is selected according to photosensitive wavelength and polymerization initiation performance.Adhesive resin, the compound with ethylenic unsaturated bond and additive are selected according to the physicals of polymerizability and the cured product wanted.These components combine and are used to constitute photosensitive composition.
Yet, use some adhesive resin, some has under the situation of the compound of ethylenic unsaturated bond and some additive separately,
(1) can not obtain to cause photopolymerisable enough energy;
(2) can not obtain stability in storage;
(3) owing to the thickness of the solidifying product of wanting, it is enough dark that radiant light can not reach therein, causes curing insufficient;
(4) the part generation oxygen inhibition that contacts with air at photosensitive composition; With
(5) under alkaline development, the performance that keeps the thread pattern live width is low.
For those problems, various measures have been taked; For example, adopt bigger light ray radiation, excessive Photoepolymerizationinitiater initiater and the placement oxygen screened film of use.Yet, for energy-conservation and minimizing production cost, the photosensitive composition that need have higher sensitivity of light.
Wherein, in the colour filter performance history that is used for color TV, liquid-crystal display, solid state image sensing device, photographic camera etc., considering to be used for the colo(u)rant dispersion resist of colour filter to boost productivity and higher sharpness.In this type of is used, to increasing day by day in the demand that more low-yieldly more promptly solidify down, can reach higher sharpness when forming pattern and have a photosensitive composition of more excellent curing depth.
The common following manufacturing of colour filter: on transparent substrate such as glass or plastics sheet surface, form the matrix (black matix) that trellis black, form three kinds or the multiple different form and aspect patterns such as red, green, blue of the tolerance range that reaches several microns then.Wherein, the configuration black matix is to improve contrast gradient and to prevent the TFT fault.Yet the resist (black matix resist) that forms this black matix has high photoresistance effect, therefore is difficult to photocuring in essence.But,, the demand of hypersensitivity is increased day by day along with the glass baseplate size increases.Simultaneously, even still can keep the almost constant resist of fine pattern live width, i.e. its excellence aspect the development latitude when needing strongly to be exposed to alkaline-based developer for a long time.
Recently, because liquid-crystal display begins to be applied to televisor,, and wish that pigment has higher concentration to the increase in demand of colour filter with excellent colour contrast.Yet, because highly enriched pigment can cause susceptibility to reduce.Therefore, for improving the susceptibility of photosensitive composition or black matix resist composition, advised using multi-functional thiol's compound (JP 10-253815A, JP 10-253816A, JP10-253817A, JP 2004-149755A etc.).
Yet, multi-functional thiol's compound of before having advised, because the polyol component of its basic framework of conduct that wherein contains is aliphatic, the problem that exists in by the photocuring product that uses this compound to obtain is: because the alkaline-resisting development of difference, the line widths shrink of thread pattern, the susceptibility of composition promptly has the insufficient problem of development latitude, although can improve.Especially, for the top black matix resist that will form the trellis pattern, it is very crucial that the phenomenon of thread pattern line widths shrink becomes.
Summary of the invention
The purpose of this invention is to provide when alkaline development that live width keeps constant excellent performance, the hypersensitivity photosensitive composition of the latitude of promptly developing excellence and black matix resist composition in thread pattern.
As the result of wholwe-hearted research, the present inventor has finished the present invention by following discovery: the problems referred to above can solve by photosensitive composition or the black matix resist composition that uses the new mercaptan compound with bis-phenol skeleton.
That is to say, the present invention relates to according among the 1-20 as described below any one new mercaptan compound, its preparation method and use the photosensitive composition and the black matix resist composition of this compound.
1. mercaptan compound by formula (1) expression:
Figure A20058003642300091
(R in the formula, 1Expression has the straight or branched alkylidene group of 1-6 carbon atom, R 2Expression has the straight or branched alkylidene group of 2-6 carbon atom, R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2-or-O-and n represent the integer of 1-5).
2. according to 1 described mercaptan compound, wherein R 1Be alkylidene group by any expression in formula (2)-(6):
-CH 2CH 2-* (2)
(symbol " * " shows the position with the sulfydryl bonding).
3. according to 1 described mercaptan compound, wherein R 2It is alkylidene group by any expression in formula (7)-(9).
-CH 2CH 2- (7)
Figure A20058003642300102
4. according to 1 described mercaptan compound, it is represented by formula (10):
(in the formula, m represents 1 or 2 integer).
5. according to 1 described mercaptan compound, it is the compound of the esterification acquisition between the carboxylic acid cpd that contains sulfydryl of diol compound and formula (12) expression of through type (11) expression:
Figure A20058003642300111
(R in the formula, 2Expression has the alkylidene group of the linearity or the branching of 2-6 carbon atom, R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2-or-O-and n represent the integer of 1-5; )
Figure A20058003642300112
(R in the formula, 1Expression has the alkylidene group of the linearity or the branching of 1-6 carbon atom).
6. method for preparing by the mercaptan compound of formula (1) expression:
Figure A20058003642300113
(all symbols have as above-mentioned identical implication in the formula), it comprises the esterification of the diol compound and the carboxylic acid cpd that contains sulfydryl that formula (12) is represented of formula (11) expression:
Figure A20058003642300114
(R in the formula, 2Expression has the linearity or the sub-branched alkyl of 2-6 carbon atom, R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2)-or-O-, n represents the integer of 1-5; )
Figure A20058003642300115
(R in the formula, 1Expression has the linearity or the sub-branched alkyl of 1-6 carbon atom).
7. a photosensitive composition comprises: the Photoepolymerizationinitiater initiater system that (A) contains each described mercaptan compound among the with good grounds 1-5; (B) contain the adhesive resin of carboxyl; (C) has the compound of ethylenically unsaturated group.
8. according to 7 described photosensitive compositions, wherein Photoepolymerizationinitiater initiater system (A) contains six aryl united imidazoles and/or aminoacetophenone compound.
9. according to 8 described photosensitive compositions, wherein six aryl united imidazoles are represented by formula (13):
Figure A20058003642300121
(in the formula, Y represents halogen atom, R 5Expression alkyl or alkoxyl group, they can have substituting group).
10. according to 7 described photosensitive compositions, wherein Photoepolymerizationinitiater initiater system (A) contains sensitizing agent.
11. according to 10 described photosensitive compositions, wherein sensitizing agent is one or more compounds that are selected from the group of being made up of benzophenone based compound, thioxanthone based compound and ketone group tonka bean camphor based compound.
12. according to 7 described photosensitive compositions, the adhesive resin (B) that wherein contains carboxyl further contains ethylenically unsaturated group.
13. resist composition that is used for the colour filter black matix, it contains: the Photoepolymerizationinitiater initiater system that (A) contains with good grounds each described mercaptan compound of 1-5, (B) has the adhesive resin of carboxyl, (C) has the compound of ethylenically unsaturated group, (D) black pigment and (E) organic solvent.
14. according to the 13 described resist compositions that are used for the colour filter black matix, the adhesive resin (B) that wherein has carboxyl further has ethylenically unsaturated group.
15. according to the 14 described resist compositions that are used for the colour filter black matix, the adhesive resin (B) that wherein has carboxyl is the bisphenol type Epocryl.
16. according to the 13 described resist compositions that are used for the colour filter black matix, wherein Photoepolymerizationinitiater initiater system (A) contains six aryl united imidazoles and/or aminoacetophenone compound.
17. according to the 16 described resist compositions that are used for the colour filter black matix, wherein six aryl united imidazoles are compounds of formula (13) expression:
Figure A20058003642300131
(all symbols have with 9 in defined identical implication).
18. according to the 16 or 17 described resist compositions that are used for the colour filter black matix, wherein Photoepolymerizationinitiater initiater system (A) contains as one or more of sensitizing agent and is selected from the compound of the group of being made up of benzophenone based compound, thioxanthone based compound and ketone group tonka bean camphor based compound.
19. according to the 13 described resist compositions that are used for the colour filter black matix, wherein black pigment (D) is that carbon black and/or titanium are black.
20., wherein except that organic solvent (E), comprise each component with following ratio according to the 13 described resist compositions that are used for the colour filter black matix:
(A) Photoepolymerizationinitiater initiater system; 2-15 quality %,
(B) has the adhesive resin of carboxyl; 10-30 quality %,
(C) has the compound of ethylenically unsaturated group; 2-20 quality % and
(D) black pigment; 40-80 quality %.
21. according to the 20 described resist compositions that are used for the colour filter black matix, the mercaptan compound of its Chinese style (1) is contained in the Photoepolymerizationinitiater initiater system (A) with 20-70 quality %.
Preferred forms of the present invention
1. the mercaptan compound that has the bis-phenol skeleton
The mercaptan compound that uses among the present invention is the mercaptan compound that has the bis-phenol skeleton in the molecule, and it is represented by formula (1):
Figure A20058003642300141
(R in the formula, 1Expression has the straight or branched alkylidene group of 1-6 carbon atom, R 2Expression has the straight or branched alkylidene group of 2-6 carbon atom, R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2-or-O-, n represents the integer of 1-5).Fashionable when the radical polymerization that carries out mercaptan compound, the resistance of the free radical of oxygen is poly-can be reduced significantly, so photosensitive composition demonstrates photosensitivity and significantly increases.In addition, because mercaptan compound according to the present invention contains the bis-phenol skeleton with high hydrophobicity, when mercaptan compound exposure and curing, even state of cure is lower, this hydrophobic performance also will give cured product high alkaline-resisting development.
In formula (1), R 1The straight chain and the branched alkylidene that preferably have 1-6 carbon atom.If carbonatoms surpasses 6, because the hydrophobic characteristics of mercaptan compound molecule itself reduces, the development latitude reduces.The alkylidene group that more preferably has the structure of any expression in formula (2)-(6) is as R 1
Figure A20058003642300142
(position of symbol " * " expression and sulfydryl bonding).Consider the stability in storage of composition, especially preferably have the mercaptan compound of the alkylidene group of arbitrary structure of expression in formula (4)-(6), this mercaptan compound forms the second month in a season or uncle's sulfydryl.
In formula (1), R 2The straight or branched alkylidene group that preferably has 2-6 carbon atom.If carbon atom surpasses 6, because the hydrophobic characteristics of mercaptan compound molecule itself reduces, the development latitude reduces.The alkylidene group that more preferably has the structure of any expression in formula (7)-(9):
Figure A20058003642300151
In formula (1), R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2-or-O-, n is the integer of 1-5 preferably.If the n value surpasses 5, because the hydrophobic characteristics of mercaptan compound molecule itself reduces, the development latitude reduces.
In addition, the preferably polyfunctional mercaptan compound of mercaptan compound of the present invention of formula (1) expression is to give black matix resist composition of the present invention with high susceptibility.Therefore, as the alcohol that is used for carrying out esterification with the carboxylic acid that contains sulfydryl of formula (12) expression, the glycol of preferred formula (11) expression, the i.e. glycol with bis-phenol skeleton of two alcoholic extract hydroxyl groups of existence in a molecule:
Figure A20058003642300152
(R in the formula, 1Expression has the straight or branched alkylidene group of 1-6 carbon atom.)
Figure A20058003642300161
(R in the formula, 2Expression has the straight or branched alkylidene group of 2-6 carbon atom, R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2-or-O-, n represents the integer of 1-5).
The specific examples of the diol compound of formula (1) expression comprises that alkylene oxide wherein such as oxyethane or propylene oxide are added to the compound on the phenolic hydroxyl group of following compounds.
Examples for compounds with phenolic hydroxyl group comprises that X is under the single bonded situation therein, 4, and 4 '-biphenol and 3,3 '-biphenol.
Therein X be-situation of CO-under, the example comprises two (4-hydroxyphenyl) ketone, two (4-hydroxyl-3,5-3,5-dimethylphenyl) ketone and two (4-hydroxyl-3,5-dichlorophenyl) ketone.
Wherein X is-SO 2-two (4-hydroxyphenyl) sulfones of examples for compounds-comprise, two (4-hydroxyl-3,5-3,5-dimethylphenyl) sulfone and two (4-hydroxyl-3,5-dichlorophenyl) sulfones of situation.
Wherein X is-CH 2-the examples for compounds of situation comprise two (4-hydroxyphenyl) methane, two (4-hydroxyl-3,5-3,5-dimethylphenyl) methane and two (4-hydroxyl-3,5-dichlorophenyl) methane.
Wherein X is-C (CF 3) 2-the examples for compounds of situation comprise two (4-hydroxyphenyl) HFC-236fa, two (4-hydroxyl-3,5-3,5-dimethylphenyl) HFC-236fa and two (4-hydroxyl-3,5-dichlorophenyl) HFC-236fa.
Wherein X is-C (CH 3) 2-the examples for compounds of situation comprise 2, two (4-hydroxyphenyl) propane, 2 of 2-, two (the 4-hydroxyls-3 of 2-, the 5-3,5-dimethylphenyl) propane, 2, two (the 4-hydroxyls-3 of 2-, the 5-dichlorophenyl) propane, 2, two (the 4-hydroxy-3-methyl phenyl) propane and 2 of 2-, two (4-hydroxyl-3-chloro-phenyl-) propane of 2-.
Much less, in the present invention, the examples for compounds with phenolic hydroxyl group is not limited to above-claimed cpd.
On the other hand, the example by the carboxylic acid that contains sulfydryl of formula (12) expression comprises Thiovanic acid, 3-thiohydracrylic acid, 2 mercaptopropionic acid, 3-sulfydryl butyric acid and 2-mercaptoisobutyric acid.Consider the package stability of photosensitive composition, the 2 mercaptopropionic acid of each self-forming second month in a season or uncle's sulfydryl, 3-sulfydryl butyric acid and 2-mercaptoisobutyric acid are particularly preferred.
The specific examples of particularly preferred mercaptan compound by formula (1) expression comprises the compound of being represented by formula (10), (14) and (15).
Figure A20058003642300171
(in the formula, m is 1 or 2 integer.)
Figure A20058003642300172
(in the formula, p is 1 or 2 integer.)
Figure A20058003642300173
(in the formula, k is 1 or 2 integer.)
Wherein, consider its reactivity, the mercaptan compound of being represented by formula (10) is preferred.
The method that the present invention of preparation formula (1) expression has the mercaptan compound of bis-phenol skeleton is not particularly limited, but the esterification between the glycol that the carboxylic acid that contains sulfydryl that mercaptan compound can through type (12) expression and formula (11) are represented and obtaining with bis-phenol skeleton.Esterification itself is that prior art is known, so this esterification can form ester in a usual manner.The esterification condition is not particularly limited, and can select the popular response condition suitably.
2. photosensitive composition and black matix corrosion stability composition
Photosensitive composition of the present invention and black matix resist composition contain the Photoepolymerizationinitiater initiater system that contains the mercaptan compound of formula (1) expression as (A) of main component, (B) has the adhesive resin of carboxyl, (C) has the compound of ethylenic unsaturated bond, and can choose wantonly and contain any various additive, comprise pigment and solvent.
2-1. Photoepolymerizationinitiater initiater system (A)
The Photoepolymerizationinitiater initiater system (A) that is used for photosensitive composition of the present invention can contain any other component except that above-mentioned mercaptan compound with bis-phenol skeleton, as those of the Photoepolymerizationinitiater initiater system being generally used for, as radical-forming agent and sensitizing agent.
(1) radical-forming agent
The example of spendable radical-forming agent comprises compound known in the colour filter black matix resist composition of the present invention, as acetophenone compound, triaizine compounds, two cyclopentadiene titanium compounds and ketoxime compound.Because photosensitivity, united imidazole and/or aminoacetophenone are preferred.
(1-1) bisglyoxaline based compound and/or phenacyl compound
Be usually used in the bisglyoxaline based compound that those any the present invention of can be used as of common photo etching and initiator system uses, but six aryl united imidazoles with formula (16) expression structure are preferred.
Figure A20058003642300181
In formula (16), Y 2, Y 3And Y 4Represent halogen atom, cyano group or nitro independently of one another, R 6, R 7, R 8, R 9And R 10Represent hydrogen atom independently of one another, can have substituent alkyl and maybe can have substituent alkoxyl group.
Above-mentioned Y 2, Y 3And Y 4The example of the halogen atom of expression comprises chlorine atom, bromine atoms and fluorine atom.
Above-mentioned R 6, R 7, R 8, R 9And R 10The example of the alkyl of expression comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl and n-hexyl.They can have substituting group such as alkoxyl group and halogen atom.Wherein, preferably have the linearity or the branched-chain alkyl of 1-6 carbon atom, more preferably have the linearity or the branched-chain alkyl of 1-3 carbon atom.
Above-mentioned R 6, R 7, R 8, R 9And R 10The example of the alkoxyl group of expression comprises methoxyl group, oxyethyl group, propoxy-, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy and positive hexyloxy.They can have substituting group such as alkoxyl group and halogen atom.Wherein, preferably have the linearity or the branched alkoxy of 1-6 carbon atom, more preferably have the linearity or the branched alkoxy of 1-3 carbon atom.
In the six aryl united imidazoles, the compound with structure of formula (13) expression is particularly preferred.
Figure A20058003642300191
In the formula, Y represents halogen atom, R 5Expression can have substituent alkyl maybe can have substituent alkoxyl group.
R 5The alkyl and the specific examples of alkoxyl group comprise R with six aryl united imidazoles of above-mentioned formula (16) expression 6-R 10The group that cited those are identical, but methyl or methoxy is particularly preferred.As the halogen atom that above-mentioned Y represents, the chlorine atom is particularly preferred.
Be used for phenacyl examples for compounds of the present invention and comprise hydroxy acetophenone compound and aminoacetophenone compound.Wherein, according to photosensitivity, the aminoacetophenone compound is particularly preferred.
The specific examples of hydroxy acetophenone compound comprises the Alpha-hydroxy methyl phenyl ketone, as
2-hydroxy-2-methyl-1-phenyl third-1-ketone,
2-hydroxy-2-methyl-1-phenyl fourth-1-ketone,
1-(4-aminomethyl phenyl)-2-hydroxy-2-methyl third-1-ketone,
1-(4-isopropyl phenyl)-2-methyl-prop-1-ketone,
1-(4-butyl phenyl)-2-hydroxy-2-methyl third-1-ketone,
2-hydroxy-2-methyl-1-(4-octyl phenyl) third-1-ketone,
1-(4-dodecylphenyl)-2-methyl-prop-1-ketone,
1-(4-p-methoxy-phenyl)-2-methyl-prop-1-ketone,
1-(4-methylbenzene sulfenyl)-2-methyl-prop-1-ketone,
1-(4-chloro-phenyl-)-2-hydroxy-2-methyl third-1-ketone,
1-(4-bromophenyl)-2-hydroxy-2-methyl third-1-ketone,
2-hydroxyl-1-(4-hydroxyphenyl)-2-methyl-prop-1-ketone,
1-(4-dimethylamino phenyl)-2-hydroxy-2-methyl third-1-ketone,
1-(4-carbonyl ethoxyl phenenyl)-2-hydroxy-2-methyl third-1-ketone,
The 1-hydroxycyclohexylphenylketone and
2-hydroxyl-1-(4-(2-hydroxyl-oxethyl)-phenyl)-2-methyl-prop-1-ketone.
The specific examples of aminoacetophenone compound comprises:
Alpha-aminoacetophenone, as
2-dimethylamino-2-methyl isophthalic acid-phenyl third-1-ketone,
2-diethylamino-2-methyl isophthalic acid-phenyl third-1-ketone,
2-methyl-2-morpholinyl-1-phenyl third-1-ketone,
2-dimethylamino-2-methyl isophthalic acid-(4-aminomethyl phenyl) the third-1 ketone,
2-dimethylamino-1-(4-ethylphenyl)-2-methyl-prop-1-ketone,
2-dimethylamino-1-(4-isopropyl phenyl)-2-methyl-prop-1-ketone,
1-(4-butyl phenyl)-2-dimethylamino-2-methyl-prop-1-ketone,
2-dimethylamino-1-(4-p-methoxy-phenyl)-2-methyl-prop-1-ketone,
2-dimethylamino-2-methyl isophthalic acid-(4-methylbenzene sulfenyl) third-1-ketone,
2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl third-1-ketone,
2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone and
2-benzyl-2-dimethylamino-1-(4-dimethylamino phenyl)-Ding-1-ketone.
The specific examples of other radical-forming agent comprises benzoin methylether, ethoxybenzoin, bitter almond oil camphor isopropyl ether, benzyl methyl ketal, alpha-halo acetophenone, Glyoxylic acid hydrate aminomethyl phenyl ester, benzyl, anthraquinone, phenanthrenequione, camphorquinone isophthaloyl benzophenone (isophthalophenone), acylphosphine oxide, acyl group oxime ester (α-acyloxime estyer), benzyl and camphorquinone.Also can use organic boron salt based compound of describing among the JP2000-249822.
(2) sensitizing agent
In the present invention, can use the sensitizing agent that is usually used in general Photoepolymerizationinitiater initiater system.Wherein, preferably use one or more compounds that is selected from the group of forming by benzophenone based compound, thioxanthone based compound and ketone group tonka bean camphor based compound, because can improve susceptibility.
The specific examples of this type of sensitizing agent comprises: the benzophenone based compound, as benzophenone, 2,4,6-tri-methyl benzophenone, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4,4 '-two (dimethylamino) benzophenone or 4,4 '-two (diethylamino) benzophenone; The thioxanthone based compound is as thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 2,4-di-isopropyl thioxanthone or 2-chloro thioxanthone; With ketone group tonka bean camphor based compound such as 3-ethanoyl tonka bean camphor, 3-ethanoyl-7-diethyl amino coumarin, 3-benzoyl tonka bean camphor, 3-benzoyl-7-diethyl amino coumarin, 3-benzoyl-ayapanin, 3; 3 '-carbonyl temparin, 3; 3 '-carbonyl two (ayapanin) or 3; 3 '-carbonyl two (5, the 7-dimethoxycoumarin).They can use separately separately, or wherein two or more can be used as the mixture use.
The mixture ratio of component is as follows separately in Photoepolymerizationinitiater initiater system (A).
Content by the mercaptan compound with bis-phenol skeleton of formula (1) expression is preferably 20-70 quality %, more preferably 30-60 quality %.If this content is lower than 20 quality %, photosensitivity and development latitude will reduce.On the other hand, if this content surpasses 70 quality %, development will worsen.
The preferred 20-80 quality of the content of radical-forming agent %, more preferably 30-70 quality %.If this content is lower than 20 quality %, photosensitivity will reduce.On the other hand, if this content surpasses 80 quality %, live width is often greater than the live width of photomask.
The content of sensitizing agent is 5-40 quality % preferably, more preferably 10-30 quality %.If this content is lower than 5 quality %, photosensitivity will reduce.It is not preferred that this content surpasses 40 quality %, because be prevented to the light transmission of photosensitive composition bottom, it is oppositely trapezoidal that this causes that the resist shape of cross section becomes, and causes resolving power to descend.
2-2. have the adhesive resin (B) of carboxyl
Be used for adhesive resin of the present invention (B) and have carboxyl on its side chain, it is major decision resist characteristic such as film toughness, thermotolerance, substrate adherence, to the solubleness of aqueous base and the component of alkali-developable.
The specific examples of adhesive resin (B) comprises the acrylic copolymer (AP) with carboxyl, epoxy (methyl) acrylate resin (EA) with carboxyl and urethane (methyl) acrylate resin (UA) with carboxyl.From considering that with the binding property of glass baseplate epoxy (methyl) acrylate resin is preferred.Particularly preferably be bisphenol type epoxy (methyl) acrylate resin with carboxylic acid.
Two or more those adhesive resins with carboxylic acid can be used in combination.
(1) has the acrylic copolymer (AP) of carboxyl
Acrylic copolymer with carboxyl can be obtained by following component copolymerization:
(a) contain the ethylenically unsaturated monomer of carboxyl; With
(b) ethylenically unsaturated monomer except above-mentioned (a) item.
Carboxylic ethylenically unsaturated monomer (a) is used to give acrylic copolymer (AP) with alkali-developable.
The specific examples that contains the ethylenically unsaturated monomer (a) of carboxyl comprises (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl succinate, 2-(methyl) acryloxy ethyl phthalic ester, (methyl) acryloxy ethyl hexahydrophthalic acid ester, (methyl) propylene dimer, toxilic acid, Ba Dousuan, methylene-succinic acid and fumaric acid.
The ethylenically unsaturated monomer (b) of use except above-mentioned (a) item is used for controlling diaphragm intensity and pigment-dispersing.
The specific examples of the ethylenically unsaturated monomer (b) except above-mentioned (a) comprising: vinyl compound, as vinylbenzene, alpha-methyl styrene, (adjacent,, to) hydroxy styrenes or vinyl-acetic ester; (methyl) acrylate, as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl ester, (methyl) vinylformic acid isopropyl esters, (methyl) n-butylacrylate, (methyl) vinylformic acid tertiary butyl ester, (methyl) vinylformic acid n-hexyl ester, (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid phenoxy group ethyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid tetrahydrofurfuryl ester, (methyl) vinyl cyanide, (methyl) vinylformic acid glycidyl esters, glycidyl allyl ether, (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxypropyl ester, N, N-dimethyl aminoethyl (methyl) acrylate, vinylformic acid trifluoroethyl ester, (methyl) vinylformic acid 2,2,3,3-tetrafluoro propyl diester, or (methyl) vinylformic acid perfluoro capryl ethyl ester; Compound with amide group; as (methyl) acrylamide, N; N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N-vinyl pyrrolidone, N-caprolactam or N-(methyl) acryloyl morpholine.
The acrylic copolymer that has ethylenically unsaturated group on the side chain also can be used without any obstacle ground, the compound of this multipolymer by in a molecule, having epoxide group and ethylenically unsaturated group ((methyl) vinylformic acid glycidyl esters for example, (methyl) vinylformic acid 3,4-epoxy group(ing) cyclohexyl methyl ester, (methyl) vinylformic acid 4-(2, the 3-epoxypropyl) butyl ester or glycidyl allyl ether) epoxy group(ing) with obtain or the isocyanate groups reaction of the part or all of hydroxyl of acrylic copolymer and the compound (as 2-methacryloxyethyl isocyanic ester) that in a molecule, has isocyanate group and ethylenically unsaturated group and obtaining as the carboxyl reaction of the part of the side chain of the acrylic copolymer that obtains by above-mentioned monomer copolymerization.
The copolymerization ratio that contains the ethylenically unsaturated monomer (a) of carboxyl and the ethylenically unsaturated monomer (b) except above-mentioned (a) preferably 5: 95-40: 60, more preferably 10: 90-50: 50.If the copolymerization ratio of above-mentioned (a) item is lower than 5, because alkali-developable reduces, pattern forms the difficulty that will become.If above-mentioned (a) copolymerization ratio surpasses 60, the alkali of photocuring part develops and carries out easily, therefore, is difficult to keep live width constant.
Molecular weight with acrylic copolymer of carboxyl and ethylenically unsaturated group is preferably 1,000-500, and 000, more preferably 3,000-200,000, be that standard is measured by GPC with the polystyrene.If molecular weight is lower than 1,000, film toughness will reduce significantly.On the other hand, if molecular weight surpasses 500,000, alkali-developable will reduce significantly.
(2) has epoxy (methyl) acrylate resin (EA) of carboxyl
Being used for epoxy (methyl) acrylate resin (EA) with carboxyl of the present invention is not specifically limited, yet, can use suitably by acid anhydrides and Resins, epoxy or epoxy compounds and the reaction product that contains between the monocarboxylic acid of unsaturated group and react epoxy (methyl) acrylate resin that obtains.
Comprise bisphenol A type epoxy resin with the example of the Resins, epoxy of the monocarboxylic acid reaction that contains unsaturated group, bisphenol-A epoxy resin, brominated bisphenol a type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, triphenyl methane type Resins, epoxy, naphthalene type Resins, epoxy, N-Racemic glycidol fundamental mode Resins, epoxy, dicyclopentadiene phenol Resins, epoxy, the phthalic acid diepoxy third fat resin, the heterocyclic ring epoxy resins, di-toluene phenol-type epoxy resin and biphenyl type epoxy resin.They can use separately separately, or its two or more can in conjunction with.
Comprise with the example of the epoxy compounds of the monocarboxylic acid reaction that contains unsaturated group, but be not confined to epoxy compounds such as bisphenol type epoxy compound, Bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol phenolic varnish type epoxy compounds, cresols phenolic varnish type epoxy compounds and aliphatic epoxy compound especially.They can use separately separately, or its two or more can be used in combination.
Comprise (methyl) vinylformic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl phthalic acid, (methyl) acryloxy ethyl hexahydrophthalic acid, (methyl) acrylic acid dimer, β-furfuryl group vinylformic acid, β-styrene acrylic, styracin, Ba Dousuan and alpha-cyano styracin with the example of the monocarboxylic acid that contains unsaturated group of Resins, epoxy or epoxy compounds reaction.This type of example that contains the monocarboxylic acid of unsaturated group also comprises as the half ester compound of the reaction product of the acrylate of hydroxyl and saturated or undersaturated dibasic acid anhydride with as the half ester compound of the reaction product that contains single glycidyl ether of unsaturated group and saturated or undersaturated dibasic acid anhydride.Each monocarboxylic acid that contains unsaturated group can use separately or its two or more can be used in combination.
The example of acid anhydrides comprises: dibasic acid anhydride such as maleic anhydride, succinyl oxide, itaconic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, methyl carbic anhydride, hexachloroendomethylene-tetrahvdrophthalic anhydride, or methyl tetrahydrophthalic anhydride; The aromatic polycarboxylic acids acid anhydride, as trimellitic acid 1,2-anhydride, PMA, or benzophenone tetracarboxylic dianhydride; With multi-carboxy anhydride's derivative, as 5-(2,5-dioxy tetrahydrofurfuryl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride or bridge two ring-[2,2,1]-heptan-5-alkene-2, the 3-dicarboxylic anhydride.They can use separately separately, or its two or more can be used in combination.
So the epoxy with carboxyl (methyl) acrylate resin (EA) that obtains has, but specifically is not limited to, and is preferred 1,000-40, and 000, more preferably 2,000-5,000 molecular weight is that standard is measured by GPC with the polystyrene.
In addition, the acid number of epoxy (methyl) acrylate resin (EA) (is meant the solid acid number of measuring according to JIS K0070, use the identical meaning hereinafter) 10mgKOH/g or more preferably, 45-160mgKOH/g more preferably, 50-140mgKOH/g more preferably, this can set up good balance between the caustic solubility of cured film and alkali resistance.If acid number is lower than 10mgKOH/g, caustic solubility will reduce.On the other hand, under some bonded situation that photosensitive composition is formed, excessive acid number will cause the feature of cured film such as alkali resistance to reduce.
(3) has urethane (methyl) acrylate resin (UA) of carboxyl
Being used for urethane (methyl) acrylate resin (UA) with carboxyl of the present invention is to compare with acrylate copolymer (AP) or epoxy (methyl) acrylate resin (EA) to have more the flexible adhesive resin, so it can be used in the flexible and resistant to bending application.
Urethane (methyl) acrylate resin (UA) with carboxyl contains the unit that derives from (methyl) acrylate with hydroxyl, derive from the unit of polyvalent alcohol and derive from the unit of polyisocyanates.More particularly, it is that origin comes from the unit formation that all has hydroxyl (methyl) acrylate at its two ends.Be that origin comes from the unit of polyvalent alcohol and the repeating unit of the unit formation that derives from polyisocyanates between two ends, they are by being present in urethane bonds and the carboxyl coupling in the repeating unit.
That is to say that the repeating structure with urethane (methyl) acrylate resin (UA) of carboxyl can be represented by formula (17).
-(ORbO-OCNHRcNHCO) n- (17)
In formula (17), ORbO represents the dehydrogenation residue of polyvalent alcohol, and what Rc represented polyisocyanates takes off the isocyanic ester residue.
Urethane (methyl) acrylate resin (UA) with carboxyl can be prepared by the reaction of (methyl) acrylate, polyvalent alcohol and the polyisocyanates that have hydroxyl at least.Here, have at least a that the compound of carboxyl should be as in polyvalent alcohol and the polyisocyanates.Preferably, use polyvalent alcohol with carboxyl.Like this, the compound that has carboxyl by use is as polyvalent alcohol and/or polyisocyanates, can prepare carboxyl wherein and be present in urethane (methyl) acrylate resin (UA) among Rb or the Rc.
Here, in formula (17), Integer n is preferably about 1-200, more preferably 2-30.If n is within this scope, the flexible of cured film can be more excellent.
In addition, if use two or more polyvalent alcohol and polyisocyanates one of at least, this repeating unit is represented a plurality of kinds.A plurality of unitary regularities can be selected from " random fully ", " block ", " local order (localized) " etc. suitably according to purpose.
Example with (methyl) acrylate of hydroxyl comprises (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid hydroxypropyl ester, (methyl) vinylformic acid hydroxybutyl ester, the alkylene oxide adduct of caprolactone or above-mentioned (methyl) acrylate, glycerine list (methyl) acrylate, glycerine two (methyl) acrylate, glycidyl methacrylate-vinylformic acid adducts, TriMethylolPropane(TMP) list (methyl) acrylate, trishydroxymethyl two (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, TriMethylolPropane(TMP)-the alkylene oxide adduct of Dipentaerythritol five (methyl) acrylate and two (methyl) acrylate.(methyl) acrylate (a) with hydroxyl can use separately or its two or more can be used in combination.Wherein, (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid hydroxypropyl ester and (methyl) hydroxybutyl acrylate are preferred, and more preferably (methyl) vinylformic acid 2-hydroxyethyl ester.When using (methyl) vinylformic acid 2-hydroxyethyl ester, synthesizing of carboxylic urethane (methyl) acrylate (UA) resin is easier.
Polymer polyatomic alcohol and/or dihydroxy compound can be as the polyvalent alcohols that uses among the present invention.The example of polymer polyatomic alcohol comprises: polyether-based glycol such as polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol; Polyester based polyvalent alcohol by the acquisition of the reaction between polyvalent alcohol and the polybasic ester; Have and derive from as the unit of hexa-methylene carbonic ether or 5-methylene carbonate polycarbonate-base glycol as structural unit; With polylactone base glycol such as polycaprolactone glycol or poly-butyrolactone glycol.
In addition, when the polymer polyatomic alcohol with carboxyl during as above-mentioned polyvalent alcohol with carboxyl, for example, the polymer polyatomic alcohol that can use following building-up process to obtain, wherein allow to have trivalent or polyprotonic acid more at high price as the coexistence of (anhydrous) trimellitic acid, preparation wherein keeps the polymer polyatomic alcohol of carboxyl thus.Can use a kind of such polymer polyatomic alcohol, maybe can be used in combination two or more of polymer polyatomic alcohol.In addition,, preferably use the molecular-weight average that has separately to be 200-2 for polymer polyatomic alcohol, those of 000, it has strengthened the excellent flexible of cured film.
Can use side chain with two alcoholic extract hydroxyl groups or straight chain compound as above-mentioned dihydroxy compound.Yet, preferred especially the dihydroxyl aliphatic carboxylic acid that uses with carboxyl.This type of dihydroxy compound can be dimethylol propionic acid or dimethylolpropionic acid.Have the dihydroxyl aliphatic carboxylic acid of carboxyl by use, carboxyl can easily be present in urethane (methyl) acrylate resin (UA).Each of these dihydroxy compound can be used separately, maybe can be used in combination its two or more.In addition, dihydroxy compound can use with polymer polyatomic alcohol.
In addition, under the situation that is used in combination polyvalent alcohol with carboxyl, or use and to have under the situation of polyisocyanates as polyisocyanates as described below of carboxyl, can use the dihydroxy compound (for example, ethylene glycol, glycol ether, the propylene glycol, 1 that do not have carboxyl, 4-butyleneglycol, 1,3-butyleneglycol, 1,5-pentanediol, neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-hexylene glycol or 1,4 cyclohexane dimethanol).
The specific examples that is used for polyisocyanates of the present invention comprises that vulcabond is as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate, MDI, (adjacent, or to)-Xylene Diisocyanate, methylene-bis (cyclohexyl isocyanate), trimethyl hexamethylene diisocyanate, hexanaphthene-1,3-dimethylene diisocyanate, hexanaphthene-1, the 4-dimethylene diisocyanate, with 1, the 5-naphthalene diisocyanate.Polyisocyanates can use separately, or its two or more can be used in combination.Also can use polyisocyanates with carboxyl.
Be used for the molecular weight with urethane (methyl) acrylate resin (UA) of carboxyl of the present invention and be not particularly limited, yet be that standard is preferably 1 by the quality molecular-weight average that GPC measures with the polystyrene, 000-40,000, more preferably 8,000-30,000.Be lower than 1,000 if having the quality molecular-weight average of urethane (methyl) acrylate resin (UA) of carboxyl, the elasticity of cured film and flexible will the deterioration.On the other hand, the quality molecular-weight average greater than 40,000 because resin becomes and can make flexible reduction too firmly.In addition, the acid number of urethane (methyl) acrylate resin (UA) is preferably 5-150mgKOH/g, more preferably 30-120mgKOH/g.If acid number is lower than 5mgKOH/g, the caustic solubility that is used for the curable resin composition of resist will reduce.On the other hand, if this acid number surpasses 150mgKOH/g, the alkali resistance of cured film etc. will worsen.
2-3. have the compound (C) of ethylenically unsaturated group
Be included in the compound with ethylenically unsaturated group (C) in the photosensitive composition of the present invention and be the compound except above-mentioned adhesive resin (B), and can be used for regulating the photosensitivity of photosensitive composition or regulating the cured product physical properties that this photosensitive composition makes, as thermotolerance and flexible.Preferably, use (methyl) acrylate.
Specific examples with compound (C) of ethylenically unsaturated group comprises: (methyl) alkyl acrylate is (as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid propyl diester, (methyl) n-butylacrylate, (methyl) vinylformic acid isobutyl, (methyl) vinylformic acid sec-butyl ester, (methyl) vinylformic acid tertiary butyl ester, (methyl) vinylformic acid polyhexamethylene, (methyl) vinylformic acid octyl group ester, (methyl) isooctyl acrylate ester, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid decyl ester,, (methyl) vinylformic acid Lauryl Ester, or (methyl) stearyl acrylate alcohol ester);
(methyl) vinylformic acid alicyclic ring family ester (as (methyl) vinylformic acid cyclohexyl ester, (methyl) vinylformic acid bornyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclopentenyl ester, or (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester);
(methyl) vinylformic acid aromatic ester (as (methyl) vinylformic acid benzyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid phenyl carbitol ester, (methyl) vinylformic acid nonyl phenylester, (methyl) vinylformic acid nonyl phenyl carbitol ester or (methyl) vinylformic acid Nonylphenoxy ester);
(methyl) acrylate (as (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid hydroxypropyl ester, (methyl) hydroxybutyl acrylate, butyleneglycol list (methyl) acrylate, glycerine (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate or glycerine two (methyl) acrylate) with hydroxyl;
Has amino (methyl) acrylate (as (methyl) vinylformic acid 2-dimethyl aminoethyl ester, (methyl) vinylformic acid 2-diethylamino ethyl ester or (methyl) vinylformic acid 2-tertiary butyl amino-ethyl ester);
Methacrylic ester (as methacryloxyethyl phosphoric acid ester, two-methacryloxyethyl phosphoric acid ester or methacryloxyethyl phenyl phosphate ester acid) with phosphorus atom;
Two (methyl) acrylate is (as ethylene glycol bisthioglycolate (methyl) acrylate, glycol ether two (methyl) acrylate, triglycol two (methyl) acrylate, four ethylenes (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate, 1,3-butyleneglycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, two-glycidyl (methyl) acrylate or dihydroxymethyl tristane two (methyl) acrylate;
Poly-(methyl) acrylate (as trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate or Dipentaerythritol six (methyl) acrylate);
The polyvalent alcohol of modification gathers (methyl) acrylate (as three (methyl) acrylate of the 6-mol propylene oxide adduct of three (methyl) acrylate of the 3-mol propylene oxide adduct of tetramethylolmethane two (methyl) acrylate of two (methyl) acrylate of the 4-mol ethylene oxide adduct of two (methyl) acrylate of the 4-mol ethylene oxide adduct of bisphenol S, dihydroxyphenyl propane, aliphatic modification, TriMethylolPropane(TMP) or TriMethylolPropane(TMP);
Polyacrylic ester (as three (acryloxy ethyl) isocyanuric acid ester of two (acryloxy ethyl) monohydroxy ethyl isocyanuric acid ester, three (acryloxy ethyl) isocyanuric acid esters or 6-caprolactone adducts) with isocyanuric acid skeleton;
Polyester acrylate (as α, ω-two acryl-(two ethylene glycol)-phthalic ester or α, ω-tetrapropylene acyl group-(ditrimethylolpropane)-tetrahydrophthalic acid ester);
(methyl) vinylformic acid glycidyl esters;
(methyl) vinylformic acid allyl ester;
ω-hydroxyl hexylyloxy ethyl (methyl) acrylate;
Polycaprolactone (methyl) acrylate;
(methyl) acryloxy ethyl phthalic ester;
(methyl) acryloxy ethyl succinate;
2-hydroxyl-3-phenoxy propyl acrylate; And phenoxyethyl acrylate.
In addition, N-vinyl compound (as N-vinyl pyrrolidone, N-vinyl formal or N-vinyl acetamide), polyester (methyl) acrylate, urethane (methyl) acrylate, epoxy (methyl) acrylate etc. can be suitable as the compound with ethylenically unsaturated group.
Wherein, according to the pattern configuration, preferred examples comprises many (methyl) acrylate, as: two (methyl) acrylate or dihydroxymethyl tristane two (methyl) acrylate of two (methyl) acrylate of the 4-mol ethylene oxide adduct of dihydroxyphenyl propane, the 4-mol propylene oxide adduct of dihydroxyphenyl propane; With according to photosensitivity, comprise trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate or Dipentaerythritol six (methyl) acrylate.
2-4. pigment (D)
Pigment (D) but blend in photosensitive composition of the present invention.The example comprises following (being represented by chromaticity index respectively): C.I. pigment Yellow 12,13,14,17,20,24,55,83,86,93,109,110,117,125,137,139,147,148,153,154,166 or 168;
C.I. pigment orange 36,43,51,55,59 or 61;
C.I. Pigment Red 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228 or 240;
C.I. pigment violet 19,23, and 29,30,37,40 or 50;
C.I. pigment Blue 15,15:1,15:4,15:6,22,60 or 64;
C.I. pigment Green 7 or 36;
C.I. pigment brown 23,25 or 26;
C.I. Pigment black 7; Black with titanium.Various pigment can use separately, or its two or more can be used in combination.
The example of the black pigment (D) that uses in black matix resist composition at colour filter of the present invention comprise carbon black, acetylene black, dim, graphite, iron black, nigrosine, dark purple black, titanium is black.Also can use by mixing the black pigment that red, green, blue three look pigment dyestuffs form.
Wherein, consider the character of photoresistance ratio and printed images, carbon black and titanium are black to be particularly preferred.Commercially available sooty example comprises following product.
Mitsubishi Chemical Corporation produces: MA7, MA8, MAI1, MA100, MA220, MA230, #52, #50, #47, #45, #2700, #2650, #2200, #1000, #990, #900.
Degussa Japan Co., Ltd. produces: Printex 95, and Printex 90, Printex 85, Printex75, and Printex 55, Printex 45, and Printex 40, and Printex 30, Printex 3, Printex A, Printex G, Special Black 4, Special Black 550, Special Black 350, SpecialBlack 250, Special Black 100.
Cabot Corporation produces: Monarch 460, and Monarch 430, and Monarch 280, Monarch 120, and Monarch 800, and Monarch 4630, REGAL 99, REGAL 99R, and REGAL 415, REGAL4 15R, REGAL 250, REGAL 250R, and REGAL 330, BLACK PEARL S480, PEARL S130.
Columbian Carbon Co. produces: Raven 11, and Raven 15, and Raven 30, Raven 35, and Raven 40, and Raven 410, Raven 420, and Raven 450, and Raven 500, Raven 780, Raven850, Raven 890H, Raven 1000, and Raven 1020, and Raven 1040, Raven 1060, and Raven 1080, and Raven 1255.
Black as titanium, that can mention is the 13M-C that Mitsubishi Materials Corporation produces.
The use that to mutually combine of the above-mentioned black pigment of mentioning.Especially, be used in combination that carbon black and titanium are black to help higher light-shading effect.
2-5. solvent (E)
In addition, according to the purposes of product, can in photosensitive composition of the present invention and black matix resist composition, add various additives to give cured product viscosity, operability, characteristic etc.For example, for the enough dispersions that obtain each component, operability and binding property and the adjusting viscosity when improving coating, can add solvent (E).
The specific examples that can be used for the volatile solvent (E) of photosensitive composition of the present invention comprises alcohol, ketone and ester.The example of this type of volatile solvent comprises methyl alcohol, ethanol, toluene, dimethylbenzene, ethylbenzene, hexanaphthene, isophorone, cellosolve acetate, diglyme, ethylene glycol diethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol list ethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, Isoamyl Acetate FCC, ethyl lactate, gamma-butyrolactone, methyl ethyl ketone, acetone and pimelinketone.They can use separately separately, or wherein two or more can be used as the mixture use.
In addition, when the purposes of considering product is difficult to use above-mentioned volatile solvent, can use reactive solvents (E).This type of reactive solvents specific examples comprises (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) methyl acrylate, (methyl) n-butylacrylate, (methyl) vinylformic acid cyclohexyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid N; N-dimethyl aminoethyl ester, N-acryloyl morpholine, N-acryl piperidines, N, N-dimethyl (methyl) acrylamide, N-vinyl pyrrolidone and N-ethyl acetamide.They can use separately separately, or wherein two or more can be used as the mixture use.When needing, above-mentioned volatile solvent can be added in the reactive solvents in addition.
The organic solvent (E) that is used for black matix resist composition of the present invention is not particularly limited, as long as this organic solvent can dissolve and disperse component in each of various above-mentioned formations black matix resist of the present invention composition.Its specific examples comprises methyl alcohol, ethanol, Virahol, toluene, dimethylbenzene, ethylbenzene, hexanaphthene, isophorone, cellosolve acetate, diglyme, ethylene glycol diethyl ether, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl ether acetic ester, the diethylene glycol monoethyl ether acetic ester, methyl methoxy base propionic ester, ethyl methoxy propyl acid esters, the methyl ethoxy propionic ester, ethyl ethoxy-c acid esters, ethyl acetate, Isoamyl Acetate FCC, ethyl lactate, acetone, methyl ethyl ketone, pimelinketone, N, dinethylformamide and N-Methyl pyrrolidone.They can use separately separately, or wherein two or more are used in combination.
It is desirable to prepare black matix resist composition of the present invention, make that solids concn is 5-30 quality %, preferred 10-25 quality % by any of these organic solvent.
2-6. other optional components
Except above-mentioned basal component, pigment dispersing agent, bonding improver, homogenize agent, development improving agent, oxidation retarder, heat polymerization inhibitors etc. can compatibly add in the black matix resist composition of the present invention.Especially in coloured composition, preferably pigment dispersing agent is sneaked in some cases, because fine dispersion coloured material and stable dispersion state are important to quality stability.
Pigment dispersing agent all has affinity to pigment and adhesive resin, and the example comprises nonionic, positively charged ion and anion surfactant and polymeric dispersant.Wherein, polymeric dispersant is preferred.Especially, can advantageously use and contain: basic functionality, nitrogen heterocyclic ring group for example is as primary, the second month in a season or uncle's amino, pyridine, pyrimidine or pyrazine; Or as the polymeric dispersant of the functional group of amide group or urethane groups.
Photosensitive composition of the present invention and black matix resist composition can contain white dyes, tensio-active agent, softening agent, flame retardant resistance, antioxidant, UV absorptivity, whipping agent, mycocide, static inhibitor, magneticsubstance, electro-conductive material, antimicrobial drug/sterilant, porous adsorbent, perfume compound etc. in addition according to purpose.
Photosensitive composition of the present invention and black matix resist composition can also contain heat polymerization inhibitors to prevent polymerization in the storage process.The specific examples of heat polymerization inhibitors comprises right-methoxyphenol, quinhydrones, pyrocatechol, tert-butyl catechol, thiodiphenylamine and N-first quinone (methoquinone).
2-7. the blend ratio of each component in the photosensitive composition
The ratio of mixture of Photoepolymerizationinitiater initiater system (A) preferably 1-40 quality %, more preferably 3-30 quality % in the photosensitive composition of the present invention.If mixture ratio is lower than 1 quality %, photosensitivity will worsen.If mixture ratio surpasses 40 quality %, the physical strength of cured product will reduce.
Adhesive resin (B) and have between the compound (C) of ethylenically unsaturated group ratio of mixture ((B): (C)) by quality ratio=50: 50-95: 5, preferred 60: 40-90: 10, more preferably 85: 15-70: 30.If the ratio of mixture of adhesive resin (B) surpasses 95 or more, photosensitivity will worsen.On the other hand, it is not preferred that the ratio of mixture of adhesive resin (B) is lower than 50, wideer because the live width of pattern is tended to.
2-8. the blending ratio of each component in the black matix resist composition
The blending ratio of each component is not particularly limited in the black matix resist composition of the present invention, but each component preferably is limited in the following scope with respect to the ratio of total content (total solids level) except organic solvent (E).
(A) preferably 2-15 quality %, more preferably 5-10 quality % of the amount of photopolymerization stopper system.If the amount of Photoepolymerizationinitiater initiater system is too little, disadvantage is that photosensitivity and development latitude reduce.If should amount too big, disadvantage be the live width of the live width of the line that forms in the resist pattern greater than photomask.
(B) have amount preferably 10-30 quality %, more preferably the 15-25 quality % of the adhesive resin of carboxyl.If the amount of adhesive resin is too little, disadvantage is to reduce with the binding property or the development latitude of base material.If the amount of being somebody's turn to do is too big, disadvantage is that the photoresistance effect reduces.
(C) preferably 2-20 quality %, more preferably 3-15 quality % of the compound amount with ethylenically unsaturated group.If it is too little to have the amount of compound of ethylenically unsaturated group, disadvantage is that photosensitivity reduces.If should amount too big, disadvantage be the live width of the live width of the line that forms in the resist pattern greater than photomask.
(D) preferably 40-80 quality %, more preferably 45-70 quality % of the amount of black pigment.If the amount of black pigment is too little, disadvantage is that the photoresistance effect reduces.If should amount too big, disadvantage be photosensitivity and reduces with the binding property of base material.
3. the preparation method of photosensitive composition and purposes
The photosensitive composition that contains pigment can prepare by various dispersion means, as passing through three-roll mill, two-roller mill machine, sand mill, masher, ball mill, kneader and paint shaker.Be to prevent the gelation that causes by polyreaction etc. during dispersion, can add stopper.After the colo(u)rant dispersion, monomer and Photoepolymerizationinitiater initiater can be mixed.In addition, be dispersed color well, can add dispersing auxiliary according to circumstances.Dispersing auxiliary helps colo(u)rant dispersion and prevents to disperse reagglomeration afterwards.In order to obtain light shield performance and the machinery and the physical property of suitable mobile or acquisition cured product, can in photosensitive composition of the present invention, add pigment extender such as barium sulfate, lime carbonate, silica, titanium dioxide, aluminum oxide or aluminium powder.
Photosensitive composition of the present invention can by be coated with as spraying, spin coating, roller coat, sieve, on the coating method paint base material such as glass, aluminium, PET film or polyester film of blade coating, dip-coating or calendering coating.Here, for obtaining the suitable coating compounds feature, minor amount of silicon oxyalkyl or fluorine based surfactant can join in the photosensitive composition of the present invention as homogenize agent or defoamer.
To pass through hotblast stove or hot-plate drying by the photosensitive composition of any coating in the above-mentioned coating method in case of necessity, generally under 60-100 ℃ condition, carry out 10-30 minute with the evaporating volatile solvent.If temperature is too high or heat-up time is oversize in the case, polymerization or crosslink part ground take place, and make the solubleness of unexposed portion in photographic developer reduce, and cause so-called burning (burn), and this is undesirable.Drying can under reduced pressure be carried out.
Forming the rough segmentation of particular configuration method of patterning with photosensitive composition of the present invention is two classes.A kind of method comprises the configuration of photosensitive composition coating for wanting, uses the light radiation curing then.Another kind method comprises photosensitive composition equably on the paint base material, with this photosensitive composition of optical radiation to solidify this photosensitive composition, the configuration that exposed portion is formed want, then by use as wash, peel off, modes such as physics polishing, chemical rightenning remove unexposed portion light cured product formation pattern.Especially under the situation of photosensitive composition of the present invention, the pattern that is fit to can form by a kind of pattern forming method in back.
Any inorganic materials such as glass and silicon; Metallic substance such as aluminium, stainless steel and copper; Resin material such as PET, polyester, polyimide, Resins, epoxy, polyethylene and polycarbonate; And paper etc. can be used as the base material that pattern of the present invention forms.Oxide treatment, acid treatment, Cement Composite Treated by Plasma, discharge process (discharge treatment) etc. can be stood to improve the binding property of photosensitive composition in the surface of base material.Because photosensitive composition is present in the surface of base material usually, the thickness of base material can be chosen selection wantonly.Resin layer that does not participate in photoresponse etc. can be provided between photosensitive composition and base material.
In the process that above-mentioned pattern forms, when uncured portion dissolving in the photosensitive composition after the optical radiation and remove when standing development treatment, the examples of solvents that is used for photographic developer comprises N-Methyl pyrrolidone, methyl alcohol, ethanol, toluene, hexanaphthene, isophorone, cellosolve acetate, diglyme, ethylene glycol diethyl ether, dimethylbenzene, ethylbenzene, methylcyclohexane, ethyl cellosolve, ethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, Isoamyl Acetate FCC, ethyl lactate, methyl ethyl ketone, acetone, pimelinketone, N, dinethylformamide, acetonitrile and alkali aqueous solution.They can use separately separately, or its two or more can be used in combination.Alkaline matter such as Trimethylamine 99 or triethylamine or tensio-active agent can join in the solvent in addition.
The example of alkali aqueous solution comprises the aqueous solution of inorganic salt such as sodium hydroxide, potassium hydroxide, yellow soda ash or salt of wormwood; The aqueous solution with organic salt such as hydroxyl tetramethyl-ammonium or hydroxyl tetraethyl ammonium.They can use separately separately, or its two or more can be used in combination.
Photosensitive composition of the present invention can be particularly suitable for forming the developable resist of fine pattern.Its specific examples comprises optical lithography resist, solder resist, anti-etching dose, colour filter resist, hologram, optics engraving and UV printing ink.
4. black matix resist preparation of compositions method
Black matix resist composition of the present invention can be by following steps production: mix or pre-mixing (B) has adhesive resin, (E) organic solvent, (D) black pigment and the optional pigment dispersing agent of carboxyl; Make mixture stand dispersion treatment; With (C) have the compound of ethylenically unsaturated group and (A) the Photoepolymerizationinitiater initiater system mix and be dissolved in this products therefrom.
The decollator that is used to carry out dispersion treatment can be following any: roller mill, as two-roller mill machine and three-roll mill; Ball mill such as ball mill and vibromill; Ball mill is as paint conditioner, continuous round disc type ball mill and continuous circular shape agitation beads grinding machine.Wherein, continuous circular shape agitation beads grinding machine especially, it can in short-term, pulverize and disperse and disperse after reach the sharp distribution of particle diameter, and wherein pulverize and dispersion process in temperature control easily, make to prevent the dispersion solution deterioration.
The following formation of continuous circular shape agitation beads grinding machine: the rotor (rotator) that wherein has the groove that is used for stirring bead is inserted into the container (right cylinder) with material inlet and outlet.The slotted section of bead between the bicylindrical body of container and rotor moves by rotor rotation, thereby pulverizes, shears and grinding, to pulverize effectively and to disperse black pigment.Sample is introduced by container end portion, forms particulate then, is then discharged by the opposite side of import.Repeat this processing up to the size-grade distribution that obtains to want.Term " retention periods " is meant wherein sample actual pulverizing and dispersive for some time in container.
For example, this type of successive annular agitation beads grinding machine can be by Inoue Manufacturing, the SPIKE MILL (trade(brand)name) that Inc. makes, or by Turbo Kogyo Co., the OB-MILL (trade(brand)name) that Ltd. makes.
The preferred dispersion condition of successive annular agitation beads grinding machine is as follows.The bead size of using (diameter) is 0.2-1.5mm, more preferably 0.4-1.0mm preferably.If bead size is lower than 0.2mm, the weight of single bead is too little, has then reduced the size reduction energy of single bead and pigment is pulverized and can not be carried out.If bead size surpasses 1.5mm, the collision frequency step-down between the bead carries out sooty at short notice and pulverizes difficulty.As bead material,, preferably have 4 or pottery such as zirconium dioxide and the aluminum oxide and the stainless steel of bigger proportion in view of high crush efficiency.
The circumferential speed of rotor is 5-20m/ second preferably, more preferably 8-15m/ second.If circumferential speed is lower than 5m/ second, then pigment can not be pulverized and disperse fully.It is not preferred that circumferential speed surpasses 20m/ second, and reason is because heat of friction pigment dispersion temperature too raises, and may takes place to worsen as thickening.
Dispersion temperature is preferably 10-60 ℃, more preferably room temperature-50 ℃.It is not preferred that temperature is lower than 10 ℃, because atmosphere moisture content may be mixed in the dispersion solution owing to the dewfall condensation.It is not preferred that temperature surpasses 60 ℃, worsens as thickening because may take place.
Retention time preferably 1-30 minute, more preferably 3-20 minute.If retention time is shorter than 1 minute, pulverizing and dispersion treatment may be insufficient.If retention time surpasses 30 minutes, then dispersion solution may worsen and thickening.
5. manufacturing method of color filter
The method of using black matix resist composition of the present invention to make colour filter below will be described., will be described with reference to the colour filter that is used for liquid-crystal display, wherein black matix resist composition, pixel and protective membrane carry out lamination in proper order with this herein.
Black matix resist composition of the present invention is applied on the transparent substrate.Then, after the dry solvent, the black matix pattern is formed by the exposure/development by photomask, cures after carrying out then, finishes the formation of black matix thus in baking oven etc.
The example of transparent substrate comprises, but is not limited to especially: unorganic glass such as silica glass, borosilicate glass and have the lime soda glass of silica coated surface; Film and sheet with polyester such as polyethylene terephthalate, polyolefine such as polypropylene and polyethylene, polycarbonate, polymethylmethacrylate and polysulfones thermoplastic resin, Resins, epoxy and thermosetting resin such as vibrin.Those transparent substrates can stand Corona discharge Treatment, ozonize in advance, or any in handling with the film of various polymkeric substance such as silane coupling agent and polyether polyols with reduced unsaturation.
Except dip-coating, coating method also comprises, roller coating machine, coiling rod, flow coating machine and mould are coated with machine and spraying, spin coating as using the method for turner.
Solvent seasoning is carried out in drying installation such as hot-plate, IR baking oven or convection oven drying.Preferred drying conditions comprises 40-150 ℃ temperature and 10 seconds-60 minutes time of drying.Perhaps, solvent can be dry under vacuum.
Exposure method comprises: the interval (slit) that the 50-200 micron is provided on sample top; Photomask is placed on it; And carry out image exposure.The example of the light source that can be used for exposing comprises: lamp source such as xenon lamp, high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp and low pressure mercury lamp; With laser source such as Argon ion laser, YAG laser apparatus, excimer laser and nitrogen laser.When only using light time, can use spectral filter with particular radiation wavelength.
Use liquid developer by soak, pouring or stirring means etc. carry out the developing process resist that develops.Liquid developer is not particularly limited, as long as it can dissolve the etchant resist of unexposed portion.For example, can with an organic solvent comprise acetone, methylene dichloride, trieline and pimelinketone.But many organic solvents may cause environmental pollution, and are harmful or relate to fire hazard.Therefore, the preferred alkali lye body photographic developer that does not have these risks that uses.The example of alkali lye body photographic developer comprises the aqueous solution that contains following component: mineral alkali reagent such as yellow soda ash, salt of wormwood, water glass, potassium silicate, sodium hydroxide and potassium hydroxide; With organic bases reagent such as diethanolamine, trolamine and tetra-alkyl ammonium hydroxide.If necessary, can add tensio-active agent, water-miscible organic solvent and have hydroxyl or the low molecular compound of carboxyl etc. in the alkali lye body photographic developer.Especially, preferably add tensio-active agent, it has the effect that improves development and resolving power and minimizing scum silica frost etc.
The tensio-active agent that is used for liquid developer comprises: the anion surfactant that has sodium naphthalene sulfonate group or benzene sulfonic acid sodium salt group separately; The nonionogenic tenside that has polyalkyleneoxy group (polyalkyleneoxy group) separately; The cats product that has the tetra-allkylammonium group separately.Developing method is not particularly limited, but is developed in preferred 10-50 ℃ in general, more preferably under 15-45 ℃ the development temperature, is undertaken by the method for developing as immersion development, spray development, brushing development or ultrasonic wave.
After cure that identical device carried out 1-120 minute when using with dry solvent under 150-300 ℃ of temperature.
The film thickness that the black matix that obtains like this has is preferably the 0.1-1.5 micron, more preferably the 0.2-1.2 micron.In addition, in order to realize the function of black matix, in those film thicknesses, optical density (OD) is preferably 3 or bigger.
In this step, in black matix, form black matix pattern with about 20-200 micron interval.In post-treatment, pixel will form in those intervals.
Secondly, the pixel of multicolour forms in the interval of black matix.The color of each pixel is three kinds of colors normally, red (R), green (G) and blue (B), and photosensitive composition is with pigment or dye coloring.At first, painted photosensitive composition paint is placed with on the transparent substrate of black matix pattern on it.Then, solvent dry pigmented layer that forms first color on whole surface in baking oven etc. at black matix.In general, colour filter is made up of the pixel of multicolour, and undesirable part of first color layer can be removed by photolithography and form the first color pixel pattern of wanting.The pixel film thickness is about 0.5-3 micron.The pixel that requires color is repeated this program to form the pixel of multicolour, form colour filter thus.The device that uses in forming the process of each pixel and reagent is preferably with to form those of black matix identical, if but they differ from one another, then without any problem.
Afterwards, if necessary, the lamination protective membrane.The material of protection mould comprises, but is not limited to acrylic resin, Resins, epoxy, silicone resin and polyimide resin especially.
In addition, as except aforesaid method those, also have the method for so-called back-exposure method, it comprises: in advance pixel is formed pattern on transparent substrate; Apply black matix resist composition; Expose from transparent substrate; Use pixel as the black matix between the mask formation pixel.
At last, if necessary, can use any ordinary method with ito transparent electrode lamination and patterning.
Brief Description Of Drawings
Fig. 1 is presented at the mercaptan (BAEMB) of 1 preparation among the synthetic embodiment 1The H-NMR collection of illustrative plates.
Fig. 2 shows the mercaptan (BAEMB) of preparation among the synthetic embodiment 1 13The C-NMR collection of illustrative plates.
Embodiment
Hereinafter, will be with reference to the synthetic embodiment that has the adhesive resin of carboxyl on mercaptan compound, radical-forming agent and its side chain, the preparation of black pigment dispersion solution is described in further detail to the present invention, and will provide the embodiment of photosensitive composition of the present invention and black matix resist composition and Comparative Examples to further describe the present invention.Yet the present invention is not limited to these embodiment.In addition, among the embodiment, " part " expression mass parts, " % " expression quality %.
(1) the synthetic embodiment of mercaptan compound
(BAEMB) synthetic of synthetic embodiment 1:2, two { 4-(the 3-sulfydryl butyryl acyloxy oxyethyl group) phenyl } propane (compound of formula (10), wherein m is 1) of 2-
Figure A20058003642300391
In the eggplant type flask of 200-ml volume, pack into 40g (hydroxyl equivalent: 246meq) 2, two { 4-(2-hydroxyl-oxethyl) phenyl } propane (BA-2 of 2-, Nippon Nyukazai Co., Ltd. make, hydroxyl value is 345mgKOH/g), 32.24g 3-sulfydryl butyric acid (Yodo Chemical Co. (268mmol), Ltd. make), 0.98g (the Junsei Chemicals Co. of tosic acid monohydrate (5.2mmol), Ltd. make) and toluene (the Junsei Chemicals Co. of 40g (2.6mmol), Ltd. make), Dean-Stark device and prolong are connected on this flask.When stirring, content is heated in 140 ℃ of oil baths.After beginning to react 4 hours, make reaction mixture sat cooling and neutralize with 10% sodium bicarbonate aqueous solution of 200ml.In addition, with reaction mixture deionized water wash 3 times, go up dehydration and dry at anhydrous magnesium sulfate (Junsei Chemicals Co., Ltd. makes) then.Then, boil off toluene, obtain the BAEMB (98.9% productive rate) of 64.4g, it is 97.2% that high performance liquid chromatography records purity.Gained BAEMB is high viscosity, colourless, transparent liquid.
Synthetic embodiment 2:2,2-two [4-{2-(3-sulfydryl butyryl acyloxy)-1-methyl ethoxy } phenyl] propane (BAPMB) (compound of formula (14)) synthetic
Figure A20058003642300401
In the eggplant type flask of 50-ml volume, pack into 40.00g (hydroxyl equivalent: 234meq.) 2, two { 4-(2-hydroxyl-1-methyl ethoxy) phenyl } propane (the Rikaresin PO-20 of 2-, hydroxyl value: 328mgKOH/g), 29.51g 3-sulfydryl butyric acid (Yodo Chemical Co. (245mmol), Ltd. make), 0.98g (the Junsei Chemicals Co. of tosic acid monohydrate (5.2mmol), Ltd. make) and toluene (the Junsei Chemicals Co. of 40g, Ltd. make), Dean-Stark device and prolong are connected on this flask.When stirring, content is heated in 140 ℃ oil bath.After beginning to react 4 hours, reaction mixture sat is cooled off, and neutralized with 10% sodium bicarbonate aqueous solution of 50ml.In addition, with reaction mixture deionized water wash 3 times, go up dehydration and dry at anhydrous magnesium sulfate (Junsei Chemicals Co., Ltd. makes) then.Then, boil off toluene, surveying acquisition 64.68g (95.1% productive rate) purity by high performance liquid chromatography is 96.6% BAPMB.Gained BAPMB is the water white liquid of high viscosity.
Synthetic embodiment 3: (EGMB) synthetic of ethylene glycol bis (3-sulfydryl butyric ester)
EGMB is synthetic according to the method for describing among the JP 2004-149755A.
Synthetic embodiment 4: (TPMB) synthetic of trimethylolpropane tris (3-sulfydryl butyric ester)
TPMB is synthetic according to the method for describing among the JP 2004-149755A.
Synthetic embodiment 5: (EGMIB) synthetic of ethylene glycol bis (2-mercaptoisobutyric acid ester)
EGMIB is synthetic according to the method for describing among the JP 2004-149755A.
[analysis condition]
Use high performance liquid chromatography to analyze by this synthetic product purity that obtains.Analysis condition shows below:
Post: Shodex 5C84E (Showa Denko K.K. manufacturing),
Elutriant is formed: acetonitrile/water=3/1 (volume ratio), and 2mM tetra-n-butyl ammoniumper chlorate,
Pump: LC-10AD (Shimadzu Corp. manufacturing),
Eluent flow rate: the 1.0ml/ branch,
Temperature: 40 ℃,
Detector: UV detector SPD-M10AVP (Shimadzu Corp. manufacturing) and
Detect wavelength: 210nm.
[structural analysis]
· 1H-NMR
BAEMB's (synthetic embodiment 1) 1The H-NMR collection of illustrative plates is shown among Fig. 1. 1H-NMR uses JEOL, and the JNM-AL400 that Ltd. makes measures in deuterochloroform, and the main peak of each chemical shift is positioned.
1H-NMR：
1.353, the methyl hydrogen atom of 1.371ppm:15 and 15 ',
1.617ppm:1 and 3 methyl hydrogen atom,
1.828,1.845ppm: mercapto hydrogen atom
2.6ppm:13 and 13 ' the methylene radical hydrogen atom and
3.3ppm:14 and 14 ' the methyne hydrogen atom.
· 13C-NMR
BAEMB's (synthetic embodiment 1) 13The C-NMR collection of illustrative plates is shown among Fig. 2. 13C-NMR uses JEOL, and the JNM-AL400 that Ltd. makes measures in deuterochloroform, and the main peak of each chemical shift is positioned.
13C-NMR：
24.74ppm:15 and 15 ' methine carbon atom,
30.98ppm:1 and 3 methine carbon atom,
31.18ppm:14 and 14 ' the methine carbon atom and
45.64ppm:13 and 13 ' the mesomethylene carbon atom and
170.86ppm:12 and 12 ' carbonylic carbon atom.
(2) radical-forming agent is synthetic
Synthetic embodiment 6:2,2 '-two (2-chlorophenyls)-4,4 ', 5,5 '-four (4-aminomethyl phenyls)-1,2 '-bisglyoxaline (below be abbreviated as MHABI) synthetic
In the eggplant type flask of 1-L volume, 4 of 27.50g (115mmol) packs into, 4 '-dimethyl benzyl (Tokyo Kasei Kogyo Co., Ltd. manufacturing), adjacent chlorinated benzene formaldehyde (the Tokyo Kasei Kogyo Co. of 16.25g (116mmol), Ltd. manufacturing), ammonium acetate (the JunseiChemicals Co. of 69.45g (901mmnol), Ltd. make) and the acetate (Junsei Chemicals Co., Ltd. manufacturing) of 450g.When stirring, content is heated and reacted 5 hours at 117 ℃.After the cooling, reaction soln under agitation little by little in the deionized water of impouring 2L, is caused 2-(2-chlorophenyl)-4, two (4-aminomethyl phenyl) imidazoles precipitations of 5-.Subsequently, with 2-(2-chlorophenyl)-4, two (4-aminomethyl phenyl) imidazoles of 5-filter and wash with water, are dissolved in then in the methylene dichloride (Junsei Chemicals Co., Ltd. makes) of 500g.The mixture of gained is placed four neck flasks of 2-L volume, be cooled to 5-10 ℃.Go through 1 hour under agitation with yellow prussiate of potash (the Junsei Chemicals Co. of 117.6g (357mmol), Ltd. manufacturing), sodium hydroxide (the Junsei Chemicals Co. of 44.7g, Ltd. make) and the mixture of the deionized water of 600g little by little add in this solution, at room temperature reacted then 18 hours.With reaction mixture deionized water wash 3 times, go up dehydration at the anhydrous magnesium sulfate (JunseiChemicals Co., Ltd. makes) of about 50g then.Then, steaming vibrating dichloromethane under reduced pressure makes the crystal of MHABI thus.With MHABI recrystallization from ethanol (Junsei Chemicals Co., Ltd. makes), filter then and drying, obtain the light yellow crystal (88.7% productive rate) of 36.5g thus.
(3) have adhesive resin synthetic of carboxyl on the side chain
Synthetic embodiment 7:EP-1's is synthetic
Epicoat 1004 (bisphenol A type epoxy resins with 185g, Japan Epoxy Resin Co., Ltd. produce, epoxy equivalent (weight) 925), the diethylene glycol monoethyl ether acetate of the quinhydrones of the vinylformic acid of 14.4g, 0.20g and 197g (below be abbreviated as DGEA, Daicel Chemical Industries, Ltd. make) pack into, and be heated to 95 ℃.After confirming the mixture solution uniform dissolution, the triphenylphosphine of the 2.0g that packs into, and integral body is heated to 100 ℃, and reacted about 30 hours, obtain the reaction product that acid number is 0.5mgKOH/g thus.Add the Tetra Hydro Phthalic Anhydride (NewJapan Chemical Co., Ltd. produces) of 96.0g to this reaction product, and integral body is heated to 90 ℃, reacted 6 hours.After the absorption of acid anhydrides disappears in confirming the IR absorption spectrum, obtain to have the solid acid number of 119mg KOH/g and the Epocryl EP-1 of 60% solids concn.
Synthetic embodiment 8:EP-2's is synthetic
Epicoat 1004 (bisphenol A type epoxy resins with 185g, Japan Epoxy Resin Co., Ltd. produce, epoxy equivalent (weight) 925), the diethylene glycol monoethyl ether acetate (DGEA) of the quinhydrones of the vinylformic acid of 14.4g, 0.20g and 181g (Daicel Chemical Industries, Ltd. produces) is packed into and is heated to 95 ℃.After confirming the mixture uniform dissolution, the triphenylphosphine of the 2.0g that packs into, and integral body is heated to 100 ℃, and reacted about 30 hours, obtain the reaction product that acid number is 0.5mgKOH/g thus.The Tetra Hydro Phthalic Anhydride (New Japan ChemicalCo., Ltd. produces) that in reaction product, adds 70.0g, and integral body is heated to 90 ℃, reacted about 6 hours, confirm that subsequently the absorption of acid anhydrides in the infrared absorption pattern (IR) disappears.As a result, obtain to have the solid acid number of 95mgKOH/g and the Epocryl EP-2 of 60% solids content.
Synthetic embodiment 9:AP-1's is synthetic
Connecting dropping funnel, thermometer, in the four neck flasks of prolong and agitator, methacrylic acid (MA) (the Kyoeisha Chemical Co. of 37.5g packs into, Ltd. produce), 19.0g methyl methacrylate (MMA) (Kyoeisha Chemical Co., Ltd. produce), 18.5g n-BMA (BMA) (Kyoeisha Chemical Co., Ltd. produce), 0.75g 2 mercapto ethanol (Wako Pure Chemical Industry Co., Ltd. produce) and methyl proxitol (PGM) (the Tokyo Kasei Kogyo Co. of 225.0g, Ltd. produce), will use nitrogen replacement 1 hour in the four neck flasks then.In addition, flask heated in oil bath reach 90 ℃, go through 1 hour then to wherein dripping 37.5g MA, 19.0g MMA, 18.5g BMA, 0.75g 2 mercapto ethanol, 225.0g PGM and 3.2g 2 step by step, 2 '-Diisopropyl azodicarboxylate (AIBN) (Wako Pure Chemical Industry, Co., mixing solutions Ltd production).Behind the polyase 13 hour, product is heated to the highest 100 ℃, the mixture with 1.0g AIBN and 15.0g methyl proxitol acetate (PMA) (Daicel ChemicalIndustries, Ltd. produces) mixes then, carry out polymerization in other 1.5 hours subsequently, leave standstill cooling then.Subsequently, replace with fresh air in the four neck flasks, glycidyl methacrylate (GMA) (the Mitsubishi Rayon Co. that in this flask, adds 61.5 mass parts then, Ltd. production), tetra-n-butyl ammonium bromide (TBAB) (the Tokyo Kasei Kogyo Co. of 3.6g, Ltd. produce) and the N-methyl quinone (Junsei Chemical, Co., Ltd. production) of 0.15g, reacted 8 hours at 80 ℃ thus, thereby GMA is added on the carboxyl of acrylic copolymer.The result obtains the acrylic copolymer (AP-1) of GMA-addition.The solids concn of AP-1 is 30.5%, and its solid acid number is 116mgKOH/g, and what it was measured by GPC is that the weight-average molecular weight of standard is 14,000 with vinylbenzene.
(4) be used for the preparation of the colo(u)rant dispersion liquid solution 1 of photosensitive composition
In the stainless cylinder of steel of 300-ml volume, Ajisper PB822 (pigment dispersing agent with 1.98g, Ajinomoto-Fine-Techno Co., Inc. produce) with 113.5g propylene glycol monomethyl ethylhexoate (below be abbreviated as PMA, Daicel Chemical Industries, Ltd. produce) dissolving, then with the Special Black 350 (carbon blacks of EP-1, the 15.0g of 12.54g, Degussa Co., Ltd. produce) and 13M-C (titanium is black, and the Mitsubishi Materials Corporation produces) mixing of 15.0g.Next, be in the zirconium bead adding reaction mixture of 0.65mm with the 200g diameter, integral body is painted the dispersion treatment that conditioner (Asada Iron Works Co., Ltd. produces) carried out 3 hours.With the filter paper filtering of above colo(u)rant dispersion liquid solution, prepare black pigment dispersion solution 1 thus by 0.8 micron pore dimension.
(5) be used for the preparation of the black pigment dispersion solution 2 of black matix resist composition
Dispersion solution 2:
1, the hexanaphthene of 874g (CH) and 1 in the PMA mixed solvent of 874g, dissolves the dispersant A jisper PB822 (Ajinomoto-Fine-Techno Co., Inc. produces) of 57g, is mixed into the EP-1 (solids content: 190g) of 317g then.Subsequently, carbon black Special Black 350 (SB 350) (Degussa Co. with 439g, Ltd. produce) and the black 13M-C (MitsubishiMaterials Corporation production) of titanium of 439g be mixed into as black pigment, follow and the dispersion agent pre-mixing.In addition, mixing solutions is used continuous circular shape agitation beads grinding machine (trade(brand)name: SpikeMill Type:SHG-4C, Inoue.Manufacturing Co., Ltd. manufacturing) disperse.The bead that uses is the zirconium bead of 0.40mm diameter, and the filling per-cent of this bead in container is 80 volume %.The circumferential speed of rotor is set to 12m/ second, and the output of black pigment dispersion solution is set to 1 liter/minute, and temperature is set to about 30 ℃.The retention time of black dispersion solution is set to 6 minutes (driving time: 1 hour).Obtain dispersion solution 2 according to aforesaid method.
Dispersion solution 3 and 4
Dispersion solution 3 with 4 by forming shown in the table 1 by the method preparation identical with dispersion solution 2.
Table 1
Dispersion agent 2 Dispersion agent 3 Dispersion agent 4
Blending amount (g) Solid is formed (g) Solid ratio of components (quality %) Blending amount (g) Solid is formed (g) Solid ratio of components (quality %) Blending amount (g) Solid is formed (g) Solid ratio of components (quality %)
The black pigment dispersion agent
Special Black 350 *1 439 439 39.0 439 439 39.0 439 439 39.0
13M-C *2 439 439 39.0 439 439 39.0 439 439 39.0
AJISPER PB822 *3 57 57 5.1 57 57 5.1 57 57 5.1
EP-1 317 190 16.9 - - - - - -
EP-2 - - - 317 190 16.9 - - -
AP-1 - - - - - - 623 190 16.9
Organic solvent
PMA
*4 1874 - - 1874 - - 1721 - -
CH *5 1874 - - 1874 - - 1721 - -
Amount to 5000 1125 100.0 5000 1125 100.0 5000 1125 100.0
*The carbon black that 1:Degussa AG produces.
*The titanium that 2:Mitsubishi Materials Corporation produces is black.
*3:Ajinomoto-Fine-Techno Co., the pigment dispersing agent that Inc. produces.
*4:Daicel Chemical Industries, the propylene glycol monomethyl ether that Ltd. produces.
*5:Wako Pure Chemical Industries, the pimelinketone that Ltd. produces.
(6) preparation of photosensitive composition
The photosensitive composition of embodiment 1-3 and Comparative Examples 1-2 is according to table 2 and 3 listed composition preparations.
(7) black matix resist preparation of compositions
The black resist composition of embodiment 4-9 and Comparative Examples 3-5 by table 4-6 listed form preparation.
(8) evaluation of photosensitive composition and black matix resist composition
[suitable development time]
Utilize spin coater to be applied over that (size: 100 * 100 * 1mm) to form the about 1 micron dry film of thickness on the glass baseplate each black matix resist composition of each photosensitive composition of embodiment 1-3 and Comparative Examples 1-2 and embodiment 4-9 and Comparative Examples 3-5, and at room temperature placed five minutes, subsequently under 90 ℃ with solvent seasoning 3 minutes.In addition, glass baseplate is used the exposure apparatus that ultrahigh pressure mercury lamp (trade(brand)name: Multi Light ML-251A/B, Ushio Inc. manufacturing) is housed, with 100mj/cm 2Photomask exposure by quartz is made makes the said composition photocuring thus.(trade(brand)name: UIT 150, Usio Inc. makes, detector: UVD-S365) measure exposure value to use the UV totalizing instrument.Quartz photomask has 4,6, line/intermittent pattern of 8,10,20,50 and 100 microns and have 4,6,8,10,20,50 and 100 microns line and all be the pattern at 50 microns interval.
Contain 0.25% Developer 9033 (Shipley Far East. by use, Co., Ltd. produce) (it is the alkali photographic developer that contains salt of wormwood) and 0.03% dodecylbenzene sulfonate (TokyoKasei Kogyo Co., Ltd. the aqueous solution (21 ℃) production) and rotation developing machine (AD-1200, Takizawa Industries, Co., Ltd. produces), make exposure and solidified photosensitive composition film further stand time dependent alkali development treatment.Afterwards, measure the live width of each line that forms by exposure by opticmicroscope (VH-Z250, KeyenceCorp. makes).Suitable development time is defined as the about 20 microns time of live width that obtains in the photocuring of the part that wherein has 20 microns live widths and 50 microns intervals in photomask.The results are shown among the table 2-6.
[resolving power]
Make each black matix resist composition of each photosensitive composition of embodiment 1-3 and Comparative Examples 1-2 and embodiment 4-9 and Comparative Examples 3-5 stand alkali in the same manner as described above and develop, comprise dry solvent, exposure, go through suitable development time then and carry out alkali and develop.Read with opticmicroscope (VH-Z250, Keyence Corp. makes) corresponding to the minimum feature between each the bar line live width of the photomask that forms by exposure, in online/intermittent pattern.The results are shown among the table 2-6.
[development latitude]
Make each photosensitive composition of embodiment 1-3 and Comparative Examples 1-2 and each black matix resist composition of embodiment 4-9 and Comparative Examples 3-5 stand the alkali development in the same manner as described above, comprise dry solvent, expose and go through suitable development time and carry out the alkali development, and further add that at development time alkali develops in 20 seconds.Using opticmicroscope (VH-Z250, Keyence Corp. makes) to read is 4,6,8,10 at the optical mask pattern center line wherein, and 20,50 and 100 microns and all are spaced apart the minimum feature on 50 microns the part.The results are shown among the table 2-6.
[OD value (optical density (OD))]
Each resist composition of embodiment 4-9 and Comparative Examples 3-5 is spun on the glass baseplate (100 * 100mm size), under the room temperature dry five minutes then, subsequently under 90 ℃ with solvent seasoning three minutes.With this product with 50mj/cm 2By the ultrahigh pressure mercury lamp exposure, after under 230 ℃, cured 60 minutes then.The glass baseplate that has applied the resist gained above the use is measured the OD value.The OD value determines that by typical curve this typical curve makes by the transmissivity at 550nm place on the standard base material of measuring known OD value.Then, each glass baseplate that applies through resist to embodiment and Comparative Examples carries out the transmissivity measurement at 550nm place to calculate the OD value.The results are shown among the table 4-6.
Table 2
Embodiment 1 Embodiment 2 Embodiment 3
Blending amount (g) Solid ratio of components (quality %) Blending amount (g) Solid ratio of components (quality %) Blending amount (g) Solid ratio of components (quality %)
The component of photosensitive composition The black pigment dispersion agent 65.0 84.4 65.0 84.4 65.0 84.4
(Special Black 350) *1 (6.18) (32.1) (6.18) (32.1) (6.18) (32.1)
(13M-C) *2 (6.18) (32.1) (6.18) (32.1) (6.18) (32.1)
(AJISPER PB822) *3 (0.81) (4.2) (0.81) (4.2) (0.81) (4.2)
(EP-1) (3.09) (16.0) (3.09) (16.0) (3.09) (16.0)
(PMA) *4 (46.68) (-) (46.68) (-) (46.68) (-)
(DGEA) *5 (2.06) (-) (2.06) (-) (2.06) (-)
Alefinically unsaturated compounds
LIGHT-ACRYLATE BP-4EA *6 0.50 2.6 0.20 1.0 0.50 2.6
ARONIX M-400 *7 0.50 2.6 0.50 2.6 - -
LIGHT-ACRYLATE DCP-A *8 - - - - 0.50 2.6
Photoepolymerizationinitiater initiater
EMK *9 0.30 1.5 0.30 1.5 0.30 1.5
MHABI 1.00 5.2 - - 1.00 5.2
Irgacure 907 *10 - - 1.00 5.2
Mercaptan compound
BAMB 0.70 3.6 1.00 5.2 1.00 5.2
Organic solvent
Pimelinketone 31.98 - 31.98 - 31.98 -
The homogenize agent
MEGAFAC R08 *11 0.02 0.1 0.02 0.1 0.02 0.1
Amount to 100.0 100.0 100.0 100.0 100.0 100.0
Assessment item Suitable development time (second) 30 20 20
Resolving power (line/interval μ m) 6 6 6
Suitable development time+20 of the development time that development latitude (μ m) is suitable second 4 6 4 8 4 8
*The carbon black that 1:Degussa AG produces.
*The titanium that 2:Mitsubishi Materials Corporation produces is black.
*3:Ajinomoto-Fine-Techno Co., the pigment dispersing agent that Inc. produces.
*4:Daicel Chemical Industries, the propylene glycol monomethyl ether that Ltd. produces.
*5:Daicel Chemical Industries, the glycol ether monomethyl ether acetate that Ltd. produces.
*6:Kyoeisha Chemical Co., the diacrylate of the 4-mol EO adduction dihydroxyphenyl propane that Ltd. produces.
*7:Toagosei Co., the dipentaerythritol acrylate that Ltd. produces.
*8:Kyoeisha Chemical Co., the three cyclo-dodecyl diacrylates that Ltd. produces.
*9:HODOGAYA CHEMICAL Co., 4,4 '-two (N, the N-diethylamino) benzophenone that Ltd. produces.
*2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl third-1-ketone that 10:Ciba Specialty Chemicals K.K. produces.
*11:DAINIPPON INK AND CHEMICALS, the fluorine cpd that INC. produces.
Table 3
Comparative Examples 1 Comparative Examples 2
Blending amount (g) Solid ratio of components (quality %) Blending amount (g) Solid ratio of components (quality %)
The component of photosensitive composition The black pigment dispersion agent 65.0 84.4 65.0 84.4
(Special Black 350) (6.18) (32.1) (6.18) (32.1)
(13M-C) (6.18) (32.1) (6.18) (32.1)
(AJISPER PB822) (0.81) (4.2) (0.81) (4.2)
(EP-1) (3.09) (16.0) (3.09) (16.0)
(PMA) (46.68) (-) (46.68) (-)
DGEA) (2.06) (-) (2.06) (-)
Alefinically unsaturated compounds
LIGHT-ACRYLATE BP-4EA 0.50 2.6 0.50 2.6
ARONIX M-400 0.50 2.6 0.50 2.6
Photoepolymerizationinitiater initiater
EMK 0.30 1.5 0.30 1.5
MHABI 1.00 5.2 1.00 5.2
Mercaptan compound
EGMB 0.70 3.6 - -
TPMB - - 0.70 3.6
Organic solvent
Pimelinketone 31.98 - 31.98 -
The homogenize agent
MEGAFAC R08 *9 0.02 0.1 0.02 0.1
Amount to 100.0 100.0 100.0 100.0
Assessment item Suitable development time (second) 25 30
Resolving power (line/interval μ m) 6 6
Suitable development time+20 of the development time that development latitude (μ m) is suitable second 6 50 4 20
Table 4
Embodiment 4 Embodiment 5 Embodiment 6
Blending amount (g) Solid is formed (quality %) Blending amount (g) Solid is formed (quality %) Blending amount (g) Solid is formed (quality %)
Black matix resist composition
The black pigment dispersion agent 70.6 83.6 70.6 83.6 70.6 83.6
(Specjal Black 350) (6.20) (32.6) (6.20) (32.6) (6.20) (32.6)
(13M-C) (6.20) (32.6) (6.20) (32.6) (6.20) (32.6)
(AJISPER PB822) (0.81) (4.3) (0.81) (4.3) (0.81) (4.3)
(EP-1) (2.68) (14.1) - (-) - (-)
EP-2) - (-) (2.68) (14.1) - (-)
(AP-1) - (-) - (-) (2.68) (14.1)
(PMA) (26.47) (-) (26.47) (-) (24.30) (-)
(DGEA) *6 (1.80) (-) (1.80) (-) - (-)
(CH) (26.47) (-) (26.47) (-) (24.30) (-)
(PGM) *7 - (-) - (-) (6.11) (-)
Alefinically unsaturated compounds
LIGHT-ACRYLATE BP-4EA *8 0.54 2.8 0.54 2.8 0.54 2.8
ARONIX M400 *9 0.55 2.9 0.55 2.9 0.55 2.9
Photoepolymerizationinitiater initiater
EMK *10 0.30 1.6 0.30 1.6 0.30 1.6
MHABI 1.00 5.3 1.00 5.3 1.00 5.3
Mercaptan compound
BAEMB 0.70 3.7 0.70 3.7 0.70 3.7
Organic solvent
CH 26.29 - 26.29 - 26.29 -
The homogenize agent
MEGAFAC R08 *11 0.02 0.1 0.02 0.1 0.02 0.1
Amount to 100.0 100.0 100.0 100.0 100.0 100.0
Assessment item
Suitable development time (second) 25 30 20
Resolving power (line/interval μ m) 6 6 6
Suitable development time+20 of the development time that development latitude (μ m) is suitable second 4 6 4 6 8 8
OD value (/ μ m) 5.3 5.1 5.4
*6:Daicel Chemical Industries, the diethylene glycol monoethyl ether acetate that Ltd. produces.
*7:Daicel ChemicalIndustries, the propylene glycol monomethyl ether that Ltd. produces.
*8:Kyoeisha Chemical Co., the diacrylate of the 4-mol EO adduction dihydroxyphenyl propane that Ltd. produces.
*9:Toagosei Co., the dipentaerythritol acrylate that Ltd. produces.
*10:HODOGAYA CHEMICAL Co., 4,4 of Ltd. production '-two (N, N-diethylamino) benzophenone.
*11:DAINIPPON INKAND CHEMICALS, the fluorine cpd that INC. produces.
Table 5
Embodiment 7 Embodiment 8 Embodiment 9
Blending amount (g) Solid is formed (quality %) Blending amount (g) Solid is formed (quality %) Blending amount (g) Solid is formed (quality %)
Black matix resist composition
The black pigment dispersion agent 70.6 83.6 70.6 83.6 70.6 83.6
(Special Black 350) (6.20) (32.6) (6.20) (32.6) (6.20) (32.6)
(13M-C) (6.20) (32.6) (6.20) (32.6) (6.20) (32.6)
(AJISPER PB822) (0.81) (4.3) (0.81) (4.3) (0.81) (4.3)
(EP-1) (2.68) (14.1) (2.68) (14.1) (2.68) (14.1)
(PMA) (26.47) (-) (26.47) (-) (26.47) (-)
(DGEA) (1.80) (-) (1.80) (-) (1.80) (-)
(CH) (26.47) (-) (26.47) (-) (26.47) (-)
Alefinically unsaturated compounds
LIGHT-ACRYLATE BP-4EA 0.54 2.8 0.54 2.8 - (-)
ARONIX M-400 0.55 2.9 0.55 2.9 0.55 2.9
LIGHT-ACRYLATE DPC-A *12 - (-) - (-) 0.54 2.8
Photoepolymerizationinitiater initiater
EMK 0.30 1.6 0.30 1.6 0.30 1.6
MHABI 1.00 5.3 - - 1.00 5.3
Irgacure 907 *13 - - 1.00 5.3 - (-)
Mercaptan compound
BAEMB - - 0.70 3.7 0.70 3.7
BAPMB 0.70 3.7 - - - -
Organic solvent
CH 26.29 - 26.29 - 26.29 -
The homogenize agent
MEGAFAC R08 0.02 0.1 0.02 0.1 0.02 0.1
Amount to 100.0 100.0 100.0 100.0 100.0 100.0
Evaluation result
Suitable development time (second) 30 15 20
Resolving power (line/interval μ m) 8 6 8
Suitable development time+20 of the development time that development latitude (μ m) is suitable second 6 8 4 8 8 10
OD value (/ μ m) 5.1 5.4 5.3
*12:Kyoeisha Chemical Co., the dihydroxymethyl tristane diacrylate that Ltd. produces.
*2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl third-1-ketone that 13:Ciba Specialty Chemicals K.K. produces
Table 6
Comparative Examples 3 Comparative Examples 4 Comparative Examples 5
Blending amount (g) Solid is formed (quality %) Blending amount (g) Solid is formed (quality %) Blending amount (g) Solid is formed (quality %)
Black matix resist composition
The black pigment dispersion agent 70.6 83.6 70.6 83.6 70.6 83.6
(Special Black 350) (6.20) (32.6) (6.20) (32.6) (6.20) (32.6)
(13M-C) (6.20) (32.6) (6.20) (32.6) (6.20) (32.6)
(AJISPER PB822) (0.81) (4.3) (0.81) (4.3) (0.81) (4.3)
(EP-1) (2.68) (14.1) (2.68) (14.1) (2.68) (14.1)
(PMA) (26.47) (-) (26.47) (-) (26.47) (-)
(DGEA) (1.80) (-) (1.80) (-) (1.80) (-)
(CH) (26.47) (-) (26.47) (-) (26.47) (-)
Alefinically unsaturated compounds
LIGHT-ACRYLATE BP-4EA 0.54 2.8 0.54 2.8 0.54 2.8
ARONIX M-400 0.55 2.9 0.55 2.9 0.55 2.9
Photoepolymerizationinitiater initiater
EMK 0.30 1.6 0.30 1.6 0.30 1.6
MHABI 1.00 5.3 1.00 5.3 1.00 5.3
Mercaptan compound
EGMB 0.70 3.7 - (-) - (-)
TPMB - (-) 0.70 3.7 - (-)
EGMIB - (-) - (-) 0.70 3.7
Organic solvent
CH 26.29 (-) 26.29 (-) 26.29 (-)
The homogenize agent
MEGAFAC R08 0.02 0.1 0.02 0.1 0.02 0.1
Amount to 100.0 100.0 100.0 100.0 100.0 100.0
Evaluation result
Suitable development time (second) 20 25 20
Resolving power (line/interval μ m) 6 6 6
Suitable development time+20 of the development time that development latitude (μ m) is suitable second 6 20 6 20 8 20
OD value (/ μ m) 5.1 5.3 5.3
Obviously find out by table 2, use each photosensitive composition of the embodiment 1 of mercaptan compound to have high sensitivity, even it makes by about 50mj/cm with bis-phenol skeleton 2Also photocurable of low exposure value, its excellence aspect the development latitude of other mercaptan compound of comparing simultaneously.Therefore, mercaptan compound of the present invention and use the photosensitive composition of this compound can be advantageously used in the alkali developable resist is as solder resist, anti-etching dose and colour filter resist.
Obviously find out by table 4 and 5, use each black matix resist composition of the embodiment 4-9 of mercaptan compound to have hypersensitivity, even it makes by about 50mj/cm with bis-phenol skeleton 2Low exposure value under also photocurable, its excellence aspect the development latitude of other aliphatic mercaptan compound of comparing simultaneously.Therefore, the black matix resist composition that contains mercaptan compound of the present invention can be advantageously used in the large size base material.
Industrial applicibility
Have the new mercaptan compound of bis-phenol skeleton and use the photosensitive composition of this compound to have high sensitivity and aspect development latitude excellence, so it can be used for suitably at photolithography and alkali develop anti-etching dose of forming pattern, welding resistance agent, colour filter resist etc.
The colour filter black matix anti-corrosion agent composition that use has a new mercaptan compound of bis-phenol skeleton have high light shield performance, high sensitivity and aspect development latitude excellence, so said composition can be used for large scale colour filter base material suitably.

Claims (21)

1. mercaptan compound by formula (1) expression:
Figure A2005800364230002C1
Wherein, R 1Expression has the straight or branched alkylidene group of 1-6 carbon atom, R 2Expression has the straight or branched alkylidene group of 2-6 carbon atom, R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2-or-O-, n represents the integer of 1-5.
2. mercaptan compound according to claim 1, wherein R 1Be alkylidene group by any expression in formula (2)-(6):
-CH 2CH 2-* (2)
Figure A2005800364230002C2
Figure A2005800364230002C3
Wherein, symbol " * " shows the position with the sulfydryl keyed jointing separately.
3. mercaptan compound according to claim 1, wherein R 2It is alkylidene group by any expression in formula (7)-(9).
-CH 2CH 2- (7)
Figure A2005800364230003C1
4. mercaptan compound according to claim 1, it is represented by formula (10):
Figure A2005800364230003C2
Wherein, m represents 1 or 2 integer.
5. mercaptan compound according to claim 1, it is the compound of the esterification acquisition between the carboxylic acid cpd that contains sulfydryl of diol compound and formula (12) expression of through type (11) expression:
Figure A2005800364230003C3
Wherein, R 2Expression has the linearity or the sub-branched alkyl of 2-6 carbon atom, R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2-or-O-, n represents the integer of 1-5,
Figure A2005800364230003C4
R wherein 1Expression has the linearity of 1-6 carbon atom or the alkylidene group of side chain.
6. a production is by the method for the mercaptan compound of formula (1) expression:
Figure A2005800364230003C5
All symbols in its Chinese style (1) have and the defined identical implication of claim 1, and it comprises the esterification by the carboxylic acid cpd that contains sulfydryl of the diol compound of formula (11) expression and formula (12) expression:
Figure A2005800364230004C1
R wherein 2Expression has the linearity or the sub-branched alkyl of 2-6 carbon atom, R 3And R 4Represent hydrogen atom independently of one another, have the alkyl or the halogen atom of 1-3 carbon atom, X represent singly-bound ,-CO-,-SO 2-,-CH 2-,-C (CF 3) 2-,-C (CH 3) 2-or-O-, n represents the integer of 1-5,
Figure A2005800364230004C2
R wherein 1Expression has the linearity or the sub-branched alkyl of 1-6 carbon atom.
7. a photosensitive composition comprises: (A) contain the Photoepolymerizationinitiater initiater system of with good grounds each described mercaptan compound of claim 1-5, (B) contain the adhesive resin of carboxyl and the compound that (C) has ethylenically unsaturated group.
8. photosensitive composition according to claim 7, wherein Photoepolymerizationinitiater initiater system (A) contains six aryl united imidazoles and/or aminoacetophenone compound.
9. photosensitive composition according to claim 8, wherein six aryl united imidazoles are represented by formula (13):
Wherein Y represents halogen atom, R 5Expression alkyl or alkoxyl group, they can have substituting group.
10. photosensitive composition according to claim 7, wherein Photoepolymerizationinitiater initiater system (A) contains sensitizing agent.
11. photosensitive composition according to claim 10, wherein sensitizing agent is one or more compounds that are selected from the group of being made up of benzophenone based compound, thioxanthone based compound and ketone group tonka bean camphor based compound.
12. photosensitive composition according to claim 7, the adhesive resin (B) that wherein contains carboxyl further contains ethylenically unsaturated group.
13. resist composition that is used for the colour filter black matix, contain: the Photoepolymerizationinitiater initiater system that (A) contains with good grounds each described mercaptan compound of claim 1-5, (B) has the adhesive resin of carboxyl, (C) has the compound of ethylenically unsaturated group, (D) black pigment and (E) organic solvent.
14. the resist composition that is used for the colour filter black matix according to claim 13, the adhesive resin (B) that wherein has carboxyl further has ethylenically unsaturated group.
15. the resist composition that is used for the colour filter black matix according to claim 14, wherein adhesive resin (B) is the bisphenol type Epocryl.
16. the resist composition that is used for the colour filter black matix according to claim 13, wherein Photoepolymerizationinitiater initiater system (A) contains six aryl united imidazoles and/or aminoacetophenone compound.
17. the resist composition that is used for the colour filter black matix according to claim 16, wherein six aryl united imidazoles are the compounds by formula (13) expression:
Figure A2005800364230005C1
Wherein all symbols have with claim 9 in defined identical implication.
18. according to claim 16 or the 17 described resist compositions that are used for the colour filter black matix, wherein Photoepolymerizationinitiater initiater system (A) contains as one or more of sensitizing agent and is selected from the compound of the group of being made up of benzophenone based compound, thioxanthone based compound and ketone group tonka bean camphor based compound.
19. the resist composition that is used for the colour filter black matix according to claim 13, wherein black pigment (D) is that carbon black and/or titanium are black.
20. the resist composition that is used for the colour filter black matix according to claim 13 wherein except that organic solvent (E), comprises each component with following ratio:
(A) Photoepolymerizationinitiater initiater system; 2-15 quality %,
(B) has the adhesive resin of carboxyl; 10-30 quality %,
(C) has the compound of ethylenically unsaturated group; 2-20 quality % and
(D) black pigment; 40-80 quality %.
21. the resist composition that is used for the colour filter black matix according to claim 20, the mercaptan compound of its Chinese style (1) is contained in the Photoepolymerizationinitiater initiater system (A) with 20-70 quality %.
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