CN1975576A - Colored photosensitive resin composition - Google Patents
Colored photosensitive resin composition Download PDFInfo
- Publication number
- CN1975576A CN1975576A CNA200610162527XA CN200610162527A CN1975576A CN 1975576 A CN1975576 A CN 1975576A CN A200610162527X A CNA200610162527X A CN A200610162527XA CN 200610162527 A CN200610162527 A CN 200610162527A CN 1975576 A CN1975576 A CN 1975576A
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- China
- Prior art keywords
- acid
- methyl
- resin composition
- photosensitive resin
- compound
- Prior art date
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Classifications
-
- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
Abstract
The invention relates to a photoresist composition, including colorant (A), bond resins (B), photopolymerization compound (C), photopolymerization solicitation agent (D) and solvent (E), wherein photopolymerization compound (C) contains phthalate acid 2,2,2-trimethyl(propylene-acyloxy)-ethyl-ester.
Description
Technical field
The present invention relates to a kind of painted photosensitive resin composition.
Background of invention
Painted photosensitive resin composition is used for making for example color filter that uses of liquid crystal, electroluminescence or plasma display panel of the imageing sensor of charge-coupled device (CCD) and complementary metal oxide semiconductor (CMOS) (CMOS) and display device.
Wherein, the color filter of imageing sensor has required to make film thinner.Have to increase the pigment concentration in the color filter so that the reduction film thickness makes color density maintain high level simultaneously.But, when the painted photosensitive resin composition that comprises high concentration pigment is used to prepare film, carry out light exposure subsequently and when eliminating unnecessary part and be formed for making the pattern of color filter, exist owing to fail to produce the problem (referring to Jap.P. H8-271723) of residue with developer removal resin with developer.
Jap.P. H10-332929 has proposed a kind of painted photosensitive resin composition, and it comprises colorant, adhesive resin, as the succinic acid 2,2 of the compound of photopolymerization, 2-three (acryloxy) Methylethyl ester, Photoepolymerizationinitiater initiater and solvent.But, exist when being used to make the pattern development of color filter, after developing, remain the problem of residue.
The inventor tries hard to find a kind of painted photosensitive resin composition that does not almost have the problems referred to above, and find in making color filter, to develop when forming pattern, comprise phthalic acid 2 as the photopolymerization compound, 2, the painted photosensitive resin composition of 2-three (acryloxy) Methylethyl ester is residual hardly residue after developing.
Summary of the invention
The purpose of this invention is to provide a kind of painted photosensitive resin composition, when making the pattern development of color filter, residual hardly residue after developing.
Also promptly, the invention provides following (1) to (4).
[1]. a kind of painted photosensitive resin composition, it comprises compound (C), Photoepolymerizationinitiater initiater (D) and the solvent (E) of colorant (A), adhesive resin (B), photopolymerization.Wherein the compound of photopolymerization (C) contains phthalic acid 2,2,2-three (acryloxy) Methylethyl ester.
[2]. the pattern that the painted photosensitive resin composition of a kind of usefulness [1] forms.
[3]. the color filter of the pattern of a kind of comprising [2].
[4]. the imageing sensor of the color filter of a kind of being equipped with [3].
Implement mode of the present invention
Painted photosensitive resin composition of the present invention comprises colorant (A), adhesive resin (B), photopolymerization compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E), and the compound of this photopolymerization (C) contains the phthalic acid 2 as key component, 2,2-three (acryloxy) Methylethyl ester.
The Compound I of photopolymerization is a kind of when optical radiation, can with the living radical or the sour polymeric compounds that produce by Photoepolymerizationinitiater initiater (D).
The Compound I of above-mentioned photopolymerization contains phthalic acid 2,2, and 2-three (acryloxy) Methylethyl ester is as key component.Phthalic acid 2,2 in above photopolymerization Compound I, the amount of 2-three (acryloxy) Methylethyl ester is preferably 10 weight % or higher, more preferably 30 weight % or higher.
The Compound I of photopolymerization in the present invention can further be used in combination with the compound of other photopolymerization.The compound of other photopolymerization is preferably the multifunctional photopolymerization compound with three or more functional groups.Multifunctional photopolymerization examples for compounds with three or more functional groups comprises for example pentaerythritol tetracrylate, pentaerythritol tetramethacrylate, pentamethyl acrylic acid dipentaerythritol ester and hexamethyl acrylic acid dipentaerythritol ester.
The amount of the above photopolymerization Compound I of representing with massfraction is preferably 5 to 90 quality % of the total solid content of painted photosensitive resin composition, more preferably 10 to 80 quality %, further more preferably 20 to 70 quality %.When the amount of photopolymerization Compound I is in above scope,, prevent from pattern, to form the undercut and the close adhesion that becomes, so it is preferred because painted photosensitive resin composition is easy to abundant curing.
Painted photosensitive resin composition of the present invention contains colorant (A).The example of above colorant (A) comprises at least a colorant that is selected from pigment and dyestuff.
Pigment is particularly including the compound that is classified as pigment in colour index (according to TheSociety of Dyers and Colourists).
The particular example of pigment comprises for example yellow uitramarine, for example the C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214 etc., orange pigment, C.I. pigment orange 13 for example, 31,36,38,40,42,43,51,55,59,61,64,65,71,73 etc., red pigment, C.I. Pigment Red 9 for example, 97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264,265 etc., blue pigment, C.I. pigment blue 15 for example, 15:3,15:4,15:6,60 etc., violet pigment, C.I. pigment violet 1 for example, 19,23,29,32,36,38 etc., viridine green, C.I. pigment Green 7 for example, 36 etc., brown, for example the C.I. pigment brown 23,25 etc., and black pigment, for example the C.I. pigment black 1,7 etc.
Wherein, preferably contain at least a C.I. of being selected from pigment yellow 13 8,139 and 150, C.I. paratonere 177,209 and 254, C.I. pigment purple 23, C.I. pigment blue 15: 3 and the pigment of 15:6 and C.I. pigment Green 7 and 36.
The example of dyestuff comprises for example amine salt of oil-soluble dyes, acid dyes, acid dyes and the sulfamide derivative of acid dyes.
The example of above dyestuff for example comprises C.I. solvent yellow 4 (following omission term C.I. solvent yellow, but only list ordinal number.Other dyestuff and tone kind are omitted in explanation similarly), 14,15,23,24,38,62,63,68,82,94,98,99 and 162, C.I. solvent red 45 and 49, C.I. solvent orange 2,7,11,15,26 and 56, C.I. solvent blue 35,37,59 and 67, C.I. Indian yellow 17,29,40 and 76, C.I. acid red 91,92,97,114,138 and 151, C.I. acid orange 51 and 63, C.I. acid blue 80,83 and 90, and acid green 9,16,25 and 27.
In addition, the dyestuff of use (A) for example can comprise by structural formula (i) to (vii) the amine salt of Biao Shi acid dyes and by structural formula (viii) to the sulfamide derivative of the acid dyes of (ix) expression.
D
-(SO
3 -)
m(C
nH2
n+1N
+H
3)
m (i)
D
-(SO
3 -)
m{(C
nH
2n+1)
2N
+H
2}
m (ii)
D
-(SO
3 -)
m{(C
nH
2n+1)
3N
+H}
m (iii)
D
-(SO
3 -)
m{(C
nH
2n+1)
4N
+}
m (iv)
D
-(SO
3 -)
m{C
eH
2e+1OC
fH
2fN
+H
3}
m (v)
D
-(SO
3 -)
m{C
nH
2n+1}(PhCH
2)
2N
+H}
m (vi)
D
-(SO
3 -)
m{C
nH
2n+1}
pY
+}
m (vii)
D
-[{SO
2NH(C
nH
2n+1)}
p][(SO
3L)
q] (viii)
D
-[{SO
2NH(C
eH
2e+1OC
fH
2f)}
p][(SO
3L)
q] (ix)
In (ix), D represents dyestuff matrix at these structural formulas (i).M represents 1 to 20 integer.N represents 1 to 20 integer.E and f represent 1 to 10 integer independently of one another.Ph represents phenyl.Py represents via nitrogen atom bonding to C
nH
2n+1Pyridine ring residue or picoline ring residue.P represents 1 to 8 integer.Q represents 0 to 8 integer.L represents hydrogen atom or monovalent cation.
The particular example of D comprises azo dyes matrix, xanthene dye matrix, anthraquinone dye matrix, kiton colors matrix and copper phthalocyaine dye matrix.
M preferably represents 1 to 10 integer, more preferably 1 to 8 integer.
N preferably represents 1 to 10 integer, more preferably 1 to 8 integer.
E and f preferably represent 1 to 8 integer, more preferably 1 to 6 integer independently of one another.
Py preferably represents picoline ring residue.
P preferably represents 1 to 6 integer, more preferably 1 to 5 integer.
Q preferably represents 0 to 6 integer, more preferably 0 to 5 integer.
The example of the monovalent cation among the L for example comprises for example (C of lithium ion, sodion, potassium ion and quaternary ammonium ion
2H
5)
3HN
+, and preferred sodion.
The example of azo dyes comprises for example by the dyestuff of structural formula (I) expression or the dyestuff of being represented by the following structure formula of knot (11) to (13).
Wherein in structural formula (I), R
30Expression C1 to C15 alkyl, C2 to the C15 alkenyl, C6 to C21 aryl or C7 to the C21 aralkyl.
Above alkyl, alkenyl, aryl and aralkyl can be unsubstituted or have substituting group.R
31To R
34Represent that independently of one another hydrogen atom, halogen atom and C1 are to the C4 alkyl.
C1 comprises for example linear alkyl to the example of C15 alkyl, for example methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base and dodecyl, branched alkyl, for example isopropyl, sec-butyl, the tert-butyl group, 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethylhexyl, 2-ethyl heptyl, 2-ethyl octyl group, 2-ethyl nonyl, 2-ethyl decyl, and naphthenic base, for example cyclopentyl, cyclohexyl, suberyl and ring octyl group.
Above alkyl can contain oxygen atom with the ehter bond form.The examples of alkyl that contains the oxygen atom of ehter bond form comprises methoxyl methylene, methoxyl ethylidene, ethoxy ethylidene, butoxy ethylidene and butoxy butylidene.
C2 comprises for example vinyl to the C15 non-limiting examples of alkenyls, the 1-propenyl, isopropenyl, the 1-butenyl group, the 2-butenyl group, the 1-pentenyl, the 1-hexenyl, the 1-heptenyl, the 1-octenyl, the 2-octenyl, 1-nonene base, 2-nonene base, 1-decene base, 2-decene base, the 1-undecenyl, the 2-undecenyl, the 1-dodecenyl succinic, the 2-dodecenyl succinic, 2-tridecylene base, 2-tridecylene base, the tetradecene base, 2-tetradecene base, 1-15 carbene bases and 2-15 carbene bases etc.
C6 comprises for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 2-furyl, 3-furyl, 2-pyrrole radicals, 3-pyrrole radicals, 2-pyridine radicals, 3-pyridine radicals, 4-pyridine radicals, 2-thienyl, 3-thienyl, 2-pyrimidine radicals, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl and 8-quinolyl etc. to the example of C21 aryl.
C7 comprises for example benzyl, benzhydryl, 1 to the example of C21 aralkyl, 2-diphenyl-ethyl, phenyl cyclopentyl-methyl, α-Jia Jibianji, phenylethyl group, Alpha-Methyl phenylethyl, Beta-methyl phenylethyl, 3-phenyl propyl, 3,3-diphenyl propyl, 4-phenyl butyl, naphthyl methyl, styryl, cinnamyl, fluorenyl, 1-benzocyclobutane thiazolinyl, 1,2,3,4-tetralyl, piperonyl and pyrene methyl etc.
Wherein, benzyl, phenyl cyclopentyl-methyl, α-Jia Jibianji, phenylethyl, Alpha-Methyl phenylethyl, Beta-methyl phenylethyl, 3-phenyl propyl, 4-phenyl butyl, styryl, cinnamyl, fluorenyl, 1-benzocyclobutane thiazolinyl and 1,2,3, the 4-tetralyl is preferred, and α-Jia Jibianji, phenylethyl, Alpha-Methyl phenylethyl, Beta-methyl phenylethyl, 3-phenyl propyl, styryl, cinnamyl, fluorenyl, 1-benzocyclobutane thiazolinyl and 1,2,3, the 4-tetralyl is further preferred.R
30Example comprise preferable methyl, ethyl, n-pro-pyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, isopropyl, sec-butyl, the tert-butyl group, 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethylhexyl, 2-ethyl heptyl and 2-ethyl octyl group, and more preferably isopropyl, the tert-butyl group, 2-ethyl-butyl, 2-ethyl pentyl group and 2-ethylhexyl.
R
31To R
34Example comprise hydrogen atom, methyl, ethyl, n-pro-pyl, normal-butyl, isopropyl, sec-butyl, the tert-butyl group, fluorine atom, chlorine atom, bromine atoms and iodine atom, and preferred hydrogen atom, methyl, ethyl, n-pro-pyl, normal-butyl, isopropyl, sec-butyl, the tert-butyl group, fluorine atom and chlorine atom.
Wherein comprise compound by structural formula (14) expression by the particular example of the preferred coloring agent of the dyestuff of structural formula (I) expression.The example of xanthene dye comprises the compound of for example being represented by structural formula (15).The example of copper phthalocyaine dye comprises the compound of for example being represented by structural formula (16).
According to solubleness and anti-the fading and spectrum when using the painted photosensitive composition that contains described colored composition to form color filter pattern, these dyestuffs are suitably selected at the solvent that is used for described coloured composition.Can use two or more the combination in them.
When the painted photosensitive resin composition that contains coloured composition of the present invention is used to form red pixel, the combination of the dyestuff of preferred choice structure formula (13), (14) and (15).
For the dyestuff of structural formula (16), preferably select the combination of C.I. acid blue 90 and C.I. solvent blue 67, so that form blue pixel.
The preferred combination of selecting C.I. solvent blue 67, C.I. acid green 9, C.I. acid green 16, C.I. solvent yellow 82 and C.I. solvent yellow 16 2 is so that form green pixel.The combination of red, indigo plant and green dye is not limited to above a kind of, and every kind of dyestuff appropriate combination in addition can be allocated the spectrogram of required pixel.
If necessary, can handle these dyestuffs (A) with rosin, perhaps it is carried out surface treatment with the pigment derivative of introducing acidity or basic group, be grafted to the surface of dye granule with macromolecular compound, remove impurity with organic solvent or water washing, perhaps handle and remove ionic impurity with ion exchange process.These processing can separately or be united and carried out.
If necessary, colorant (A) can disperse with spreading agent or part or all of adhesive resin (B), the solution that obtains disperseing, and wherein pigment or dyestuff evenly disperse.
The example of above spreading agent comprises for example kation, negative ion, nonionic, both sexes, polyester-based or polyamine based surfactants, its can be separately or two or more unite use.
The example of described surfactant comprises polyethylene oxide alkyl ethers, polyoxyethylene alkyl phenyl ether, polyethylene glycol di, sorbitan fatty acid ester, modified fat acid polyester, enhanced tertiary amine polyurethane and polyethylene imine based.
With the form of trade mark, particular example comprises that KP (derives from Shin-Etsu Chemical Co., Ltd.), POLYFLOW
TR(derive from Kyoeisha Chemical Co., Ltd.), Ftop
TR(derive from Tohchem Products Co., Ltd.), Megafac
TR(derive from Dainippon Ink﹠amp; Chemicals Inc.), Fluorad
TR(derive from Sumitomo 3M Co., Ltd.), AsahiGuard
TRAnd Surfron
TR(deriving from Asahi Glass Co.Ltd.), Solsperse
TR(derive from Zeneca Co., Ltd.), EFKA
TR(derive from EFKA Chemicals Co., Ltd.) and PBS821 (derive from Ajinomoto Co., Lnc.).
When using spreading agent, its amount of representing with massfraction is preferably 0.1 to 100 quality %, and 5 to 50 quality % more preferably are for the colorant of 100 quality %.When the dispersion dosage that uses is in above scope, tend to preferably obtain homodisperse solution.
The amount that is used for the colorant (A) of the painted photosensitive resin composition of representing with massfraction of the present invention is preferably 20 to 65 quality %, more preferably 25 to 60 quality %, further more preferably 27 to 55 quality %, 30 to 50 quality % most preferably are with respect to the solid content of painted photosensitive resin composition.
The term solid content that is used for this instructions is for according to the requirement in the painted photosensitive resin composition, in the component of compound (C), Photoepolymerizationinitiater initiater (D) and other interpolation of colorant (A), adhesive resin (B), photopolymerization in the total amount of 25 ℃ (room temperatures) time non-liquid composition.
When the content of colorant (A) was in above scope, preferably because the colour density abundance in the color filter that forms, and the pattern that forms had sufficient physical strength, so composition can contain the adhesive resin above aequum.
Painted photosensitive resin of the present invention contains adhesive resin (B).Above adhesive resin (B) contains preferably derived from (methyl) acrylic acid structural unit.Term (methyl) acrylic acid is represented acrylic acid and/or methacrylic acid.The content of representing with mole fraction derived from above (methyl) acrylic acid structural unit is preferably 16mol% to 40mol%, and more preferably 18mol% is to 36mol%, with respect to the amount of the entire infrastructure unit that constitutes adhesive resin (B).When the content of (methyl) acrylic acid structural unit is in above scope do not tend in developing process, dissolve because there is pixel portion, and after developing on no pixel portion residual hardly residue, so it is preferred.
The monomer example derived from the adhesive resin structural unit that is different from derived from (methyl) acrylic acid structural unit comprises for example aromatic vinyl compound; esters of unsaturated carboxylic acids; the aminoalkyl ester of unsaturated carboxylic acid; the unsaturated carboxylic acid glycidyl esters; the unsaturated carboxylic acid vinyl esters; unsaturated ethers; vinyl cyanide compound; unsaturated amides; the unsaturated acyl imines; aliphatics conjugated diolefine and have the big monomer of single acryloyl group or monomethyl acryloyl group at the polymer chain end.By structural formula (II) or (III) expression structural unit also can be listed in above structural unit.
Wherein structural formula (II) and (III) in R
10And R
11Represent that independently of one another hydrogen atom or C1 are to the C6 alkyl.
R
10And R
11Comprise hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, n-pentyl, 1-methyl butyl, 2-methyl butyl, 3-methyl butyl, 1-ethyl propyl, 2-ethyl propyl, n-hexyl, 1-methyl amyl, 2-methyl amyl, 3-methyl amyl, 4-methyl amyl, 1-ethyl-butyl, 2-ethyl-butyl and 3-ethyl-butyl, preferred hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl and the tert-butyl group, and more preferably hydrogen atom, methyl and ethyl.
The particular example of above adhesive resin preferably includes methacrylic acid/methacrylic acid benzyl ester multipolymer, methacrylic acid/methacrylic acid benzyl ester/styrol copolymer, methacrylic acid/methacrylic acid benzyl ester/IBOMA multipolymer, methacrylic acid/styrene/methacrylic acid benzyl ester/N-phenylmaleimide multipolymer, methacrylic acid/by the structural unit of structural formula (V) expression (R in the structural formula (II) wherein
10And R
11Represent methyl and hydrogen atom respectively at this)/methacrylic acid benzyl ester multipolymer, by the structural unit of structural formula (II) expression (R in the structural formula (II) wherein
10And R
11Represent methyl and hydrogen atom respectively at this)/methacrylic acid benzyl ester multipolymer and methacrylic acid/by the structural unit of structural formula (III) expression (R in the structural formula (III) wherein
10And R
11Represent methyl and hydrogen atom respectively at this)/styrene/methacrylic acid three suberyl ester copolymers.
The acid number that is used for adhesive resin of the present invention (B) is preferably 50 to 150, and more preferably 60 to 135, further more preferably 70 to 135.When acid number is in above scope, because the dissolving resin degree tends to increase the dissolving of promotion unexposed portion in the developer in developing process, and the susceptibility of resin is tended to increase the pattern that keeps exposed portion, and the ratio that increases remaining film thickness, so it is preferred.This acid number be with in and the value measured of the form of the required potassium hydroxide amount (mg) of 1g acrylate copolymer, and usually by use potassium hydroxide solution titration determination.
The massfraction content of adhesive resin (B) is preferably 15 to 40 quality %, more preferably 18 to 38 quality %, and further more preferably 21 to 36 quality % are with respect to the solid content of painted photosensitive resin composition.When the content of adhesive resin (B) is in above scope, because formed sharp keen pattern and tended to improve the more height ratio of pattern resolution and remaining film thickness, so it is preferred.
Comprise that adhesive resin by the structure division of structural formula (II) expression is by making methacrylic acid and the copolymerization of methacrylic acid benzyl ester obtain bi-component polymeric, then with the compound of representing by structural formula (II-1) (wherein in the structural formula (II-1), R
11The expression hydrogen atom) reaction and preparation, described adhesive resin for example be methacrylic acid/by the structure division of structural formula (II) expression (wherein in the structural formula (II), R
10And R
11Represent methyl and hydrogen atom respectively)/methacrylic acid benzyl ester multipolymer.
Methacrylic acid/by the structure division of structural formula (III) expression (wherein in structural formula (III), R
10And R
11Represent methyl and hydrogen atom respectively)/methacrylic acid benzyl ester/methacrylic acid three ring decyl ester multipolymers can react with glycidyl methacrylate by the multipolymer that makes methacrylic acid benzyl ester, methacrylic acid and have a monomethacrylates of tristane structure and obtain.
Weight-average molecular weight based on the polystyrene calibration criterion of adhesive resin (B) is 5,000 to 100,000, more preferably 6,000 to 90,000, and further more preferably 7,000 to 80,000.When molecular weight was in above scope, because film hardness tends to improve, the ratio of remaining film thickness and pattern resolution were tended to because unexposed portion is better and higher for the solubleness of developer, so it is preferred.
Painted photosensitive resin composition of the present invention contains Photoepolymerizationinitiater initiater (D).The example of above Photoepolymerizationinitiater initiater (D) comprises that triaizine compounds, aceotphenone compound, diimidazole compound, living radical produce body and acid produces body.
The example of above triaizine compounds for example comprises,
2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines,
2, two (the trichloromethyl)-6-(4-methoxyl naphthyl) of 4--1,3,5-triazines,
2, two (the trichloromethyl)-6-(4-methoxyl-styrene) of 4--1,3,5-triazines,
2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl of 4-]-1,3,5-triazines,
2, two (trichloromethyl)-6-[2-(furans-2-yl) vinyl of 4-]-1,3,5-triazines,
2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl of 4-]-1,3,5-triazines,
2, two (trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl of 4-]-1,3,5-triazines.
The example of above aceotphenone compound for example comprises, diethoxy acetophenone, 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl) phenyl] oligomer of propane-1-ketone and 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone is preferred.
Above diimidazole examples for compounds for example comprises,
2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-the tetraphenyl diimidazole,
2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-carbonyl ethoxyl phenenyl) diimidazole,
2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (4-bromophenyl) diimidazole,
2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (2, the 4-dichlorophenyl) diimidazole,
2,2 '-two (2-bromophenyls)-4,4 ', 5,5 '-the tetraphenyl diimidazole,
2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-the tetraphenyl diimidazole,
2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-four (m-methoxyphenyl) diimidazole,
2,2 '-two (2, the 6-dichlorophenyl)-4,4 ', 5,5 '-the tetraphenyl diimidazole,
2,2 '-two (2-nitrobenzophenones)-4,4 ', 5,5 '-the tetraphenyl diimidazole,
2,2 '-two (2-aminomethyl phenyls)-4,4 ', 5,5 '-the tetraphenyl diimidazole etc.
Living radical produces body and produces living radical when optical radiation.The example that above living radical produces body comprises for example benzoin compound, benzophenone cpd, thioxanthones compound, triaizine compounds, oxime compound etc.
Above benzoin examples for compounds comprises for example benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether etc.
The example of above benzophenone cpd for example comprise benzophenone, o-benzoyl yl benzoic acid methyl esters, 4-phenyl benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 3; 3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2; 4,6-tri-methyl benzophenone etc.
Above thioxanthones examples for compounds comprises for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
The example of triaizine compounds comprises same compound listed above.
The example of above oxime compound for example comprises; O-acyl group oxime compound, special 1-(4-phenyl sulfenyl phenyl) butane-1; 2-diketone-2-oxime-O-benzoic ether, 1-(4-phenyl sulfenyl phenyl) octane-1,2-diketone-2-oxime-O-benzoic ether, 1-(4-phenyl sulfenyl phenyl) octane-1-ketone-oxime-O-acetic acid esters, 1-(4-phenyl sulfenyl phenyl) butane-1-ketone-oxime-O-acetic acid esters etc.
Except above example, the example that living radical produces body for example can comprise 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, 10-butyl-2-chloro-acridine ketone, 2-EAQ, benzil, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc.
The example that above acid produces body for example comprises, salt, for example 4-hydroxy phenyl dimethyl sulfonium tosilate, 4-hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate, nitrobenzyl toluene sulfonate, benzoin toluene sulfonate etc.
Produce in the body at above living radical, some compounds produce living radical and acid simultaneously, and for example comprise triazine type Photoepolymerizationinitiater initiater, also produce body as acid.
The quality of Photoepolymerizationinitiater initiater (D) is preferably 0.1 to 20 quality % than content, and 1 to 15 quality % more preferably is with respect to the total amount of adhesive resin (B) and photopolymerization compound (C).When the content of Photoepolymerizationinitiater initiater is in above scope, because improved photosensitivity, the time shutter is shortened, improved throughput rate, prevent simultaneously because excessive sensitivity minimizes live width in the lines resolution and from the gap in the pattern that amplifies, so it is preferred.
Painted photosensitive resin composition of the present invention can further contain Photoepolymerizationinitiater initiater auxiliary agent (G).Photoepolymerizationinitiater initiater auxiliary agent (G) is used in combination with Photoepolymerizationinitiater initiater (D) usually, and plays the photopolymerization compounds polymerization that promotion is caused by Photoepolymerizationinitiater initiater.
The example of Photoepolymerizationinitiater initiater auxiliary agent (G) comprises amines, alkoxy anthracene compound, thioxanthones compound etc.
The example of above amines for example comprises, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, 4-diethylamino ethyl benzoate, 4-dimethylaminobenzoic acid isopentyl ester, 2-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone and 4,4 '-two (ethylmethylamino) benzophenone etc., and wherein, 4,4 '-two (diethylamino) benzophenone is preferred.
Above alkoxy anthracene examples for compounds for example comprises 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.
Above thioxanthones examples for compounds comprises for example 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
Photoepolymerizationinitiater initiater auxiliary agent (G) can be separately or two or more unite use.Can use commercially available Photoepolymerizationinitiater initiater auxiliary agent (G).The example of Photoepolymerizationinitiater initiater auxiliary agent (G) comprises organic amine compound, for example EAB-F (4,4 '-two (diethylamino) benzophenone, derive from Hodogaya Chemical Co., Ltd.).
The example of combination that is used for Photoepolymerizationinitiater initiater (the D)/Photoepolymerizationinitiater initiater auxiliary agent (G) of the painted photosensitive resin composition of the present invention for example comprises, diethoxy acetophenone/4,4 '-two (diethylamino) benzophenone, 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone/4,4 '-two (diethylamino) benzophenone, benzyldimethylketal/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone/4,4 '-two (diethylamino) benzophenone, 1-hydroxycyclohexylphenylketone/4,4 '-two (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone/4,4 '-oligomer of two (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone/4,4 '-two (diethylamino) benzophenone etc.Wherein, 2-methyl-2-morpholinyl-1-(4-methyl mercapto phenyl) propane-1-ketone/4,4 '-two (diethylamino) benzophenone is preferred the use.
For 1 part of Photoepolymerizationinitiater initiater (D), the amount of these Photoepolymerizationinitiater initiater auxiliary agents (G) of use is preferably 0.01 to 10 part, more preferably 0.01 to 5 part.
The example that is used for the solvent (E) of painted photosensitive resin composition of the present invention comprises for example ether, aromatic hydrocarbon, ketone, alcohol, ester, acid amides etc.
The example of above ether comprises for example tetrahydrofuran, oxinane, 1, the 4-dioxan, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, the propylene glycol monopropyl ether acetic acid esters, methylcellosolve acetate, ethyl cellosolve acetate, the ethyl carbitol acetate, acetate of butyl carbitol, propylene glycol methyl ether acetate, the methoxyacetic acid butyl ester, the methoxyacetic acid pentyl ester, anisole, phenetol, methyl anisole etc.
The example of above aromatic hydrocarbon comprises for example benzene,toluene,xylene, sym-trimethyl benzene etc.
The example of above ketone comprises for example acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone etc.
The example of above alcohol comprises for example methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine etc.
The example of above ester comprises for example ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, Arrcostab, methyl lactate, ethyl lactate, the glycolic methyl esters, the glycolic ethyl ester, the glycolic butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the 3-hydroxypropionate methyl esters, the 3-hydroxypropionate ethyl ester, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 2-ethylene lactic acid methyl esters, 2-ethylene lactic acid ethyl ester, 2-ethylene lactic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester, acetate 3-methoxyl butyl ester, acetate 3-methyl-3-methoxyl butyl ester, gamma-butyrolacton etc.
The example of above acid amides comprises for example N, dinethylformamide, N,N-dimethylacetamide etc.
The example of other solvent comprises for example N-Methyl pyrrolidone, dimethyl sulfoxide etc.
Above solvent can be separately or with two or more uses.
Wherein, the preferred solvent that contains propylene glycol methyl ether acetate that uses.When solvent (E) when containing propylene glycol methyl ether acetate, its quality is preferably 50 to 97 quality % than content for the solvent total amount, more preferably 60 to 95 quality %.
The quality of solvent (E) is preferably 70 to 90 quality % than content for the total amount of painted photosensitive resin composition, more preferably 75 to 88 quality %.When the content of solvent (E) is in above scope since the good uniform plane in using and fully color density and when forming color filter the excellence display characteristic, it is preferred.
Painted photosensitive resin composition of the present invention can contain surfactant.The example of surfactant comprises siloxy group surfactant, fluorine surfactant and fluorine silicon oxyalkyl surfactant.
The example of above siloxy group surfactant comprises the surfactant with siloxane bond.The particular example of commercial product comprises that Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA and polyether modified siloxane oil SH8400 (derive from Toray Silicone Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (derive from Shin-Etsu Silicone Co., Ltd.) and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (derive from GE Toshiba Silicone Co., Ltd.).
The example of above fluorine surfactant comprises the surfactant with fluorohydrocarbon chain.The particular example of commercial product comprises Fluorad
TRFC430 and FC431 (derive from Sumitomo 3MCo., Ltd.), Megafac
TRF142D, F171F172, F173, F177, F183, F470, F475 and R30 (derive from Dainippon Ink ﹠amp; Chemicals Inc.), Eftop
TREF301, EF303, EF351 and EF352 (derive from New Akita Chemical Co., Ltd.), Surfron
TRS381, S382, SC101 and SC105 (derive from Asahi Glass Co., Ltd.), E5844 (deriving from Daikin Fine Chemical Laboratory), BM-1000 and BM-1100 (deriving from BM Chemie) etc.
The example that more than has the silicone surfactant of fluorine atom comprises the surfactant with siloxane bond and fluorohydrocarbon chain.Particular example comprises Megafac
TRR08, BL20, F475, F477 and F443 (derive from Dainippon Ink ﹠amp; Chemicals Inc.).These surfactants can be separately or two or more unite use.
Painted photosensitive resin composition of the present invention can contain and has 1,000 or more low-molecular-weight organic acid.Above organic acid example comprises and for example being disclosed among the Jap.P. H5-343631.Particular example comprises malonic acid, oxalic acid, succinic acid, glutaric acid, hexane diacid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid (TPA), citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid and methacrylic acid, and preferred malonic acid, oxalic acid, fumaric acid and phthalic acid.When containing molecular weight is 1,000 or during lower organic acid, the residue after developing tends to show more performance.
Painted photosensitive resin composition of the present invention can further contain adjuvant, for example filler, the macromolecular compound except adhesive resin, adhesion promotor, antioxidant, UV absorbing agent, aggregation inhibitor, organic amine, hardening agent etc.
The example of above filler comprises for example fine granular, for example glass and aluminium oxide.
The example of the macromolecular compound except above adhesive resin comprises for example polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-fluoroalkyl acrylate etc.
The example of above adhesion promotor for example comprises, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane etc.
The example of above antioxidant for example comprises 4,4 '-thiobis (the 6-tert-butyl group-3-methylphenol), 2,6 di tert butyl 4 methyl phenol etc.
The example of above UV absorbing agent comprises for example benzotriazole type, for example 2-(the 2-hydroxyl-3-tert-butyl group-5-aminomethyl phenyl)-5-chlorobenzotriazole, benzophenone type, for example 2-hydroxyl-4-octyloxy benzophenone, benzoate type, for example 2,4-two-tert-butyl-phenyl-3,5-two-tertiary butyl-4-hydroxy benzoate and triazine type, for example 2-(4,6-diphenyl-1,3,5-triazines-2-yl)-the own oxygen base of 5-phenol.
The example of above aggregation inhibitor comprises sodium polyacrylate etc.
Add organic amine compound and prevent in development residue, and produce the pixel that base substrate is had excellent close adhesion at the unexposed area of base material area deposition.
The example of above organic amine compound for example comprises, single alkanamine, n-propylamine for example, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, the monocycle alkanamine, cyclohexylamine for example, the 2-methyl cyclohexylamine, 3-methylcyclohexyl amine, 4-methylcyclohexyl amine, two alkanamines, methyl ethylamine for example, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, di-sec-butylamine, two tert-butylamines, two n-amylamines, two n-hexylamines, monoalkyl monocycle alkanamine, methyl cyclohexylamine for example, ethyl cyclohexylamine, two cycloalkanes amine, dicyclohexyl amine for example, three alkanamines, dimethyl amine for example, methyl-diethyl-amine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyl-di-n-propylamine, ethyl-di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, three tert-butylamines, tri-n-amyl amine, three n-hexylamines, dialkyl group monocycle alkanamine, dimethyl cyclohexyl amine for example, diethyl cyclohexylamine, monoalkyl two cycloalkanes amine, methyl bicyclic hexylamine for example, the ethyl dicyclohexyl amine, tricyclohexyltin amine, monoalkanolamine, 2-ethylaminoethanol for example, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, the mononaphthene hydramine, 4-amino-1-cyclohexanol for example, the dioxane hydramine, diethanolamine for example, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two-I-butanolamine, two n-amyl alcohol amine, two n-hexyl alcohol amine, two cycloalkanes hydramine, for example two (4-cyclohexanol) amine, three alkanolamines, triethanolamine for example, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, three n-hexyl alcohol amine, three cycloalkanes hydramine, three (4-cyclohexanol) amine for example, the amino alkane glycol, 3-amino-1 for example, the 2-propylene glycol, 2-amino-1, ammediol, 4-amino-1, the 2-butylene glycol, 4-amino-1, the 3-butylene glycol, 3-dimethylamino-1, the 2-propylene glycol, 3-diethylamino-1, the 2-propylene glycol, 2-dimethylamino-1, ammediol and 2-diethylamino-1, ammediol, the Aminocycloalkane glycol, 4-amino-1 for example, 2-cyclohexanediol and 4-amino-1, the 3-cyclohexanediol, contain amino cyclanone methyl alcohol, 1-amino cyclopentyl ketone methyl alcohol for example, 4-amino cyclopentyl ketone methyl alcohol, contain amino naphthenic hydrocarbon methyl alcohol, the amino cyclohexanone methyl alcohol of 1-for example, the amino cyclohexanone methyl alcohol of 4-, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylamino cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, 4-diethylamino cyclohexane methanol, amino carboxylic acid, Beta-alanine for example, the 2-aminobutyric acid, the 3-aminobutyric acid, the 4-aminobutyric acid, the amino different acetate of 2-, the amino different acetate of 3-, the 2-aminovaleric acid, the 5-aminovaleric acid, 6-aminocaprolc acid, 1-amino-cyclopropane formic acid, 1-aminocyclohexane formic acid, 4-aminocyclohexane formic acid, aromatic amine, aniline for example, o-toluidine, between methylaniline, to methylaniline, to ethylaniline, to n-propylbenzene amine, cumidine, to n-butyl aniline, p-tert-butyl-aniline, naphthalidine, the 2-naphthylamines, N, the N-dimethylaniline, N, the N-diethylaniline, to methyl-N, the N-dimethylaniline, aminobenzyl alcohol, for example adjacent aminobenzyl alcohol, between aminobenzyl alcohol, to aminobenzyl alcohol, to dimethylamino benzylalcohol, to diethylamino benzylalcohol, amino-phenol, o-aminophenol for example, m-aminophenol, para-aminophenol, to dimethylamino phenol with to diethylamino phenol, aminobenzoic acid, for example gavaculine, p-aminobenzoic acid, ESCAROL 507, to the diethyl amino yl benzoic acid.
The example of above hardening agent for example comprises when heating with the carboxyl reaction of adhesive resin and carries out the compound that crosslinked compound and self-polymerization make colored pattern curing.Above examples for compounds comprises for example epoxy compound and oxetane compound, and preferably uses oxetane compound.
The example of above epoxy compound comprises for example epoxy resin, bisphenol A type epoxy resin for example, bisphenol-A epoxy resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, phenolic resin varnish type epoxy resin, other aromatic epoxy resin, cycloaliphatic epoxy resin, the heterocyclic ring epoxy resins, glycidyl esters type resin, glycidyl group amine type resin and epoxidation oils, the brominated derivative of these epoxy resin, aliphatics except epoxy resin, alicyclic or aromatic epoxy compound and brominated derivative thereof, epoxidation butadiene (being total to) polymkeric substance, epoxidized isoprene (being total to) polymkeric substance, (methyl) glycidyl acrylate, (being total to) polymkeric substance of isocyanuric acid triglycidyl group ester etc.
The example of above oxetane compound comprises for example carbonic ester-dioxetane, xylylene-dioxetane, adipate-dioxetane, terephthalate-dioxetane, cyclohexane-carboxylic acid-dioxetane etc.
When containing epoxy or oxetane compound as hardening agent, the compound of ring-opening polymerization is given birth in the oxetanes environment-development that painted photosensitive resin composition of the present invention can contain the epoxy radicals that can make epoxy compound and oxetane compound.Described examples for compounds comprises that for example polyvalent carboxylic acid, polyvalent carboxylic acid's acid anhydride, acid produce body etc.
Above polyvalent carboxylic acid's example for example comprises, aromatic series polyvalent carboxylic acid, for example phthalic acid, 3,4-dimethyl phthalic acid, m-phthalic acid, terephthalic acid (TPA), pyromellitic acid, trihemellitic acid, 1,4,5, the 8-naphthalene tetracarboxylic acid, 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid, aliphatics polyvalent carboxylic acid, succinic acid for example, glutaric acid, hexane diacid, 1,2,3, the 4-ethylene-dimalonic acid, maleic acid, fumaric acid, itaconic acid, alicyclic polyvalent carboxylic acid, hexahydrophthalic acid for example, 3,4-dimethyl tetrahydro phthalic acid, six hydrogen m-phthalic acids, six hydrogen terephthalic acid (TPA)s, 1,2,4-cyclopentane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, the cyclopentane tetracarboxylic acid, 1,2,4,5-cyclohexane tetrabasic carboxylic acid.
The example of above polyvalent carboxylic acid's acid anhydride for example comprises, the aromatic series polyvalent carboxylic acid, phthalic anhydride for example, PMA, the trihemellitic acid acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, aliphatics polyvalent carboxylic acid, itaconic anhydride for example, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, the tricarballylic acid acid anhydride, maleic anhydride, 1,2,3,4-ethylene-dimalonic acid dianhydride, alicyclic polyvalent carboxylic acid, for example hexahydrophthalic anhydride, 3,4-dimethyl tetrahydro phthalic anhydride, 1,2 4-cyclopentane front three acid anhydrides, 1,2,4-cyclohexane front three acid anhydrides, the cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, dicyclo amylene dicarboxylic acid anhydride (himic anhydride), nadic anhydride, and carboxylic acid anhydrides, for example ethylene glycol bisthioglycolate (tritrimellitate) with ester group, glyceryl three (trimellitate) acid anhydrides.
The commercially available hardening agent of epoxy resin can be used as above carboxylic acid anhydrides.The example of above epoxy curing agent comprises for example Adeka Hardener
TREH-700 (deriving from ADEKACorp.) and Rikacid
TR, MH-700 (all derives from New Japan Chemical Co., Ltd.).Acid produces body with those are identical as mentioned above.
Above hardening agent can be united use separately or with two or more.
The method of the photosensitive resin composition that preparation the present invention is painted comprises for example such method, wherein for example the colorant of pigment (A) is dispersed in the presence of spreading agent and forms the solution that colorant disperses in the solvent (E), in this solution, add the adhesive resin (B) be dissolved in solvent solution, photopolymerization compound (C), Photoepolymerizationinitiater initiater (D) and be dissolved in other adjuvant of solvent if desired, further add solvent then if desired.
Painted photosensitive resin composition of the present invention is sealed in usually and is used in the container transport and store.
Following description uses painted photosensitive resin composition of the present invention to prepare the conventional method of the color filter of imageing sensor.This method comprises successively to base substrate and applying and dry painted photosensitive resin composition, makes applying and dry Thinfilm pattern exposure of obtaining with I line ledex, light expose and thermal treatment after make the continuous processing of image alkaline development.Repeat above technology continuously for every kind of color (three or four kind of color), form pixel, produce color filter.
More specifically, painted photosensitive resin composition of the present invention is by on the suitable base substrate of paints such as rotary coating machine, make the thickness of dry film be generally 0.1 to 5 μ m, preferred 0.2 to 2 μ m, this substrates coated is under 100 ℃ in baking oven dry 3 minutes then, produces the film of smooth coating.
Base substrate is had no particular limits, but comprise glass plate, plastic sheet, aluminium sheet, be used for the base substrate of electronic component, for example the siloxane wafer of image component, in addition comprise transparent plastic sheet, resin molding, CRT display screen, teletron light receiving surface, have the wafer combination of solid-state image element, the base substrate of the photoreceptor of the contact image sensor of the CCD on it, BBD, CID and BASIS, use thin film semiconductor, LCD face, color electronography art and electrochromism (EC) display for example.Equally preferably apply high adherence and handle, to improve the cohesive between base substrate and the color filter layer to base substrate.Particularly, at first apply base substrate thinly, form the pattern of painted photosensitive resin composition or painted photosensitive resin composition then and can contain silane coupling agent in advance with silane coupling agent.
When the surface irregularity of base substrate, the film of leveling is applied to base substrate, eliminating projection, thereby for coating forms flat surface, then can be to this surface application painted photosensitive resin composition of the present invention.For example, the Sensor section of imageing sensor, for example CCD is made up of photoelectric conversion section (photodiode) and reading gate part, and wherein photoelectric conversion section produces the electronics be equivalent to the light amount that receives on silica-based plinth base material, and the electronics that produces of reading gate part output.But light arrives the reading gate part and produces noise and can't export correct data, makes to form the light screen layer on the top of reading gate part, may form a projection owing to the photodiode part that does not have the light screen layer.If colored photoresist is applied over out-of-flatness surface and directly forms color filter, light path is elongated so, makes the image that forms deepen and also step-down of light focusing.In order to improve this problem, preferably between CCD and color filter, form transparent leveling film, to fill projection.The examples of materials of this leveling film comprises photosensitive resin composition of the present invention, thermoset resin, for example acrylic acid or epoxy resin and light curable resin.
After having applied photosensitive resin composition, usually, produce dry filming with the base substrate of coating preliminary drying evaporating solvent under reduced pressure.For example, can list a kind of method, wherein substrates coated remains on 50 to 120 ℃ of temperature, under the pressure of 0.1 to 10 holder.The example of preliminary drying method comprises with hot air and drying, and heats on hot plate or dry (80 to 140 ℃ and 50 to 200 seconds).
Usually also carry out back baking, so that make the resin combination of coating fully solidify and strengthen to develop the physical strength of the pattern that obtains afterwards, to form lasting film.For example, making in the color filters with three kinds of colors, afterwards the pattern that will at first form with the painted photosensitive resin composition of other color apply, light exposes and twice of image developing technology.In this technology, preferably carry out back baking, with the painted photosensitive resin composition that prevents to apply because colour mixture takes place in light exposure and image developing and pattern lacks.The baking of this back is similar to the preliminary drying method to be carried out, but at high temperature carry out and the time ratio preliminary drying long.For example, the back baking was carried out under 100 to 250 ℃ 1 to 60 minute.
Developer to the painted photosensitive resin composition that is used to develop is not particularly limited, and can use conventional known developer.Wherein, the preferred quaternary ammonium salt water-based organic basic solution of tetramethylammonium hydroxide (TMAH) for example.
Can be for example by on the Sensor section that forms on the base substrate, forming the leveling film, form color filter of the present invention thereon according to above method then, put on lens material with lithography process and thermal treatment then and form lens pattern, use internal corrosion technology to form single element lens to entire area subsequently, make the imageing sensor that color filter is housed among the present invention.
When containing the thin color filter of high concentration pigment, can reduce the residue after developing when constructed in accordance, produce and have the color filter that does not almost have defective in high color purity and the manufacture process.Painted photosensitive resin composition of the present invention is specially adapted to the color filter of shop drawings image-position sensor.
Embodiment
Will present invention is described according to following examples, but what need not say is that the present invention is not limited to these embodiment more.
Synthesizing of＜resin (B1) 〉
The 333g propylene glycol methyl ether acetate is joined in the 1L flask that stirrer, thermometer, reflux condenser, tap funnel and gas inlet pipe are housed.Then by gas inlet pipe input nitrogen, with the atmosphere of nitrogen replacement flask.Then the solution in the flask is heated to 100 ℃, use tap funnel through 2 hours to wherein adding 22.0g (0.10mole) (FA-513M, derive from Hitachi Chemical Co., Ltd.) potpourri of methacrylic acid dicyclopentenyl ester, 70.5g (0.40mole) methacrylic acid benzyl ester, 43.0g (0.5mole) methacrylic acid, 3.6g azoisobutyronitrile and 164g propylene glycol methyl ether acetate.After interpolation is finished, further stirred this potpourri 5 hours down at 100 ℃.
Finish after the stirring, by gas inlet pipe air is imported in the flask, atmosphere wherein is replaced into air, adds 35.5g (0.25mole (mole fraction that is used for the methacrylic acid of this reaction is 50mol%)) glycidyl methacrylate, 0.9g three (dimethylamino) methylphenol and 0.145g quinhydrones then.Be reflected at 110 ℃ and continue 6 hours, produce the solution (solids content is that 38.5 quality % and acid number are 80mgKOH/g) that contains resin B 1.
Acid number at this is to contain for example value of the required potassium hydroxide amount of polymkeric substance (mg) measurement of the acidic group of carboxylic acid with 1g in the basis.It is usually by the potassium hydroxide aqueous solution titration determination with concentration known.
The weight-average molecular weight of resin B 1 is 9,000, based on the polystyrene calibration criterion.
Weight-average molecular weight based on the above adhesive resin of polystyrene calibration criterion is measured by the GPC method, and the condition of described method is as follows.
Equipment: HLC-8120GPC (derives from Toso Co., Ltd.)
Post: TSK-GZL G2000HXL
Column temperature: 40 ℃
Solvent: THF
Flow velocity: 1.0ml/min
The solid concentration of sample solution: 0.001 to 0.01 quality %
Injection rate IR: 50 μ l
Detecting device: refractive index
The standard substance that is used to calibrate: TSK polystyrene standard F-40, F-4, F-1, A-2500 and A-500 (derive from Toso Co., Ltd.).
The following component that is used for present embodiment that provides and can represent with abbreviation hereinafter.
(A-1) colorant: C.I. pigment blue 15: 6
(A-2) colorant: C.I. pigment Violet 23
(B-1) resin B 1 (solids content in propylene glycol methyl ether acetate is the solution of 38.5 quality %)
(C-1) compound of photopolymerization: DPHA (six acrylic acid dipentaerythritol ester) (derives from Nippon Kayaku Co., Ltd.)
(C-2) compound of photopolymerization: phthalic acid 2,2,2-three (acryloxy) Methylethyl ester (derives from Shin-Nakamura Chemical Co., Ltd.)
(C-3) compound of photopolymerization: succinic acid 2,2,2-three (acryloxy) Methylethyl ester (derives from Shin-Nakamura Chemical Co., Ltd.)
(D-1) Photoepolymerizationinitiater initiater: 2, two (the trichloromethyl)-6-piperonyl-1,3,5-triazines of 4-.
(D-2) Photoepolymerizationinitiater initiater: 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone
(G-1) Photoepolymerizationinitiater initiater auxiliary agent: 4,4 '-two (diethylamino) benzophenone
(E-1) solvent: propylene glycol methyl ether acetate
(E-2) solvent: 3-ethoxyl ethyl propionate
(F-1) Megafac F475 (derives from Dainippon Ink ﹠amp; Chemicals Co., Ltd.)
Embodiment 1
[preparing painted photosensitive resin composition 1]
With (A-1) 4.968 mass parts
(A-2) 1.242 mass parts
Acrylic spreading agent 2.174 mass parts
(B-1) 16.569 mass parts
(C-2) 2.126 mass parts
(D-1) 0.425 mass parts
(D-2) 0.510 mass parts
(G-1) 0.170 mass parts
(E-1) 63.610 mass parts
(E-2) 8.200 mass parts and
(F-1) 0.005 mass parts
Mix and produce painted photosensitive resin composition 1.
[forming pattern 1]
Then with SumiResist
TRPR-1300Y-PG (derive from Sumitomo ChemicalCo., Ltd.) be spun to (#1737 derives from Corning Co.) on the glass plate, be heated to 100 ℃ 1 minute, remove volatile constituent and form the thick resin bed of 0.5 μ m.This glass plate is heated 15 minutes with curing resin layer at 230 ℃, and formation has the mounting medium that leveling is filmed.Be spun to the above painted photosensitive resin composition (redness) that obtains on this mounting medium and be heated to 100 ℃ 3 minutes, remove volatile constituent to form painted photosensitive resin composition film.After cooling, via photomask with this painted photosensitive resin composition film of I line (wavelength is 365nm) irradiation.With the light source of ultrahigh pressure mercury lamp as the I line, light was walked abreast before irradiation.The light intensity of irradiation is 150mJ/cm
3Use photomask, make that it can be the lines form formation colour element of 3 μ m, 4 μ m, 5 μ m, 6 μ m, 7 μ m, 8 μ m, 9 μ m, 10 μ m, 20 μ m, 30 μ m, 40 μ m, 50 μ m and 100 μ m with live width.Then the glass baseplate (painted photosensitive resin composition film forms) after the light exposure is immersed developer (CIS DEVELOPER at 23 ℃ on this glass baseplate surface, derive from ENFTechnology Co.) 80 seconds develop, and produce glass plate with line image and gap pattern with the washing of purifying waste water.
[estimating 1]
The transmittance (400nm is to the mean value of 780nm) that has wherein dissolved the coating base substrate of filming is 99.9%.
[forming pattern 2]
SumiResist PR-1300Y-PG (deriving from Sumitomo Chemical Co.) is spun on the silicon wafer and 100 ℃ of heating 1 minute, removes volatile constituent and form the thick resin bed of 0.5 μ m.Then this silicon wafer is heated 15 minutes with curing resin layer at 230 ℃, formation has the mounting medium that leveling is filmed.The above painted photosensitive resin composition 1 that obtains is spin-coated on this mounting medium and 100 ℃ of heating 1 minute, removes volatile constituent and form painted photosensitive resin composition layer.Be used for from exposure sources (Nikon NSR I9C, derive from Nikon Corp.) the I line, 30 positions via the mask that forms pattern (phase place that 2 μ m square pixel form), with 10 ms intervals through 20 to 310 milliseconds of painted photosensitive resin composition layers of obtaining of irradiation progressively.The mounting medium of exposure was developed at 23 ℃ of immersion developers (CIS DEVELOPER derives from ENF Technology Co.) in 60 seconds.After the development, wash mounting medium and dry with water, producing live width is that 2.0 μ m and thickness are the color filter with check pattern pixel of 0.7 μ m.
[estimating 2]
With the xsect of scanning electron microscope (S-4500 derives from Hitachi Ltd.) observation pattern, confirming does not have residue and pattern to have excellent adhesion on the part of dissolving when developing.
Comparative Examples 1
[preparing painted photosensitive resin composition 2]
Prepare painted photosensitive resin composition 2 by mixing component similar to Example 1, except the C-2 among the embodiment 1 is changed into the C-3.
[estimating 1]
Use the step similar, except the painted photosensitive resin composition 1 among the embodiment 1 is changed into the painted photosensitive resin composition 2 to embodiment 1.After having dissolved coating layer, the transmittance of the base substrate of coating (400nm is to the mean value of 780nm) is 98.9%.
[estimating 2]
Prepare sample in the mode that is similar to embodiment 1, except the painted photosensitive resin composition 1 among the embodiment 1 is changed into the painted photosensitive resin composition 2.With the xsect of sem observation pattern, find in the part pattern, to have to ring and when development, have residue to adhere to the part of dissolving.
Comparative Examples 2
[preparing painted photosensitive resin composition 3]
Prepare painted photosensitive resin composition 3 by mixing component similar to Example 1, except the C-2 among the embodiment 1 is changed into the C-1.
[estimating 1]
Use the step similar, except the painted photosensitive resin composition 1 among the embodiment 1 is changed into the painted photosensitive resin composition 3 to embodiment 1.After having dissolved coating layer, the transmittance (400nm is to the mean value of 780nm) of coating base substrate is 98%.
Prepare sample in the mode that is similar to embodiment 1, except the painted photosensitive resin composition 1 among the embodiment 1 is changed into the painted photosensitive resin composition 3.With the xsect of sem observation pattern, find that pattern has excellent adhesion, but when developing, have residue to adhere to the part of dissolving.
Industrial applicibility
Painted photosensitive resin composition of the present invention can be used for forming and contains the thin of high concentration pigment Colour filter, and this colour filter that obtains can suitably be used for imageing sensor and liquid crystal display Device equipment.
Claims (4)
1. painted photosensitive resin composition, the compound (C), Photoepolymerizationinitiater initiater (D) and the solvent (E) that comprise colorant (A), adhesive resin (B), photopolymerization, wherein the compound of photopolymerization (C) contains phthalic acid 2,2,2-three (acryloxy) Methylethyl ester.
2. pattern that forms with the painted photosensitive resin composition of claim 1.
3. color filter that comprises the pattern of claim 2.
4. imageing sensor that the color filter of claim 3 is housed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005343327 | 2005-11-29 | ||
| JP2005343327A JP4682824B2 (en) | 2005-11-29 | 2005-11-29 | Colored photosensitive resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1975576A true CN1975576A (en) | 2007-06-06 |
Family
ID=38125722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200610162527XA Pending CN1975576A (en) | 2005-11-29 | 2006-11-27 | Colored photosensitive resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4682824B2 (en) |
| KR (1) | KR20070056962A (en) |
| CN (1) | CN1975576A (en) |
| TW (1) | TW200731007A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102081304A (en) * | 2009-12-01 | 2011-06-01 | 信越化学工业株式会社 | Negative resist composition and patterning process |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100973644B1 (en) * | 2007-07-18 | 2010-08-02 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| KR101478405B1 (en) * | 2012-06-19 | 2015-01-02 | 주식회사 엘지화학 | Light-curing ink composition, color filter and display device using the same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0317650A (en) * | 1989-06-15 | 1991-01-25 | Nippon Synthetic Chem Ind Co Ltd:The | Image forming method |
| JP2699015B2 (en) * | 1989-09-21 | 1998-01-19 | 富士写真フイルム株式会社 | Photopolymerizable composition |
| JPH07140656A (en) * | 1993-11-16 | 1995-06-02 | Nippon Oil & Fats Co Ltd | Photopolymerizable composition |
| JP3893262B2 (en) * | 2000-09-14 | 2007-03-14 | キヤノン株式会社 | Water-based photocurable resin composition, water-based ink, ink cartridge, recording unit, and ink jet recording apparatus |
| JP4043801B2 (en) * | 2002-02-22 | 2008-02-06 | ザ・インクテック株式会社 | Photosensitive composition |
| JP2003295429A (en) * | 2002-03-28 | 2003-10-15 | Tamura Kaken Co Ltd | Photosensitive resin composition |
| JP2004195664A (en) * | 2002-12-16 | 2004-07-15 | Konica Minolta Holdings Inc | Image formation method and printed matter |
| JP2005148717A (en) * | 2003-10-20 | 2005-06-09 | Mitsubishi Chemicals Corp | Coloring composition for color filter, color filter and liquid crystal display device |
-
2005
- 2005-11-29 JP JP2005343327A patent/JP4682824B2/en not_active Expired - Fee Related
-
2006
- 2006-11-06 TW TW095140933A patent/TW200731007A/en unknown
- 2006-11-24 KR KR1020060116745A patent/KR20070056962A/en not_active Application Discontinuation
- 2006-11-27 CN CNA200610162527XA patent/CN1975576A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102081304A (en) * | 2009-12-01 | 2011-06-01 | 信越化学工业株式会社 | Negative resist composition and patterning process |
| CN102081304B (en) * | 2009-12-01 | 2013-03-20 | 信越化学工业株式会社 | Negative resist composition and patterning process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007148062A (en) | 2007-06-14 |
| JP4682824B2 (en) | 2011-05-11 |
| KR20070056962A (en) | 2007-06-04 |
| TW200731007A (en) | 2007-08-16 |
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Application publication date: 20070606 |