CN100520577C - Photosensitive composition for forming light shading film, black bottom formed from said light shading film for photosensitive composition - Google Patents
Photosensitive composition for forming light shading film, black bottom formed from said light shading film for photosensitive composition Download PDFInfo
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- CN100520577C CN100520577C CNB2005101271853A CN200510127185A CN100520577C CN 100520577 C CN100520577 C CN 100520577C CN B2005101271853 A CNB2005101271853 A CN B2005101271853A CN 200510127185 A CN200510127185 A CN 200510127185A CN 100520577 C CN100520577 C CN 100520577C
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Abstract
In the photosensitive composition for forming a light shielding film containing (a) carbon black as a light shielding pigment, (b) a photopolymerizable compound, and (c) a photopolymerization initiator, the dispersion particle diameter of the carbon black is set at 100-250 nm, preferably 150-200 nm.
Description
Technical field
The present invention relates to photomask formation and form the black matrix that forms with photosensitive composite with photosensitive composite, by this photomask, say that in further detail the photomask that relates to the black matrix that is suitable for forming liquid crystal panel, plasma display etc. forms and forms the black matrix that forms with photosensitive composite with photosensitive composite, by this photomask.
The application advocates the right of priority of No. the 2004-350590, the Japanese application for a patent for invention of on Dec 3rd, 2004 application, and with its content quotation in this.
Background technology
Liquid crystal panel; particularly TN mode, STN mode liquid crystal panel have following structure: the black matrix that is provided for emphasizing picture contrast on glass substrate; stack gradually transparent protective film, transparency electrode, alignment films, liquid crystal, transparency electrode, transparent protective film, backlight etc. thereon, be provided for keeping the bubble-tight hermetic unit of above-mentioned component ends simultaneously.Color filter especially also is set under the situation of color liquid crystal panel in addition.In addition, in the liquid crystal panel that uses TFT (thin film transistor (TFT)), usually for the TFT shading is used.In such liquid crystal panel, in order to keep the image of high-contrast, the shading rate of black matrix need be more than 1.5 in the OD value.And, require above-mentioned black matrix thin as much as possible from the problem of color filter and transparent protective film planarization.Black matrix can be unworthy of the honour usually by the following method, promptly, the photomask that contains light-proofness pigment and photoresist is formed with photosensitive composite to be dissolved in the solvent etc., it is coated on the base plate of liquid crystal panel, after carrying out drying, form with photoetching process, but if want to form the black matrix that approaches and have high OD value, just must use the pigment with good light-proofness, at present normally used is the big carbon black of shading rate.(for example, referring to Patent Document 1 (spy opens flat 9-No. 166869 communiques), patent documentation 2 (spy opens flat 11-No. 84125 communiques))
But, if go for enough light-proofnesss,, need when being coated with photosensitive composite, this photomask formation make the thickness thickening with regard to photomask formation photosensitive composite in the past, perhaps increase the amount of photonasty pigment with respect to photoresist.When using such method, owing to help to improve the permeability decline of photomask formation with the light of the ultraviolet region of the photonasty (light sensitivity) of photosensitive composite, thus there is the problem of the remarkable variation of light sensitivity.In addition, for forming the black matrix that forms with photosensitive composite, require it to have good shape by this photomask.
Summary of the invention
The present invention proposes in view of the above problems, and its purpose is to provide the light sensitivity height, forms the photomask formation photosensitive composite of the black matrix of excellent in shape when can make the thickness attenuation.
To achieve these goals, photomask of the present invention forms and use photosensitive composite, it is characterized in that containing (a) as the carbon black of light-proofness pigment, (b) optical polymerism compound and (c) Photoepolymerizationinitiater initiater, and the dispersion particle diameter of this carbon black is 150-250nm.
Thus, can improve photomask and form, and can improve the light sensitivity of photomask formation with photosensitive composite with the ultraviolet transmittance in the photosensitive composite.In addition, can form with photosensitive composite by above-mentioned photomask and form the good black matrix of shape.
In addition, by using specific optical polymerism compound and Photoepolymerizationinitiater initiater, can further improve photomask and form the light sensitivity of using photosensitive composite with respect to above-mentioned carbon black.
Photomask formation of the present invention owing to the particle diameter of having adjusted as the carbon black of light-proofness pigment, has improved ultraviolet transmittance with photosensitive composite, so can be used in the thickness attenuation that obtains same OD value when improving light sensitivity.Black matrix by using said composition to form can keep high picture contrast, and can make display device such as good liquid crystal panel, plasma display.
Description of drawings
Fig. 1 is the figure of the relation of expression amounts of carbon black and OD value.
Embodiment
Photomask of the present invention forms with photosensitive composite and contains (a) as the carbon black of light-proofness pigment, (b) optical polymerism compound and (c) Photoepolymerizationinitiater initiater.So,, can improve described photomask and form the transmittance of using the photosensitive composite middle-ultraviolet lamp by the particle diameter of the carbon black of above-mentioned (a) composition or dispersion particle diameter are in the scope of specific value.By improving transmittance, can improve photomask and form the light sensitivity of using photosensitive composite.
As the ultraviolet ray that forms to photomask with the photosensitive composite irradiation, the light that can use the wavelength according to exposure machine that g line (436nm), h line (405nm), i line (365nm), j line (330nm), k line various open-wire lines such as (310nm) are mixed, this light is relevant with the polymerization efficiency of initiation of Photoepolymerizationinitiater initiater.That is, photomask forms light sensitivity and the various open-wire line (g, h, i, j, k line) of using photosensitive composite and forms the bigger relation of existence between the transmittance of photosensitive composite of using with respect to photomask.But, because the OD value of the actual black matrix of using is in 2-5 scope, so (the OD value accent of 400nm-780nm) is 1.5 o'clock ultraviolet (uv) transmission ratio together with the visible region by using in order accurately to measure transmittance, can obtain the numerical value of transmittance more accurately, for example can obtain carbon amount as shown in fig. 1 and the relation between the OD value.
As known from the above, the OD value that photomask is formed with photosensitive composite in order to obtain enough light sensitivity under above-mentioned wavelength is adjusted at 1.5 o'clock, form the transmittance of the i line of using photosensitive composite for above-mentioned photomask, be preferably more than 0.25%, more preferably more than 0.3%, further preferred more than 0.4%.When being lower than this transmittance, there is the possibility of light sensitivity step-down.In addition, also relevant for the initiated polymerization of light trigger, its transmittance is preferably more than 0.15 the j line, more preferably more than 0.3.In addition, also relevant for the initiated polymerization of light trigger, its transmittance is preferably more than 0.05 the k line, more preferably more than 0.1.
Below, form for above-mentioned photomask of the present invention and to use photosensitive composite, describe as the order of the carbon black of light-proofness pigment, (b) optical polymerism compound, (c) Photoepolymerizationinitiater initiater, other composition according to (a).
Form with in the photosensitive composite at photomask of the present invention, the dispersion particle diameter by carbon black that (a) that mix used as light-proofness pigment is defined as 100nm-250nm, can obtain desirable ultraviolet (uv) transmission ratio.In addition, the lower limit of the dispersion particle diameter of above-mentioned carbon black is preferably more than the 150nm, more preferably more than the 170nm.
In addition, as the higher limit of the dispersion particle diameter of carbon black more preferably below the 200nm.
Form with in the photosensitive composite at above-mentioned photomask, if the not enough 100nm of the dispersion particle diameter of carbon black, then Zhao She ultraviolet transmittance is low, existence can not obtain the possibility of enough light sensitivity, be difficult to make carbon black to form with evenly dispersion in the photosensitive composite simultaneously, thereby have the possibility that can not obtain uniform OD value at photomask.In contrast, if making the dispersion particle diameter of carbon black is more than above, the preferred 150nm of 100nm, then can obtain enough ultraviolet transmittances, can obtain the light sensitivity that needs, simultaneously can improve dispersiveness, obtain to have the photomask formation photosensitive composite of uniform OD value.In addition, be more than the 170nm by the dispersion particle diameter that makes carbon black, can obtain better ultraviolet (uv) transmission ratio, improve light sensitivity, can further improve dispersiveness simultaneously, can obtain to have the photomask formation photosensitive composite of OD value more uniformly.
In addition, form with in the photosensitive composite at above-mentioned photomask, if the dispersion particle diameter of carbon black surpasses 250nm, though then can obtain enough ultraviolet transmittances, but carbon black can precipitate in photomask forms with photosensitive composite, is difficult to make its even dispersion.In addition, be difficult to form the black matrix (it is big that roughness becomes) that forms excellent in shape with photosensitive composite with this photomask.In contrast, be below the 250nm if make the dispersion particle diameter of carbon black, then can obtain enough ultraviolet transmittances, the light sensitivity that acquisition needs can make its even dispersion simultaneously.In addition, be below the 200nm by the dispersion particle diameter that makes carbon black, then can obtain enough ultraviolet transmittances, the light sensitivity that acquisition needs can further be improved dispersiveness simultaneously, can further make operation become easy.
In addition, generally want to keep the image of high-contrast, photomask is formed the black matrix shading rate that forms with the photosensitive composite coating preferably count more than 1.5 with the OD value, preferred more than 3.0, more preferably more than 4.0.
Above-mentioned (b) optical polymerism compound is that polymerization is carried out in the irradiation of accepting light such as ultraviolet ray, and carries out solidified material.As the optical polymerism compound, the compound that preferably has the two keys of ethene, specifically, can enumerate acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monomethyl ester, acrylic acid-2-hydroxyl ethyl ester, methacrylic acid-2-hydroxyl ethyl ester, the glycol monoethyl ether acrylate, the glycol monoethyl ether methacrylate, the ethylene glycol monoethyl ether acrylate, the ethylene glycol monoethyl ether methacrylate, acrylic acid glyceride, glyceral methacrylate, acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, isobutyl acrylate, isobutyl methacrylate, acrylic acid 2-Octyl Nitrite, methacrylic acid 2-Octyl Nitrite, benzyl acrylate, benzyl methacrylate, glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butanediol dimethylacrylate, propylene glycol diacrylate, the propylene glycol dimethylacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, tetra methylol propane tetraacrylate, tetra methylol propane tetramethyl acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, 1,6-hexanediyl ester, 1,6-hexanediol dimethacrylate, the carbethoxyl group diacrylate, monomers such as カ Le De epoxy diacrylate, the oligomer class; Make polyester prepolyer reaction that (methyl) acrylic acid and polyalcohols and monoacid or polyprotonic acid condensation obtain and polyester (methyl) acrylate; After making polynary alcohol radical and having the compound reaction of two isocyanate group, (methyl) acrylic acid is reacted and poly-urethane (methyl) acrylate that obtains with it; Epoxy (methyl) acrylate resin that makes the reaction of epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresols phenolic resin varnish type epoxy resin, bakelite type epoxy resin, tris-phenol type epoxy resin, poly carboxylic acid poly glycidyl ester, polyvalent alcohol poly glycidyl ester, aliphatics or alicyclic epoxy resin, amine epoxy resin, dihydroxy benzenes type epoxy resin and (methyl) acrylic acid and obtain etc.The resin that can also suitably make the reaction of multi-anhydride and above-mentioned epoxy (methyl) acrylate resin in addition and obtain.
In addition, as the optical polymerism compound, can also suitably use compound with formula (I) expression.Compound with formula (I) expression itself is preferred compound from the high viewpoint of photo-curable.That is, form with regard to the photomask of the compound that contains useful formula (I) expression and to use photoresist, can recently further improve light sensitivity by improving ultraviolet transmission.
[Chemical formula 1]
Wherein, be base with the X of the compound of formula (I) expression with formula (II) expression.
[Chemical formula 2]
In addition, be to remove acid anhydride's (CO-O-CO-) residue of forming of back with the Y of the compound of formula (I) expression from dicarboxylic anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, anhydride phthalic acid, tetrahydrochysene anhydride phthalic acid, six hydrogen anhydride phthalic acids, methyl endo-methylene group tetrahydrochysene anhydride phthalic acid, chlorendic anhydride, methyl tetrahydrochysene anhydride phthalic acid, glutaric anhydrides.In addition, the Z with the compound of formula (I) expression removes the residue that forms behind two acid anhydrides from tetracarboxylic dianhydrides such as PMA, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydrides.
The content of above-mentioned optical polymerism compound with respect to this compound and (c) total amount 100 weight portions of Photoepolymerizationinitiater initiater be 60-99.9 weight portions.Can not expect enough thermotolerances, chemical resistance when containing quantity not sufficient 60 weight portions, the formation ability of filming when surpassing 99.9 weight portions in addition causes that sometimes photocuring is bad.
In above-mentioned, having enumerated its molecule self as the optical polymerism compound can polymeric compounds, but in the present invention, (b-1) polymer binder and (b-2) potpourri of photopolymerization monomer also be comprised in (b) optical polymerism compound.
As above-mentioned (b-1) polymer binder,, preferably can carry out the bonding agent of alkaline development from the easy degree of developing.
Can enumerate acrylic acid particularly, methacrylic acid etc. have carboxyl monomer and, methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, acrylic acid-2-hydroxyl ethyl ester, methacrylic acid-2-hydroxyl ethyl ester, methacrylic acid-2-hydroxypropyl acrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid benzene oxygen ester, methacrylic acid benzene oxygen ester, isobornyl acrylate, IBOMA, glycidyl methacrylate, styrene, acrylamide, the multipolymer of vinyl cyanide etc.; And resin such as phenol phenolic varnish type epoxy acrylic ester polymer, phenol phenolic varnish type epoxy methacrylates polymkeric substance, cresols phenolic varnish type epoxy acrylic ester polymer, cresols phenolic varnish type epoxy methacrylates polymkeric substance, bisphenol-a epoxy acrylate polymkeric substance, bisphenol S type epoxy acrylic ester polymer.Owing to introduced acryloyl group or methacryl in above-mentioned resin, so improved cross-linking efficiency, photostability, the chemical resistance of filming are good.The content that acrylic acid, methacrylic acid that constitutes above-mentioned resin etc. has a monomer component of carboxyl is preferably the scope of 5-40 weight %.
When (b) composition is become to be grouped into (b-2) by (b-1) composition, best (b-1) components matching amount is at (b-1) composition, (b-2) composition and (c) account for 10-60 weight portions in Photoepolymerizationinitiater initiater total amount 100 weight portions, be coated with during above-mentioned use level less than 10 weight portions, be difficult to form film when dry, thereby can not fully improve the overlay film intensity after the curing.Development can descend when in addition, use level surpassed 60 weight portions.
In addition, as (b-2) photopolymerization monomer, can enumerate methyl acrylate, methyl methacrylate, acrylic acid-2-hydroxyl ethyl ester, methacrylic acid-2-hydroxyl ethyl ester, methacrylic acid-2-hydroxypropyl acrylate, glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, the propylene glycol dimethylacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, tetra methylol propane tetraacrylate, tetra methylol propane tetramethyl acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, 1,6-hexanediyl ester, benzyl acrylate, benzyl methacrylate, the carbethoxyl group diacrylate, カ Le De epoxy diacrylate, acrylic acid, methacrylic acid etc., but be not limited to these.
When (b) composition is become to be grouped into (b-2) by (b-1) composition, (b-2) use level of composition with respect to (b-1) composition, (b-2) composition and (c) total amount 100 weight portions of Photoepolymerizationinitiater initiater preferably in the scope of 15-50 weight portions, can cause that photocuring is bad during use level less than 15 weight portions, can not obtain sufficient thermotolerance, chemical resistance, the formation ability of filming when surpassing 50 weight portions in addition can variation.
As particularly preferred (c) Photoepolymerizationinitiater initiater, can enumerate with formula (III) expression compound at least a.
[chemical formula 3]
(in the formula (III), X is the base with formula (IV) or formula (V) expression, R
1Be phenyl, C
1-C
20Alkyl, CN, NO
2Perhaps C
1-C
4Haloalkyl, R
2Be C
2-C
12Acyl group, C
4-C
6Enoyl-(ア Le ケ ノ イ Le).)
[chemical formula 4]
(in the formula (IV), R
3-R
7Be hydrogen, halogen, C
1-C
12Alkyl, phenyl or thiophenyl (C
6H
5S-).)
[chemical formula 5]
(in the formula (V), R
8-R
9Be hydrogen, halogen, C
1-C
12Alkyl or phenyl.)
With the compound of formula (III) expression is that available spy opens the compound that the method put down in writing in 2000-No. 80068 communiques obtains.Above-claimed cpd is compared very high with other known Photoepolymerizationinitiater initiater to the sensitivity of light, can activate effectively Photoepolymerizationinitiater initiater is solidified by shining very small amount of light.In addition,, the transmittance of outside line can be improved, and light sensitivity, the development profile (margin) of photomask formation can be further improved with photosensitive composite by using aforesaid carbon black.The good color filter of colour developing that shows contrast height and R, G, B can form the rectilinearity height thus, can not peel off and residual good carbon black pattern, so can be provided.
As compound Photoepolymerizationinitiater initiater in addition with formula (III) expression; can enumerate 1-hydroxycyclohexylphenylketone; 2-hydroxyl-2-methyl-1-phenyl-propane-1-ketone; 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxyl-2-methyl-1-propane-1-ketone; 1-(4-isopropyl phenyl)-2-hydroxyl-2-methylpropane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxyl-2-methylpropane-1-ketone; 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone; two (4-dimethylaminophenyl) ketone; 2-methyl-1-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; 4-benzoyl-4 '-methyl dimethoxy base sulfide; 4-dimethylaminobenzoic acid; 4-dimethylaminobenzoic acid methyl esters; 4-dimethylaminobenzoic acid ethyl ester; 4-dimethylaminobenzoic acid butyl ester; 4-dimethylamino-2-ethylhexyl benzoic acid; 4-dimethylamino-2-isoamyl benzene formic acid; benzyl-β-methoxy ethyl acetal; the phenyl dimethyl ketal; 1-phenyl-1; 2-propanedione-2-(o-ethoxy carbonyl) oxime; o-benzoyl methyl benzoate; 2; 4-diethyl thioxanthone; 2-clopenthixal ketone; 2; 4-dimethyl thioxanthones; 1-chlorine-4-phenoxy group thioxanthones; thioxanthene; 2-diuril ton; 2; 4-diethyl thioxanthene; 2-methyl thioxanthene; 2-isopropyl thioxanthene; 2-EAQ; the prestox anthraquinone; 1; 2-benzo anthraquinone; 2; 3-diphenyl anthraquinone; azoisobutyronitrile; benzoyl peroxide; cumene peroxide; 2-mercaptobenzimidazole; 2-mercaptobenzoxazole; 2-mercaptobenzothiazoler; 2-(o-chlorphenyl)-4; 5-two (m-methoxyphenyl)-imidazole radicals dipolymers; benzophenone; 2-chlorobenzophenone; p; p '-two dimethylamino benzophenone; 4; 4 '-two diethylamino benzophenone; 4; 4 '-dichloro benzophenone; 3; 3 '-dimethyl-4-methoxy benzophenone; benzil; benzoin; benzoin methylether; benzoin ethyl ether; benzoin iso-propylether; benzoin n-butylether; the benzoin isobutyl ether; the benzoin butyl ether; acetophenone; 2; 2-diethoxy acetophenone; p-dimethyl acetophenone; p-dimethylamino propiophenone; dichloroacetophenone; trichloroacetophenone; p-tert-butyl benzene ethyl ketone; p-dimethylamino benzoylformaldoxime; p-tert-butyl group trichloroacetophenone; p-tert-butyl group dichloroacetophenone; α; α-dichloro-4-metaphenoxy acetophenone; thioxanthones; 2-methyl thioxanthones; 2-isopropyl thioxanthone; Dibenzosuberone; amyl group-4-dimethylaminobenzoic acid ester; 9-phenylacridine; 1; 7-two-(9-acridinyl) heptane; 1; 5-two-(9-acridinyl) pentane; 1; 3-two-(9-acridinyl) propane; p-methoxyl triazine; 2; 4; 6-three (trichloromethyl)-s-triazines; 2-methyl-4; 6-two (trichloromethyl)-s-triazines; 2-[2-(5-methylfuran-2-yl) vinyl]-4; 6-two (trichloromethyl)-s-triazines; 2-[2-(furans-2-yl) vinyl]-4; 6-two (trichloromethyl)-s-triazines; 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4; 6-two (trichloromethyl)-s-triazines; 2-[2-(3; 4-Dimethoxyphenyl) vinyl]-4; 6-two (trichloromethyl)-s-triazines; 2-(4-methoxyphenyl)-4; 6-two (trichloromethyl)-s-triazines; 2-(4-ethoxybenzene vinyl)-4; 6-two (trichloromethyl)-s-triazines; 2-(4-n-butoxy phenyl)-4; 6-two (trichloromethyl)-s-triazines; 2; 4-two-trichloromethyl-6-(3-bromine-4-methoxyl) phenyl-s-triazine; 2; 4-two-trichloromethyl-6-(2-bromine-4-methoxyl) phenyl-s-triazine; 2; 4-two-trichloromethyl-6-(3-bromine-4-methoxyl) styryl phenyl-s-triazine; 2,4-two-trichloromethyl-6-(2-bromine-4-methoxyl) styryl phenyl-s-triazine etc.
In the present invention, wherein, the also preferred p-triazines such as methoxyl triazine of using; 2,4,6-three (trichloromethyl)-s-triazines, 2-methyl-4,6-two (trichloromethyl)-s-triazines, 2-[2-(5-methylfuran-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazines, 2-[2-(furans-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazines, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4,6-two (trichloromethyl)-s-triazines, 2-[2-(3,4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-s-triazines, 2-(4-methoxyphenyl)-4,6-two (trichloromethyl)-s-triazines, 2-(4-ethoxybenzene vinyl)-4,6-two (trichloromethyl)-s-triazines, 2-(4-n-butoxy phenyl)-4,6-two (trichloromethyl)-s-triazines etc. have the triaizine compounds such as triazines of halogenated methyl, 2-(o-chlorphenyl)-4, imidazole-based compounds such as 5-two (m-methoxyphenyl)-imidazole radicals dipolymers, and 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-amino ketones compounds such as 1-ketone.
In addition, photomask of the present invention forms with photosensitive composite and preferably contains compound and at least a other compound of representing as the usefulness formula (III) of Photoepolymerizationinitiater initiater.Photomask formation, can be activated by the light of very microirradiation amount effectively by containing the above-mentioned two kinds of compounds as Photoepolymerizationinitiater initiater with photosensitive composite at least.This is because when photomask forms with the different compound of coexistence electronic band spectrum in the photosensitive composite, has expanded the actual wavelength zone that Photoepolymerizationinitiater initiater has the light of high light sensitivity, perhaps between at least two kinds of compounds interaction has taken place.Thus, photomask of the present invention forms and can further improve light sensitivity and improve the development profile with photosensitive composite, thus can be more easily with linear high, do not peel off and residual good form forms the black matrix pattern.To be expressed as (i)-(iii) with the compound of formula (III) expression and the preferred example in other at least a combination of compounds below.
(i) with the combination of at least a Photoepolymerizationinitiater initiater in the O-acyl group oxime compound of above-mentioned formula (III) expression and the compound except above-mentioned O-acyl group oxime compound (the compound Photoepolymerizationinitiater initiater of representing with above-mentioned formula (III) in addition).
In above-mentioned O-acyl group oxime compound, from light sensitivity and the viewpoint that obtains easy degree, the R in the preferred formula (III) to light
1Be n-hexyl (C
6H
13-), R
2R when being benzoyl, X usefulness formula (IV) expression
3, R
4, R
6, R
7Be H and R
5Be thiophenyl (C
6H
5S-) the formula that is shown in (VI) in 1,2-acetyl caproyl, 1-[4-(thiophenyl) phenyl]-, 2-(O-benzoyl oximes).
[chemical formula 6]
In addition, more preferably higher following compound in above-mentioned O-acyl group oxime compound to the light sensitivity of light, described compound is R in formula (III)
1Be methyl, R
2R when being acetyl group, X usefulness formula (V) expression
8Be ethyl, R
9Be the エ ノ Application in the formula that is shown in (VII) of methyl, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl group oxime).
[chemical formula 7]
(ii) use above-mentioned formula (III) expression and X can use the Photoepolymerizationinitiater initiater of formula (IV) expression and the combination of triaizine compounds.
Especially as triaizine compounds, especially preferably use formula (VIII), formula (IX), formula (X) (R
1, R
2Expression C
1-C
3Alkyl) expression triaizine compounds.In addition, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone also can use in the same manner with above-mentioned triaizine compounds.
[chemical formula 8]
[chemical formula 9]
[Chemical formula 1 0]
(iii) use above-mentioned formula (III) expression and X can use the Photoepolymerizationinitiater initiater of formula (V) expression and the combination of 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone.In addition, also can replace 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone similarly to be used in combination with above-mentioned triaizine compounds.
Wherein, with the compound of formula (III) expression and the blending ratio of the compound (particularly triaizine compounds, imidazole-based compounds and amino ketones compound) except the compound of representing with formula (III) is 10:90-90:10 according to weight ratio preferably, preferred especially 20:80-80:20.With the compound of formula (III) expression with except when the blending ratio of the compound the compound of formula (III) expression is in above-mentioned scope, two kinds of compounds can interact effectively, can further improve photomask and form light sensitivity, the development profile of using photosensitive composite.
The combined amount of above-mentioned (c) composition can (account for 0.1-30 weight portions in polymer binder, photopolymerization monomer, Photoepolymerizationinitiater initiater total amount 100 weight portions at the optical polymerism compound.
Owing between amounts of carbon black that in the photomask that is become to be grouped into by (a)-(c) forms with photosensitive composite total amount 100 weight portions, adds and OD value, set up the proportionate relationship of Fig. 1, so want to make the shading rate of black matrix to count more than 1.5, just need make the carbon black combined amount reach 20 weight portions at least with respect to (a)-(c) composition total amount 100 weight portions with the OD value.
Photomask of the present invention forms with in the photosensitive composite, except the carbon black of (a) composition, can also be in the scope that the shading performance is reduced, and in order to adjust tone, perhaps add other pigment for high resistance value more.Can suitably use Colour Index (C.I.) to be numbered following pigment as such pigment.
Yellow uitramarine: C.I.20,24,83,86,93,109,110,117,125,137,138,139,147,148,153,154,166,168
Orange pigment: C.I.36,43,51,55,59,61
Red pigment: C.I.9,97,122,123,149,168,177,180,192,215,216 or 217,220,223,224,226,227,228,240
Violet pigment: C.I.19,23,29,30,37,40,50
Blue pigment: C.I.15,16,22,60,64
Viridine green: C.I.7,36
Brown pigments: C.I.23,25,26
The pigment of representative etc.
The amount of pigment (amount that also comprises carbon black) that in photomask of the present invention forms with photosensitive composite, adds preferably with respect to (b) optical polymerism compound (perhaps polymer binder and photopolymerization monomer) and (c) Photoepolymerizationinitiater initiater total amount 100 weight portions be 20-1.50 weight portions, preferred 25-100 weight portions, the more preferably scope of 30-80 weight portions.If above-mentioned scope less than 20 weight portions, then carbon black can not have enough light-proofnesss, and in addition, if surpass 150 weight portions, then the amount of photoresist composition reduces, and can cause that curing is bad, can not form good black matrix.
In addition, the carbon black of above-mentioned (a) composition and the pigment of above-mentioned adding, the solution as using spreading agent to disperse with suitable concentration (for example 10-20%) can mix with other composition.As above-mentioned spreading agent, have no particular limits, for example poly-ethylene imine (polyethyleneimine) of preferred use is, urethane resin is, the acrylic resin macromolecule dispersing agent.
Except above-mentioned, can also in forming with photosensitive composite, photomask of the present invention cooperate the organic solvent that is used to improve coating, adjusts viscosity.As above-mentioned organic solvent, can enumerate benzene, toluene, dimethylbenzene, MEK, acetone, methyl isobutyl ketone, cyclohexanone, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, diglycol, glycerine, glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, 3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, the propylene glycol monomethyl ether propionic ester, the dihydroxypropane single-ether propionic ester, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate etc.What wherein be fit to is 3-methoxyl butylacetic acid ester, has revealed good dissolubility because it not only forms with respect to photomask with the solvable component list in the photosensitive composite, and has made the dispersiveness of insoluble compositions such as pigment become good.Above-mentioned organic additive can use 50-500 weight portions with respect to polymer binder, photopolymerization monomer, Photoepolymerizationinitiater initiater with as carbon black total amount 100 weight portions of light-proofness pigment.
In addition, also can in forming with photosensitive composite, above-mentioned photomask add thermal polymerization inhibitor, defoamer, surfactant etc.As above-mentioned thermal polymerization inhibitor, can be known in the past, can enumerate quinhydrones, quinhydrones list ether etc.As above-mentioned defoamer, can be known in the past, can enumerate silicone-based, fluorine based compound.In addition, above-mentioned surfactant can be known in the past, can enumerate compounds such as negative ion system, kation system, nonionic system.
Below (1) photomask is formed and describe with the modulator approach of photosensitive composite, the formation method of (2) photomask.
(1) photomask forms the modulator approach with photosensitive composite
Add (a) as carbon black, (b) optical polymerism compound, (c) Photoepolymerizationinitiater initiater of light-proofness pigment and the organic additive that adds as required, mix (disperse, mix) with stirring machines such as three roller mills, bowl mill, sand mills, filter with 5 μ m film filters and modulate photomask formation photosensitive composite.
(2) the formation method of black matrix (photomask)
With the photomask of modulation form contact transfer printing type apparatus for coating such as using print roll coating device, counter-rotating spreader, bar type spreader with photosensitive composite or spinner (rotary apparatus for coating), curtain coating device non-contact type apparatus for coating such as (curtain flow coater) is coated on the glass substrate with clean surface of thick 0.5-1.1mm.
In above-mentioned modulation and coating, form the adaptation of using photosensitive composite in order to improve glass substrate and photomask, silane coupling agent can be pre-mixed or be coated on the described substrate.
After finishing above-mentioned coating, with electric hot plate under 80 ℃-120 ℃, preferred 90 ℃-100 ℃ temperature dry 60 seconds-120 seconds, perhaps, at room temperature placed several hours~several days, perhaps in warm air heater, infrared heater, place dozens of minutes~several hours and remove desolvate after, coating film thickness is adjusted into the scope of 0.5-5 μ m, then by egative film mask (ネ ガ マ ス Network), is 30-2000mJ/cm with ultraviolet, excimer laser isoreactivity energy line in irradiation energy line amount
2Scope in expose.Above-mentioned irradiation energy line amount can change slightly according to the kind of the photomask photosensitive composite that uses.To use developer solution to develop through the photomask that exposure obtains, thereby form the black matrix pattern by infusion process, spraying process etc.As the developer solution that is used to develop, can enumerate the aqueous solution of the material of organic classes such as monoethanolamine, diethanolamine, triethanolamine and NaOH, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc.
The black matrix that obtains with above-mentioned manufacture method can be used for various display device such as liquid crystal panel, plasma display.
Embodiment
Below embodiments of the invention are narrated, but the present invention is not limited by this at all.
(synthesis example of resin)
Open 2001-354735 record according to the spy, in the four-hole boiling flask of 500mL, add bisphenol fluorene type epoxy resin 235g (epoxide equivalent 235) and tetramethyl-ammonium chloride 110mg, 2,6-di-t-butyl-4-methylphenol 100mg and acrylic acid 72.0g, on one side be blown into air to speed wherein with 25mL/ minute, 90-100 ℃ under be heated dissolving on one side.Then, under the state of solution maintenance muddiness, slowly heat up, be heated to 120 ℃ it is dissolved fully.Wherein solution gradually becomes transparent thickness state, continues to stir under this state.
, measure acid number therebetween, continue heated and stirred up to being below the 1.0mgKOH/g.Acid number reaches desired value needs 12 hours.Cool to room temperature then, thus the bisphenol fluorene type epoxy acrylate of usefulness formula [3] expression of water white transparency and solid shape obtained.Then, in the above-mentioned bisphenol fluorene type epoxy acrylate 307.0g that so obtains, add propylene glycol methyl ether acetate 600g and make its dissolving, mix biphenyl tetracarboxylic dianhydride 78g and teabrom 1g then, heat up at leisure and under 110-115 ℃, make its reaction 4 hours.After confirming that anhydride group disappears, mix 1,2,3,6-tetrahydrochysene anhydride phthalic acid 38.0g makes its reaction 6 hours under 90 ℃, thus acquisition compound 1 (the Y/Z mol ratio in the formula=50.0/50.0).The disappearance of acid anhydrides can be confirmed by IR spectrum.
(transmittance measurement)
In following embodiment 1-4 and comparative example 1,2, to use spinner (1H-360s: ミ カ サ (strain) system) that photomask is formed and be coated on the quartz plate with photosensitive composite, make its optical density reach 1.5 this moment.The photomask formation of this coating is formed the film of using photosensitive composite with dry 2 minutes of electric hot plate and formation photomask with photosensitive composite under 90 ℃.
Then, measure the ultraviolet transmittance of the film of above-mentioned formation with the UV measuring appliance.
For embodiment 1-4 and comparative example 1,2, use photosensitive composite with the composition modulation photomask formation that is shown in the following table 1, and estimate.Also have, in present embodiment and comparative example, do not carried out the UV measurement under the condition of polymerization initiator cooperating.
[table 1]
Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 2 | |
The dispersion particle diameter (nm) of carbon black | 80 | 100 | 150 | 200 | 250 | 300 |
Disperse liquid measure (20% carbon) (g) | 200 | ← | ← | ← | ← | ← |
Resin | Compound 1 | ← | ← | ← | ← | ← |
Amount (g) | 500 | ← | ← | ← | ← | ← |
Solvent | 3-methoxyl butylacetic acid ester | ← | ← | ← | ← | ← |
Amount (g) | 600 | ← | ← | ← | ← | ← |
Transmittance (%) | 0.2 | 0.25 | 0.35 | 0.4 | 0.42 | 0.45 |
Surface roughness Ra (nm) | 20 | 25 | 30 | 45 | 62 | 70 |
By above-mentioned table 1 as can be known, variation has taken place according to the particle diameter of carbon black in the transmittance of i line, disperse particle diameter be more than the 100nm, especially disperse particle diameter be 150nm when above transmittance good.In addition, surfaceness is that 300nm is bad when above disperseing particle diameter as can be known, below the 250nm, especially be good below the 200nm.
In following embodiment 5-8 and comparative example 3,4, modulated according to the composition shown in the table 2 and the OD value to be adjusted into photomask that 3.5 actual black matrix uses to form and use photosensitive composite, and estimated.
Use spinner (1H-360s ミ カ サ (strain) system) to be coated on the glass basis material with photosensitive composite this photomask formation, make its thickness reach 1.4 μ m this moment, and the photomask that will be coated with formation forms the film of using photosensitive composite with dry 2 minutes of electric hot plate and formation photomask with photosensitive composite under 90 ℃.
Then, with exposure machine (EXM-1066-E01: オ-Network system) with 10mJ/cm
2For at interval from 50mJ/cm
2Irradiation energy line amount expose up to 300mJ/cm
2To develop for 100 seconds with spraying method with 0.04% potassium hydroxide developer solution through the photomask that exposure obtains.
In the black matrix that obtains, measured the live width of 20 μ m lines under each exposure, with the exposure light sensitivity of expression with respect to the same formation of 20 μ m mask live widths 20 μ m lines.In addition, estimate after the observation line shape, wherein good with zero expression, with * represent to use (roughness is big).
[table 2]
Comparative example 3 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 4 | |
The dispersion particle diameter (nm) of carbon black | 80 | 100 | 150 | 200 | 250 | 300 |
Disperse liquid measure (20% carbon) (g) | 200 | ← | ← | ← | ← | ← |
Resin | Compound 1 | ← | ← | ← | ← | ← |
Amount (g) | 500 | ← | ← | ← | ← | ← |
Solvent | 3-methoxyl butylacetic acid ester | ← | ← | ← | ← | ← |
Amount (g) | 400 | ← | ← | ← | ← | ← |
Optical polymerism compound (monomer) | DPHA | ← | ← | ← | ← | ← |
Amount (g) | 50 | ← | ← | ← | ← | ← |
Polymerization initiator | CGI242 (Cib a Specialty Chemicals Inc. system) | ← | ← | ← | ← | ← |
Amount (g) | 1 | ← | ← | ← | ← | ← |
Exposure light sensitivity (mJ/cm 2) | 300 | 180 | 150 | 100 | 100 | 100 |
Wire shaped | ○ | ○ | ○ | ○ | ○ | × |
By above-mentioned table 2 as can be known, variation has taken place with the dispersion particle diameter of carbon black in exposure light sensitivity and wire shaped, exposure light sensitivity and wire shaped are especially all anti-in use when above-mentioned dispersion particle diameter is 100-250nm, and particularly exposure light sensitivity and wire shaped are all good when disperseing particle diameter to be 150-200nm.
More than, the preferred embodiment of the invention is illustrated, but the present invention is not limited to these embodiment.Without departing from the spirit and scope of the present invention, can add, omit, replace, reach other change to its formation.
Claims (6)
1. a photomask forms and uses photosensitive composite, it is characterized in that containing (a) as the carbon black of light-proofness pigment, (b) optical polymerism compound and (c) Photoepolymerizationinitiater initiater, the dispersion particle diameter of described carbon black is 100-250nm, described (b) optical polymerism compound contains the compound of useful formula (I) expression
In the formula (I), X is the group with formula (II) expression,
Y be from dicarboxylic anhydride remove the acid anhydride promptly-residue that forms behind the CO-O-CO-, Z removes the residue that forms behind two acid anhydrides from the tetracarboxylic dianhydride.
2. photomask as claimed in claim 1 forms and uses photosensitive composite, and the dispersion particle diameter that it is characterized in that described carbon black is 150-200nm.
3. a photomask forms and uses photosensitive composite, it is characterized in that containing (a) as the carbon black of light-proofness pigment, (b) optical polymerism compound and (c) Photoepolymerizationinitiater initiater, its OD value is more than 3.0, and described (b) optical polymerism compound contains the compound of useful formula (I) expression
In the formula (I), X is the group with formula (II) expression,
Y be from dicarboxylic anhydride remove the acid anhydride promptly-residue that forms behind the CO-O-CO-, Z removes the residue that forms behind two acid anhydrides from the tetracarboxylic dianhydride.
4. photomask as claimed in claim 1 forms and uses photosensitive composite, it is characterized in that optical density is that the transmittance of 1.5 o'clock i line is more than 0.25%.
5. photomask as claimed in claim 1 forms and use photosensitive composite, it is characterized in that described (c) Photoepolymerizationinitiater initiater contains at least a in the compound that useful formula (III) represents,
In the formula (III), X is the group with formula (IV) or formula (V) expression, R
1Be phenyl, C
1-C
20Alkyl, CN, NO
2Perhaps C
1-C
4Haloalkyl, R
2Be C
2-C
12Acyl group, C
4-C
6Enoyl-,
In the formula (IV), R
3-R
7Be hydrogen, halogen, C
1-C
12Alkyl, phenyl or thiophenyl are C
6H
5S-,
In the formula (V), R
8-R
9Be hydrogen, halogen, C
1-C
12Alkyl or phenyl.
6. black matrix, it is formed with photosensitive composite by the described photomask of claim 1 and forms.
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JP4949809B2 (en) * | 2006-11-14 | 2012-06-13 | 東京応化工業株式会社 | Colored photosensitive resin composition |
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WO2010038978A2 (en) * | 2008-09-30 | 2010-04-08 | Kolon Industries, Inc. | Photopolymer resin composition |
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KR20150115514A (en) * | 2014-04-04 | 2015-10-14 | 동우 화인켐 주식회사 | Black-colored photosensitive resin composition and black matrix prepared by using the same |
CN108089400B (en) * | 2017-12-28 | 2020-06-05 | 深圳市华星光电技术有限公司 | Photoresist and preparation method thereof |
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