CN103376650A - Manufacturing method of photosensitive substrate composition for forming light shielding layer - Google Patents
Manufacturing method of photosensitive substrate composition for forming light shielding layer Download PDFInfo
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- CN103376650A CN103376650A CN2013101358391A CN201310135839A CN103376650A CN 103376650 A CN103376650 A CN 103376650A CN 2013101358391 A CN2013101358391 A CN 2013101358391A CN 201310135839 A CN201310135839 A CN 201310135839A CN 103376650 A CN103376650 A CN 103376650A
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Abstract
The present invention provides a photosensitive substrate composition for forming a light shielding layer which has no needle pore and has high quality. The photosensitive substrate composition for forming the light shielding layer according to the invention is characterized in that filtering is performed after surfactant component (H) of a polymer with weight average molecular weight in 10000-50000 to 2.5-10mass% for dispersing the surfactant component (H), the photosensitive substrate component (A), the pigment component (G) and the organic solvent component (S) after filtering. Preferably the filtering is performed by the PTFE film with hole diameter smaller than 1 mu m.
Description
Technical field
The present invention relates to a kind of light shield layer and form the manufacture method of using the photonasty substrate composition.
Background technology
For example, for the color filter that uses in the colour display device, usually has to be called as the cancellate black light shield layer encirclement of black matrix by the structure of the pixel of red (R), green (G), blue (B) formation of all kinds.
As one of manufacture method of described color filter, proposed to form as the next door, with ink-jetting style with black matrix the method (for example, following patent documentation 1) of the dyed layer of color filter.
In addition, not only in color filter, sometimes also in various display device, by the border between each pixel black matrix is set and realizes that the contrast of image improves.
Black matrix for example uses the anti-corrosion agent composition that contains black pigment and forms by photoetching process.As black pigment, normal operation carbon black (for example, patent documentation 1).
Yet the impurity that exists in anti-corrosion agent composition, foreign matter become the flaw (surface imperfection) that produces the resist pattern, the reason of pin hole.Put down in writing a kind of manufacture method of anti-corrosion agent composition in the patent documentation 2, in order to remove the minuteness particle that in resist solution keeping, produces, and comprised the operation of using filter with specific potential to filter anti-corrosion agent composition.
In addition, make in the process of color filter, it is important making the uniform film thickness after the coating, therefore the general surfactant (for example, patent documentation 3) that the photonasty substrate composition is had the levelling effect that adds.
In the manufacture method of the above-mentioned anti-corrosion agent composition that contains filter progress, normally after base material component etc. is all mixed, through filter progress.
The prior art document
Patent documentation
[patent documentation 1] TOHKEMY 2004-325736 communique
[patent documentation 2] TOHKEMY 2004-212975 communique
[patent documentation 3] TOHKEMY 2010-107957 communique
Summary of the invention
When making black matrix, the impurity that exists in photonasty base material, organic solvent, foreign matter etc. can make black matrix surface produce pin hole etc., cause the uneven homogenize of pattern etc.
In order to make the high-quality black matrix that does not produce pin hole etc., need to remove impurity in photonasty base material, the organic solvent, foreign matter etc.
In view of the foregoing, the inventor etc. find a kind of method, when making black matrix, make anti-corrosion agent composition by filtering as the laggard row of the surfactivity dilution agent that makes an addition to the polymkeric substance in the anti-corrosion agent composition, can make thus the high-quality black matrix that does not produce pin hole etc.
The present invention is that a kind of light shield layer forms the manufacture method with the photonasty substrate composition, it is characterized in that, be to filter after the surfactant component (H) of 10000～50000 polymkeric substance is diluted to 2.5～10 quality % weight-average molecular weight, this surfactant component (H), photonasty base material component (A), pigment composition (G) and Elements in Organic Solvents (S) after the filtration are disperseed.
According to the present invention, can provide the high-quality light shield layer that does not produce pin hole etc. to form manufacture method with the photonasty substrate composition.
Description of drawings
Fig. 1 is the synoptic diagram of the uneven width evaluation method of expression.
Embodiment
" light shield layer forms the manufacture method with the photonasty substrate composition "
The manufacture method that light shield layer of the present invention forms with the photonasty substrate composition is characterised in that, be to filter after the surfactant component (H) of 10000～50000 polymkeric substance is diluted to 2.5～10 quality % weight-average molecular weight, this surfactant component (H), photonasty base material component (A), pigment composition (G) and Elements in Organic Solvents (S) after the filtration are disperseed.
For the light shield layer that utilizes manufacture method of the present invention to make form with the photonasty substrate composition (below be sometimes referred to as the photonasty substrate composition.), because the surfactant component (H) that has diluted (below, be called (H) composition.) through filter progress, the condensed matter that therefore produces in the dilution is removed, present when forming light shield layer not produce the high-quality of pin hole etc.
As above-mentioned (H) composition, usually use the commercially available product of the concentration of 40～50 quality %, the synthetic and material of preparation, the ultimate density of (H) composition in the composition is engaged in the photonasty substrate composition as the mode of 2.5～10 quality %.At this moment, can be that (H) composition of the concentration of above-mentioned 40～50 quality % itself directly makes an addition to the method in the composition, prepare composition after also can beforehand dilution becoming (H) composition of concentration of above-mentioned 2.5～10 quality %, but need this procedure of dilution.The inventor etc. find first: because the surfactant of this higher concentration of 40～50 quality % is diluted, for some reason, the part of this surfactant may be condensed.And, find in the lump by removing in advance this condensation product, thereby can suppress the generation of pin hole etc., finish thus the present invention.
(H) composition
(H) composition that photonasty substrate composition among the present invention is contained for example is preferably the fluoro-alkyl that has carbon number 1～20 on the side chain and (wherein, can be interrupted by ehter bond, ester bond, carbonyl, amino-formate bond.) and the polymkeric substance of lyophily group.
As fluoro-alkyl, as long as making carbon number is 1～20, then be not particularly limited, can be by ehter bond (O-), ester bond (CO-O-), carbonyl (CO-), amino-formate bond (NH-CO-O-) interruption, but the fluoro-alkyl that is not preferably interrupted by these groups is namely with-C
kH
lF
m(k represents 1～20 integer, and l represents 0～40 integer, and m represents 1～41 integer, l+m=2k+1.) expression fluoro-alkyl.
At this, in recent years, reported that having carbon number that fluorine replaces is that the compound of the perfluoroalkyl more than 7 exists the ecology influences such as carcinogenicity, also may become the object as the important new service regeulations (SNUR) of the ecology influence dependency rule of the U.S..Therefore, as fluoro-alkyl, preferably contain the perfluoroalkyl of carbon number 1～5 and the fluoro-alkyl that remaining carbon atom is not replaced by fluorine.The carbon number of perfluoroalkyl more preferably 3～5.
On the other hand, as the lyophily group, can enumerate and be included in known nonionic in the past is group in the surfactant, preferably contains the group of the alkylidene that is interrupted by ehter bond, ester bond or carbonyl.Wherein, the material that preferably contains polyalkylene oxide base (polyethylene oxide base, polypropyleneoxide base, polybutylene oxide base etc.).
The mol ratio of fluoro-alkyl and lyophily group, also different and different according to the composition of photonasty substrate composition, but be preferably 4: 6～9: 1, more preferably 4: 6～8: 2, more preferably 5: 5～7: 3.
Such surfactant can obtain by making the monomer that has at least above-mentioned fluoro-alkyl and the monomer generation polymerization with above-mentioned lyophily group.As the monomer with fluoro-alkyl and the monomer with lyophily group, respectively preferred following formula (h1), (h2) represented monomer.
In the above-mentioned formula (h1), R
1hExpression hydrogen atom or methyl, R
2hThe alkylidene of the straight chain shape of expression carbon number 1～15, preferred carbon number 1～10, a chain or ring-type, R
fThe perfluoroalkyl of expression carbon number 1～5, preferred carbon number 3～5.
In the above-mentioned formula (h2), R
3hExpression hydrogen atom or methyl, R
4hThe alkylidene of expression carbon number 2～4, R
5hThe alkyl of expression hydrogen atom or carbon number 1～15, preferred carbon number 1～10.
In addition, in the above-mentioned formula (h2), p represents 1～50 integer.
Concrete example as the represented monomer of above-mentioned formula (h1), can enumerate (methyl) acrylic acid 2,2,2-trifluoro ethyl ester, (methyl) acrylic acid 2,2,3,3,3-, five fluorine propyl ester, (methyl) acrylic acid 2-(perfluoro butyl) ethyl ester, (methyl) acrylic acid 2-(perfluor-3-methyl butyl) ethyl ester etc.
In addition, concrete example as the represented monomer of above-mentioned formula (h2), [for example can enumerate (methyl) acrylic acid methoxy poly (ethylene glycol) ester, the quantity of ethylene glycol repeat units (r) is 1～50 material], (methyl) acrylic acid methoxyl polypropylene glycol ester [for example, the quantity of propylene glycol repetitive (r) is 1～50 material], poly-(ethylidene-propylidene) diol ester of (methyl) acrylic acid methoxyl [for example, the summation of the quantity of the quantity of ethylene glycol repeat units and propylene glycol repetitive (r) is 2～50 material], poly-(ethylidene-tetramethylene) diol ester of (methyl) acrylic acid methoxyl [for example, the summation of the quantity of the quantity of ethylene glycol repeat units and tetramethylene glycol repetitive (r) is 2～50 material], poly-(ethylidene-propylidene) diol ester of (methyl) acrylic acid butoxy [for example, the summation of the quantity of the quantity of ethylene glycol repeat units and propylene glycol repetitive (r) is 2～50 material], poly-(ethylidene-propylidene) diol ester of (methyl) acrylic acid octyloxy [for example, the summation of the quantity of the quantity of ethylene glycol repeat units and propylene glycol repetitive (r) is 2～50 material], (methyl) acrylic acid bay oxygen base macrogol ester [for example, the quantity of ethylene glycol repeat units (r) is 2～50 material], (methyl) acrylic acid bay oxygen base gathers (ethylidene-propylidene) diol ester [for example, the summation (r) of the quantity of the quantity of ethylene glycol repeat units and propylene glycol repetitive is 2～50 material], polyglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate, polyethylene glycol-propylene glycol (methyl) acrylate, polyethylene glycol-butylene glycol (methyl) acrylate, polystyrene-based ethyl (methyl) acrylate, or the LIGHTESTER HOA-MS of chemical company of common prosperity society system, LIGHT ESTER HOMS etc.
Mol ratio when making the represented monomer polymerization of the represented monomer of above-mentioned formula (h1) and above-mentioned formula (h2) is preferably 4: 6～9: 1, and more preferably 4: 6～8: 2, more preferably 5: 5～7: 3.
(H) composition, in the scope of not damaging effect of the present invention, can also be on the basis of the represented monomer of the represented monomer of above-mentioned formula (h1) and above-mentioned formula (h2), polymerization (methyl) alkyl acrylate.As the concrete example of (methyl) alkyl acrylate, can enumerate (methyl) acrylate methyl esters, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid n-octyl, (methyl) 2-EHA, (methyl) acrylic acid ester in the different ninth of the ten Heavenly Stems, (methyl) lauryl acrylate, (methyl) acrylic acid hexadecane ester, (methyl) stearyl acrylate ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) isobornyl acrylate etc.
This surfactant can be any in atactic polymers and the graft polymer, but is preferably graft polymer.By being set as graft polymer, can keeping the intermiscibility with (A) alkali-soluble base material, and can further improve the levelling effect.In addition, in the situation of graft polymer, even increase content, can not worry yet and gonorrhoea occurs.
The sp value of surfactant is preferably 8.0～9.5 (cal/cm
3)
1/2Be above-mentioned scope by making the sp value, can raising and the intermiscibility of base material component and solvent and improve effect as surfactant.In addition, the sp value can be measured according to the method for putting down in writing in the TOHKEMY 2005-290128 communique for example.
In addition, the weight-average molecular weight of contained base material is 10000～50000 in the surfactant, is preferably 10000～30000.The levelling effect of the surfactant that usually is made of the few compound of the carbon number in the fluoro-alkyl is low, but be above-mentioned scope by making weight-average molecular weight, even thereby be for example in the less situation of the carbon number below 5 at the carbon number of fluoro-alkyl, also can obtain sufficient levelling effect.In addition, be above-mentioned scope by making weight-average molecular weight, can access coating homogeneity, the good photonasty substrate layer of flatness.
That is, usually in surfactant, by having the surfactivity effect is brought into play at insoluble position and the solubility position of solvent.Yet, in low-molecular-weight surfactant, using in the situation of the few fluoro-alkyl of carbon number as insoluble position, since too small as the effect at insoluble position, sufficient surfactivity effect therefore be can not get.In addition, when increasing the ratio at insoluble position, the solubility position can be reduced, and therefore can not obtain sufficient dissolubility.Relative therewith, in the situation of having used the few fluoro-alkyl of carbon number, be more than 10000 by the weight-average molecular weight that makes surfactant, can increase the amount at the insoluble position (fluoro-alkyl) in 1 molecular surface active agent, therefore the dissolubility to solvent can be reduced, the surfactivity effect can be guaranteed.Therefore in addition, the ratio at solubility position also gets a promotion, and sterically hindered by based on this solubility position can prevent the intensive of fluoro-alkyl.In addition, owing to the dissolubility that can guarantee solvent, also be difficult to produce gonorrhoea even therefore increase the addition of surfactant.
In addition, in the situation of spin coating photonasty substrate composition, the photonasty substrate composition is dripped in substrate, make substrate rotation and be coated with.In the situation of having used low-molecular-weight surfactant in the past, can eliminate streak (striation), but the liquid holdup of photonasty substrate composition can occur, therefore the final bossing that can form the photonasty substrate composition in the end in the end of substrate.That is, cause being coated with homogeneity, flatness variation.Relative therewith, in the photonasty substrate composition in the present invention, because the use weight-average molecular weight is the surfactant more than 10000, even therefore in spin coating, also can eliminate the projection of end.Particularly the solid component concentration in the photonasty substrate composition is in the situation more than the 30 quality %, has larger effect for the elimination of end bosses.
And then, in the situation of utilizing slot coated to be coated with, usually there is the tendency of the solid component concentration that reduces the photonasty substrate composition.In the situation of the solid component concentration that reduces the photonasty substrate composition, the flowability of photonasty substrate composition can become greatly, and therefore the thickness of the photonasty substrate composition of process coating becomes inhomogeneous easily.In addition, although the operation with the photonasty substrate composition drying of process coating is arranged, but in case the impact of the concentration change when being subject to surface tension, temperature, drying in the photonasty substrate combination deposits yields that be coated with etc., when drying process, cause from the end of substrate and to return liquid, the easier variation of the homogeneity of thickness to central portion.Particularly in the situation of having used large substrate, very large on the inhomogeneity impact of thickness.To this, the use weight-average molecular weight is the surfactant more than 10000 in photonasty substrate composition of the present invention, therefore can improve film thickness uniformity.
Among the present invention, usually adjust with the concentration of 40～50 quality % in solvent as (H) composition of polymkeric substance.As this solvent, for example can enumerate with Elements in Organic Solvents described later (S) (below, be called (S) composition.) identical solvent, preferably with the solvent phase that uses as (S) composition solvent together.
Form in the manufacture method of using the photonasty substrate composition at light shield layer of the present invention, utilize solvent that (H) composition is diluted to 2.5～20 quality %, utilize the solution after filter filters dilution.As this solvent, for example same solvent of preferred and the solvent phase that contains stoste or the solvent identical with (S) composition.
The filter that uses in above-mentioned filter progress is not particularly limited, and can use known filter.Preferred PTFE film (poly tetrafluoroethylene), PP film (polypropylene screen), the PE film (polyethylene film) of using particularly preferably uses PTFE film (poly tetrafluoroethylene).
As above-mentioned filter, in order to remove the condensation product that produces in the solution after dilution, preferably making the aperture is 0.01～0.9 μ m, and more preferably 0.02～0.6 μ m is particularly preferably 0.05～0.3 μ m.
In above-mentioned filter progress, filtration unit, filter method are not particularly limited, and can use known filtration unit, filter method.
This surfactant component (H), photonasty base material component (A), pigment composition (G) and Elements in Organic Solvents (S) after the filtration are disperseed, make light shield layer and form and uses the photonasty substrate composition.
(A) composition
(A) composition that uses in the manufacture method of light shield layer formation of the present invention with the photonasty substrate composition is not particularly limited, and can use in the past known composition.For example, can enumerate contain alkali-soluble base material (A1) (below, be called (A1) composition.), optical polymerism compound (A2) (below, be called (A2) composition.) and Photoepolymerizationinitiater initiater (A3) (below, be called (A3) composition.) and the composition that can be cured by light such as irradiation ultraviolet radiations.Shine the partly solidified of light by making, and can access the pattern of required form.
(A1) composition
In the present invention, (A1) composition can use following alkali-soluble base material (A1-1) (below, be called (A1-1) composition.) or following alkali-soluble base material (A1-2) with photo-curable (below, be called (A1-2) composition.)。
(A1-1) composition
As (A1-1) composition, can enumerate: be selected from acrylic acid, methacrylic acid etc. have in the monomer of carboxyl more than a kind be selected from methyl acrylate, methyl methacrylate, ethyl acrylate, β-dimethyl-aminoethylmethacrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, 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, isobornyl methacrylate, glycidyl methacrylate, styrene, acrylamide, the multipolymer that forms more than a kind in the vinyl cyanide etc.;
The base materials 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.
These base materials have been owing to imported acryloyl group or methacryl, so cross-linking efficiency is improved, and the photostability of filming, drug resistance are excellent.
Consist of in the monomer component of above-mentioned (A1-1) composition, the content that acrylic acid, methacrylic acid etc. has a monomer component of carboxyl is preferably the scope of 5～40 quality %.
(A1-2) composition
As (A1-2) composition, can enumerate the polymkeric substance shown in the following general formula (1).Therefore compound shown in this general formula (1) in the photomask that contains this compound forms with the photonasty base material, by improving transmission of ultraviolet rays, can further improve light sensitivity owing to itself have optical polymerism (photo-curable).
(in the formula, X is the group shown in the following chemical formula (2), Y be from dicarboxylic anhydride, remove the acid anhydride (CO-O-CO-) and residue, Z be from the tetracarboxylic dianhydride, remove 2 acid anhydrides and residue.)
As the concrete example of the dicarboxylic anhydride that derives from above-mentioned Y (removing the front dicarboxylic anhydride of acid anhydride), such as enumerating maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl carbic anhydride, chlorendic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride etc.
In addition, as the concrete example of the tetracarboxylic dianhydride who derives from above-mentioned Z (removing the front tetracarboxylic dianhydride of 2 acid anhydrides), such as enumerating the tetracarboxylic dianhydrides such as pyromellitic acid acid anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, xenyl ether tetracarboxylic dianhydride etc.
(A1) composition can use separately a kind, also can be mixed with two or more.In addition, can only use above-mentioned (A1-1) composition, also can only use (A1-2) composition, can also both and usefulness.
The weight-average molecular weight (Mw) of (A1) composition among the present invention (utilizing the polystyrene conversion benchmark of gel permeation chromatography) is not particularly limited, but be preferably 1000～1000000, more preferably 3000～50000, most preferably be 5000～15000.Than the upper limit of this scope hour, have the dissolubility to the resist solvent that is enough to as resist, when larger than the lower limit of this scope, resist patterned section shape is good.
(A2) composition
As (A2) composition among the present invention, can enumerate methyl acrylate, methyl methacrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, TEGDMA, tetraethylene glycol diacrylate, the TEG 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, pentaerythritol tetramethylacrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, the dipentaerythritol tetraacrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, 1, the 6-hexanediyl ester, benzyl acrylate, benzyl methacrylate, phenolphthalein base (Cardo) epoxy diacrylate, acrylic acid, methacrylic acid etc., but be not limited to these materials.
(A2) composition can be used alone or two or more kinds may be used.
In addition, among the present invention, the polymkeric substance with alkali-soluble of optical polymerism is included in above-mentioned (A1) composition, and the monomer with optical polymerism is included in (A2) composition.
State in the use in the situation of (A1-1) composition, (A2) composition is preferably the scope of 5～500 mass parts with respect to these (A1-1) composition 100 mass parts.Preferred scope is 20～300 mass parts.
Be more than the lower limit of above-mentioned scope by the use level that makes (A2) composition, thereby the curing when being difficult to produce exposure is bad, can access sufficient thermotolerance, drug resistance.In addition, aspect obtaining that good tunicle forms ability, film after preventing from developing is residual, be preferably set to below the higher limit of above-mentioned scope.
(A3) composition
(A3) composition as among the present invention is not particularly limited, and can use the material that proposes with Photoepolymerizationinitiater initiater as photosensitive composite up to now.For example; can enumerate the 1-hydroxycyclohexylphenylketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-(4-(2-hydroxyl-oxethyl) phenyl)-2-hydroxy-2-methyl-1-propane-1-ketone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone; two (4-dimethylaminophenyl) ketone; 2-methyl isophthalic acid-(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 thioether; the 4-dimethylaminobenzoic acid; 4-dimethylaminobenzoic acid methyl esters; EDMAB; 4-dimethylaminobenzoic acid butyl ester; 4-dimethylamino-2-ethylhexyl benzoic acid; 4-dimethylamino-2-isoamyl benzene formic acid; benzyl-'beta '-methoxy ethyl acetal; the benzil dimethyl ketal; 1-phenyl-1; 2-propanedione-2-(adjacent ethoxy carbonyl) oxime; o-benzoyl yl benzoic acid methyl esters; 2; the 4-diethyl thioxanthone; CTX; 2; 4-dimethyl thioxanthones; 1-chloro-4-propoxyl group thioxanthones; thioxanthene; 2-diuril ton; 2; 4-diethyl thioxanthene; 2-methyl thioxanthene; 2-isopropyl thioxanthene; the 2-EAQ; the prestox anthraquinone; 1; 2-benzo anthraquinone; 2; 3-diphenyl anthraquinone; azoisobutyronitrile; benzoyl peroxide; cumene peroxide; 2-mercaptobenzimidazole; the 2-mercaptobenzoxazole; 2-mercaptobenzothiazole; 2-(Chloro-O-Phenyl)-4; 5-two (m-methoxyphenyl)-imidazole radicals dipolymer; benzophenone; the 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 methyl ether; the benzoin ethylether; the benzoin isopropyl ether; the benzoin n-butyl ether; the benzoin isobutyl ether; the benzoin butyl ether; acetophenone; 2; the 2-diethoxy acetophenone; to dimethyl acetophenone; to the dimethylamino propiophenone; dichloroacetophenone; trichloroacetophenone; p-tert.-butyl acetophenone; to the dimethylamino benzoylformaldoxime; to tert-butyl group trichloroacetophenone; to tert-butyl group dichloroacetophenone; α; α,α-dichloro-4-phenoxy acetophenone; thioxanthones; 2-methyl thioxanthones; ITX; Dibenzosuberone; amyl group-4-dimethylaminobenzoic acid ester; the 9-phenylacridine; 1; 7-pair-(9-acridinyl) heptane; 1; 5-pair-(9-acridinyl) pentane; 1; 3-pair-(9-acridinyl) propane; to the methoxyl triazine; 2; 4; 6-three (trichloromethyl) s-triazine; 2-methyl-4; two (trichloromethyl) s-triazine of 6-; 2-[2-(5-methylfuran-2-yl) vinyl]-4; two (trichloromethyl) s-triazine of 6-; 2-[2-(furans-2-yl) vinyl]-4; two (trichloromethyl) s-triazine of 6-; 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4; two (trichloromethyl) s-triazine of 6-; 2-[2-(3; the 4-Dimethoxyphenyl) vinyl]-4; two (trichloromethyl) s-triazine of 6-; 2-(4-methoxyphenyl)-4; two (trichloromethyl) s-triazine of 6-; 2-(4-ethoxybenzene vinyl)-4; two (trichloromethyl) s-triazine of 6-; 2-(4-n-butoxy phenyl)-4; two (trichloromethyl) s-triazine of 6-; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) phenyl s-triazine; 2; 4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) phenyl s-triazine; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) styryl phenyl s-triazine; 2,4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) styryl phenyl s-triazine etc.
Among these, can preferably use triazines such as methoxyl triazines; 2,4,6-three (trichloromethyl) s-triazine, 2-methyl-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(furans-2-yl) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (trichloromethyl) s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-ethoxybenzene vinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-n-butoxy phenyl)-4, two (trichloromethyl) s-triazine etc. of 6-have the triaizine compounds such as triazines of halogenated methyl; 2-(Chloro-O-Phenyl)-4,5-two (the m-methoxyphenyl)-imidazole-based compounds such as imidazole radicals dipolymer; And 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-amino ketones compounds such as 1-ketone.
In the present invention, as (A3) composition, may be used Multiple components.
Form in the manufacture method of using the photonasty substrate composition at light shield layer of the present invention, the use level of above-mentioned (A3) composition is preferably the scope of 0.1～30 mass parts with respect to (A1) composition 100 mass parts.
(S) composition
In light shield layer of the present invention forms manufacture method with the photonasty substrate composition, in order to improve coating, to adjust viscosity, and (A) composition is dissolved in (S) composition.
As (S) composition, can enumerate benzene, toluene, dimethylbenzene, MEK, acetone, methyl isobutyl ketone, cyclohexanone, methyl alcohol, ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerine, the glycol monomethyl methyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, diethylene glycol monomethyl ether, TC, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, acetic acid 3-methoxyl butyl ester, acetic acid 3-methyl-3-methoxyl butyl ester, propylene glycol monomethyl ether (PGMEA), the propylene glycol monomethyl ether propionic ester, propylene glycol list ethylether propionic ester, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate etc.Wherein, acetic acid 3-methoxyl butyl ester not only forms with the solvable composition in the photonasty substrate composition for light shield layer and shows good dissolubility, and the dispersiveness of the insoluble compositions such as pigment is become well, is preferred therefore.
(S) use amount of composition is not particularly limited, and can suitably set according to coating film thickness with the concentration that can be applied to substrate etc.The viscosity that light shield layer among the present invention forms with the photonasty substrate composition is 5～100cp, is preferably 10～50cp, more preferably 20～30cp.In addition, solid component concentration is 5～100 quality %, is preferably the scope of 20～50 quality %.
Manufacture method of the present invention preferably has following operation: (A) composition is dissolved in (S) composition, is that filter below the 1 μ m filters with the substrate solution of gained with the aperture.
Have in manufacture method of the present invention in the situation of filter progress of substrate solution, as concrete embodiment, for example can enumerate following operation: in advance (A) composition is dissolved in (S) composition, to be added into separately in this substrate solution through (H) composition that filters out after the dilution, filter the substrate solution that contains this (H) composition.
The filter that uses in the filter progress of above-mentioned substrate solution is not particularly limited, and can use known filter.Preferred PTFE film (poly tetrafluoroethylene), PP film (polypropylene screen), the PE film (polyethylene film) of using particularly preferably uses PTFE film (poly tetrafluoroethylene).
As above-mentioned filter, owing to also need to remove fine impurity, foreign matter, therefore preferably making the aperture is 0.01～0.9 μ m, and more preferably 0.05～0.6 μ m is particularly preferably 0.1～0.3 μ m.
In the present invention, preferred: make as described above after the filtration (H) composition and (A) after composition is dissolved in (S) composition and the substrate solution of gained is filtered, disperse with (G) composition again.Disperse the method for (G) composition to be not particularly limited, can be undertaken by interpolation (G) composition in substrate solution and the method such as stir.
(G) composition
Among the present invention, as (G) composition, can use the black pigments such as carbon black.In addition, can also with and adjust the material of tone etc. with black, red, blue, green, yellow, purple pigment.Pigment can suitably use known pigment.
Particularly, in as pigment and the situation with carbon black and other pigments, if 15 quality % in the not enough all pigment of carbon black then can form in the situation with the light sensitivity of photonasty substrate composition and improve shading rate not reducing above-mentioned light shield layer.
Among the present invention, as (G) composition, preferred Shi Yong perylene be black pigment (below, Jian Cheng is perylene pigment.)。As concrete example, can enumerate the represented De perylene pigment of following general formula (I) and the represented De perylene pigment of following general formula (II).The product that in addition, can preferably use BASF AG to make is called the commercially available product of K0084, K0086 etc.
(in the formula, R
1, R
2The alkylidene that represents independently respectively carbon number 1～3, R
3, R
4Represent independently respectively hydrogen atom, hydroxyl, methoxyl or acetyl group.)
(in the formula, R
5, R
6The alkylidene that represents independently respectively carbon number 1～7.)
The compound that above-mentioned general formula (I) is represented and the represented compound of general formula (II) can use the method for putting down in writing in for example Japanese kokai publication sho 62-1753 communique, the Japanese Patent Publication 63-26784 communique to synthesize.That is, with perylene-3,5,9,10-tetrabasic carboxylic acid or its dianhydride and amine add thermal response as raw material in water or organic solvent.Then, in sulfuric acid, precipitate again or in water, organic solvent or their mixed solvent, carry out recrystallization by the crude product with gained, can access object thus.
The ， perylene pigment can be used alone or two or more kinds may be used in the present invention.
In addition, be in disperse state for light shield layer is formed with photonasty substrate composition Zhong De perylene pigment, the mean grain size of preferred Shi perylene pigment is 10～1000nm.
The content that light shield layer of the present invention forms with photonasty substrate composition Zhong De perylene pigment is preferably 5～250 mass parts with respect to (A1) composition 100 mass parts.More preferably scope is 10～200 mass parts.The content of Tong Guo Shi perylene pigment is more than the lower limit of above-mentioned scope, can obtain good light-proofness.In addition, prevent ill-exposed, solidify bad aspect, the content of preferred Shi perylene pigment is below the higher limit of above-mentioned scope.
Close at Hun in the situation of Shi Yong perylene pigment and above-mentioned pigment, pigment, the use amount of other pigment, pigment is preferred to be that mode more than the 85 quality % is set in Zhao perylene pigment shared ratio in the summation of pigment overall, Ji perylene pigment and other pigments.More preferably more than the 90 quality %, also can be 100 quality %.
By more than above-mentioned lower limit, thus the light sensitivity in the time of can obtaining to use above-mentioned light shield layer to form to form the thick film that surpasses 2 μ m with the photonasty substrate composition, and can reach the good shading rate of photomask.
In addition, light shield layer of the present invention forms in the manufacture method of using the photonasty substrate composition, preferably the operation through again filtering after (G) composition is disperseed.At this moment, for (G) composition after preventing from disperseing is removed, preferably using the large filter in aperture, for example aperture is the filter of 0.6～1.5 μ m.The filter that again uses in the filter progress can use known filter so long as do not remove the filter of pigment and just be not particularly limited.Can preferably use PTFE film (poly tetrafluoroethylene), PP film (polypropylene screen), PE film (polyethylene film).
In addition, in light shield layer forms with the photonasty substrate composition, can add hot polymerization inhibitor, defoamer.
As above-mentioned hot polymerization inhibitor, can be known material in the past, can enumerate quinhydrones, Hydroquinone monoethylether etc.
As above-mentioned defoamer, can be known defoamer in the past, can enumerate silicone-based, fluorine based compound.
The formation method of＜light shield layer 〉
Below, as forming an embodiment that forms the method for light shield layer with the photonasty substrate composition with light shield layer, the example of the method that forms black matrix is described.
At first, use roll coater, reverse coating machine (reverse coater), rod to be coated with contact transfer printing type apparatus for coating or the non-contact type apparatus for coating such as spin coater (rotary apparatus for coating), curtain formula curtain coater (curtain flow coater) such as machine, form at substrate coating light shield layer and use the photonasty substrate composition.Substrate can use the substrate with transmitance, and for example thickness is the glass substrate of 0.5～1.1mm.
Form the adaptation of using the photonasty substrate composition, in advance silane-coating coupling agent on glass substrate in order to improve glass substrate and light shield layer.Perhaps when forming the preparation of using the photonasty substrate composition, adds light shield layer silane coupling agent.
After the above-mentioned coating, make its drying and desolventizing.Drying means is not particularly limited, and for example can be any following method: (1) utilize heating plate under 80 ℃～120 ℃, preferred 90 ℃～100 ℃ temperature method of dry 60 seconds～120 seconds; (2) at room temperature place several hours～several days method; (3) put into storage heater, infrared heater dozens of minutes～several hours and the method for desolventizing.
Then, across the minus mask, irradiation ultraviolet radiation, excimer laser isoreactivity energy-ray carry out the part exposure.The energy-ray amount of irradiation forms difference, for example preferred 30～2000mJ/cm with the difference of the composition of photonasty substrate composition according to light shield layer
2About.
Film after using developer solution to exposure develops, and forms thus black matrix pattern.Developing method is not particularly limited, such as using infusion process, spray-on process etc.As the concrete example of developer solution, can enumerate the developer solution of the organic systems such as monoethanolamine, diethanolamine, triethanolamine, the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, ammoniacal liquor, quaternary ammonium salt etc.
Use the photonasty substrate composition according to the light shield layer formation that utilizes manufacture method of the present invention to obtain, even thickness surpasses 2 μ m, also can utilize photoetching process to form good pattern.Therefore, can form the light shield layer of the thick films such as black matrix of thick film.
Thereby this is considered to can realize the light of substrate composition transmission exposure and cover the such characteristic of visible light as the light-proofness pigment owing to Tong crosses Shi Yong perylene pigment.
＜distance piece 〉
In addition, in order in having liquid crystal and be accommodated in the liquid crystal display of two structures between substrate, to make two intervals between substrate keep certain, use light shield layer of the present invention to form with photosensitive polymer combination light shield layer that form, that thickness is certain, can double as to be held on the distance piece that the state between these two substrates arranges.Thickness to light shield layer with such distance piece function is not particularly limited, and is preferably to surpass 2 μ m.
In liquid crystal display in the past, the spacer arrangement that will be formed by spherical spacer particle or photonasty substrate composition is between 2 plate bases.In the situation of having used spherical spacer particle, apply vibration, when impacting, distance piece is mobile in liquid crystal, and the alignment films of being located on the substrate inner face may be impaired, if but utilize the present invention then can solve this kind problem.In addition, in the situation of having used as described above the distance piece that is formed by the photonasty substrate composition, need to form separately black matrix, if but utilize the present invention then do not need to form separately black matrix, the manufacturing process of liquid crystal display can be reduced.
And then, because distance piece has light-proofness, can prevent that therefore the distance piece part is owing to " whiting " that often be in the light transmissive state and cause.
＜color filter 〉
According to the present invention, can form black matrix with thick film.Therefore, thus especially in by the formation that forms the black matrix in the method that dyed layer forms color filter in the peristome of ink-jetting style at preformed black matrix, preferred light shield layer of the present invention forms uses the photonasty substrate composition.Black matrix in the method plays the effect of so-called next door (cofferdam (bank)).
In the present invention, the thickness of the black matrix that uses as the next door in the ink-jetting style (cofferdam) is not particularly limited, and preferably surpasses 2 μ m.
Use the light shield layer of making in the manufacture method of the present invention to form with the method for photonasty substrate composition formation as the black matrix in next door (cofferdam), can similarly carry out with the formation method of above-mentioned light shield layer.
And; after the black matrix that forms as next door (cofferdam); repeatedly carry out being coated with in the peristome of this black matrix with ink-jetting style the operation and the operation that makes this painted liquid-solidization of China ink of painted black liquid; form dyed layer; and then form as required transparent protective film, can make color filter thus.The method of utilizing ink-jetting style to form dyed layer can be used known method.
According to the present invention, can form the black matrix that uses as next door (partition) in the ink-jetting style with thick film, can prevent that therefore the painted black liquid of giving for the peristome of black matrix from surpassing that the next door is overflowed and produce the situation of colour mixture between pixel.
In addition, compare with the situation of black matrix thin (next door is low), can use low viscous painted black liquid.
In addition, also can as in the past, utilize photoetching process to form color filter.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not defined as following embodiment.
＜embodiment 1～3, reference example 1～6 and comparative example 1～10 〉
[(A) alkali soluble resin is synthetic]
At first, in the 500ml four-hole boiling flask, drop into bisphenol fluorene type epoxy resin (epoxide equivalent 235) 235g, tetramethyl ammonium chloride 110mg, 2,6-di-tert-butyl-4-methy phenol 100mg and acrylic acid 72.0g, on one side be blown into air to the speed with 25ml/ minute wherein, at 90～100 ℃ carry out heating for dissolving on one side.Then, be slowly to heat up under the state of gonorrhoea at solution, be heated to 120 ℃ it is dissolved fully.At this moment, the solution transparent thickness that becomes gradually, but still continue to stir.Measure acid number during this, continue to add thermal agitation until less than 1.0mgKOH/g.Until reaching desired value, acid number needs 12 hours.Then be cooled to room temperature, obtain bisphenol fluorene type acrylic acid epoxy ester water white transparency and solid shape, that following formula (a4) is represented.
Next, in the above-mentioned bisphenol fluorene type acrylic acid epoxy ester 307.0g of gained thus, add acetic acid 3-methoxyl butyl ester 600g, after dissolving, mix benzophenone tetracarboxylic dianhydride 80.5g and tetraethylammonium bromide 1g, slowly heat up, make its reaction 4 hours at 110～115 ℃.After confirming the disappearance of anhydride group, mix 1,2,3,6-tetrabydrophthalic anhydride 38.0g, make its reaction 6 hours at 90 ℃, obtain resin (A-1).The disappearance of anhydride group utilizes IR spectrum to confirm.Weight-average molecular weight is 3400.
[light shield layer forms the preparation with the photonasty substrate composition]
Shown in the table 1 described as follows, add (S) solvent at (A) alkali soluble resin, (E) photopolymerization monomer, (H) surfactant with (D) in the colorant, solid component concentration is adjusted into 15 quality % or 17 quality %, carry out mixing in 2 hours with stirring machine, prepared light shield layer formation photonasty substrate composition.In addition, the use level of each composition in the table 1 is " mass parts ".
[table 1]
(A) alkali soluble resin that uses in the table 1, (E) photopolymerization monomer, (B) emulsion, (D) colorant and (S) details of organic solvent is as follows.
(A)-1: in resin (A-1), add acetic acid 3-methoxyl butyl ester and be adjusted to the preparation liquid that solid component concentration is 50 quality %
(E)-1: dipentaerythritol acrylate
(B)-1:IRGACURE OXE02 (Ciba company system)
(B)-2:IRGACURE369 (Ciba company system)
(D)-1: carbon black (drive state pigment company system, concentration of carbon: 55%, solvent: acetic acid 3-methoxyl butyl ester)
(S)-1: acetic acid 3-methoxyl butyl ester/cyclohexanone/propylene glycol monomethyl ether=60/20/20 (mass ratio)
Shown in the details table 2 described as follows of (H) surfactant that uses in the table 1 in addition.In the table 2, the ratio of the inventory of each monomer when the monomer total amount of the numeral in the parantheses in the multipolymer (H)-1～(H)-7 during with synthetic copolymer is made as 100 mass parts.
[table 2]
[uneven width evaluation]
Use rotary coating machine (MIKASA company system), the reference example 1～6 of above-mentioned gained, the light shield layer formation of comparative example 1～4 are coated respectively on the glass substrate (1737 glass) of 100mm * 100mm with the photonasty substrate composition, then, be positioned on the wide glass sheet of the 5mm that heating plate arranges, 90 ℃ carry out 120 second prebake.Use surface roughness measurement machine SurfcorderSE-2300 ((strain) little slope institute system) to measure the uneven width of this moment.It the results are shown in table 1.
In addition, so-called uneven width refers to measure as shown in Figure 1 position as uneven width (nm).Conduct heat from glass sheet owing to the heat transfer to glass substrate only becomes, therefore cause convection current from heated position, light-blocking resin composition is upspring, this thing of upspringing is pearl.This upspring thing less, be that the part that becomes as thin as a wafer of thickness is fewer, then its coating homogeneity, flatness are better.
As shown in Table 1, used in the reference example 1～6 of the specific surfactant of molecular weight more than 10000, can obtain uneven width is little, coating homogeneity and flatness is good light shield layer and form and use the photonasty substrate composition.On the other hand, used in the comparative example 1～4 of molecular weight less than other surfactants of 10000, uneven width is large, and coating homogeneity and flatness are poor.
(embodiment 1)
When the preparation of the composition of reference example 1, with acetic acid 3-methoxyl butyl ester (H) composition ((H)-2) being diluted to concentration from stoste (40 quality %) is after the 10 quality %, utilizing the aperture is that the PTFE film (PALL company system) of 0.05 μ m filters, in addition, adopt and to obtain light shield layer with the same method of reference example 1 and form and use the photonasty substrate composition.
The glass substrate with clean surface at thickness 1mm uses rotary coating machine (TR25000: chemical industry company system is answered in Tokyo), mode take dry film thickness as 1.2 μ m is coated with the light shield layer formation photonasty substrate composition of gained, carry out 2 minutes dryings at 90 ℃, formed light shield layer and formed the film (photographic layer) of using the photonasty substrate composition.
Next, utilize exposure machine (EXM-1066-E01:ORC company system) to expose.After the exposure, utilize 0.04% potassium hydroxide developer solution to carry out for 60 seconds by spray pattern and develop.And then, 200 ℃ carry out 30 minutes after cure, form matrix pattern, the dot pattern of the 20 μ m of thickness 1.0 μ m, the black matrix of isolated patterns.
Having or not of the pin hole of the black matrix of Visual Confirmation gained, the result does not confirm pin hole, can obtain good black matrix.
(comparative example 5)
(H) composition is filtered, in addition, adopt method similarly to Example 1 to obtain light shield layer formation photonasty substrate composition.And then the light shield layer of use gained forms uses the photonasty substrate composition, adopts method similarly to Example 1, has formed photographic layer, black matrix.The pin hole of the black matrix of Visual Confirmation have or not results verification to tens pin hole.
(comparative example 6)
Less than (H) composition not being diluted and filtering, in addition, adopt method similarly to Example 1 to obtain light shield layer formation photonasty substrate composition.But, add separately solvent, so that (H) composition becomes 10 quality % in the same manner with respect to ultimate density and the embodiment 1 that light shield layer forms with the photonasty substrate composition.And then the light shield layer of use gained forms uses the photonasty substrate composition, adopts method similarly to Example 1, has formed photographic layer, black matrix.The pin hole of the black matrix of Visual Confirmation have or not results verification to tens pin hole.
(embodiment 2)
Composition is changed to the composition of reference example 2, in addition, adopt similarly to Example 1 method to obtain light shield layer and form and use the photonasty substrate composition.And then the light shield layer of use gained forms uses the photonasty substrate composition, adopts method similarly to Example 1, has formed photographic layer, black matrix.
Having or not of the pin hole of the black matrix of Visual Confirmation gained, the result does not confirm pin hole, can obtain good black matrix.
(comparative example 7)
(H) composition is filtered, in addition, adopt method similarly to Example 2 to obtain light shield layer formation photonasty substrate composition.And then the light shield layer of use gained forms uses the photonasty substrate composition, adopts method similarly to Example 2, has formed photographic layer, black matrix.The pin hole of the black matrix of Visual Confirmation have or not results verification to tens pin hole.
(comparative example 8)
Less than (H) composition not being diluted and filtering, in addition, adopt method similarly to Example 2 to obtain light shield layer formation photonasty substrate composition.But, add separately solvent, so that (H) composition becomes 10 quality % in the same manner with respect to ultimate density and the embodiment 2 that light shield layer forms with the photonasty substrate composition.And then the light shield layer of use gained forms uses the photonasty substrate composition, adopts method similarly to Example 2, has formed photographic layer, black matrix.The pin hole of the black matrix of Visual Confirmation have or not results verification to tens pin hole.
(embodiment 3)
Composition is changed to the composition of reference example 6, in addition, adopt similarly to Example 1 method to obtain light shield layer and form and use the photonasty substrate composition.And then the light shield layer of use gained forms uses the photonasty substrate composition, adopts method similarly to Example 1, has formed photographic layer, black matrix.
Having or not of the pin hole of the black matrix of Visual Confirmation gained, the result does not confirm pin hole, can obtain good black matrix.
(comparative example 9)
(H) composition is filtered, in addition, adopt method similarly to Example 3 to obtain light shield layer formation photonasty substrate composition.And then the light shield layer of use gained forms uses the photonasty substrate composition, adopts method similarly to Example 3, has formed photographic layer, black matrix.The pin hole of the black matrix of Visual Confirmation have or not results verification to tens pin hole.
(comparative example 10)
Less than (H) composition not being diluted and filtering, in addition, adopt method similarly to Example 3 to obtain light shield layer formation photonasty substrate composition.But, add separately solvent, so that (H) composition becomes 10 quality % in the same manner with respect to ultimate density and the embodiment 3 that light shield layer forms with the photonasty substrate composition.And then the light shield layer of use gained forms uses the photonasty substrate composition, adopts method similarly to Example 3, has formed photographic layer, black matrix.The pin hole of the black matrix of Visual Confirmation have or not results verification to tens pin hole.
By the result of embodiment 1～3 and comparative example 5～comparative example 10 as can be known, by filtering after the dilution of (H) composition, even under the molecular weight of (H) composition is situation large like this more than 10000, also can not produced the high-quality black matrix of pin hole.
Show that according to above-mentioned result the manufacture method that light shield layer of the present invention forms with the photonasty substrate composition can access the high-quality black matrix that does not produce pin hole.
Claims (5)
1. a light shield layer forms the manufacture method of using the photonasty substrate composition, it is characterized in that,
To be to filter after the surfactant component (H) of 10000～50000 polymkeric substance is diluted to 2.5～10 quality % as weight-average molecular weight,
This surfactant component (H), photonasty base material component (A), pigment composition (G) and Elements in Organic Solvents (S) after the filtration are disperseed.
2. light shield layer according to claim 1 forms the manufacture method with the photonasty substrate composition, wherein,
Described filtration is that the following PTFE film of 1 μ m carries out with the aperture.
3. light shield layer according to claim 1 and 2 forms the manufacture method with the photonasty substrate composition, wherein,
Described photonasty base material component (A) contains alkali-soluble base material (A1).
4. each described light shield layer forms the manufacture method with the photonasty substrate composition according to claim 1～3, wherein,
Described photonasty base material component (A) contains optical polymerism compound (A2).
5. light shield layer according to claim 4 forms the manufacture method with the photonasty substrate composition, wherein,
Described photonasty base material component (A) contains Photoepolymerizationinitiater initiater (A3).
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