CN101750890A

CN101750890A - Photosensitive black-colored resin composition, black matrix substrate, and manufacturing method of color filter

Info

Publication number: CN101750890A
Application number: CN200910222196A
Authority: CN
Inventors: 村上元彦; 三木雅之; 藤井幸男; 山田英幸; 盐见秀数
Original assignee: Seiren Co Ltd; Sumitomo Chemical Co Ltd
Current assignee: Seiren Co Ltd; Sumitomo Chemical Co Ltd
Priority date: 2008-11-12
Filing date: 2009-11-12
Publication date: 2010-06-23
Also published as: KR20100053476A; TW201032002A; JP2010170093A

Abstract

The present invention relates to photosensitive black-colored resin composition, a black matrix substrate, and a manufacturing method of a color filter. The project of the invention is to provide the photosensitive black-colored resin composition used for forming a black matrix of walls without special substrate preparation such as plasma treatment, such that it is possible to prevent mixed color due to interfusion of different color between adjacent colourful pixel layers and prevent pixel defect, e.g. local white exposure. The photosensitive black-colored resin composition, relative to the content of whole solid component fluorine, contains 0.0008-0.005% of fluorine series surface active agent having fluoroalkyl on branched chains by mass.

Description

Photosensitive black-colored resin composition, black matrix substrate and manufacturing method of color filter

Technical field

The present invention relates to photosensitive black-colored resin composition, black matrix substrate and manufacturing method of color filter.At length, relate to the partition pattern formation photosensitive black-colored resin composition that constitutes color filter, particularly relate to the black matrix formation that becomes the light-proofness next door that is used for ink jet printing mode manufacturing color filter and use photosensitive black-colored resin composition, also relate to black matrix substrate that uses this photosensitive black-colored resin composition preparation and the manufacturing method of color filter of using this black matrix substrate.

Background technology

Color filter is to be assembled into the optical element that makes the display image colorize in the liquid crystal indicator and use, or is assembled into the optical element that uses in order to obtain coloured image in the solid-state imager.Such color filter is known the color filter that has the colored pattern that comprises a plurality of colour element layers that adjoin each other and form on the same plane on the substrate.Wherein, colored pattern for example is made of the colour element layer of 3 primary colors of red pixel layer, green pixel layer and blue pixel layer, and the colour element interlayer of adjacency becomes the black matrix of light shield layer.Versicolor colour element layer is to be colored as versicolor transparent layer, black matrix be black and be the layer that does not see through visible light substantially.

Conventional manufacture method as color filter, the known photosensitive composition layer that on substrate, forms, this photosensitive composition layer comprises the solid constituent of the photosensitive composition that contains the shades of colour colorant, by the photomask irradiation light, utilization is to the character of the photosensitive composition layer of the dissolubility variation of developer solution, on substrate, form the manufacture method (for example, the spy opens flat 7-271020 communique) of the photoetching process mode of colored pattern.

But, in the color filter manufacturing method of photoetching process mode, behind substrate surface coating photosensitive composition, be necessary to repeat to develop and remove the step that does not need part, manufacturing step complexity by photomask exposure.And then the depreciable cost of the equipment such as cost burden, coating apparatus, exposure sources and developing apparatus of expensive photomask is necessary.Therefore, be reduced to purpose, replace photoetching process, proposed to form the scheme of colour element layer by ink jet printing method with the simplification and the manufacturing cost of manufacturing step.

In the ink jet printing method, usually will have the black matrix of light-proofness as the next door, form the colour element layer by peristome printing inkjet printing ink in this black matrix, when printing, owing to there is the restriction of the solid component concentration of inkjet printing ink, for obtain desired bed thickness and colour saturation, the volume (aperture area * next door height) with respect to the peristome of black matrix is necessary to print the inkjet printing ink of several times with upper volume.Thus, the inkjet printing ink of printing overflows from peristome, exceeds the black matrix that becomes the next door, has also immersed inkjet printing ink on the peristome of adjacency, takes place " colour mixture ".

Problem at this " colour mixture ", for example, by in the atmosphere of fluorine compounds such as tetrafluoromethane, carrying out Cement Composite Treated by Plasma, only make the black matrix surface fluorination, make the method that increases with respect to the lyophobicity of inkjet printing ink (for example, No. 3328297 communique of Jap.P.), in addition, following method has been proposed, be added with organic silicon compound or organofluorine compound, the scheme with respect to the black matrix of the lyophobicity of inkjet printing ink (for example, the spy opens flat 7-35915 communique, and the spy opens the 2006-163233 communique) is given in formation.

In addition, the spy opens in the 2007-256357 communique and discloses, become the next door the black matrix surface whole negative ions detected intensity add up at 1 o'clock so that the method that the detected intensity of fluorine ion is 0.3～0.6 mode to be constituted.

In No. 3328297 communique disclosed method of Jap.P., by Cement Composite Treated by Plasma with the black matrix surface fluorination, therefore the lyophobicity with respect to inkjet printing ink is even on the black matrix surface, but plasma treatment step is necessary, the method that can not say so and oversimplify.

In addition, Te Kaiping 7-35915 communique, spy open in the disclosed method of 2006-163233 communique, the composition that use contains organo-silicon compound or organofluorine compound forms black matrix, therefore can form the black matrix of having given with respect to the lyophobicity of inkjet printing ink, can prevent the colour mixture that takes place of sneaking into, still deficiency aspect the uniform lyophobicity of guaranteeing black matrix surface integral body owing to the heterochromatic printing ink in the colour element interlayer of adjacency.The lyophobicity on black matrix surface is inhomogeneous, as the peristome printing inkjet printing ink of the black matrix of the pixel region that the next door surrounded the time, the bad problem of filling of printing ink takes place partly, and pixel defect problems such as " leaking white (pulling out け in vain) " just takes place.Like this, taking place partly to leak in the color filter for preparing under the white state, leaking the white problem that light leak takes place that partly has.

In addition, when using the composition that contains organo-silicon compound or organofluorine compound to form black matrix, at first, above-mentioned composition is coated on substrate surface on the whole.Then, by having the photomask exposure of desired pattern, afterwards, carry out development treatment and on substrate surface, form black matrix.Like this, for the substrate that has formed black matrix, when particularly forming the big black matrix of next door height, on the pairing substrate surface of the peristome of the black matrix that next door surrounded, the situation of remaining organo-silicon compound or organofluorine compound is arranged.

At this, the spy opens in the 2007-256357 communique disclosed method, though stipulated to become the detected intensity of the black matrix surface fluorine ion in next door, does not stipulate the detected intensity of the pairing substrate surface fluorine ion of peristome of black matrix.Therefore, the spy opens can not the say so method of the problem that taken place when solving on the pairing substrate surface of the peristome of black matrix remaining organofluorine compound of 2007-256357 communique disclosed method.

Organo-silicon compound or organofluorine compound are on the pairing substrate surface of the peristome of black matrix when remaining, this substrate surface of formation colour element layer is also given the lyophobicity with respect to inkjet printing ink, because the lyophobicity of the substrate surface of peristome causes taking place to leak in vain.

Summary of the invention

Therefore, the purpose of this invention is to provide following photosensitive black-colored resin composition, this photosensitive black-colored resin composition can form the black matrix that becomes the next door, it is not implemented the such special surface of Cement Composite Treated by Plasma and handles, the colour mixture that takes place of sneaking into can be prevented, the generation of pixel defectives such as local leakage is white can be prevented owing to the heterochromatic printing ink of the colour element interlayer of adjacency.In addition, provide black matrix substrate that uses this photosensitive black-colored resin composition preparation and the manufacturing method of color filter of using this black matrix substrate.

Photosensitive black-colored resin composition of the present invention, it is the photosensitive black-colored resin composition that is used to form black matrix, described black matrix is the black matrix of color filter of black matrix that has a plurality of colour element layers and be arranged in the colour element interlayer of adjacency on substrate, it is characterized in that

In the content with respect to the fluorine of all solids composition, containing the fluorine that has fluoro-alkyl on side chain is surfactant 0.0008～0.005 quality %.

The present invention is a photosensitive black-colored resin composition, and it is used to form black matrix, and described black matrix is the black matrix of color filter of black matrix that has a plurality of colour element layers and be arranged in the colour element interlayer of adjacency on substrate.And in the photosensitive black-colored resin composition, in the content with respect to the fluorine of all solids composition, containing the fluorine that has fluoro-alkyl on side chain is surfactant 0.0008～0.005 quality %.In content with respect to the fluorine of all solids composition, contain the photosensitive black-colored resin composition that the ormal weight fluorine is a surfactant, this photosensitive black-colored resin composition can form the black matrix that becomes the next door, it is endowed the lyophobicity with respect to inkjet printing ink, can prevent the colour mixture that takes place of sneaking into owing to the heterochromatic printing ink of the colour element interlayer of adjacency, guarantee uniform lyophobicity, can prevent the generation of pixel defectives such as local leakage is white.

The fluorine that has fluoro-alkyl on side chain is the content of surfactant, in content with respect to the fluorine of all solids composition, during less than 0.0008 quality %, the lyophobicity of the black matrix that forms is insufficient, the colour mixture that not only can not give full play to the colour element interlayer of adjacency prevents effect, and in the surperficial structure that produces Bei Naer eddy flow nest sample of black matrix, not preferred.In addition, the fluorine that has fluoro-alkyl on side chain is that the content of surfactant is in the content with respect to the fluorine of all solids composition, when surpassing 0.005 quality %, though substrate center portion is no problem, pixel defectives such as local leakage is white take place near the colour element layer the substrate peripheral part (edge part).

In the photosensitive black-colored resin composition of the present invention, above-mentioned fluorine is that surfactant is a benchmark with the total 100 quality % of entire infrastructure unit preferably, is the compound with the ratio of structural unit 1～40 quality % shown in structural unit 20～98 quality % shown in structural unit 1～40 quality % shown in the following formula (1a), the following formula (1b) and the following formula (1c).

[Chemical formula 1]

[in the formula, R ¹, R ³And R ⁶The alkyl of representing hydrogen atom or carbon number 1～5 independently of one another, R ²The alkyl of expression hydrogen atom, carbon number 1～5, hydroxyl or-(Si (CH ₃) ₂O) _m-Si (CH ₃) ₃, R ⁴The alkylidene of expression carbon number 2～8, R ⁵The aryl of alkyl, acyl group or the carbon number 6～20 of expression hydrogen atom, carbon number 1～12.L ¹, L ², and L ³Represent singly-bound, alkylidene or substituted alkylene independently of one another.X ¹Expression-CO ₂-,-CONY ¹-or arlydene, X ²Expression-O-,-CO ₂-,-CONY ²-, the heterocycle residue of arlydene or divalent.Rf represents fluoro-alkyl.N represents 2～20 integer.In addition, m represents 0～3 integer, Y ¹And Y ²The alkyl of representing hydrogen atom or carbon number 1～5 independently of one another.]

According to the present invention, the fluorine that contains in the photosensitive black-colored resin composition is that surfactant is the compound with ad hoc structure.Thus, photosensitive black-colored resin composition is the photosensitive black-colored resin composition that can form black matrix, and it can more effectively prevent the colour mixture between the colour element of adjacency, can more effectively prevent the generation of pixel defectives such as leak-stopping is white.

The present invention is a black matrix substrate, and it is the black matrix substrate that is used to make color filter, and this color filter has a plurality of colour element layers and is positioned at the black matrix of the colour element interlayer of adjacency on substrate,

It is the black matrix substrate that has formed black matrix, and described black matrix is to use above-mentioned photosensitive black-colored resin composition to prepare.

According to the present invention, black matrix substrate be used to make color filter formation the substrate of black matrix, described color filter has a plurality of colour element layers and is positioned at the black matrix that becomes the next door of the colour element interlayer of adjacency on substrate.And black matrix substrate forms the black matrix of using above-mentioned photosensitive black-colored resin composition preparation on substrate.Such black matrix substrate has to be given with uniform state with respect to the lyophobicity of inkjet printing ink and the black matrix that becomes the next door that obtains.Therefore, can prevent by the inkjet printing ink of ink jet printing method in the peristome printing of black matrix, exceed the black matrix that becomes the next door and printing ink is invaded the peristome generation colour mixture of adjacency, also can prevent partly printing ink simultaneously and fill bad problem, promptly prevent pixel defectives such as Lou white.

In black matrix substrate of the present invention, in the testing result of the negative ion that detects by flight time type secondary ion mass spectrometry meter (TOF-SIMS), the detected intensity ratio that adds up to 1 o'clock fluorine ion of the detected intensity of whole negative ions, surface for black matrix is more than 0.15 and less than 0.3, and preferred below 0.05 for the pairing substrate surface of the peristome of black matrix.

Black matrix substrate of the present invention, in the testing result of the negative ion that detects by flight time type secondary ion mass spectrometry meter (TOF-SIMS), all the detected intensity of negative ions adds up to 1 and the detected intensity ratio of fluorine ion during normalization, surface for black matrix is more than 0.15 and less than 0.3, and is below 0.05 for the pairing substrate surface of the peristome of black matrix.Such black matrix substrate has to be given with uniform state with respect to the lyophobicity of inkjet printing ink and the black matrix that becomes the next door that obtains.Therefore, can prevent by the inkjet printing ink of ink jet printing method in the peristome printing of black matrix, exceed the black matrix that becomes the next door and printing ink is invaded the peristome generation colour mixture of adjacency, also can prevent partly printing ink simultaneously and fill bad problem, promptly prevent pixel defectives such as Lou white.

The detected intensity of surperficial fluorine ion of black matrix that becomes the next door is than less than 0.15 o'clock, and black matrix is insufficient with respect to the lyophobicity of inkjet printing ink, and the colour mixture that can not give full play to the colour element interlayer of adjacency prevents effect.In addition, the detected intensity of the surperficial fluorine ion of black matrix ratio is 0.3 when above, and pixel defectives such as local leakage is white take place near the colour element layer the substrate peripheral part (edge part).And then, the detected intensity ratio of the pairing substrate surface fluorine ion of the peristome of black matrix was above 0.05 o'clock, the substrate surface that is formed with the colour element layer is also given the lyophobicity with respect to inkjet printing ink, pixel defectives such as near the leakage of the colour element layer generation part the substrate peripheral part (edge part) is white, the colour mixture that the lyophobicity on while black matrix surface is brought prevents that effect from reducing.

In addition, in the black matrix substrate of the present invention, below above-3.0 μ m of the preferred 1.2 μ m of the thickness of black matrix.

According to the present invention, the thickness of the black matrix that black matrix substrate had is 1.2～3.0 μ m.Thickness is during less than 1.2 μ m, can not fill the printing ink of the q.s when realizing the necessary colour saturation of color reproduction at the peristome of black matrix, and is not preferred.Thickness surpasses 3.0 μ m, then not only be difficult to prepare the black matrix substrate that can form high-precision partition pattern, and when using this black matrix substrate to make color filter, it is big that the difference of height in colour element layer and next door becomes, and the design of the liquid crystal cell difficulty that becomes, not preferred.

In addition, the present invention is a manufacturing method of color filter, and described color filter has a plurality of colour element layers and is positioned at the black matrix of the colour element interlayer of adjacency on substrate, it is characterized in that this method comprises:

Use above-mentioned photosensitive black-colored resin composition, on substrate, form black matrix, the preparation black matrix substrate the black matrix substrate preparation process and

In the pixel region that the pairing next door of peristome of the black matrix that forms on black matrix substrate is surrounded, by ink jet printing mode printing inkjet printing ink, the pixel layer that forms the colour element layer forms step.

According to the present invention, manufacturing method of color filter is the manufacturing method of color filter of black matrix that has a plurality of colour element layers and be positioned at the colour element interlayer of adjacency on substrate, and it comprises that black matrix substrate preparation process and pixel layer form step.In the black matrix substrate preparation process, use above-mentioned photosensitive black-colored resin composition, on substrate, form and given the black matrix that becomes the next door that obtains with respect to the lyophobicity of inkjet printing ink, preparation black matrix substrate with uniform state.And pixel layer forms in the step, in the pixel region that the pairing next door of peristome of the black matrix that forms on black matrix substrate is surrounded, forms the colour element layer by ink jet printing mode printing inkjet printing ink.Pixel layer forms in the step, printing-ink in the pixel region that the next door surrounded in having the black matrix substrate in next door, described next door is endowed lyophobicity with respect to inkjet printing ink with uniform state, can make color filter, it can prevent to surpass the black matrix that becomes the next door and invade printing ink generation colour mixture at the peristome of adjacency, the bad problem of filling of printing ink partly can be prevented, promptly pixel defectives such as Lou white can be prevented.

Description of drawings

Purpose of the present invention, characteristic and advantage can be clear and definite by following detailed description and accompanying drawing.

Figure 1A～Fig. 1 C is the figure that shows the manufacture method order of black matrix substrate.

Fig. 2 A and Fig. 2 B are the figure that shows the manufacturing method of color filter order.

Fig. 3 A and Fig. 3 B are the figure that summary shows color filter structure.

Fig. 4 is to use the surperficial enlarged photograph of color filter of the photosensitive black-colored resin composition preparation of embodiment.

Fig. 5 is to use the surperficial enlarged photograph of color filter of the photosensitive black-colored resin composition preparation of comparative example.

Embodiment

Explain preferred implementation of the present invention below with reference to accompanying drawing.

Photosensitive black-colored resin composition of the present invention is the composition that is used to form the black matrix of color filter, and described color filter has a plurality of colour element layers and is positioned at the black matrix that becomes the next door of the colour element interlayer of adjacency on substrate.Photosensitive black-colored resin composition can be a minus, also can be eurymeric, more preferably can set the negative light-sensitive resin combination of high light intensity.

(photosensitive black-colored resin composition of minus)

The photosensitive black-colored resin composition of minus contains opacifier, adhesive resin, have the ethylenic unsaturated link and compound, Photoepolymerizationinitiater initiater, photopolymerization that can addition polymerization cause auxiliary agent, fluorine described later is surfactant and solvent.

Opacifier can be that dyestuff also can be the pigment of organic or inorganic.In addition, also dyestuff and pigment can be used with the state that mixes.As inorganic pigment, can enumerate the such metallic compound of metal oxide or metal complex, particularly, can enumerate the oxide of metals such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony or composite metal oxide, nitride, oxides of nitrogen.In addition, as organic pigment, can enumerate the compound that is categorized as pigment in the color index (distribution of The Society of Dyersand Colourists company).

Particularly, when forming black matrix, use black pigment as opacifier.As black pigment, for example, can enumerate carbon black, spy opens flat 5-311109 communique or special graphite, the spy who opens records such as flat 6-11613 communique to open the azo that inorganic black pigment, spy that flat 4-322219 communique or spy open records such as flat 3-274503 communique open record such as flat 2-216102 communique is organic black pigments such as melanin, C.I. pigment black 1, C.I. pigment black 7 etc.Be colored as the photosensitive black-colored resin composition of black and then can contain red pigment, viridine green, blue pigment, yellow uitramarine, green pigment, magenta pigment etc. as pigment.

As the particle diameter of opacifier, in mean grain size, preferred 0.005～0.2 μ m, more preferably 0.01～0.1 μ m.Opacifier with such particle diameter for example can be by known method manufacturings such as kneading methods.

In addition, with respect to all solids composition of photosensitive black-colored resin composition, in Quality Percentage, preferably contain opacifier 5～30 quality %.The content of opacifier then not only can not form the light-proofness next door with sufficient optical density with the thickness of regulation, and " fold " or " limit of collapsing " such harmful effect of next door cross sectional shape takes place less than 5 quality %, and is not preferred.In addition, the content of opacifier surpasses 30 quality %, and then the flowability of photosensitive black composition reduces, and is difficult to form the next door of homogeneous film thickness.

Adhesive resin is in the photosensitive black-colored resin composition of minus, for the resin combination layer that uses this photosensitive black-colored resin composition to form give its light not irradiation area be dissolved in the composition of the character of developer solution.In addition, adhesive resin also has in the resin combination layer that uses photosensitive black-colored resin composition to form, as the function of the dispersion medium that opacifier is disperseed.

The adhesive resin that uses in the photosensitive black-colored resin composition as minus, for example, can enumerate acrylic acid series copolymer, make the epoxy compound and the reaction product of carboxylic acid and then the polycarboxylic acid resin that obtains with the anhydride reaction of polybasic carboxylic acid etc. that have 2 above epoxy radicals in the molecule.

As acrylic acid series copolymer, for example, can enumerate the monomer that contains carboxyl and can with the multipolymer of other monomers of its copolymerization.

As the monomer that contains carboxyl, for example, can enumerate the unsaturated carboxylic acid that has at least 1 carboxyl in the unsaturated polybasic carboxylic acid equimoleculars such as unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturated tricarboxylic acids.Wherein, as unsaturated monocarboxylic, for example, can enumerate acrylic acid, methacrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid etc.As unsaturated dicarboxylic, for example, can enumerate maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc.Unsaturated polybasic carboxylic acid can be its acid anhydrides, can be maleic anhydride, itaconic anhydride, citraconic anhydride etc. particularly.In addition, unsaturated polybasic carboxylic acid can be its single (2-methacryloxy alkyl) ester, particularly, for example be mono succinate (2-acryloxy ethyl) ester, mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloxy ethyl) ester, phthalic acid list (2-methacryloxyethyl) ester etc.Unsaturated polybasic carboxylic acid can be list (methyl) acrylate of its two terminal dicarboxyl polymkeric substance, ω-carboxyl polycaprolactone mono acrylic ester, ω-carboxyl polycaprolactone monomethacrylates etc. specifically.The above-mentioned monomer that contains carboxyl can be distinguished and uses separately or mix more than 2 kinds and to use.

As can with above-mentioned other monomers that contain the monomer copolymerization of carboxyl, for example, can enumerate styrene, α-Jia Jibenyixi, neighbour-vinyltoluene, between-vinyltoluene, right-vinyltoluene, right-chlorostyrene, neighbour-methoxy styrene, between-methoxy styrene, p-methoxystyrene, neighbour-vinyl benzyl methyl ether, between-the vinyl benzyl methyl ether, right-the vinyl benzyl methyl ether, neighbour-vinyl benzyl glycidyl ether, between-the vinyl benzyl glycidyl ether, right-the vinyl benzyl glycidyl ether, aromatic ethenyl compounds such as indenes; Methyl acrylate, methyl methacrylate, the acrylic acid ethyl ester, the methacrylic acid ethyl ester, acrylic acid n-pro-pyl ester, methacrylic acid n-pro-pyl ester, the acrylic acid isopropyl esters, the methacrylic acid isopropyl esters, n-butylacrylate, the methacrylic acid n-butyl, the acrylic acid isobutyl, the methacrylic acid isobutyl, acrylic acid sec-butyl ester, methacrylic acid sec-butyl ester, the acrylic acid tertiary butyl ester, the methacrylic acid tertiary butyl ester, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester acrylic acid, the 2-hydroxy-propyl ester, methacrylic acid 2-hydroxy-propyl ester, acrylic acid 3-hydroxy-propyl ester, methacrylic acid 3-hydroxy-propyl ester, acrylic acid 2-hydroxybutyl ester, methacrylic acid 2-hydroxybutyl ester, acrylic acid 3-hydroxybutyl ester, methacrylic acid 3-hydroxybutyl ester, acrylic acid 4-hydroxybutyl ester, methacrylic acid 4-hydroxybutyl ester, the acrylic acid allyl ester, ALMA, the acrylic acid benzyl ester, the methacrylic acid benzyl ester, the acrylic acid cyclohexyl ester, the methacrylic acid cyclohexyl ester, phenyl acrylate, the methacrylic acid phenylester, acrylic acid 2-methoxy ethyl ester, methacrylic acid 2-methoxy ethyl ester, acrylic acid 2-phenoxy group ethyl ester, methacrylic acid 2-phenoxy group ethyl ester, methoxyl diglycol acrylate, methoxyl diglycol methacrylate, methoxyl triethylene glycol acrylate, methoxyl triethylene glycol methacrylate, the MPEG acrylate, the MPEG methacrylate, methoxyl dipropylene glycol acrylate, methoxyl dipropylene glycol methacrylate, isobornyl acrylate, IBOMA, acrylic acid dicyclopentadienyl ester, methacrylic acid dicyclopentadienyl ester, acrylic acid 2-hydroxyl-3-phenoxy propyl ester, methacrylic acid 2-hydroxyl-3-phenoxy propyl ester, the glycerine mono acrylic ester, unsaturated carboxylate types such as glycerin monomethyl acrylic ester; Acrylic acid 2-amino-ethyl ester, methacrylic acid 2-amino-ethyl ester, acrylic acid 2-dimethyl aminoethyl ester, methacrylic acid 2-dimethyl aminoethyl ester, acrylic acid 2-aminopropyl ester, methacrylic acid 2-aminopropyl ester, acrylic acid 2-dimethylaminopropyl ester, methacrylic acid 2-dimethylaminopropyl ester, acrylic acid 3-aminopropyl ester, methacrylic acid 3-aminopropyl ester, acrylic acid 3-dimethylaminopropyl ester, unsaturated carboxylic acid aminoalkyl ester classes such as methacrylic acid 3-dimethylaminopropyl ester; Unsaturated carboxylic acid glycidyl esters classes such as acrylic acid glycidyl esters, methyl propenoic acid glycidyl base ester; Vinyl esters of carboxylic acids classes such as vinyl-acetic ester, vinyl propionate base ester, butyric acid vinyl esters, benzoic acid vinyl esters; Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether; Cyano group vinyl compounds such as vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, ethenylidene dintrile; Unsaturated acyl amines such as acrylamide, Methacrylamide, α-chloropropene acid amides, N-2-hydroxyethyl acrylamide, N-2-hydroxyethyl Methacrylamide; Unsaturated acid imides such as maleimide, N-phenylmaleimide, N-cyclohexyl maleimide; Aliphatics conjugated dienes such as 1,3-butadiene, isoprene, chlorbutadiene; The end of the polymer molecular chain of polystyrene, polymethacrylate, poly-methyl methacrylate base ester, polyacrylic acid n-butyl, polymethylacrylic acid n-butyl, polysiloxane has the macromonomer class of single acryloyl group or monomethyl acryloyl group etc.These monomers can be distinguished and use separately or mix more than 2 kinds and to use.

The content that contains the monomeric unit of carboxyl in the above-mentioned multipolymer in Quality Percentage, is generally about 10～50 quality %, about preferred 15～40 quality %.

As aforesaid propylene acid based polymer, for example, can enumerate (methyl) acrylic acid/(methyl) methyl acrylate multipolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester multipolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyethyl ester/(methyl) acrylic acid benzyl ester multipolymer, (methyl) acrylic acid/(methyl) methyl acrylate/polystyrene macromolecular monomer copolymer, (methyl) acrylic acid/(methyl) methyl acrylate/poly-methyl methacrylate base ester large molecule monomer copolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester/polystyrene macromolecular monomer copolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl ester/poly-methyl methacrylate base ester large molecule monomer copolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyethyl ester/(methyl) acrylic acid benzyl ester/polystyrene macromolecular monomer copolymer, (methyl) acrylic acid/(methyl) acrylic acid 2-hydroxyethyl ester/(methyl) acrylic acid benzyl ester/poly-methyl methacrylate base ester large molecule monomer copolymer, methacrylic acid/styrene/(methyl) acrylic acid benzyl ester/N-phenylmaleimide multipolymer, (methyl) acrylic acid/mono succinate (2-acryloxy ethyl) ester/styrene/(methyl) acrylic acid benzyl ester/N-phenylmaleimide multipolymer, (methyl) acrylic acid/mono succinate (2-acryloxy ethyl) ester/styrene/(methyl) acrylic acid allyl ester/N-phenylmaleimide multipolymer (methyl) acrylic acid/(methyl) acrylic acid benzyl ester/N-phenylmaleimide/styrene/glycerine list (methyl) acrylate copolymer etc.(methyl) acrylate is represented acrylate or methacrylate.

Wherein, preferable methyl acrylic acid benzyl ester/methacrylic acid copolymer, methacrylic acid benzyl ester/methacrylic acid/styrol copolymer, methyl methacrylate/methacrylic acid copolymer, methyl methacrylate/methacrylic acid/styrol copolymer etc.

The scope of the polystyrene conversion weight average molecular weight preferred 3000～400000 of aforesaid propylene acid based polymer, more preferably 5000～100000 scope.In addition, acid number is preferred 30～250, more preferably 60～180 scope.

Can be used as the polycarboxylic acid resin that adhesive resin uses, for example, can enumerate the condensed polymer (open flat 4-355450 communique, spy with reference to the spy and open that flat 9-40745 communique, spy are opened flat 9-325494 communique, the spy opens the 2000-281738 communique) of the compound shown in the following formula (2) and polyprotonic acid or its acid anhydrides, or as epoxy compound and the resultant of reaction of polybasic carboxylic acid and/or monocarboxylic acid and the condensed polymer of polyprotonic acid or its acid anhydrides etc. of the precursor of formula (2).

[Chemical formula 2]

[in the formula, R ⁷And R ⁸Alkyl or the halogen atom of representing hydrogen atom, carbon number 1～5 respectively independently, R ¹⁰Expression hydrogen atom or methyl, X represents the residue of the divalent of following formula (2-1)～(2-7) shown in any, R ⁹Expression can have the alkylidene of substituent carbon number 1～10, and the integer of p table 0～5 shows that q represents 1～10 integer.]

[chemical formula 3]

As polyprotonic acid, for example, can enumerate methylene tetrahydrophthalic acid (acid of メチ Le エ Application De メチレ Application テトラヒ De ロ Off タ Le), chlorendic acid, methyl tetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetrabasic carboxylic acid, 4 in the maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyl, the biphenyltetracarboxyacid acid headed by 4 '-biphenyl dicarboxylic acid, biphenyl ether tetrabasic carboxylic acid etc.As the acid anhydrides of polyprotonic acid, can enumerate the acid anhydrides of above-mentioned polyprotonic acid etc.

Polyprotonic acid or its acid anhydrides can be distinguished and use separately or mix more than 2 kinds and to use.

The use amount of polyprotonic acid or multi-anhydride with respect to the objectification compound of reactions such as the compound shown in the formula (2) and the integral molar quantity of polyprotonic acid or its multi-anhydride, with molar ratio computing, is generally 5～95%, preferred about 10～90%.In addition, in the above-mentioned adhesive resin, preferably contain the resin of poly carboxylic acid.

The acid number of the adhesive resin that uses in the photosensitive black-colored resin composition of minus is generally 70～170, and preferred 80～140.In addition, the polystyrene conversion weight average molecular weight of adhesive resin is generally 1000～50000, and preferred 1500～20000.

The adhesive resin that uses in the photosensitive polymer combination of minus, with respect to all solids composition of photosensitive black-colored resin composition, in Quality Percentage, with 5～90 quality %, preferably the scope with 10～60 quality % contains usually.

Contained in the photosensitive black-colored resin composition as minus, have ethylenic unsaturated link and a compound that can addition polymerization, for example, be selected from the compound that has 1 ethylenic unsaturated link endways at least, the compound that preferably has 2 above ethylenic unsaturated links, it can be monomer, also can be prepolymers such as dimer, tripolymer and oligomer, can be their potpourri or their multipolymer etc.

As above-mentioned monomer, for example, can enumerate the acid amides etc. of ester, unsaturated carboxylic acid and the aliphatic polyamine compound of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid and maleic acid and aliphatic polyol compound.

Ester as unsaturated carboxylic acid and aliphatic polyol compound, for example, can enumerate glycol diacrylate, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, the tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexane diol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acrylyl oxy-ethyl) chlorinated isocyanurates, acrylate such as polyester acrylic ester oligomer; The tetramethylene glycol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethylacrylate, the hexane diol dimethylacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, the D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylate, two [right-(3-metacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane, two-methacrylates such as [right-(metacryloxy ethoxy) phenyl] dimethylmethane; Ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3 butylene glycol diitaconate, 1, itaconates such as 4-butylene glycol diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates; Crotonatess such as ethylene glycol bisthioglycolate crotonates, tetramethylene glycol two crotonatess, pentaerythrite two crotonatess, D-sorbite four or two crotonatess; Iso-crotonic acid esters such as ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, D-sorbite four iso-crotonic acid esters; Maleates such as ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc.

Acid amides as unsaturated carboxylic acid and aliphatic polyamine compound, for example, can enumerate di-2-ethylhexylphosphine oxide-acrylamide, di-2-ethylhexylphosphine oxide-Methacrylamide, 1, the 6-hexa-methylene is two-acrylamide, 1, and the 6-hexa-methylene is two-Methacrylamide, diethylene triamine three acrylamides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.

As other examples of monomer, for example, can enumerate that the polyisocyanate compound that has the isocyanate group more than 2 in 1 molecule and the vinyl monomer shown in the following formula (3) carry out addition and vinyl carbamate compound of obtaining etc.

[chemical formula 4]

[in the formula, R ²¹And R ²²Represent hydrogen atom or methyl respectively independently.]

As above-mentioned vinyl carbamate compound, can enumerate urethane acrylate class, the spy that compound, the spy of containing 2 above polymerism vinyl in 1 molecule of special public clear 48-41708 communique record open clear 51-37193 communique record and open the polyfunctional acrylic ester or the methacrylates such as polyester acrylate class of records such as clear 48-64183 communique, special public clear 49-43191 communique and special public clear 52-30490 communique.In addition, also can use the then will Vol.20 of association of Japan, No.7, the material of introducing as photo-curable monomer and oligomer in 300～308 pages (1984).

Above-mentioned use amount with ethylenic unsaturated link and compound that can addition polymerization with respect to all solids composition of photosensitive black-colored resin composition, in Quality Percentage, is generally 0.5～50 quality %, preferred 1～40 quality %.

The Photoepolymerizationinitiater initiater that contains in the photosensitive black-colored resin composition as minus, so long as can cause polymeric compounds with ethylenic unsaturated link and compound that can addition polymerization, just there is no particular limitation, and can enumerate acetophenone and be Photoepolymerizationinitiater initiater, benzoin and be Photoepolymerizationinitiater initiater, benzophenone series Photoepolymerizationinitiater initiater, thioxanthones is that Photoepolymerizationinitiater initiater, triazine are that Photoepolymerizationinitiater initiater, oxadiazole is a Photoepolymerizationinitiater initiater etc.

As acetophenone is Photoepolymerizationinitiater initiater, for example, can enumerate diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl-oxethyl) phenyl] propane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino-1-(4-methylbenzene sulfenyl) propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] oligomer etc. of propane-1-ketone.

As benzoin is Photoepolymerizationinitiater initiater, for example, can enumerate benzoin, benzoin methyl ether, benzoin ethylether, benzoin isopropyl ether, benzoin isobutyl ether etc.

As the benzophenone series Photoepolymerizationinitiater initiater; for example; can enumerate benzophenone, neighbour-benzoyl benzoic acid methyl ester, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl sulphur, 3; 3 '; 4; 4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone etc.

As thioxanthones is Photoepolymerizationinitiater initiater, for example, can enumerate 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.

As triazine is Photoepolymerizationinitiater initiater, for example, can enumerate 2, two (the trichloromethyl)-6-p-methoxystyrene bases of 4--s-triazine, 2, two (the trichloromethyl)-6-of 4-(1-is right-dimethylaminophenyl-1, the 3-butadienyl)-the s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyrene base-s-triazine, 2-(naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-ethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4-butoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-methoxy ethyl)-naphthalene-1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl group)-naphthalene-1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-[4-(2-butoxyethyl group)-naphthalene-1-yl]-4,6-pair-trichloromethyl-s-triazine, 2-(2-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-5-methyl-naphthalene-2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-naphthalene-2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(5-methoxyl-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4,7-dimethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(6-ethoxy-naphthalene-2-yl)-4,6-pair-trichloromethyl-s-triazine, 2-(4,5-dimethoxy-naphthalene-1-yl)-4,6-pair-trichloromethyl-s-triazine, 4-[is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-methyl-right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-methyl-right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N, N-two (phenyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(right-N-chloroethyl carbonylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-[is right-N-(right-methoxyphenyl) carbonylamino phenyl] and 2,6-two (trichloromethyl)-s-triazine, between 4-[-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and bromo-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, and N-two (ethoxy carbonyl methyl) aminophenyl-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N, N-two (ethoxy carbonyl methyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-bromo-is right-N, and N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-chloro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-[neighbour-fluoro-is right-N, and N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and bromo-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and chloro-is right-N, and N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, between 4-[-and fluoro-is right-N, N-two (chloroethyl) aminophenyl]-2,6-two (trichloromethyl)-s-triazine, 4-(-bromo-is right-N-ethoxy carbonyl methylamino phenyl) and-2,6-two (trichloromethyl)-s-triazine, 4-(-chloro-is right-N-ethoxy carbonyl methylamino phenyl) and-2,6-two (trichloromethyl)-s-triazine, 4-(-fluoro-is right-N-ethoxy carbonyl methylamino phenyl) and-2,6-two (trichloromethyl) number triazine, 4-(neighbour-bromo-right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-chloro-right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-fluoro-right-N-ethoxy carbonyl methylamino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(-bromo-is right-N-chloroethyl amino phenyl) and-2,6-two (trichloromethyl)-s-triazine, 4-(-chloro-is right-N-chloroethyl amino phenyl) and-2,6-two (trichloromethyl)-s-triazine, 4-(-fluoro-is right-N-chloroethyl amino phenyl) and-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-bromo-right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-chloro-right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine, 4-(neighbour-fluoro-right-N-chloroethyl amino phenyl)-2,6-two (trichloromethyl)-s-triazine etc.

Zuo is a Photoepolymerizationinitiater initiater Wei oxadiazole, for example, can enumerate 2-trichloromethyl-5-styryl-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(right-the cyano styrene base)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyrene base)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(right-the butyl phenyl ether vinyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(right-hydroxystyrene based)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(right-the chlorostyrene base)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(right-methoxyphenyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(right-butoxy phenyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(2-naphthyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(β-(2-benzofuranyl) vinyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(β-(6-methoxyl-2-benzofuranyl) vinyl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(2-benzofuranyl)-1,3,4-oxadiazole etc.

In addition; as Photoepolymerizationinitiater initiater, for example, can use 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide, 2,2 '-two (neighbour-chlorphenyl)-4,4 '; 5; 5 '-tetraphenyl-1,2 '-di-imidazoles, 10-butyl-2-chloro-acridine ketone, 2-EAQ, dibenzoyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methyl ester, two cyclopentadiene titanium compounds etc.In the above-mentioned Photoepolymerizationinitiater initiater, preferred to use the triazine that has imported trichloromethyl be Photoepolymerizationinitiater initiater, imported trichloromethyl De oxadiazole is Photoepolymerizationinitiater initiater.

As the triazine that has imported trichloromethyl is Photoepolymerizationinitiater initiater, for example, can enumerate 2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-piperonyl-1,3,5-triazines of 4-, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(5-methylfuran-2-yl) ethylidine of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(furans-2-yl) ethylidine of 4-]-1,3, the 5-triazine, 2, two (trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) ethylidine of 4-]-1,3,5-triazines, 2, two (the trichloromethyl)-6-[2-(3 of 4-, the 4-Dimethoxyphenyl) ethylidine]-1,3,5-triazines etc.

As having imported trichloromethyl De oxadiazole is Photoepolymerizationinitiater initiater, for example, can enumerate 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(right-the cyano styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxystyrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(right-the butyl phenyl ether vinyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(β-(2-benzofuranyl) vinyl)-1,3,4-oxadiazole etc.

Above-mentioned Photoepolymerizationinitiater initiater can be used alone or in combination of two or more kinds respectively.

The photosensitive black-colored resin composition of minus can contain photopolymerization and cause auxiliary agent.Cause auxiliary agent as photopolymerization, for example can enumerate, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethyl aminoethyl ester, N, the N-dimethyl-p-toluidine, 4,4 '-two (dimethylamino) benzophenone (common name michaelis ketone), 4,4 '-two (diethylamino) benzophenone, 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.These photopolymerization cause auxiliary agent and can be used alone or in combination of two or more kinds respectively.

When using above-mentioned photopolymerization to cause auxiliary agent, its use amount is generally 0.01～10 mole with respect to 1 mole of Photoepolymerizationinitiater initiater.

Photoepolymerizationinitiater initiater and photopolymerization cause total use amount of auxiliary agent, with respect to all solids composition of photosensitive black-colored resin composition, in Quality Percentage, are generally 1～50 quality %, are preferably 3～30 quality %.

As the solvent that contains in the photosensitive black-colored resin composition, for example, can enumerate ester class, ethers, ketone, aromatic hydrocarbon based etc.

As the ester class, for example, can enumerate alkyl esters such as acetate ethyl ester, ro-butyl acetate, acetate isobutyl, formic acid amyl group ester, acetate isopentyl ester, acetate isobutyl, propionic acid butyl ester, butyric acid isopropyl esters, butyric acid ethyl ester, butyric acid butyl ester, lactic acid methyl ester, lactic acid ethyl ester; Alkoxy acetic acid alkyl esters such as glycolic acid methyl ester, glycolic acid ethyl ester, glycolic acid butyl ester, methoxyacetic acid methyl ester, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxyacetic acid methyl ester, ethoxyacetic acid ethyl ester; Hydracrylic acid alkyl esters such as 3-hydracrylic acid methyl ester, 3-hydracrylic acid ethyl ester; 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxy-propionic acid methyl ester, 3-ethoxy-propionic acid ethyl ester, the 2 hydroxy propanoic acid methyl ester, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl diester, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl diester, 2-ethoxy-propionic acid methyl ester, 2-ethoxy-propionic acid ethyl ester, 2-hydroxy-2-methyl propionic acid methyl ester, 2-hydroxy-2-methyl propionic acid ethyl ester, 2-methoxyl-2 Methylpropionic acid methyl ester, 2-ethoxy-2 Methylpropionic acid ethyl ester, the pyruvic acid methyl ester, the pyruvic acid ethyl ester, the pyruvic acid propyl diester, the acetoacetate methyl ester, the acetoacetate ethyl ester, 2-ketobutyric acid methyl ester, 2-ketobutyric acid ethyl ester etc.

As ethers, for example, can enumerate diethylene glycol dimethyl ether, tetrahydrofuran, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diglycol monotertiary methyl ether, carbiphene, diglycol monotertiary butyl ether, methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.

As ketone, for example, can enumerate methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc.

As aromatic hydrocarbon based, for example, can enumerate toluene, dimethylbenzene, trimethylbenzene etc.

In the above-mentioned solvent, preferably use 3-ethoxy-propionic acid methyl ester, 3-ethoxy-propionic acid ethyl ester, ethyl cellosolve acetate, lactic acid ethyl ester, diglycol dimethyl (ジメテ Le) ether, acetate butyl ester, 3-methoxypropionic acid methyl ester, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol and methyl proxitol acetate.

Above-mentioned solvent can be distinguished and uses separately or mix more than 2 kinds and to use, and its use amount in the quality percentage of all solids constituent concentration in the photosensitive black-colored resin composition, is selected in the scope of 2～50 quality % usually.

(photosensitive black-colored resin composition of eurymeric)

It is surfactant and solvent that the photosensitive black-colored resin composition of eurymeric contains opacifier, adhesive resin, emulsion, fluorine described later.

Opacifier that contains in the photosensitive black-colored resin composition of eurymeric and solvent can use the opacifier and the solvent that contain in the photosensitive black-colored resin composition with aforesaid minus same.

Adhesive resin is in the photosensitive black-colored resin composition of eurymeric, for the resin combination layer that uses this photosensitive black-colored resin composition to form give its light not irradiation area be dissolved in the composition of the character of developer solution.In addition, adhesive resin also has in the resin combination layer that uses photosensitive black-colored resin composition to form, as the function of the dispersion medium that opacifier is disperseed.

The adhesive resin that uses in the photosensitive black-colored resin composition as eurymeric, for example, can enumerate the alkali soluble resins that macromolecular compound that macromolecular compound that linear phenol-aldehyde resin, polyhydroxystyrene resin etc. contain the phenol hydroxyl, methacrylic acid copolymer, acrylic copolymer etc. contain carboxyl etc. contains phenol hydroxyl or carboxyl.In addition, as alkali soluble resins, preferably has the alkali soluble resins of curable.As alkali soluble resins with curable, for example, can enumerate have vinyl, the alkali soluble resins with curable of epoxy radicals, oxetanyl, tetrahydrofuran base, butyrolactone skeleton etc.

As the emulsion of in the photosensitive black-colored resin composition of eurymeric, using, for example, can enumerate the compound etc. of (the キノ Application ジアジ De) base that has the diazonium quinone.As the diazonium naphtoquinone compounds, for example, can enumerate 1,2-diazobenzene diazide sulfonic acid ester, 1,2-diazonium naphthoquinone sulphonate, 1,2-diazonium benzoquinones sulfonic acid amides, 1,2-diazo naphthoquinone sulfonic acid amides class etc.Preferably, 1, the 2-diazonium naphthoquinone sulphonate.

More than the photosensitive black-colored resin composition of such minus and eurymeric macromolecular compound, adhesion promoter, antioxidant, ultraviolet light absorber, the aggegation that can also contain beyond hot polymerization inhibitor, filling agent, the adhesive resin prevent adjuvants such as agent.

Hot polymerization inhibitor is in order to prevent when the preservation of photosensitive black-colored resin composition, has ethylenic unsaturated link and compound that can addition polymerization and causes thermal polymerization and contain.As hot polymerization inhibitor, for example, can enumerate quinhydrones, right-metoxyphenol, two-tert-butyl group-p-Cresol, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), the inferior cerium salt of N-nitroso-phenyl hydramine etc.When containing hot polymerization inhibitor, its content in Quality Percentage, is generally about 0.01～5 quality % with respect to the total amount of photosensitive black-colored resin composition.In addition, as filling agent, for example, can enumerate glass, aluminium oxide etc.

As the macromolecular compound beyond the adhesive resin, for example, can enumerate polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-fluoroalkyl acrylate etc.

As adhesion promoter, for example, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, 3-sulfydryl propyl trimethoxy silicane etc.

As antioxidant, for example, can enumerate 2,2-thiobis (4-methyl-6-tert butyl phenol), 2,6-two-tert-butyl phenol etc.In addition, as ultraviolet light absorber, for example, can enumerate 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone etc.In addition, prevent agent, for example, can enumerate sodium polyacrylate etc. as aggegation.

In addition, photosensitive black-colored resin composition of the present invention can also contain organic carboxyl acid, organic amine compound etc.

As organic carboxyl acid, for example, can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, diethacetic acid, enanthic acid, aliphatic monocarboxylic acid such as sad; Aliphatic dicarboxylic acids such as ethane diacid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, brassylic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, rhizome of Chinese monkshood camphoronic acid; Benzoic acid, toluic acid, cumic acid, half

Acid,

Aromatic monocarboxylates such as woods acid; Aromatic multi-carboxy acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; Phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamic acid methyl ester, cinnamic acid benzyl ester, cinnamylidene acetate, coumaric acid, the organic carboxyl acid of umbellic acid equimolecular quantity below 1000 etc.

As organic amine compound, the preferred organic amine compound of molecular weight below 1000 that use, for example, can enumerate n-pro-pyl amine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, just-amylamine, just-hexyl amine, just-heptyl amine, just-octyl amine, just-nonyl amine, just-decyl amine, just-undecyl amine, just-lauryl amine, cyclo-hexylamine, neighbour-methylcyclohexyl amine ,-methylcyclohexyl amine, right-methylcyclohexyl amine, neighbour-ethyl cyclo-hexylamine ,-single (ring) alkyl amines such as ethyl cyclo-hexylamine, right-ethyl cyclo-hexylamine; Two (ring) alkyl amines such as Methylethyl amine, diethylamide, methyl n-pro-pyl amine, ethyl n-pro-pyl amine, two-n-pro-pyl amine, diisopropylamine, di-n-butyl amine, diisobutyl amine, two-tert-butylamine, two-just-amylamine, two-just-hexyl amine, methylcyclohexyl amine, ethyl cyclo-hexylamine, dicyclohexyl amine; Three (ring) alkyl amines such as dimethylethyl amine, methyl diethylamide, triethylamine, dimethyl n propyl group amine, diethyl n-pro-pyl amine, methyl two-n-pro-pyl amine, ethyl two-n-pro-pyl amine, three-n-pro-pyl amine, triisopropylamine, three-n-butylamine, triisobutyl amine, three-tert-butylamine, three-just-amylamine, three-just-hexyl amine, dimethylcyclohexylam,ne, diethyl cyclo-hexylamine, methyl bicyclic hexyl amine, ethyl dicyclohexyl amine, thricyclohexyl amine; The 2-ethylaminoethanol, single (ring) alkanol amine such as 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, 4-amino-1-cyclohexanol; Two (ring) alkanol amines such as diethanolamine, two-just-Propanolamine, diisopropanolamine, two-just-butanolamine, two isobutyl hydramine, two-just-amylalcohol amine, two-just-hexanol amine, two (4-cyclohexanol) amine; Three (ring) alkanolamines such as triethanolamine, three-just-Propanolamine, triisopropanolamine, three-just-butanolamine, three isobutyl hydramine, three-just-amylalcohol amine, three-just-hexanol amine, three (4-cyclohexanol) amine; 3-amino-1,2-propane diol, 2-amino-1,3-propane diol, 4-amino-1,2-butylene glycol, 4-amino-1,3 butylene glycol, 4-amino-1,2-cyclohexane diol, 4-amino-1,3-cyclohexane diol, 3-dimethylamino-1,2-propane diol, 3-diethylamino-1,2-propane diol, 2-dimethylamino-1,3-propane diol, 2-diethylamino-1, amino (ring) alkane glycols such as 3-propane diol; 1-Aminocyclopentane methyl alcohol, 4-Aminocyclopentane methyl alcohol, 1-aminocyclohexane methyl alcohol, 4-aminocyclohexane methyl alcohol, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylamino cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, 4-diethylamino cyclohexane methanol etc. contain amino cycloalkanes methyl alcohol class; Aminocarboxylic acids such as Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaprolc acid, 1-1-aminocyclopropane-1-carboxylic acid, 1-aminocyclohexane carboxylic acid, 4-aminocyclohexane carboxylic acid etc.

In addition, for example, the amino compound that directly combines with phenyl can be enumerated compound that amino combines with phenyl by carbochain etc.As the above-mentioned amino compound that directly combines with phenyl, for example, can enumerate aniline, neighbour-methylaniline ,-methylaniline, right-methylaniline, right-ethylaniline, right-n-pro-pyl aniline, right-isopropyl aniline, right-n-butyl aniline, right-tert-butyl group aniline, 1-naphthylamine, 2-naphthylamine, N, accelerine, N, N-diethylaniline, right-methyl-N, aromatic amines such as accelerine; Neighbour-aminobenzyl alcohol ,-aminobenzyl alcohol, right-aminobenzyl alcohol, right-the dimethylamino benzyl alcohol, right-aminobenzyl alcohols such as diethylamino benzyl alcohol; O-aminophenol ,-amino-phenol, para-aminophenol, right-dimethylamino phenol, right-amino phenols such as diethylamino phenol; M-anthranilic acid, Para-Aminobenzoic, right-dimethylaminobenzoic acid, right-aminobenzoic acids such as diethyl amino yl benzoic acid (derivant) class etc.

Above-mentioned organic carboxyl acid, organic amino compounds can be distinguished and use separately or mix more than 2 kinds and to use.When using above-mentioned organic carboxyl acid, organic amino compounds, its content in the photosensitive black-colored resin composition is with respect to the total amount of photosensitive black-colored resin composition, in Quality Percentage, be generally 0.001～15 quality %, be preferably 0.01～10 quality %.

The formation of feature is that to contain the fluorine that has fluoro-alkyl on side chain be surfactant in the photosensitive black-colored resin composition of the present invention.

The fluorine that has fluoro-alkyl on side chain is that surfactant can be any one of non-ionics, cationic surfactant, anionic surface active agent.At this, the general name of the so-called fluoro-alkyl fluoro-alkyl that to be the fluoro-alkyl (perfluoroalkyl) that replaced by fluorine atom of the whole hydrogen atoms in the alkyl and a part of hydrogen atom in the alkyl replaced by fluorine atom can be the group arbitrarily of straight chain shape, a chain.(for example, the CF that contains oxygen atom in the fluoro-alkyl ₃-(OCF ₂CF ₂) ₂-etc.) be also included within the definition of fluoro-alkyl of the present invention.The preferred carbon number 3～12 of the chain length of fluoro-alkyl, in addition, preferred straight chain shape perfluoroalkyl.

Fluorine is that surfactant is a benchmark with the total 100 quality % of entire infrastructure unit preferably, is the compound with the ratio of structural unit 1～40 quality % shown in structural unit 20～98 quality % shown in structural unit 1～40 quality % shown in the following formula (1a), the following formula (1b) and the following formula (1c).

[chemical formula 5]

R ¹, R ², R ³And R ⁶At least 1 when being the alkyl of carbon number 1～5, this alkyl can be that the straight chain shape also can be a chain, as its example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl.R ⁴The alkylidene of the carbon number 2～8 of expression can be that the straight chain shape also can be a chain, as its example, can enumerate ethylidene, propylidene (methyl ethylidene), trimethylene, tetramethylene, hexa-methylene.R ⁵When being the alkyl of carbon number 1～12, this alkyl can be that the straight chain shape also can be a chain, as its example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, 2-ethylhexyl, dodecyl.R ⁵When being acyl group, as its example, can enumerate acetyl group, propiono, benzoyl, its carbon number is generally about 2～10.R ⁵When being the aryl of carbon number 6～20,, can enumerate phenyl, tolyl, naphthyl as its example.L ¹, L ²And L ³At least 1 this alkylidene can be that the straight chain shape also can be a chain, as its example, can enumerate ethylidene, propylidene, trimethylene, tetramethylene, hexa-methylene when being alkylidene, its carbon number normally about 2～8.L ¹, L ²And L ³At least 1 when being substituted alkylene, as its example, the hydrogen atom that can enumerate the alkylidene of a such straight chain shape of ethylidene, propylidene, trimethylene, tetramethylene, hexa-methylene or a chain is replaced by the such aryl of phenyl or hydroxyl and obtains, its carbon number normally 2～20.X ¹And X ²At least 1 as its example, can enumerate phenylene, naphthylene when being arlydene, its carbon number normally 6～20.X ²When being the heterocycle residue of divalent,, can enumerating from pyridine ring, pyrimidine ring, pyrazine ring, the such heterocycle of thiazole ring and remove the residue that 2 hydrogen atoms form, its carbon number normally 3～10 as its example.Y ¹And Y ²At least 1 when being the alkyl of carbon number 1～5, this alkyl can be that the straight chain shape also can be a chain, as its example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl.

In addition, fluorine is a surfactant and then preferred, the R in the formula (1a) ²Be-(Si (CH ₃) ₂O) _m-Si (CH ₃) ₃The expression compound promptly, uses the monomer contain fluoro-alkyl and the two keys of ethylenic at least and contains the organosilicon chain and fluorine based copolymer that the monomer polymerization of the two keys of ethylenic obtains.

And, the photosensitive black-colored resin composition of the 1st embodiment of the present invention, in the content with respect to the fluorine of all solids composition, (8～50ppm) fluorine are surfactant to contain 0.0008～0.005 quality %.Such photosensitive black-colored resin composition can be preferably used as the formation black matrix, and described black matrix is the black matrix of color filter of the black matrix that becomes the next door that has a plurality of colour element layers and be arranged in the colour element interlayer of adjacency on substrate.

That is to say, by using in content with respect to the fluorine of all solids composition, (8～50ppm) fluorine that have fluoro-alkyl on side chain are the photosensitive black-colored resin composition of surfactant to contain 0.0008～0.005 quality %, formation becomes the black matrix in next door, it gives the lyophobicity with respect to inkjet printing ink, can prevent by the sneaking into of heterochromatic printing ink of the colour element interlayer of adjacency and the colour mixture that takes place, guarantee uniform lyophobicity, can prevent that pixel defectives such as local leakage is white from taking place.In the photosensitive black-colored resin composition of the 1st embodiment, the fluorine that has fluoro-alkyl on side chain is the content of surfactant self, mass ratio according to the shared fluorine of its molecular weight, can suitably adjust, usually, be that 0.01～0.03 quality % is (about 100～300ppm) with respect to all solids composition.

The fluorine that has fluoro-alkyl on side chain is the content of surfactant, in content with respect to the fluorine of all solids composition, during less than 8ppm, the lyophobicity of the black matrix that becomes the next door that forms is insufficient, the colour mixture that not only can not give full play to the colour element interlayer of adjacency prevents effect, and the structure of black matrix surface generation Bei Naer eddy flow nest sample, not preferred.In addition, the fluorine that has fluoro-alkyl on side chain is the content of surfactant, in the content with respect to the fluorine of all solids composition, when surpassing 50ppm, the central portion of substrate is no problem, but pixel defectives such as local leakage is white take place near the colour element layer the substrate peripheral part (edge part).

At this, in fluorine with respect to all solids composition, the fluorine that has fluoro-alkyl on side chain is that the content of surfactant can followingly be obtained, that is, the fluorine that will have fluoro-alkyl on side chain is that the fluorine that has fluoro-alkyl in the molecular weight of surfactant in the shared mass ratio of fluorine and all solids composition on side chain is that the shared mass ratio of surfactant multiplies each other and obtains.In addition, the fluorine-containing composition that exists in the solid constituent only is the fluorine that has fluoro-alkyl on side chain when being surfactant, in the solid constituent fluorine content can burn by oxygen-ion chromatography analysis obtains.

The fluorine that has fluoro-alkyl on side chain is a surfactant, also has the situation of fluorine except the fluoro-alkyl of side chain, also comprises this fluorine, can make content with respect to the fluorine of all solids composition in above-mentioned scope.In addition, when existing in the fluorine that has fluoro-alkyl on the side chain in the solid constituent and be the fluorine-containing composition beyond the surfactant, also comprise the fluorine of this fluorine-containing composition, be desirably in the above-mentioned scope with respect to the content of the fluorine of all solids composition.

In addition, fluorine is the molecular weight of surfactant, considers with respect to the deliquescent aspect of solvent from preventing property of colour mixture, preventing property of picture element flaw and surfactant self, with polystyrene conversion preferred 15000～25000.

In addition, photosensitive black-colored resin composition of the present invention except formation becomes the black matrix in next door, also can use in the formation for the light spacer (Off オトスペ one サ) of controlling cel-gap (liquid crystal セ Le ギヤ Star プ).The light spacer that uses photosensitive polymer combination of the present invention to form can prevent to disturb valid pixel with high-precision spacing and shape configuration column (post).

(black matrix substrate)

Then, the black matrix substrate that uses aforesaid photosensitive black-colored resin composition to form is described.

Black matrix substrate is used to make color filter, described color filter has a plurality of colour element layers and is positioned at the black matrix that becomes the next door of the colour element interlayer of adjacency on substrate, aforesaid photosensitive black-colored resin composition is coated on formation photosensitive black-colored resin composition layer on the substrate, to this photosensitive black-colored resin composition layer irradiation light, make black matrix substrate by photomask by the photosensitive black-colored resin composition layer development that makes irradiation.

Figure 1A～Fig. 1 C is the figure of the manufacture method order of expression black matrix substrate 7.The manufacturing of black matrix substrate 7 is to prepare as the substrate 2 of the base material that forms black matrix and begin.

As substrate 2, for example, except glass substrate, silicon substrate etc., can enumerate resin substrates such as polycarbonate substrate, polyester substrate, aromatic polyamide substrate, polyamideimide-based plate, polyimide substrate.In addition, substrate 2 can be implemented the pre-treatment such as agent treated, Cement Composite Treated by Plasma, ion plating processing, sputter process, gas-phase reaction processing, vacuum evaporation processing by reagent such as silane coupling agent agent.

Then, the aforesaid photosensitive black-colored resin composition of the present invention of coating on surface of thickness direction of substrate 2.As coating process, for example, can use known coating processes such as method of spin coating (spin-coating method), curtain coating rubbing method, roller rubbing method, slot coated method, slit and rotary process, non-rotating coating (スピ Application レスコ one ト) method.After being applied to photosensitive black-colored resin composition on substrate 2 surfaces, drying also makes solvent evaporates, shown in Figure 1A, forms the photosensitive black-colored resin composition layer 1 of the thickness with regulation on substrate 2.

Then, shown in Figure 1B, by 3 pairs of photosensitive black-colored resin composition layers of photomask, 1 irradiation light 4.At this, among Figure 1B, be to use that the photosensitive black-colored resin composition of minus forms and describe with photosensitive black-colored resin composition layer 1.

Photomask 3 for example is provided with light shield layer 32 on surfaces such as glass plates 31 and obtains.By light shield layer 32, light 4 cresteds.The part that light shield layer 32 is not set in the glass plate 31 is transmittance section 33, and light 4 sees through transmittance section 33 and shines photosensitive black-colored resin composition layer 1, and the pattern of photosensitive black-colored resin composition layer 1 transfer printing transmittance section 33 also is exposed.In addition, in order to improve exposure sensitivity, also can be in oxygen barrier film such as glass plate 31 surface coated PVA.

As light 4, use ultraviolet rays such as g line (wavelength 436nm), i line (wavelength 365nm) usually.Preferred light 4 is with directional light irradiation photosensitive black-colored resin composition layer 1, usually by the irradiations such as (not shown) of mask array.Can use the exposure device of known projection exposure device or agency (プロキシ) mode to be undertaken at the exposure of photosensitive black-colored resin composition layer 1, also can use with the maskless describing device of laser and carry out as light source by photomask 3.The exposure of light 4 can be according to the optical source wavelength that uses in the kind of the kind or the content of the content of opacifier in the photosensitive black composition, adhesive resin, the kind with ethylenic unsaturated link and compound that can addition polymerization or content, Photoepolymerizationinitiater initiater or content and the exposure device, pick up wavelength, power and suitably select.

Develop behind the end exposure at photosensitive black-colored resin composition layer 1.During development, photosensitive black-colored resin composition layer 1 after the exposure is contacted with developer solution get final product.

As developer solution, for example can use alkaline aqueous solution.As alkaline aqueous solution, for example can use NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-aqueous solution of water-soluble alkaline compounds such as 7-undecylene, its concentration is with respect to alkaline aqueous solution, in Quality Percentage, be generally 0.001～10 quality %, about preferred 0.01～1 quality %.Above-mentioned alkaline aqueous solution can contain water miscible organic solvent such as methyl alcohol, ethanol, surfactant etc.As developer solution, can be with an organic solvent, for example, the solvent that contains in can the appropriate combination photosensitive black-colored resin composition and using.

Developing method, there is no particular limitation, for example, can be by immersing development method (immersion development method), sprinkle development method, spray development method, the method developments such as (liquid low-lying area (liquid is contained り) development methods) of wing formula (パ De Le) development method.Development temperature is 10～40 ℃ scope normally, development time normally 10～300 seconds.

By developing, in the photosensitive black-colored resin composition layer 1 light 4 non-irradiated light not irradiation area be dissolved in developer solution and be removed.On the other hand, the irradiate light zone of the photosensitive black-colored resin composition layer 1 of light 4 irradiations remains on the substrate 2, shown in Fig. 1 C, can prepare the black matrix substrate 7 that is formed with black matrix (partition pattern) 5BM on substrate 2 surfaces.By development treatment, dissolve the peristome 7a that the part of removing photosensitive black-colored resin composition layer 1 becomes black matrix 5BM.

In the present embodiment, in black matrix substrate 7, preferred 1.2～3.0 μ m of the next door height of black matrix 5BM (thickness of black matrix 5BM) A.The next door height A of black matrix 5BM is less than 1.2 μ m, then can not fill inkjet printing ink for the q.s of realizing the necessary colour saturation of color reproduction at the peristome 7a of black matrix 5BM, and is not preferred.The next door height A surpasses 3.0 μ m, then not only be difficult to prepare the black matrix substrate 7 that has formed high-precision partition pattern, and when using this black matrix substrate 7 to make color filters, it is big that the difference of height in colour element layer and next door becomes, and it is difficult, not preferred that the design of liquid crystal cell becomes.

In addition, in the present embodiment, below the width of cloth B of the black matrix 5BM median septum of black matrix substrate 7 is set in about 50 μ m usually, about preferred 10～20 μ m.In addition, generally be rectangular-shaped as the peristome 7a of the black matrix 5BM of next door institute area surrounded, consider that from the fillibility of printing ink its bight can be that radius is the r shape about number μ m.When the peristome 7a of black matrix 5BM was square, one side length C of its peristome 7a was set in about 20～150 μ m usually.In addition, when the peristome 7a of black matrix 5BM was rectangle, the size of its peristome 7a was set in about 20～150 μ m * 70～500 μ m usually.

The black matrix substrate 7 for preparing after the development treatment when using alkaline aqueous solution as developer solution, is washed after the development treatment, heat treated.In order to make black matrix 5BM not cause dissolving or the such distortion of swelling with respect to the inkjet printing ink enough stability of performance, heat treated was carried out 5～30 minutes with 150～250 ℃ usually.

As above in the black matrix substrate 7 of Zhi Zaoing, black matrix 5BM is owing to use photosensitive black-colored resin composition preparation of the present invention, therefore is made of the next door that is endowed with uniform state with respect to the lyophobicity of inkjet printing ink.Therefore, by the inkjet printing ink of ink jet printing method in the peristome 7a of black matrix 5BM printing, colour mixture takes place in the peristome 7a that can prevent printing ink from exceeding the black matrix 5BM that becomes the next door and invade adjacency, can prevent partly printing ink and fill bad problem, promptly can prevent pixel defectives such as Lou white.

In addition, passing through flight time type secondary ion mass spectrometry meter (Time of FlightSecondary Ion Mass Spectroscopy, abbreviation: TOF-SIMS) in the testing result of the negative ion of Jian Ceing, the detected intensity of whole negative ions of black matrix substrate 7 add up to 1 and the detected intensity ratio of fluorine ion during normalization, surface for the black matrix 5BM that becomes the next door is more than 0.15 and less than 0.3, and preferred below 0.05 for the pairing substrate of the peristome 7a of black matrix 5BM 2 surfaces.

The surface of black matrix 5BM, with the pairing substrate of the peristome 7a of black matrix 5BM 2 surfaces in the detected intensity ratio of fluorine ion, fluorine is the content of surfactant in the photosensitive black-colored resin composition that uses when forming black matrix 5BM by adjusting, and can be controlled at the scope of regulation.

Use is in the content with respect to the fluorine of all solids composition, (8～50ppm) fluorine are photosensitive black-colored resin composition surfactant, aforesaid to contain 0.0008～0.005 quality %, by on substrate 2, forming black matrix 5BM, the detected intensity of the surperficial fluorine ion of black matrix 5BM is than more than 0.15 and less than 0.3, and the detected intensity of the pairing substrate 2 surperficial fluorine ions of peristome 7a that can make black matrix 5BM is than being black matrix substrate 7 below 0.05.

The surface of black matrix 5BM, with the pairing substrate of the peristome 7a of black matrix 5BM 2 surfaces in the black matrix substrate 7 that obtains than the scope that is controlled at aforesaid regulation of the detected intensity of fluorine ion, it has the black matrix 5BM that becomes the next door, and described black matrix 5BM is given with uniform state with respect to the lyophobicity of inkjet printing ink and obtains.Therefore, can prevent to exceed the black matrix 5BM that becomes the next door and printing ink is invaded the peristome 7a of adjacency colour mixture is taken place at the inkjet printing ink of the peristome 7a of black matrix 5BM printing, can prevent partly printing ink simultaneously and fill bad problem, promptly can prevent pixel defectives such as Lou white by ink jet printing method.

The detected intensity of surperficial fluorine ion of black matrix 5BM that becomes the next door is than less than 0.15 o'clock, and the black matrix 5BM that becomes the next door is insufficient with respect to the lyophobicity of inkjet printing ink, and the colour mixture that can not give full play to the colour element interlayer of adjacency prevents effect.Pixel defectives such as in addition, the detected intensity of the surperficial fluorine ion of black matrix 5BM is than 0.3 when above, and near the leakage of the colour element layer generation part substrate 2 peripheral parts (edge part) is white.And then, the detected intensity ratio of the pairing substrate 2 surperficial fluorine ions of the peristome 7a of black matrix 5BM was above 0.05 o'clock, also give lyophobicity for substrate 2 surfaces that are formed with the colour element layer with respect to inkjet printing ink, pixel defectives such as near the leakage of the colour element layer generation part substrate 2 peripheral parts (edge part) is white, the colour mixture that the lyophobicity on the surface of while black matrix 5BM is brought prevents that effect from reducing.

(manufacturing of color filter)

Then, manufacturing method of color filter of the present invention is described.Fig. 2 A and Fig. 2 B are the figure that shows the order of manufacturing method of color filter.Fig. 3 A and Fig. 3 B are the skeleton diagrams that shows color filter structure.Manufacturing method of color filter comprises that black matrix substrate preparation process and pixel layer form step.

＜black matrix substrate preparation process 〉

The black matrix substrate preparation process is the step of preparation black matrix substrate, and as above-mentioned, preparation forms the black matrix substrate 7 of black matrix 5BM on substrate 2.

＜pixel layer forms step 〉

In pixel layer forms step, the pixel region that the next door surrounded that forms on the black matrix substrate 7, be on the peristome 7a of black matrix 5BM by ink jet printing mode printing inkjet printing ink, form the colour element layer.The colour element layer is made of 3 original color color pixel layers of the colour element layer of redness, green colour element layer and blue colour element layer.

Pixel layer forms in the step, shown in Fig. 2 A, corresponding to the shades of colour of the colour element layer that forms, use ink jet printing with a 10R, 10G, 10B, the versicolor inkjet printing ink 11R of printing, 11G, 11B on the peristome 7a of the regulation of black matrix 5BM.As the ink jet printing head, be not particularly limited, can use known heads such as piezoelectricity mode, bubble jet (バ Block Le ジエ Star ト) (registered trademark) mode, electrostatic means, preferred especially piezoelectricity mode.In addition, as inkjet printing ink, can use the monomer of bridging property molecule of the known colorant, spreading agent, utilization heat or the light producing high-molecular that contain the modulation of useful known method or the known inkjet printing ink of oligomer, adhesive resin, polymerization initiator and solvent etc.

When the peristome 7a that versicolor

inkjet printing ink

11R, 11G, 11B are printed on black matrix 5BM regulation goes up, because the solid component concentration of shades of colour printing ink has restriction, therefore in the colour element layer that forms, for obtain desired bed thickness and colour saturation, with respect to the volume (aperture area * next door height) of the peristome 7a of black matrix 5BM, the printing several times are necessary with

inkjet printing ink

11R, 11G, the 11B of upper volume.

The pixel layer of present embodiment forms in the step, the peristome 7a that has given with respect to the black matrix 5BM of the lyophobicity of

inkjet printing ink

11R, 11G, 11B with uniform state goes up printing shades of

colour printing ink

11R, 11G, 11B, colour mixture takes place in the peristome 7a that can prevent printing ink from exceeding the black matrix 5BM that becomes the next door and invade adjacency, can prevent partly printing ink and fill bad problem, promptly can prevent pixel defectives such as Lou white.

The peristome 7a of the regulation of black matrix 5BM goes up the versicolor inkjet printing ink 11R of printing, 11G, 11B, be exposed to heat or light, then shown in Fig. 2 B, corresponding to the peristome 7a of the black matrix 5BM that is printed with shades of colour printing ink, form the colour element layer 5G and the blue colour element layer 5B of red colour element layer 5R, green.Like this, as shown in Figure 3A, can be manufactured on the substrate 2 color filter 6 that forms by the black matrix 5BM that becomes the next door of the colour element layer 5R of 3 primary colors, colored pattern 5 that 5G, 5B constitute and the colour element interlayer that is positioned at adjacency.Color filter 6 as shown in Figure 3A, corresponding to the peristome 7a that forms foursquare black matrix 5BM, versicolor

colour element layer

5R, 5G, 5B have been formed, corresponding to the peristome 7a that forms rectangular black matrix 5BM, form versicolor

colour element layer

5R, 5G, 5B, thus, color filter 60 shown in can shop drawings 3B.

(embodiment)

Below, using embodiment and then explain the present invention, the present invention is not limited to these embodiment.

(fluorine is the influence of surface-active contents in the photosensitive black-colored resin composition)

＜fluorine is the synthetic of surfactant 〉

[fluorine is the synthetic of surfactant 1]

Possessing stirring apparatus, condenser pipe, in the glass flask of thermometer, add acrylate list amount body 29 weight portions that contain fluoro-alkyl shown in the following formula (4), the unsaturated list amount of organosilyl ethylenic that contains body 26 weight portions shown in the following formula (5), side chain has mono acrylic ester compound (single end is a methoxy-ether) 45 weight portions of polyoxyethylene (molecular weight 400), propylene glycol monomethyl ether 200 weight portions, in the stream of nitrogen gas, reflux down, dropping is as azobis isobutyronitrile 1 weight portion of polymerization initiator, carried out polyreaction in 12 hours 80 ℃ of backflows, obtaining fluorine is surfactant 1.

[chemical formula 6]

[chemical formula 7]

Fluorine is that surfactant 1 is following compound, promptly is to have in formula (1a) R ¹Be methyl, X ¹Be-CO ₂-, L ¹Be ethylidene, R ²Be-(Si (CH ₃) ₂O) ₁-Si (CH ₃) ₃Structural unit 26 quality %; In formula (1b), R ³Be hydrogen atom, L ²Be singly-bound, R ⁴Be that ethylidene, n are 9, R ⁵Be the structural unit 45 quality % of methyl; And in formula (1c), R ⁶Be methyl, X ²Be-CO ₂-, L ³Be that ethylidene, Rf are the compounds of ratio of the structural unit 29 quality % of perfluoro hexyl.

[fluorine is the synthetic of surfactant 2]

Except mono acrylic ester compound (single end is a methoxy-ether) 58 weight portions that unsaturated single amount body 18 weight portions of organosilyl ethylenic, side chain have polyoxyethylene (molecular weight 400) that contain shown in acrylate list amount body 21 weight portions that contain fluoro-alkyl shown in the formula of changing to (4), the formula (5), and then add beyond 2-hydroxyethyl-methacrylate 3 weight portions, with fluorine be that surfactant 1 is similarly operated and carried out polyreaction, obtaining fluorine is surfactant 2.

Fluorine is that surfactant 2 is following compounds, promptly is to have in formula (1a) R ¹Be methyl, X ¹Be-CO ₂-, L ¹Be ethylidene, R ²Be-(Si (CH ₃) ₂O) ₁-Si (CH ₃) ₃Structural unit 18 quality %; In formula (1a), R ¹Be methyl, X ¹Be-CO ₂-, L ¹Be ethylidene, R ²Be the structural unit 3 quality % of hydroxyl; In formula (1b), R ³Be hydrogen atom, L ²Be singly-bound, R ⁴Be that ethylidene, n are 9, R ⁵Be the structural unit 58 quality % of methyl; And in the formula (1c), R ⁶Be methyl, X ²Be-CO ₂-, L ³Be that ethylidene, Rf are the compounds of ratio of the structural unit 21 quality % of perfluoro hexyl.

(embodiment 1)

With opacifier [black pigment (C.I. pigment black 7) 40 mass parts and polycarbamate are the potpourri of spreading agent 12 mass parts] 52 mass parts, adhesive resin [resultant of reaction of compound 300 mass parts shown in the following formula (6) and biphenyl tetracarboxylic dianhydride 50 mass parts and tetrabydrophthalic anhydride 50 mass parts] 33 mass parts, have ethylenic unsaturated link and compound dipentaerythritol acrylate 11 mass parts that can addition polymerization, 2 of Photoepolymerizationinitiater initiater, two (the trichloromethyl)-6-piperonyls-1 of 4-, 3,5-triazine 5.0 mass parts, photopolymerization causes dimetone 3.0 mass parts of auxiliary agent, 0.68 mass parts is (with respect to the content of all solids composition: 65ppm, fluorine content with respect to all solids composition: 11ppm) fluorine is a surfactant 1, mix with propylene glycol monomethyl ether 358 mass parts of solvent, obtain the photosensitive black-colored resin composition of embodiment 1.

[chemical formula 8]

(embodiment 2)

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition is that 130ppm is (with respect to the fluorine content of all solids composition: 22ppm), similarly to Example 1, obtain the photosensitive black-colored resin composition of embodiment 2.

(embodiment 3)

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition is that 210ppm is (with respect to the fluorine content of all solids composition: 35ppm), similarly to Example 1, obtain the photosensitive black-colored resin composition of embodiment 3.

(embodiment 4)

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition is that 160ppm is (with respect to the fluorine content of all solids composition: 27ppm), similarly to Example 1, obtain the photosensitive black-colored resin composition of embodiment 4.

(embodiment 5)

By fluorine is that to change to fluorine be surfactant 2 to surfactant 1, except the fluorine with respect to all solids composition is that the content of surfactant 2 is that 260ppm is (with respect to the fluorine content of all solids composition: 45ppm), similarly to Example 1, obtain the photosensitive black-colored resin composition of embodiment 5.

(comparative example 1)

Except not adding fluorine is the surfactant 1, similarly to Example 1, obtains the photosensitive black-colored resin composition of comparative example 1.

(comparative example 2)

By fluorine is that surfactant 1 changes to the silicon-type surfactant shown in the following formula (7), except the content with respect to the surfactant of all solids composition is 100ppm, similarly to Example 1, obtain the photosensitive black-colored resin composition of comparative example 2.

[chemical formula 9]

[in the formula, POA represents the polyoxyalkylene structure.In addition, Ac represents acetyl group.]

(comparative example 3)

The addition of the silicon-type surfactant shown in the change formula (7), same with comparative example 2 except the content with respect to the surfactant of all solids composition is 80ppm, obtain the photosensitive black-colored resin composition of comparative example 3.

(comparative example 4)

The addition of the silicon-type surfactant shown in the change formula (7), same with comparative example 2 except the content with respect to the surfactant of all solids composition is 160ppm, obtain the photosensitive black-colored resin composition of comparative example 4.

(comparative example 5)

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition is that 32ppm is (with respect to the fluorine content of all solids composition: 6ppm), similarly to Example 1, obtain the photosensitive black-colored resin composition of comparative example 5.

(comparative example 6)

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition is that 320ppm is (with respect to the fluorine content of all solids composition: 54ppm), similarly to Example 1, obtain the photosensitive black-colored resin composition of comparative example 6.

The manufacturing of＜black matrix substrate 〉

Photosensitive black-colored resin composition with embodiment 1～5 and comparative example 1～6 utilizes spin-coating method to be coated on alkali-free glass substrate (model: #1737 respectively, コ one ニ Application グ Co., Ltd. system) on, heated for 90 seconds at 100 ℃ after the vacuum drying, on alkali-free glass substrate, form the photosensitive black-colored resin composition layer of the solid constituent that contains each photosensitive black-colored resin composition.The photosensitive black-colored resin composition layer that forms is carried out the coating condition that 230 ℃ * 20 minutes thickness after the thermal treatment are reflected as spin coater, adjust the thickness of the thickness of photosensitive black-colored resin composition layer thus for regulation.The thickness of this photosensitive black-colored resin composition layer becomes black matrix median septum height described later.Thickness uses film thickness gauge (trade name: Dektak, the ULVAC of Co., Ltd. system) to measure.

Then, on the alkali-free glass substrate that has formed the photosensitive black-colored resin composition layer, the photomask of the partition pattern by having regulation, (exposure is 100mJ/cm with proximity gap 150 μ m irradiation ultraviolet radiations ²: convert with the I line) expose.As partition pattern, use possesses and has CD19 μ m, the photomask of the repeat patterns of rectangular peristome 66 * 226 μ m.

Then, photosensitive black-colored resin composition layer after the exposure is passed through developer solution (CD liquid: the Off イ of Fuji Le system エレ Network トロニ Network マテリア Le Co., Ltd. system, dilute 50 times) carry out 26 ℃ * 80 seconds sprinkle develop, then wash with pure water, in cleaning oven, burnt till, obtained forming the black matrix substrate of black matrix (partition pattern) by 230 ℃ * 20 minutes.

For the black matrix in the black matrix substrate of the photosensitive black-colored resin composition manufacturing of using embodiment 4 and embodiment 5, measure the contact angle that uses various standard solvent, utilize the Zismann method to measure surface energy, measurement result is respectively 22.9nN/m and 23.0nN/m.

The manufacturing of＜color filter 〉

[preparation of inkjet printing ink]

Preparation contains the C.I. pigment blue 15 of 15 mass parts as colorant: 6,2 mass parts C.I. pigment Violet 23s, 7 mass parts polyester are that spreading agent, surplus are the blue-colored agent dispersing liquid as the dipropylene glycol monomethyl ether acetate (DPMA) of solvent.Similarly according to forming preparation green coloring agent dispersing liquid and red colored agent dispersing liquid shown in the table 1.

[table 1]

In the table 1, PR242 represents C.I. paratonere 242, and PR177 represents C.I. paratonere 177, and PG36 represents the C.I. pigment green 36, and PY150 represents C.I. pigment yellow 150, and PB15:6 represents the C.I. pigment blue 15: 6, and PV23 represents the C.I. pigment Violet 23.In addition, EDGAC represents diethylene glycol monoethyl ether acetate, and DPMA represents the dipropylene glycol monomethyl ether acetate.

Add acryl resin 4 mass parts in blue pigment dispersion liquid 61 mass parts of preparation, as diglycol monotertiary butyl ether (BDG) 35 mass parts of solvent, prepare blue inkjet printing ink.Similarly, prepare green inkjet printing ink, red inkjet printing ink according to forming shown in the table 2.

[table 2]

In the table 2, EDGAC represents diethylene glycol monoethyl ether acetate, and DPMA represents the dipropylene glycol monomethyl ether acetate, and BDG represents the diglycol monotertiary butyl ether.

[preparation of color filter]

In the peristome of the black matrix in each black matrix substrate that the photosensitive black-colored resin composition that uses embodiment 1～5 and comparative example 1～6 is made, use the ink jet printing head, fill red ink 120pL, green ink 120pL, blue ink 130pL simultaneously, 40 ℃ * 2 minutes predrying after, toasted the preparation color filter at 230 ℃ * 20 minutes.

[evaluation]

Each color filter for as above preparing carries out visualization and microscopic examination, and evaluation is filled situation at the printing ink of the peristome of black matrix, the adjacent pixels interlayer has non-mixed color.Fill situation as printing ink, pay special attention to the periphery (edges abut pixel) of color filter picture and go up the printing ink filling that takes place bad (leaking white), estimate in the lump with the occupied state of picture central portion.Do not leak the living situation of white hair and be " zero ", the situation that has the leakage white hair to give birth to is " * ".As the colour mixture of adjacent pixels interlayer, the situation that colour mixture does not take place is " zero ", and the situation that colour mixture takes place is " * ".And as comprehensive evaluation, any one situation that does not all have to take place of " leaking white " and " colour mixture " is " zero ", and the situation that any one takes place is " * ".Evaluation result is as shown in table 3.

[table 3]

Can be clear and definite by table 3, in the content with respect to the fluorine of all solids composition, containing 8～50ppm fluorine is surfactant, uses the color filter of the photosensitive black-colored resin composition preparation of embodiment 1～5, colour mixture does not take place, and pixel defectives such as white do not take place to leak yet.

In addition, Fig. 4 represents to use the surperficial enlarged photograph of color filter of the photosensitive black-colored resin composition preparation of embodiment, and Fig. 5 represents to use the surperficial enlarged photograph of color filter of the photosensitive black-colored resin composition preparation of comparative example.In the surperficial enlarged photograph of Fig. 4,5 color filter, pixel defectives such as color filter generation colour mixture, the leakage of the photosensitive black-colored resin composition preparation of use comparative example is white are used the color filter of the photosensitive black-colored resin composition preparation of embodiment that colour mixture does not take place in contrast, are leaked pixel defectives such as white.

(influence of the detected intensity of fluorine ion ratio in the black matrix substrate)

The preparation of＜photosensitive black-colored resin composition 〉

[preparation of photosensitive black-colored resin composition 1]

With opacifier [black pigment (C.I. pigment black 7) 40 mass parts and polycarbamate are the potpourri of spreading agent 12 mass parts] 52 mass parts, adhesive resin [resultant of reaction of compound 300 mass parts shown in the above-mentioned formula (6) and biphenyl tetracarboxylic dianhydride 50 mass parts and tetrabydrophthalic anhydride 50 mass parts] 33 mass parts, have ethylenic unsaturated link and compound dipentaerythritol acrylate 11 mass parts that can addition polymerization, 2 of Photoepolymerizationinitiater initiater, two (the trichloromethyl)-6-piperonyls-1 of 4-, 3,5-triazine 5.0 mass parts, photopolymerization causes dimetone 3.0 mass parts of auxiliary agent, 2.8 mass parts is (with respect to the content of all solids composition: 260ppm, fluorine content with respect to all solids composition: 47ppm) fluorine is a surfactant 1, mix with propylene glycol monomethyl ether 358 mass parts of solvent, obtain photosensitive black-colored resin composition 1.

[preparation of photosensitive black-colored resin composition 2]

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition is that 210ppm is (with respect to the fluorine content of all solids composition: 40ppm), same with photosensitive black-colored resin composition 1, obtain photosensitive black-colored resin composition 2.

[preparation of photosensitive black-colored resin composition 3]

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition is that 105ppm is (with respect to the fluorine content of all solids composition: 20ppm), same with photosensitive black-colored resin composition 1, obtain photosensitive black-colored resin composition 3.

[preparation of photosensitive black-colored resin composition 4]

Except not adding fluorine is the surfactant 1, same with photosensitive black-colored resin composition 1, obtains photosensitive black-colored resin composition 4.

[preparation of photosensitive black-colored resin composition 5]

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition be 35ppm (with respect to the fluorine content of all solids composition: same 6ppm) with photosensitive black-colored resin composition 1, obtain photosensitive black-colored resin composition 5.

[preparation of photosensitive black-colored resin composition 6]

The change fluorine is the addition of surfactant 1, except the content with respect to all solids composition is that 315ppm is (with respect to the fluorine content of all solids composition: 57ppm), same with photosensitive black-colored resin composition 1, obtain photosensitive black-colored resin composition 6.

The manufacturing of＜black matrix substrate 〉

(embodiment 6)

Utilize spin-coating method to be coated on alkali-free glass substrate (type kind: #1737 photosensitive black-colored resin composition 1, コ one ニ Application グ Co., Ltd. system) on, after the vacuum drying, heated for 90 seconds down at 100 ℃, on alkali-free glass substrate, form the photosensitive black-colored resin composition layer of the solid constituent that contains photosensitive black-colored resin composition 1.The thickness of photosensitive black-colored resin composition layer after heat-treating 20 minutes under 230 ℃ that forms is reflected as the coating condition of spin coater, adjusts the thickness of the thickness of photosensitive black-colored resin composition layer thus for regulation.The thickness of this photosensitive black-colored resin composition layer becomes black matrix median septum height described later.Thickness uses film thickness gauge (trade name: Dektak, the ULVAC of Co., Ltd. system) to measure, and its result is 1.6 μ m.

Then, photosensitive black-colored resin composition layer after the exposure is passed through developer solution (CD liquid: the Off イ of Fuji Le system エレ Network トロニ Network マテリア Le Co., Ltd. system, dilute 50 times) carry out 26 ℃ 80 second sprinkle develop, then wash with pure water, in cleaning oven,, obtained forming the black matrix substrate of the embodiment 6 of black matrix (partition pattern) by carrying out burning till in 20 minutes at 230 ℃.

For the black matrix substrate of the embodiment 6 that obtains, use TRIFT2 (the mensuration beam diameter: the fluorine ion in the pairing substrate surface of peristome of the surface of mensuration black matrix and black matrix 5～10 μ m) of the Physical Electronics society system of flight time type secondary ion mass spectrometry meter (TOF-SIMS).Carry out on the uper side surface that is determined near the bad pairing black matrix of the portion in edge of easy generation printing ink filling of fluorine ion and the peristome surface of black matrix, compares with respect to each surperficial all strength ratio of the integrated value of the signal intensity of negative ions with fluorine ion.

The measurement result of fluorine ion is in the black matrix substrate of embodiment 6, and the detected intensity ratio of the uper side surface fluorine ion of black matrix is 0.28, and the detected intensity ratio of the pairing substrate surface fluorine ion of the peristome of black matrix is 0.03.

(embodiment 7)

Except photosensitive black-colored resin composition 1 being changed to photosensitive black-colored resin composition 2, similarly to Example 6, obtaining the next door height is the black matrix substrate of the embodiment 7 of 1.5 μ m.The measurement result of fluorine ion is in the black matrix substrate of embodiment 7, and the detected intensity ratio of the uper side surface fluorine ion of black matrix is 0.22, and the detected intensity ratio of the pairing substrate surface fluorine ion of the peristome of black matrix is 0.02.

(embodiment 8)

Except photosensitive black-colored resin composition 1 being changed to photosensitive black-colored resin composition 3, similarly to Example 6, obtaining the next door height is the black matrix substrate of the embodiment 8 of 2.3 μ m.The measurement result of fluorine ion is in the black matrix substrate of embodiment 8, and the detected intensity ratio of the uper side surface fluorine ion of black matrix is 0.29, and the detected intensity ratio of the pairing substrate surface fluorine ion of the peristome of black matrix is 0.04.

(comparative example 7)

Except photosensitive black-colored resin composition 1 being changed to photosensitive black-colored resin composition 4, similarly to Example 6, obtaining the next door height is the black matrix substrate of the comparative example 7 of 1.6 μ m.The measurement result of fluorine ion is in the black matrix substrate of comparative example 7, and the detected intensity ratio of the uper side surface fluorine ion of black matrix is below 0.001, and the detected intensity ratio of the pairing substrate surface fluorine ion of the peristome of black matrix is below 0.001.

(comparative example 8)

Except photosensitive black-colored resin composition 1 being changed to photosensitive black-colored resin composition 5, similarly to Example 6, obtaining the next door height is the black matrix substrate of the comparative example 8 of 1.6 μ m.The black matrix substrate of comparative example 8 in the measurement result of fluorine ion is, the detected intensity ratio of the uper side surface fluorine ion of black matrix is 0.12, and the detected intensity ratio of the pairing substrate surface fluorine ion of the peristome of black matrix is 0.02.

(comparative example 9)

Except photosensitive black-colored resin composition 1 being changed to photosensitive black-colored resin composition 6, similarly to Example 6, obtaining the next door height is the black matrix substrate of the comparative example 9 of 1.6 μ m.The measurement result of fluorine ion is in the black matrix substrate of comparative example 9, and the detected intensity ratio of the uper side surface fluorine ion of black matrix is 0.33, and the detected intensity ratio of the pairing substrate surface fluorine ion of the peristome of black matrix is 0.18.

The manufacturing of＜color filter 〉

[preparation of inkjet printing ink]

Preparation contains the C.I. pigment blue 15 of 15 mass parts colorants: 6,2 mass parts C.I. pigment Violet 23s, polyester are the blue-colored agent dispersing liquid of dipropylene glycol monomethyl ether acetate 77 mass parts of spreading agent 7 mass parts, solvent.Similarly, according to the composition shown in the above-mentioned table 1, preparation green coloring agent dispersing liquid and red colored agent dispersing liquid.

Add dipropylene glycol butyl ether 35 mass parts of acryl resin 4 mass parts, solvent in blue pigment dispersion liquid 61 mass parts of preparation, prepare blue inkjet printing ink.Similarly, according to the composition shown in the above-mentioned table 2, prepare green inkjet printing ink, red inkjet printing ink.

[preparation of color filter]

On the peristome of the black matrix in the black matrix substrate of embodiment 6～8 and comparative example 7～9, use the ink jet printing head, fill red ink 120pL, green ink 120pL, blue ink 130pL simultaneously, after under 40 ℃ predrying 2 minutes, toast 20 minutes preparation color filters down at 230 ℃.

[evaluation]

Each color filter for as above preparing carries out visualization and microscopic examination, and evaluation is filled situation at the printing ink of the peristome of black matrix, the adjacent pixels interlayer has non-mixed color.Fill situation as printing ink, pay special attention to the periphery (edges abut pixel) of color filter picture and go up the printing ink filling that takes place bad (leaking white), estimate in the lump with the occupied state of picture central portion.Do not leak the living situation of white hair and be " zero ", the situation that has the leakage white hair to give birth to is " * ".As the colour mixture of adjacent pixels interlayer, the situation that colour mixture does not take place is " zero ", and the situation that colour mixture takes place is " * ".And, as comprehensive evaluation, when " leak white " and " colour mixture " any one evaluation result all is " zero ", be " zero ", when any one is " * ", be " * ".Evaluation result is as shown in table 4.

[table 4]

Show by table 4, the detected intensity ratio of the surperficial fluorine ion of black matrix is more than 0.15 and less than 0.3, and the detected intensity of the pairing substrate surface fluorine ion of the peristome of black matrix ratio is below 0.05, use the color filter of the black matrix substrate preparation of embodiment 6～8, colour mixture does not take place, and pixel defectives such as white do not take place to leak yet.

The present invention does not break away from its purport or principal character, can implement with other variety of ways.Therefore, aforesaid embodiment is an illustration only in all respects, and scope of the present invention is not illustrated book and limits shown in claims.And then, belong to claims distortion or the change also all within the scope of the invention.

Claims

1. photosensitive black-colored resin composition, it is the photosensitive black-colored resin composition that is used to form black matrix, described black matrix is the black matrix of color filter of black matrix that has a plurality of colour element layers and be arranged in the colour element interlayer of adjacency on substrate, it is characterized in that,

In the content with respect to the fluorine of all solids composition, containing 0.0008～0.005 quality % has fluoro-alkyl on side chain fluorine is surfactant.

2. photosensitive black-colored resin composition according to claim 1, it is characterized in that, above-mentioned fluorine is a surfactant, total 100 quality % with the entire infrastructure unit are benchmark, it is compound with the ratio of structural unit 1～40 quality % shown in structural unit 20～98 quality % shown in structural unit 1～40 quality % shown in the following formula (1a), the following formula (1b) and the following formula (1c)

[Chemical formula 1 0]

In the formula, R ¹, R ³And R ⁶The alkyl of representing hydrogen atom or carbon number 1～5 independently of one another, R ²The alkyl of expression hydrogen atom, carbon number 1～5, hydroxyl or-(Si (CH ₃) ₂O) _m-Si (CH ₃) ₃, R ⁴The alkylidene of expression carbon number 2～8, R ⁵The aryl of alkyl, acyl group or the carbon number 6～20 of expression hydrogen atom, carbon number 1～12, L ¹, L ², and L ³Represent singly-bound, alkylidene or substituted alkylene independently of one another, X ¹Expression-CO ₂-,-CONY ¹-or arlydene, X ²Expression-O-,-CO ₂-,-CONY ²-, the heterocycle residue of arlydene or divalent, Rf represents fluoro-alkyl, n represents 2～20 integer, m represents 0～3 integer, Y ¹And Y ²The alkyl of representing hydrogen atom or carbon number 1～5 independently of one another.

3. black matrix substrate, it is the black matrix substrate that has formed the black matrix of using claim 1 or 2 described photosensitive black-colored resin composition preparations, it is used to be manufactured on the color filter of the black matrix of the colour element interlayer that has a plurality of colour element layers on the substrate and be positioned at adjacency, and it is the black matrix substrate that has formed the black matrix with peristome.

4. black matrix substrate according to claim 3, it is characterized in that, utilize in the testing result of the negative ion that flight time type secondary ion mass spectrometry meter (TOF-SIMS) detects, the detected intensity ratio that adds up to 1 o'clock fluorine ion of the detected intensity of whole negative ions, surface for black matrix is more than 0.15 and less than 0.3, and is below 0.05 for the pairing substrate surface of the peristome of black matrix.

5. according to claim 3 or 4 described black matrix substrates, it is characterized in that the thickness of black matrix is below above-3.0 μ m of 1.2 μ m.

6. manufacturing method of color filter, this method are the manufacturing method of color filter of black matrix that has a plurality of colour element layers and be positioned at the colour element interlayer of adjacency on substrate, it is characterized in that, comprising:

Use claim 1 or 2 described photosensitive black-colored resin compositions, on substrate, form black matrix, the black matrix substrate preparation process of preparation black matrix substrate and

In the pixel region that the pairing next door of peristome of the black matrix that forms on black matrix substrate is surrounded, the pixel layer that forms the colour element layer by ink jet printing mode printing inkjet printing ink forms step.