CN101317108A - Method for manufacture of color filter, color filter, and display device - Google Patents

Abstract

Disclosed is a method for manufacture of a color filter, which can form a pixel with highly precise alignment and free from the concern of undesirable color mixing, and can manufacture a color filter that shows no display unevenness when installed in a display element at low cost and with high efficiency. The method comprises: forming septa each having a light-shielding property on a substrate; spraying each of a red-colored ink (R), a green-colored ink (G) and a blue-colored ink (B) onto a concave part formed by partitioning with the septa by ink-jet system to accumulate each of the inks R, G and B on the concave part, thereby forming colored layers having each of the three colors; irradiating the colored layers with an active energy ray to cure all of the colored layers, and further curing the colored layers with heat, wherein each of the inks comprises a polymerizable ink comprising a coloring agent, a polymerizable compound and a polymerization initiator and the amout of solvent in the ink is less than 50wt%.

Description

Manufacturing method of color filter, color filter and display device

Technical field

The present invention relates to color filter and manufacture method thereof, and display device.

Background technology

Display device has with color filter: on substrates such as glass respectively with red, green, the blue scattergram picture of rectangular configuration, the structure that its border is divided with dark dividing walls such as black matrixes.As such manufacturing method of color filter, what knew is method as described below in the past, that is: as substrates such as supporter use glass, utilize 1) decoration method, 2) print process, 3) carry out the coating of painted photoresist liquid repeatedly, exposure and coloring phototonus resin liquid method (the painted resist method of developing, for example, open clear 63-298304 communique with reference to the Jap.P. spy), 4) will be formed at image on the interim supporter be needed on successively on the final or interim supporter method (for example, Jap.P. is opened clear 61-99103 communique with reference to the spy), 5) by being coated on, painted in advance photoresist liquid forms dyed layer on the interim supporter, direct this photosensitive color layer of transfer printing on substrate successively, and expose and develop, and the method for number of times that said process is repeated the number of aforesaid operations color waits the method (transfer printing mode) (for example, opening clear 61-99102 communique with reference to the Jap.P. spy) that forms multicolor image.In addition, the method for knowing (for example, with reference to Japanese patent laid-open 8-227012 communique) that the use ink-jet method is arranged.

In these methods, though painted resist method can the positional precision highland makes color filter, in the coating of photographic layer resin liquid loss many, the not talkative cost that helps.On the other hand, in the ink-jet method, the resin liquid loss is few, and helps cost, but has the problem of locations of pixels low precision.In order to overcome these problems, also proposed to form black matrix with painted resist method, make the manufacturing method of color filter of rgb pixel of ink-jet method.But, just find that upper end or its edge form circle if observe the section shape of the black matrix that forms with this manufacture method, drip the of all kinds black liquid of penetrating afterwards and cross black matrix easily, therefore, exist cause ooze out, overflow, with the trouble of the colour mixture of pixel adjacent and dawn etc.In order to prevent this problem, the character that makes black matrix and black liquid have mutual repulsion is disclosed, or improve and deceive the method (for example, with reference to Japanese patent laid-open 6-347637 communique, Japanese patent laid-open 7-35915 communique, Japanese patent laid-open 10-142418 communique) of matrix clearance portion the wetting state of black liquid.But in these methods, black matrix needs special starting material with painted resist or black liquid, maybe needs to improve the operation (surface modification treatment) of the surface energy of deceiving the matrix clearance portion, causes the problem on the cost.In addition, disclose adopt use monofunctional monomer and polyfunctional monomer and adhere to after the black liquid that solidifies with active ray immediately, the method for boosting productivity (for example, opening the 2002-371216 communique) with reference to the Jap.P. spy.But the characteristic of this China ink liquid is insufficient, causes when being installed to display device, and unequal problem takes place to show.

Summary of the invention

The present invention makes in view of described problem in the past, and manufacturing method of color filter, color filter and display device are provided.

The inventor etc. carry out intent research in view of such actual conditions in order to address the above problem.It found that, by using the polymerism China ink liquid of no-solvent type, utilize ink-jetting style to form pixel, can prevent to become the oozing out of black liquid of all kinds, overflow, with the unfavorable condition of defectives such as the colour mixture of pixel adjacent and dawn, can access the good color filter that does not show inequality, thereby the inventor etc. have finished the present invention.

That is, the invention provides following method etc.

First viewpoint of the present invention provides a kind of manufacturing method of color filter, on substrate, form next door with light-proofness, utilize ink-jetting style, to the recess spraying red (R) of dividing by this next door, the black liquid of green (G) and blue (B), make described R, G, and B China ink liquid is deposited in described recess and forms dyed layer, used the dyed layer of each black liquid in formation after, utilize the curing of the dyed layer of activation-energy-ray, after the curing of panchromatic dyed layer, utilize the curing of the dyed layer of heat again, wherein, described each black liquid is formed by polymerism China ink liquid, described polymerism China ink liquid contains colorant, polymerizable compound and polymerization initiator, and the quantity of solvent in the black liquid is below the 50 weight %.Second viewpoint of the present invention provides according to the described manufacturing method of color filter of first viewpoint, and wherein, the quantity of solvent in the black liquid is that the following polymerism China ink liquid of 50 weight % is free-radical polymerised composition.

The 3rd viewpoint of the present invention provides according to the described manufacturing method of color filter of first viewpoint, and wherein, the quantity of solvent in the black liquid is that the following polymerism China ink liquid of 50 weight % is cationically polymerizable composition.

The 4th viewpoint of the present invention provides according to each described manufacturing method of color filter in first～the 3rd, wherein, uses the photosensitive composite that contains colorant, polymerizable compound and Photoepolymerizationinitiater initiater to form the next door with light-proofness on the substrate.

The 5th viewpoint of the present invention provides according to the described manufacturing method of color filter of the 4th viewpoint, and wherein, the height with next door of light-proofness is 1～20 μ m.

The 6th viewpoint of the present invention provides the color filter that each described manufacturing method of color filter of utilizing first～the 5th viewpoint is made.

The 7th viewpoint of the present invention provides the display device that the described color filter of the 6th viewpoint has been installed.

Can provide according to the present invention, can positional precision form pixel that does not have colour mixture etc. and the manufacturing method of color filter that can make color filter with low cost and high-level efficiency well.

In addition, can provide according to the present invention, can provide positional precision to have well not have colour mixture etc. pixel, do not show uneven color filter when being installed on display device.

And then, can provide according to the present invention, can provide not show uneven display device.

Embodiment

Below, describe the present invention in detail.

Manufacturing method of color filter of the present invention is to form the next door with light-proofness on substrate, utilize ink-jetting style, to the recess spraying red (R) of dividing by this next door, the black liquid of green (G) and blue (B), make described R, G, and B China ink liquid is deposited in described recess and forms dyed layer, used the dyed layer of each black liquid in formation after, utilize the curing of the dyed layer of activation-energy-ray, after the curing of panchromatic dyed layer, utilize the manufacturing method of color filter of the curing of hot dyed layer again, described each black liquid is formed by polymerism China ink liquid, described polymerism China ink liquid contains colorant, polymerizable compound and polymerization initiator, and the quantity of solvent in the black liquid is below the 50 weight %.

In the present invention, each polymerism China ink liquid carries out photographic fixing because the UV after utilizing record solidifies, therefore, volatile ingredient is few, in addition, because volumetric contraction is little after solidifying, therefore, thickness is homogeneous in the effective range of pixel, thereby can improve the homogeneity of thickness of homogeneity, the liquid crystal layer of look.

On the other hand, in the system of using the black liquid of dilution,, need to drip and penetrate a large amount of black liquid,, need give sufficient ink-resistant fluidity to dividing plate in order to prevent colour mixture for the optical concentration that shows that rgb pixel is required.But, in the present invention, use no-solvent type polymerism China ink liquid, can reduce and drip the amount of penetrating, therefore, do not need to give excessive ink-resistant fluidity, can realize that the shorteningization of production process and cost reduce.

In addition, by share curing process and heat curing operation, can improve the manufacturing efficient and the characteristic of color filter simultaneously based on activation-energy-ray.

Below, polymerism China ink liquid at first is described.

[polymerism China ink liquid]

The polymerism that uses among the present invention China ink liquid comprises: contain colorant, polymerizable compound, and polymerization initiator, and utilize the activation-energy-ray polymerization reaction take place and the polymerism coloured composition that solidifies.

(colorant)

Can add known colorant (dyestuff, pigment) in the above-mentioned colored resin composition.When using the pigment in this known colorant, pigment optimization is dispersed in the colored resin composition, so the particle diameter of pigment is preferably below the 0.1 μ m, more preferably below the 0.08 μ m.

The example of above-mentioned known dyestuff or pigment comprises: Victoria's pure blue B O (C.I.42595), aramine (C.I.41000), H B (C.I.26150) is deceived in liposoluble, C.I. pigment yellow 1, C.I. pigment yellow 3, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 5, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 60, C.I. pigment yellow 61, C.I. pigment yellow 65, C.I. pigment yellow 71, C.I. pigment yellow 73, C.I. pigment yellow 74, C.I. pigment yellow 81, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 95, C.I. pigment yellow 97, C.I. pigment yellow 98, C.I. pigment yellow 100, C.I. pigment yellow 101, C.I. pigment yellow 104, C.I. pigment yellow 106, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 113, C.I. pigment yellow 114, C.I. pigment yellow 116, C.I. pigment yellow 117, C.I. pigment yellow 119, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 6, C.I. pigment Yellow 12 7, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 152, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 156, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 17 5, C.I. pigment yellow 180, C.I. pigment yellow 185;

C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73; C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38;

C.I. paratonere 1, C.I. paratonere 2, C.I. pigment red 3, C.I. pigment red 4, C.I. paratonere 5, C.I. paratonere 6, C.I. paratonere 7, C.I. paratonere .8, C.I. Pigment Red 9, C.I. paratonere 10, C.I. paratonere 11, C.I. paratonere 12, C.I. paratonere 14, C.I. paratonere 15, C.I. paratonere 16, C.I. paratonere 17, C.I. paratonere 18, C.I. paratonere 19, C.I. pigment red 21, C.I. paratonere 22, C.I. paratonere 23, C.I. pigment red 30, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 37, C.I. pigment red 38, C.I. pigment red 40, C.I. pigment red 41, C.I. pigment red 42, C.I. pigment red 4 8:1, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. pigment red 4 9:1, C.I. pigment red 4 9:2, C.I. paratonere 50:1, C.I. paratonere 52:1, C.I. paratonere 53:1, C.I. paratonere 57, C.I. paratonere 57:1, C.I. paratonere 57:2, C.I. paratonere 58:2, C.I. paratonere 58:4, C.I. paratonere 60:1, C.I. paratonere 63:1, C.I. paratonere 63:2, C.I. paratonere 64:1, C.I. pigment red 81: 1, C.I. pigment Red 83, C.I. pigment Red 88, C.I. Pigment Red 9 0:1, C.I. Pigment Red 97, C.I. paratonere 101, C.I. paratonere 102, C.I. paratonere 104, C.I. paratonere 105, C.I. paratonere 106, C.I. paratonere 108, C.I. pigment red 112, C.I. paratonere 113, C.I. paratonere 114, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 146, C.I. pigment red 149, C.I. paratonere 150, C.I. paratonere 151, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 172, C.I. paratonere 174, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 188, C.I. paratonere 190, C.I. paratonere 193, C.I. paratonere 194, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 208, C.I. paratonere 209, C.I. pigment red 21 5, C.I. pigment red 21 6, C.I. paratonere 220, C.I. paratonere 224, C.I. paratonere 226, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 245, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 264, C.I. paratonere 265;

C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60

C.I. pigment Green 7, C.I. pigment green 36

C.I. pigment brown 23, C.I. pigment brown 25

C.I. pigment black 1, C.I. pigment black 7 etc.

As the colorant among the present invention, in above-mentioned colorant, preferred C.I. paratonere 254 in the colored resin composition of (i) R (red), preferred C.I. pigment green 36 in the colored resin composition of (ii) G (green), preferred C.I. pigment blue 15 in the colored resin composition of (iii) B (indigo plant): 6.In addition, also can make up several uses of above-mentioned pigment.

The combination of the preferred pigment mentioned above that share in the present invention, can be enumerated: the combination of C.I. paratonere 254 and C.I. paratonere 177, C.I. paratonere 224, C.I. pigment yellow 13 9 or C.I. pigment Violet 23; C.I. the combination of pigment green 36 and C.I. pigment yellow 150, C.I. pigment yellow 13 9, C.I. pigment yellow 185, C.I. pigment yellow 13 8 or C.I. pigment yellow 180; C.I. pigment blue 15: 6, with the combination of C.I. pigment Violet 23 or C.I. pigment blue 60.

Like this and under other the colorant situation about share, more than the preferred 80 quality % of the content of the C.I. paratonere 254 in the pigment, more than the especially preferred 90 quality %.Under situation about share with other colorants, more than the preferred 50 quality % of the content of the C.I. pigment green 36 in the pigment, more than the especially preferred 60 quality %.Under situation about share with other colorants, the C.I. pigment blue 15 in the pigment: more than the preferred 80 quality % of 6 content, more than the especially preferred 90 quality %.

Above-mentioned pigment optimization uses with the form of dispersion liquid.This dispersion liquid can be by add mixing the composition that described pigment and described spreading agent obtain in polymerizable compound described later, make its dispersion and prepare.The dispersion machine that uses when making described pigment dispersing, do not limit especially, for example can enumerate and make work towards storehouse nation, " topical reference book of pigment ", first published, towards storehouse bookstore, 2000, kneader (kneader), roller mill (roll mill), masher (attritor), Ultra-micro-grinding machine (super mill), high speed dispersion device (dissolver), homogeneous mixer (homomixer), the sand mill known dispersion machines such as (sand mill) of record in 438 pages.And then also can grind by the machinery of 310 pages of records of the document, utilize the broken pigment of friction force micro mist.

The preferred number average bead diameter of the colorant that uses among the present invention (pigment) is 0.001～0.1 μ m, more preferably 0.01～0.08 μ m.If the discontented 0.001 μ m of the number average bead diameter of pigment, then the surface energy of particle becomes big, and therefore, cohesion is difficult to carry out pigment dispersing easily, and, be difficult to stably keep disperse state, therefore not preferred.In addition, if the elimination of the polarized light that pigment causes greater than 0.1 μ m, then takes place for the number average bead diameter of pigment, contrast reduces, and is not preferred.In addition, be meant and the diameter of a circle of the electron micrograph image area identical of particle that at this said " particle diameter " in addition, " number average bead diameter " is meant the mean value of the particle diameter that 100 particles are obtained.

By the particle diameter of the pigment that reduces to disperse, can improve the contrast of colored pixels.In order to reduce particle diameter, the jitter time of regulating the pigment dispersing thing gets final product.In the dispersion, can use above-mentioned known dispersion machine.Preferred 10～30 hours of jitter time, more preferably 18～30 hours, most preferably 24～30 hours.If jitter time was less than 10 hours, then pigment particle size is big, the elimination of the polarized light that generation pigment causes, and contrast reduces sometimes.On the other hand, greater than 30 hours, then the viscosity of dispersion liquid rose, and is difficult to sometimes spray from ink gun as if jitter time.In addition, for the difference with the contrast of the colored pixels more than the dichromatism is made as in 600, regulate pigment particle size, the contrast that is made as expectation gets final product.

Utilize the contrast of each colored pixels of the color filter that described polymerism China ink liquid forms preferred more than 2000, more preferably more than 2800, so that preferred more than 3000, most preferably more than 3400.If constituting the contrast of each colored pixels of color filter is below 2000, when then observing the image of liquid crystal indicator, stay the impression of turning white on the whole with this contrast, be difficult to differentiate, therefore not preferred.In addition, in the difference of the contrast of each colored pixels preferred 600, more preferably in 410, and then in preferred 350, most preferably in 200.If it is the difference of the contrast of each colored pixels is in 600, and is then when black display, roughly the same from the light leak amount of each colored pixels, thereby the color coordination of black display is good, therefore preferred.

In this manual, " contrast of colored pixels " is meant: about R, the G that constitutes color filter, the contrast that B estimates respectively by each color.The assay method of contrast is as described below.In the overlapping polarization plates in the both sides of determinand, under the state that the direction of polarized light that makes polarization plates is parallel to each other,, measure the brightness Y1 of the light of the polarization plates of having passed through opposite side from the polarization plates side irradiation backlight of a side.Secondly, make under the mutually orthogonal state of polarization plates,, measuring the brightness Y2 of the light of the polarization plates of having passed through opposite side from the polarization plates side irradiation backlight of a side.The measured value that use obtains is calculated contrast with Y1/Y2.Also have, the polarization plates that is used for the mensuration of contrast is used the identical polarization plates of polarization plates that adopts with the liquid crystal indicator that uses this color filter.

(polymerizable compound)

The polymerizable compound that uses among the present invention is for example to utilize the free-radical polymerised compound that solidifies based on the polyreaction of free radical activity kind or utilize the cationically polymerizable compound that solidifies based on the cationic polymerization of cationic species.

(free-radical polymerised compound)

The concrete compound example of the free-radical polymerised compound that uses among the present invention comprises compound shown below, but is not limited to these.

The example of the monofunctional monomer with an ethene unsaturated double-bond that uses among the present invention comprises: the butanediol mono acrylic ester; N, the N-dimethyl amino ethyl acrylate; the 2-hydroxyethylmethacry,ate; 2-hydroxyethyl methacrylate; the hydroxypropyl acrylate; 2-methoxy ethyl acrylate; the N-caprolactam; the N-vinyl pyrrolidone; acryloyl morpholine; the N-vinyl formamide; the cyclohexyl acrylate; the cyclohexyl methyl acrylate; two cyclopentyl-methyl acrylate; glycidyl acrylate; iso-bornyl acrylate; the isodecyl acrylate; the phenoxymethyl acrylate; hard ester group acrylate; the tetrahydrofurfuryl acrylate; the 2-phenoxyethyl acrylate; 2-hydroxypropyl acrylate; 4-hydroxybutyl acrylate; the isobutyl acrylate; tert-butyl group acrylate; isooctyl acrylate; iso-bornyl acrylate; methoxyl triethylene glycol acrylate; 2-ethoxyethyl group acrylate; the tetrahydrofurfuryl acrylate; 3-methoxyl butylacrylic acid ester; the benzyl acrylate; ethoxy ethoxy ethyl propylene acid esters; the butoxyethyl group acrylate; ethoxy diethylene glycol acrylate; methoxyl dipropylene glycol acrylate; methylphenoxy ethyl propylene acid esters; dipropylene glycol acrylate etc.

Another cure component of the black liquid that uses among the present invention i.e. the above monomer of 2 officials energy, the example of oligomer comprises: ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, ethoxylation 1, the 6-hexanediyl ester, neopentyl glycol two (methyl) acrylate, ethoxylation neopentyl glycol two (methyl) acrylate, ethoxylated neopentylglycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropyleneglycol diacrylate, 1,4-butylene glycol two (methyl) acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1, the ammediol diacrylate, dihydroxymethyl-tristane diacrylate, hydroxyl trimethylace tonitric neopentylglycol diacrylate, 1,3-butylene glycol two (methyl) acrylate, ethoxylation bisphenol-A two (methyl) acrylate, propoxylated bisphenol two (methyl) acrylate, cyclohexanedimethanol two (methyl) acrylate, dihydroxymethyl two cyclopentane diacrylates, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, the propoxylation trimethylolpropane triacrylate, pentaerythritol triacrylate, the tetra methylol propane triacrylate, the tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, butyrolactone modification trimethylolpropane triacrylate, ethoxylation cyamelide triacrylate, three (2-hydroxyethyl isocyanuric acid ester) triacrylate, the third oxygen acid esters glyceryl triacrylate, the tetramethylol methane tetraacrylate, tetramethylol methane tetraacrylate, the double trimethylolpropane tetraacrylate, the ethoxylation tetramethylol methane tetraacrylate, dipentaerythritol acrylate, the few acrylate of neopentyl glycol, 1, the few acrylate of 4-butylene glycol, 1, the few acrylate of 6-hexanediol, the few acrylate of trimethylolpropane, the few acrylate of pentaerythrite, urethane acrylate, the ethoxy propylene acid esters, polyester acrylate etc.

These compounds can use a kind of or use two or more as required.

(cationically polymerizable compound)

The cationically polymerizable compound that uses among the present invention is the compound that utilizes the cationic species polymerization reaction take place that produced by Photoepolymerizationinitiater initiater to be cured.

As the cationically polymerizable compound, can use as the various known cationically polymerizable monomer known to the cationically photopolymerizable monomer.As the cationically polymerizable monomer, for example, can enumerate Japanese patent laid-open 6-9714 number, Jap.P. spy opens 2001-31892, Jap.P. spy and opens 2001-40068, Jap.P. spy and open 2001-55507, Jap.P. spy and open 2001-310938, Jap.P. spy and open 2001-310937, Jap.P. spy and open the vinyl ether compound put down in writing in each communique such as 2001-220526, oxetane compound, and compound such as oxirane compound.

As the concrete example of the cationically polymerizable compound that has vinyl ether in functional group, can use polyurethane series vinyl ether (vinyl ether urethane), ester is vinyl ether etc.These oligomer can be used alone or as a mixture.

Concrete example as aromatic epoxy resin, can enumerate the polyglycidyl ether of polyhydric phenol with at least one aromatic ring or its alkylene oxide adducts, for example, bisphenol-A, Bisphenol F or they again with the glycidol ether of the compound of epoxyalkane addition, epoxy-Novolak resin, bisphenol-A phenolic varnish glycidol ether, bisphenol-A phenolic varnish glycidol ether etc.

In addition, concrete example as alicyclic epoxy resin, can enumerate: the polyglycidyl ether that will have the polyvalent alcohol of at least one ester ring type ring, or the compound that contains the CHO structure that obtains with the oxygenant epoxidation of the compound that contains cyclohexene, cyclopentene ring or the compound that contains the cyclopentane oxide structure, maybe will have the compound that contains the vinyl cyclohexane oxide structure that the compound of vinyl cyclohexane structure obtains with the oxygenant epoxidation.For example, can enumerate hydrogenation bisphenol-A diglycidyl ether, 3,4-epoxy radicals cyclohexyl methyl-3,4-epoxy radicals cyclohexane carboxylic acid ester, 3,4-epoxy radicals-1-methylcyclohexyl-3,4-epoxy radicals-1-methylcyclohexanecarboxylic acid ester, 6-methyl-3,4-epoxy radicals cyclohexyl methyl-6-methyl-3,4-epoxy-cyclohexane carboxylate, 3,4-epoxy radicals-3-methyl cyclohexane ylmethyl-3,4-epoxy radicals-3-methylcyclohexanecarboxylic acid ester, 3,4-epoxy radicals-5-methyl cyclohexane ylmethyl-3,4-epoxy radicals-5-methylcyclohexanecarboxylic acid ester, 2-(3,4-epoxy radicals cyclohexyl-5,5-spiral shell-3, the 4-epoxy radicals) cyclohexane-Jian dioxs, two (3,4-epoxy radicals cyclohexyl methyl) adipate, the vinyl cyclohexene dioxide, 4-vinyl epoxy-cyclohexane, two (3,4-epoxy radicals-6-methyl cyclohexane ylmethyl) adipate, 3,4-epoxy radicals-6-methylcyclohexyl carboxylate, di-2-ethylhexylphosphine oxide (3, the 4-epoxy-cyclohexane), the bicyclopentadiene diepoxide, ethylene glycol bisthioglycolate (3,4-epoxy radicals cyclohexyl methyl) ether, di-2-ethylhexylphosphine oxide (3,4-epoxy-cyclohexane carboxylate), epoxy radicals six hydrogen phthalandione dioctyls, epoxy radicals six hydrogen phthalandiones two-2-ethylhexyl etc.

As the concrete example of aliphatic epoxy resin, multipolymer of homopolymer, glycidyl acrylate or the glycidyl methacrylate of the compound that contains epoxy radicals, glycidyl acrylate or the glycidyl methacrylate that can enumerate the poly glycidyl ester of polyglycidyl ether, the aliphatic long-chain polyprotonic acid of aliphatic polyol or its alkylene oxide addition product, the aliphatic long-chain unsaturated hydrocarbon is obtained with the oxygenant oxidation etc.As representative compounds, can enumerate 1, the 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, the triglycidyl group ether of glycerine, the triglycidyl group ether of trimethylolpropane, the four glycidyl group ether of pentaerythrite, the four glycidyl group ether of carbitol, six glycidyl ethers of dipentaerythritol, the diglycidyl ether of polyglycol, the glycidyl ether of polyvalent alcohols such as the diglycidyl ether of polypropylene glycol, and make propylene glycol, aliphatic polyol such as glycerine and one or more alkylene oxide additions and the poly epihydric alcohol base ether of the polyester polyol that obtains, the diglycidyl ester of aliphatic long-chain dibasic acid.And then, can enumerate single glycidyl ether, the glycidyl esters of higher fatty acid, epoxidised soybean oil, octyl epoxy stearate, butyl epoxy stearate, the epoxidation linseed wet goods of the Aethoxy Sklerol that single glycidyl ether of aliphatics higher alcohol or phenol, cresols, butylphenol or they and alkylene oxide addition obtain.

If the one-tenth that these irradiations by activation-energy-ray have curable is divided into below the 50 quality % of total ink amount, then the intensity by common activation-energy-ray can not obtain sufficient curable.Therefore, needs prolong counter-measures such as irradiation time.Therefore, it is desirable for the one-tenth component with curable is more than the 50 quality % of total black liquid, more preferably has more than the 60 quality %.

(polymerization initiator)

As the polymerization initiator that uses among the present invention, can be used the radical polymerization initiator that the irradiation that utilizes activation-energy-ray produces the free radical activity kind, causes the polymerization of free-radical polymerised compound with polymerizable compound, any of the cationic polymerization initiators that reach and produce cationic species, causes the cationically polymerizable compound.

-radical polymerization initiator-

In the present invention, can enumerate following spendable Photoepolymerizationinitiater initiater.As benzophenone series; can enumerate benzophenone; the benzoyl benzoic acid; the 4-phenyl benzophenone; 4; 4-diethylamino benzophenone; 3; 3 '-dimethyl-4-methoxy benzophenone; 4-benzoyl-4 '-dimethyl diphenyl sulfide etc.; as thioxanthones be; can enumerate thioxanthones; 2-chlorine xanthone; 2; the 4-diethyl thioxanthone; 1-chloro-4-propoxyl group thioxanthones; isopropyl xanthone etc.; as acetophenone be; can enumerate 2-methyl isophthalic acid-(4-methyl sulphur) phenyl-2-morpholinyl propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butanone-1; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; the 1-hydroxycyclohexylphenylketone; 2; 2-dimethyl-2-hydroxy acetophenone; 2; 2-dimethoxy-2-phenyl acetophenone; 4-phenoxy group dichloroacetophenone; diethoxy acetophenone; 1-hydroxycyclohexylphenylketone etc.; as benzoin be; can enumerate benzoin methyl ether; the benzoin isobutyl ether; benzyl methyl ketal etc.; as acylphosphine oxide be; can enumerate 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; two (2; 4, the 6-trimethylbenzoyl) acylphosphine oxide etc.

-cationic polymerization initiators-

As cationic polymerization initiators, can preferably use diazo salt, salt compounded of iodine, sulfonium salt, iron arene complex compound and organic polyhalogen compound.As diazo salt, salt compounded of iodine and sulfonium salt, can enumerate special public clear 54-14277 number of Jap.P., special public clear 54-14278 number of Jap.P., Jap.P. spy and open the compound of putting down in writing in clear 51-56885 number, No. the 3708296th, United States Patent (USP), No. the 3853002nd, United States Patent (USP) etc.

As the light cationic polymerization initiators, for example, can illustration aromatic series diazo salt, aromatic series sulfonium salt, aromatic series salt compounded of iodine, aromatic ring alkene metal derivative compound, silicon compound/aluminium complex etc.

(solvent)

Described in the present invention solvent is meant the solvent of record in water, alcohols, the ketone etc. " new edition solvent pocket book (organic synthesis scientific institution volume, the distribution of Ao Mu (オ-system) company) ", and the weight in the black liquid is preferred below 50%, more preferably below 30%.

(ink-jet recording)

In the present invention, ink-jet recording is to utilize ink gun that black liquid is penetrated recess on the substrate of being divided by the next door with light-proofness (below, be sometimes referred to as " light-proofness next door "), forms dyed layer, activation-energy-ray such as irradiation ultraviolet radiation then makes the mode of black liquid-solidization.

As the ejaculation condition of black liquid, from penetrating stable aspect, preferably black liquid is heated to 40～70 ℃, reduce black fluid viscosity after, with its ejaculation.Usually, the viscosity ratio aqueous ink height of polymerism China ink liquid, therefore, the viscosity amplitude of fluctuation that temperature change causes is big.The viscosity change directly produces big influence to drop size, drop issuing velocity, causes the image quality deterioration, therefore, need remain on black liquid temp constant as far as possible.

The ink gun that uses among the present invention (below, also abbreviate head sometimes as) can use known ink gun, can use continous way, some on-demand.In the thermal head in an on-demand,, preferably has the form of the operating valve of record in Japanese patent laid-open 9-323420 number in order to spray.Piezoelectric heads for example can be used the head of record in European patent A277703 number, European patent A278590 number etc.Head preferably has temp regulating function, can manage the temperature of black liquid.Preferred set the ejaculation temperature, control black liquid temp and make the amplitude of fluctuation of viscosity in ± 5% so that the viscosity when penetrating becomes the mode of 5～25mPas.In addition, the preferred 1～500kHz of driving frequency.

(curing of black liquid)

In the curing of R, G, B black liquid of all kinds, use the energy source of the activation-energy-ray send the corresponding wavelength region may of the induction wavelength that has with polymerism China ink liquid, promote polymerizing curable and carry out exposure-processed.As energy source, for example, can suitably select to use the energy source of polymerization initiators such as ultraviolet ray, far ultraviolet, g ray, h ray, i ray, KrF excimer laser, ArF excimer laser, electron ray, X ray, molecular ray or the ion beam induction of 200～450nm.Specifically, can suit to use to send to belong to 250～450nm, the light source of the active ray of the wavelength region may of preferred 365 ± 20nm, for example, LD, LED (light emitting diode), fluorescent light, Cooper-Hewitt lamp, metal halide lamp, carbon arc lamp, xenon lamp, chemical lamp etc. carry out exposure-processed.Optimized light source can be enumerated LED, high-pressure mercury-vapor lamp, metal halide lamp.

The irradiation time of activation-energy-ray can suitably be set according to the combination of polymerizable compound and polymerization initiator, but for example, with illumination 20mW/cm ²Under the situation of exposure, the time shutter can be made as 1～30 second.

[the light-proofness next door makes of photosensitive composite (dark composition)]

The light-proofness next door of each pixel is formed by the photosensitive composite that contains colorant (below, also be called " dark composition ").At this, dark composition is meant the composition with high optical concentration, and its value is 2.0～10.0.The optical concentration preferred 2.5～6.0, especially preferred 3.0～5.0 of dark composition.In addition, this dark color composition preferably makes its curing with light-initiated system as described later, and is therefore, also important to the optical concentration of exposure wavelength (being generally ultraviolet ray).That is, its value is 2.0～10.0, and is preferred 2.5～6.0, most preferably 3.0～5.0.If less than 2.0, then exist the next door shape can not become the trouble of the shape of expectation, if greater than 10.0, then can not initiated polymerization, be difficult to make next door itself.As long as have described character, the colorant in the composition (dark body) can be organism (various pigments such as dyestuff, pigment), or various forms of carbon, also can be their combination.

(colorant)

The colorant that uses in the above-mentioned dark composition is specifically described.

Dark composition among the present invention can suit to use organic pigment, inorganic pigment, dyestuff etc., except metal oxide powder, metal sulfide powder, the so-called opacifiers of metal powder such as carbon black, titanium dioxide, four iron oxide, can also use the potpourri etc. of the pigment of red, blue, green etc.Can use known colorant (dyestuff, pigment) in the dark composition.Under the situation of the pigment in using this known colorant, preferably be dispersed in the dark composition.

From shortening the observation of development time, the ratio of the colorant in the solid state component of described dark composition is by 30～70 quality %, more preferably 40～60 quality %, and then preferred 50～55 quality %.

As above-mentioned known dyestuff or pigment, specifically, can suit to use the Jap.P. spy and open the look material of record in 2005-17716 communique [0038]～[0040] or pigment or Jap.P. spy that the Jap.P. spy opens record in 2005-361447 communique [0068]～[0072] open the colorant of putting down in writing in 2005-17521 communique [0080]～[0088].

In the present invention, preferred black colorant in described colorant.As black colorant, and then illustrative words, can enumerate carbon black, titanium carbon, iron oxide, titanium dioxide, graphite etc., wherein preferred carbon black.

Above-mentioned pigment optimization uses with the state of dispersion liquid.This dispersion liquid can make an addition to organic solvent described later (or vehicle) by mixing the composition that described pigment and pigment dispersing agent obtain, and makes its dispersion and prepares.Described vehicle is meant when coating is in liquid condition, makes the part of the medium of pigment dispersing, comprises liquid the combination with described pigment and makes the part (bonding agent) of curing of coating and with the composition (organic solvent) of its dissolved dilution.As the spreading agent that when making described pigment dispersing, uses, do not limit especially, for example, can enumerate towards storehouse nation and make work, " topical reference book of pigment ", first published is towards storehouse bookstore, 2000, kneader (kneader), roller mill (roll mill), masher (attritor), Ultra-micro-grinding machine (super mill), high speed dispersion device (dissolver), homogeneous mixer (homomixer), the sand mill known dispersion machines such as (sand mill) of record in 438 pages.And then also can grind by the machinery of 310 pages of records of the document, utilize the broken pigment of friction force micro mist.

From the viewpoint of dispersion stabilization, the preferred number average bead diameter of the colorant that uses among the present invention (pigment) is 0.001～0.1 μ m, more preferably 0.01～0.08 μ m.Also have, be meant and the diameter of a circle of the electron micrograph image area identical of particle that at this said " particle diameter " in addition, " number average bead diameter " is meant the mean value of the particle diameter that 100 particles are obtained.

Dark composition also comprises polymerizable compound and Photoepolymerizationinitiater initiater at least except described colorant (dark body).In addition, as required, can also contain known adjuvant, for example, plastifier, filling agent, stabilization agent, polymerization inhibitor, surfactant, solvent, adhesion promoter etc.And then dark composition preferably softens under the temperature below 150 ℃ at least or has stickability, more preferably has thermoplasticity.From described viewpoint, the plastifier that also can add intermiscibility is composition modified with dark color.

As the method that dark composition is solidified, use light-initiated system.Photoepolymerizationinitiater initiater is the irradiation (also being called exposure) by luminous ray, ultraviolet ray, far ultraviolet, X ray etc. as used herein, can produce the compound of the spike of the polymerization that causes multi-functional monomer described later, can cause suitably selection the system from known Photoepolymerizationinitiater initiater or photopolymerization.

The example of photopolymerizer comprises: contain trihalomethyl group compound, acridine based compound, acetophenone based compound, di-imidazole compound, triazine based compound, benzoin based compound, benzophenone based compound, α-diketone based compound, encircle quinone based compound, xanthone based compound, diazonium based compound etc. more.

The object lesson of photopolymerizer comprises: the Jap.P. spy opens San Lu that the trihalomethyl group put down in writing in the 2001-117230 communique replaces and contains the trihalomethyl group compound for the San Lu Dai oxadiazole compound of putting down in writing in No. 4212976 instructions of trihalomethyl group-s-triaizine compounds, United States Patent (USP) of putting down in writing in Jia oxazole derivatives or s-pyrrolotriazine derivatives, No. 4239850 instructions of United States Patent (USP) etc.; 9-phenylacridine, 9-pyridine radicals acridine, 9-pyrazinyl acridine, 1, two (9-acridinyl) ethane, 1 of 2-, two (9-acridinyl) propane, 1 of 3-, two (9-acridinyl) butane, 1 of 4-, two (9 acridinyl) pentanes, 1 of 5-, two (9-acridinyl) hexanes, 1 of 6-, two (9-acridinyl) heptane, 1 of 7-, two (9-acridinyl) octanes, 1 of 8-, two (9-acridinyl) nonanes, 1 of 9-, two (9-acridinyl) decane, 1 of 10-, two (9-acridinyl) undecanes, 1 of 11-, acridine based compounds such as two (9-acridinyl) alkanes such as two (9-acridinyl) dodecanes of 12-; 6-(p-methoxyphenyl)-2, two (the trichloromethyl)-s-triazines of 4-, 6-(p-(N, two (ethoxy carbonyl methyl) amino of N-) phenyl)-2, triazine based compounds such as two (the trichloromethyl)-s-triazines of 4-; And 9,10-dimethylbiphenyl azophenlyene, Michler's keton, benzophenone/Michler's keton, six aryl di-imidazoles/mercaptobenzimidazoles, benzyl dimethyl ketal, thioxanthones/amines, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-the di-imidazoles.

In above-mentioned, preferably contain to be selected from and contain at least a of trihalomethyl group compound, acridine based compound, acetophenone based compound, di-imidazole compound, triazine based compound, especially preferably contain and be selected from least a of the compound that contains trihalomethyl group and acridine based compound.It is useful from versatility and cheap aspect to contain trihalomethyl group compound, acridine based compound.

As containing the trihalomethyl group compound, especially preferred 2-trichloromethyl-5-(to the styrene styryl)-1,3, the 4-oxadiazole, as the acridine based compound, especially preferred 9-phenylacridine, and then preferred 6-[p-(N, two (ethoxy carbonyl methyl) amino of N-) phenyl]-2, two (the trichloromethyl)-s-triazines of 4-, 2-(to the butyl phenyl ether vinyl)-5-trichloromethyl-1,3,4-oxadiazole etc. contain the trihalomethyl group compound, reach Michler's keton, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-di-imidazoles.

Described Photoepolymerizationinitiater initiater can use separately, also can share two or more.As the total amount in the dark composition of described Photoepolymerizationinitiater initiater, 0.1～20 quality % of total solid state component (quality) of preferred dark composition, especially preferred 0.5～10 quality %.If the discontented 0.1 quality % of described total amount, then the efficient of the photocuring of composition is low, and exposure needs for a long time sometimes, if greater than 20 quality %, then when developing, the picture pattern of formation lacks sometimes, or patterned surfaces pleat takes place sometimes easily splits.

Also can share hydrogen donor in the described Photoepolymerizationinitiater initiater.As this hydrogen donor, from making the better aspect of sensitivity, preferably with undefined mercaptan based compound, amine compound etc." hydrogen donor " described herein is meant the compound that hydrogen atom can be provided to the free radical that is produced by described Photoepolymerizationinitiater initiater by exposure.

Described mercaptan based compound is to serve as female ring with phenyl ring or heterocycle, and has the mercaptan that directly is combined in this mother's ring more than one, preferred 1～3, and more preferably 1～2 compound (below, be called " mercaptan is hydrogen donor ").In addition, described amine compound is to serve as female ring with phenyl ring or heterocycle, and has the amino that directly is combined in this mother's ring more than one, preferred 1～3, and more preferably 1～2 compound (below, be called " amine is hydrogen donor ").Also have, these hydrogen donors also can have mercapto and amino simultaneously.

As above-mentioned mercaptan is the concrete example of hydrogen donor, can enumerate 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thio biphosphole, 2-sulfydryl-2,5-dimethyl aminopyridine etc.Wherein, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, especially preferred 2-mercaptobenzothiazole.

As above-mentioned amine is the concrete example of hydrogen donor, can enumerate 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, ethyl-4-dimethylaminobenzoic acid ester, 4-dimethylamino benzoic acid, 4-dimethylamino benzonitrile etc.Wherein, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, especially preferred 4,4 '-two (diethylamino) benzophenone.

Described hydrogen donor can be used alone or in mixture of two or more, when developing, be difficult for coming off from the image that forms from the permanent support body, but also the aspect of raising intensity and sensitivity, it is that hydrogen donor and more than one amine are hydrogen donor that preferred compositions is used more than one mercaptan.

As described mercaptan is that hydrogen donor and amine are the concrete example of the combination of hydrogen donor, can enumerate 2-mercaptobenzothiazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone etc.Preferred combination is 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (diethylamino benzophenone, especially preferred combination be 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone.

Having made up described mercaptan is that hydrogen donor and described amine are under the situation of hydrogen donor, mercaptan be hydrogen donor (M) and amine be hydrogen donor (A) mass ratio (M: A) usually preferred 1: 1～1: 4, more preferably 1: 1～1: 3.As the total amount in the dark composition of described hydrogen donor, 0.1～20 quality % of total solid state component (quality) of preferred dark composition, especially preferred 0.5～10 quality %.

As the multi-functional monomer (polymerizable compound) of dark composition, can use following compound separately or with other combination of monomers.Specifically, can enumerate the tert-butyl group (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, triethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, 2-ethyl-2-butyl-propane diol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, polyoxy ethylization trimethylolpropane tris (methyl) acrylate, three (2-(methyl) acryloxy ethyl) isocyanuric acid ester, 1, the 4-di isopropenylbenzene, 1,4-dihydroxy benzenes two (methyl) acrylate, decamethylene glycol two (methyl) acrylate, styrene, the diallyl fumarate, the trimellitic acid triallyl ester, lauryl (methyl) acrylate, (methyl) acrylamide, two (methyl) acrylamides of xylylene etc.

In addition, can also use 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, polyethyleneglycol (methyl) acrylate etc. to have the reactant of diisocyanate such as the compound of hydroxyl and hexamethylene diisocyanate, toluene diisocyanate, Xylene Diisocyanate.

Wherein, especially preferred tetramethylol methane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate, three (2-acryloxy ethyl) isocyanuric acid ester.

As the content in the dark composition of multi-functional monomer, with respect to total solid state component (quality) of dark composition, preferred 5～80 quality %, especially preferred 10～70 quality %.If the discontented 5 quality % of described content, then the exposure portion of composition is to the resistance variation of alkaline developer, if greater than 80 quality %, the tackiness during then as dark composition increases, the operability variation.

(light-proofness next door)

The light-proofness next door of each pixel is formed by above-mentioned dark composition.The light-proofness next door isolates two above pixel groups, and it is in the majority to be generally black, but is not limited to black.The light-proofness next door is preferably by exposing dark photopolymerizable composition under oxygen-lean atmosphere, develop then and form.

Be meant under the inert gas under the oxygen-lean atmosphere when making described dark composition photocuring, decompression down, can intercept under the protective seam of oxygen, these concrete condition is as described below.

Inert gas is meant N ₂, H ₂, CO ₂Etc. rare gas classes such as common gas or He, Ne, Ar.Wherein, from security or the easiness of obtaining, cost problem, the suitable N that utilizes ₂

Be meant below the 500hPa the following state of preferred 100hPa under the decompression.

The protective seam that can intercept oxygen for example can enumerate that the Jap.P. spy opens clear 46-2121 number or each communique of special public clear 56-40824 number of Jap.P. in polyvinylether/maleic anhydride polymkeric substance of putting down in writing; the water soluble salt of carboxyalkyl cellulose; the water-soluble cellulose ether class; the water soluble salt of carboxyalkyl starch; polyvinyl alcohol (PVA); polyvinylpyrrolidone; various polyacrylamides; various water soluble polyamides; polyacrylic water soluble salt; gelatin; the oxirene polymkeric substance; the water soluble salt of the group that constitutes by various starch and analog thereof; the multipolymer of styrene/maleic acid; maleic ester resin; and their two or more combination etc.Wherein, the especially combination of the pure and mild polyvinylpyrrolidone of preferably polyethylene.The preferred saponification rate of polyvinyl alcohol (PVA) is more than 80%, 1～75 quality % of the soluble resin bed solid state component of content preferred bases of polyvinylpyrrolidone, more preferably 1～50 quality %, and then preferred 10～40 quality %.

The preferred 75cm of oxygen transmission coefficient of the protective seam that can intercept oxygen of Zhi Zuoing like this ³/ m ²It is below 1000hPa, more preferably 50cm ³/ m ²It is below 1000hPa, most preferably 25cm ³/ m ²It is below 1000hPa.At the oxygen transmission coefficient greater than 75cm ³/ m ²Under the situation of it 1000hPa, can not intercept oxygen effectively, therefore, be difficult to the light-proofness next door is formed desirable shape.

From preventing the viewpoint of colour mixture, the height in above light-proofness next door, preferred 1～20 μ m, more preferably 1.5～10 μ m, and then preferred 2～5 μ m.

(photosensitive transfer printing material)

As easily and the low-cost method that realizes described light-proofness next door, there is use on interim supporter, to have the method for the photosensitive transfer printing material that layer and oxygen barrier layer by the dark composition of photonasty form at least successively.Under the situation of using such material, protected by oxygen barrier layer by the layer that the dark composition of photonasty forms, therefore, become under the oxygen-lean atmosphere automatically.Therefore, need under inert gas or under the decompression, not carry out exposure process, so have the advantage that directly to utilize the operation of present situation.

Above-mentioned photosensitive transfer printing material also can have thermoplastic resin as required.Described thermoplastic resin is an alkali-soluble, comprises resinous principle at least and constitutes, and as this resinous principle, preferred softening point is substantially at the resin below 80 ℃.By such thermoplastic resin is set, in light-proofness described later next door formation method, can bring into play good adhesiveness with the permanent support body.

At the alkali-soluble thermoplastic resin below 80 ℃, can enumerate the saponified etc. of saponified, the vinyltoluene of saponified, the styrene of ethene and acrylate copolymer and (methyl) acrylate copolymer and (methyl) acrylate copolymers such as saponified, poly-(methyl) acrylate, (methyl) butyl acrylate and vinyl acetate of (methyl) acrylate copolymer etc. as softening point.

Thermoplastic resin can suitably be selected at least a of above-mentioned thermoplastic resin and use, and then can use based on " plastics performance handbook (Japan Plastics Industry Federation, all Japan plastics forming operation federation write, the census of manufacturing can be issued, October 25 nineteen sixty-eight distribution), the resin that be dissolvable in water aqueous alkali of softening point in about organic polymer below 80 ℃.

In addition,,, substantial softening point can also be reduced to below 80 ℃ and use at the organic polymer material more than 80 ℃ about softening point by in this organic polymer material, adding the various plastifier have with the intermiscibility of this polymer substance.In addition, for the purpose of adjusting with the bonding force of interim supporter, can substantial softening point be not more than in 80 ℃ the scope, in these organic polymer materials, add various polymkeric substance or supercooling material, adhere to improver or surfactant, release agent etc.

As the concrete example of preferred plasticizer, can enumerate polypropylene glycol, polyglycol, dioctyl phthalate (dop), diheptyl phthalate ester, dibutyl phthalate ester, three cresyls (Network レ ジ Le) phosphate, cresyl diphenyl phosphoester biphenyl, diphenyl phosphoester.

As the interim supporter in the above-mentioned photosensitive transfer printing material, can be from chemical and hot stable, and suitably select in the material that constitutes by flexible material.Specifically, thin slice or their duplexers such as preferred Telfon (registered trademark), polyethylene terephthalate, polycarbonate, tygon, polypropylene.As the thickness of described supporter, that suitable is 5～300 μ m, preferred 20～150 μ m.

(substrate)

Substrate (permanent support body) as constituting color filter can use metallicity supporter, metal adhesion supporter, glass, pottery, synthetic resin film etc.Especially preferably enumerate good glass of the transparency and dimensional stability or synthetic resin film.

(formation in light-proofness next door)

Below, illustrate and use photosensitive transfer printing material, form the situation in light-proofness next door.The interim supporter of preparation is provided with the dark composition layer of photonasty, oxygen barrier layer, and then this oxygen barrier layer is provided with the photosensitive transfer printing material of screening glass.At first, peel off remove screening glass after, the surface of the oxygen barrier layer that will expose fits on the permanent support body (substrate), is heated pressurization and stacked (duplexer) by stacked machine etc.Stacked machine can use the suitable stacked machine of selecting from known stacked machine, vacuum laminated machine etc. in the past, in order further to boost productivity, can also use the stacked machine of automatic cutting.

Secondly, between interim supporter and photo-sensitive resin, peel off, remove interim supporter.Then, the photomask that configuration is wished above the face of removing after removing interim supporter from the light source irradiation ultraviolet ray, uses predetermined process liquid to carry out development treatment after irradiation.As the developer solution that is used in development treatment, use the dilute aqueous solution of alkaline matter, also can also add has the blended organic solvent that has on a small quantity with water.As being used in light-struck light source, can enumerate middle pressure～extra-high-pressure mercury vapour lamp, xenon lamp, metal halide lamp etc.

As suitable alkaline matter, (for example can enumerate alkali metal hydroxide, NaOH, potassium hydroxide), the alkali carbonate class (for example, sodium carbonate, sal tartari), the alkali metal hydrogencarbonate class (for example, sodium bicarbonate, saleratus), the alkali metal silicate salt (for example, sodium silicate, potassium silicate), alkali silicate (metasilicate) class (for example, sodium silicate, potassium silicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxide class (for example, tetramethyl ammonium hydroxide), tertiary sodium phosphate etc.Preferred 0.01～30 quality % of the concentration of alkaline matter, pH preferred 8～14.

As described " having blended organic solvent " with water, for example, can suit to enumerate methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, diacetone alcohol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-butyrolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams, N-Methyl pyrrolidone etc.Has preferred 0.1～30 quality % of concentration with the blended organic solvent of water.And then, can also add known surfactant, as this surfactant, preferred 0.01～10 quality %.

Described developer solution can be used as body lotion or spray liquid.Under the situation of the uncured portion of removing photo-sensitive resin, can be combined in the developer solution method with rotating brush or moistening sponge wiping etc.The liquid temperature of developer solution preferred usually about room temperature to 40 ℃.Development time depends on its kind under the situation of the alkalescence of composition, developer solution of photo-sensitive resin or temperature, interpolation organic solvent and concentration etc., but be generally 10 seconds～and about 2 minutes.If too short, then the development of non-exposed portion is insufficient sometimes, and simultaneously, ultraviolet absorbance is also insufficient, if too long, then the portion of exposure sometimes is also etched.Under any situation, all be difficult to the light-proofness next door is shaped as suitable shape.After development treatment, can also add washing step.By this developing procedure, light-proofness next door shape is formed as described above.

Then, for the space in the light-proofness next door that in above-mentioned developing procedure, forms, make the pigmented fluids composition that forms rgb pixel enter this space, but before forming each pixel, the fixed in shapeization in light-proofness next door also can, its method does not limit especially, but can enumerate following method.That is, 1) develop after, expose again (being sometimes referred to as post-exposure), 2) develop after, under lower temperature, carry out heat treated etc.Heat treated described herein is meant: the substrate that will have a light-proofness next door heats in electric furnace, exsiccator etc. or uses infra-red light irradiation.

At this, carry out above-mentioned 1) situation under exposure be 500～3000mJ/cm under atmosphere ², preferred 1000～2000mJ/cm ², under the situation under the oxygen-lean atmosphere, can also be to expose than its low exposure.In addition, carry out described 2) situation under heating-up temperature be 50～120 ℃, preferred about 70～100 ℃, be about 10～40 minutes its heat time heating time.Be lower than in temperature under 50 ℃ the situation, the curing in light-proofness next door may not carried out, and under greater than 120 ℃ situation, light-proofness next door shape may be collapsed.

(formation of each pixel)

Ink-jetting style about using in order to form each pixel can use described known method.

Preferably after forming each pixel, the heating process of carrying out heat treated (what is called is cured processing) is set, carries out curing based on heat.That is, for substrate with photopolymerisable layer by rayed, heating or irradiation infrared lamp in electric furnace, exsiccator etc.The thickness of the layer of composition that the time of heating and time are depended on photosensitive composite or formation, but usually from obtaining sufficient solvent resistance, alkali resistance, and the viewpoint of ultraviolet absorbance, preferably about 120 ℃～about 250 ℃ big heating about 10 minutes～about 120 minutes down.

The pattern of the color filter of Xing Chenging does not limit especially like this, can be striated for common black matrix shape, can be clathrate yet, and then can be the triangle arrangement shape.

[display device]

Display device of the present invention is meant display device such as liquid crystal indicator, plasma scope display device, EL display device, CRT display device etc.The definition of display device or the explanation of each display device for example are described in " electronic console equipment (the wooden clear husband's work of assistant assistant, (strain) census of manufacturing can nineteen ninety distribution) ", " display apparatus (she blows along the chapter work, and industry books (strain) are put down into distribution in the first year) " etc.

The especially preferred liquid crystal indicator of display device of the present invention.About liquid crystal indicator, for example be described in " LCD Technology of future generation (Uchida Tatsuo compiles, and (strain) census of manufacturing can be issued in 1994) ".The liquid crystal indicator that can be suitable for the present invention is not particularly limited, and for example goes for the liquid crystal indicator of the variety of way of record in described " LCD Technology of future generation ".The present invention is effective to the liquid crystal indicator of colored TFT mode in these especially.Liquid crystal indicator about colored TFT mode for example is described in " colored TFT LCD (upright publication (strain) distribution in 1996 altogether) ".And then the present invention can certainly be applicable to the extended liquid crystal indicators in visual angle such as pixel partitioning scheme such as transverse electric field type of drive, MVA such as IPS.About these modes, for example be described in " the up-to-date trend in EL, PDP, LCD display technology and market (the calendar year 2001 distribution of eastern beautiful research centre (East レ リ サ-チ セ Application -) investigation department) " 43 pages.

Liquid crystal indicator is made of various members such as electrode base board, polarization film, phase retardation film, backlight, gap material, compensation film for angular field of view except color filter.Black matrix of the present invention goes for the liquid crystal indicator that these known members constitute.About these members, for example be recorded in the market of " ' 94 LCD peripheral material chemicals (chemicals) (island Itou Kentaro (strain) シ-エ system シ-(CMC) distribution in 1994) ", " present situation of 2003 liquid crystal relevant markets is always ground distribution in 2003 with prospect in future (last volume) (good lucky (strain) Ji Meile of Fuji (キ メ ラ) of table)) ".

[object purposes]

Color filter of the present invention can be applicable to purposes such as portable terminals such as TV, personal computer, liquid crystal projection apparatus, game machine, mobile phone, digital camera, car omniselector with having no particular limits.

The disclosure of Japanese publication 2005-342904 whole in reference are recorded in this instructions.

Below, illustrative embodiment in the notebook invention.

<1>

A kind of manufacturing method of color filter, on substrate, form next door with light-proofness, utilize ink-jetting style, to the recess spraying red (R) of dividing, green (G), and the black liquid of blue (B) by this next door, make described R, G, and B China ink liquid be deposited in described recess and form dyed layer, after the formation of the dyed layer that uses each black liquid, utilize the curing of the dyed layer of activation-energy-ray, after the curing of panchromatic dyed layer, and then utilize the curing of dyed layer of heat, wherein

Described each black liquid is formed by polymerism China ink liquid, and described polymerism China ink liquid contains colorant, polymerizable compound and polymerization initiator, and the quantity of solvent in the black liquid is below the 50 weight %.

<2>

According to＜1〉described manufacturing method of color filter, wherein,

Polymerism China ink liquid is free-radical polymerised composition.

<3>

According to＜1〉described manufacturing method of color filter, wherein,

Polymerism China ink liquid is cationically polymerizable composition.

<4>

According to＜3〉described manufacturing method of color filter, wherein,

Described cationically polymerizable composition contains the compound that is selected from vinyl ether compound, oxetane compound, reaches oxirane.

<5>

According to＜1〉described manufacturing method of color filter, wherein,

The composition that has curable in the polymerism China ink liquid is more than the 50 quality %.

<6>

According to＜1〉described manufacturing method of color filter, wherein,

Described active energy ray has the wavelength of 250～450nm.

<7>

According to＜6〉described manufacturing method of color filter, wherein,

Described active energy ray has the wavelength of 365 ± 20nm.

<8>

According to＜6〉described manufacturing method of color filter, wherein,

Being solidificated in of dyed layer of described utilization heat carried out under 120 ℃～250 ℃ 10 minutes～120 minutes.

<9>

According to＜1〉described manufacturing method of color filter, wherein,

Described next door is formed by the photosensitive composite that contains colorant, polymerizable compound and Photoepolymerizationinitiater initiater, and the optical concentration of described photosensitive composite is 2.5～6.0.

<10>

According to＜9〉described manufacturing method of color filter, wherein,

It is that hydrogen donor or amine are hydrogen donor that described photosensitive composite also contains mercaptan.

<11>

According to＜9〉described manufacturing method of color filter, wherein,

The amount in photosensitive composite of described copolymerization initiating agent is 0.5～10 quality %.

<12>

According to＜9〉described manufacturing method of color filter, wherein,

Described next door is by utilizing light that described photosensitive composite is solidified to form under the protective seam that can intercept oxygen.

<13>

According to＜9〉described manufacturing method of color filter, wherein,

Height with next door of light-proofness is 1～20 μ m.

<14>

A kind of color filter, wherein,

It is to utilize＜1〉described manufacturing method of color filter manufacturing.

<15>

A kind of display device, wherein,

Be equipped with＜14〉described color filter.

Embodiment

Below, enumerate embodiment, the present invention more specifically is described.Material shown in following examples, reagent, ratio, equipment, operation etc. only otherwise break away from the present invention just can suitably be changed.Thereby scope of the present invention is not limited to concrete example shown below.Also have, in following embodiment, under the situation of special requirement not, " % " reach " part ", represents that " quality % " reaches " mass parts ", and molecular weight is represented weight-average molecular weight.

[embodiment 1]

(next door makes the method for making with black photosensitive composition)

Black photosensitive composition K1 can obtain by as described below, that is: at first measure in the table 1 the K pigment dispersing thing 1 of the amount of record, propylene glycol monomethyl ether, in following mixing of 24 ℃ of temperature (± 2 ℃) and with 150RPM, stirred in 10 minutes, then, measure butanone, bonding agent 2, Hydroquinone monomethylether, DPHA liquid, 2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methylamino)-3 '-bromophenyl]-the s-triazine, surfactant 1, under 25 ℃ of temperature (± 2 ℃), add successively, under 40 ℃ of temperature (± 2 ℃) with 150RPM, stirred and obtained in 30 minutes.Also have, the amount of record is a mass parts in the table 1, and details is seen following composition.

＜K pigment dispersing thing 1 〉

Carbon black (Otto Dix (デ グ Star サ) corporate system, Nipex35) 13.1%

Spreading agent (following compound 1) 0.65%

Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand) 6.72%

Propylene glycol methyl ether acetate 79.53%

Compound 1

＜bonding agent 2 〉

Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.8 ten thousand) 27%

Propylene glycol methyl ether acetate 73%

＜DPHA liquid 〉

Dipentaerythritol acrylate (contains polymerization inhibitor MEHQ 500ppm, Japanese chemical drug (strain) system, trade name: KAYARAD DPHA) 76%

Propylene glycol methyl ether acetate 24%

＜surfactant 1 〉

Following works 130%

Butanone 70%

Works 1

(n＝6，x＝55，y＝5，Mw＝33940，Mw/Mn＝2.55

PO: epoxypropane, EO: oxirane)

[table 1] (mass parts)

Black-colored photosensitive resin composition	K1
		K pigment dispersing thing 1 (carbon black)	5
Propylene glycol methyl ether acetate	8
		Butanone	53
Bonding agent 2	9.1
		Hydroquinone monomethyl ether	0.002
DPHA	4.2
		2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methylamino)-3 '-bromophenyl]-the s-triazine	0.16
Surfactant 1	0.044

(formation in light-proofness next door)

After UV cleaning device cleaning alkali-free glass substrate, use clean-out system to scrub, carry out ultrasonic cleaning with ultrapure water again.This substrate of 120 ℃ of following thermal treatments 3 minutes, make the surface state stabilization.

Cool off this substrate, temperature transfers to after 23 ℃, and (FAS Asian company system, trade name: MH-1600) coating is by the black photosensitive composition K1 that constitutes forming described in the above-mentioned table 1 with coating machine with the glass substrate with slit-shaped mouth.Then,, after the flowability of overlay disappears, under 120 ℃, cured 3 minutes, obtain the black photosensitive layer K1 of thickness 10 μ m with 30 seconds an of part of VCD (chemical industry (strain) system is answered in Minton dryer, Tokyo) dry solvent.

With the close induction type exposure machine with ultrahigh pressure mercury lamp (Hitachi Hith-tech Electronic Engineering Corp.'s system), with substrate and the vertical state that erects of mask (quartzy exposed mask) with picture pattern, the distance of setting between exposed mask face and the black-colored photosensitive resin composition layer K1 is 200 μ m, under blanket of nitrogen, with exposure 300mJ/cm ²Carry out pattern exposure.

Then, spray pure water with spray spout, make the uniform surface ground of black-colored photosensitive resin composition layer K1 moistening after, with 23 ℃, 80 seconds, flat mouth pressure 0.04MPa, to KOH is that developer solution (contains KOH, non-ionic surfactant, trade name: CDK-1, Fujiphoto electronics synthesis material (Off イ Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ) (strain) system) spray development, obtain the composition image.Then, clean mouth, under the pressure of 9.8MPa, spray ultrapure water, remove residue, under atmosphere, with exposure 2000mJ/cm with UHV (ultra-high voltage) ²Carry out post-exposure, obtain the black next door of optical concentration 3.9.

(preparation of free-radical polymerised black liquid)

The preparation of dispersible pigment dispersion

The composition that mixes following table 2 stirred 1 hour with stirrer.Mixture after being mixed is disperseed with Chinese mugwort lattice (ア イ ガ-) grinding machine, obtain the pigment dispersing thing of R, G, B.Dispersion condition is as described below, fills the zirconium oxide bead of 0.65mm with 70% filling rate that is:, and peripheral speed is made as 9m/ second, and jitter time is 1 hour.

[table 2] (mass parts)

	R dispersible pigment dispersion 1	G dispersible pigment dispersion 1	B dispersible pigment dispersion 1
				Paratonere 254	9.8	-	-
Paratonere 177	2.5	-	-
				Pigment green 36	-	10.5	-
Pigment yellow 150	-	4.5	-
				Pigment blue 15: 6	-	-	3.2
Pigment Violet 23	-	-	4.7
				Monomer; HDDA (Daicel UPC (strain) system)	30	25	37
Spreading agent; BYK-168 (Bi Ke chemistry Japan (strain) system)	8	10	5

The preparation of China ink liquid

With the composition mixing R of table 3, each dispersible pigment dispersion of G, B, stirred 1 hour with stirrer, obtain R China ink liquid 1, G China ink liquid 1, B China ink liquid 1.

[table 3] (mass parts)

	R China ink liquid 1	G China ink liquid 1	B China ink liquid 1
				R dispersible pigment dispersion 1	10	-	-
G dispersible pigment dispersion 1	-	10	-
				B dispersible pigment dispersion 1	-	-	10
Monomer; DPCA60 (Japanese chemical drug (strain) system)	0.9	0.8	0.9
				Monomer; HDDA (Daicel UPC (strain) system)	15	15	15
Photoepolymerizationinitiater initiater; イ Le ガ キ ユ ア 1870 (Ciba (strain) system)	3.9	3.9	3.9

(utilizing the recording method of the rgb pixel of free-radical polymerised black liquid)

Use the piezoelectricity mode, drip as described below to the recess that surrounds by the light-proofness next door and penetrate R China ink liquid 1, G China ink liquid 1, the B China ink liquid 1 that obtains in above-mentioned.

Head has 318 mouths to have the density of 150 mouths at every 25.4mm, fixes by 1/2 of mouth interval that it is staggered on two mouth column directions, drips at every 25.4mm at substrate upper edge mouth column direction and penetrates 300.By warm water is circulated, become 50 ± 0.5 ℃ near head and black hydraulic control be made as the ejection part in head.

Spray from the black liquid of head by the piezoelectric drive signal control of giving head, each drips can spray 6～42pl, and in the present embodiment, glass substrate is carried in the position of 1mm below head, simultaneously, utilizes head to drip and penetrates.Transporting velocity can be set in 50～200mm/ scope of second.In addition, Piezoelectric Driving frequency maximum can be 4.6KHz, by these settings, can control the amount of penetrating of dripping.

In the present embodiment, control transporting velocity, driving frequency make that the amount of being coated with of R, G, B pigment separately becomes 1.1,1.8,0.75g/m ², penetrate R, G, B to dripping with R, G, the B corresponding concave part of hope.

Drip the black liquid of penetrating and be delivered to exposure portion, utilize ultraviolet LED (UV-LED) to expose.In the present embodiment, UV-LED uses a day inferior chemistry system NCCU033.The light of about 100mW by connecting the electric current of about 500mA, takes place from the ultraviolet light of a chip output wavelength 365nm in this LED from chip.It is spaced a plurality of with 7mm, obtains 0.3W/cm on the surface ²Power.Drip the time of back till the exposure of penetrating, and the time shutter can be by medium transporting velocity and the distance on the throughput direction of head and LED change.In the present embodiment, after about 0.5 second, expose after the land.

According to the distance and the setting of transporting velocity, can be at 0.01～15J/cm with the exposure on the medium ²Between regulate.In embodiment own, regulate the exposure energy by transporting velocity.

Use with black West Asia (ウ シ オ) motor system spectroradiometer URS-40D principal value of integral between the wavelength 220nm to 400nm in the mensuration of these exposure powers, exposure energy.Cured 30 minutes in 230 ℃ of baking boxs by the glass substrate that will drip after penetrating, make together full solidification of light-proofness next door, each pixel.

The black liquid that constitutes each pixel of the color filter obtain like this is contained in the gap, light-proofness next door firmly, not have to find to become ooze out, overflow, and the unfavorable condition of defectives such as the colour mixture of adjacent pixels and dawn.

(formation of ITO electrode)

The glass substrate that will be formed with described color filter is put into sputter equipment, under 100 ℃, and vacuum metallizing on whole

The ITO of thickness (indium tin oxide) under 240 ℃, annealed 90 minutes then, made the ITO crystallization, formed ito transparent electrode.

Measure (Mitsubishi Chemical's (strain) system " Le Tesi (ロ レ ス ) "; Measure the sheet impedance with four probe method) the ITO impedance of color filter, the result shows the i.e. 12 Ω/ of low-down value.This is considered to because the application of the invention has unexpectedly improved the flatness on color filter surface.

[embodiment 2]

(making in light-proofness next door)

With the method identical, make the light-proofness next door with embodiment 1.

(preparation of cationically polymerizable China ink liquid)

The preparation of dispersible pigment dispersion

At first, pigment, monomer and spreading agent shown in the following table 4 are put into bowl mill, use the zirconium oxide bead of diameter 0.6mm, disperse to obtain dispersible pigment dispersion after 16 hours.

[table 4] (mass parts)

	R dispersible pigment dispersion 2	G dispersible pigment dispersion 2	B dispersible pigment dispersion 2
				Paratonere 254	13	-	-
Paratonere 177	3	-	-
				Pigment green 36	-	14	-
Pigment yellow 150	-	6	-
				Pigment blue 15: 6	-	-	4
Pigment Violet 23	-	-	6
				Monomer; The proud Ke Saitan of A Rong (ア ロ Application オ キ セ Application) (East Asia synthetic (strain) system)	77	72	85
Spreading agent; Plug fine jade Si Pasi (ソ Le ス パ-ス) (system that infectious coryza is beautiful to be played (Le-Block リ ゾ-Le) (strain))	6.5	8	4.2

The preparation of China ink liquid

Mix the composition shown in the following table 5,, obtain the black liquid of RGB with the membrane filter filtration of 0.5 μ m.

[table 5] (mass parts)

[utilizing the recording method of the rgb pixel of cationically polymerizable China ink liquid]

Free-radical polymerised black liquid among the embodiment 1 instead of outside the above-mentioned cationically polymerizable China ink liquid, with the method identical with embodiment 1, is made color filter, form ito transparent electrode.

The black liquid that constitutes each pixel of the color filter obtain like this is contained in the gap, light-proofness next door firmly, not have to find to become ooze out, overflow, and the unfavorable condition of defectives such as the colour mixture of adjacent pixels and dawn.(Mitsubishi Chemical's (strain) makes " Le Tesi (ロ レ ス ) " in addition, after measured; Measure the sheet impedance with four probe method) the ITO impedance of color filter, the result shows the i.e. 11 Ω/ of low-down value.This is considered to because the application of the invention has unexpectedly improved the flatness on color filter surface.

[embodiment 3]

(method for making of black-colored photosensitive transfer materials)

On the interim supporter of polyethylene terephthalate film of thickness 75 μ m, use the slit-shaped mouth, coating is dried by the thermoplastic resin coating liquid that following prescription H1 constitutes.Then, coating is dried by the middle layer coating liquid that following prescription P1 constitutes.And then the black photosensitive composition K2 of coating table 6 is dried.On interim supporter, the thermoplastic resin that dry film thickness is 14.6 μ m is set thus, middle layer, the dry film thickness that dry film thickness is 1.6 μ m is the black photosensitive layer of 5 μ m, last pressure dressing protective film (polypropylene films of thickness 12 μ m).

Make the black photosensitive layer all-in-one-piece black-colored photosensitive transfer materials of interim supporter, thermoplastic resin, middle layer (oxygen Obstruct membrane) and black (K) like this.

＜thermoplastic resin is with applying liquid: prescription H1 〉

11.1 parts of methyl alcohol

6.36 parts of propylene glycol methyl ether acetates

52.4 parts of butanone

Methyl acrylate/2-ethyl six acrylate/benzyl methacrylate/methacrylic acid copolymer (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight=100,000,

) 5.83 parts

Styrene/acrylic acid co-polymer (multipolymer ratio of components (mol ratio)=63/37, molecular weight 10,000,

) 13.6 parts

2,9.1 parts in two [4-(methacryloxy polyethoxy) phenyl] propane (Xin Zhong village chemical industry (strain) system) of 2-

The fluorine based polymer

1 0.54 parts in surfactant

＜middle layer is with applying liquid: prescription P1 〉

PVA205 (polyvinyl alcohol (PVA), (strain) Kuraray system, saponification degree=88%, the degree of polymerization 550)

32.2 part

14.9 parts of polyvinylpyrrolidones (ISP Japanese firm system, K-30)

524 parts of distilled water

429 parts of methyl alcohol

[table 6] (mass parts)

Black-colored photosensitive resin composition	K2
		K pigment dispersing thing 1 (carbon black)	10
Propylene glycol methyl ether acetate	8
		Butanone	53
Bonding agent 2	9.1
		Hydroquinone monomethyl ether	0.002
DPHA liquid	4.2
		2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methylamino)-3 '-bromophenyl]-the s-triazine	0.16
Surfactant 1	0.044

The glass washing agent liquid utilization spray that is adjusted to 25 ℃ was sprayed for 20 seconds to alkali-free glass substrate, simultaneously, clean with rotating brush with nylon hair, after the pure water spray Cleaning for High Capacity, utilize spray to spray for 20 seconds silane coupling agent liquid (N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane 0.3 quality % aqueous solution, trade name: KBM603, SHIN-ETSU HANTOTAI's chemical industry), tilt with the pure water spray.This substrate was heated 2 minutes with 100 ℃ with substrate preparation heating arrangement.

Remove diaphragm from the black-colored photosensitive transfer materials of above-mentioned method for making, making; so that the mode that the surface of the surface of the dark photographic layer that exposes after removing and silane coupling agent processing glass substrate contacts is overlapped on the described silane coupling agent treatment substrate that obtains; use stacked machine (Co., Ltd. Hitachi's industry system (LamicII type)); at described 100 ℃ down on 2 minutes the substrate of heating, minute carry out stacked with 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transporting velocity 2.2m/.Then, with the interim supporter of polyethylene terephthalate from the interface peel of thermoplastic resin, remove interim supporter.After peeling off interim supporter, with the close induction type exposure machine with ultrahigh pressure mercury lamp (Hitachi Hith-tech Electronic Engineering Corp.'s system), with substrate and the vertical state that erects of mask (quartzy exposed mask) with picture pattern, the distance of setting between exposed mask face and this dark color photosensitive polymer combination layer is 200 μ m, with exposure 70mJ/cm ²Carry out pattern exposure.

Then, being developer solution (contain 2.5% triethanolamine, contain nonionic surfactant, contain polypropylene-based defoamer, trade name: T-PD1, Fujiphoto system) with triethanolamine sprays development with 30 ℃, 50 seconds, flat mouth pressure 0.04MPa, removes thermoplastic resin and oxygen barrier layer.

Then, to use carbonic acid Na be developer solution (contain the sodium bicarbonate of 0.06 mol, the sodium carbonate of same concentrations, 1% nekal, anionic surfactant, defoamer, stabilizing agent, trade name: T-CD1, Fujiphoto system) sprays development with 29 ℃, 30 seconds, pyramid type mouth pressure 0.15MPa, dark photosensitive polymer combination layer is developed, obtain the composition pixel.

Then, use washing agent (to contain phosphate silicate non-ionic surfactant defoamer stabilizing agent, trade name [T-SD1 (Fujiphoto system)], utilization is carried out residue with 33 ℃, 20 seconds, the spray of pyramid type mouth pressure 0.02MPa and rotating brush with nylon hair and is removed, and obtains the image of black (K).

Then, and then to this substrate, from this dark color photosensitive polymer combination layer side, with ultrahigh pressure mercury lamp with 500mJ/cm ²Light carry out post-exposure after, with 200 ℃ of thermal treatments 15 minutes, obtain the light-proofness next door.

[preparation of free-radical polymerised black liquid]

The composition of dispersible pigment dispersion and black liquid instead of beyond the following table 7,8, with the method identical with embodiment 1, is prepared free-radical polymerised black liquid.

[table 7] (mass parts)

	R dispersible pigment dispersion 3	G dispersible pigment dispersion 3	B dispersible pigment dispersion 3
				Paratonere 254	9.8	-	-
Paratonere 177	2.5	-	-
				Pigment green 36	-	10.5	-
Pigment yellow 150	-	4.5	-
				Pigment blue 15: 6	-	-	3.2
Pigment Violet 23	-	-	4.7
				Monomer; HDDA (Daicel UPC (strain) system)	30	25	37
Spreading agent; BYK-168 (Bi Ke chemistry Japan (strain) system)	8.2	10	5.3

[table 8] (mass parts)

	R China ink liquid 3	G China ink liquid 3	B China ink liquid 3
				R dispersible pigment dispersion 3	20	-	-
G dispersible pigment dispersion 3	-	20	-
				B dispersible pigment dispersion 3	-	-	20
Monomer; DPCA60 (Japanese chemical drug (strain) system)	1.1	1	1.2
				Monomer; HDDA (Daicel UPC (strain) system)	15	15	15
Photoepolymerizationinitiater initiater; イ Le ガ キ ユ ア 1870 (Ciba (strain) system)	3.9	3.9	3.9

With embodiment 1 in the same manner, use the head of piezoelectricity mode, the RGB China ink liquid that obtains in above-mentioned is dripped to the recess that is surrounded by the light-proofness next door penetrates, make color filter, form ito transparent electrode.

The black liquid that constitutes each pixel of the color filter obtain like this is contained in the gap, light-proofness next door firmly, not have to find to become ooze out, overflow, and the unfavorable condition of defectives such as the colour mixture of adjacent pixels and dawn.In addition, measure (Mitsubishi Chemical's (strain) system " Le Tesi (ロ レ ス ) "; Measure the sheet impedance with four probe method) the ITO impedance of color filter, the result shows the i.e. 11 Ω/ of low-down value.This is considered to because the application of the invention has unexpectedly improved the flatness on color filter surface.

[embodiment 4]

The black-colored photosensitive resin composition K2 of embodiment 3 is changed to the black-colored photosensitive resin composition K3 of the composition shown in the following table 9, and it is the black photosensitive layer of 7 μ m that dry film thickness is set, and in addition, makes the light-proofness next door in the same manner with embodiment 3.

[table 9] (mass parts)

Black-colored photosensitive resin composition	K3
		K pigment dispersing thing 1 (carbon black)	7
Propylene glycol methyl ether acetate	8
		Butanone	53
Bonding agent 2	9.1
		Hydroquinone monomethyl ether	0.002
DPHA liquid	4.2
		2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methylamino)-3 '-bromophenyl]-the s-triazine	0.16
Surfactant 1	0.044

(preparation of free-radical polymerised black liquid)

Except the composition with dispersible pigment dispersion and black liquid changes to following table 10,, prepare free-radical polymerised black liquid with the method identical with embodiment 3.

[table 10] (mass parts)

	R China ink liquid 4	G China ink liquid 4	B China ink liquid 4
				R dispersible pigment dispersion 3	20	-	-
G dispersible pigment dispersion 3	-	20	-
				B dispersible pigment dispersion 3	-	-	20
Monomer; DPCA60 (Japanese chemical drug (strain) system)	1.1	1	1.2
				Monomer; HDDA (Daicel UPC (strain) system)	15	15	15
Photoepolymerizationinitiater initiater; イ Le ガ キ ユ ア 1870 (Ciba (strain) system)	3.9	3.9	3.9
				3-ethoxy-propionic acid methyl esters	17	17	17
Solid state component (quality %)	70	70	70

With embodiment 1 in the same manner, use the piezoelectricity mode, the RGB China ink liquid that obtains in above-mentioned is dripped to the recess that is surrounded by the light-proofness next door penetrates drop, make color filter, form the ITO electrode.

The black liquid that constitutes each pixel of the color filter obtain like this is contained in the gap, light-proofness next door firmly, not have to find to become ooze out, overflow, and the unfavorable condition of defectives such as the colour mixture of adjacent pixels and dawn.(Mitsubishi Chemical's (strain) makes " Le Tesi (ロ レ ス ) " in addition, after measured; Measure the sheet impedance with four probe method) the ITO impedance of color filter, the result shows the i.e. 12 Ω/ of low-down value.This is considered to because the application of the invention has unexpectedly improved the flatness on color filter surface.

[embodiment 5]

(making in light-proofness next door)

The black-colored photosensitive resin composition K2 of embodiment 3 is changed to the black-colored photosensitive resin composition K4 of the composition shown in the following table 11, and it is the black photosensitive layer of 10 μ m that dry film thickness is set, in addition, with embodiment 3 in the same manner, make the light-proofness next door.

[table 11] (mass parts)

Black-colored photosensitive resin composition	K4
		K pigment dispersing thing 1 (carbon black)	5
Propylene glycol methyl ether acetate	8
		Butanone	53
Bonding agent 2	9.1
		Hydroquinone monomethyl ether	0.002
DPHA liquid	4.2
		2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methylamino)-3 '-bromophenyl]-the s-triazine	0.16
Surfactant 1	0.044

(free-radical polymerised black liquid)

Except the composition with dispersible pigment dispersion and black liquid changes to following table 12,, prepare free-radical polymerised black liquid with the method identical with embodiment 3.

[table 12] (mass parts)

	R China ink liquid 5	G China ink liquid 5	B China ink liquid 5
				R dispersible pigment dispersion 3	20	-	-
G dispersible pigment dispersion 3	-	20	-
				B dispersible pigment dispersion 3	-	-	20
Monomer; DPCA60 (Japanese chemical drug (strain) system)	1.1	1	1.2
				Monomer; HDDA (Daicel UPC (strain) system)	15	15	15
Photoepolymerizationinitiater initiater; イ Le ガ キ ユ ア 1870 (Ciba (strain) system)	3.9	3.9	3.9
				3-ethoxy-propionic acid methyl esters	40	40	40
Solid state component (quality %)	50	50	50

With embodiment 1 in the same manner, use the piezoelectricity mode, the RGB China ink liquid that obtains in above-mentioned is dripped to the recess that is surrounded by the light-proofness next door penetrates, make color filter, form the ITO electrode.

The black liquid that constitutes each pixel of the color filter obtain like this is contained in the gap, light-proofness next door firmly, not have to find to become ooze out, overflow, and the unfavorable condition of defectives such as the colour mixture of adjacent pixels and dawn.In addition, measure (Mitsubishi Chemical's (strain) system " Le Tesi (ロ レ ス ) "; Measure the sheet impedance with four probe method) the ITO impedance of color filter, the result shows the i.e. 12 Ω/ of low-down value.This is considered to because the application of the invention has unexpectedly improved the flatness on color filter surface.

[comparative example 1]

Prepare the black liquid of the composition of following table 13, utilize ink-jet method,, penetrate and R, G, black liquid that the B pattern is corresponding so that the amount of being coated with of pigment and embodiment 1 identical mode is dripped to the recess of the glass substrate of embodiment 1 with light-proofness next door.

[table 13] (mass parts)

	R dispersible pigment dispersion 6	G dispersible pigment dispersion 6	B dispersible pigment dispersion 6
				Paratonere 254	3.2	-	-
Paratonere 177	0.83	-	-
				Pigment green 36	-	2.6	-
Pigment yellow 150	-	1.1	-
				Pigment blue 15: 6	-	-	1.6
Pigment Violet 23	-	-	2.4
				Glycerine	4	4	4
Ethylene glycol	5	5	5
				Monoethanolamine	1	1	1
The styrene-propene acid resin	4	4	4
				Water	82	82	82

Drip penetrate after, carry out air dry in 30 minutes, and then 150 ℃ of dryings.Then, with embodiment 1 in the same manner, cure, obtain color filter.

Observable color filter is sneaked into the pigment of the black liquid of other colors that stride across the light-proofness next door as a result in each pixel of R, G, B, find colour mixture, the form and aspect that can not get wishing.

[comparative example 2]

Being formed with on the described substrate in light-proofness next door, carry out plasma treatment appts, under following condition, carry out plasma treatment, in addition, penetrate R, G, R pattern by dripping equally with comparative example 1, carry out heat curing, make color filter.

(processing of plasma hydrophobization)

By following method, carry out the plasma hydrophobization and handle.

Be formed with on the described substrate in light-proofness next door, using negative electrode coupling scheme parallel plate-type plasma treatment appts, carrying out the plasma hydrophobization by following condition and handle.

Using gases: CF ₄

Gas flow: 80sccm

Pressure: 40Pa

RF power: 50W

Processing time: 30 seconds

The black liquid of each pixel of formation of the color filter that carries out plasma treatment and the next door hydrophobization is made is housed in the gap, light-proofness next door, do not ooze out, overflow, with the defectives such as colour mixture of adjacent pixels, but concentration reduces or the unfavorable condition of small defectives such as dawn finding to become with the border in next door.

[comparative example 3]

Drip penetrate R, G, B China ink liquid after, in 230 ℃ of baking boxs, do not cure, in addition, with embodiment 1 in the same manner, make color filter, form ito transparent electrode.

The black liquid that constitutes each pixel of the color filter obtain like this is contained in the gap, light-proofness next door firmly, not have to find to become ooze out, overflow, and the unfavorable condition of defectives such as the colour mixture of adjacent pixels and dawn.But (Mitsubishi Chemical's (strain) makes " Le Tesi (ロ レ ス ) " after measured; Measure the sheet impedance with four probe method) the ITO impedance of color filter, the result shows the i.e. 200 Ω/ of very high value.

[embodiment 6]

Use the color filter that obtains in embodiment 1～5, the comparative example 3, make liquid crystal indicator as described below.

(formation of gap material)

To open the identical method of putting down in writing in [embodiment 1] of 2004-240335 communique of gap material formation method, form the gap material on the ito transparent electrode of in above-mentioned, making with the Jap.P. spy.

(the liquid crystal aligning control formation of projection)

Use following positive-working photosensitive resin layer with coating liquid, on the ito transparent electrode that has formed described gap material, form liquid crystal aligning control projection.

But, expose, develop and cure operation and use following method.

So that the photomask of regulation disposes close induction type exposure machine (Hitachi Hith-tech Electronic Engineering Corp.'s system) apart from the mode of the surface 100 μ m of photo-sensitive resin, across this photomask, utilize ultrahigh pressure mercury lamp, can 150mJ/cm with irradiation ²Carry out the close induction type exposure.

Then, use the fountain developing apparatus, 2.38% tetramethyl-ammonium hydroxide aqueous solution is being developed when substrate sprayed for 30 seconds under 33 ℃.Like this, develop remove photo-sensitive resin do not need part (exposure portion), obtain on color filter side group plate, being formed with the liquid crystal aligning control that constitutes by the photo-sensitive resin that is patterned into desirable shape base plate for liquid crystal display device with projection.

Then, under 230 ℃, cure the base plate for liquid crystal display device that is formed with this liquid crystal aligning control usefulness projection, on base plate for liquid crystal display device, form the liquid crystal aligning control projection that is cured thus.

＜positive-working photosensitive resin layer is write out a prescription with coating liquid 〉

Eurymeric resist liquid (Fujiphoto electronics synthesis material (the Off イ of Fuji Le エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ) (Co., Ltd.) system FH-2413F)

53.3 part

46.7 parts of butanone

0.04 part of McGee Huo Ke (メ ガ Off ア Star Network) F-780F (big Japanese ink chemical industry (strain) system)

(making of liquid crystal indicator)

On the above-mentioned base plate for liquid crystal display device that obtains and then the alignment films that is made of polyimide is set.

Then, the sealant of the position printing epoxy resin of the black matrix housing that is provided with in the mode that is equivalent to the pixel groups of surrounding color filter, and drippage MVA pattern liquid crystal, make its with the counter substrate applying after, the substrate of applying heat-treated and make sealant cures.Attach the polarization plates HLC2-2518 of (strain) three upright magnetic (サ Application リ Star Star) systems on the two sides of the liquid crystal cells that obtains like this.Then, constitute the backlight of three-wavelength cold-cathode tube light source (Lai Dike of Toshiba (ラ イ テ Star Network) (strain) makes FWL18EX-N), it is disposed at a side that becomes the back side of the liquid crystal cells that is provided with described polarization plates, form liquid crystal indicator.

(evaluation)

With visualization make liquid crystal indicator 1～4 display white that obtains situation, and show display quality under the situation of black.The results are shown in the table 14.

[table 14]

The liquid crystal display cells numbering	The color filter that uses	Display quality
			1	Embodiment 1	There is not inequality
2	Embodiment 2	There is not inequality
			3	Embodiment 3	There is not inequality
4	Embodiment 4	There is not inequality
			5	Embodiment 5	There is not inequality
6	Comparative example 3	Inequality is arranged

As known from Table 14, used liquid crystal indicator 1～5 not have inequality,, used the liquid crystal indicator of the color filter in the comparative example 3 to find to have inequality with respect to this according to the color filter of embodiments of the invention 1～5.

According to the present invention as can be known, provide can positional precision to form the pixel that does not have colour mixture etc. well, can make the manufacturing method of color filter of color filter with low cost and high-level efficiency.

In addition, according to the present invention as can be known, provide positional precision to have well not have colour mixture etc. pixel, do not show uneven color filter when being installed on display device.

According to the present invention as can be known, provide the display device that does not show inequality.

All documents of putting down in writing in this instructions, patented claim, and technical manual according to each document, patented claim, and technical manual as with reference to the situation about being written into and the identical degree of situation of record specifically and individually, be written in this instructions as reference.

Claims (15)

1. a manufacturing method of color filter is characterized in that,

On substrate, form next door with light-proofness, utilize ink-jetting style, black liquid to the recess spraying red (R) of dividing, green (G) and blue (B) by described next door, make described R, G, and B China ink liquid be deposited in described recess and form dyed layer, used the dyed layer of each black liquid in formation after, utilize the curing of the dyed layer of activation-energy-ray, after the curing of panchromatic dyed layer, utilize the curing of the dyed layer of heat again

Described each black liquid is formed by polymerism China ink liquid, and described polymerism China ink liquid contains colorant, polymerizable compound and polymerization initiator, and the quantity of solvent in the black liquid is below the 50 weight %.

2. manufacturing method of color filter according to claim 1 is characterized in that,

Polymerism China ink liquid is free-radical polymerised composition.

3. manufacturing method of color filter according to claim 1 is characterized in that,

Polymerism China ink liquid is cationically polymerizable composition.

4. manufacturing method of color filter according to claim 3 is characterized in that,

Described cationically polymerizable composition contains the compound that is selected from vinyl ether compound, oxetane compound and oxirane compound.

5. manufacturing method of color filter according to claim 1 is characterized in that,

The composition with curable in the polymerism China ink liquid is more than the 50 quality %.

6. manufacturing method of color filter according to claim 1 is characterized in that,

Described active energy ray has the wavelength of 250～450nm.

7. manufacturing method of color filter according to claim 6 is characterized in that,

Described active energy ray has the wavelength of 365 ± 20nm.

8. manufacturing method of color filter according to claim 6 is characterized in that,

Being solidificated in of dyed layer of described utilization heat carried out under 120 ℃～250 ℃ 10 minutes～120 minutes.

9. manufacturing method of color filter according to claim 1 is characterized in that,

Described next door is formed by the photosensitive composite that contains colorant, polymerizable compound and Photoepolymerizationinitiater initiater, and the optical concentration of described photosensitive composite is 2.5～6.0.

10. manufacturing method of color filter according to claim 9 is characterized in that,

It is that hydrogen donor or amine are hydrogen donor that described photosensitive composite also contains mercaptan.

11. manufacturing method of color filter according to claim 9 is characterized in that,

The amount of described Photoepolymerizationinitiater initiater in photosensitive composite is 0.5～10 quality %.

12. manufacturing method of color filter according to claim 9 is characterized in that,

Described next door is solidified to form described photosensitive composite by utilize light under the protective seam that can intercept oxygen.

13. manufacturing method of color filter according to claim 9 is characterized in that,

Height with next door of light-proofness is 1～20 μ m.

14. a color filter is characterized in that,

Utilize the described manufacturing method of color filter of claim 1 to make.

15. a display device is characterized in that,

The described color filter of claim 14 is installed.