CN100510799C - Color filter, process for manufacturing color filter, and liquid crystal display device - Google Patents

Abstract

A color filter including colored pixels of at least two or more colors, in which the colored pixels contain at least pigment particles, the contrast of each colored pixel is not lower than 2000 and the difference between the contrast of the colored pixel having the lowest contrast and the contrast of the colored pixel having the highest contrast among the colored pixels of two or more colors is not more than 600; a process for manufacturing the same; and a liquid crystal display device using the color filter.

Description

Color filter is used to make the method and the liquid crystal indicator of color filter

Technical field

The present invention relates to a kind of color filter, the liquid crystal indicator that is used to make the method for described color filter and uses described color filter, described color filter is preferred for giant-screen equipment such as notebook computer or TV monitor.

Background technology

Color filter is absolutely necessary parts for LCD (below be also referred to as " liquid crystal indicator ").Liquid crystal indicator is very compact, has the performance that is equivalent to or is better than conventional CRT monitor, and beginning replaced C RT display.

In order to form the coloured image of liquid crystal indicator, will become to constitute each color of pixel of color filter by the optical colour of color filter, and the light that makes up these colors is to form coloured image.Usually, three of RGB kinds of color pixel form coloured image.As the material that constitutes color filter, since thermotolerance and sunproof requirement, the main material that wherein organic pigment is scattered in resin such as the acrylic compounds (acryl) that uses.Yet, because the use of organic pigment, in this color filter, because the light scattering of granules of pigments produces depolarization, promptly so-called depolarisation effect, and this causes contrast to reduce.

In recent years, because liquid crystal indicator is used for TV and watch-dog, so the demand of display quality is become strict.Particularly, the raising of the raising of the color rendering scope of liquid crystal indicator and contrast is an essential condition.In the color filter of routine (referring to, Japanese Patent Application Publication (JP-A) number 2001-194658 for example), because depolarization, contrast is about 800 to 1500, and has hard to sayly reached enough contrast performance.

In addition, if the contrast height of whole color filter, then because when the balance of the contrast of each pixel of RGB not simultaneously, the light quantity difference of from each pixel of RGB, leaking, for example when the light quantity of leaking from the B pixel is big, also occur liquid crystal indicator in the black colourity that shows from the problem of achromic point to light blue direction displacement.Even the contrast height of color filter, when the contrast of polaroid is hanged down, the contrast of LCD degree is also still low, in addition, even the contrast height of polaroid, when polaroid when the quadrature transmittance of about 400nm is high, also occur liquid crystal indicator in the black colourity that shows from the problem of achromic point to light blue direction displacement.

Summary of the invention

The present invention considers that above-mentioned situation finishes, and provides: a kind of color filter, and wherein the contrast height of each pixel demonstrates distinct image, and the contrast of each pixel of RGB obtains balance, and black display performance excellence; Be used to make the method for described color filter; With liquid crystal indicator with this color filter.Equally, have the pixel of high-contrast and polaroid by combination with high-contrast, the invention provides the liquid crystal indicator of the image that shows the distinctness with high-contrast, wherein the contrast of each pixel of RGB obtains balance, and aspect black display performance excellence.

A first aspect of the present invention provides the color filter of the colored pixels that comprises two or more color, wherein each colored pixels comprises granules of pigments at least, the contrast of each colored pixels is not less than 2000, and among the colored pixels of two or more color, have the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast and be not more than 600.

A second aspect of the present invention is provided for making the method for the color filter of first aspect, described method comprises by a kind of colored photosensitive resin composition and forms resin bed, described colored photosensitive resin composition comprises (1) alkali soluble resins, (2) monomer or oligomer, (3) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system and (4) granules of pigments.

A third aspect of the present invention provides the liquid crystal indicator of the color filter that comprises first aspect.

A fourth aspect of the present invention provides a kind of liquid crystal indicator, that described liquid crystal indicator comprises is backlight, polaroid, at least two substrates, by the liquid crystal layer of described substrate support, the electrode of at least a portion of described substrate, settling, with the color-filter layer of at least a portion of described substrate, settling, wherein said color-filter layer is the color filter of first aspect, and described polaroid has the quadrature transmittance that is equal to or higher than 99.95 degree of polarization and is equal to or less than 0.05% at 400nm.

The accompanying drawing summary

Fig. 1 is the schematic cross section that shows an example of liquid crystal indicator of the present invention.

Fig. 2 is the cross-sectional view that shows another example of liquid crystal indicator of the present invention.

Fig. 3 is the schematic cross section that shows another example of liquid crystal indicator of the present invention.

Implement best mode of the present invention

At first, color-filter layer of the present invention (following abbreviate as in some cases " color filter ") will be described, will describe method and the liquid crystal indicator that is used to make color filter successively then.

＜color-filter layer 〉

Color-filter layer of the present invention is the color filter with colored pixels of two or more color.Each colored pixels comprises granules of pigments at least.The contrast of each colored pixels is not less than 2000, and in the colored pixels of two or more color, has the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast and is not more than 600.

＜contrast 〉

The contrast of each colored pixels of color filter of the present invention is not less than 2000, more preferably is not less than 2800, also preferably is not less than 3000, most preferably is not less than 3400.If the contrast of each colored pixels that constitutes color filter is less than 2000, then when observation had the image of liquid crystal indicator of this color filter, observed image turned white generally, and is difficult to see, thereby this is not preferred.In addition, have the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast and be not higher than 600,, also preferably be not higher than 350, most preferably be not higher than 200 more preferably no higher than 410.When the contrast of the colored pixels with minimum contrast and the difference of contrast with colored pixels of high-contrast surpass 600, because it is very different from the light quantity of black each colored pixels part that shows, leaking, even so when based on liquid crystal indicator when the white color characteristics that shows is regulated color, the phenomenon that color balance is disintegrated also takes place in black the demonstration, the color reprodubility deterioration, thus this is not preferred.

Contrast refers to constitute the contrast of each pixel of R (red), the G (green) of color filter and B (indigo plant), estimates according to color separately.

The method of measuring contrast is as follows: polaroid is covered on the both sides of the object that will measure, the polarization direction of polaroid is parallel to each other, and in this case, backlight from the side use of a polaroid, and measurement is by the brightness Y1 of the light of another polaroid.Then, backlight from the side use of a polaroid under the situation of polaroid quadrature, and measurement is by the brightness Y2 of the light of another polaroid.The measured value that use obtains calculates contrast with Y1/Y2.At this, as polaroid, can use the G1220DUN that produces by Nitto Denko, and, can use colour brightness meter (trade name: BM-5 is produced by Topcon) as surveying instrument.The polaroid that uses in measuring contrast is identical with the polaroid that uses in the liquid crystal indicator that uses described color filter.

＜colored pixels 〉

The colored pixels of color filter of the present invention is formed by colored resin composition.The colored pixels that is preferably formed at least a color of color filter of the present invention comprises C.I. paratonere 254 or C.I. pigment green 36 or C.I. pigment blue 15: 6 as colorant.By comprising these colorants, can make color filter with high-contrast.

(colorant)

In the present invention, preferred colorant is C.I. paratonere 254, (ii) C.I. pigment green 36 in G (green) colored resin composition and the (iii) C.I. pigment blue 15 in B (indigo plant) colored resin composition in (i) R (red) colored resin composition: 6.

In the dry film that the thickness coating colored resin composition with 1.0 to 3.0 μ m obtains, (i) content of middle C.I. paratonere 254 is preferably 0.80 to 0.96g/m ², more preferably 0.82 to 0.94g/m ², be preferably 0.84 especially to 0.92g/m ²

In the dry film that the thickness coating colored resin composition with 1.0 to 3.0 μ m obtains, (ii) the content of middle C.I. pigment green 36 is preferably 0.90 to 1.34g/m ², more preferably 0.95 to 1.29g/m ², be preferably 1.01 especially to 1.23g/m ²

In the dry film that the thickness coating colored resin composition with 1.0 to 3.0 μ m obtains, (iii) middle C.I. pigment blue 15: 6 content is preferably 0.59 to 0.67g/m ², more preferably 0.60 to 0.66g/m ², be preferably 0.61 especially to 0.65g/m ²

In addition, except that above-mentioned pigment, can use the pigment that is different from above-mentioned pigment by making up them.Its instantiation comprise can replenish use wherein give following dyestuff or pigment pigment with colour index (C.I.) value.

-additional dyestuff that uses or pigment-

If necessary, except that above-mentioned colorant (pigment), known colorant (dyestuff, pigment) can also be joined in the colored resin composition.During pigment among using known colorant, pigment is scattered in the colored resin composition equably suits.Owing to this reason, the preferred particulates diameter is equal to or less than 0.1 μ m, especially preferably is equal to or less than 0.08 μ m.

The known dyestuff or the example of pigment comprise Victoria's pure blue B O (C.I.42595), and auramine (C.I.41000), Fat are deceived HB (C.I.26150), 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 15, 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. pigment Red 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. pigment Red170, C.I. pigment Red171, 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. pigment Red180, 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. pigment Red226, 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, the C.I. pigment blue 15: 3, the C.I. pigment blue 15: 4, the C.I. pigment blue 15: 6, the C.I. pigment blue 60, the C.I. pigment Green 7, the 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.

The instantiation of the preferred colorant that uses is included in JP-A No.2005-17716 in the present invention, pigment and the dyestuff described in 0038 to 0054 section, at JP-ANo.2004-361447, the pigment of describing in 0068 to 0072 section, with at JP-A No.2005-17521, the colorant of describing in 0080 to 0088 section.

In the present invention, the example of the preferred compositions of the common above-mentioned pigment that uses comprises: 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 and the combination of C.I. pigment Violet 23 or C.I. pigment blue 60.

Under common situation about using, the content of C.I. paratonere 254 preferably is equal to or greater than 80 quality % in pigment, especially preferably is equal to or greater than 90%.Under common situation about using, the content of C.I. pigment green 36 preferably is equal to or greater than 50 quality % in pigment, especially preferably is equal to or greater than 60 quality %.Under common situation about using, C.I. pigment blue 15 in pigment: 6 content preferably is equal to or greater than 80 quality %, especially preferably is equal to or greater than 90 quality %.

Use suits as dispersion with pigment.Join in the described after a while organic solvent (or vehicle) by the composition that premixed pigment and pigment dispersion are obtained, and, can prepare this dispersion its dispersion.Vehicle refers to wherein dispersed color when coating is in liquid state, comprises the part as liquid, and with the bonding medium with cured coating film of pigment (bonding agent) and dissolving and dilute this composition of filming (organic solvent).The decollator that uses during for dispersed color is not particularly limited, but example comprises known decollator, as kneader, roller mill, masher, super grinding machine, dissolver, uniform mixer and the sand mill of describing at following document for example: 438 parts of " the Dictionary of Pigment " that is shown by Kunizo Asakura, first published, Asakurashoten, 2000.In addition, utilize the friction force that causes by the mechanical lapping of in the document 310 parts, describing, pigment can be separated subtly.

The number average particle diameter of the colorant of Shi Yonging (granules of pigments) is preferably 0.001 to 0.1 μ m in the present invention, more preferably 0.01 to 0.08 μ m.When the number average particle diameter of pigment is 0.001 to 0.1 μ m, can stably keep disperse state, the contrast that does not cause simultaneously the depolarization by pigment to cause reduces, thus this is preferred." particle diameter " refers to that the particle in the supposition electron micrograph is the diameter with bowlder of the same area as used herein, and " number average particle diameter " refers to the average of 100 particles when all obtaining above-mentioned particle diameter for a plurality of particles.

By reducing the particle diameter of the pigment that disperses, can be implemented in the contrast of the colored pixels that limits among the present invention.By regulating the jitter time of pigment dispersion, can realize the reduction of particle diameter.For dispersed color, can use above-mentioned known decollator.Jitter time is preferably 10 to 35 hours, more preferably 10 to 30 hours, also be preferably 18 to 30 hours, most preferably be 24 to 30 hours.When jitter time less than 10 hours the time, the granules of pigments diameter is big, may produce the depolarization that pigment causes, may reduce contrast in some cases.On the other hand, when jitter time surpassed 35 hours, the viscosity of dispersion may increase, and coating may become difficult in some cases.

For the contrast that makes the colored pixels with minimum contrast and the difference of contrast with colored pixels of high-contrast are not more than 600.Can regulate the contrast of granules of pigments diameter need to obtain.

The colored resin composition that forms color filter in the present invention is preferably except that colorant, at least also comprises (1) alkali soluble resins, the colored resin composition of (2) monomer or oligomer and (3) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.

To illustrate that below these components (1) are to (3).

(1) alkali soluble resins

As the alkali soluble resins among the present invention (below, abbreviate " bonding agent " in some cases as), preferably has polar group such as carboxylic acid group or the carboxylic acid group's on side chain polymkeric substance.Example is included in the maleic acid of methacrylic acid copolymer, acrylic copolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid and the partial esterification described in the following patent literature: JP-A No.59-44615, Japanese patent application publication (JP-B) No.54-34327, JP-B No.58-12577, JP-BNo.54-25957, JP-A No.59-53836 and JP-A No.59-71048.The cellulose derivative that has the carboxylic acid group on side chain also is an example.Can also preferably use the polymkeric substance that adds cyclic acid anhydride with hydroxyl.Particularly preferred example is included in (methyl) benzyl acrylate and (methyl) acrylic acid multipolymer of describing among the USP No.4139391, and the multiple copolymer of (methyl) benzyl acrylate, (methyl) acrylic acid and another kind of monomer.These binder polymers with polar group can use separately, perhaps can be with the wherein common form use of using the composition of common film forming polymer.Content with binder polymer of polar group is generally 20 to 50 quality % with respect to the total solids content of colored resin composition, is preferably 25 to 45 quality %.

(2) monomer or oligomer

Preferred monomers or oligomer are to have two or more alkene formula unsaturated double-bonds among the present invention, and the monomer or the oligomer that carry out addition polymerization by photoirradiation.But the example is included in the alkene formula unsaturated group that has at least one addition polymerization in the molecule, and has the compound of the boiling point that is equal to or higher than 100 ℃ at normal pressure.Example comprises the acrylate of simple function group and the methacrylate of simple function group, for example polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate and (methyl) acrylic acid phenoxy ethyl; Polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, pentaerythrite four (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, hexanediol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate; Multi-functional acrylate that obtains by the following method and multi-functional methacrylate: oxirane or epoxypropane are added to multi-functional alcohol, on trimethylolpropane and glycerine, and with its (methyl) acroleic acid esterification.

Other example is included in the urethane acrylate of describing among JP-B No.48-41708, JP-B No.50-6034 and the JP-ANo.51-37193; The polyester acrylate of in JP-B No.49-43191 and JP-BNo.52-30490, describing; Multi-functional acrylate and methacrylate are as the epoxy acrylate as epoxy resin and (methyl) acrylic acid reaction product.

In the middle of them, preferred trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate and dipentaerythritol five (methyl) acrylate.

In addition, preferred examples is included in " the polymerizable compound B " that describes among the JP-A No.11-133600.

These monomers or oligomer can use separately or by two or more is mixed.The content of described monomer or oligomer is generally 5 to 50 quality % with respect to the total solids content of colored resin composition, is preferably 10 to 40 quality %.

(3) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system

The example of Photoepolymerizationinitiater initiater in the present invention or Photoepolymerizationinitiater initiater system is included in ortho position polyketone aldehyde (polyketaldonyl) compound of describing among the USPNo.2367660, the acyloin ether of in USPNo.2448828, describing, the aromatics acyloin compound of in USP No.2722512, describing that is replaced by α-hydrocarbon, the multinuclear naphtoquinone compounds of in USP No.3046127 and USP No.2951758, describing, the triarylimidazoles dipolymer of in USP No.3549367, describing and to the combination of amino ketones, benzothiazole compound of describing in JP-B No.51-48516 and trihalomethyl group s-triazine, trihalomethyl group s-triazine of describing in USP No.4239850 and the San Lu that describes in USPNo.4212976 are for Jia oxadiazole compound.Particularly, preferred trihalomethyl group s-triazine, San Lu are for Jia oxadiazole and triarylimidazoles dipolymer.

In addition, in JP-A No.2004-317898 (0026 section) and JP-A No.2003-131378 (0064 to 0087 section), described and to be used for Photoepolymerizationinitiater initiater of the present invention or Photoepolymerizationinitiater initiater system.

In addition, preferred examples is included in " the polymerization initiator C " that describes among the JP-A No.11-133600.

These Photoepolymerizationinitiater initiaters or Photoepolymerizationinitiater initiater system can be used separately or by two or more is mixed.Especially preferably use two or more.When using at least two kinds of Photoepolymerizationinitiater initiaters, can improve display performance, and particularly, can reduce the scattering of display.

The content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system is generally 0.5 to 20 quality % with respect to the total solids content of colored resin composition, is preferably 1 to 15 quality %.

(other adjuvant)

-solvent-

In the present invention, except that said components, can also be with an organic solvent in colored resin composition.The example of organic solvent comprises methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate and caprolactam.

-surfactant-

In the color filter that routine is used, exist each color of pixel is concentrated realizing the problem of high excitation, and in fact, the nonuniform film thickness of pixel is thought uneven color.Owing to this reason, require to improve the film thickness change when forming (coating) resin bed of the film thickness that directly influences pixel.

In color filter of the present invention, from controlling uniform film thickness and effectively preventing the viewpoint of inhomogeneous coating (the inhomogeneous color that is caused by film thickness change), preferred colored resin composition comprises suitable surfactant.

The preferred embodiment of surfactant is included in disclosed surfactant among JP-A No.2003-337424 and the JP-ANo.11-133600.

-thermal polymerization inhibitor-

In the present invention, preferred colored resin composition comprises thermal polymerization.The example of described thermal polymerization inhibitor comprises p-dihydroxy-benzene, hydroquinone monomethyl ether, p methoxy phenol, BHT, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole and phenothiazine.The example of described thermal polymerization inhibitor also is included in those that describe among the JP-A No.2004-317898 (0029 section).

-ultraviolet light absorber-

In the present invention, if necessary, colored resin composition can comprise ultraviolet light absorber.The example of ultraviolet light absorber is included in compound, salicylate system, benzophenone series, benzotriazole system, cyanoacrylate system, nickel chelate system and the hindered amine system of describing among the JP-A No.5-72724.

Particularly, example comprises phenyl salicytate, salicylic acid-4-tert-butyl group phenyl ester, 2,4-di-tert-butyl-phenyl-3 ', 5 '-two-t-4 '-hydroxybenzoate, salicylic acid-4-tert-butyl group phenyl ester, 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, Octabenzone, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, ethyl-2-cyano group-3,3-diphenylacrylate ester, 2,2 '-hydroxyl-4-methoxy benzophenone, nickel dibutyl dithiocarbamate, two (2,2,6,6-tetramethyl-4-pyridine-sebacate, salicylic acid-4-tert-butyl group phenyl ester, phenyl salicytate, 4-hydroxyl-2,2,6,6-tetramethyl piperidine condensation product, succinic acid-two (2,2,6,6-tetramethyl-4-piperidyl)-ester, 2-[2-hydroxyl-3, two (α, the α-Er Jiajibianji) phenyl of 5-]-2H-benzotriazole and 7-{[4-chloro-6-(diethylamino)-5-triazine-2-yl] amino }-3-phenyl cumarin.

In JP-A No.2003-5382 (0080 to 0081 section), details have been described also.

In the present invention, colored resin composition can also be included in " bonding agent " and other adjuvant except that above-mentioned adjuvant of describing among the JP-A No.11-133600.

＜resin transmits material 〉

Can make color filter of the present invention by transmitting resin transmission material (photosensitive resin transmission material).The preferred resin of describing in JP-A No.5-72724 that uses transmits material, and promptly integrated (integrated-type) film forms color filter.The example of the structure of described integrated film comprises wherein with the structure of interim carrier/thermoplastic resin/middle layer/resin bed/diaphragm with this order lamination.

In the present invention, can form the resin bed that resin transmits material by using above-mentioned colored resin composition.

(interim carrier)

The interim carrier that preferred resin transmits material has pliability, and does not produce significant deformation, contraction or elongation under pressure or pressure and heating.The example of this carrier comprises polyethylene terephthalate film, tri cellulose acetate membrane, polystyrene film and polycarbonate membrane, especially, and preferred especially biaxial stretch-formed polyethylene terephthalate film.

The thickness of interim carrier is not particularly limited, but is generally the scope of 5 to 200 μ m, and particularly, from being easy to processing and multiduty viewpoint, the scope of 10 to 150 μ m is favourable and preferred.In addition, interim carrier can be transparent, perhaps can comprise the silicon, alumina sol, chromic salts or the zirconates that are transformed into dyestuff.

(thermoplastic resin)

As the component of in thermoplastic resin, using, preferred disclosed organic polymer material in JP-A No.5-72724, and preferred especially a kind of component is selected from by the dimension block-regulations (particularly, according to American Material Testing Method, the polymkeric substance softening point mensuration of ASTMD1235) softening point of measuring is about 80 ℃ or lower organic polymer material.Particularly, example includes organic polymer, for example polyolefin such as tygon and polypropylene; The multipolymer of ethylene copolymer such as ethene and vinyl acetate and saponified, ethene thereof and acrylate or its are saponified; Polyvinylchloride, the multipolymer of vinyl chloride copolymer such as vinyl chloride and vinyl acetate and saponified, poly-inclined to one side 1, the 1-dichloroethylene, poly-inclined to one side 1,1-dichloroethylene (polyvinilidene chloride) multipolymer, polystyrene, the multipolymer of styrol copolymer such as styrene and (methyl) acrylate or its are saponified, polyvinyl toluene, the multipolymer of polyvinyl toluene multipolymer such as vinyltoluene and (methyl) acrylate or its are saponified, poly-(methyl) acrylate, (methyl) acrylate copolymer is as the multipolymer of (methyl) butyl acrylate and vinyl acetate, and polyamide such as vinyl acetate copolymer nylon, the nylon of copolymerization, the nylon of the nylon of N-alkoxy methylization and N-dimethyl amination.In addition, can be with reference to the description of JP-A No.2004-205732 (0038 to 0044 section).

(middle layer)

Transmit in the material at resin, preferably provide the middle layer to prevent that component is mixed when being coated with a plurality of coatings and store after coating.Preferably use the oxygen screened film that in JP-A No.5-72724, is described as " separation layer " as the middle layer, and in this case, increase exposure sensitivity, reduce the time load of exposure device, and boost productivity with oxygen function of shielding.

As the oxygen screened film, preferably have the low oxygen perviousness and be dispersed or dissolved in water or alkaline aqueous solution in film, and the described film selection that can in known film, suit.As the resin that can be used for the middle layer, can be with reference to the description of JP-A No.2005-17521 (0095 to 0101 section), and in the middle of them, particularly preferably be the combination of polyvinyl alcohol (PVA) and polyvinyl pyrrolidone.

(diaphragm)

Preferably providing thin diaphragm on the thermoplastic resin to prevent to pollute and damage during in storage.Described diaphragm can be made up of or materials similar identical with the material of interim carrier, and must peel off from thermoplastic resin easily.As the diaphragm material, for example, silicone paper and polyolefin or ptfe sheet suit.

(being used to prepare the method that resin transmits material)

Can prepare resin by the following method and transmit material: use the coating solution (coating solution of thermoplastic resin) of the component of wherein dissolving thermoplastic resin on interim carrier, to be coated with, and be dried so that thermoplastic resin to be provided, afterwards, coating comprises the intermediate layer material solution of the solvent of heat of solution plastic resin layer not and is dried on thermoplastic resin, afterwards, by using the solvent application and the drying of not dissolving the middle layer, provide the resin bed of colored resin composition.

Alternatively; can also prepare resin by the following method and transmit material: the thin slice in thermoplastic resin and middle layer is wherein settled in preparation on above-mentioned interim carrier; wherein on diaphragm, settle the thin slice of resin bed; and make described middle layer contact their laminations with described resin bed; perhaps the thin slice of thermoplastic resin is wherein settled in preparation on interim carrier; wherein on diaphragm, settle the thin slice in resin bed and middle layer, and make described thermoplastic resin contact their laminations with described middle layer.

Transmit in the material at resin, the thickness of the resin bed of colored resin composition is preferably 1.0 to 5.0 μ m, and more preferably 1.0 to 4.0 μ m are preferably 1.0 to 3.0 μ m especially.

The preferred thickness of each layer is not particularly limited to other, but the thickness of preferred thermoplastic resin layer is 2 to 30 μ m usually, and the thickness in middle layer is that the thickness of 0.5 to 3.0 μ m and diaphragm is 4 to 40 μ m.

Can carry out coating in above-mentioned manufacture method by known coating apparatus, and in the present invention, preferably adopt the coating apparatus (slit type coater) of narrow slit type nozzle to be coated with by using.

(narrow slit type nozzle)

Can pass through known coating process coating colored resin composition, and be dried formation resin transmission material, and in the present invention, preferred use is coated with at the narrow slit type nozzle that the part of discharging solution has slit-shaped apertures.Particularly, use narrow slit type nozzle and the slit type coater of in following patent, describing aptly: JP-A No.2004-89851, JP-A No.2004-17043, JP-ANo.2003-170098, JP-A No.2003-164787, JP-A No.2003-10767, JP-ANo.2002-79163 and JP-A No.2001-310147.

＜be used to make the method for color filter 〉

(resin bed)

Color filter of the present invention is preferably red (R), green (G) and blue (B) each resin bed forms such color filter by following colored resin composition respectively: use C.I. paratonere 254 as the colored resin composition of colorant, use the colored resin composition of C.I. pigment green 36 and use the C.I. pigment blue 15 at least at least at least: 6 colored resin composition.

Using aforesaid colorant is effectively for having high-contrast, and particularly, even when described color filter is used for the large-screen lc display device, to realizing that high excitation and wide color reprodubility also are effective.

By known method,, can make color filter of the present invention as repeatedly repeat on substrate to form resin bed and the method by exposure imaging according to number of colors.Where necessary, can adopt the structure of wherein using the black matrix interval boundary.

In said method, the example that forms the method for resin bed on substrate comprises: (a) by using known coating apparatus to be coated with the method for various colored resin compositions, (b) pass through to use the laminating machine laminating resin to transmit the method for material.

(a) by using the coating of coating apparatus

In the method that is used for making color filter of the present invention, can be by known coating process coating colored resin composition, described known coating process is for for example, the spin-coating method of describing in USP No.2681294, curtain coating method, slit rubbing method, dip coating, airblade coating method, rolling method, coiling bar type rubbing method, gravure rubbing method and use the extrusion coated method of loading hopper.Especially, particularly, can use aptly at＜resin and transmit material〉in the slit type coater that illustrates.The preferred embodiment of slit type coater comprise above-mentioned those.When forming resin bed by coating, its film thickness is preferably 1.0 to 3.0 μ m, and more preferably 1.0 to 2.5 μ m are preferably 1.0 to 2.0 μ m especially.

(b) lamination of use laminating machine

Transmit material by the use resin, and, the resin bed that forms film can be laminated on the substrate of describing after a while by using heating and/or the roller that pressurizes or plate extruding or hot pressing.Example is included in laminating machine and the laminating method of describing in the following patent: JP-A No.7-110575, JP-A No.11-77942, JP-A No.2000-334836 and JP-A No.2002-148794.From the viewpoint of small amount of impurities, the preferred method of in JP-A No.7-110575, describing of using.When using resin to transmit material to form resin bed, preferred film thickness with＜transmit material in the preferred film thickness of description identical.

(substrate)

In the present invention,, for example, use transparent substrates, and example comprises known glass plate, as having soda-lime glass plate, low thermal expansion glass, alkali-free glass and quartz glass plate and the plastic foil of silicon oxide film from the teeth outwards as the substrate that forms color filter on it.

In substrate,, can make the adhesiveness of transmitting material with colored resin composition or resin become better by carrying out coupling processing in advance.As described coupling processing, use the method for in JP-ANo.2000-39033, describing aptly.The film thickness of substrate is not particularly limited, but is generally 700 to 1200 μ m.

(oxygen screened film)

When making color filter of the present invention, when forming resin bed, the oxygen screened film can also be placed on the resin bed, thereby can increase exposure sensitivity by the coating colored resin composition.The example of described oxygen screened film comprises and transmits material at＜resin〉(middle layer) in those identical films of illustrating.The film thickness of oxygen screened film is not particularly limited, but is preferably 0.5 to 3.0 μ m.

(exposure and development)

Repeatedly be repeated below step by quantity and can obtain color filter: the mask of appointment is positioned over above the resin bed that forms on the substrate according to color, afterwards, via mask, thermoplastic resin and middle layer exposure light, use developer to develop from the top of mask then.

At this,,, can select and use light source aptly as long as it can irradiation can make the light of the wavelength zone (for example 365nm, 405nm etc.) that resin bed solidifies as exposure light source.Particularly, example comprises ultrahigh pressure mercury lamp, high-pressure sodium lamp and metal halide lamp.Exposure light amount normally about 5 is to 200mJ/cm ², preferably about 10 to 100mJ/cm ²

Developer is not particularly limited, but can uses known developer, as the developer of in JP-A No.5-72724, describing.Preferred wherein resin bed carries out the developer that lysotype is developed.For example, preferably be contained in 0.05 to 5mol/L concentration, the developer of the compound of pKa=7 to 13.In addition, can add a small amount of organic solvent that compatibility is arranged with glassware for drinking water.

There is the example of the organic solvent of compatibility to comprise methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, diacetone alcohol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzylalcohol, acetone, methyl ethyl ketone, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams and N-Methyl pyrrolidone with glassware for drinking water.The concentration of described organic solvent is preferably 0.1 quality % to 30 quality %.

In addition, known surfactant can be joined in the developer.Described surfactant concentrations is preferably 0.01 quality % to 10 quality %.

As the method for developing, can use known method, develop, spray development, spray and rotation as oar formula (paddle) and develop and immersion development.

Illustrate that at this spray develops, developer is sprayed onto on the exposure resin bed afterwards, can remove uncured portion by using perforated water spray.Preferably before developing, use perforated water spray to spray the relatively poor alkaline solution of dissolving resin layer wherein to remove thermoplastic resin and middle layer.Preferably after developing, use the agent of perforated water spray spray washing, and when using brush scrubbing, remove the development residue.

As described washing agent, can use known washing agent, and preferred (trade name: T-SD1, by Fuji Photo Film Co., Ltd. produces, and comprises phosphate, silicate, non-ionic surfactant, defoamer and stabilizing agent; Or trade name: T-SD2, by Fuji Photo Film Co., Ltd. produces, and comprises sodium carbonate and phenoxy group ethylene oxide based surfactants).

The fluid temperature of developer is preferably 20 ℃ to 40 ℃, and the pH of developer is preferably 8 to 13.

In the manufacturing of color filter, described in JP-A No.11-248921 and Jap.P. No.3255107, preferred viewpoint from reducing cost, form substrate by covering the colored resin composition that forms color filter, form transparency electrode thereon, and be used for the teat formation spacer of subregion orientation by covering.

When covering colored resin composition, because the levelling of coating solution covers each time and all reduces film thickness by continuous coating.Owing to this reason, preferably cover four kinds of colors of K (deceiving) RGB, and cover the teat that is used for the subregion orientation.On the other hand, when use had the transmission material of thermoplastic resin, because thickness keeps constant, the color of covering was preferably 3 or 2 kind of color.

Covering and the distortion of lamination resin bed when transmitting material and the viewpoint of maintenance constant thickness from preventing, the size of substrate preferably is equal to or greater than 25 μ m * 25 μ m, especially preferably is equal to or greater than 30 μ m * 30 μ m.

＜liquid crystal indicator 〉

As long as dispose color filter of the present invention, wherein the contrast of each colored pixels is not less than 2000, and in the colored pixels of above-mentioned two or more color, have the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast and be not more than 600, then liquid crystal indicator of the present invention is not particularly limited.Can adopt various display modes, as ECB (ECB electrically controlled birefringence), TN (twisted-nematic), IPS (in-plane switching), FLC (ferroelectric liquid crystal), OCB (optical compensation curved), STN (supertwist is to row), VA (vertical orientated), HAN (hybrid orientation is to row) and GH (object main body).Described device is characterised in that and uses above-mentioned color filter, thereby can realize high excitation, simultaneously, can realize high display quality, and described device can also be used for the large-screen lc display device aptly, as the display and the TV monitor of notebook computer.

In one embodiment, liquid crystal indicator of the present invention is to comprise following liquid crystal indicator: backlight, polaroid, at least two substrates, by the liquid crystal layer of described substrate support, the color filter of settling on the electrode of settling at least a portion of described substrate and at least a portion at described substrate, wherein color-filter layer is a color filter of the present invention, and described polaroid has the quadrature transmittance that is equal to or higher than 99.95 degree of polarization and is equal to or less than 0.05% at 400nm.The pixel and combination that have high-contrast by use with polaroid of high-contrast, a kind of liquid crystal indicator can be provided, described liquid crystal indicator shows the harsh image with high-contrast, obtaining balance aspect the contrast of each pixel of RGB, and aspect black display performance excellence.

＜polaroid 〉

In one embodiment of the invention, the degree of polarization of polaroid is equal to or higher than 99.95, more preferably is equal to or higher than 99.97, most preferably is equal to or higher than 99.99.When degree of polarization less than 99.95 the time, be equal to or higher than 2000 even the contrast of color-filter layer is increased to, the light that also may take place to be caused by polaroid leaks, and may reduce the display density of black, thereby this is not preferred.

Degree of polarization is as giving a definition:

Degree of polarization=((Tp-Tc)/(Tp+Tc)) ^0.5* 100

Tp: the transmittance when parallel combination polaroid

Tc: the transmittance when the vertical cartel polaroid

From being suppressed at the viewpoint of the black equilibrium displacement that high-contrast produces, in one embodiment of the invention, polaroid is that degree of polarization is equal to or higher than 99.95, and the quadrature transmittance at 400nm is equal to or less than 0.05% such polaroid in addition.Described quadrature transmittance more preferably is equal to or less than 0.03%, also preferably is equal to or less than 0.01%.When the quadrature transmittance surpasses 0.05%, may occur in the black equilibrium displacement that high-contrast produces easily.

For example, by iodine or dyeing are adsorbed onto on the polyvinyl alcohol (PVA), by stretching and orientation, make the polaroid among the present invention subsequently.Thereby, show the function of the polaroid that passes through as the polarized light that only allows on certain direction of vibration.The preferred embodiment of iodine type of polarization sheet comprises the HCL2-5618 (degree of polarization of being produced by SanritzCorporation 99.979, quadrature transmittance at 400nm: 0.01%), HLC2-2518 (degree of polarization 99.991, quadrature transmittance at 400nm: 0.01%), UHLC2-5618 (degree of polarization 99.975, quadrature transmittance at 400nm: 0.01%), LLC2-9118 (degree of polarization 99.982, quadrature transmittance at 400nm: 0.01%), LLC2-9218 (degree of polarization 99.974, quadrature transmittance at 400nm: 0.02%) and LLC2-81-18 (degree of polarization 99.985 is at the quadrature transmittance of 400nm: 0.01%).The preferred embodiment of dye type polaroid comprises the HC2-6018 that produced by SanritzCorporation, and (degree of polarization 99.952 is at the quadrature transmittance of 400nm: 0.02%).In the middle of them, from keeping the viewpoint of contrast for a long time, preferred iodine polaroid type.Viewpoint from color balance, the polaroid type (for example, HLC2-5618 (ash), HLC2-2518 (ash), UHLC2-5618 (ash), LLC2-9118 (ash), LLC2-9218 (ash), the LLC2-81-18 (ash) that produces by SanritzCorporation) that more preferably has grey.In addition, from being suppressed at the viewpoint of the black equilibrium displacement that high-contrast produces, for example, most preferably has the HLC2-2518 (0.01%) (producing) that is equal to or less than 0.05% quadrature transmittance by Sanritz Corporation at 400nm.

(liquid crystal layer)

As the liquid crystal layer that uses in the present invention, can use various liquid crystal modes, as ECB (ECB electrically controlled birefringence), TN (twisted-nematic), IPS (in-plane switching), FLC (ferroelectric liquid crystal), OCB (optical compensation curved), STN (supertwist is to row), VA (vertical orientated), HAN (hybrid orientation is to row) and GH (object main body).In the middle of them, the liquid crystal layer that in liquid crystal mode such as TN, MVA, IPS, PVA and OCB, uses preferably.More preferably have high animation display performance and almost do not have MVA, IPS (super IPS), PVA and the ocb mode of visual angle independence, and the PVA pattern that most preferably has high black contrast is wherein leaked MVA pattern of taking measures and IPS (super IPS) pattern with contrast of raising to the light around the orientation control teat.

(electrode)

The electrode of Shi Yonging refers to be used for electric field is applied to electrode on the liquid crystal molecule of liquid crystal layer in the present invention.Under situation, on the liquid crystal side of two substrates of supporting liquid crystal layer, form electrode as the liquid crystal mode of TN, MVA, PVA and OCB.Under the situation of IPS pattern, with electrode arrangement at least one side of two substrates of supporting liquid crystal.As material, for example, can use indium tin oxide target (ITO).

(screen size)

In the present invention, when screen size became bigger, effect showed more significantly.Therefore, the screen size of liquid crystal indicator of the present invention preferably is equal to or greater than 10 inches, more preferably is equal to or greater than 15 inches, most preferably is equal to or greater than 20 inches.

(backlight)

In the present invention, as backlight, can use cold-cathode tube (CCFL), external electrode cold-cathode tube (EEFL), FFL and LED.

As cold-cathode tube (CCFL), usually, use such cold-cathode tube, described cold-cathode tube adopts the emission wavelength that has in the wavelength zone of red, green and blue, wherein uses optical plate to launch from the light of this cold-cathode tube and changes the white plane light source into.In the luminophor of described cold-cathode tube,, use Y usually as red luminophor ₂O ₃: the Eu fluorophor.As green luminophores, use LaPO usually ₄: Ce, Tb fluorophor.As blue luminophor, use BaMgAl usually ₁₀O ₁₇: Eu fluorophor and Sr ₁₀(PO ₄) ₆Cl ₂: the Eu fluorophor.Use wherein the fluorescent light of electrode arrangement in seal as the light source of using backlight, in described seal, settle fluorescent membrane and rare gas is encapsulated into wherein, described fluorescent membrane is to consider white balance, and these fluorophor obtain by mixing with suitable mixture ratio.

The preferred light-emitting device of the spike length that has between 520 to 540nm that uses is as LED.More specifically, use light emitting diode.In JP-A No.2004-78102, described in detail and used the backlight of this light emitting diode.

Promptly, the such LED-backlit of preferred use, described LED-backlit comprises red (R) LED, green (G) LED and indigo plant (B) LED, the spike length of wherein red (R) LED is equal to or greater than 610nm, the spike length of green (G) LED is in the scope of 530 ± 10nm, and the spike length of blue (B) LED is equal to or less than 480nm.Particularly, long by the spike of green (G) LED in 520 to 540 scope, can widen the reproduction district of the green of liquid crystal indicator of the present invention.In the present invention, the spike of green (G) LED is long preferred in 520 to 540nm scope, more preferably in 525 to 535nm scope.The example of spike length green (G) LED in above-mentioned scope comprises that DG1112H is (by Stanley Electric Co., Ltd. production), UG1112H is (by Stanley Electric Co., Ltd. production), E1L51-3G is (by ToyodaGosei Co., Ltd. production), E1L49-3G (by Toyoda Gosei Co., ltd. produces) and NSPG500S (producing) by Nichia Corporation.

In the present invention, as the LED-backlit light source, also preferred red (R) LED that uses.In this case, as long as it is the LED that spike length is equal to or greater than 610nm, LED is not particularly limited.The spike of red (R) LED is long preferably to be equal to or greater than 610nm, more preferably in the scope of 615nm to 640nm.Therefore, the chroma point of red NTSC specification can reproduce by described liquid crystal indicator.

The example of red (R) LED comprises that FR1112H is (by Stanley Electric Co., Ltd. production), FR5366X (by Stanley Electric Co., Ltd. produces), NSTM515AS (R) (producing), GL3ZR2D1COS (producing) and GM1JJ35200AE (producing) by Sharp Corporation by Sharp Corporation by NichiaCorporation.

In the present invention, as the LED-backlit light source, also preferred indigo plant (B) LED that uses.In this case, as long as it is the LED that spike length is equal to or less than 480nm, LED is not particularly limited.The spike of blue (R) LED is long preferably to be equal to or less than 480nm, more preferably in the scope of 465nm to 475nm.Therefore, the chroma point of blue NTSC specification can reproduce by liquid crystal indicator of the present invention.

The example of blue (B) LED comprises that DB1112H is (by Stanley Electric Co., Ltd. production), DB5306X is (by Stanley Electric Co., Ltd. production), E1L51-3B is (by Toyoda GoseiCo., Ltd. production), E1L4E-SB1A (by Toyoda Gosei Co., Ltd. produces), NSPB630S (producing) and NSPB310A (producing) by Nichia Corporation by Nichia Corporation.

Spike length described here is to use the Co. by Otsuka Electronics, and the spectrometer MCPD-2000 that Ltd. produces is obtained by the spectral measurement value.

The disclosure of Japanese patent application No.2004-296385 and 2005-58015 is combined in this by reference.

Embodiment

To use embodiment to illustrate in greater detail the present invention, but the invention is not restricted to these embodiment.Below, unless otherwise indicated, " part " and " % " refers to " mass parts " and " quality % " respectively.

Embodiment 1 to 8 and 9a to 16a and comparative example 1 and 2

The manufacturing of embodiment 1[color filter]

The preparation of-photosensitive resin transmission material-

Use narrow slit type nozzle, the coating solution of the thermoplastic resin that will be made up of following prescription H1 is coated on the interim carrier of polyethylene terephthalate film that thickness is 75 μ m, and drying.Then, the coating solution in coating and the dry middle layer of forming by following prescription P1.In addition; coating and the dry resin combination K1 that is grouped into by the one-tenth of the K1 of prescription described in the following table 1; to provide build on interim carrier is the thermoplastic resin of 14.6 μ m; build is that middle layer and the build of 1.6 μ m is the photosensitive resin layer of 2.4 μ m, and by pressure adhering protective film (thickness is the polypropylene screen of 12 μ m).

Therefore, prepare wherein interim carrier, thermoplastic resin, middle layer (oxygen screened film) and black (K) photosensitive resin layer and form whole photosensitive resin transmission material, and this photosensitive resin transmission material is denoted as K1.

The coating solution of thermoplastic resin: prescription H1

11.1 parts of methyl alcohol

6.36 parts of propylene glycol methyl ether acetates

52.4 parts of methyl ethyl ketones

The multipolymer of methyl methacrylate/acrylic acid-2-ethyl caproite/benzyl methacrylate/methacrylic acid

(copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, weight-average molecular weight=100,000,

)

5.83 part

The multipolymer of styrene/acrylic (copolymerization ratio of components (mol ratio)=63/37, weight-average molecular weight=10,000,

) 13.6 parts

Wherein use the compound of bisphenol-A with 2 equivalent five ethylene glycol monomethacrylates dehydrating condensations

(trade name: 2, two [4-(methacryloxy polyethoxy) phenyl] propane of 2-, by Shin-NakamuraChemical Co., Ltd. produces) 9.1 parts

0.54 part in surfactant 1 (trade name: MEGAFACE F780F, by Dainippon Ink andChemicals, Incorporated produces)

The coating solution in middle layer: prescription P1

PVA205 (polyvinyl alcohol (PVA), by Kurary Co., Ltd. produces, saponification degree=88%, the degree of polymerization 550)

32.2 part

14.9 parts of polyvinyl pyrrolidones (trade name: K-30, by ISP Japan, Ltd. produces)

524 parts of distilled water

429 parts of methyl alcohol

Then, prepare photosensitive resin according to method same as described above and transmit material R1, G1 and B1, difference is to change into following colored photosensitive resin composition R1, G1 or the B1 that is grouped into by the one-tenth described in the following table 1 with transmit the colored photosensitive resin composition K1 that uses in the manufacturing of material K1 at photosensitive resin.

Table 1

Unit: mass parts

Table 2

Unit: mass parts

The formation of-black (K) image-

Using spray, with the T-SD1 (trade name, by Fuji Photo Film Co., Ltd. produces) that is controlled to be 25 ℃; Comprise phosphate, silicate, non-ionic surfactant, defoamer and stabilizing agent) glass detergent solution (1 to 10 times of dilute solution (using the pure water dilution)) spray in the time of 20 seconds, use has the rotating brush washing alkali-free glass substrate of nylon hair, use the pure water spray to wash, and use spray, with silane coupled solution (0.3 quality % aqueous solution of N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, trade name: KBM603, by Shin-Etsu Chemical Co., Ltd. produce) sprayed 20 seconds, use the pure water spray washing subsequently.Use the substrate pre-heating device, this substrate is heated to 100 ℃, last 2 minutes.(can use T-SD2 to replace T-SD1 as detergent solution.)

Peel off and be used for the diaphragm that photosensitive resin transmits material K1; and using the rubber rollers temperature is 130 ℃; line pressure is that 100N/cm and transfer rate are 2.2m/ minute laminating machine (Lamic II; by Hitachi Industries Co.; Ltd. produce), it is laminated on the substrate of 100 ℃ of heating.

After boundary surface between interim carrier and thermoplastic resin is peeled off interim carrier, keeping under the substrate situation vertical with mask (quartzy exposed mask) with picture pattern, with the distance setting between exposed mask surface and the photosensitive resin layer is 200 μ m, and use and have the proximity printing instrument of ultrahigh pressure mercury lamp (by Hitachi High-Tech Electronics Engineering Co., Ltd. produce), with 70mJ/cm ²Exposure carry out pattern exposure.

Then, under the flat burner pressure of 0.04MPa, (be prepared as follows: use pure water stock solution dilution (1 to 12 with triethanolamine base developer; Ratio with 1 mass parts stock solution and 11 mass parts pure water mixes), described stock solution is by mixing the preparation of triethanolamine (30 quality %), propylene glycol, glycerine (glycelol) monostearate, polyoxyethylene sorbitan monostearate and stearyl ether (amounting to 0.1 quality %) and pure water (remainder)) it was developed 50 seconds at 30 ℃ of sprays, and remove thermoplastic resin and middle layer.Then, air is blown on the surface of substrate, used the pure water spray washing subsequently 10 seconds to remove moisture.Then, air is blown on the substrate to reduce the water on substrate.

Subsequently, under 0.15MPa pressure, adopt circular cone build nozzle, and usefulness sodium carbonate base developer (T-CD1 (trade name), by Fuji Photo Film Co., Ltd. produces; Comprise 0.38 mol sodium bicarbonate, 0.47 mol sodium carbonate, 5 quality % nekals, anionic surfactant, defoamer and stabilizing agent) 1 to 5 dilute solution (diluting) with pure water) it was developed 30 seconds at 29 ℃ of sprays, photosensitive resin layer is developed to obtain forming the image of pattern.

Subsequently, by under 0.02MPa pressure, use circular cone build nozzle, washing agent with pure water dilution (1 to 10) (comprises phosphate, silicate, non-ionic surfactant, defoamer and stabilizing agent, trade name: T-SD1, by Fuji Photo Film Co., Ltd. produces) sprayed 20 seconds at 33 ℃, and use rotating brush to clean with nylon hair, remove residue to obtain black (K) image.(, can use T-SD2 to replace T-SD1) as washing agent.

Afterwards, also use ultrahigh pressure mercury lamp,, use 500mJ/cm from the both sides of resin bed ²Light with the substrate post-exposure, and 220 ℃ of thermal treatments 15 minutes.

Use this substrate of aforesaid brush washing formation K image thereon, use the pure water spray to wash, under the situation of not using silane coupled solution, it is transferred in the substrate pre-heating device.

The formation of-red (R) pixel-

According to transmitting the identical method of method of material K1 with photosensitive resin, and the usability photopolymer resin transmits material R1, forms thereon on the substrate of black (K) pixel and obtains redness (R) pixel.Exposure is 40mJ/cm ², and use sodium carbonate base developer to carry out developing in 35 seconds at 35 ℃.

The thickness of photosensitive resin layer R1 is 2.0 μ m, and the coating weight of pigment C.I. paratonere 254 and C.I. paratonere 177 is respectively 0.88 and 0.22g/m ²

Reuse this substrate that aforesaid brush washing forms the R pixel thereon, use the pure water spray to wash, and under the situation of not using silane coupled solution, use the substrate pre-heating device that it was heated 2 minutes at 100 ℃.

The formation of-green (G) pixel-

According to transmitting the identical step of step of material R1 with photosensitive resin, and the usability photopolymer resin transmits material G1, forms thereon on the substrate of red (R) pixel and obtains green (G) pixel.Exposure is 40mJ/cm ², and use sodium carbonate base developer to carry out developing in 45 seconds at 34 ℃.With with identical method in the formation of green (G) pixel, be used to estimate the monochromatic substrate that contrast is measured by on the alkali-free glass substrate, forming green (G) dyed layer preparation.

The thickness of photosensitive resin layer G1 is 2.0 μ m, and the coating weight of pigment C.I. pigment green 36 and C.I. pigment yellow 150 is respectively 1.12 and 0.48g/m ²

Reuse aforesaid brush and wash the substrate that forms R and G image on it, use the pure water spray to wash, and under the situation of not using silane coupled solution, use the substrate pre-heating device that it was heated 2 minutes at 100 ℃.

The formation of-blue (B)-

According to transmitting the identical step of step of material R1 with photosensitive resin, and the usability photopolymer resin transmits material B 1, forms thereon on the substrate of red (R) pixel and green pixel (G) and obtains blueness (B) pixel.Exposure is 30mJ/cm ², and use sodium carbonate base developer to carry out developing in 40 seconds at 36 ℃.With with identical method in the formation of blue (B) pixel, be used to estimate the monochromatic substrate that contrast is measured by on the alkali-free glass substrate, forming blue (B) dyed layer preparation.

The thickness of photosensitive resin layer B1 is 2.0 μ m, and the coating weight of pigment C.I. pigment Blue15:6 and C.I. pigment Violet 23 is respectively 0.63 and 0.07g/m ²

Reuse this substrate that aforesaid brush washing forms R, G and B pixel thereon, use the pure water spray to wash, and under the situation of not using silane coupled solution, use the substrate pre-heating device that it was heated 2 minutes at 100 ℃.

This substrate that forms R, G and B pixel and K image is thereon cured 50 minutes to obtain the target color filter at 240 ℃.

At this, with the preparation of colored photosensitive resin composition K1, R1, G1 and the B1 described in the instruction card 1.

Obtain colored photosensitive resin composition K1 by the following method: at first with amount weighing K pigment dispersion 1 and the propylene glycol methyl ether acetate described in the table 1, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, the weighing methyl ethyl ketone, bonding agent 1, the hydroquinone monomethyl ether, DPHA solution, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methylamino)-the 3-bromophenyl]-s-triazine and surfactant 1, their temperature at 25 ℃ (± 2 ℃) are added with this order, and they were stirred 30 minutes under the temperature of 40 ℃ (± 2 ℃) and 150rpm.

In the composition of prescription described in the K1, K pigment dispersion 1 composed as follows:

13.1 parts of carbon blacks (trade name: NIPEX35 is produced by Degussa Japan)

N, N '-two-(3-diethylamino propyl group)-5-{4-[2-oxo-1-(2-oxo-2,3-dihydro-1H-benzimidazole-5-base carbamyl)-propyl group azo]-benzoyl-amido }-0.65 part of a benzenedicarboxamide

6.72 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

79.53 parts of propylene glycol methyl ether acetates

Obtain colored photosensitive resin composition R1 by the following method: at first with the amount weighing R pigment dispersion 1 described in the table 1, R pigment dispersion 2 and propylene glycol methyl ether acetate, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 1, bonding agent 2, DPHA solution, 2-trichloromethyl-5-(to the styryl methyl)-1,3, the 4-oxadiazole, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methylamino)-the 3-bromophenyl]-s-triazine and phenothiazine, their temperature at 24 ℃ (± 2 ℃) are added with this order, and it was stirred 30 minutes under 150rpm, in addition, with amount weighing adjuvant 1 and the surfactant 1 described in the table 1, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 5 minutes under 30rpm, and use nylon wire #200 that it is filtered.

In the composition described in the table 1, R pigment dispersion 1 composed as follows:

C.I.P.R.254 (IRGAPHOR RED B-CF is produced by Ciba Specialty Chemicals)

8 parts

N, N '-two-(3-diethylamino propyl group)-5-{4-[2-oxo-1-(2-oxo-2,3-dihydro-1H-benzimidazole-5-base carbamyl)-propyl group azo]-benzoyl-amido }-0.8 part of a benzenedicarboxamide

8 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

83.2 parts of propylene glycol monomethyl ether acetate acid esters

R pigment dispersion 2 (producing) composed as follows by Fuji Film Arch:

C.I.P.R.177 (CROMOPHTAL RED A2B is produced by Ciba Specialty Chemicals)

18 parts

12 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

70 parts of propylene glycol methyl ether acetates

Use motor-driven mill M-50 (producing) and diameter zirconia bead, above-mentioned composition is disperseed 27 hours to prepare pigment dispersion composition with the circumferential speed of 9m/s as 0.65mm by Aiger Japan.Be displayed in Table 3 the number average particle diameter of the pigment of this moment.

Obtain colored photosensitive resin composition G1 by the following method: at first with the amount weighing G pigment dispersion 1 described in the table 1, Y pigment dispersion 1 and propylene glycol methyl ether acetate, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 1, cyclohexanone, bonding agent 1, DPHA solution, 2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methylamino)-the 3-bromophenyl]-s-triazine and phenothiazine, their temperature at 24 ℃ (± 2 ℃) are added with this order, this potpourri was stirred 30 minutes under 150rpm, in addition, with the amount weighing surfactant 1 described in the table 1, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 5 minutes under 30rpm, and use nylon wire #200 that it is filtered.

In the composition described in the table 1, G pigment dispersion 1 composed as follows:

C.I.P.G.36 (Rionol Green 6YK, Toyo Ink Mfg, Co., Ltd.) 14 parts

23 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

N, N '-two-(3-diethylamino propyl group)-5-{4-[2-oxo-1-(2-oxo-2,3-dihydro-1H-benzimidazole-5-base carbamyl)-propyl group azo]-benzoyl-amido }-1.4 parts of benzenedicarboxamides

61.6 parts of propylene glycol methyl ether acetates

Y pigment dispersion 1 composed as follows:

15 parts of C.I.P.Y.150 (BAYPLAST YELLOW 5GN 01, Bayer Ltd.)

9 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

N, N '-two-(3-diethylamino propyl group)-5-{4-[2-oxo-1-(2-oxo-2,3-dihydro-1H-benzimidazole-5-base carbamyl)-propyl group azo]-benzoyl-amido }-1.5 parts of benzenedicarboxamides

74.5 parts of propylene glycol methyl ether acetates

Use motor-driven mill M-50 (producing) and diameter zirconia bead, above-mentioned composition is disperseed 28 hours to prepare pigment dispersion composition with the circumferential speed of 9m/s as 0.65mm by Aiger Japan.Be displayed in Table 3 the number average particle diameter of the pigment of this moment.

Obtain colored photosensitive resin composition B1 by the following method: at first with amount weighing B pigment dispersion 1 and the propylene glycol methyl ether acetate described in the table 1, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 1, bonding agent 3, DPHA solution, 2-trichloromethyl-5-(to the styryl styryl)-1,3,4-oxadiazole and phenothiazine, their temperature at 25 ℃ (± 2 ℃) are added with this order, this potpourri was stirred 30 minutes under the temperature of 40 ℃ (± 2 ℃) and 150rpm, in addition, with the amount weighing surfactant 1 described in the table 1, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 5 minutes under 30rpm, and use nylon wire #200 that it is filtered.

In the composition described in the table 1, B pigment dispersion 1 composed as follows:

11.28 parts of C.I.P.B.15:6 (Rionol Blue ES, by Toyo Ink Mfg, Ltd. produces)

0.72 part of C.I.P.V.23 (Hostaperm Violet RL-NF is produced by Clariant Japan)

0.6 part of EFKA-745 (producing) by EFKA ADDITIVES B.V.

0.75 part of Disparon DA-725 (by Kusumoto Chemicals, Ltd. produces)

86.65 parts of propylene glycol methyl ether acetates

Use motor-driven mill M-50 (producing) and diameter zirconia bead, above-mentioned composition is disperseed 27 hours to prepare pigment dispersion composition with the circumferential speed of 9m/s as 0.65mm by Aiger Japan.Be displayed in Table 3 the number average particle diameter of the pigment of this moment.

Bonding agent 1 composed as follows:

27 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=78/22 mol ratio, weight-average molecular weight 37,000)

73 parts of propylene glycol methyl ether acetates

Bonding agent 2 composed as follows:

27 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid/methyl methacrylate=38/25/37 mol ratio, weight-average molecular weight 38,000)

73 parts of propylene glycol methyl ether acetates

Bonding agent 3 composed as follows:

27 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid/methyl methacrylate=36/22/42 mol ratio, weight-average molecular weight 38,000)

73 parts of propylene glycol methyl ether acetates

DPHA solution composed as follows:

76 parts of dipentaerythritol acrylates (comprise 500ppm polymerization initiator MEHQ500ppm, trade name: KAYARAD DPHA, by Nippon Kayaku Co., Ltd. produces)

24 parts of propylene glycol methyl ether acetates

Surfactant 1 (trade name: MEGAFACE F780F, by Dainippon Ink andChemicals, Incorporated produces) composed as follows:

40 parts of C ₆F ₁₃CH ₂CH ₂OCOCH=CH ₂, 55 parts of H (OCH (CH ₃) CH ₂) ₇OCOCH=CH ₂With 5 parts of H (OCH ₂CH ₂) ₇OCOCH=CH ₂Multipolymer, weight-average molecular weight 30,000

30 parts

70 parts of 30% solution of Methylethyl

Embodiment 2 to 7, comparative example 1 and 2

According to prescription and the preparation method identical with embodiment 1, and by jitter time being changed into the time described in the table 3, preparation target color filter.

Embodiment 8

Prepare the target color filter according to the method identical with embodiment 1, difference is that the colored photosensitive resin composition G1 and the B1 that will use change into G2 described in the following table 1 and B2 respectively in embodiment 1.

Obtain colored photosensitive resin composition G2 by the following method: at first with the amount weighing G pigment dispersion 2 described in the table 1, Y pigment dispersion 2 and propylene glycol methyl ether acetate, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 1, cyclohexanone, bonding agent 1, DPHA solution, 2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methylamino)-the 3-bromophenyl]-s-triazine and phenothiazine, their temperature at 24 ℃ (± 2 ℃) are added with this order, this potpourri was stirred 30 minutes under 150rpm, in addition, with the amount weighing surfactant 1 described in the table 1, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 5 minutes under 30rpm, and use nylon wire #200 that it is filtered.

In the composition described in the table 1,, use GT-2 (trade name is produced by Fuji Film Electronics Materials) as the composition of G pigment dispersion 2.

As the composition of Y pigment dispersion 2, use CF Yellow EX3393 (trade name is produced by MikuniColor Ltd.).

Obtain colored photosensitive resin composition B2 by the following method: at first with the amount weighing B pigment dispersion 2 described in the table 1, B pigment dispersion 3 and propylene glycol methyl ether acetate, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 1, bonding agent 3, DPHA solution, 2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methylamino)-the 3-bromophenyl]-s-triazine and phenothiazine, their temperature at 25 ℃ (± 2 ℃) are added with this order, this potpourri was stirred 30 minutes under the temperature of 40 ℃ (± 2 ℃) and 150rpm, in addition, with the amount weighing surfactant 1 described in the table 1, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 5 minutes under 30rpm, and use nylon wire #200 that it is filtered.

In the composition described in the table 1,, use CF BlueEX3357 (trade name is produced by Mikuni Color Ltd.) as the composition of B pigment dispersion 2.

As the composition of B pigment dispersion 3, use CF Blue EX3383 (trade name is produced by MikuniColor Ltd.).

Embodiment 9a

The manufacturing of＜color filter (by using the coating production of narrow slit type nozzle) 〉

The formation of-black (K) image-

Use UV washing facility washing alkali-free glass substrate, use washing agent to scrub, and use ultrapure water to carry out supersound washing.With substrate 120 ℃ of thermal treatments 3 minutes with surface of stability state.

Make the substrate cooling, temperature is controlled at 23 ℃, and use glass substrate coating machine (producing) to be coated with the colored photosensitive resin composition K1 that is grouped into by the one-tenth described in the table 1 by Hirata Corporation with narrow slit type nozzle.Subsequently, use vacuum dryer (trade name: VCD, by Tokyo OhkaKogyo Co., Ltd. produces) dry a part of solvent 30 seconds so that coating lose flowability, and with its 120 ℃ of prebake 3 minutes to obtain the photosensitive resin layer K1 that thickness is 2.4 μ m.

Keeping under the substrate situation vertical with mask (quartzy exposed mask) with picture pattern, with the distance setting between exposed mask surface and the photosensitive resin layer is 200 μ m, and use and have the proximity printing instrument of ultrahigh pressure mercury lamp (by Hitachi Hi-Tech Electronics Engineering Co., Ltd. produce), with 300mJ/cm ²Exposure carry out pattern exposure.

Then, use spray spout to spray pure water to drench the surface of photosensitive resin layer K1 equably, under the flat burner pressure of 0.04MPa, use KOH base developer (to comprise KOH and non-ionic surfactant, trade name: CDK-1, produce by Fuji Film Electomaterials) it was developed 80 seconds at 23 ℃ of sprays, to obtain forming the image of pattern.Subsequently, use the UHV (ultra-high voltage) Washing spray nozzle under the pressure of 9.8MPa, to spray ultrapure water to remove residue, and ultrapure water is sprayed onto on two surfaces of substrate to remove the photosensitive resin layer of developer and dissolving, uses air knife to remove moisture subsequently to obtain black (K) image.Subsequently, with it 220 ℃ of thermal treatments 30 minutes.

The formation of-red (R) pixel-

According to form the identical step of black (K) image, and use the colored photosensitive resin composition R3a that is grouped into by the one-tenth described in the last table 2, form thereon on the substrate of black (K) image and form heat treated redness (R) pixel.

The thickness of photosensitive resin layer R3a is 1.6 μ m, and the coating weight of pigment C.I. paratonere 254 and C.I. paratonere 177 is respectively 0.88g/m ²And 0.22g/m ²

With with identical method in the formation of green (G) pixel, be used to estimate the monochromatic substrate that contrast is measured by on the alkali-free glass substrate, forming red (R) dyed layer preparation.

The formation of-green (G) pixel-

According to form the identical step of black (K) image, and use the colored photosensitive resin composition G3a that is grouped into by the one-tenth described in the last table 2, form formation heat treated green (G) pixel on the substrate of black (K) image and redness (R) pixel thereon.

The thickness of photosensitive resin layer R3a is 1.6 μ m, and the coating weight of pigment C.I. pigment green 36 and C.I. pigment yellow 150 is respectively 1.12g/m ²And 0.48g/m ²

With with identical method in the formation of green (G) pixel, be used to estimate the monochromatic substrate that contrast is measured by on the alkali-free glass substrate, forming green (G) dyed layer preparation.

The formation of-blue (B) pixel-

According to form the identical step of black (K) image, and use the following colored photosensitive resin composition B3a that is grouped into by the one-tenth described in the last table 2, form formation heat treated blueness (B) pixel on the substrate of black (K) image and redness (R) and green (G) pixel thereon.

The thickness of photosensitive resin layer G3a is 1.6 μ m, and pigment C.I. pigment blue 15: 6 and the coating weight of C.I. pigment violet .23 be respectively 0.63g/m ²And 0.07g/m ²

With with identical method in the formation of green (B) pixel, be used to estimate the monochromatic substrate that contrast is measured by on the alkali-free substrate, forming blue (B) dyed layer preparation.

According to the preparation method of colored photosensitive resin composition R1, G1 and B1, prepare colored photosensitive resin composition R3a, G3a and B3a respectively.

Jitter time and the number average particle diameter of colored photosensitive resin composition R3a, G3a and B3a have been displayed in Table 4.

Embodiment 10a to 15a

With with embodiment 9a in identical method, and the use prescription manufacturing objective color filter identical with embodiment 9a, difference is to change jitter time described in table 4.

Embodiment 16a

With with embodiment 9a in identical method manufacturing objective color filter, difference is colored photosensitive resin composition G3a and B3a are changed into colored photosensitive resin composition G4a and B4a respectively.

According to the preparation method of colored photosensitive resin composition G2 and B2, prepare colored resin composition G4a and B4a respectively.

Estimate

The measurement of-contrast-

By following measuring method, measure the contrast that constitutes by each colored pixels of the above-mentioned color filter that obtains, and calculate the poor contrast of various colored pixels.The results are shown in table 3 and 4.

(measuring the method for contrast)

The three-wavelength cold-cathode tube light source (FWL18EX-N of diffusion substrate is disposed in use, produce by ToshibaLighting and Technology Corporation) as backlight, color filter or monochromatic substrate are placed in two polaroid (trade names: G1220DUN, produce by Nitto Denko Corporation) between, and the chromatic value Y of the light that passes through when settling with cross Nicols of the chromatic value Y of the light that passes through when polaroid is settled with parallel Nicol obtains contrast.In order to measure colourity, use colour brightness meter (trade name: BM-5 is produced by TOPCON Corporation).

Two polaroids of following arrangement, color filter and colour brightness meter.One in the polaroid is placed on from 13mm backlight place.With diameter is that 11mm and length are that the right cylinder of 20mm is placed on from 40 to 60mm places backlight.Make and pass cylindrical light action in being placed on the measuring samples at 65mm backlight place.Use is placed on the colour brightness meter from 400mm backlight place, measures by being placed on the light from another polaroid at 100mm backlight place.Taking measurement of an angle of colour brightness meter is 2 °.Set light dosage backlight and make that the brightness of measuring is 1280cd/m when not placing sample and two polaroids are settled with parallel Nicol ²

[manufacturing of liquid crystal indicator and evaluation]

Form ITO (indium tin oxide target) transparent electrode layer on the pixel of each color filter of in embodiment 1 to 8 and 9a to 16a and comparative example 1 and 2, making, in addition, settle alignment film of polyimide thereon.On the position corresponding with the outside framework of the black matrix of the periphery of the pixel group that is placed in color filter, printing comprises the sealant of the epoxy resin of spacer particle, and with the pressure of 10kg/cm mutual lamination color filter substrate with to substrate.Then, the glass substrate of lamination was made sealant cures in 90 minutes 150 ℃ of thermal treatments, to obtain the laminated material of two glass substrate.This glass substrate laminated material is outgased under vacuum, make pressure get back to atmospheric pressure afterwards, liquid crystal is injected in two gaps between the glass substrate to obtain liquid crystal cells.

The measurement that-Hei shows-

Make each panel of LCD that adopts the color filter of making in embodiment 1 to 8 and 9a to 16a and comparative example 1 and 2 become black the demonstration, measure the colourity of this moment, colour killing colourity is defined as (x, y, Y=0.333,0.333,0.08), and the aberration of calculating and this color.The results are shown in table 3 and 4.Measure the black colourity that shows by the following method.Use three-wavelength cold-cathode tube light source as backlight, with two polaroid (trade names: G1220DUN, produce by Nitto Denko Corporation) settle with cross Nicols, color filter is placed between the polaroid, and use colour brightness meter (trade name: BM-5 is produced by TOPCON Corporation) to measure the colourity of the light that leaks.Preferably be equal to or less than 5 with the aberration of achromic point.When difference surpasses 5 because black the demonstration be coloured, from rather than preferred.

The method of-measurement vividness-

When showing the pure color of red, green and blue on the black display background of each panel of LCD of the color filter of in using embodiment 1 to 8 and 9a to 16a and comparative example 1 and 2, making, use 50 objects on sense organ, to estimate vividness.Use is estimated according to the Pyatyi of the order of higher vividness, and adopts average as evaluation of estimate.

The results are shown in the table 3 of embodiment 1 to 8 and comparative example 1 and 2.Embodiment 9a to 16a the results are shown in the table 4.In table 3 and 4, A represents to be not less than 4 and be not higher than 5, and B represents to be not less than 3 and less than 4, and C represents less than 3.

From table 3 and 4, color filter of the present invention has the high-contrast of each pixel, show distinct image, contrast balance with various pixels of RCB, and excellence aspect black display performance, in the described color filter of the present invention, the contrast of each colored pixels is not less than 2000, and in the colored pixels of three kinds of colors, have the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast and be not more than 600.On the other hand, the contrast of each colored pixels low contrast that has each pixel less than the color filter of 2000 comparative example 1 wherein, and the image that shows lacks vividness, and wherein have the contrast balance that color filter that the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast surpass 600 comparative example 2 does not have the various pixels of RGB in the colored pixels of three kinds of colors, and because the contrast of red colored pixel is low, so red to little red to displacement, and black display performance is poor.

Embodiment 9 to 28 and comparative example 3 to 10

Embodiment 9 and 25

The manufacturing of＜color filter (by using the coating production of narrow slit type nozzle) 〉

The formation of-black (K) image-

Use UV washing facility washing alkali-free glass substrate, use washing agent to scrub, and use ultrapure water to carry out supersound washing.With substrate 120 ℃ of thermal treatments 3 minutes with surface of stability state.

Make the substrate cooling, temperature is controlled at 23 ℃, and use glass substrate coating machine (trade name: MH-1600 is produced by FAS Japan) to be coated with the colored photosensitive resin composition K2 that is grouped into by the one-tenth described in the following table 5 with narrow slit type nozzle.Subsequently, use vacuum dryer (trade name: VCD, by Tokyo Ohka Kogyo Co., Ltd. produce) dry a part of solvent 30 seconds so that coating lose flowability, use EBR (sword type crimping wheel rim (Edge Bead Rim)) rod to remove unnecessary coating solution, and it is cured 3 minutes to obtain the photosensitive resin layer K2 that thickness is 2.4 μ m at 120 ℃ in the substrate periphery.

Keeping under the substrate situation vertical with mask (quartzy exposed mask) with picture pattern, with the distance setting between exposed mask surface and the photosensitive resin layer is 200 μ m, and use proximity printing instrument (by Hitachi Hi-Tech Electronics Engineering Co., Ltd. produces) with 300mJ/cm with ultrahigh pressure mercury lamp ²Exposure carry out pattern exposure.

Then, use spray spout to spray pure water to drench the surface of photosensitive resin layer K2 equably, under the flat burner pressure of 0.04MPa, use (comprises KOH and non-ionic surfactant with the KOH base developer of 100 times of pure water dilutions, trade name: CDK-1, produce by Fuji Film Arch) it was developed 80 seconds at 23 ℃ of sprays, to obtain forming the image of pattern.Subsequently, use the UHV (ultra-high voltage) Washing spray nozzle under the pressure of 9.8MPa, to spray ultrapure water to remove residue to obtain black (K) image.Subsequently, with it 220 ℃ of thermal treatments 30 minutes.

Table 5

Unit: mass parts

Table 6

Unit: mass parts

The formation of-red (R) pixel-

According to form the identical step of black (K) image, and use the following colored photosensitive resin composition R3 that is grouped into by the one-tenth described in the last table 5, form thereon and form heat treated redness (R) pixel on the substrate of black (K) image, and on black (K) image, form 25 * 25 μ m squares redness (R) pattern.Exposure is 150mJ/cm ², and use sodium carbonate base developer to carry out developing in 60 seconds at 23 ℃.

The thickness of redness (R) pixel that forms is 1.6 μ m, and the coating weight of C.I.P.R.254 and C.I.P.R.177 is respectively 0.88g/m ²And 0.22g/m ²

The formation of-green (G) pixel-

According to form the identical step of black (K) image, and use the following colored photosensitive resin composition G3 that is grouped into by the one-tenth described in the last table 5, form thereon and form heat treated green (G) pixel on the substrate of black (K) image and redness (R) pixel, and in the substrate of the spacer that forms by black (K) image and redness (R) pattern formation green (G) pattern.Exposure is 150mJ/cm ², and use sodium carbonate base developer to carry out developing in 60 seconds at 23 ℃.

The thickness of green (G) pixel that forms is 1.6 μ m, and the coating weight of C.I.P.G.36 and C.I.P.Y.150 is respectively 1.12g/m ²And 0.48g/m ²

The formation of-blue (B) pixel-

According to form the identical step of black (K) image, and use the following colored photosensitive resin composition B3 that is grouped into by the one-tenth described in the last table 5, form thereon on the substrate of black (K) image and redness (R) and green (G) pixel and form heat treated blueness (B) pixel, and in the substrate of the spacer that forms by black (K) image and redness (R) and green (G) pattern formation blueness (B) pattern to obtain the target color filter.Exposure is 150mJ/cm ², and use sodium carbonate base developer to carry out developing in 60 seconds at 23 ℃.

The thickness of blueness (B) pixel that forms is 1.6 μ m, and the coating weight of C.I.P.B.15:6 and C.I.P.V.23 is respectively 0.63g/m ²And 0.07g/m ²

At this, explanation is gone up the preparation of colored photosensitive resin composition K2, R3, G3 and the B3 described in the table 5.

Obtain colored photosensitive resin composition K2 by the following method: at first with amount weighing K pigment dispersion 2 and the propylene glycol methyl ether acetate described in the table 5, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 5, bonding agent 1, the hydroquinone monomethyl ether, DPHA solution, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methyl)-the 3-bromophenyl]-s-triazine and surfactant 2, their temperature at 25 ℃ (± 2 ℃) are added with this order, and this potpourri was stirred 30 minutes under the temperature of 40 ℃ (± 2 ℃) and 150rpm.

In the composition described in table 5 and 6, K pigment dispersion 2 composed as follows:

13.1 parts of carbon blacks (trade name: Special Black 250 is produced by Degussa)

5-[3-oxo-2-[4-[3, two (3-diethylamino propyl group amino carbonyl) phenyl of 5-] amino carbonyl] phenylazo]-0.65 part of the amino benzimidazolone of bytyry

6.72 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

79.53 parts of propylene glycol methyl ether acetates

Bonding agent 4 composed as follows:

27 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=78/22 mol ratio, weight-average molecular weight 40,000)

73 parts of propylene glycol methyl ether acetates

DPHA solution composed as follows:

76 parts of dipentaerythritol acrylates (comprise 500ppm polymerization initiator MEHQ, trade name: KAYARAD DPHA, by Nippon Kayaku Co., Ltd. produces)

24 parts of propylene glycol monomethyl ethers

Surfactant 2 composed as follows:

40 parts of C ₆F ₁₃CH ₂CH ₂OCOCH=CH ₂, 55 parts of H (OCH (CH ₃) CH ₂) ₇OCOCH=CH ₂With 5 parts of H (OCH ₂CH ₂) ₇OCOCH=CH ₂Multipolymer, weight-average molecular weight 30,000

30 parts

70 parts of methyl isobutyl ketones

Obtain colored photosensitive resin composition R3 by the following method: at first with the amount weighing R pigment dispersion 3 described in the table 5, R pigment dispersion 4 and propylene glycol methyl ether acetate, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 5, bonding agent 2, DPHA solution, 2-trichloromethyl-5-(to the styryl methyl)-1,3, the 4-oxadiazole, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methyl)-the 3-bromophenyl]-s-triazine and phenothiazine, their temperature at 24 ℃ (± 2 ℃) are added with this order, this potpourri was stirred 30 minutes under 150rpm, in addition, with the amount weighing surfactant 2 described in the table 5, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 30 minutes under 30rpm, and use nylon wire #200 that it is filtered.

In the composition described in table 5 and 6, R pigment dispersion 3 composed as follows:

C.I. paratonere is 254 8.0 parts

5-[3-oxo-2-[4-[3, two (3-diethylamino propyl group amino carbonyl) phenyl of 5-] amino carbonyl] phenylazo]-0.8 part of the amino benzimidazolone of bytyry

8.0 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

83.2 parts of propylene glycol methyl ether acetates

R pigment dispersion 4 composed as follows:

C.I. paratonere is 177 18 parts

12 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

70 parts of propylene glycol methyl ether acetates

Bonding agent 5 composed as follows:

The random copolymers of benzyl methacrylate/methacrylic acid/methyl methacrylate=38/25/37 mol ratio, weight-average molecular weight 30,000) 27 part

73 parts of propylene glycol methyl ether acetates

Obtain colored photosensitive resin composition G3 by the following method: at first with the amount weighing G pigment dispersion 3 described in the table 5, Y pigment dispersion 3 and propylene glycol methyl ether acetate, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ether ketone described in the table 5, cyclohexanone, bonding agent 5, DPHA solution, 2-trichloromethyl-5-(to the styryl methyl)-1,3, the 4-oxadiazole, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methyl)-the 3-bromophenyl]-s-triazine and phenothiazine, their temperature at 24 ℃ (± 2 ℃) are added with this order, this potpourri was stirred 30 minutes under 150rpm, in addition, with the amount weighing surfactant 2 described in the table 5, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 5 minutes under 30rpm, and use nylon wire #200 that it is filtered.

In the composition described in table 5 and 6, G pigment dispersion 3 composed as follows:

C.I. pigment green 36 is 18 parts

12 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

35 parts of cyclohexanone

35 parts of propylene glycol methyl ether acetates

Y pigment dispersion 3 (trade name: CF Yellow EX3393, produce by Mikuni Color Ltd.)

Obtain colored photosensitive resin composition B3 by the following method: at first with the amount weighing B pigment dispersion 4 described in the table 5, B pigment dispersion 5 and propylene glycol methyl ether acetate, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 5, bonding agent 6, DPHA solution, 2-trichloromethyl-5-(to the styryl methyl)-1,3, the 4-oxadiazole, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methyl)-the 3-bromophenyl]-s-triazine and phenothiazine, their temperature at 25 ℃ (± 2 ℃) are added with this order, this potpourri was stirred 30 minutes under the temperature of 40 ℃ (± 2 ℃) and 150rpm, in addition, with the amount weighing surfactant 2 described in the table 5, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 5 minutes under 30rpm, and use nylon wire #200 that it is filtered.

In the composition described in table 5 and 6,

B pigment dispersion 4 (trade name: CF Blue EX3357, produce by Mikuni Color Ltd.)

B pigment dispersion 5 (trade name: CF Blue EX3383, produce by Mikuni Color Ltd.)

Bonding agent 6 composed as follows:

The random copolymers of benzyl methacrylate/methacrylic acid/methyl methacrylate=36/22/42 mol ratio, weight-average molecular weight 30,000) 27 part

73 parts of propylene glycol methyl ether acetates

[embodiment 10 to 16 and comparative example 3 to 6]

According to the method manufacturing objective color filter identical with embodiment 9, difference is that the colored photosensitive resin composition R3, the G3 that will be in embodiment 9 use and the composition of B3 change into colored photosensitive resin composition R4, G4 described in the table 5 and the composition of B4 respectively, use motor-driven mill M-50 (producing) and diameter zirconia bead, and disperse described material with the preparation pigment dispersion composition with the circumferential speed of 9m/s as 0.65mm by Aiger.The jitter time that in table 8 and 9, has shown the number average particle diameter and the composition of this moment of pigment.

In the composition described in table 5 and 6, G pigment dispersion 4 composed as follows:

C.I. pigment green 36 is 14 parts

23 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

N, N '-two-(3-diethylamino propyl group)-5-{4-[2-oxo-1-(2-oxo-2,3-dihydro-1H-benzimidazole-5-base carbamyl)-propyl group azo]-benzoyl-amido }-1.4 parts of benzenedicarboxamides

61.6 parts of propylene glycol methyl ether acetates

Y pigment dispersion 4 composed as follows:

C.I. pigment yellow is 150 15 parts

9 parts in polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, weight-average molecular weight 37,000)

N, N '-two-(3-diethylamino propyl group)-5-{4-[2-oxo-1-(2-oxo-2,3-dihydro-1H-benzimidazole-5-base carbamyl)-propyl group azo]-benzoyl-amido }-1.5 parts of benzenedicarboxamides

74.5 parts of propylene glycol methyl ether acetates

B pigment dispersion 6 composed as follows:

C.I. pigment blue 15: 6 11.28 parts

C.I. pigment Violet 23 is 0.72 part

0.6 part of EFKA-745 (producing) by EFKA ADDITIVES B.V.

0.75 part of Disparon DA-725 (by Kusumoto Chemicals, Ltd. produces)

86.65 parts of propylene glycol methyl ether acetates

The manufacturing of-liquid crystal indicator (embodiment 9 to 16,25 and 27, comparative example 3 to 6)-

Not (PVA display mode) (not having rib (rib))

Forming ITO film (in embodiment 27, forming spacer thereon) on the color-filter layer of above-mentioned manufacturing

Form PVA display mode pattern by ITO (indium tin oxide target) transparency electrode with to substrate (TFT substrate).In addition, settle alignment film of polyimide thereon.The coating encapsulant is so that to form width be 0.5mm and be the hermetic unit of 40 μ m highly on the position corresponding with the outside framework of the black matrix of the periphery of the pixel group that is placed in color filter, drip PVA display mode liquid crystal, and in the relative glass substrate of decompression (not being higher than 13Pa) laminated.Make pressure get back to normal pressure, and apply load element thickness is controlled to be 4 μ m.In this case, by using metal halide lamp and use ultraviolet ray cutting less than 340nm, under nitrogen atmosphere exposure light make become in 340 to 390nm accumulation light quantity corresponding 3,000mJ/cm ²Light quantity so that the encapsulant photocuring.To be administered on the both sides of this liquid crystal cells by the polaroid HLC2-2518 that Sanritz Corporation produces.Then, use as the FR1112H of red (R) LED (by Stanley Electric Co., Ltd. the chip-type LED of Sheng Chaning), as the DG1112H of green (G) LED (by Stanley Electric Co., Ltd. the chip-type LED of Sheng Chaning) with as the DB1112H (by Stanley Electric Co., the chip-type LED that Ltd. produces) of blue (B) LED, set up side light type backlight, and it is arranged on the rear side of the liquid crystal cells with polaroid, obtains liquid crystal indicator.

Liquid crystal indicator above in Fig. 1, having shown.

Fig. 1 is the schematic cross section that has shown the liquid crystal indicator 10 of the foregoing description.In Fig. 1,12 is polaroid, and 14 is substrate, and 16 is the ITO film, and 18 is alignment films, and 20 is liquid crystal, and 22 is alignment films, and 24 is the ITO film, and 26 is color filter, and 28 is substrate, and 30 is polaroid, and 32 is backlight and 34 for spacer.

[embodiment 17 and 26] (making color filter) by transmitting

The preparation of-photosensitive resin transmission material-

Use narrow slit type nozzle, the coating solution of the thermoplastic resin that will be made up of following prescription H2 is coated on the interim carrier of polyethylene terephthalate film that thickness is 75 μ m, and drying.Then, the coating solution in coating and the dry middle layer of forming by following prescription P2.In addition; coating and dry by the colored photosensitive resin composition K2 that becomes to be grouped into described in the last table 5; to provide build on interim carrier is the thermoplastic resin of 14.6 μ m; build is the middle layer of 1.6m and the photosensitive resin layer of 2.4 μ m, and diaphragm (thickness is the polypropylene screen of 12 μ m) is adhered thereto.

Thus, the wherein interim carrier of preparation, thermoplastic resin, middle layer (oxygen screened film) and black (K) photosensitive resin layer form whole photosensitive resin and transmit material, and this sample called after photosensitive resin is transmitted material K2.

The coating solution of-thermoplastic resin: prescription H2-

11.1 parts of methyl alcohol

6.36 parts of propylene glycol methyl ether acetates

52.4 parts of methyl ether ketone

The multipolymer of methyl methacrylate/acrylic acid-2-ethyl caproite/benzyl methacrylate/methacrylic acid (copolymerization ratio of components (mol ratio)=55/30/10/5, weight-average molecular weight=100,000,

)

5.83 part

The multipolymer of styrene/acrylic (copolymerization ratio of components (mol ratio)=65/35, weight-average molecular weight=10,000,

) 13.6 parts

Wherein use the compound of bisphenol-A with 2 equivalent five ethylene glycol monomethacrylates dehydrating condensations

(trade name: BPE-500, by Shin-Nakamura Chemical Co., Ltd. produces)

9.1 part

0.54 part in surfactant 2 (trade name: MEGAFACE F780F, by Dainippon Ink and Chemicals, Incorporated produces)

The coating solution in-middle layer: prescription P2-

PVA205 (polyvinyl alcohol (PVA), by Kuraray Co., Ltd. produces, saponification degree=88%, the degree of polymerization 550)

32.2 part

14.9 parts of polyvinyl pyrrolidones (trade name: K-30 is produced by BASF)

524 parts of distilled water

429 parts of methyl alcohol

Then, prepare photosensitive resin according to method same as described above and transmit material R5, G5 and B5, difference be with transmit at photosensitive resin the colored photosensitive resin composition K2 that uses in the preparation of material K2 change into by on the one-tenth described in the table 6 following colored photosensitive resin composition R5, the G5 or the B5 that are grouped into.

The formation of-black (K) image-

When the glass detergent solution that will be controlled at 25 ℃ sprays 20 seconds, use has the rotating brush washing alkali-free glass substrate of nylon hair, use the pure water spray to wash, and use spray, with silane coupled solution (0.3 quality % aqueous solution (trade name: KBM603 of N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, by Shin-Etsu Chemical Co., Ltd. produces) sprayed 20 seconds, use the pure water spray that it is washed subsequently.Use the substrate pre-heating device, this substrate was heated 2 minutes at 100 ℃.

Peel off and be used for the diaphragm that photosensitive resin transmits material K2; and using the rubber rollers temperature is 130 ℃; line pressure is that 100N/cm and transfer rate are that 2.2m/ minute laminating machine is (by HitachiIndustries Co.; Ltd. produce (Lamic Model II)), it is laminated on 2 minutes the substrate of 100 ℃ of heating.

After peeling off diaphragm; keeping under the substrate situation vertical with mask (quartzy exposed mask) with picture pattern; with the distance setting between exposed mask surface and the photosensitive resin layer is 200 μ m; and use proximity printing instrument (by Hitachi Hi-Tech ElectronicsEngineering Co., Ltd. produces) with 70mJ/cm with ultrahigh pressure mercury lamp ²Exposure carry out pattern exposure.

Then, under the flat burner pressure of 0.04MPa, (comprise 2.5% triethanolamine with triethanolamine base developer, comprise non-ionic surfactant, comprise the polypropylene-base defoamer, trade name: T-PD1, by Fuji Photo Film Co., Ltd. produce) it was developed 50 seconds at 30 ℃ of sprays, and remove thermoplastic resin and oxygen screen layer.

Subsequently, under 0.15MPa pressure, use circular cone build nozzle, with sodium carbonate base developer (sodium carbonate, 1% nekal, anionic surfactant, defoamer and the stabilizing agent that comprise 0.06 mol sodium bicarbonate, have same concentrations, trade name: T-CD1, by Fuji Photo Film Co., Ltd. produces) it was developed 30 seconds at 29 ℃ of sprays, photosensitive resin layer is developed to obtain forming the pixel of pattern.

Subsequently, under 0.02MPa pressure, adopt circular cone build nozzle, the use washing agent (comprise phosphate, silicate, non-ionic surfactant, defoamer and stabilizing agent, trade name: T-SD1, by FujiPhoto Film Co., Ltd. produce), remove residue at 33 ℃ of rotating brushes that use spray and have a nylon hair, last 20 seconds, obtain black (K) image.Afterwards, also use ultrahigh pressure mercury lamp, from a side of resin bed with 500mJ/cm ²Light make the substrate post-exposure, and with it 220 ℃ of thermal treatments 15 minutes.

Reuse this substrate of aforesaid brush washing formation K image thereon, use the pure water spray to wash, and under the situation of not using silane coupled solution, use the substrate pre-heating device that it was heated 2 minutes at 100 ℃.

The formation of-red (R) pixel-

According to transmitting the identical step of material K2 with photosensitive resin, and the usability photopolymer resin transmits material R5, forms redness (R) pattern that forms red (R) pixel and 28 * 28 μ m squares on the substrate of black (K) image thereon.Exposure is 40mJ/cm ², use sodium carbonate base developer to carry out developing in 35 seconds, and carry out thermal treatment in 15 minutes at 220 ℃ at 35 ℃.

The film thickness of photosensitive resin layer R5 is 2.0 μ m, and the coating weight of pigment C.I. paratonere 254 and C.I. paratonere 177 is respectively 0.88g/m ²And 0.22g/m ²

Reuse this substrate that aforesaid brush washing forms the R pixel thereon, use the pure water spray to wash, and under the situation of not using silane coupled solution, use the substrate pre-heating device that it was heated 2 minutes at 100 ℃.

The formation of-green (G) pixel-

According to transmitting the identical step of material K2 with photosensitive resin, and the usability photopolymer resin transmits material G5, form thereon on the substrate of red (R) pixel and form green (G) pixel and green (G) pattern, with whole redness (R) pattern covers on redness (R) pattern.Exposure is 40mJ/cm ², use sodium carbonate base developer to carry out developing in 45 seconds, and carry out thermal treatment in 15 minutes at 220 ℃ at 34 ℃.

The film thickness of photosensitive resin layer G5 is 2.0 μ m, and the coating weight of pigment C.I. pigment green 36 and C.I. pigment yellow 150 is respectively 1.12g/m ²And 0.48g/m ²

Reuse this substrate that aforesaid brush washing forms R and G pixel thereon, use the pure water spray to wash, and under the situation of not using silane coupled solution, use the substrate pre-heating device that it was heated 2 minutes at 100 ℃.

The formation of-blue (B) pixel-

According to transmitting the identical step of material K2 with photosensitive resin, and the usability photopolymer resin transmits material B 5, forms formation blueness (B) pixel on the substrate of red (R) pixel and green (G) pixel thereon.Exposure is 30mJ/cm ², use sodium carbonate base developer to carry out developing in 40 seconds at 36 ℃.

The film thickness of photosensitive resin layer B5 is 2.0 μ m, and pigment C.I. pigment blue 15: 6 and the coating weight of C.I. pigment Violet 23 be respectively 0.63g/m ²And 0.67g/m ²

This substrate that forms R, G and B pixel and K image is thereon cured 50 minutes with the manufacturing objective color filter at 240 ℃.

The method that is used for colored photosensitive resin composition G5 described in the preparation table 6 and B5 is according to the method that is used to prepare colored photosensitive resin composition G3 and B3.

Obtain colored photosensitive resin composition R5 by the following method: at first with the amount weighing R pigment dispersion 3 described in the table 6, R pigment dispersion 4 and propylene glycol methyl ether acetate, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 10 minutes under 150rpm, then, with the amount weighing methyl ethyl ketone described in the table 6, bonding agent 5, DPHA solution, 2-trichloromethyl-5-(to the styryl methyl)-1,3, the 4-oxadiazole, 2, two (trichloromethyl)-6-[4-(N of 4-, N-di ethoxy carbonyl methyl)-the 3-bromophenyl]-s-triazine and phenothiazine, their temperature at 24 ℃ (± 2 ℃) are added with this order, they were stirred 10 minutes under 150rpm, then, with the amount weighing ED152 described in the table 6, they are mixed in the temperature of 24 ℃ (± 2 ℃), this potpourri was stirred 20 minutes under 150rpm, in addition, with the amount weighing surfactant 2 described in the table 6, its temperature at 24 ℃ (± 2 ℃) is added, this potpourri was stirred 30 minutes under 30rpm, and use nylon wire #200 that it is filtered.* ED152 is phosphate-based special activating agent (trade name: HIPLAAD ED152, by KusumotoChemicals, Ltd. produces).

[embodiment 18 to 24 and 26 and comparative example 7 to 10]

Obtain the target color filter according to the method identical with embodiment 17, difference is that the colored photosensitive resin composition R5, the G5 that will be in embodiment 17 use and the composition of B5 change into colored photosensitive resin composition R6, G6 described in the table 6 and the composition of B6 respectively, use motor-driven mill M-50 (producing) and diameter zirconia bead, and disperse described material with the preparation pigment dispersion composition with the circumferential speed of 9m/s as 0.65mm by Aiger.The jitter time that in table 8 and 9, has shown the number average particle diameter and the composition of this moment of pigment.

The manufacturing of-liquid crystal indicator and assembling (embodiment 18 to 24 and 26, comparative example 7 to 10)-

Forming ITO film (in embodiment 28, forming spacer thereon) on the color-filter layer of above-mentioned manufacturing.

(being used for the preparation of the sensitization transmission material of teat)

To be coated on by the coating solution that above-mentioned prescription H2 forms on the interim carrier of polyethylene terephthalate film that thickness is 75 μ m, and drying so that being provided, build is the thermoplastic resin of 15 μ m.

Then, will be coated on the described thermoplastic resin, and drying so that being provided, build is the middle layer of 1.6 μ m by the coating solution that above-mentioned prescription P2 forms.

The coating solution of the teat photosensitive resin layer that will be made up of following prescription A is coated on the middle layer, and dry be the photosensitive resin layer of the liquid crystal aligning control usefulness teat of 2.0 μ m so that build to be provided.

The coating solution of-teat photosensitive resin layer: prescription A-

53.3 parts of positive-type resist solution

(trade name: FH-2413F is produced by Fuji Film Electromaterials)

46.7 parts of methyl ethyl ketones

2 0.04 parts in surfactant

In addition, the polypropylene screen that will be 12 μ m as the thickness of coverlay is administered on the photosensitive resin laminar surface, transmit material with the preparation teat with sensitization, wherein thermoplastic resin, middle layer, photosensitive resin layer and coverlay are pressed on the interim carrier with this sequential layer.

(formation of teat)

The teat that obtains from above transmits on the material with sensitization and peels off coverlay, with the surface of photosensitive resin layer with settle a side surperficial overlapping of the ITO film of color filter side substrate, and use laminating machine (by Hitachi Industries Co., Ltd. produce (Lamic Model II)), be 100N/cm in line pressure ², temperature is 130 ℃, and transfer rate is to carry out lamination under 2.2m/ minute the condition.Afterwards, only the interim carrier that will transmit material of the border between thermoplastic resin is peeled off and is removed.In this case, photosensitive resin layer, middle layer and thermoplastic resin are pressed on the color filter side substrate with this sequential layer.

Then, the short range instrument that exposes is placed in as outermost thermoplastic resin top, makes photomask be positioned at distance, and use ultrahigh pressure mercury lamp, with 70mJ/cm from the surface of photosensitive resin layer 100 μ m ²Irradiation, carry out short range exposure via photomask.Afterwards, use the spraying type developing apparatus, 1% triethanolamine aqueous solution was sprayed 30 seconds to substrate, with dissolving and remove thermoplastic resin and middle layer at 30 ℃.In this stage, photosensitive resin layer does not fully develop.

Subsequently, use the spraying type developing apparatus, when 33 ℃ are ejected into 0.085mol/L sodium carbonate, 0.085mol/L sodium bicarbonate and 1% nekal aqueous solution on the substrate, carry out developing so that the unwanted part (uncured portion) of photosensitive resin layer is developed and is removed in 30 seconds.And, in the substrate of the spacer that forms by lamination redness (R) and green (G) pattern and on coloring film side substrate, form the teat of forming by the photosensitive resin layer that forms the shape that needs.Then, the color filter side substrate that forms teat was thereon cured 50 minutes at 240 ℃.Thereby, being formed by green (G) pixel in the substrate of the spacer that red by lamination (R) and green (G) forms highly is the spacer of 3.4 μ m, and on color filter side substrate formation to have highly be the teat that is used to control liquid crystal aligning of 1.5 μ m and semicircle longitudinal cross-section shape.

In addition, make 20 inches liquid crystal indicators of the present invention according to the method identical with embodiment 9, difference is with respect to the color filter side substrate that as above obtains, with the three-wavelength cold-cathode tube light source (CCFL: cold-cathode fluorescence lamp that changes into backlight, produce by Samson Electronics Company Limited), condition is to use HC2-6018 as polaroid in embodiment 26, and uses the identical polaroid of polaroid with comparative example 3 to 6 in comparative example 7 to 10 respectively.

Settle KRGB, spacer and liquid crystal aligning control with on the color filter substrate of teat thereon, alignment film of polyimide is set.On the position corresponding with the outside framework of the black matrix of the periphery of the pixel group that is placed in color filter, printing comprises the epoxy encapsulant of spacer particle, and at 10kg/cm ²Pressure under mutual lamination color filter substrate and to substrate (TFT substrate).Then, the glass substrate of lamination is made sealant cures in 90 minutes 150 ℃ of thermal treatments, obtain the laminated material of two glass substrate.This glass substrate laminated material is outgased under vacuum, afterwards, make pressure get back to atmospheric pressure, and liquid crystal is injected in two gaps between the glass substrate.After finishing injection, use bonding agent, by inlet partly being sealed to obtain liquid crystal cells with ultraviolet irradiation.

The backlight of CCFL constructed in both sides at this liquid crystal cells, and it is arranged on the dorsal part of the liquid crystal cells of giving polaroid, to obtain liquid crystal indicator.

Liquid crystal indicator above in Fig. 2, having shown.Fig. 2 is the schematic cross section that shows the liquid crystal indicator 10A that relates to the foregoing description.In Fig. 2, identical symbol is added on the parts identical with parts among Fig. 1.12 is polaroid, and 14 is substrate, and 16 is the ITO film, and 18 is alignment films, and 20 is liquid crystal, and 22 is alignment films, and 24 is the ITO film, and 26 is color filter, and 28 is substrate, and 30 is polaroid, and 34 is that spacer and 36 is teat.

[embodiment 27]

(liquid resistor)

Form color filter according to the method identical with embodiment 9, difference is not form spacer by the various pixels of lamination.

[manufacturing of liquid crystal indicator]

By sputtering ITO, form after the ELD on the color filter of in embodiment 27, making, form spacer by the following method.

(preparation of the photosensitive resin composition S of spacer)

According to the method that is used to prepare colored photosensitive resin composition R3, preparation is used photosensitive resin composition S:34.0 mass parts methacrylic acid/allyl methacrylate copolymer (mol ratio=20/80 by the following spacer of forming, weight-average molecular weight=40,000), 1.8 mass parts dipentaerythritol acrylate, 7.1 the suspending liquid (trade name: MIBK-ST of mass parts 30 quality % silicon dioxide gels in methyl isobutyl ketone, by Nissan Chemical Industries, Ltd. produce), 0.001 mass parts phenothiazine, 0.17 mass parts 2,4-pair-(trichloromethyl)-6-[4-(N, N-di ethoxy carbonyl methylamino)-3-bromophenyl]-s-triazine, 0.02 mass parts Victoria's pure blue B OHM, 0.01 mass parts surfactant 2,7.4 mass parts ethyl methyl ketone, 8.6 mass parts 1-methoxyl-2-propyl-acetic acid ester and 0.5 mass parts methyl alcohol.

(manufacturing of spacer)

Then, according to the identical step of step of the method for formation black (K) image of embodiment 9, and use the spacer of preparation to transmit material S with photosensitive resin, form spacer on the color filter substrate of sputtering ITO thereon, condition is that exposure is 40mJ/cm ², the KOH base developer that the dilution of using among the use embodiment 9 is 100 times carries out developing in 80 seconds at 23 ℃, and carries out thermal treatment in 30 minutes at 230 ℃.

In addition, according to the method identical,, make liquid crystal indicator for the color filter side substrate that obtains above with embodiment 9.

As with the liquid crystal indicator of the color filter that uses embodiment 9 relatively, display performance is good equally, but the device of the embodiment 9 that the number of manufacture steps more preferably by is still less made with low cost.

Liquid crystal indicator on Fig. 3 has shown.Fig. 3 is the schematic cross-section that shows the liquid crystal indicator 10B of the foregoing description 27.In Fig. 3, identical symbol is added on the parts identical with parts among Fig. 2.12 is polaroid, and 14 is substrate, and 16 is the ITO film, and 18 is alignment films, and 20 is liquid crystal, and 22 is alignment films, and 24 is the ITO film, and 26 is color filter, and 28 is substrate, and 30 is polaroid, and 34A is that the spacer and 36 of colored photosensitive resin composition is teat.

[embodiment 28] (transmission)

Form color filter according to the method identical with embodiment 17, difference is that the substrate of spacer does not form by the various pixels of lamination.

[manufacturing of liquid crystal indicator]

By sputtering ITO, form ELD on the color filter of in the foregoing description 28, making.

Subsequently, according to the method identical with embodiment 27, preparation spacer photosensitive resin composition S, and according to transmitting the identical method of method of material K2 with photosensitive resin, the preparation photosensitive resin transmits material S, and use sensitization to transmit material S and obtain spacer on the color filter substrate, condition is that exposure is 40mJ/cm ², the KOH base developer that the dilution of using among the use embodiment 9 is 100 times carries out developing in 40 seconds at 36 ℃, and carries out thermal treatment in 30 minutes at 230 ℃.

Afterwards,, be formed for the teat of liquid crystal aligning control, and,, make liquid crystal indicator for the color filter side substrate that obtains above according to the method identical with embodiment 17 according to the method identical with embodiment 17.

As with the liquid crystal indicator of the color filter that uses embodiment 17 relatively, display performance is good equally, but the device of the embodiment 17 that the number of manufacture steps more preferably by is still less made with low cost.

[evaluation]

The measurement of-contrast-

Measure the contrast of each colored pixels that constitutes the color filter that obtains above by following measuring method, and calculate the poor contrast of various colored pixels.The results are shown in table 8 and 9.

The measurement of-particle diameter-

Number average particle diameter as pigment, use transmission electron microscope (JEOL.Ltd., the JEM-2010-electron microscope) photograph image of shooting granules of pigments, employing is to have the diameter of bowlder of the same area as particle diameter at the supposition image, measure this diameter of 100 particles, and obtain average.

(measuring the method for contrast)

Use three-wavelength cold-cathode tube light source as backlight, color filter is arranged on two polaroid (trade names: G1220DUN, produce by Nitto Denko Corporation) between, and the chromatic value Y by the light that passes through when the arranged parallel polaroid obtains contrast divided by the chromatic value Y of the light that passes through when polaroid is settled with cross Nicols.In order to measure colourity, use colour brightness meter (trade name: BM-5 is produced by TOPCON).

The measurement that-Hei shows-

Make the liquid crystal indicator that adopts the color filter of making in embodiment 9 to 28 and the comparative example 3 to 10 become black the demonstration, measure the colourity of this moment, colour killing colourity is defined as (x, y, Y=0.333,0.333,0.08), and the aberration Δ E between calculating and this color.The results are shown in table 8 and 9.Measure the black colourity that shows by the following method.Backlight and the polaroid that use is used in the liquid crystal indicator that will measure, settle backlight and polaroid to make two polaroids become cross Nicols, color filter is placed between the polaroid, and use colour brightness meter (trade name: BM-5 is produced by TOPCON) to measure the colourity of the light that leaks.And the aberration between the achromic point preferably is equal to or less than 5.When difference surpassed 5, black demonstration was coloured, and therefore, this is not preferred.

The method of-evaluation vividness-

When on the black display background of the liquid crystal indicator of the color filter that is using embodiment 9 to 28 and comparative example 3 in 10, to make during demonstration red, green and blue pure color, on sense organ, estimate vividness by 50 experimenters.Use is estimated vividness according to the Pyatyi of the order of high definition more, and adopts average as evaluation of estimate.The results are shown in table 8 and 9.A represents to be not less than 4 and be not higher than 5, and B represents to be not less than 3 and less than 4, and C represents less than 3.

-overall assessment-

According to the standard shown in the following table 7, carry out the overall assessment of the display quality of liquid crystal indicator.The results are shown in table 8 and 9.

Table 7

From table 8 and 9, liquid crystal indicator of the present invention has the high-contrast of each pixel, show distinct image, obtaining balance aspect the contrast of the various pixels of RGB, and excellence aspect black display performance, liquid crystal indicator wherein of the present invention disposes contrast wherein and is not less than 2000 polaroid, in the colored pixels of three kinds of colors, have the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast and be not more than 600, degree of polarization is not less than 99.95, and is not higher than 0.05% at the quadrature transmittance of 400nm.

On the other hand, the contrast that disposes each colored pixels wherein is less than the comparative example 3 of 2000 color filter and the low contrast that 7 liquid crystal indicators have each pixel, and the image that shows lacks vividness; And dispose the comparative example 4 of following color filter and liquid crystal indicator imbalance aspect the contrast of the various pixels of RGB of 8, have that low contrast by red colored pixels causes to of the demonstration of little red to displacement, and be wanting at black display performance, in described color filter, among the colored pixels of three kinds of colors, have the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast and surpass 600.In addition, even when use has the color filter of the high-contrast of various colored pixels and little poor contrast, use the liquid crystal indicator of the polaroid described in the comparative example 5,6,9 and 10 also to have big and aberration achromic point, low aspect black display performance, and distinct image can not be provided.

Industrial usability

According to the present invention, a kind of colour filter can be provided, described colour filter has the high-contrast ratio, and And particularly, even at large-screen lc display unit such as laptop computer displays or televimonitor During middle the use, also can realize enough color reprodubilities. In addition, by in liquid crystal indicator Use described colour filter, can realize distinct, have high color purity and have high black demonstration matter The coloured image of amount shows.

In addition, according to the present invention, have the pixel of high-contrast and have high-contrast by combination Polarizer can provide to have high-contrast, shows distinct image, in the various pixels of RGB The contrast aspect be balanced, and aspect black display performance the liquid crystal indicator of excellence.

Claims (12)

1. color filter, described color filter comprises the colored pixels of two or more color, each of wherein said colored pixels comprises granules of pigments at least, the contrast of each of described colored pixels is not less than 2000, and among the colored pixels of described two or more color, have the contrast of colored pixels of minimum contrast and the difference of contrast with colored pixels of high-contrast and be not more than 600, the number average particle diameter of wherein said granules of pigments is 0.01 to 0.08 μ m.

2. the described color filter of claim 1, wherein the described colored pixels of at least a color comprises C.I. paratonere 254.

3. the described color filter of claim 1, wherein the described colored pixels of at least a color comprises the C.I. pigment green 36.

4. the described color filter of claim 1, wherein the described colored pixels of at least a color comprises the C.I. pigment blue 15: 6.

5. method that is used to make color filter as claimed in claim 1, described method comprises: form resin bed by colored photosensitive resin composition, described colored photosensitive resin composition comprises (1) alkali soluble resins, (2) monomer or oligomer, (3) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system and (4) granules of pigments.

6. the described method that is used to make color filter of claim 5, the formation of wherein said resin bed comprise by using narrow slit type nozzle to be coated with described colored photosensitive resin composition.

7. the described method that is used to make color filter of claim 5, the formation of wherein said resin bed comprise by using laminating machine will wherein settle the resin of colored photosensitive resin composition resin bed to transmit material layer on interim carrier and being pressed on the substrate.

8. liquid crystal indicator, described liquid crystal indicator comprises color filter as claimed in claim 1.

9. liquid crystal indicator, described liquid crystal indicator comprises: backlight, polaroid, at least two substrates, by the liquid crystal layer of described substrate support, the electrode of settling at least a portion of described substrate, with the color-filter layer of at least a portion of described substrate, settling

Wherein said color-filter layer is the color filter that limits as claim 1, and

Described polaroid has the quadrature transmittance that is not less than 99.95 degree of polarization and is not higher than 0.05% at 400nm.

10. the described liquid crystal indicator of claim 9, wherein the described colored pixels of at least a color comprises C.I. paratonere 254.

11. the described liquid crystal indicator of claim 9, wherein the described colored pixels of at least a color comprises the C.I. pigment green 36.

12. the described liquid crystal indicator of claim 9, wherein the described colored pixels of at least a color comprises the C.I. pigment blue 15: 6.

Images