CN101398497A

CN101398497A - Color filter and manufacure method

Info

Publication number: CN101398497A
Application number: CNA2008101610254A
Authority: CN
Inventors: 中川干雄; 辻畑茂朝
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2007-09-28
Filing date: 2008-09-24
Publication date: 2009-04-01
Anticipated expiration: 2028-09-24
Also published as: TW200928458A; JP2009098691A; KR101506229B1; CN101398497B; JP5455344B2; KR20090033089A; TWI437284B

Abstract

The present invention provides a filter which is characterized by at least comprising a coloring pattern. The occupation rate of secondary particles in the image obtained from the result of the coloring pattern surface is lower than 40%. The coloring pattern is formed by endowing the photo-curing composition containing paint with average particle diameter of 15-150nm on a substrate. The photo-curing composition preferably comprises the following components at least: an organic solvent, the paint with average particle diameter of 15-150nm, the polymer of copolymerization unit containing the monomer represented by the general formula (1), a photo-curing compound and a photopolymerization initiating agent. Additionally the invention provides a method for manufacturing the filter with the optimized photo-curing composition.

Description

Color filter and manufacture method thereof

Technical field

The present invention relates to color filter and this manufacturing method of color filter, relate to the color filter and the manufacture method thereof of contrast excellence in more detail.

Background technology

The following manufacturing of color filter: contain the pigment dispensing composition, polyfunctional monomer, Photoepolymerizationinitiater initiater, alkali soluble resin and other composition that have disperseed organic pigment or inorganic pigment and make coloring photosensitive combination, use said composition, by formation colored patterns such as photoetching processes, make thus.

In recent years, color filter not only also has the tendency of expansion in monitor but also the purposes in televisor in the purposes of liquid crystal indicator (LCD), be accompanied by the tendency that this purposes enlarges, and requires the color characteristics at the height of aspects such as colourity, contrast.Particularly therefore contrast is subjected to gazing at especially owing to the picture quality to display device has significant impact.

At above-mentioned requirements, require to make it disperse (good dispersion stabilization) with finer state dispersed color (good dispersiveness) with stable status.When dispersiveness is insufficient, have following problems: produce fringe (fringe) or concave-convex surface on the formed painted resist film, the colourity of the color filter of manufacturing or dimensional accuracy reduce, perhaps the remarkable deterioration of contrast.

The main cause that reduces of degree as a comparison, the light leak in the time of can enumerating the polaroid orthogonal configuration that the scattering backlight that causes owing to the pigment particles in the composition produces.Therefore, for the high-contrastization of color filter, think that the mean grain size in the coloured composition is more little preferred more.

As selecting pigment particles to improve the technology of contrast, disclose following method etc.: using mean grain size is the method (for example opening 2003-248115 number referring to the spy) of the pigment of 100～300nm; Use ultrasonic attenuation type particle size distribution device to measure mean grain size, and select the particle of specialized range, specifically select D ₈₄Be that 1.0 μ m are following, D ₅₀Be that 0.5 μ m is following, D ₁₆Be that 0.3 μ m is following, maximum peak is the method (for example opening 2005-165307 referring to the spy) of the following pigment particles of 0.5 μ m.But, during with the particle diameter miniaturization of pigment, the surface area of pigment particles increases, therefore, cohesiveness between pigment particles strengthens, take into account dispersed and dispersion stabilization with higher level and be mostly the comparison difficulty,, wish further high-contrastization even present situation is to realize satisfying the high-contrastization of realistic scale according to above-mentioned technology.

Summary of the invention

The present invention finishes in view of above-mentioned prior art problems, realizes following purpose.

That is, the invention provides color filter and this manufacturing method of color filter that can obtain high-contrast.

The inventor etc. concentrate on studies, and found that, are controlled at below the setting by the occupation rate with 2 particles of pigment in the formed colored pattern overlay film, can address the above problem, thereby finish the present invention.

That is it is as follows, to be used to the means that address the above problem.

＜1〉a kind of color filter, it is characterized in that, it contains colored pattern, the occupation rate of utilizing 2 particles in the resulting image of result that AFM (atomic force microscope) observes on this colored pattern surface is below 40%, and described colored pattern is to be that the Photocurable composition of the pigment of 15～150nm is given on substrate and being formed with containing mean grain size.

＜2〉according to＜1〉described color filter, it is characterized in that described Photocurable composition contains: organic solvent; Mean grain size is the pigment of 15～150nm; Contain polymkeric substance from the copolymerization units of monomer shown in the following general formula (1); The optical polymerism compound; And Photoepolymerizationinitiater initiater.

[in the general formula (1), R ¹Expression hydrogen atom or replace or do not have the alkyl of replacement.R ²The expression alkylidene.W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y represents-NR ³-,-O-,-S-or-N=, and be situated between and be connected with the N atom and form ring texture by the atomic group that is adjacent.R ³Expression hydrogen atom, alkyl or aryl.M and n represent 0 or 1 independently of one another.]

＜3 〉, it is characterized in that in described general formula (1), Y is situated between and is connected with the N atom and the ring texture that forms is the condensed ring structure by adjacent atomic group according to＜2〉described color filter.

＜4〉according to＜2〉or＜3〉described color filter, it is characterized in that described polymkeric substance is for further containing the graft copolymer from the copolymerization units of the polymerism oligomer that has the ethylenic unsaturated link endways.

＜5〉according to＜2 〉～＜4 in each described color filter, it is characterized in that described polymkeric substance is for further containing the polymkeric substance from the copolymerization units of the monomer with acidic group.

＜6〉according to＜2 〉～＜5 in each described color filter, it is characterized in that described Photocurable composition further contains alkali soluble resin.

＜7〉a kind of manufacturing method of color filter, it comprises: photosensitive film forms operation, this operation is by with Photocurable composition directly or be situated between to be given by other layer form photosensitive film on substrate, and described Photocurable composition contains pigment that organic solvent, mean grain size are 15～150nm, contains polymkeric substance, optical polymerism compound and Photoepolymerizationinitiater initiater from the copolymerization units of monomer shown in the following general formula (1); Colored pattern forms operation, this operation forms colored pattern by formed photosensitive film is carried out pattern exposure and development successively, and the occupation rate of 2 particles in the resulting image of the result who utilizes atomic force microscope to observe of this colored pattern is below 40%.

As one of preferred version of the present invention, can list following proposal: even when using the pigment of fine particle size, be used for the formation of colored pattern by the solidification compound that will use pigment dispensing composition, also can obtain the color filter of light transmission and contrast excellence with high pigment-dispersing and dispersion stabilization.

According to the present invention, can provide color filter and this manufacturing method of color filter that can obtain high-contrast.

Embodiment

Below be elaborated with regard to pigment dispensing composition of the present invention, Photocurable composition, color filter and manufacture method thereof.

Color filter of the present invention is characterised in that to have colored pattern, the occupation rate of 2 particles in the resulting image of the result who utilizes AFM to observe on this colored pattern surface is below 40%, and described colored pattern applies that to contain mean grain size be that the Photocurable composition of the pigment of 15～150nm forms.The occupation rate of 2 particles need be preferably below 25% for below 40%, more preferably below 10%.

Here, 1 particle diameter of pigment can pass through electron microscope (Hitachi High-Technologies Corporation Co., Ltd. makes, S-4800), with multiplying power be 100,000 times, n=100 with on measure.

The mean grain size of pigment can be by using dynamic light scattering type particle size distribution device (a day machine dress (strain) is made Microtrack UPA-150), and diluting with dispersion medium as required and measure.

The occupation rate of 2 particles among the present invention is meant, in the image after the processing that noise in the observation image on the film surface of having implemented to utilize AFM (atomic force microscope) to obtain or particulate etc. are removed, calculate 2 particles face integration rate with respect to whole of image, be occupation rate, adopt the value that records by following method among the present invention.

The occupation rate of 2 particles of＜pigment 〉

(Veeco Instruments makes, NanoScope IIIa, TappingMode) the film surface of the formed colored pattern of observation, the observation image on acquisition surface with AFM.

Here, under the situation of wanting to estimate the colored pattern that has used specific pigment dispensing composition, the condition that will be on the 0.7mm glass substrate reaches 2.0 μ m with dry film thickness applies, dry and overlay film (colored pattern) that form gets final product as subject.

Then, for the gained image, use that U.S.'s National Institutes of Health makes image processing program " Image J ", carry out treatment of picture according to following order, thereby try to achieve the occupation rate of 2 particles in the image.

1. the noise and the ripple of removal of images after changing gray scale, level of corrections carry out binaryzation by techniques of discriminant analysis.

2. cut apart contacted particle by the Watershed method.

3. select the above particle of 50nm, calculate occupation rate.

When measuring the occupation rate of 2 particles under this condition, be 42～45% times in the occupation rate, for example occupation rate that surpass 40%, the contrast that has the color filter of this colored pattern hardly is the practical sufficient state of.

As under this condition, promptly containing in the colored pattern of pigment that mean grain size is 15～150nm, the occupation rate that makes 2 particles in the image that records under these conditions is the method below 40%, can enumerate the solidification compound that when forming colored pattern, uses the aggegation that can suppress pigment, and the dry aggegation in when overlay film forms, suppressing to film, as concrete method, the Photocurable composition that can enumerate the dispersiveness of for example using micro pigment and its excellent in stability forms the method for colored pattern etc.

Below the Photocurable composition of the dispersiveness of using micro pigment and its excellent in stability is formed colored pattern method be specifically described.

＜pigment dispensing composition 〉

Among the present invention, as with fine pigment equably and one of the method for stably disperseing under the situation along with the worry of effluxion generation aggegation not, adopt following method: the polymkeric substance that is about to contain from the copolymerization units of monomer shown in the following general formula (1) uses as pigment dispersing resin.

(containing to come the polymkeric substance of the copolymerization units of monomer shown in the self-drifting (1))

Preferably contain the polymkeric substance that comprises from the copolymerization units of monomer shown in the following general formula (1) in the Photocurable composition of formation colored pattern of the present invention.

In Photocurable composition of the present invention, particular polymers can be used as pigment dispersing agent and plays a role.In the following description, will " contain to come the polymkeric substance of the copolymerization units of monomer shown in the self-drifting (1) " sometimes and suitably be called " specific pigment spreading agent " and describe.

In the general formula (1), R ¹Expression hydrogen atom or replace or do not have the alkyl of replacement.R ²The expression alkylidene.W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y represents-NR ³-,-O-,-S-or-N=, and be situated between and be connected with the N atom and form ring texture by the atomic group that is adjacent.R ³Expression hydrogen atom, alkyl or aryl.M and n represent 0 or 1 respectively independently.

Below be elaborated to becoming as the monomer shown in the general formula (1) of the essential copolymerization units in the particular polymers of important component of the present invention.

In the general formula (1), R ¹Expression hydrogen atom or replace or do not have the alkyl of replacement.

As R ¹Shown alkyl, preferably carbon number is 1～12 alkyl, is more preferably carbon number and is 1～8 alkyl, special preferably carbon number is 1～4 alkyl.

At R ¹When shown alkyl is substituted alkyl,, for example can enumerate hydroxyl, alkoxy, aryloxy group, acyloxy, halogen group etc. as the substituting group that can import.

As R ¹Shown preferred alkyl can be enumerated methyl, ethyl, propyl group, normal-butyl, isobutyl, the tert-butyl group, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl etc. particularly.

R ²The expression alkylidene.

As R ²Shown alkylidene, preferably carbon number is 1～12 alkylidene, is more preferably carbon number and is 1～8 alkylidene, special preferably carbon number is 1～4 alkylidene.

R ²Shown alkylidene also can have substituting group in the time can importing, as this substituting group, can enumerate for example hydroxyl, alkoxy, aryloxy group, acyloxy etc.

As R ²Shown preferred alkylidene can be enumerated methylene, ethylidene, propylidene, trimethylene, tetramethylene etc. particularly.

W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, be preferably-C (=O) O-or-CONH-.

Y represents-NR ³-,-O-,-S-or-N=, and be situated between and be connected with the N atom and form ring texture by the atomic group that is adjacent.

R ³Expression hydrogen atom, alkyl or aryl are preferably hydrogen atom or methyl.

Y is preferably especially-S-,-NH-or-N=.

Be situated between as Y and be connected with the N atom and the ring texture that forms by the atomic group that is adjacent, can enumerate single ring architectures such as imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, and condensed ring structure such as benzimidazole ring, benzothiazole ring, benzoxazole ring, purine ring, quinazoline ring, perimidine ring, from with the viewpoint of the compatibility of pigment, be preferably the condensed ring structure.In the condensed ring structure, can especially preferably enumerate benzimidazole ring, benzothiazole ring and benzoxazole ring.

X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.X is preferably especially-O-,-S-,-CONH-,-NHCONH-and-NHC (=O) S-.

M and n represent 0 or 1 independently of one another, and preferred especially m and n are 1 simultaneously.

The preferred concrete example of the monomer shown in the general formula (1) (monomer M-1～monomer M-18) is listed below, but the present invention is not limited to these.

From giving the viewpoint of dispersing of pigments stability, particular polymers of the present invention is preferably especially and contains from the copolymerization units of monomer shown in the above-mentioned general formula (1) and from the graft copolymer of the copolymerization units of the polymerism oligomer that has the ethylenic unsaturated link endways.

This have the polymerism oligomer of ethylenic unsaturated link endways owing to be the compound with regulation molecular weight, therefore is also referred to as big monomer.In the following description, sometimes " the polymerism oligomer that has the ethylenic unsaturated link endways " of the present invention suitably is called " polymerism oligomer " or " big monomer ".

Constitute by polymer chain part with in the part that its end has a polymerisable functional group of ethylenic unsaturated double-bond according to the required polymerism oligomer that uses among the present invention.From obtaining the viewpoint of required graft polymer, this group with ethylenic unsaturated double-bond preferably only has at an end of polymer chain.Group as having the ethylenic unsaturated double-bond is preferably (methyl) acryloyl group, vinyl, is preferably (methyl) acryloyl group especially.

In addition, the number-average molecular weight of the polystyrene conversion of this big monomer (Mn) is preferably 1000～10000 scope, is preferably 2000～9000 scope especially.

The part of above-mentioned polymer chain is generally homopolymer or the multipolymer that is formed by at least a monomer that is selected from (methyl) alkyl acrylate, styrene and derivant, vinyl cyanide, vinyl acetate and the butadiene or is polyethylene oxide, polypropyleneoxide, polycaprolactone.

Above-mentioned polymerism oligomer is preferably the oligomer shown in the following general formula (2).

General formula (2)

In the general formula (2), R ¹¹And R ¹³Represent hydrogen atom or methyl independently of one another.

R ¹²Expression contains the linking group that carbon number is 1～12 alkylidene, and this linking group can be that carbon number is 1～12 alkylidene, also can be the group that a plurality of these alkylidenes are situated between and are formed by connecting by ester bond, ehter bond, amido link etc.R ¹²Preferably carbon number is that 1～4 alkylidene or carbon number are the group that 1～4 alkylidene is situated between and is formed by connecting by ester bond.R ¹²Shown alkylidene also can further have substituting group (for example hydroxyl).

Y represents not have substituent phenyl, have phenyl that 1 carbon number is 1～4 alkyl or-COOR ¹⁴Here, R ¹⁴The expression carbon number is that 1～6 alkyl, phenyl or carbon number are 7～10 aralkyl.Y be preferably phenyl or-COOR ¹⁴, R here ¹⁴The expression carbon number is 1～12 alkyl.

Q represents 20～200 integer.

As the preferred example of the polymerism oligomer (big monomer) that can in specific pigment spreading agent synthetic, use among the present invention, can enumerate poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate and gather (methyl) isobutyl acrylate, the polymkeric substance of (methyl) acryloyl group is arranged at a molecular end bonding of polystyrene.As the polymerism oligomer that can obtain from the market, can enumerate the polymethylmethacrylate oligomer (Mn=6000, trade name: AA-6, East Asia synthetic chemical industry Co., Ltd. system) of the polystyrene oligomer (Mn=6000, trade name: AS-6, East Asia synthetic chemical industry Co., Ltd. system) of a terminal methyl group propylene acidylate, a terminal methyl group propylene acidylate and the positive butyl ester oligomer of polyacrylic acid (Mn=6000, trade name: AB-6, East Asia synthetic chemical industry Co., Ltd. system) of a terminal methyl group propylene acidylate.

Specific pigment spreading agent of the present invention preferably further contains the copolymerization units from the monomer with acidic group.Further contain copolymerization units by the specific pigment spreading agent, for example pigment dispensing composition of the present invention is applicable to when the pattern that utilizes photoetching process to carry out forms, can further improve pattern and form property from monomer with acidic group.

As monomer, can enumerate unsaturated monocarboxylic acid classes such as acrylic acid, methacrylic acid, crotonic acid, α-Lv Daibingxisuan, cinnamic acid with acidic group; Unsaturated dicarboxylic or its acid anhydride classes such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid; Unsaturated polybasic carboxylic acid more than 3 yuan or its acid anhydride class; List ((methyl) acryloxyalkyl) the ester class of the polybasic carboxylic acids more than 2 yuan such as mono succinate (2-acryloxy ethyl) ester, mono succinate (2-methacryloxyethyl) ester, phthalic acid list (2-acryloxy ethyl) ester, phthalic acid list (2-methacryloxyethyl) ester; List (methyl) esters of acrylic acid of two terminal carboxyl group polymkeric substance such as ω-carboxyl-polycaprolactone single-acrylate, ω-carboxyl-polycaprolactone monomethacrylates etc.

Specific pigment spreading agent of the present invention in the scope of not damaging its effect, but also can further contain the vinyl monomer of copolymerization as copolymer composition.

As spendable vinyl monomer here, be not particularly limited the ester class of for example preferred (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, ethene ethers, vinyl alcohol, phenylethylene, (methyl) vinyl cyanide etc.As the object lesson of this vinyl monomer, for example can enumerate following compound.

As the example of (methyl) esters of acrylic acid, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) 2-EHA, (methyl) acrylic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) acrylic acid stearyl, (methyl) acrylic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid diethylene glycol monomethyl ether, (methyl) acrylic acid diethylene glycol monoethyl ether, (methyl) acrylic acid triethylene glycol monomethyl ether, (methyl) acrylic acid Triethylene glycol ethyl ether, (methyl) polyalkylene glycol acrylate monomethyl ether, (methyl) polyalkylene glycol acrylate list ether, (methyl) acrylic acid beta-phenoxy ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy macrogol ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid two cyclopentene oxygen base ethyl esters, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid two ring pentyl esters, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid tribromophenoxy ethyl ester etc.

In addition, when expression arbitrary in " acrylic acid, methacrylic acid " or both, be designated as " (methyl) acrylic acid " sometimes in this instructions.

As the example of crotonates class, can enumerate butyl crotonate and the own ester of crotonic acid etc.

The example of vinyl ester can be enumerated vinyl acetate, propionate, vinyl butyrate, methoxyacetic acid vinyl acetate and vinyl benzoate etc.

The example of maleic acid diester class can be enumerated dimethyl maleate, diethyl maleate and dibutyl maleate etc.

The example of dimethyl ester class can be enumerated dimethyl fumarate, DEF and dibutyl fumarate etc.

The example of itaconic acid diester class can be enumerated dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.

As (methyl) acrylic amide; can enumerate (methyl) acrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-propyl group (methyl) acrylamide; N-isopropyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tert-butyl group (methyl) acrylamide; N-cyclohexyl (methyl) acrylamide; N-(2-methoxy ethyl) (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N, N-diethyl (methyl) acrylamide; N-phenyl (methyl) acrylamide; N-benzyl (methyl) acrylamide; (methyl) acryloyl morpholine; diacetone acrylamide etc.

As the example of phenylethylene, can enumerate styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, with hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. of group that can be by the acidic materials deprotection (for example t-Boc etc.) protection.

As the example of vinyl ethers, can enumerate methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.

Preferred configuration as specific pigment spreading agent of the present invention, can preferably enumerate following multipolymer: it contains the copolymerization units from monomer shown in the above-mentioned general formula (1) of 2～50 quality %, and further contains the copolymerization units from the polymerism oligomer that has the ethylenic unsaturated link endways of 10～90 quality %, the copolymerization units from the monomer with acidic group of 1～30 quality %, the copolymerization units from vinyl monomer of 0～20 quality %.

The preferred molecular weight of specific pigment spreading agent of the present invention is preferably 15000～200000, is preferably 8000～100000 in number-average molecular weight (Mn) in weight-average molecular weight (Mw).In addition, molecular weight can be measured by gel permeation chromatography (GPC).

Below enumerate the concrete example (exemplary compounds 1～exemplary compounds 16) and the weight-average molecular weight thereof of the specific pigment spreading agent that can in Photocurable composition of the present invention, preferably use, but the present invention is not limited to these.

Exemplary compounds (1): the polymethyl methacrylate copolymer (10/90 quality %, weight-average molecular weight 50000) of above-mentioned monomer M-2/ terminal methyl group propylene acidylate

Exemplary compounds (2): the polymethyl methacrylate copolymer of above-mentioned monomer M-2/ methacrylic acid/terminal methyl group propylene acidylate (10/15/75 quality %, weight-average molecular weight 25000)

Exemplary compounds (3): the polymethyl methacrylate copolymer of above-mentioned monomer M-3/ 2-hydroxyethyl methacrylate/terminal methyl group propylene acidylate (5/10/85 quality %, weight-average molecular weight 40000)

Exemplary compounds (4): the polymethyl methacrylate copolymer of above-mentioned monomer M-3/ methacrylic acid/benzyl methacrylate multipolymer/terminal methyl group propylene acidylate (15/5/10/65 quality %, weight-average molecular weight 60000)

Exemplary compounds (5): the polymethyl methacrylate copolymer (10/90 quality %, weight-average molecular weight 80000) of above-mentioned monomer M-4/ terminal methyl group propylene acidylate

Exemplary compounds (6): the polymethyl methacrylate copolymer of above-mentioned monomer M-4/ methacrylic acid/terminal methyl group propylene acidylate (10/15/75 quality %, weight-average molecular weight 30000)

Exemplary compounds (7): the polymethyl methacrylate copolymer of above-mentioned monomer M-5/ acrylic acid/terminal methyl group propylene acidylate (25/15/60 quality %, weight-average molecular weight 60000)

Exemplary compounds (8): the butyl polyacrylate multipolymer (15/85 quality %, weight-average molecular weight 40000) of above-mentioned monomer M-5/ terminal methyl group propylene acidylate

Exemplary compounds (9): the polymethyl methacrylate copolymer of above-mentioned monomer M-6/ 2-hydroxyethyl methacrylate/terminal methyl group propylene acidylate (15/10/75 quality %, weight-average molecular weight 80000)

Exemplary compounds (10): the polymethyl methacrylate copolymer (12/88 quality %, weight-average molecular weight 50000) of above-mentioned monomer M-6/ terminal methyl group propylene acidylate

Exemplary compounds (11): the polymethyl methacrylate copolymer of above-mentioned monomer M-7/ methacrylic acid/terminal methyl group propylene acidylate (10/15/75 quality %, weight-average molecular weight 25000)

Exemplary compounds (12): above-mentioned monomer M-7/ methacrylic acid/benzyl methacrylate/methoxy polyethylene glycol methacrylate-styrene polymer multipolymer (10/10/50/30 quality %, weight-average molecular weight 40000)

Exemplary compounds (13): the polystyrene copolymer of above-mentioned monomer M-10/ 2-hydroxyethyl methacrylate/terminal methyl group propylene acidylate (5/10/85 quality %, weight-average molecular weight 20000)

Exemplary compounds (14): the polymethyl methacrylate copolymer of above-mentioned monomer M-10/ methacrylic acid/terminal methyl group propylene acidylate (10/15/75 quality %, weight-average molecular weight 25000)

Exemplary compounds (15): above-mentioned monomer M-10/ methoxy polyethylene glycol methacrylate-styrene polymer multipolymer (15:85 quality %, weight-average molecular weight 15000)

Exemplary compounds (16): the polymethyl methacrylate copolymer of above-mentioned monomer M-13/ methacrylic acid/terminal methyl group propylene acidylate (10/15/75 quality %, weight-average molecular weight 20000)

Above-mentioned multipolymer as the specific pigment spreading agent among the present invention can followingly obtain: with the monomer shown in the above-mentioned general formula (1), as required and polymerism oligomer or other monomer of usefulness in solvent, carry out free radical polymerization, thereby obtain.Radical polymerization initiator can use known compound, the preferred azo series initiators (dimethyl-2 for example that uses, 2 '-azo two (2 Methylpropionic acid ester), azobis isobutyronitriles, 2, two (2-amidine propane) 2 hydrochlorides of 2 '-azo etc.), superoxide (benzoyl peroxide, potassium persulfate etc.).Except initiating agent, can also add chain-transferring agent (for example 2 mercapto ethanol, 3-mercaptopropionic acid, 2-mercaptoacetic acid, lauryl mercaptan) and synthesize.

In addition, concrete synthesis example is in the back narration.

Specific pigment spreading agent content in pigment dispensing composition is 0.5～100 quality %, 3～70 quality % more preferably with respect to the quality optimization of pigment described later.The amount of pigment dispersing agent can obtain sufficient pigment dispersing effect in this scope the time.In addition, even interpolation more than the pigment dispersing agent of 100 quality %, also can't be expected the effect of the further raising of pigment dispersing effect sometimes.

Pigment dispensing composition of the present invention be in organic solvent, contain pigment, the specific pigment spreading agent forms, and as required, can use other one-tenth such as resinous principle to assign to constitute.

Because this pigment dispensing composition contains the specific pigment spreading agent, so the dispersing of pigments in the organic solvent is in good condition, can obtain good color characteristics, when for example constituting color filter, can obtain high-contrast simultaneously.Particularly can bring into play the dispersion effect of the excellence of organic pigment.

(mean grain size is the pigment of 15～150nm)

Among the present invention, the pigment that contains mean grain size in the color filter colored pattern and be 15～150nm is for realizing that high-contrast is essential, but, then can suitably select known in the past various inorganic pigments or organic pigment to use as pigment so long as satisfy the pigment of this particle diameter.

No matter pigment is inorganic pigment or organic pigment, all is preferably high-transmission rate, when considering this point, preferably uses the particle diameter little pigment of trying one's best, when also considering operability, the mean grain size that needs pigment in above-mentioned scope, the scope of 15～50nm more preferably.

The mean grain size of the pigment here is the mean grain size of 2 particles of expression, specifically, can measure by above-mentioned method.

Above-mentioned inorganic pigment can be enumerated the metallic compound shown in metal oxide, the metal complex etc., can enumerate the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and the composite oxides of above-mentioned metal etc. particularly.

Above-mentioned organic pigment for example can be enumerated following pigment.

C.I. pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;

C.I. pigment orange 36,38,43,71;

C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;

C.I. pigment violet 19,23,32,37,39;

C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66;

C.I. pigment Green 7,36,37;

C.I. pigment brown 25,28;

C.I. pigment black 1,7.

Pigment among the present invention is not particularly limited, more preferably following pigment.

C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185;

C.I. pigment orange 36,71;

C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264;

C.I. pigment violet 19,23,37;

C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66;

C.I. pigment Green 7,36;

C.I. pigment black 7.

These organic pigments can use separately, perhaps make up various the use in order to improve colour purity.Below enumerate the concrete example of combination.

For example, as red pigment, can use anthraquione pigmentss, perylene pigment, diketopyrrolo-pyrrole series pigments separately or use at least a kind in them is that yellow uitramarine, isoindoline are that yellow uitramarine, quinophthalone are that yellow uitramarine Huo perylene is mixing of red pigment etc. with bisdiazo.For example, anthraquione pigmentss can be enumerated C.I. paratonere 177 ， perylene pigments can enumerate C.I. paratonere 155, C.I. paratonere 224, and the diketopyrrolo-pyrrole series pigments can be enumerated C.I. paratonere 254, from the viewpoint of color reproducibility, preferably with the mixing of C.I. pigment yellow 13 9.In addition, the mass ratio of red pigment and yellow uitramarine is preferably 100:5～100:50.When being lower than 100:5, being difficult to suppress the transmittance of 400nm～500nm sometimes, thereby can't improving colour purity.In addition, when surpassing 100:50, predominant wavelength is offset to the short wavelength sometimes, from the skew increase of NTSC (NTSC) target tone.Particularly, as above-mentioned mass ratio, the scope of 100:10～100:30 is only.In addition, during for each other combination of red pigment, can adjust according to colourity.

In addition, viridine green can use the halogenated phthalocyanines series pigments separately, and perhaps using itself and bisdiazo is that yellow uitramarine, quinophthalone are that yellow uitramarine, azomethine are that yellow uitramarine or isoindoline are mixing of yellow uitramarine.For example, the preferred C.I. pigment Green 7 of this example, 36,37 with the mixing of C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.The mass ratio of viridine green and yellow uitramarine is preferably 100:5～100:150.Above-mentioned mass ratio is during less than 100:5, thereby the transmittance that is difficult to suppress 400～450nm sometimes can't improve colour purity.When surpassing 100:150, predominant wavelength is to long wavelength shifted, from the skew increase of NTSC target tone sometimes.Above-mentioned mass ratio is preferably the scope of 100:30～100:120 especially.

As blue pigment, can use phthualocyanine pigment separately, perhaps can use itself Yu dioxazine is mixing of violet pigment.For example preferred C.I. pigment blue 15: 6 with the mixing of C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment is preferably 100:0～100:50, more preferably 100:5～100:30.

In addition, as the pigment that black matrix" is used, can enumerate that independent carbon black, titanium are black, iron oxide, titanium dioxide or their mixing, the combination that preferred carbon black and titanium are deceived.In addition, the mass ratio that carbon black and titanium are black is preferably the scope of 100:0～100:60.When surpassing 100:60, dispersion stabilization reduces sometimes.

When preparing Photocurable composition of the present invention, preferably this pigment is disperseed in solvent in advance and obtain pigment dispensing composition, the content of pigment is preferably 40～90 quality %, 50～80 quality % more preferably with respect to the total solid composition (quality) of said composition in this pigment dispensing composition.The content of pigment is in above-mentioned scope the time, and color depth is abundant, to guaranteeing that excellent color characteristics is effective.

(organic solvent)

Employed organic solvent in the preparation as pigment dispensing composition among the present invention or Photocurable composition can be enumerated acetate 1-methoxyl-2-propyl ester, 1-methoxyl-2-propyl alcohol, glycol monoethyl ether, diethylene glycol monomethyl ether, ethyl acetate, butyl acetate, ethyl lactate, acetone, MEK, methyl isobutyl ketone, cyclohexanone, n-propanol, 2-propyl alcohol, normal butyl alcohol, cyclohexanol, ethylene glycol, diethylene glycol, toluene, dimethylbenzene etc.

In addition, the addition of organic solvent can wait suitably according to the purposes of pigment dispensing composition and select, but owing to be used for the preparation of Photocurable composition described later in the present invention, therefore from the viewpoint of operability, the mode that can reach 5～50 quality % according to the concentration of the solid constituent that contains pigment and pigment dispersing agent is added.

The preparation method of pigment dispensing composition is not particularly limited, for example can followingly obtain: use vertical or horizontal sand mill, sell excellent comminutor, slit comminutor, ultrasonic dispersing machine etc., the bead that utilization is formed by the glass of 0.01～1mm particle diameter, zirconia etc. carries out differential with pigment, pigment dispersing agent and solvent and looses and handle, thereby obtains.

In addition, also can be before carrying out the bead dispersion, use two rollers, three rollers, bowl mill, rotary screen (trommel), dispersion machine, kneading machine, two-way kneading machine, refiner, stirring machine, single screw rod or double screw extrusion machine etc., carry out mixing dispersion treatment while give stronger shearing force.

In addition, for details mixing, that disperse, be recorded in the T.C.Patton work " Paint Flowand Pigment Dispersion " (John Wiley and Sons society periodical in 1964) etc.

Pigment dispensing composition of the present invention is owing to being used for the preparation that color filter forms the Photocurable composition of usefulness, and is therefore preferably solvable in aqueous alkali.

＜Photocurable composition 〉

The Photocurable composition that forms colored pattern contains above-mentioned pigment dispensing composition, optical polymerism compound, Photoepolymerizationinitiater initiater and forms, and preferably further contains alkali soluble resin, as required, also can contain other composition.

This Photocurable composition is owing to contain above-mentioned specific pigment spreading agent, and therefore in composition, pigment keeps with good disperse state, can obtain good color characteristics, simultaneously, when constituting color filter, can suppress the pigment aggegation in the film, can obtain high-contrast.

Below, each contained in the Photocurable composition of the present invention composition is described in detail.

(pigment dispensing composition)

The Photocurable composition that colored pattern forms usefulness uses at least a of above-mentioned pigment dispensing composition to constitute.The details of the pigment dispensing composition of the present invention of formation Photocurable composition as previously mentioned.

As the content of the pigment dispensing composition in the Photocurable composition, with respect to the total solid composition (quality) of Photocurable composition, the content of pigment is preferably the amount of the scope of 5～70 quality %, more preferably the amount of the scope of 15～60 quality %.The content of pigment dispensing composition is in this scope the time, and color depth is abundant, for guaranteeing that color characteristics is effective.

(alkali soluble resin)

Photocurable composition of the present invention preferably contains at least a of alkali soluble resin.By in Photocurable composition, containing alkali soluble resin, this Photocurable composition is applicable to further improves pattern and form property when utilizing photolithographic pattern to form.

Alkali soluble resin is the wire organic high molecular polymer, can have in the alkali soluble resin of at least 1 group (for example carboxyl, phosphate, sulfonic group etc.) that promotes alkali-soluble suitably to select from molecule (being the molecule of main chain with acrylic acid series copolymer, styrene based copolymer preferably).Wherein, more preferably solvable in organic solvent, and the alkali soluble resin that can develop by weak alkaline aqueous solution.

For example can use the method for utilizing known radical polymerization in the manufacturing of alkali soluble resin.The kind of the temperature when utilizing free radical polymerization manufactured alkali soluble resin, pressure, radical initiator and each polymerizing condition such as amount, solvent types thereof can easily be set for those skilled in the art, also can determine condition experimentally.

As above-mentioned wire organic high molecular polymer, preferably on side chain, has the polymkeric substance of carboxylic acid.For example can enumerate the spy opens clear 59-44615 number; special public clear 54-34327 number; special public clear 58-12577 number; special public clear 54-25957 number; the spy opens clear 59-53836 number; the spy opens the methacrylic acid copolymer that clear 59-71048 number each communique is put down in writing; the acryllic acid multipolymer; itaconic acid copolymer; the crotonic acid multipolymer; maleic acid; partial esterification maleic acid etc.; and the acid cellulose derivant that on side chain, has carboxylic acid; the material that obtains having addition acid anhydrides on the polymkeric substance of hydroxyl etc., and then preferably enumerate on side chain high molecular polymer with (methyl) acryloyl group.

In these materials, especially preferably by (methyl) benzyl acrylate/(methyl) acrylic copolymer or multiple copolymer that (methyl) benzyl acrylate/(methyl) acrylic acid/other monomer forms.

In addition, also can enumerate material of 2-hydroxyethyl methacrylate being carried out copolymerization and obtaining etc. as useful compound.This polymkeric substance can use after amount is mixed arbitrarily.

Except that above-mentioned, can enumerate the big monomer/benzyl methacrylate of (methyl) acrylic acid 2-hydroxy propyl ester/polystyrene/methacrylic acid copolymer that the spy opens the record of flat 7-140654 communique, the acrylic acid 2-hydroxyl-big monomer/benzyl methacrylate of 3-phenoxy group propyl ester/polymethylmethacrylate/methacrylic acid copolymer, the big monomer/methyl methacrylate of 2-hydroxyethyl methacrylate/polystyrene/methacrylic acid copolymer, the big monomer/benzyl methacrylate of 2-hydroxyethyl methacrylate/polystyrene/methacrylic acid copolymer etc.

For the concrete formation unit of alkali soluble resin, preferred especially (methyl) acrylic acid and the multipolymer that can form with other monomer of its copolymerization.

As can with other monomer of above-mentioned (methyl) acrylic acid copolymer, can enumerate (methyl) alkyl acrylate, (methyl) acrylic acid aryl ester, vinyl compound etc.Here, the hydrogen atom of alkyl and aryl also can be substituted the base replacement.

As the concrete example of above-mentioned (methyl) alkyl acrylate and (methyl) acrylic acid aryl ester, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, benzyl acrylate, CA, acrylic acid naphthalene ester, cyclohexyl acrylate etc.

In addition, as above-mentioned vinyl compound, for example can enumerate styrene, α-Jia Jibenyixi, vinyltoluene, glycidyl methacrylate, vinyl cyanide, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, the big monomer of polystyrene, the big monomer of polymethylmethacrylate, CH ₂=CR ⁴R ⁵(R here, ⁴Expression hydrogen atom or carbon number are 1～5 alkyl, R ⁵The expression carbon number is 6～10 aromatic hydrocarbon ring), CH ₂=C (R ⁴) (COOR ⁶) (R here, ⁴Expression hydrogen atom or carbon number are 1～5 alkyl, R ⁶The expression carbon number is that 1～8 alkyl or carbon number are 6～12 aralkyl) etc.

These can copolymerization other monomer can use a kind or be used in combination more than 2 kinds separately.Other monomer that preferably can copolymerization is for being selected from CH ₂=CR ⁴R ⁵, CH ₂=C (R ⁴) (COOR ⁶), in (methyl) phenyl acrylate, (methyl) benzyl acrylate and the styrene at least a kind, preferred especially CH ₂=CR ⁴R ⁵And/or CH ₂=C (R ⁴) (COOR ⁶).These R ⁴, R ⁵And R ⁶Be respectively meaning same as described above.

The content of the alkali soluble resin in the Photocurable composition with respect to the total solid composition of said composition be preferably 1～20 quality %, more preferably 2～15 quality %, be preferably 3～12 quality % especially.

(optical polymerism compound)

Photocurable composition of the present invention contains at least a of optical polymerism compound.

The optical polymerism compound that can use in the present invention is the addition polymerization compound with at least 1 ethylenic unsaturated double-bond, can be from having at least one, selecting the compound of preferred terminal olefinic link formula unsaturated link more than 2.Such compound group is well-known in the art, can be not particularly limited to use them among the present invention.They for example have monomer, prepolymer, i.e. 2 polymers, 3 polymers and oligomer or their potpourri and their chemical forms such as multipolymer.Example as monomer and multipolymer thereof, can enumerate unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) or its ester class, amide-type, the amide-type that ester, unsaturated carboxylic acid and the aliphatic polyamine compound that preferably uses unsaturated carboxylic acid and aliphatic polyol compound to form forms.In addition, also preferred the use has addition reaction that the substituent esters of unsaturated carboxylic acids of nucleophilicities such as hydroxyl or amino, sulfydryl or amide-type and simple function or polyfunctional isocyanate's class or epoxies form and with the dehydration condensation thing of simple function or the formation of polyfunctional carboxylic acid etc.In addition, also preferably has the addition reaction that substituent esters of unsaturated carboxylic acids of electrophilicitys such as isocyanate group, epoxy radicals or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol form and have the substituent esters of unsaturated carboxylic acids of detachment such as halogen group, toloxyl or the substituted reactant of amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol formation.In addition, as other example, can also use the compound group that is substituted by unsaturated phosphonic acids, styrene, vinethene etc. to replace above-mentioned unsaturated carboxylic acid.

The example of the monomer of the ester that forms as aliphatic polyol compound and unsaturated carboxylic acid, as acrylate, glycol diacrylate is arranged, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, the tetramethyl omega-diol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloxy ethyl) isocyanuric acid ester, the polyester acrylic oligomer ester, isocyanuric acid oxirane (EO) modification triacrylate etc.

As methacrylate, tetramethyl glycol dimethylacrylate is arranged, the triethylene glycol dimethylacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, the D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylate, two (to (3-methacryloxy-2-hydroxyl propoxyl group) phenyl) dimethylmethane, two-(to (methacryloxy ethoxy) phenyl) dimethylmethane etc.

As itaconate, ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3 butylene glycol diitaconate, 1 are arranged, 4-butylene glycol diitaconate, tetramethyl glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc.As crotonates, ethylene glycol bisthioglycolate crotonates, tetramethyl glycol two crotonatess, pentaerythrite two crotonatess, D-sorbite four crotonatess etc. are arranged.As the iso-crotonic acid ester, ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, D-sorbite four iso-crotonic acid esters etc. are arranged.As maleate, ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc. are arranged.

As other the example of ester, the aliphatic alcohol that for example also can preferably use special public clear 51-47334, spy to open clear 57-196231 record be ester class, spy open that clear 59-5240, spy open that the compound with aromatic series pastern bone frame, spy that clear 59-5241, spy open flat 2-226149 record open flat 1-165613 record contain amino compound etc.In addition, above-mentioned ester monomer also can use with the form of potpourri.

In addition, the object lesson of the monomer of the acid amides that forms as aliphatic polyamine compound and unsaturated carboxylic acid, methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, 1 are arranged, 6-hexa-methylene bisacrylamide, 1, the two Methacrylamides of 6-hexa-methylene, Diethylenetriamine three acrylamides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.As the example that other preferred acid amides is a monomer, can enumerate the compound with cyclohexylidene structure of special public clear 54-21726 record.

In addition, the polyurethane series addition polymerization compound that also preferably utilizes the addition reaction of isocyanates and hydroxyl and make, as this concrete example, for example can enumerate making the polyisocyanate compounds that has the isocyanate group more than 2 in the vinyl monomer shown in the following general formula (A) and 1 molecule carry out addition and containing the vinyl urethane compound etc. of the polymerism vinyl more than 2 in 1 molecule obtaining of putting down in writing in the special public clear 48-41708 communique with hydroxyl.

CH ₂＝C(R ³⁴)COOCH ₂CH(R ³⁵)OH (A)

(wherein, R ³⁴And R ³⁵Expression H or CH ₃)

In addition, also preferred spy opens the urethane acrylate class of record in clear 51-37193 number, special fair 2-32293 number, special fair 2-16765 number, special public clear 58-49860 number, special public clear 56-17654 number, special public clear 62-39417 number, the urethanes class with oxirane pastern bone frame of special public clear 62-39418 number record.In addition, open clear 63-260909 number, spy and open the addition polymerization compounds that has amino structure or sulfide structure in the molecule of record in flat 1-105238 number by using the spy to open clear 63-277653 number, spy, can obtain the excellent especially optical polymerism composition of film speed.

As other example, can enumerate that the spy opens that polyester acrylate class, the epoxy resin put down in writing in clear 48-64183 number, special public clear 49-43191 number, special public clear 52-30490 number each communique react with (methyl) acrylic acid and polyfunctional acrylate or the methacrylates such as epoxy acrylate class that obtain.In addition, specific unsaturated compound, the spy that can also enumerate special public clear 46-43946 number, special fair 1-40337 number, special fair 1-40336 number record opens the vinyl phosphonate based compound of flat 2-25493 number record etc.Under certain conditions, the preferred structure that contains perfluoroalkyl of using the spy to open clear 61-22048 number record.And the material that can use Japan then to introduce as photo-curable monomer and oligomer in the will Vol.20 of association, No.7,300～308 pages (1984).

For these addition polymerization compounds, its structure, separately use or and the details of using method such as usefulness, addition can set arbitrarily according to the performance design of final Photocurable composition.For example can go out to send and select from following viewpoint.

From the sensitivity aspect, the more structure of unsaturated group mass contg of preferred per 1 molecule is preferably more than 2 official's energy under for most situations.In addition, in order to improve the curing film strength, it can be the above structure of 3 officials energy, and, by with the compound of different functional number, different polymerizable group (for example acrylate, methacrylate, polystyrene compound, vinyl ether based compound) and be used for regulating sensitivity and intensity the two also be effective.

In addition, for with Photocurable composition in the compatibility, dispersed of other composition binder polymer, Photoepolymerizationinitiater initiater, colorants (pigment) such as (for example) alkali soluble resins, the selection of addition polymerization compound and using method also are important factors, for example, can improve compatibility sometimes by the use of low-purity compound or the also usefulness more than 2 kinds.

In addition, also can be and select specific structure in order to improve with the adhesiveness of substrate etc.The consumption of addition polymerization compound is preferably 5～70 quality %, the scope of 10～60 quality % more preferably with respect to the involatile composition in the Photocurable composition.In addition, they may be used alone, two or more kinds can also be used.In addition, viewpoints such as the size that the using method of addition polymerization compound can hinder from the polymerization to oxygen, exploring degree, photographic fog, variations in refractive index, surface tackiness are at random selected suitable structure, proportioning, addition.

(Photoepolymerizationinitiater initiater)

Photocurable composition of the present invention contains at least a of Photoepolymerizationinitiater initiater.

As Photoepolymerizationinitiater initiater, for example can enumerate the spy and open Lu that flat 57-6096 communique put down in writing for the Jia oxadiazole, special public clear 59-1281 communique, the spy opens halogenated methyl-s-triazine isoreactivity halogenide that clear 53-133428 communique etc. is put down in writing, U.S. Pat P-4318791, the ketal that each instructions of Europe patent disclosure EP-88050A etc. is put down in writing, aromatic carbonyls such as acetal or benzoin alkylether class, the aromatic ketone compounds such as benzophenone that U.S. Pat P-4199420 instructions is put down in writing, (thia) xanthene ketone or acridine compound that the Fr-2456741 instructions is put down in writing, compounds such as Coumarins that Te Kaiping 10-62986 communique is put down in writing or di-imidazoles, the organic boron complex of sulfonium of Te Kaiping 8-015521 communique etc. etc.

Wherein, as Photoepolymerizationinitiater initiater, preferred acetophenone system, ketal system, benzophenone series, benzoin system, benzoyl system, xanthone system, active halogenide (triazine system, halogen are for first oxadiazole system, coumarin series), acridine system, di-imidazoles system, oxime ester system etc.

As above-mentioned acetophenone is Photoepolymerizationinitiater initiater, for example can preferably enumerate 2,2-diethoxy acetophenone, to dimethylamino benzoylformaldoxime, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, to dimethylamino benzoylformaldoxime, 4 '-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-tolyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1 etc.

Above-mentioned ketal is that Photoepolymerizationinitiater initiater for example can preferably be enumerated benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetals etc.

As above-mentioned benzophenone series Photoepolymerizationinitiater initiater, for example can preferably enumerate benzophenone, 4,4 '-(two dimethylamino) benzophenone, 4,4 '-(two diethylamino) benzophenone, 4,4 '-dichloro benzophenone etc.

Above-mentioned benzoin system or benzoyl are that Photoepolymerizationinitiater initiater for example can preferably be enumerated benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoic acid ester etc.

Above-mentioned xanthone is that Photoepolymerizationinitiater initiater for example can preferably be enumerated diethyl thioxanthone, diisopropyl thioxanthones, single isopropyl thioxanthone, clopenthixal ketone etc.

(triazine is oxadiazole system as the reactive halogen Photoepolymerizationinitiater initiater, coumarin series) Photoepolymerizationinitiater initiater, for example can preferably enumerate 2, two (the trichloromethyl)-6-p-methoxyphenyls of 4--s-triazine, 2, two (the trichloromethyl)-6-of 4-are to methoxyl-styrene-s-triazine, 2, two (the trichloromethyl)-6-(1-is to dimethylaminophenyl)-1 of 4-, 3-butadienyl-s-triazine, 2, two (the trichloromethyl)-6-xenyls of 4--s-triazine, 2, two (the trichloromethyl)-6-(to methyl biphenyl) of 4--s-triazine, to hydroxyl-oxethyl styryl-2,6-two (trichloromethyl)-s-triazine, methoxyl-styrene-2,6-two (trichloromethyl)-s-triazine, 3,4-dimethoxy-styryl-2,6-two (trichloromethyl)-s-triazine, 4-benzo tetrahydrofuran-2,6-two (trichloromethyl)-s-triazine, 4-(adjacent bromo-is right-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (chloromethyl)-s-triazine, 4-is (right-N, N-(di ethoxy carbonyl amino)-phenyl)-2,6-two (chloromethyl)-s-triazine, 2-trichloromethyl-5-styryl-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(cyano styrene base)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(naphtho--1-yl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3, the 4-oxadiazole, 3-methyl-5-amino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-chloro-5-diethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-butyl-5-dimethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin etc.

Above-mentioned acridine is that Photoepolymerizationinitiater initiater for example can preferably be enumerated 9-phenylacridine, 1, two (9-acridinyl) heptane of 7-etc.

Above-mentioned di-imidazoles is that Photoepolymerizationinitiater initiater for example can preferably be enumerated 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole base dipolymer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole base dipolymer, 2-(2, the 4-Dimethoxyphenyl)-4,5-diphenyl-imidazole base dipolymer etc.

Except that above-mentioned; can also enumerate 1-phenyl-1; 2-propanedione-2-(adjacent ethoxy carbonyl) oxime, o-benzoyl-4 '-(benzo sulfydryl) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl carbonyl-diphenylphosphine acyl group oxide, hexafluoro phosphorus-trialkyl Ben Ji phosphonium salt etc.

Operable Photoepolymerizationinitiater initiater is not to be defined in above Photoepolymerizationinitiater initiater among the present invention, can also use other known Photoepolymerizationinitiater initiater.For example can enumerate the vicinal polyketoaldonyl compound that No. 2367660 instructions of United States Patent (USP) put down in writing, the alpha-carbonyl compound that No. the 2367661st, United States Patent (USP) and No. 2367670 instructions are put down in writing, the acyloin ether that No. 2448828 instructions of United States Patent (USP) put down in writing, the aromatic series acyloin compound that is replaced by α-hydrocarbon that No. 2722512 instructions of United States Patent (USP) put down in writing, the multinuclear naphtoquinone compounds that No. the 3046127th, United States Patent (USP) and No. 2951758 instructions are put down in writing, the combination of United States Patent (USP) triallyl imidazole dimer/p-aminophenyl ketone that No. 3549367 instructions is put down in writing, benzothiazole based compound/trihalomethyl group-s-triazine based compound that special public clear 51-48516 communique is put down in writing etc.

In addition, can also and use these Photoepolymerizationinitiater initiaters.

The content of Photoepolymerizationinitiater initiater in Photocurable composition is preferably 0.1～15.0 quality %, 0.5～10.0 quality % more preferably with respect to the total solid composition of said composition.The content of Photoepolymerizationinitiater initiater can carry out polyreaction in above-mentioned scope the time well, can form the good film of intensity.

From the purpose of the long wavelengthization of the raising of the free-radical generating efficient of Photoepolymerizationinitiater initiater (radical initiator), wavelength photoreceptor, Photocurable composition of the present invention can also contain sensitizer.

The sensitizer that can use in the present invention preferably makes the sensitizer of its sensitizing with electron transport mechanism or energy transfer mechanism for radical initiator.

As the sensitizer that can use in the present invention, can enumerate the sensitizer that belongs to the following compounds of enumerating and have absorbing wavelength in the wavelength region may of 300nm～450nm.

As the example of preferred sensitizer, can enumerate the compounds that belongs to following and have the sensitizer of absorbing wavelength in 330nm～450nm zone.

It is (for example luxuriant and rich with fragrance for example can to enumerate the polynuclear aromatic same clan, anthracene, pyrene perylene, benzophenanthrene, 9,10-dialkoxy anthracene), xanthene class (fluorescein for example, eosin, erythrosine, rhodamine B, rose-red), thioxanthene ketone (isopropyl thioxanthone, diethyl thioxanthone, clopenthixal ketone), cyanines class (thiophene carbon cyanines (Thiacarbocyanine) for example, oxygen carbon cyanines (oxacarbocyanine)), part cyanines class (part cyanines for example, carbon part cyanines), phthalocyanines, thiazide (thionine for example, methylene blue, toluidine blue), acridine (acridine orange for example, the chloro flavine, acridine yellow), anthraquinone class (for example anthraquinone), side's sour cyanines (squarylium) class (for example sour cyanines in side), acridine orange, Coumarins (for example 7-diethylamino-4-methylcoumarin), coumarin ketone, phenothiazines, the azophenlyene class, styryl benzene class, azo-compound, diphenyl methane, triphenyl methane, the diphenylethyllene benzene class, carbazoles, porphyrin, spiro-compound, quinacridone, indigo, styrene, pyrylium compound, pyrroles's methine compound, the Pyrazolotriazole compound, benzothiazole compound, barbituric acid derivatives, the thiobarbituricacid derivant, acetophenone, benzophenone, thioxanthones, aromatic ketone compounds such as michler's ketone, heterogeneous ring compounds such as N-Fang oxazolidinone etc.

Photocurable composition of the present invention also preferably contains common sensitizer.Common sensitizer in the Photocurable composition of the present invention has further raising sensitizing coloring matter or initiating agent to the sensitivity of active radioactive ray or suppress the effects such as polymerization obstruction of the polymerizable compound that oxygen causes.

Example as so common sensitizer; can enumerate amine; 3173 pages (1972) of people such as M.R.Sander work " Journal of Polymer Society " the 10th volume for example; special public clear 44-20189 communique; the spy opens clear 51-82102 communique; the spy opens clear 52-134692 communique; the spy opens clear 59-138205 communique; the spy opens clear 60-84305 communique; the spy opens clear 62-18537 communique; the spy opens clear 64-33104 communique; the compounds of No. 33825 records of Research Disclosure etc. can be enumerated triethanolamine particularly; the ESCAROL 507 ethyl ester; to the formoxyl xylidin; to methyl mercapto xylidin etc.

As other example that is total to sensitizer, can enumerate mercaptan and sulfide-based, for example can enumerate the spy and open clear 53-702 communique, special public clear 55-500806 communique, spy and open di-sulphide compounds that mercaptan compound, the spy of flat 5-142772 communique record open clear 56-75643 communique etc., can enumerate 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene etc. particularly.

In addition, as other example, hydrogen donor, the spy that can enumerate the organometallics (for example tributyl tin acetate etc.) of amino-acid compound (for example N-phenylglycine etc.), special public clear 48-42965 communique record, special public clear 55-34414 communique record opens the sulphur compound of flat 6-308727 communique record (for example trithiane etc.) etc.

The viewpoint of the raising of the curing rate that brings from the balance of polymerization growth rate and chain transfer, the content of these common sensitizers is the scope of 0.1～30 quality % with respect to the quality optimization of the total solid composition of Photocurable composition, the more preferably scope of 1～25 quality %, the more preferably scope of 0.5～20 quality %.

Below, the composition beyond above-mentioned is described.

(solvent)

Photocurable composition of the present invention generally can use solvent preferably to prepare with mentioned component.

As solvent, can enumerate the ester class, for example ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate; Alkyl esters, 3-oxo-alkyl propionates classes (for example 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate) such as methyl lactate, ethyl lactate, glycolic methyl esters, glycolic ethyl ester, glycolic butyl ester, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-oxo-methyl propionate, 3-oxo-ethyl propionate; 2-oxo-methyl propionate, 2-oxo-ethyl propionate, 2-oxo-alkyl propionates classes such as 2-oxo-propyl propionate (2-methoxypropionic acid methyl esters for example, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-oxo-2 Methylpropionic acid methyl esters, 2-oxo-2 Methylpropionic acid ethyl ester, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester), methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxo-methyl butyrate, 2-oxo-ethyl butyrate etc.;

Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, methyl glycol acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethylether acetate, propylene glycol propyl ether acetate etc.;

Ketone, for example MEK, cyclohexanone, 2-heptanone, 3-heptanone etc.;

Aromatic hydrocarbon based, for example toluene, dimethylbenzene etc.

Preferred 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate etc. in these.

Solvent can also be used in combination more than 2 kinds except can using separately.

(other composition)

Can contain various additives such as macromolecular compound beyond fluorinated organic compound, thermal polymerization inhibitor, filling agent, specific pigment spreading agent and the above-mentioned alkali soluble resin, surfactant, adhesion promoter, antioxidant, ultraviolet light absorber, anti-agglutinant in the Photocurable resin composition of the present invention as required.

＜fluorinated organic compound 〉

By containing fluorinated organic compound, can improve the solution properties (particularly mobile) when making coating liquid, can improve the homogeneity and the solution saving property of coating thickness.That is, can reduce the interfacial tension of substrate and coating liquid, thereby improve wellability substrate, raising is to the coating of substrate, even when forming film about several μ m with a spot of liquid measure thus, also can form the film of the little uniform thickness of uneven thickness, be effective from this respect.

The fluorine-containing rate of fluorinated organic compound be preferably 3～40 quality %, more preferably 5～30 quality %, be preferably 7～25 quality % especially.Fluorine-containing rate is in this scope the time, and the viewpoint of saving property from coating thickness homogeneity and solution is that effectively the dissolubility in composition is also good.

As fluorinated organic compound, for example can enumerate Megaface F171, Megaface F172, Megaface F173, Megaface F177, Megaface F141, Megaface F142, Megaface F143, Megaface F144, Megaface R30, Megaface F437 (above DIC Corporation system), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3M (strain) system), Surfron S-382, Surfron SC-101, Surfron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC1068, Surfron SC-381, Surfron SC-383, Surfron S393, Surfron KH-40 (above Asahi Glass (strain) system) etc.

Coating inequality or uneven thickness when fluorinated organic compound applies the coat film attenuation that forms to preventing from for example to make are effective especially.In addition, also be effective in causing the slot coated that solution is used up easily.

The addition of fluorinated organic compound is preferably 0.001～2.0 quality %, 0.005～1.0 quality % more preferably with respect to the gross mass of pigment dispensing composition or Photocurable composition.

＜thermal polymerization 〉

It also is effective that Photocurable composition of the present invention contains thermal polymerization.Thermal polymerization for example can be enumerated various azo based compounds, superoxide based compound; above-mentioned azo based compound can be enumerated azo two (azobis) based compound, and above-mentioned superoxide based compound can be enumerated ketone peroxide, ketal peroxide, hydroperoxides, dialkyl peroxide, diacyl peroxide, peroxyester, peroxy dicarbonate etc.

＜surfactant 〉

From improving the viewpoint of coating, the various surfactants of preferred use constitute in the Photocurable composition of the present invention, can use the various surfactants of nonionic system, kation system, negative ion system.Be preferably wherein that to belong to nonionic be surfactant and the fluorochemical surfactant with perfluoroalkyl.

As the object lesson of fluorochemical surfactant, can enumerate Megaface (registered trademark) series of DIC Corporation system, Fluorad (registered trademark) series of 3M corporate system etc.

Except that above-mentioned,, can enumerate filling agents such as glass, aluminium oxide as the object lesson of the additive in the Photocurable composition; Itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid, acid cellulose derivant, polymkeric substance and acid anhydrides addition and the material that obtains, pure soluble nylon with hydroxyl, by bisphenol-A and epichlorokydrin form alkali soluble resins such as phenoxy resin; Surfactants such as nonionic system, kation system, negative ion system, be in particular phthalocyanine derivates (commercially available product EFKA-745 (down gloomy industry corporate system)); Organic siloxane polymer KP-341 (chemical industrial company of SHIN-ETSU HANTOTAI system), (methyl) acrylic acid series (being total to) polymer P olyflow No.75, No.90, No.95 (oil chemistry industrial group of common prosperity society system), W001 kations such as (abundant merchant's corporate systems) are surfactant;

As the example of other additive etc., can enumerate polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, (Pluronic L10, the L31 of BASF AG's system, L61, L62,10R5,17R2,25R2, nonionics such as Tetronic 304,701,704,901,904,150R1 are surfactant to sorbitan fatty acid ester; W004, W005, W017 negative ion such as (abundant merchant's corporate systems) are surfactant; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKApolymer 401, EFKA polymer 450 (above gloomy industry corporate system down), Disperse aid6, Disperse aid 8, Disperse aid 15, Disperse aid 9100 macromolecule dispersing agents such as (San Nopco Limited systems); Various Solsperse spreading agents (Zeneca corporate system) such as Solsperse 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000; Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification corporate system) and Isonet S-20 (Sanyo changes into corporate system); Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorinated benzotriazole, alkoxy benzophenone; And anti-agglutinant such as sodium polyacrylate.

In addition, the alkali dissolution of seeking to promote uncured portion, and when further improving the development of Photocurable composition, can in Photocurable composition, add organic carboxyl acid, preferred molecular weight is the low-molecular-weight organic carboxyl acid below 1000.For example can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, acid, diethyl acetate, enanthic acid, aliphatics monocarboxylic acid such as sad particularly; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, malonic acid methyl esters, malonic ester, dimethyl malenate, methyl succinate, succinic acid tetramethyl ester, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid; Aromatic series monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, adjacent mesitylenic acid, a mesitylenic acid; Aromatic multi-carboxy acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, mellophanic acid, Pyromellitic Acid; Other carboxylic acids such as phenylacetate, hydratropic acid, hydrocinnamic acid, mandelic acid, succinic acid phenyl ester, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, Chinese cassia tree fork acetate, coumaric acid, umbellic acid.

＜thermal polymerization inhibitor 〉

Preferably further be added with thermal polymerization inhibitor in the Photocurable composition of the present invention, for example quinhydrones, p methoxy phenol, di-t-butyl-paracresol, 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 etc. are useful.

Photocurable composition of the present invention can by in above-mentioned pigment dispensing composition, contain alkali soluble resin, optical polymerism compound and Photoepolymerizationinitiater initiater (preferably with solvent), and as required therein adjuvant such as mixed surfactant be prepared.

＜color filter and manufacture method thereof 〉

The following making of color filter of the present invention: use above-mentioned Photocurable composition of the present invention, on substrates such as glass, form, thereby make through painted film (colored pattern).

Specifically, with above-mentioned Photocurable composition directly or be situated between and give (preferably applying) on substrate by painting methods such as rotation coating, slot coated, curtain coating coating, roller coat by other layer, form photosensitive film, Jie is exposed to formed photosensitive film by the mask pattern of regulation, after exposure, utilize developer solution that uncured development removed, thereby form the colored pattern (for example colored pixels) of (for example 3 looks or 4 looks) of all kinds, thereby can make most preferred color filter.

Thus, can be on technology the little ground of difficulty, high-quality and make the color filter that uses in liquid crystal indicator or the solid-state imager at low cost.

At this moment, as the employed radioactive ray of exposure, be preferably ultraviolet rays such as g line, h line, i line, j line especially.

Give the drying (prebake) of (being preferably coating) formed film of Photocurable composition of the present invention on substrate and can use heating plate, baking oven etc., under 50～140 ℃ temperature ranges, 10～300 seconds condition, carry out.

In the development, make uncured stripping after the exposure to developer solution, only stay cured portion.Development temperature is generally 20～30 ℃, development time and was generally for 20～90 seconds.

Developer solution so long as dissolve the film of Photocurable composition of uncured portion but the developer solution that do not dissolve solidified portion just, can use any developer solution.Specifically, can use the combination or the alkaline aqueous solution of various organic solvents.

Above-mentioned organic solvent can be enumerated the above-mentioned organic solvent that can use during above-mentioned Photocurable composition as preparation or solvent and those solvents of listing.

As above-mentioned alkaline aqueous solution, for example can enumerate NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicylo [5,4,0]-mode that alkali compounds such as 7-undecylene reach 0.001～10 quality %, preferred 0.01～1 quality % according to concentration dissolves and the alkaline aqueous solution that obtains.

In addition, when using alkaline aqueous solution as developer solution, generally water washs (rinsing) after development.

After the development, after washing is removed unnecessary developer solution and implemented drying, generally under 100～240 ℃ temperature, implement heat treated (afterwards curing).

Curing after above-mentioned is the heating of carrying out after development in order to make completion of cure, carries out about 200 ℃～250 ℃ heating (hard roasting (hard bake)) usually.Curing processing after this can followingly carry out: the coat film after will developing uses heating plate or heating arrangements such as convection oven (heated air circulation type dryer), high frequency heating machine according to above-mentioned condition, carries out with continous way or batch (-type).

By each color being repeated above operation successively, can make the color filter that is formed with through the cured film of multi-color coloring according to required tone number.

Photocurable composition of the present invention is given on substrate when forming film, and the dry thickness of film is generally 0.3～5.0 μ m, is preferably 0.5～3.5 μ m, most preferably is 1.0～2.5 μ m.

The colored pattern that forms on this substrate is owing to the pigment of fine particle size evenly and stably disperses, so the occupation rate of 2 particles in the resulting image of the result who utilizes AFM to observe on overlay film surface can reach below 40%.

As the substrate that uses in the color filter, for example can enumerate alkali-free glass, soda-lime glass, PYREX (registered trademark) glass, the quartz glass that uses in the liquid crystal indicator etc. and on them, be attached with the photo-electric conversion element substrate that uses in the substrate, solid-state imager etc. of nesa coating for example silicon substrate etc. and plastic base.Usually be formed with the blackstreak (black stripe) of isolating each pixel on these substrates.

Preferably have gas-barrier layer and/or solvent resistance layer on the surface of plastic base.

When Jie gives Photocurable composition by other layer on substrate,, can enumerate gas-barrier layer, solvent resistance layer etc. as other layer.

Main colored pattern purposes with color filter is that the center is illustrated in above-mentioned, but also means of the present invention similarly can be applicable to the formation of the black matrix" of isolating each colored pixels that constitutes color filter.

Black matrix" can followingly form: will use the Photocurable composition of the present invention (pigment dispensing composition) of black pigments such as carbon black, titanium be black to expose, develop as pigment, cure after further carrying out as required afterwards, promote the curing of film, thereby form.

[embodiment]

Be described more specifically the present invention by the following examples, but only otherwise exceed purport of the present invention, be not limited to following embodiment.In addition, if not otherwise specified, " part " expression " mass parts ".

[synthesis example 1]

(synthesizing of monomer 1)

9.51 parts of 2-aminopyrimidines are dissolved in 30 parts of the pyridines, and are heated to 45 ℃.Drip 17.1 parts of 2-methacryloxyethyl isocyanates therein, and under 50 ℃ heated and stirred 5 hours again.This reactant liquor is injected 200 parts of distilled water and stirring simultaneously, filter out the precipitate and the washing of gained, thereby obtain 23.8 parts of monomers 1.

(synthesizing of polymkeric substance 1)

With 5.0 parts of above-mentioned monomers 1, (AA-6: East Asia Synesis Company system) 37.5 parts, 7.5 parts of methacrylic acids and MPEG 167 mass parts are directed in the there-necked flask of nitrogen displacement to have the polymethylmethacrylate of methacryl endways; with stirring machine (new eastern science (strain) system: Three one motor) stir; on one side nitrogen is flowed in the flask, on one side heat temperature raising to 78 ℃.Add dimethyl-2 therein, and 2 '-azo two (2 Methylpropionic acid esters) (make with the pure medicine of light (strain): V-601) 0.1 part, 78 ℃ of following heated and stirred 2 hours.After 2 hours, add 0.1 part of V-601 again, and heated and stirred 3 hours, obtain 30% solution of polymkeric substance 1 (above-mentioned exemplary compounds (2)).

[synthesis example 2]

Except 9.51 parts of 2-aminopyrimidines used in monomer 1 in the synthesis example 1 synthetic being become 13.3 parts of amino benzimidazoles of 2-,, obtain 30% solution of polymkeric substance 2 (above-mentioned exemplary compounds (6)) by the method identical with synthesis example 1.

[synthesis example 3]

(synthesizing of monomer 3)

13.8 parts in 13.3 parts of 2-mercaptobenzimidazoles and sal tartari is dissolved in 30 parts of the dimethyl sulfoxide (DMSO)s, and is heated to 45 ℃.Drip 22.9 parts of 1-chloro-4-methyl-benzenes therein, and under 50 ℃ heated and stirred 5 hours again.This reactant liquor is injected 200 parts of distilled water and stirring simultaneously, filter out the precipitate and the washing of gained, thereby obtain 25.6 parts of monomers 3.

(synthesizing of polymkeric substance 3)

Except the monomer in the synthesis example 11 being become monomer 3,, obtain 30% solution of polymkeric substance 3 (above-mentioned exemplary compounds (14)) by the method identical with synthesis example 1.

[embodiment 1]

The preparation of＜pigment dispensing composition 〉

(forming (1))

10 parts of the red pigments (C.I. paratonere 254) that 1 particle diameter is 28nm

26.6 parts of 30% solution of polymkeric substance 1 (specific pigment spreading agent)

63.4 parts of propylene glycol methyl ether acetates

In forming (1), add 0.3mm zirconia bead, disperseed 4 hours, obtain dispersible pigment dispersion (painted paste) (1) with ball mill (beads mill).(day machine dress (strain) system: Microtrac) measure, the result is 50nm with the size-grade distribution meter with the mean grain size of the pigment of gained dispersible pigment dispersion.

In addition, the mean grain size of 1 of red pigment particle is by electron microscope ((strain) Hitachi High-Technologies Corporation system: S-4800) measure.

The preparation of＜Photocurable composition 〉

Mix following composition, the preparation color filter is made the Photocurable composition (1) of usefulness.

(1) 48.0 part of dispersible pigment dispersion

3.3 parts of methacrylic acids/benzyl methacrylate multipolymer

(mol ratio 30/70, weight-average molecular weight 10000,45% propylene glycol methyl ether acetate solution)

Dipentaerythritol acrylate 2.9g

Irgacure 369 (Ciba Specialty Chemicals system) 0.2g

Hydroquinone monomethyl ether 0.01g

Propylene glycol methyl ether acetate 45g

The making of＜colored pattern 〉

To be coated on the glass substrate of 0.7mm, by the Photocurable composition (1) that said method obtains at 100mJ/cm ²(illumination is 20mW/cm ²) condition under it is solidified, forming thickness is the red light solidification compound layer (colored pattern) of 2.0 μ m.

The occupation rate of＜2 particles is measured 〉

(Veeco Instruments make NanoScopeIIIa, TappingMode) observes, and obtains surperficial observation image with AFM with the film surface of the colored pattern that forms.

Then, use image processing program " Image J " to carry out Flame Image Process in the following order, obtain the occupation rate of 2 particles in the image the gained image.

2. cut apart contacted particle by the Watershed method.

3. select the above particle of 50nm, calculate occupation rate.

Calculate the occupation rate of 2 particles of the dispersion liquid that embodiment 1 obtains by said method, the result is 22%.

[embodiment 2]

The preparation of＜pigment dispensing composition 〉

(forming (2))

14.0 parts of the viridine greens (C.I. pigment green 36) that 1 particle diameter is 20nm

37.3 parts of 30% solution of polymkeric substance 1 (specific pigment spreading agent)

48.7 parts of propylene glycol methyl ether acetates

In forming (2), add 0.3mm zirconia bead, disperseed 5 hours, obtain dispersible pigment dispersion (painted paste) (2) with ball mill.The mean grain size of the pigment of gained dispersible pigment dispersion is measured with the size-grade distribution meter, and the result is 55nm.

The preparation of＜Photocurable composition 〉

Mix following composition, the preparation color filter is made the Photocurable composition (2) of usefulness.

(2) 48.0 parts of dispersible pigment dispersions

4.0 parts of methacrylic acids/benzyl methacrylate multipolymer

Dipentaerythritol acrylate 3.5g

Irgacure 369 (Ciba Specialty Chemicals system) 0.2g

Hydroquinone monomethyl ether 0.01g

Propylene glycol methyl ether acetate 44g

The making of＜colored pattern 〉

Except becoming Photocurable composition (2), operation similarly to Example 1 obtains colored pattern.

The occupation rate of＜2 particles is measured 〉

Utilize the occupation rate of 2 particles of method calculating similarly to Example 1, the result is 28%.

[embodiment 3]

The preparation of＜pigment dispensing composition 〉

(forming (3))

Blue pigment (the C.I. pigment blue 15: 6) 10.0 parts that 1 particle diameter is 25nm

23.3 parts of 30% solution of polymkeric substance 1 (specific pigment spreading agent)

66.6 parts of propylene glycol methyl ether acetates

In forming (3), add 0.3mm zirconia bead, disperseed 6 hours, obtain dispersible pigment dispersion (painted paste) (3) with ball mill.The mean grain size of the pigment of gained dispersible pigment dispersion is measured with the size-grade distribution meter, and the result is 46nm.

The preparation of＜Photocurable composition 〉

Except dispersible pigment dispersion (1) being become dispersible pigment dispersion (3), all other is operated similarly to Example 1, preparation Photocurable composition (3).

The making of＜colored pattern 〉

Except Photocurable composition (1) being become Photocurable composition (3), operation obtains colored pattern similarly to Example 1.

The occupation rate of＜2 particles is measured 〉

Utilize the occupation rate of 2 particles of method calculating similarly to Example 1, the result is 38%.

[embodiment 4]

Except polymkeric substance 1 being become polymkeric substance 2, all other is operated similarly to Example 1, obtains dispersible pigment dispersion (4), Photocurable composition (4) and colored pattern.

[embodiment 5]

Except polymkeric substance 1 being become polymkeric substance 2, all other is operated similarly to Example 2, obtains dispersible pigment dispersion (5), Photocurable composition (5) and colored pattern.

[embodiment 6]

Except polymkeric substance 1 being become polymkeric substance 2, all other is operated similarly to Example 3, obtains dispersible pigment dispersion (6), Photocurable composition (6) and colored pattern.

[embodiment 7]

Except polymkeric substance 1 being become polymkeric substance 3, all other is operated similarly to Example 1, obtains dispersible pigment dispersion (7), Photocurable composition (7) and colored pattern.

[embodiment 8]

Except polymkeric substance 1 being become polymkeric substance 3, all other is operated similarly to Example 2, obtains dispersible pigment dispersion (8), Photocurable composition (8) and colored pattern.

[embodiment 9]

Except polymkeric substance 1 being become polymkeric substance 3, all other is operated similarly to Example 3, obtains dispersible pigment dispersion (9), Photocurable composition (9) and colored pattern.

[comparative example 1]

The preparation of＜pigment dispensing composition 〉

(forming (10))

10.0 parts of the red pigments (C.I. paratonere 254) that 1 particle diameter is 28nm

Spreading agent

6.0 parts of (BYK-Chemie GmbH makes BYK-161) (relatively pigment dispersing agents)

84.0 parts of propylene glycol methyl ether acetates

In forming (10), add 0.3mm zirconia bead, disperseed 2 hours, obtain dispersible pigment dispersion (painted paste) (10) with ball mill.The mean grain size of the pigment of gained dispersible pigment dispersion is measured with the size-grade distribution meter, and the result is 90nm.

The preparation of＜Photocurable composition 〉

Except becoming dispersible pigment dispersion (10), all other is operated similarly to Example 1, preparation Photocurable composition (10).

The making of＜colored pattern 〉

Except becoming Photocurable composition (10), operation similarly to Example 1 obtains colored pattern.

The occupation rate of＜2 particles is measured 〉

Utilize the occupation rate of 2 particles of method calculating similarly to Example 1, the result is 49%.

[comparative example 2]

The preparation of＜pigment dispensing composition 〉

(forming (11))

Spreading agent

8.4 parts of (BYK-Chemie GmbH makes BYK-161) (relatively pigment dispersing agents)

77.6 parts of propylene glycol methyl ether acetates

In forming (11), add 0.3mm zirconia bead, disperseed 2 hours, obtain dispersible pigment dispersion (painted paste) (11) with ball mill.The mean grain size of the pigment of gained dispersible pigment dispersion is measured with the size-grade distribution meter, and the result is 81nm.

The preparation of＜Photocurable composition 〉

Except becoming dispersible pigment dispersion (11), all other is operated similarly to Example 1, preparation Photocurable composition (11).

The making of＜colored pattern 〉

Except becoming Photocurable composition (11), operation similarly to Example 1 obtains colored pattern.

The occupation rate of＜2 particles is measured 〉

Utilize the occupation rate of 2 particles of method calculating similarly to Example 1, the result is 55%.

[comparative example 3]

The preparation of＜pigment dispensing composition 〉

(forming (12))

Spreading agent

84.0 parts of propylene glycol methyl ether acetates

In forming (12), add 0.3mm zirconia bead, disperseed 2 hours, obtain dispersible pigment dispersion (painted paste) (12) with ball mill.The mean grain size of the pigment of gained dispersible pigment dispersion is measured with the size-grade distribution meter, and the result is 97nm.

The preparation of＜Photocurable composition 〉

Except becoming dispersible pigment dispersion (12), all other is operated similarly to Example 1, preparation Photocurable composition (12).

The making of＜colored pattern 〉

Except becoming Photocurable composition (12), operation similarly to Example 1 obtains colored pattern.

The occupation rate of＜2 particles is measured 〉

Utilize the occupation rate of 2 particles of method calculating similarly to Example 1, the result is 60%.

The mensuration of＜contrast 〉

Contrast is that the color filter that will make in the foregoing description and the comparative example is arranged between 2 polaroids, in a side light source is set, and at its opposition side nitometer (TOPCON corporate system BM-5A) is set, and carries out the mensuration of brightness (transmitted intensity).The ratio of the brightness of the brightness by polarization axle when parallel when vertical is calculated contrast.The results are shown in following table 1.

Table 1

	Use resin	Mean grain size (nm)	Offspring occupation rate (%)	Contrast
	Use resin	Mean grain size (nm)	Offspring occupation rate (%)	Contrast	Embodiment 1	Polymkeric substance 1	50	22	10700
Embodiment 2	Polymkeric substance 1	55	28	15600	Embodiment 1	Polymkeric substance 1	50	22	10700
Embodiment 2	Polymkeric substance 1	55	28	15600	Embodiment 3	Polymkeric substance 1	46	38	12000
Embodiment 4	Polymkeric substance 2	60	25	10300	Embodiment 3	Polymkeric substance 1	46	38	12000
Embodiment 4	Polymkeric substance 2	60	25	10300	Embodiment 5	Polymkeric substance 2	58	30	14800
Embodiment 6	Polymkeric substance 2	52	41	11000	Embodiment 5	Polymkeric substance 2	58	30	14800
Embodiment 6	Polymkeric substance 2	52	41	11000	Embodiment 7	Polymkeric substance 3	62	27	9800
Embodiment 8	Polymkeric substance 3	63	33	14000	Embodiment 7	Polymkeric substance 3	62	27	9800
Embodiment 8	Polymkeric substance 3	63	33	14000	Embodiment 9	Polymkeric substance 3	54	43	10400
Comparative example 1	BYK-161	90	49	8000	Embodiment 9	Polymkeric substance 3	54	43	10400
Comparative example 1	BYK-161	90	49	8000	Comparative example 2	BYK-161	81	55	10200
Comparative example 3	BYK-161	97	60	6500	Comparative example 2	BYK-161	81	55	10200

As shown in Table 1, according to color filter colored pattern of the present invention, can realize high-contrast.

＜used the preparation of the color filter of Photocurable composition 〉

Go up at the glass substrate of 100mm * 100mm (1737, Corning corporate system) and to apply black light solidification compound CK-9910L (FUJIFILM Electronic Materials Co., Ltd. system), with 120 ℃ heating plates drying 120 seconds (prebake).Afterwards, be situated between by photomask at 100mJ/cm ²(illumination is 20mW/cm ²) under expose, use 1% aqueous solution of alkaline-based developer CDK-1 (FUJIFILM Electronic Materials Co., Ltd. system) to cover filming after the exposure, and static 60 seconds.After static, pure water is scattered wash-out developer with the shower shape.Then, with the heat treated 1 hour (afterwards curing) in 220 ℃ baking oven of filming of as above having implemented exposure and having developed, thereby on glass substrate, form color filter BM pattern.

Then apply Photocurable composition (1), make thickness reach 2.0 μ m, with 90 ℃ 60 seconds of heating plates drying.Afterwards, be situated between by photomask at 100mJ/cm ²(illumination is 20mW/cm ²) under expose, use 1% aqueous solution of alkaline-based developer CDK-1 to cover filming after the exposure, and static 60 seconds.After static, pure water is scattered wash-out developer with the shower shape.Then, with the heat treated 1 hour (afterwards curing) in 220 ℃ baking oven of filming of as above having implemented exposure and having developed, thereby on glass substrate, form the red pattern (pigmentary resin overlay film) that color filter is used.Use Photocurable composition (2), (3),, on glass substrate, form the colored pattern (pigmentary resin overlay film) that color filter is used, thereby made painted filter substrate (color filter) A with above-mentioned same operation.

In addition, except Photocurable composition being become (4), (5), (6), all other is operated equally, has made color filter B.In addition, except Photocurable composition being become (7), (8), (9), all other is operated equally, has made color filter C.In addition, except Photocurable composition being become (10), (11), (12), all other is operated equally, has made color filter D.

The evaluation of＜color filter 〉

For the painted filter substrate of making (color filter), the following evaluation.The results are shown in table 2.

(3) contrast

On the pigmentary resin overlay film of painted filter substrate, place polaroid and clamping pigmentary resin overlay film, use the BM-5A of Topcon corporate system to measure the brightness of the brightness of polaroid when parallel when vertical, the brightness of brightness when parallel when vertical, with the value of gained (brightness during=brightness when parallel/vertical) as the index that is used to estimate contrast.It is high more to be worth big more expression contrast.

Table 2

	Contrast
	Contrast	Color filter A	4000
Color filter B	3800	Color filter A	4000
Color filter B	3800	Color filter C	3750
Color filter D	2900	Color filter C	3750

Claims

1. color filter, it is characterized in that, it contains colored pattern, the occupation rate of 2 particles in the resulting image of the result who utilizes atomic force microscope to observe on this colored pattern surface is below 40%, and described colored pattern is to be that the Photocurable composition of the pigment of 15～150nm is given on substrate and being formed with containing mean grain size.

2. color filter according to claim 1 is characterized in that described Photocurable composition contains: organic solvent; Mean grain size is the described pigment of 15～150nm; Contain polymkeric substance from the copolymerization units of monomer shown in the following general formula (1); The optical polymerism compound; And Photoepolymerizationinitiater initiater,

In the general formula (1), R ¹Expression hydrogen atom or replace or do not have the alkyl of replacement; R2 represents alkylidene; W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene; X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-; Y represents-NR ³-,-O-,-S-or-N=, and be situated between and be connected with the N atom and form ring texture by the atomic group that is adjacent; R ³Expression hydrogen atom, alkyl or aryl; M and n represent 0 or 1 independently of one another.

3. color filter according to claim 2 is characterized in that, in described general formula (1), Y is situated between and is connected with the N atom and the ring texture that forms is the condensed ring structure by adjacent atomic group.

4. color filter according to claim 2 is characterized in that, described polymkeric substance is for further containing the graft copolymer from the copolymerization units of the polymerism oligomer that has the ethylenic unsaturated link endways.

5. color filter according to claim 2 is characterized in that, in described general formula (1), Y is situated between and is connected with the N atom and the ring texture that forms is the condensed ring structure by adjacent atomic group; And described polymkeric substance is for further containing the graft copolymer from the copolymerization units of the polymerism oligomer that has the ethylenic unsaturated link endways.

6. color filter according to claim 2 is characterized in that, described polymkeric substance is for further containing the polymkeric substance from the copolymerization units of the monomer with acidic group.

7. color filter according to claim 2 is characterized in that, in described general formula (1), Y is situated between and is connected with the N atom and the ring texture that forms is the condensed ring structure by adjacent atomic group; And described polymkeric substance is for further containing the polymkeric substance from the copolymerization units of the monomer with acidic group.

8. color filter according to claim 2 is characterized in that, described polymkeric substance is for further containing the graft copolymer from the copolymerization units of the polymerism oligomer that has the ethylenic unsaturated link endways; And described polymkeric substance further contains the copolymerization units from the monomer with acidic group.

9. color filter according to claim 2 is characterized in that, in described general formula (1), Y is situated between and is connected with the N atom and the ring texture that forms is the condensed ring structure by adjacent atomic group; Described polymkeric substance is for further containing the graft copolymer from the copolymerization units of the polymerism oligomer that has the ethylenic unsaturated link endways; And described polymkeric substance further contains the copolymerization units from the monomer with acidic group.

10. according to each described color filter of claim 2～9, it is characterized in that described Photocurable composition further contains alkali soluble resin.

11. a manufacturing method of color filter is characterized in that, comprises following operation:

Photosensitive film forms operation, this operation is by with Photocurable composition directly or be situated between to be given by other layer form photosensitive film on substrate, and described Photocurable composition contains pigment that organic solvent, mean grain size are 15～150nm, contains polymkeric substance, optical polymerism compound and Photoepolymerizationinitiater initiater from the copolymerization units of monomer shown in the following general formula (1);

Colored pattern forms operation, this operation forms colored pattern by the described photosensitive film that forms is carried out pattern exposure and development successively, and the occupation rate of 2 particles in the resulting image of the result who utilizes atomic force microscope to observe of this colored pattern is below 40%;

In the general formula (1), R ¹Expression hydrogen atom or replace or do not have the alkyl of replacement; R ²The expression alkylidene; W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene; X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-; Y represents-NR ³-,-O-,-S-or-N=, and be situated between and be connected with the N atom and form ring texture by the atomic group that is adjacent; R ³Expression hydrogen atom, alkyl or aryl; M and n represent 0 or 1 independently of one another.