CN101398497B

CN101398497B - Color filter and manufacure method

Info

Publication number: CN101398497B
Application number: CN2008101610254A
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: 2012-06-27
Anticipated expiration: 2028-09-24
Also published as: CN101398497A; KR20090033089A; TWI437284B; JP2009098691A; KR101506229B1; TW200928458A; JP5455344B2

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 manufacturing approach thereof

Technical field

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

Background technology

Color filter is made as follows: contain the pigment dispensing composition, polyfunctional monomer, Photoepolymerizationinitiater initiater, alkali soluble resin and other composition that have disperseed organic pigment or inorganic pigment and process coloring photosensitive combination; Use said composition; Through 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 receives special gazing at owing to the picture quality to display device has significant impact.

To 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 pigment particles below the 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 that comparison is difficult, even present situation is to realize satisfying the high-contrastization of realistic scale according to above-mentioned technology, hopes further high-contrastization.

Summary of the invention

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

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

The inventor etc. concentrate on studies, and the result finds, is controlled at below the setting through the occupation rate with 2 particles of pigment in the formed colored pattern overlay film, can address the above problem, thereby accomplish the present invention.

That is the means that, are used to address the above problem are following.

< 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 said 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 said 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 formula (1); The optical polymerism compound; And Photoepolymerizationinitiater initiater.

[in the general formula (1), R ¹The expression hydrogen atom, or replace or do not have a substituted alkyl.R ²The expression alkylidene.W representes-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X representes-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y representes-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 said 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.

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

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

< 6>according to each described color filter in < 2 >～< 5 >, it is characterized in that said 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 through with Photocurable composition directly or be situated between to be given by other layer and on substrate, form photosensitive film, and said 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 formula (1); Colored pattern forms operation; This operation forms colored pattern through 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 enumerate out following proposal: even when using the pigment of fine particle size; Be used for the formation of colored pattern through the solidification compound that will use pigment dispensing composition, also can obtain the excellent color filter of light transmission and contrast with high pigment-dispersing and dispersion stabilization.

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

Embodiment

Below be elaborated with regard to pigment dispensing composition of the present invention, Photocurable composition, color filter and manufacturing approach 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 said 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 through 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 surperficial observation image of the film 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 through following method among the present invention.

< occupation rates 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 through techniques of discriminant analysis.

2. cut apart contacted particle through the Watershed method.

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

When under this condition, measuring the occupation rate of 2 particles, be 42～45% times in the occupation rate, the 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 specify.

< pigment dispensing composition >

Among the present invention; As with fine pigment equably and one of the method for under the situation along with the worry of effluxion generation aggegation not, stably disperseing, adopt following method: the polymkeric substance that is about to contain from the copolymerization units of monomer shown in the 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 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 following explanation, 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 " to describe.

In the general formula (1), R ¹The expression hydrogen atom, or replace or do not have a substituted alkyl.R2 representes alkylidene.W representes-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X representes-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y representes-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 ¹The expression hydrogen atom, or replace or do not have a substituted alkyl.

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

Y representes-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 representes-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 following explanation, 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 the homopolymer that formed by at least a monomer that is selected from (methyl) alkyl acrylate, styrene and derivant, vinyl cyanide, vinyl acetate and the butadiene or multipolymer, or is polyethylene oxide, polypropyleneoxide, polycaprolactone.

Above-mentioned polymerism oligomer is preferably the oligomer shown in the 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 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 ester bond.R ¹²Shown alkylidene also can further have substituting group (for example hydroxyl).

Y representes 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 representes 20～200 integer.

As the preferred example of the polymerism oligomer (monomer greatly) that can in specific pigment spreading agent synthetic, use among the present invention, can enumerate the polymkeric substance that gathers (methyl) methyl acrylate, gathers (methyl) n-butyl acrylate and gather (methyl) isobutyl acrylate, (methyl) acryloyl group is arranged at a molecular end bonding of polystyrene.As the polymerism oligomer that can obtain, 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 from market.

Specific pigment spreading agent of the present invention preferably further contains the copolymerization units from the monomer with acidic group.Further contain copolymerization units through the specific pigment spreading agent, when for example pigment dispensing composition of the present invention being applicable to that the pattern that utilizes photoetching process to carry out forms, can further improving pattern and become second nature 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 is in the scope of not damaging its effect, but the vinyl monomer that also can further contain copolymerization is as copolymer composition.

As spendable vinyl monomer here; Not special the qualification, 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) acrylic amide, N-methyl (methyl) acrylic amide, N-ethyl (methyl) acrylic amide, N-propyl group (methyl) acrylic amide, N-isopropyl (methyl) acrylic amide, N-normal-butyl (methyl) acrylic amide, the N-tert-butyl group (methyl) acrylic amide, N-cyclohexyl (methyl) acrylic amide, N-(2-methoxy ethyl) (methyl) acrylic amide, N; N-dimethyl (methyl) acrylic amide, N, N-diethyl (methyl) acrylic amide, N-phenyl (methyl) acrylic amide, N-benzyl (methyl) acrylic amide, (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 AMS etc. of group that can be through 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 through 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 obtain as follows: 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-TGA, lauryl mercaptan) and synthesize.

In addition, concrete synthetic example is narrated in the back.

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

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 through 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 special to limit 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 squints 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, monoethylene glycol, diethylene glycol, toluene, xylene etc.

In addition; The addition of organic solvent can wait according to the purposes of pigment dispensing composition suitably and select; But because the preparation of the Photocurable composition of stating after being used 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 special to be limited; For example can obtain as follows: 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, the pigment aggegation in the film can be suppressed, high-contrast can be obtained.

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

(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.Through in Photocurable composition, containing alkali soluble resin, this Photocurable composition is applicable to further improves pattern and become second nature when utilizing photolithographic pattern to form.

Alkali soluble resin is the wire organic high molecular polymer, can from molecule (being the molecule of main chain with acrylic acid series copolymer, styrene based copolymer preferably), 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.Wherein, more preferably solvable in organic solvent, and the alkali soluble resin that can develop through 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 to 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 and open clear 59-44615 number, special public clear 54-34327 number, special public clear 58-12577 number, special public clear 54-25957 number, spy and open clear 59-53836 number, spy and open methacrylic acid copolymer that clear 59-71048 number each communique puts down in writing, acryllic acid multipolymer, itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc. and have the acid cellulose derivant of carboxylic acid on the side chain, having addition acid anhydrides on the polymkeric substance of hydroxyl and the material that obtains 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 with 2-hydroxyethyl methacrylate carry out copolymerization and material of 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 flat 7-140654 communique record, 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, AMS, vinyltoluene, GMA, 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 combination to use 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 property 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 limit ground not especially among the present invention and use them.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 NCO, epoxy radicals or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol form and have esters of unsaturated carboxylic acids or amide-type that halogen group, toloxyl etc. break away from substituents and simple function or the substituted reactant of 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 acrylic ester; Glycol diacrylate, triethylene glycol diacrylate, 1 are arranged; 3-butanediol diacrylate, tetramethyl omega-diol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylic ester, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol acrylate, D-sorbite triacrylate, D-sorbite tetraacrylate, D-sorbite five acrylic ester, D-sorbite six acrylic ester, three (acryloxy ethyl) isocyanuric acid ester, polyester acrylic oligomer ester, isocyanuric acid oxirane (EO) modification triacrylate etc.

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

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 acrylic amides, 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 property 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 NCO more than 2 in the vinyl monomer shown in the 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 property compounds that has amino structure or sulfide structure in the molecule of record in flat 1-105238 number through 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 acrylic ester or the methacrylates such as epoxy acrylate class that obtain.Specific unsaturated compound, the spy that in addition, 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 property compounds, its structure, separately use or and the details of method of application such as usefulness, addition can come setting 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 abilities under for most situation.In addition; In order to improve the curing film strength; It can be the above structure of 3 officials ability; And, through with the compound of different functional number, various polymerization property group (for example acrylic ester, 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 method of application also are important factors; For example, can improve compatibility sometimes through 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 property 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 can use separately, also can more than 2 kinds and use.In addition, viewpoints such as the size that the method for application of addition polymerization property compound can hinder from the polymerization to oxygen, exploring degree, photographic fog property, 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 halogen that flat 57-6096 communique puts down in writing and open aromatic carbonyls such as ketal, acetal or benzoin alkylether class that each instructions of halogenated methyl-s-triazine isoreactivity halogenide that clear 53-133428 communique etc. put down in writing, U.S. Pat P-4318791, the open EP-88050A of Europe patent etc. puts down in writing, aromatic ketone compounds such as benzophenone that U.S. Pat P-4199420 instructions is put down in writing, (thia) xanthene ketone that the Fr-2456741 instructions is put down in writing or acridine compound, spy for first oxadiazole, special public clear 59-1281 communique, spy and open the organic boron complex of sulfonium that compound, spies such as Coumarins that flat 10-62986 communique puts down in writing or di-imidazoles open flat 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.

As the Photoepolymerizationinitiater initiater of reactive halogen Photoepolymerizationinitiater initiater (triazine Xi 、 oxadiazole system, coumarin series), 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) of 4--1,3-butadiene base-s-triazine, 2; Two (the trichloromethyl)-6-xenyls of 4--s-triazine, 2, two (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 is amino)-phenyl)-2; 6-two (chloromethyl)-s-triazine, 4-(right-N, N-(di ethoxy carbonyl is amino)-phenyl)-2,6-two (chloromethyl)-s-triazine, 2-trichloromethyl-5-styryl-1; 3; 4-oxadiazole, 2-trichloromethyl-5-(cyano styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphtho--1-yl)-1; 3; 4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4-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; No. 2722512 instructions of United States Patent (USP) put down in writing by the substituted aromatic series acyloin of α-hydrocarbon compound; 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.

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

Photocurable composition of the present invention also preferably contains common sensitizer.Common sensitizer in the Photocurable composition of the present invention have 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 people such as amine, for example M.R.Sander works " Journal of Polymer Society " the 10th volume 3173 pages of (1972), special public clear 44-20189 communique, spies and open clear 51-82102 communique, spy and open clear 52-134692 communique, spy and open clear 59-138205 communique, spy and open clear 60-84305 communique, spy and open the compound etc. that clear 62-18537 communique, spy are opened clear 64-33104 communique, Research Disclosure33825 number record, can enumerate triethanolamine, ESCAROL 507 ethyl ester particularly, to the formoxyl xylidin, to the 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 scope of 1～25 quality % more preferably further is preferably the 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 to come 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, xylene 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, BC acetate, propylene glycol methyl ether acetate etc. in these.

Solvent can also make up and use 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, anti-oxidant, ultraviolet light absorber, anti-agglutinant in the Photocurable resin composition of the present invention as required.

< fluorinated organic compound >

Through containing fluorinated organic compound, can improve the solution properties (particularly mobile) when processing 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 the 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 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 article 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, (nonionics such as the Pluronic L10 of BASF AG's system, L31, L61, L62,10R5,17R2,25R2, Tetronic304,701,704,901,904,150R1 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 polymer100, EFKA polymer400, EFKApolymer401, EFKA polymer450 (more than gloomy industry corporate system down), Disperse aid6, Disperse aid8, Disperse aid15, Disperse aid9100 macromolecule dispersing agents such as (San Nopco Limited systems); Solsperse3000,5000,9000,12000,13240,13940,17000,24000,26000, various Solsperse spreading agents (Zeneca corporate system) such as 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, seek to promote uncured alkali dissolution property, and when further improving the development property 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 through 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 prepare.

< color filter and manufacturing approach thereof >

Color filter of the present invention is made as follows: use above-mentioned Photocurable composition of the present invention, on substrates such as glass, form through painted film (colored pattern), thereby make.

Specifically; Give (preferably applying) with direct perhaps Jie of above-mentioned Photocurable composition on substrate by other layer through painting methods such as rotation coating, slot coated, curtain coating coating, roller coat; Form photosensitive film, be situated between and formed photosensitive film made public, after exposure, utilize developer solution that uncured development removed by the mask pattern of stipulating; Thereby form the colored pattern (for example colored pixels) of (for example 3 looks or 4 looks) of all kinds, thereby can process 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 uncured Photocurable composition film 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 enumerating out.

As above-mentioned alkaline aqueous solution; For example can enumerate NaOH, potassium hydroxide, sodium carbonate, soda mint, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, TMAH, 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 after development, carrying out in order to make completion of cure, carries out about 200 ℃～250 ℃ heating (hard roasting (hard bake)) usually.Curing processing after this can carry out as follows: 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).

Through 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 on this substrate, forms 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 can means of the present invention likewise be applicable to the formation of the black matrix" of isolating each colored pixels that constitutes color filter.

Black matrix" can form as follows: will use the Photocurable composition of the present invention (pigment dispensing composition) of black pigments such as carbon black, titanium be black to make public, develop as pigment; Cure after further carrying out as required afterwards; Promote the curing of film, thereby form.

[embodiment]

Below through embodiment the present invention is described more specifically, but only otherwise exceed purport of the present invention, be not limited to following embodiment.In addition, if do not specify " part " expression " mass parts ".

[synthetic 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)).

[synthetic example 2]

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

[synthetic 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)

Monomer 1 in will synthesizing example 1 becomes the monomer 3, through the method identical with synthetic routine 1, obtains 30% solution of polymkeric substance 3 (above-mentioned exemplary compounds (14)).

[embodiment 1]

< 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 through electron microscope ((strain) Hitachi High-Technologies Corporation system: S-4800) measure.

< 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

Irgacure369 (Ciba Specialty Chemicals system) 0.2g

Hydroquinone monomethyl ether 0.01g

Propylene glycol methyl ether acetate 45g

< making of colored pattern >

To be coated on the glass substrate of 0.7mm, through 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.

< occupation rate of 2 particles is measured >

(Veeco Instruments makes 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, obtain the occupation rate of 2 particles in the image according to following order to the gained image.

2. cut apart contacted particle through 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 through said method, the result is 22%.

[embodiment 2]

< 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.

< 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

< making of colored pattern >

Except becoming Photocurable composition (2), operate equally with embodiment 1, obtain colored pattern.

< occupation rate of 2 particles is measured >

Utilize the occupation rate of calculating 2 particles with embodiment 1 same method, the result is 28%.

[embodiment 3]

< 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.

< preparation of Photocurable composition >

Except dispersible pigment dispersion (1) is become the dispersible pigment dispersion (3), all other and embodiment 1 operate equally, preparation Photocurable composition (3).

< making of colored pattern >

Except Photocurable composition (1) is become the Photocurable composition (3), operate equally with embodiment 1, obtain colored pattern.

< occupation rate of 2 particles is measured >

Utilize the occupation rate of calculating 2 particles with embodiment 1 same method, the result is 38%.

[embodiment 4]

Except polymkeric substance 1 is become the polymkeric substance 2, all other and embodiment 1 operate equally, obtain dispersible pigment dispersion (4), Photocurable composition (4) and colored pattern.

[embodiment 5]

Except polymkeric substance 1 is become the polymkeric substance 2, all other and embodiment 2 operate equally, obtain dispersible pigment dispersion (5), Photocurable composition (5) and colored pattern.

[embodiment 6]

Except polymkeric substance 1 is become the polymkeric substance 2, all other and embodiment 3 operate equally, obtain dispersible pigment dispersion (6), Photocurable composition (6) and colored pattern.

[embodiment 7]

Except polymkeric substance 1 is become the polymkeric substance 3, all other and embodiment 1 operate equally, obtain dispersible pigment dispersion (7), Photocurable composition (7) and colored pattern.

[embodiment 8]

Except polymkeric substance 1 is become the polymkeric substance 3, all other and embodiment 2 operate equally, obtain dispersible pigment dispersion (8), Photocurable composition (8) and colored pattern.

[embodiment 9]

Except polymkeric substance 1 is become the polymkeric substance 3, all other and embodiment 3 operate equally, obtain dispersible pigment dispersion (9), Photocurable composition (9) and colored pattern.

[comparative example 1]

< 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.

< preparation of Photocurable composition >

Except becoming dispersible pigment dispersion (10), all other and embodiment 1 operate equally, preparation Photocurable composition (10).

< making of colored pattern >

Except becoming Photocurable composition (10), operate equally with embodiment 1, obtain colored pattern.

< occupation rate of 2 particles is measured >

Utilize the occupation rate of calculating 2 particles with embodiment 1 same method, the result is 49%.

[comparative example 2]

< 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.

< preparation of Photocurable composition >

Except becoming dispersible pigment dispersion (11), all other and embodiment 1 operate equally, preparation Photocurable composition (11).

< making of colored pattern >

Except becoming Photocurable composition (11), operate equally with embodiment 1, obtain colored pattern.

< occupation rate of 2 particles is measured >

Utilize the occupation rate of calculating 2 particles with embodiment 1 same method, the result is 55%.

[comparative example 3]

< 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.

< preparation of Photocurable composition >

Except becoming dispersible pigment dispersion (12), all other and embodiment 1 operate equally, preparation Photocurable composition (12).

< making of colored pattern >

Except becoming Photocurable composition (12), operate equally with embodiment 1, obtain colored pattern.

< occupation rate of 2 particles is measured >

Utilize the occupation rate of calculating 2 particles with embodiment 1 same method, the result is 60%.

< mensuration of contrast >

Contrast is that the color filter that makes 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 result is shown in below table 1.

Table 1

	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 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 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
					Comparative example 2	BYK-161	81	55	10200
Comparative example 3	BYK-161	97	60	6500

Can know that by table 1 color filter according to the present invention is used colored pattern, can realize high-contrast.

< having 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 make public, use 1% WS 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, use the BM pattern thereby on glass substrate, form color filter.

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 make public, use 1% WS 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 is become (4), (5), (6), all other is operated equally, has made color filter B.In addition, except Photocurable composition is become (7), (8), (9), all other is operated equally, has made color filter C.In addition, except Photocurable composition is become (10), (11), (12), all other is operated equally, has made color filter D.

< evaluation of color filter >

For the painted filter substrate of making (color filter), estimate as follows.The result is 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
		Color filter A	4000
Color filter B	3800
		Color filter C	3750
Color filter D	2900

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 said colored pattern is given Photocurable composition on substrate and formed, and said 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 formula (1); The optical polymerism compound; And Photoepolymerizationinitiater initiater,

In the general formula (1), R ¹The expression hydrogen atom does not perhaps have substituted alkyl; R ²The expression alkylidene; W representes-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene; X representes-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-; Y representes-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 or alkyl; M and n represent 1 independently of one another.

2. color filter according to claim 1 is characterized in that, in said 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.

3. color filter according to claim 1 is characterized in that, said polymkeric substance is for further containing the graft copolymer from the copolymerization units of the polymerism oligomer that has the ethylenic unsaturated link endways.

4. color filter according to claim 1 is characterized in that, in said 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 said 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 1 is characterized in that, said polymkeric substance is for further containing the polymkeric substance from the copolymerization units of the monomer with acidic group.

6. color filter according to claim 1 is characterized in that, in said 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 said 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 1 is characterized in that, said 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 said polymkeric substance further contains the copolymerization units from the monomer with acidic group.

8. color filter according to claim 1 is characterized in that, in said 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; Said 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 said polymkeric substance further contains the copolymerization units from the monomer with acidic group.

9. according to each described color filter of claim 1～8, it is characterized in that said Photocurable composition further contains alkali soluble resin.

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

Photosensitive film forms operation; This operation is through with Photocurable composition directly or be situated between to be given by other layer and on substrate, form photosensitive film, and said 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 formula (1);

Colored pattern forms operation; This operation forms colored pattern through the said 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%;