CN102272237B

CN102272237B - Pigment dispersion composition for color filters, and color filters

Info

Publication number: CN102272237B
Application number: CN2010800038526A
Authority: CN
Inventors: 中熊大英; 丝谷一男; 米原博; 前川文彦; 木下宏司
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2009-09-09
Filing date: 2010-09-06
Publication date: 2013-12-11
Anticipated expiration: 2030-09-06
Also published as: JP4687835B2; WO2011030726A1; CN102272237A; KR20110056316A; KR101214921B1; TWI478987B; JPWO2011030726A1; TW201125934A

Abstract

A pigment dispersion composition for color filters which comprises a coloring agent, a resin, and an organic solvent that can dissolve the resin, characterized by containing, as the coloring agent, a modified pigment (D) that comprises a pigment (A), and a modified polyamine (B) and a polymer (P) which are present on the surface of the pigment (A); and color filters. The modified polyamine (B) is a product obtained by reacting a vinyl copolymer (B-1) with amino groups of a polyamine, said vinyl copolymer (B-1) having, at one terminal, a functional group that can react with an amino group and thereby form an amide linkage. The polymer (P) is a polymer prepared by polymerizing at least one polymerizable unsaturated monomer (C) that is soluble in a non-aqueous solvent and that forms a polymer insoluble or slightly soluble in a non-aqueous solvent. Thus, color filters which exhibit excellent dispersion stability and contrast can be produced using a general-purpose pigment.

Description

Pigment dispersing composition for color filters and colour filter

Technical field

The present invention relates to the pigment dispersing composition for color filters as coloured material by pigment.

Background technology

Generally for colour filter, on the substrate that is provided with the mesh-shape shading film layer that is called black matrix, in the situation that transmission-type is for transmission red, green, blue 3 primary colors optionally, in the situation that reflection-type is for optionally reflect cyan, magenta, yellow 3 primary colors, form the color solidification film layer corresponding with shades of colour in each mesh of black matrix, and this versicolor mesh is arranged regularly.In addition, " mesh " of above-mentioned black matrix is called as " pixel ".

Colour filter is used in the color monitors such as colored individual imaging apparatus, liquid color display, color CRT.In recent years, for the urgent expectation of the higher image quality to colour filter, thus the high-contrast of seeking.

About the manufacture method of colour filter, the staining that in early days dyestuff is used as to tinting material is main flow, but, in order to tackle above-mentioned requirements, recently, uses the colo(u)rant dispersion method of the pigment of the excellences such as thermotolerance, photostabilization, chemical reagent resistance to become main flow.With regard to this colo(u)rant dispersion method, general extensive carry out " photolithography " as follows: in the pigment dispensing composition by using dispersion agent that colo(u)rant dispersion is obtained in adhesive resin, add photopolymerization monomer, Photoepolymerizationinitiater initiater, obtain the colo(u)rant dispersion resist, described colo(u)rant dispersion resist-coating is also dry on base material, after being exposed by photomask, develop and process with thermofixation, thereby form the cured coating film layer of colo(u)rant dispersion resist in pixel portions.

As manufacture the method for colour filter by being somebody's turn to do " photolithography ", a kind of pigment dispersing composition for color filters has for example been proposed, it contains pigment, coupling agent, on main chain or side chain, has N, the acrylic copolymer of N-disubstituted amido and acidic groups and solvent, the transparency, developability, excellent in light-resistance, and excellent storage stability (for example, referring to Patent Document 1).Yet the method also may not fully meet in recent years the requirements at the higher level characteristic to dispersion stabilization and long-term storing stability, the transparency etc.

To this, oneself knows following method: at the pigment using general and resin and organic solvent, as raw material, carry out when mixing, be made as specific ratios by the solids component ratio (mass conversion) by this pigment and this resin, and adopt planetary-type mixer to be undertaken mixing by this raw material on one side this organic solvent evaporation removal on one side, thereby obtain the pigment dispersing liquid for colour filter (for example, referring to Patent Document 2) that dispersion stabilization and long-term storing stability, the transparency etc. are excellent.Yet, Yi Bian the method usually needs the solids component ratio monitor and carried out mixingly, for reaching firmly thick, need mixingly for a long time, so can not be called easy compounding process.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2003-64293 communique (paragraph [0002]～[0008])

Patent documentation 2: TOHKEMY 2006-111752 communique

Summary of the invention

The problem that invention will solve

Problem of the present invention is, provides pigment that a kind of use is general to supply with the pigment dispersing composition for color filters of the colour filter of dispersion stabilization excellence and contrast gradient excellence.

Solve the method for problem

The inventor had before invented a kind of pigment, it is characterized in that, there is polymkeric substance in surface of pigments, this polymkeric substance is that the polymkeric substance that contains the polymerizability unsaturated group by dissolving in non-aqueous solvent and at least one dissolve in non-aqueous solvent and become (the TOHKEMY 2008-88211 communique) that the polymerizability unsaturated monomer A polymerization of insoluble or indissoluble obtains after polymerization, and find when the pigment dispersing composition for color filters of this pigment has been used in modulation dispersion stabilization excellent (Japanese Patent Application 2009-529445 communique).

The inventor further finds, the modified pigment that dissolves in the polymkeric substance that contains the polymerizability unsaturated group of non-aqueous solvent by the polymkeric substance replacement that use is had to certain ad hoc structure is applied to the pigment dispensing composition that colour filter is used, can obtain the colour filter of the contrast gradient excellence of dispersion stabilization excellence and color filter pixel section, thereby complete the present invention.

, the invention provides a kind of pigment dispersing composition for color filters, it is the pigment dispersing composition for color filters that contains tinting material and resin and can dissolve the organic solvent of this resin, use modified pigment (D) as tinting material, described modified pigment (D) is to have the modified pigment of modified polyamine (B) and polymkeric substance (P) on pigment (A) surface, described modified polyamine (B) reacts and forms by the amino that makes to have the ethylenic copolymer (B-1) that can react with amino the functional group that forms amido linkage and a polyamine at an end, described polymkeric substance (P) dissolves in non-aqueous solvent by least one and becomes polymerizability unsaturated monomer (C) polymerization of insoluble or indissoluble and obtain after polymerization.

The present invention also provides a kind of colour filter that uses the pigment dispersing composition for color filters of aforementioned record.

The invention effect

According to the present invention, can provide a kind of pigment dispersing composition for color filters that uses general pigment to supply with the colour filter of dispersion stabilization excellence and contrast gradient excellence.

Embodiment

(modified pigment (D))

Be used as the modified pigment (D) of tinting material in the present invention, can be by under the existence of general pigment (A), non-aqueous solvent and modified polyamine (B), polymerizability unsaturated monomer (C) polymerization that makes at least one dissolve in this non-aqueous solvent and become insoluble or indissoluble after polymerization is that so-called in-situ polymerization obtains, and described modified polyamine (B) is that the amino that makes to have the ethylenic copolymer (B-1) that can react with amino the functional group that forms amido linkage and a polyamine at an end reacts and forms.

(pigment (A))

The pigment used in the present invention (A) is for being selected from known habitual pigment dyestuff or at least one pigment in mineral dye.In addition, the present invention also applicable untreated pigment, process any in pigment.

As pigment (A), can enumerate: so far for the commercially available pigment of colour filter be recorded in " color index brief guide " (up-to-date pigment brief guide, Japan pigment technology association compiles, 1977 annuals), (CMC publishes " up-to-date pigment applications technology ", 1986 annuals), the known habitual pigment in " printing-ink technology " (CMC publish, 1984 annuals) etc.

As especially general the pigment that is used in colour filter, particularly, for example can enumerate: C.I. Pigment red 254, C.I. Pigment red 177, C.I. pigment orange 71 reds such as grade, C.I. pigment green 36, C.I. Pigment green 58, C.I. the phthalocyanine such as pigment Green 7, C.I. pigment Blue 15: 6, C.I. blue pigment such as Pigment blue 22 grades, C.I. pigment Violet 23, C.I. pigment violet 50 purple dyes such as grade, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150, C.I. Pigment Yellow 73 20 yellow pigments such as grade, C.I. Pigment black 7, carbon black, the black black pigment etc. that waits of titanium, these pigment can be used alone, also two or more can be mixed to use as required.

Generally, with regard to the transparency of the cured coating film of pigment dispersing liquid for colour filter, less this transparency of the particle diameter of contained pigment is higher, but its primary particle size is preferably the scope of 10～80nm, is particularly preferably the scope of 30～50nm.During primary particle size is not enough 10nm, because the aggregation of pigment uprises to become, be difficult to disperse, and the transparency can descend while surpassing 80nm.

Wherein, in order to bring into play to greatest extent effect of the present invention, particularly preferably use C.I. Pigment green 58.

(non-aqueous solvent)

The non-aqueous solvent used in the present invention is the organic solvent that is necessary for aliphatics and/or ester ring type hydrocarbon system solvent.As aliphatics and/or ester ring type hydrocarbon system solvent, for example can enumerate: normal hexane, normal heptane, octane; Shell chemical company goods " LAWS " or " Mineral Spirit EC "; Exxon Mobil chemical company goods " Isopar C ", " Isopar E ", " Isopar G ", " Isopar H ", " Isopar L ", " Isopar M ", " No. 3, Naphtha ", " No. 5, Naphtha " or " No. 6, Naphtha "; Idemitsu Petrochemical Co., Ltd.'s goods " No. 7, Solvent ", " IP Solvent 1016 ", " IP Solvent 1620 ", " IP Solvent 2028 " or " IP Solvent 2835 "; Japan Energy Co., Ltd's (Japan Energy) goods " Whitesol "; Maruzen Petrochemical Co., Ltd.'s goods " Marukasol 8 " etc.

In addition,, also can mix other organic solvents and use in not impaired scope in effect of the present invention.As such organic solvent, particularly, such as enumerating: aromatic hydrocarbons series solvent classes such as Maruzen Petrochemical Co., Ltd.'s goods " SWASOL 100 to 150 ", toluene or dimethylbenzene; The ester classes such as ritalin, vinyl acetic monomer, n-butyl acetate or amyl acetate-n; The ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), Methyl amyl ketone or pimelinketone; Perhaps alcohols such as methyl alcohol, ethanol, n-propyl alcohol, Virahol or propyl carbinol.

When mixing is used, more than the usage quantity of aforementioned aliphatics and/or ester ring type hydrocarbon system solvent is preferably 50% quality, more than being more preferably 60% quality.

(modified polyamine (B))

The modified polyamine used in the present invention (B) has the ethylenic copolymer (B-1) that can react with amino the functional group that forms amido linkage (below, will " ethylenic copolymer (B-1) that have the functional group that can react with amino the formation amido linkage at an end " referred to as ethylenic copolymer (B-1)) and the amino of polyamine reacts the modified polyamine (B) formed for making at an end.The known polyamine generally adsorptivity to pigment is high, and therefore modified polyamine of the present invention (B) can improve the dispersion stabilization of pigment in hydrophobic solvent.Its result thinks, because the dispersion particle diameter of the modified pigment (D) that aftermentioned polymerizability unsaturated monomer (C) is obtained in the surface of pigments polymerization becomes thinner, is therefore preferred.

(polyamine)

The polyamine used in the present invention refers to the polymkeric substance that comprises the repeating unit with primary amino or secondary amino group.As such polyamine, be preferably at least one in the group of selecting free PAH, polyvinylamine and polymine to form.In addition, also can be the multipolymer of PAH, polyvinylamine or polymine and other polymerizable monomers.

While using the multipolymer of PAH, polyvinylamine or polymine and other polymerizable monomers, the amine value of polyamine of the present invention is preferably more than 50, is more preferably more than 300.The adsorptive power deficiency of the polyamine of amine value less than 50 to pigment, the dispersiveness of the modified pigment of gained likely reduces.These polyamine classes can only be used a kind of, also can mix use multiple.Wherein, from the viewpoint of industrial easy acquisition, preferably PAH or polymine, wherein, as most preferred polyamine, can enumerate PAH.As its reason, think: owing to generally forming the polymer architecture of branch-like with respect to polymine, PAH forms the polymer architecture of straight chain shape, so amine is high to the anchor effect of pigment.

The number-average molecular weight of the polyamine in the present invention is preferably 150～100000, is more preferably 600～20000.During the number-average molecular weight less than 150 of the polyamine used in the present invention, adsorptive power deficiency to pigment, colo(u)rant dispersion likely becomes difficulty, on the other hand, while surpassing 100000 amount, likely cause rising, the gelation of viscosity while not only reacting with vinyl polymer, and the molecular weight of polymkeric substance becomes excessive, likely because pigment gathering each other causes dispersed the reduction.

(PAH)

The PAH of using in the present invention can optionally obtain the allyl amine polymerization by known method under the existence of polymerization starter under chain transfer catalyst exists, and also can use commercially available product.As commercially available product, PAH series such as the PAA-01 commercially available by Nitto Boseiki Co., Ltd., PAA-03, PAA-05, PAA-15, PAA-10C.

(polyvinylamine)

The polyvinylamine used in the present invention, for example can utilize under the existence of polymerization starter, and after optionally under chain transfer catalyst exists, by known method, making the polymerization of N-vinyl formamide, the so known the whole bag of tricks of reaction that is hydrolyzed obtains.

(polymine)

The polymine used in the present invention can obtain the azacyclopropane polymerization by known method, also can use commercially available product.As commercially available product, polymine series such as the SP-003 commercially available by Nippon Shokubai Co., Ltd, SP-006, SP-012, SP-018, SP-200, P-1000.

(ethylenic copolymer (B-1))

For the ethylenic copolymer used in the present invention (B-1), as react the functional group that forms amido linkage with amino, can enumerate the oxygen carbonyls such as halogen formyl radical, methoxycarbonyl such as carboxyl, chloroformyl.Wherein carboxyl can easily import ethylenic copolymer, is preferred.

In order to obtain having at an end ethylenic copolymer of carboxyl, for example can enumerate the method that simultaneously has the chain-transfer agent with carboxyl when polymerization.As the chain-transfer agent with carboxyl, such as enumerating the thiocarboxylic acid classes such as Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid.In addition, also can be by using 4,4 '-azo is two-4-cyanopentanoic acid etc. have carboxyl polymerization starter, utilize the method for living radical polymerization synthesized polymer monomer to obtain.

Become the polymerizable monomer of the raw material of ethylenic copolymer (B-1), such as the homopolymer that can enumerate (methyl) alkyl acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) ethyl acrylate, or these esters each other or the multipolymer of these esters and following material: the alkenyl benzenes such as vinylbenzene, alpha-methyl styrene, Vinyl toluene; Or vinyl acetate, vinyl pyridine, acrylamide, Methacrylamide, dimethylaminoethyl methacrylate, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate etc.In these polymerizable monomers, can use one kind or two or more.

But, preferably do not use that have can for example carboxyl equates or the polymerizable monomer of the high functional group that compares with amino functional group reactive and that form amido linkage with the amino reaction.Due to the vinyl polymer that has comprised this polymerizable monomer in raw material not only at the end of this ethylenic copolymer, random this functional group that is grafted with on the main chain of multipolymer also, therefore may carry out gelation with in the reacting of PAH, the performance of the modified pigment of gained likely reduces.Particularly, the polymerizable monomers such as divinyl, isoprene, chloroprene, (methyl) vinylformic acid, methylene-succinic acid, maleic anhydride, owing to containing the group that has hyperergy for amino, therefore preferably are not used as the raw material of ethylenic copolymer (B-1).

With regard to liquid crystal indicator etc., owing to requiring further to improve the display characteristic such as identification, therefore sometimes require to control the length of delay of the colored pixels layer that forms colour filter.In this case, by aforementioned ethylenic copolymer (B-1), contain the alkyl that carbonatoms is 10～24, thereby the length of delay that can control pixel is to the negative direction.That is to say, as long as will contain (methyl) acrylate of the alkyl that carbonatoms is 10～24, be used as one of raw material.(methyl) acrylate of the alkyl that to contain carbonatoms be 10～24 can be any of straight chain shape, branch-like, but illustration (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid myristin, (methyl) aliphatic acrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid mountain Yu ester etc.As coordinate the component of this (methyl) acrylate that contains the alkyl that carbonatoms is 10～24 in ethylenic copolymer (B-1), be preferably 10～100 quality %, more preferably 20～100 quality %.During the quantity not sufficient 10 quality % of (methyl) acrylate of the alkyl that to contain carbonatoms be 10～24, desired length of delay adjustment capability likely can't be brought into play.

Ethylenic copolymer (B-1) can be by being heated, carry out as required slaking and obtain above-mentioned various polymerizable monomers under the existence of polymerization starter in reaction vessel.As reaction conditions, be for example that according to polymerization starter and solvent and difference, but temperature of reaction is 30～150 ℃, is preferably 60～120 ℃.Can be not influenced even polymerization is carried out under the existence of non-reactive solvent yet.

As polymerization starter, the superoxide such as can enumerating peroxidized t-butyl perbenzoate, di-t-butyl peroxide, cumene hydroperoxide, acetyl peroxide, benzoyl peroxide, lauroyl peroxide etc.; Diisopropyl azodicarboxylate, azo two-2, the azo-compound of 4-methyl pentane nitrile, azo two cyclohexanenitriles etc. and so on etc.

As non-reactive solvent, for example can enumerate: the aliphatic hydrocarbon series solvent of hexane, mineral wet goods and so on; The aromatic hydrocarbons series solvent of benzene,toluene,xylene etc. and so on; The ester series solvent of N-BUTYL ACETATE etc. and so on; The pure series solvent of methyl alcohol, butanols etc. and so on; The non-proton property polar solvent of dimethyl formamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, pyridine etc. and so on etc.Can be used together these solvents.With regard to these solvents, can suitably select the solvent that can dissolve the ethylenic copolymer (B-1) of gained to use.

With regard to the molecular weight of the ethylenic copolymer (B-1) that uses in the present invention, number-average molecular weight is preferably 500～100000 scope, is more preferably 1000～20000 scope.During number-average molecular weight less than 500, likely can't keep the sufficient steric exclusion effect as pigment dispersing agent, likely cause the rising of the viscosity of vinyl polymer, the decline of solvent solubility at 100000 o'clock and surpass, in two kinds of situations, the performance of the modified pigment of gained all descends.

In addition, modified polyamine of the present invention (B) preferably can make a kind of or its above compound in ethylenic copolymer (B-1) and the choosing group that freely following (B-2)～(B-5) forms react with aforementioned polyamine.

(b1) there is the ethylenic copolymer of the functional group that can react with amino at an end, the amount of the functional group that can react from amino, the ethylenic copolymer (B-2) that multipolymer forms or the multipolymer ratio of components is different with aforementioned ethylenic copolymer (B-1).

As aforementioned ethylenic copolymer (B-2), optimal ethylene base co-polymer (B-2-1).Ethylenic copolymer (B-2-1) preferably be take scope that the ratio of % by weight and the % by weight of the functional group that can react with amino of an end that is positioned at aforementioned ethylenic copolymer (B-2-1) of the functional group that can react with amino of the end that is positioned at aforementioned ethylenic copolymer (B-1) is 0.4～0.8 and is (B-1)/(B-2-1)=0.25～4.0 with the molar ratio (B-1)/(B-2-1) of aforementioned ethylenic copolymer (B-1) mode is reacted with modified polyamine.(hereinafter referred to as ethylenic copolymer (B-2-1))

In addition, as aforementioned ethylenic copolymer (B-2), optimal ethylene base co-polymer (B-2-2).The ethylenic copolymer of ethylenic copolymer (B-2) for a plurality of polymerization of vinyl monomer are formed, the difference of the Tg of the Tg of aforementioned ethylenic copolymer (B-1) and aforementioned ethylenic copolymer (B-2-2) is more than 20 ℃, and preferably take the mode that the molar ratio (B-1)/(B-2-2) of aforementioned ethylenic copolymer (B-1) and aforementioned ethylenic copolymer (B-2-2) is (B-1)/(B-2-2)=0.25～4.0 and react with modified polyamine.(hereinafter referred to as ethylenic copolymer (B-2-2))

(b2) there is (methyl) acrylate (B-3) of polyalkylene glycol chain.(hereinafter referred to as (methyl) acrylate (B-3)).Wherein, preferably so that the mode that aforementioned polyalkylene glycol chain contains with the ratio of 1～30 % by weight with respect to molecule integral body with modified polyamine, react.

(b3) an end have the functional group that can react with amino polyester, there is the polymeric amide of the functional group that can react with amino or there is the polyesteramide (B-4) (hereinafter referred to as polymkeric substance (B-4)) of the functional group that can react with amino at an end at an end.Wherein aforementioned modified polyamine preferably reacts with modified polyamine in the mode that contains these residues with the ratio of 1～50 % by weight with respect to molecule integral body.

(b4) monocarboxylic acid or (methyl) acrylate (B-5).Wherein preferably in the mode that contains these residues with the ratio of 1～30 % by weight with respect to molecule integral body, with modified polyamine, react.

((b1) ethylenic copolymer (B-2-1))

Aforementioned ethylenic copolymer (B-2-1) at an end, have can from the functional group of amino reaction and the multipolymer different with aforementioned ethylenic copolymer (A), preferably take the end that is positioned at aforementioned ethylenic copolymer (B-1) the functional group of react with amino % by weight and be positioned at scope that the ratio of % by weight of the functional group of reacting with amino of an end of aforementioned ethylenic copolymer (B-2-1) is 0.4～0.8 and be (B-1)/(B-2-1)=0.25～4.0 with the molar ratio (B-1)/(B-2-1) of aforementioned ethylenic copolymer (B-1) mode is reacted with modified polyamine.

Particularly, ethylenic copolymer (B-2-1) is for to have the ethylenic copolymer of carboxyl, and is the multipolymer different from aforementioned ethylenic copolymer (B-1) molecular weight.The content of the carboxyl of the end of the adjustment of molecular weight by being positioned at ethylenic copolymer carries out, the % by weight of the carboxyl of ethylenic copolymer is preferably 1～10 scope, and the % by weight of carboxyl that is positioned at an end of aforementioned ethylenic copolymer (B-1) is preferably 0.4～0.8 scope with the ratio of % by weight of the carboxyl of an end that is positioned at aforementioned ethylenic copolymer (B-2-1).(still, make the molecular weight of the aforementioned ethylenic copolymer of molecular weight ratio (B-1) of aforementioned ethylenic copolymer (B-2-1) now large.)

In addition, with regard to the ratio of the residual chain of ethylenic copolymer (B-2-1) (the residual chain of ethylenic copolymer described herein (B-2-1) refers to part remaining after carboxyl reaction) and the residual chain of ethylenic copolymer (B-1), molar ratio (B-1)/(B-2-1) with aforementioned ethylenic copolymer (B-1), be preferably (B-1)/(B-2-1)=0.25～4.0.

((b1) ethylenic copolymer (B-2-2))

Aforementioned ethylenic copolymer (B-2-2) is for a plurality of polymerization of vinyl monomer are formed, and for the difference of the Tg of the Tg of aforementioned ethylenic copolymer (B-1) and aforementioned ethylenic copolymer (B-2) be the ethylenic copolymer more than 20 ℃.In addition, Tg herein is defined as the value of measuring by the tB-ln δ peak of DSC (differential scanning calorimetry mensuration) or dynamic viscoelastic.

As previously mentioned, preferably take the mode that the molar ratio (B-1)/(B-2-2) of aforementioned ethylenic copolymer (B-1) and aforementioned ethylenic copolymer (B-2-2) is (B-1)/(B-2-2)=0.25～4.0 reacts with modified polyamine.

Particularly, the Tg of ethylenic copolymer (B-2-2) is preferably 100 ℃～-50 ℃, and according to the Tg of ethylenic copolymer (B-1), and different, Tg is particularly preferably 60 ℃～-50 ℃.

((b2) (methyl) acrylate (B-3))

In aforementioned (methyl) acrylate (B-3), what is called has polyalkylene glycol chain, means the state of polyalkylene glycol (methyl) acrylate.Particularly, polyalkylene glycol is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and these mixture etc., wherein preferred polyoxyethylene glycol, polypropylene glycol.

(methyl) acrylate (B-3) preferably reacts with modified polyamine in the mode that contains aforementioned polyalkylene glycol chain with the ratio of 1～30 % by weight with respect to molecule integral body.

((b3) polymkeric substance (B-4))

Aforementioned polymer (B-4) is specially arbitrary polymkeric substance of following (b3-1)～(b3-3).

(b3-1) there is the polyester of the functional group that can react with amino at an end,

(b3-2) there is the polymeric amide of the functional group that can react with amino at an end,

(b3-3) there is the polyesteramide of the functional group that can react with amino at an end.

(b3-1) polyester that has at an end functional group that can react with amino specifically refers to the polyester that has endways carboxyl.It can utilize following the whole bag of tricks to synthesize.

Can enumerate: (a) addition reaction, (b) of monocarboxylic acid compound addition lactone compound are made to condensation reaction of monocarboxylic acid compound, hydroxy carboxylic acid compound and 3 kinds of composition condensations of lactone compound etc. to addition reaction, (c) of hydroxy carboxylic acid compound's addition lactone compound.

(b3-2) there is the polymeric amide of the functional group that can react with amino at an end, specifically refer to the polymeric amide that there is endways carboxyl.It is for preparing the lactan such as ε-caprolactam, omega-lauric lactam or the aminocarboxylic acids such as hexosamine, 11-aminoundecanoic acid as raw material.

(b3-3) polyesteramide that has at an end functional group that can react with amino specifically refers to the ester that has endways carboxyl and the cocondensation compound of acid amides.It can be by making to use in the manufacture of aforementioned polyester and polymeric amide hydroxycarboxylic acid, caprolactone etc. and the incompatible preparation of the cocondensations such as aminocarboxylic acid, hexanolactam.

Aforementioned polymer (B-4) is preferably reacted with modified polyamine in the mode that contains these residues with the ratio of 1～50 % by weight with respect to molecule integral body.Residue herein means polymer moieties remaining after carboxyl reaction.

((b4) monocarboxylic acid or (methyl) acrylate (B-5))

Aforementioned monocarboxylic acid is so long as have the compound of 1 hydroxy-acid group and be not particularly limited in 1 molecule, particularly, can enumerate the aliphatic monocarboxylic acids such as acetic acid, propionic acid, sad, n-nonanoic acid, capric acid, sad, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, different n-nonanoic acid, eicosanoic acid, M-nitro benzoic acid, to aromatic monocarboxylates such as butylbenzoic acids.

In addition, (methyl) acrylate used in the present invention for example can be enumerated (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, the homopolymer of (methyl) alkyl acrylates such as (methyl) ethyl acrylate, perhaps these esters each other or the multipolymer of these esters and following material: vinylbenzene, alpha-methyl styrene, the alkenyl benzenes such as Vinyl toluene, vinyl acetate, vinyl pyridine, acrylamide, Methacrylamide, dimethylaminoethyl methacrylate, N hydroxymethyl acrylamide, N-butoxymethyl acrylamide, (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate etc.

Aforementioned monocarboxylic acid, aforementioned (methyl) acrylate preferably react with modified polyamine in the mode that contains these residues with the ratio of 1～30 % by weight with respect to molecule integral body.Residue herein means monocarboxylic acid or (methyl) acrylate remaining after carboxyl reaction.

(polyamine reacts with ethylenic copolymer (B-1's))

Aforementioned polyamine and aforementioned ethylenic copolymer (B-1) or with for example reacting of the mixture of aforementioned ethylenic copolymer (B-1)～compound (B-5) can be under stream of nitrogen gas, below 200 ℃, carry out.Can use the known polymerizing catalysts such as tin system or titanium system in reaction.In addition as required, can use and react the non-reactive solvents such as irrelevant toluene, dimethylbenzene, Solvesso.The solvent used not necessarily will be removed.

Ethylenic copolymer (B-1) is preferably roughly 20～95% scope to the percentage of grafting of polyamine, when 30～90% scope and the affinity of diluting solvent, film-forming resin and with the balance excellence of the affinity of pigment, thereby particularly preferably.Percentage of grafting herein means the reacting weight of the total amount of the amino that the carboxyl of ethylenic copolymer (B-1) has with respect to polyamine, means the % of the residual chain of ethylenic copolymer (B-1) that modified polyamine of the present invention has, that the amido linkage of take is intermediary (the residual chain of ethylenic copolymer described herein (B-1) refers to part remaining after carboxyl reaction).

During the residual chain less than 20% of aforementioned ethylenic copolymer (B-1) that aforementioned modified polyamine has, easily cause pigment gathering each other, thereby likely produce the deficiency of viscosity degradation effect, on the impact of printing ink epithelium.In addition, when the residual chain of aforementioned ethylenic copolymer (B-1) that aforementioned modified polyamine has surpasses 95%, amino deficiency as the functional group with pigment generation absorption, have according to pigment the tendency that dispersion stabilization reduces, still likely produce deficiency, printing ink epithelium bad of viscosity degradation effect.

(reacting of a kind of or its above compound in the group that polyamine forms with choosing free aforementioned (B-2)～(B-5))

For example reacting of polyamine and a kind of or its above compound in the choosing group that freely aforementioned (B-2)～(B-5) forms can be under stream of nitrogen gas, below 200 ℃, carry out.Can use the known polymerizing catalysts such as tin system or titanium system in reaction.In addition as required, can use and react the non-reactive solvents such as irrelevant toluene, dimethylbenzene, Solvesso.The solvent used not necessarily will be removed, and also can directly be used as 1 composition of pigment dispersing agent.

Polyamine can carry out also can carrying out successively with ethylenic copolymer (B-1) with a kind of or its above the reacting of compound in the choosing group that freely aforementioned (B-2)～(B-5) forms simultaneously.

(other compositions)

The modified polyamine used in the present invention (B) can contain the non-reactive solvent used when the manufacture of modified polyamine (B), again adds other solvent after the non-reactive solvent that also can use when manufacture is removed in distillation in addition.

In order to there is the cross-linking set with polymkeric substance (P) by aftermentioned polymerizability unsaturated monomer (C) polymerization is obtained on the modified polyamine (B) used in the present invention, also preferably import the polymerizability unsaturated group.As its reason, be due to: by making polymkeric substance (P) and modified polyamine (B) crosslinked, coverage pigment surface more securely.As in the upper method that imports the polymerizability unsaturated group of modified polyamine (B), for example have: after making polyamine and ethylenic copolymer (B-1) reacts, thereby add the method etc. of glycidyl methacrylate importing polymerizability unsaturated group.

(dissolve in non-aqueous solvent and become the polymerizability unsaturated monomer (C) of insoluble or indissoluble after polymerization)

The polymerizability unsaturated monomer (C) that dissolves in this non-aqueous solvent and become insoluble or indissoluble after polymerization used in the present invention specifically has such as: olefines that (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl or (methyl) isopropyl acrylate or (methyl) vinyl cyanide, vinyl acetate, vinylchlorid, vinylidene chloride, vinyl fluoride or vinylidene fluoride are such etc. so-called not containing the ethene base system monomer class of reactive polar groups (functional group), the ethene base system monomer class of the amide bonds such as (methyl) acrylamide, dimethyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide, N-octyl group (methyl) acrylamide, diacetone-acryloamide(DAA), dimethylamino propyl acrylamide or alkoxylate N-methylolation (methyl) acrylic amide, dialkyl group [(methyl) acryloyloxyalkyl] phosphoric acid ester or (methyl) acryloyloxyalkyl phosphate ester acid class or dialkyl group [(methyl) acryloyloxyalkyl] phosphorous acid esters or (methyl) acryloyloxyalkyl acid phosphorous acid esters, the chloro-2-acid of (methyl) vinylformic acid 3-phosphorus acyloxy propyl ester that the alkylene oxide adducts, (methyl) glycidyl acrylate, (methyl) vinylformic acid methyl glycidyl ester etc. of above-mentioned (methyl) acryloyloxyalkyl phosphate ester acid class or acid phosphorous acid esters of take are representative containing the ester cpds of the ethene base system monomer of epoxy group(ing) and phosphoric acid or phosphorous acid or their acid ester class etc. contains the ethene base system monomer class of phosphorus atom, with (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) vinylformic acid-3-hydroxy butyl ester, (methyl) vinylformic acid-4-hydroxy butyl ester, the chloro-2-hydroxypropyl acrylate of (methyl) vinylformic acid-3-, fumaric acid two-2-hydroxyl ethyl ester or fumaric acid list-2-hydroxyethyl mono—n—butylester, or polypropylene glycol or polyethyleneglycol (methyl) acrylate, or " PLACCEL FM, the FA monomer " affixture etc. of the hydroxy alkyl ester class of polymerizable unsaturated carboxylic acids such as (Daicel (daicel) KCCs manufacture caprolactone addition monomer) or they and 6-caprolactone is representative, with (methyl) vinylformic acid, β-crotonic acid, toxilic acid, fumaric acid, the unsaturated monocarboxylic such as methylene-succinic acid or citraconic acid or dicarboxylic acid are representative, the polymerizable unsaturated carboxylic acids classes such as the monoesters class of these dicarboxylic acid and monohydroxy-alcohol, or aforementioned polymerizable unsaturated carboxylic acids hydroxy alkyl ester class and toxilic acid, succsinic acid, phthalic acid, the hexahydrobenzene dioctyl phthalate, the tetrahydrochysene phthalic acid, the benzene tricarbonic acid, the benzene tertacarbonic acid, " Na Dike acid (himic acid) ", various unsaturated carboxylic acid classes and " Cardura E " that the affixture of the acid anhydrides of the polycarboxylic acids such as tetrachloro-phthalic acid or lauryl succsinic acid is such, monocarboxylic single glycidyl esters such as coco-nut oil fatty acid glycidyl ester or sad glycidyl ester or and butylglycidyl ether, the affixture of the mono-epoxy compounds such as oxyethane or propylene oxide, or the affixture of they and 6-caprolactone, the perhaps polymerizability unsaturated monomer class of the such hydroxyl of hydroxyl vinyl ether, (methyl) vinylformic acid dialkylaminoalkyl ester classes such as (methyl) dimethylaminoethyl acrylate, (methyl) vinylformic acid lignocaine ethyl ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid (Beta-methyl) glycidyl ester, (methyl) allyl glycidyl ether or make the polymerizable unsaturated carboxylic acids class or the vinyl monomer of the hydroxyl such as phthalic acid list-2-(methyl) acryloxy mono ethyl ester and aforementioned polybasic acid anhydride etc. the various unsaturated carboxylic acids and " Epiclon 200 " such as mole affixture, " Epiclon 400 ", " Epiclon 441 ", " Epiclon 850 " or " Epiclon 1050 " (epoxy resin that DIC (strain) manufactures), perhaps " Epikote 828 ", " Epikote 1001 " or " Epikote 1004 (japan epoxy resin Co., Ltd. manufacture epoxy resin), " Araldite 6071 " or " Araldite 6084 " (epoxy resin that Switzerland's Ciba-Geigy (Ciba Geigy) company manufactures) and " Chisso Nox 221 " (epoxy compounds that intelligence rope (Chisso) Co., Ltd. manufactures), or the various polyepoxy compounds that have at least 2 epoxy group(ing) in 1 molecule such as " Denacol EX-611 " (epoxy compounds that Nagase chemical Co., Ltd manufactures) carry out the polymerizability unsaturated monomer class containing epoxy group(ing) such as the polymerizable compound containing epoxy group(ing) that addition reaction obtains by equimolar ratio, mole affixture, isocyanato-(methyl) ethyl propenoates etc. such as (methyl) vinylformic acid 2-hydroxyl ethyl ester-hexamethylene diisocyanate have the α containing isocyanate group such as the monomer of isocyanate group and vinyl, β-ethylene unsaturated monomer class, the silicon such as vinyl Ethoxysilane, Alpha-Methyl acryloyl-oxy propyl trimethoxy silicane, (methyl) vinylformic acid trimethylsiloxy group ethyl ester, " KR-215, X-22-5002 " (Shin-Etsu Chemial Co., Ltd's goods) are the polymerizability unsaturated monomer class containing alkoxysilyl such as monomer class, and with (methyl) vinylformic acid, β-crotonic acid, toxilic acid, fumaric acid, the unsaturated monocarboxylic such as methylene-succinic acid or citraconic acid or dicarboxylic acid are representative, the α such as the monoesters class of these dicarboxylic acid and monohydroxy-alcohol, β-ethene unsaturated carboxylic acid class, or (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid-2-hydroxy butyl ester, (methyl) vinylformic acid-3-hydroxy butyl ester, (methyl) vinylformic acid-4-hydroxy butyl ester, the chloro-2-hydroxypropyl acrylate of (methyl) vinylformic acid-3-, fumaric acid two-2-hydroxyl ethyl ester, the α such as fumaric acid list-2-hydroxyl ethyl ester-mono—n—butylester or polyethyleneglycol (methyl) acrylate, beta-unsaturated carboxylic acid hydroxy alkyl ester class and toxilic acid, succsinic acid, phthalic acid, the hexahydrobenzene dioctyl phthalate, the tetrahydrochysene phthalic acid, the benzene tricarbonic acid, the benzene tertacarbonic acid, " Na Dike acid ", the carboxylic α such as affixture of the acid anhydrides of the polycarboxylic acids such as tetrachloro-phthalic acid or lauryl succsinic acid, β-ethylene unsaturated monomer class etc.

Wherein, preferably use following alkyl (methyl) esters of acrylic acid of the C3 such as (methyl) methyl acrylate, (methyl) ethyl propenoate.Further, in order to change the surface property of surface of pigments, the interaction of raising and pigment dispersing agent or pigment dispersing resin, preferably make the polymerizability unsaturated monomer that contains the functional groups such as carboxyl, sulfonic group, phosphate, hydroxyl, dimethylamino of at least one carry out copolymerization.

In addition, in order when using modified pigment (D), not make modified polyamine (B) and polymkeric substance (P) stripping from pigment (A), more preferably that polymkeric substance (P) is crosslinked.As the multifunctional polymerization unsaturated monomer as crosslinking component, for example can enumerate Vinylstyrene, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, 1, 3-butyleneglycol two (methyl) acrylate, 1, 4-butyleneglycol two (methyl) acrylate, 1, 6-hexylene glycol two (methyl) acrylate, neopentylglycol dimethacrylate, trimethylolpropane tris oxyethyl group three (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate or allyl methacrylate(AMA) etc.

In addition, usining in the use range that the polymkeric substance of at least one polymerizability unsaturated monomer (C) that dissolves in this non-aqueous solvent and become insoluble or indissoluble after polymerization as essential component do not dissolve in this non-aqueous solvent system, also can use other polymerizability unsaturated monomer.As other polymerizability unsaturated monomer, for example can enumerate aforementioned (methyl) alkyl acrylate or aforementioned (methyl) alkyl acrylate spendable polymerizability unsaturated monomer in addition that carbonatoms is the alkyl more than 4 that have.

The modified pigment (D) that the present invention uses is by under existing at pigment (A), modified polyamine (B), makes at least one dissolve in this non-aqueous solvent and the polymerizability unsaturated monomer (C) that becomes insoluble or indissoluble after polymerization carries out polymerization and obtains.

Pigment (A) and modified polyamine (B) are preferably mixed before carrying out polymerization.

By mixing, with modified polyamine (B), the surface of pigment (A) is soaked, (pigment (A) and modified polyamine (B)) interface formed thus becomes the place of polymerization, after mixing aforementioned pigment (A) and modified polyamine (B), further mix aforementioned polymerizability unsaturated monomer (C), carry out again polymerization, can obtain the modified pigment applied with polymkeric substance (P).Due to this method, be that pigment (A) utilizes the fine and place that stably disperses nonessential of dispersion stabilizer, therefore the surface treatment etc. that is used to form the pigment (A) of fine dispersion state may not need, thereby can be applicable to the pigment of the kind of wide region.

As blending means, can use such as homogenizer, dispersion machine, ball mill, paint shaker, kneader, roller mill, ball mill, attritor, sand mill etc.In the present invention, no matter the form of the pigment used also can be used any form of slurry, wet cake, powder.That is,, in manufacture method of the present invention, also can use the such aqueous pigment of wet cake.

By after aforementioned pigment (A) and modified polyamine (B) mixing, further mixed polymerization unsaturated monomer (C) and aftermentioned polymerization starter, then carry out polymerization, thus can obtain modified pigment (D).

Now, the usage quantity of modified polyamine (B) can be carried out optimizing aptly according to purpose, therefore is not particularly limited, but, with respect to 100 parts of pigment (A), usually uses 1～200 part, is more preferably 2～50 parts, more preferably 3～30 parts.

In addition, the usage quantity of aforementioned polymerizability unsaturated monomer (C) also can be carried out optimizing aptly according to purpose, therefore is not particularly limited, but with respect to 100 parts of pigment (A), usually use 1～200 part, be more preferably 1～50 part, more preferably 1～30 part.

The final modified polyamine (B) applied on pigment and the amount of polymkeric substance (P), with respect to 100 parts of pigment (A), preferably used 2～400 parts, is more preferably 3～100 parts, more preferably 4～60 parts.Now, with respect to 100 parts of aforementioned modified polyamines (B), at least one aforementioned polymerizability unsaturated monomer (C) is preferably used with the ratio of 10～400 parts usually, is more preferably 30～400 parts, more preferably 50～200 parts.

Under the existence of aforementioned pigment (A), aforementioned non-aqueous solvent and modified polyamine (B), the method that makes aforementioned polymerizability unsaturated monomer (C) carry out polymerization, although, as long as by known habitual polymerization process, usually carry out under the existence of polymerization starter.As the polymerization starter related to, can be separately or use following substances with the form of two or more and use: Diisopropyl azodicarboxylate (AIBN), 2, the free radical generation polymerizing catalysts such as 2-azo two (2-methylbutyronitrile), benzoyl peroxides, t-butyl per(oxy)benzoate, the 2 ethyl hexanoic acid tert-butyl ester, tert-butyl hydroperoxide, ditertiary butyl peroxide or Cumene Hydroperoxide 80.

Therefore because polymerization starter is difficult to be dissolved in this non-aqueous solvent system, preferably first be dissolved in aforementioned polymerizability unsaturated monomer (C), then add the method in the mixed system of pigment (A) and modified polyamine (B).

In addition, aforementioned polymerizability unsaturated monomer (C) or the aforementioned polymerizability unsaturated monomer (C) that has dissolved polymerization starter also can add by dripping method under the state that has reached polymerization temperature, thereby but under the normal temperature state before intensification, add and fully mix after heated up the again method that makes its polymerization stable, be therefore preferred.

Polymerization temperature is generally the scope of 60 ℃～130 ℃.In addition, in the situation that pigment (A) is pigment dyestuff, while being quite high high temperature due to polymerization temperature, the metamorphosis such as rotten and crystalline growth of this pigment are remarkable sometimes, therefore preferably at 70～100 ℃, carry out polymerization in this case.

After polymerization, the removals such as non-aqueous solvent of using when filtering polymerization, thus further carry out the polymer-coated pigment that drying, pulverizing can obtain powder.Filter method can be used Nutsche suction filtration machine, pressure filter etc.In addition, drying can be carried out drying by known drying installations such as box like dryer, Vacuumdrier, conveyor dryer, spray driers.And pulverizing can be used the known shredding units such as mortar, hammer mill, disk grinder, pin rod pulverizer, airflow milling.

(pigment dispersing composition for color filters)

Pigment dispersing composition for color filters of the present invention obtains by modified pigment (D) being scattered in the resin solution that has mixed the pigment dispersing agents such as resin and organic solvent.Now, can use known habitual pigment dispersion method, can carry out colo(u)rant dispersion by the dispersion machine by ball mill, sand mill, ball mill, three rolling grinding machines, paint setter, attritor, dispersator, ultrasonic wave etc.As concrete dispersing apparatus, can enumerate: superfine apex shredder (the longevity skill is ground industrial and manufactured), super apex shredder (the longevity skill is ground industrial and manufactured), Draiswerke PM-DCP stirring-type ball mill device (manufacture of De Laishi company), molecule shredder (Pico grain mill) (shallow field ironworker (strain) manufacture) etc.

That during as colo(u)rant dispersion, uses grinds medium, for example can enumerate, zirconium white system or steel grind medium, wherein particularly preferably the zirconium white system of antifriction consumption excellence grind medium.In addition, the diameter that grinds medium is preferably the scope of 0.01～3.0mm, is particularly preferably the scope of 0.05～0.5mm.The diameter that grinds medium is greater than in the situation of 3.0mm, and it is insufficient that the wet type Crushing of Ultrafine can become, thereby not preferred.

The pigment dispersing agent used during as colo(u)rant dispersion, can be used the known pigment dispersing agent that is generally used for colo(u)rant dispersion.If can enumerate: the resin type dispersion agents such as the intermediate of the intermediate of tensio-active agent, pigment or derivative, dyestuff or derivative or polyamide-based resin, polyurethane series resin, polyester based resin, acrylic resin for example.In above-mentioned various dispersion agent, preferably use polyester system and acrylic resin.

As the commercially available product of resin type dispersion agent, for example can use: Bi Ke chemical company goods " DISPERBYK-130 ", " DISPERBYK-161 ", " DISPERBYK-162 ", " DISPERBYK-163 ", " DISPERBYK-170 ", " DISPERBYK-171 ", " DISPERBYK-174 ", " DISPERBYK-180 ", " DISPERBYK-182 ", " DISPERBYK-183 ", " DISPERBYK-184 ", " DISPERBYK-185 ", " DISPERBYK-2000 ", " DISPERBYK-2001 ", " DISPERBYK-2020 ", " DISPERBYK-2050 ", " DISPERBYK-2070 ", " DISPERBYK-2096 ", " DISPERBYK-2150 ", Ciba company goods " EFKA1503 ", " EFKA4010 ", " EFKA4020 ", " EFKA4300 ", " EFKA4330 ", " EFKA4340 ", " EFKA4520 ", " EFKA4530 ", " EFKA5054 ", " EFKA7411 ", " EFKA7422 ", " EFKA7431 ", " EFKA7441 ", " EFKA7461 ", " EFKA7496 ", " EFKA7497 ", Lubrizol Corp.'s goods " Solsperse 3000 ", " Solsperse 9000 ", " Solsperse 13240 ", " Solsperse 13650 ", " Solsperse 13940 ", " Solsperse 17000 ", " Solsperse 18000 ", " Solsperse 20000 ", " Solsperse 21000 ", " Solsperse 20000 ", " Solsperse 24000 ", " Solsperse 26000 ", " Solsperse 27000 ", " Solsperse 28000 ", " Solsperse 32000 ", " Solsperse 36000 ", " Solsperse 37000 ", " Solsperse 38000 ", " Solsperse 41000 ", " Solsperse 42000 ", " Solsperse 43000 ", " Solsperse 46000 ", " Solsperse 54000 ", " Solsperse 71000 ", aginomoto fine chemistry Co., Ltd. goods " Ajisper PB-711 ", " Ajisper PB-821 ", " Ajisper PB-822 ", " Ajisper PB-814 ", " Ajisper PB-824 " etc.

In addition, also use flow agent capable of being combined, coupling agent, positively charged ion are tensio-active agent etc.In the present invention, these dispersion agents also can two or more also be used.

The organic solvent used during as colo(u)rant dispersion, for example can enumerate: toluene, dimethylbenzene, the aromatic series series solvents such as anisole, vinyl acetic monomer, propyl acetate, N-BUTYL ACETATE, propylene glycol monomethyl ether acetate, the acetic ester series solvents such as dihydroxypropane single-ether acetic ester, the propionic ester series solvents such as ethoxyethyl propionate, methyl alcohol, the pure series solvent such as ethanol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol ether, the ether series solvents such as diethylene glycol dimethyl ether, methylethylketone, methyl iso-butyl ketone (MIBK), the ketone series solvents such as pimelinketone, the aliphatic hydrocarbon series solvents such as hexane, N, dinethylformamide, butyrolactam, METHYLPYRROLIDONE, aniline, the nitrogen compound series solvents such as pyridine, the lactone series solvents such as gamma-butyrolactone, the such carbamate of the mixture of 48: 52 of Urethylane and urethanum, water etc.Wherein, particularly preferably propionic ester, alcohol system, ether system, ketone system, nitride compound, lactone are the material of isopolarity solvent and water soluble.In the situation that use the organic solvent of water soluble, also can make itself and water also use.In the present invention, these solvents also can two or more also be used.

Usage rate about various materials is not particularly limited, but, usually with respect to 100 parts of modified pigments (D), uses the pigment dispersing agent of 5～200 parts, preferably uses 10～100 pigment dispersing agent, further preferably uses 10～60 pigment dispersing agent; As for organic solvent, add up to 10～25% according to the solid component content that makes modified pigment (D) and pigment dispersing agent, preferably in 10～20% mode, use.

(colour filter)

Pigment dispersing composition for color filters of the present invention can be applicable to manufacture has redness, green, the shades of colour pixel portions of blueness and the colour filter of black matrix.

When manufacturing colour filter, can adopt any in the known habitual manufacture method such as photolithography, ink jet method, print process.Photolithographic example below is described.

Photolithography is as follows: will be by the monomer or the oligopolymer that make light solidified, Photoepolymerizationinitiater initiaters etc. are mixed in pigment dispersing composition for color filters of the present invention aptly and the Photocurable composition obtained is coated the side surface that be provided with black matrix of colour filter with transparency carrier, after heat drying (prebaking), irradiate ultraviolet ray or the visible ray of 200～500nm wavelength region across photomask, thereby carry out pattern exposure, make to solidify at the photocurable compound at the position corresponding with pixel portions, then by developing solution, unexposed portion is developed, non-pixel portions is removed, thereby pixel portions is bonded to transparency carrier.The method forms the pixel portions that the curing colouring covering film by Photocurable composition forms on transparency carrier.Modulation black, redness, green and blue modified pigment (D) Photocurable composition separately, form black matrix by repeating aforementioned operation, further can be manufactured on the colour filter that prescribed position has the shades of colour pixel portions such as redness, green, blueness.

In addition, in order to form redness, green and blue etc. pixel portions, also can and with the modified pigment (D) of yellow modified pigment (D), purple.In addition, also can carry out heat treated (baking afterwards) to colour filter integral body after photocuring as required.

As the method for aforementioned Photocurable composition being coated on the transparency carriers such as glass, such as enumerating spin-coating method, rolling method, ink jet method etc.In addition, although the heat drying condition of the Photocurable composition after coating according to the kind of each composition, mixing ratio etc. and different, is generally about 50～150 ℃, 1～15 minute.

In addition, as the developing method after pattern exposure, such as enumerating paddling process (liquid is contained the り method), pickling process, spray method etc.After the exposure of Photocurable composition, developing, the transparency carrier of the pixel portions that formed necessary color wash and drying.

The colour filter so obtained, by using the heating units such as hot plate, baking oven 100～280 ℃ of heat treated (baking afterwards) of carrying out the specified time, in can the volatile component in removal is filmed, make to remain in the unreacted photocurable compound thermofixation in the curing colouring covering film of Photocurable composition, thereby complete colour filter.

Utilize photolithographic color filter manufacturing method although described in detail in the colo(u)rant dispersion method, but the colour filter of having applied pigment dispersing composition for color filters of the present invention is not limited to the method, also can manufacture by for example methods such as electrodip process, transfer printing, micella electrolytic process, PVED (PhotovoltaicElectrodeposition, photoelectricity deposition) method.

Embodiment

The present invention is described by the following examples.As long as no explanation in advance especially, " part " and " % " is quality criteria.

Synthesizing of<synthesis example 1 vinyl polymer (X1) >

Make 10 parts of 100 parts of dimethylbenzene and thioglycolic acids remain on 80 ℃ in nitrogen, stir, simultaneously the mixture by 2 parts of formations of 54 parts of methyl methacrylates, 36 parts of butyl acrylates and polymerization starter (" PERBUTYL (registered trademark) O " [effective constituent is the manufactures of peroxide-2-ethyl hexanoic acid tert-butyl, Japanese grease (strain)]) with dropping in 4 hours.After dripping end, within every 4 hours, add " PERBUTYL (registered trademark) O " 0.5 part, stir 12 hours at 80 ℃.Reaction adds for adjusting the dimethylbenzene of nonvolatile component after finishing, and obtaining nonvolatile component is xylene solution (X1) 50%, have the ethylenic copolymer of carboxyl at an end.The weight-average molecular weight of this resin is 5000, and acid number is 60.5mgKOH/g.

Synthesizing of<synthesis example 2 vinyl polymers (X2) >

Make 100 parts of dimethylbenzene remain on 80 ℃ in nitrogen, stir, simultaneously the mixture by 0.2 part of formation of 68 parts of β-dimethyl-aminoethylmethacrylates, methacrylic acid-29 parts of 2-ethylhexyls, 3 parts of thioglycolic acids and polymerization starter (" PERBUTYL (registered trademark) O " [effective constituent is the manufactures of the peroxidation 2 ethyl hexanoic acid tert-butyl ester, Japanese grease (strain)]) with dropping in 4 hours.After dripping end, within every 4 hours, add " PERBUTYL (registered trademark) O " 0.5 part, stir 12 hours at 80 ℃.Reaction adds for adjusting the dimethylbenzene of nonvolatile component after finishing, and obtaining nonvolatile component is xylene solution 50%, have the ethylenic copolymer (X2) of carboxyl at an end.The weight-average molecular weight of this resin is 7000, and acid number is 18.0mgKOH/g, and second-order transition temperature Tg is 38 ℃.

Synthesizing of<synthesis example 3 vinyl polymers (X3) >

Make 100 parts of dimethylbenzene remain on 80 ℃ in nitrogen, stir, simultaneously the mixture by 0.3 part of formation of 66 parts of β-dimethyl-aminoethylmethacrylates, methacrylic acid-28 parts of 2-ethylhexyls, 6 parts of thioglycolic acids and polymerization starter (" PERBUTYL (registered trademark) O " [effective constituent is the manufactures of the peroxidation 2 ethyl hexanoic acid tert-butyl ester, Japanese grease (strain)]) with dropping in 4 hours.After dripping end, within every 4 hours, add " PERBUTYL (registered trademark) O " 0.5 part, stir 12 hours at 80 ℃.Reaction adds for adjusting the appropriate dimethylbenzene of nonvolatile component after finishing, and obtaining nonvolatile component is xylene solution 50%, have the ethylenic copolymer (X3) of carboxyl at an end.The weight-average molecular weight of this resin is 4000, and acid number is 36.0mgKOH/g, and second-order transition temperature Tg is 38 ℃.

Synthesizing of<synthesis example 4 vinyl polymers (X4) >

Make 100 parts of dimethylbenzene remain on 80 ℃ in nitrogen, stir, simultaneously the mixture by 0.15 part of formation of 66 parts of lauryl methacrylate(LMA)s, methacrylic acid-28 parts of 2-ethylhexyls, 6 parts of thioglycolic acids and polymerization starter (" PERBUTYL (registered trademark) O " [effective constituent is the manufactures of the peroxidation 2 ethyl hexanoic acid tert-butyl ester, Japanese grease (strain)]) with dropping in 4 hours.After dripping end, within every 4 hours, add " PERBUTYL (registered trademark) O " 0.5 part, stir 12 hours at 80 ℃.Reaction adds for adjusting the appropriate dimethylbenzene of nonvolatile component after finishing, and obtaining nonvolatile component is xylene solution 50%, have the ethylenic copolymer (X4) of carboxyl at an end.The weight-average molecular weight of this resin is 4500, and acid number is 36.0mgKOH/g, and second-order transition temperature Tg is-51 ℃.

Synthesizing of<synthesis example 5 vinyl polymers (X5) >

Make 100 parts of dimethylbenzene remain on 80 ℃ in nitrogen, stir, simultaneously the mixture by 0.15 part of formation of 94 parts of lauryl methacrylate(LMA)s, 6 parts of thioglycolic acids and polymerization starter (" PERBUTYL (registered trademark) O " [effective constituent is the manufactures of the peroxidation 2 ethyl hexanoic acid tert-butyl ester, Japanese grease (strain)]) with dropping in 4 hours.After dripping end, within every 4 hours, add " PERBUTYL (registered trademark) O " 0.5 part, stir 12 hours at 80 ℃.Reaction adds for adjusting the appropriate dimethylbenzene of nonvolatile component after finishing, and obtaining nonvolatile component is xylene solution 50%, have the ethylenic copolymer (X5) of carboxyl at an end.The weight-average molecular weight of this resin is 5500, and acid number is 36.0mgKOH/g, and second-order transition temperature Tg is-65 ℃.

Synthesizing of<synthesis example 6 vinyl polymers (X6) >

Make 100 parts of dimethylbenzene remain on 80 ℃ in nitrogen, stir, simultaneously the mixture by 0.15 part of formation of 94 parts of methacrylic acid cetyl esters, 6 parts of thioglycolic acids and polymerization starter (" PERBUTYL (registered trademark) O " [effective constituent is the manufactures of the peroxidation 2 ethyl hexanoic acid tert-butyl ester, Japanese grease (strain)]) with dropping in 4 hours.After dripping end, within every 4 hours, add " PERBUTYL (registered trademark) O " 0.5 part, stir 12 hours at 80 ℃.Reaction adds for adjusting the appropriate dimethylbenzene of nonvolatile component after finishing, and obtaining nonvolatile component is xylene solution 50%, have the ethylenic copolymer (X6) of carboxyl at an end.The weight-average molecular weight of this resin is 5000, and acid number is 36.0mgKOH/g.

Synthesizing of<synthesis example 7 vinyl polymers (X7) >

To packing 30 parts of ion exchanged waters and 30 parts of Virahols remain on 80 ℃ in nitrogen in the flask that possesses stirrer, reflux cooler, nitrogen flushing pipe, thermometer into, stir, simultaneously the mixture by 0.8 part of formation of 40 parts of N-vinyl formamides, 8 parts of 2 mercapto ethanols and polymerization starter (" PERBUTYL (registered trademark) O " [effective constituent is the manufactures of the peroxidation 2 ethyl hexanoic acid tert-butyl ester, Japanese grease (strain)]) with dropping in 4 hours.After reaction finishes, add for adjusting the appropriate ion exchanged water of nonvolatile component, obtain nonvolatile component the vinyl polymer (X7) that is 40%.

Synthesizing of<synthesis example 8 polyvinylamine multipolymers (PA-1) >

125 parts of the vinyl polymers (X7), 141 parts of 20% sodium hydroxide solutions that to the nonvolatile component that adds gained in synthesis example 7 in the flask that possesses stirrer, reflux cooler, nitrogen flushing pipe, thermometer, are 40%, stir also 80 ℃ of reactions 16 hours.After reaction finishes, add acetone and make the resinous principle precipitation, then separated, drying, obtain the solids component of polyvinylamine multipolymer (PA-1).The amine value of polyvinylamine multipolymer (PA-1) is 1174mgKOH/g, and the percent hydrolysis of the N-vinyl formamide calculated by the amine value is 90%.

Synthesizing of<synthesis example 9 polyvinylamine multipolymers (PA-2) >

125 parts of the vinyl polymers (X7), 42 parts of 20% sodium hydroxide solutions that to the nonvolatile component that adds gained in synthesis example 7 in the flask that possesses stirrer, reflux cooler, nitrogen flushing pipe, thermometer, are 40%, stir also 80 ℃ of reactions 2 hours.After reaction finishes, add acetone and make the resinous principle precipitation, then separated, drying, obtain the solids component of polyvinylamine multipolymer (PA-2).The amine value of polyvinylamine multipolymer (PA-2) is 305mgKOH/g, and the percent hydrolysis of the N-vinyl formamide calculated by the amine value is 23%.

Synthesizing of<synthesis example 10 modified polyamines (BJ-1) >

To possessing stirrer, reflux cooler, the nitrogen flushing pipe, in the flask of thermometer, pack into by 100 parts of dimethylbenzene and PAH 20% aqueous solution (day east " PAA-05 " that (strain) manufactures that twist flax fibers and weave, number-average molecular weight is about 5000) mixture of 37.5 parts of formations, stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, simultaneously to reaction soln backflow dimethylbenzene, and add wherein 168.8 parts of the ethylenic copolymers (X1) of gained in synthesis example 1 (as the ethylenic copolymer (B-1) in the application) are warming up to the material after 140 ℃, carry out reaction in 8 hours at 140 ℃.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-1) that is 40%.The weight-average molecular weight of this resin is 7500, and the amine value is 32.5mgKOH/g.

Synthesizing of<synthesis example 11 modified polyamines (BJ-2) >

To possessing stirrer, reflux cooler, the nitrogen flushing pipe, in the flask of thermometer, pack into by 54.5 parts of dimethylbenzene, 19.0 parts of the ethylenic copolymers of gained (X2) in synthesis example 2 (as the ethylenic copolymer (B-1) in the application), 38.0 parts of the ethylenic copolymers of gained (X3) in synthesis example 3 (as the ethylenic copolymer (B-2-1) in the application) and PAH 20% aqueous solution (day east " PAA-05 " that (strain) manufactures that twist flax fibers and weave, number-average molecular weight is about 5000) mixture of 7.5 parts of formations, stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, simultaneously to reaction soln backflow dimethylbenzene, and carry out reaction in 8 hours at 140 ℃.

After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-2) that is 40%.The weight-average molecular weight of this resin is 10000, and the amine value is 22.0mgKOH/g.

Synthesizing of<synthesis example 12 modified polyamines (BJ-3) >

To pack in the flask that possesses stirrer, reflux cooler, nitrogen flushing pipe, thermometer 10.5 parts of PAH 20% aqueous solution " PAA-03 " and polyethylene glycol-propylene glycol monomethyl acrylate (" Blemmer 70PEP-350B ", the average glycol chain number that day oil (strain) is manufactured is 5, average propylene glycol chain number be 2) (as (methyl) acrylate (B-3) in the application) 1.5 parts, stir under stream of nitrogen gas and stirred at 50 ℃, react 3 hours simultaneously.52.8 parts of the ethylenic copolymers (X3) of gained in 35.2 parts of dimethylbenzene, the synthesis example 3 of then packing into (as the ethylenic copolymer (B-1) in the application), stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, carry out reaction in 8 hours simultaneously to reaction soln backflow dimethylbenzene, and at 140 ℃.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-3) that is 40%.The weight-average molecular weight of this resin is 8000, and the amine value is 31.0mgKOH/g.

Synthesizing of<synthesis example 13 modified polyamines (BJ-4) >

1.6 parts of 100 parts of the modified polyamines (BJ-3) that is 40% to the nonvolatile component that adds gained in synthesis example 12 in the flask that possesses stirrer, reflux cooler, nitrogen flushing pipe, thermometer and glycidyl methacrylate, 80 ℃ of reactions 8 hours.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-4) that is 40%.

Synthesizing of<synthesis example 14 modified polyamines (BJ-5) >

To possessing stirrer, reflux cooler, the nitrogen flushing pipe, add 11 parts of dimethylbenzene in the flask of thermometer, polymine (Epomine SP-006, Japan's catalyst chemical industry (strain) is manufactured, molecular-weight average is about 600) 7.5 parts, stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, simultaneously to reaction soln backflow dimethylbenzene, and add wherein 168.8 parts of the ethylenic copolymers (X1) of gained in synthesis example 1 (as the ethylenic copolymer (B-1) in the application) are warming up to the material after 140 ℃, carry out reaction in 8 hours at 140 ℃.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-5) that is 40%.

Synthesizing of<synthesis example 15 modified polyamines (BJ-6) >

To 7.5 parts of the polyvinylamine multipolymers (PA-1) that adds gained in 11 parts of dimethylbenzene, synthesis example 8 in the flask that possesses stirrer, reflux cooler, nitrogen flushing pipe, thermometer, stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, simultaneously to reaction soln backflow dimethylbenzene, and add wherein 152 parts of the ethylenic copolymers (X1) of gained in synthesis example 1 (as the ethylenic copolymer (B-1) in the application) are warming up to the material after 140 ℃, carry out reaction in 8 hours at 140 ℃.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-6) that is 40%.

Synthesizing of<synthesis example 16 modified polyamines (BJ-7) >

To 7.5 parts of the polyvinylamine multipolymers (PA-2) that adds gained in 11 parts of dimethylbenzene, synthesis example 9 in the flask that possesses stirrer, reflux cooler, nitrogen flushing pipe, thermometer, stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, simultaneously to reaction soln backflow dimethylbenzene, and add wherein 42.2 parts of the ethylenic copolymers (X1) of gained in synthesis example 1 (as the ethylenic copolymer (B-1) in the application) are warming up to the material after 140 ℃, carry out reaction in 8 hours at 140 ℃.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-7) that is 40%.

Synthesizing of<synthesis example 17 modified polyamines (BJ-8) >

To possessing stirrer, reflux cooler, the nitrogen flushing pipe, in the flask of thermometer, pack into by 100 parts of dimethylbenzene and PAH 20% aqueous solution (day east " PAA-05 " that (strain) manufactures that twist flax fibers and weave, number-average molecular weight is about 5000) mixture of 37.5 parts of formations, stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, simultaneously to reaction soln backflow dimethylbenzene, and add wherein 172.5 parts of the ethylenic copolymers (X4) of gained in synthesis example 4 (as the ethylenic copolymer (B-1) in the application) are warming up to the material after 140 ℃, carry out reaction in 8 hours at 140 ℃.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-8) that is 40%.The weight-average molecular weight of this resin is 6200, and the amine value is 46.0mgKOH/g.

Synthesizing of<synthesis example 18 modified polyamines (BJ-9) >

To possessing stirrer, reflux cooler, the nitrogen flushing pipe, in the flask of thermometer, pack into by 100 parts of dimethylbenzene and PAH 20% aqueous solution (day east " PAA-05 " that (strain) manufactures that twist flax fibers and weave, number-average molecular weight is about 5000) mixture of 32.8 parts of formations, stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, simultaneously to reaction soln backflow dimethylbenzene, and add wherein 99.4 parts of materials that are warming up to after 140 ℃ of ethylenic copolymer (X5) of gained in 75 parts of the ethylenic copolymers (X2) of gained in synthesis example 2 (as the ethylenic copolymer (B-1) in the application) and synthesis example 5, carry out reaction in 8 hours at 140 ℃.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-9) that is 40%.The weight-average molecular weight of this resin is 7000, and the amine value is 35.7mgKOH/g.

Synthesizing of<synthesis example 19 modified polyamines (BJ-10) >

To possessing stirrer, reflux cooler, the nitrogen flushing pipe, in the flask of thermometer, pack into by 100 parts of dimethylbenzene and PAH 20% aqueous solution (day east " PAA-05 " that (strain) manufactures that twist flax fibers and weave, number-average molecular weight is about 5000) mixture of 32.8 parts of formations, stir under stream of nitrogen gas and stirred at 140 ℃ simultaneously, use the tripping device dephlegmate, simultaneously to reaction soln backflow dimethylbenzene, and add wherein 174.4 parts of the ethylenic copolymers (X6) of gained in synthesis example 6 (as the ethylenic copolymer (B-1) in the application) are warming up to the material after 140 ℃, carry out reaction in 8 hours at 140 ℃.After reaction finishes, add for adjusting the appropriate dimethylbenzene of nonvolatile component, obtain nonvolatile component the modified polyamine (BJ-10) that is 40%.The weight-average molecular weight of this resin is 8000, and the amine value is 31.7mgKOH/g.

In the four-hole boiling flask that possesses thermometer, stirrer, reflux cooler and nitrogen ingress pipe, pack into 800 parts of heptane, 170 parts of N-BUTYL ACETATEs, be warming up to 90 ℃, while reaching this temperature, with within 5 hours, dripping by 50 parts of 950 parts of ethyl acrylates, dimethylaminoethyl methacrylate, 2, the mixture of two (2-methylbutyronitrile) the 7 parts of formations of 2 '-azo after dripping end, keeps proceeding in 10 hours reaction at this temperature.Add afterwards the solution that 0.2 part of tert.-butyl pyrocatechol is dissolved in to 15 parts of N-BUTYL ACETATEs and obtains, after further adding 30 parts of 15 parts of glycidyl methacrylate, dimethylaminoethanol, be warming up to 80 ℃, by reaction at this temperature 10 hours, obtain dissolving in the solution of the polymkeric substance that contains the polymerizability unsaturated group (BH-1) of non-aqueous solvent.

Synthesizing of<modification example 1 modified pigment (1) >

Using 200 parts of the wet cakes of C.I. Pigment green 58 (pigment part 50%), in the synthesis example 10 of solids component 200 parts of polyethylene wide-necked bottles of packing into of 10 parts of modified polyamines (BJ-1), 400 parts of the zirconium oxide beads of 1.25mm, heptane of gained, paint wobbler (Japan essence machine Co., Ltd.) and carry out mixing in 90 minutes.After being diluted with 100 parts of heptane, remove zirconium oxide bead, thereby make the pigment mixed solution.

400 parts of the pigment mixed solutions of gained are packed into possess thermometer, after the removable flask of stirrer, reflux cooler and nitrogen ingress pipe, add by 2 parts of N-tert-butyl acrylamide sulfonic acid are dissolved in to the material that 20 parts of ion exchanged waters obtain, further add by by 2, two (the 2-methylbutyronitriles) 2 parts of 2 '-azo are dissolved in the polymerizable monomer composition of 5 parts of 3 parts of methyl methacrylates and Ethylene glycol dimethacrylate and the material obtained.At room temperature continue to stir after 30 minutes, be warming up to 80 ℃, at this temperature, sustained reaction is 15 hours.After cooling, filtered polymer treatment pigment is separated with polymer solvent.By hot air dryer, the polymer pigment of gained, is pulverized with pulverizer after 5 hours 100 ℃ of dryings, thereby obtained modified pigment (1).

Synthesizing of<modification example 2～21 modified pigments (2)～(21) >

Except the pigment used (A), modified polyamine (BJ-1) change to the pigment and modified polyamine (B) that table 1～table 5 puts down in writing, prepare similarly to Example 1 the pigment mixed solution.

Use 400 parts of the pigment mixed solutions of gained, except polymer monomer (C) being changed to the polymerizable monomer (C) that table 1～table 5 puts down in writing, obtain similarly to Example 1 modified pigment (2)～(21).

Table 1

(C.I.Pigment Green 58): the wet cake of C.I. Pigment green 58 (pigment part 50%)

(C.I.Pigment Red 254): the powder of C.I. Pigment red 254

(C.I.Pigment Blue 15:6): C.I. pigment Blue 15: 6 powder

(C.I.Pigment Yellow 150): the powder of C.I. Pigment Yellow 73 150

Table 2

Table 3

Table 4

Table 5

The wet cake of PG 58:C.I. Pigment green 58 (pigment part 50%)

Using 192 parts of the wet cakes of C.I. Pigment green 58 (pigment part 52%), in the comparison synthesis example 1 of solids component 200 parts of polyethylene wide-necked bottles of packing into of 5 parts, polymkeric substance (BH-1), 400 parts of the zirconium oxide beads of 1.25mm, heptane of gained, paint wobbler (Japan essence machine Co., Ltd.) and carry out mixing in 90 minutes.After being diluted with 100 parts of heptane, remove zirconium oxide bead.400 parts of the pigment mixed solutions of gained are packed into possess thermometer, after the removable flask of stirrer, reflux cooler and nitrogen ingress pipe, stir and add by 2 parts of N-tert-butyl acrylamide sulfonic acid are dissolved in to the material that 20 parts of ion exchanged waters obtain, further add by by 2, two (the 2-methylbutyronitriles) 2 parts of 2 '-azo are dissolved in the polymerizable monomer composition of 3 parts of 5 parts of Ethylene glycol dimethacrylate and butyl methacrylate and the material obtained.At room temperature continue to stir after 30 minutes, be warming up to 80 ℃, at this temperature, sustained reaction is 15 hours.After cooling, filtered polymer treatment pigment is separated with polymer solvent.By hot air dryer, the polymer pigment of gained, is pulverized with pulverizer after 5 hours 100 ℃ of dryings, thereby obtained comparison modified pigment (1).

The making of<embodiment 1 dispersible pigment dispersion (1) and colour filter >

Add 65 parts of zirconium oxide beads that are dissolved in 26.8 parts of solution that obtain of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) and 0.5mm by 1.5 parts of (1) 5 part of the modified pigment by gained in modification example 1 and Ajisper PB-821 (pigment dispersing agent that aginomoto fine chemistry Co., Ltd. manufactures) in the polyethylene wide-necked bottle, paint after wobbler (Japan essence machine Co., Ltd.) carries out disperseing in 2 hours, thereby remove zirconium oxide bead, obtain dispersible pigment dispersion (1).Pass through dispersator, 13.5 parts of 75.00 parts of dispersible pigment dispersions and 5.50 parts of polyester acrylate resins (ARONIX M7100, East Asia synthetic chemical industry Co., Ltd. manufacture), 5.00 parts of dipentaerythritol acrylates (KAYARADDPHA, Nippon Kayaku K. K manufacture), 1.00 parts of benzophenone (KAYACURE BP-100, Nippon Kayaku K. K manufacture), UCAResterEFP are stirred, strainer by aperture 1.0 μ m is filtered, and obtains colo(u)rant dispersion resist (colored resist).On the 1mm heavy sheet glass, use the spin coater coating pigment to disperse resist, so that utilize spectrophotometer MCPD-3000 that great mound electronics (strain) manufactures, by the colour examining of C2 light source, calculate tristimulus coordinates y value for y=0.48, thereafter dry 5 minutes of 60 ℃ of preparations and formation is filmed.Then after photomask carries out UV-induced pattern exposure, after unexposed portion is cleaned in 0.5% aqueous sodium carbonate, clean with pure water again, then by the filming 230 ℃ of heat treated 15 minutes and cured coating film of gained, thereby form colour filter.The viscosity of the dispersible pigment dispersion so obtained (1) and the briliancy of color filter pixel section, contrast gradient are estimated by following method, and are recorded in table 6.

(viscosity)

Use Brookfield company goods " Digital Viscometer DV-II Pro " to measure viscosity.The common low dispersion liquid of preferred viscosities.

(briliancy)

As for briliancy (Y value), make the spectrophotometer MCPD-3000 manufactured with large mound electronics (strain), the Y value of measuring CIE color development system colourity by the colour examining of C2 light source.Herein, briliancy (Y value) is larger, is evaluated as the vision lightness higher.

(contrast gradient)

This color filter pixel section is arranged between 2 Polarizers, in a side, light source is set, further at its opposition side, the mensuration that the CCD photographic camera carries out briliancy is set.By polarizing axis become when parallel with become when vertical between recently the calculating of briliancy (penetrating light intensity).

Except change like that modified pigment (1) according to table 6 and table 7, by method similarly to Example 1, carry out colo(u)rant dispersion, application, evaluation.

The making of<embodiment 4 dispersible pigment dispersions (4) and colour filter >

Add 65 parts of zirconium oxide beads that are dissolved in 26.8 parts of solution that obtain of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) and 0.5mm by 1.5 parts of (4) 5 parts of modified pigments by obtaining in modification example 4 and Ajisper PB-821 (pigment dispersing agent that aginomoto fine chemistry Co., Ltd. manufactures) in the polyethylene wide-necked bottle, paint after wobbler (Japan essence machine Co., Ltd.) carries out disperseing in 2 hours, thereby remove zirconium oxide bead, obtain dispersible pigment dispersion (4).Pass through dispersator, 13.5 parts of 75.00 parts of dispersible pigment dispersions and 5.50 parts of polyester acrylate resins (ARONIX M7100, East Asia synthetic chemical industry Co., Ltd. manufacture), 5.00 parts of dipentaerythritol acrylates (KAYARADDPHA, Nippon Kayaku K. K manufacture), 1.00 parts of benzophenone (KAYACURE BP-100, Nippon Kayaku K. K manufacture), UCAResterEFP are stirred, strainer by aperture 1.0 μ m is filtered, and obtains colo(u)rant dispersion resist (colored resist).On the 1mm heavy sheet glass, use the spin coater coating pigment to disperse resist, so that utilize spectrophotometer MCPD-3000 that great mound electronics (strain) manufactures, by the colour examining of C2 light source, calculate tristimulus coordinates y value for y=0.107, thereafter dry 5 minutes of 60 ℃ of preparations and formation is filmed.Then after photomask carries out UV-induced pattern exposure, after unexposed portion is cleaned in 0.5% aqueous sodium carbonate, clean with pure water again, then by the filming 230 ℃ of heat treated 15 minutes and cured coating film of gained, thereby form colour filter.The viscosity of the dispersible pigment dispersion so obtained (4) and the briliancy of color filter pixel section, contrast gradient are estimated by following method, and are recorded in table 6.

The making of<embodiment 5 dispersible pigment dispersions (5) and colour filter >

Add 65 parts of zirconium oxide beads that are dissolved in 26.8 parts of solution that obtain of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) and 0.5mm by 1.5 parts of (5) 5 parts of modified pigments by obtaining in modification example 5 and Ajisper PB-821 (pigment dispersing agent that aginomoto fine chemistry Co., Ltd. manufactures) in the polyethylene wide-necked bottle, paint after wobbler (Japan essence machine Co., Ltd.) carries out disperseing in 2 hours, thereby remove zirconium oxide bead, obtain dispersible pigment dispersion (5).Pass through dispersator, 13.5 parts of 75.00 parts of dispersible pigment dispersions and 5.50 parts of polyester acrylate resins (ARONIX M7100, East Asia synthetic chemical industry Co., Ltd. manufacture), 5.00 parts of dipentaerythritol acrylates (KAYARADDPHA, Nippon Kayaku K. K manufacture), 1.00 parts of benzophenone (KAYACURE BP-100, Nippon Kayaku K. K manufacture), UCAResterEFP are stirred, strainer by aperture 1.0 μ m is filtered, and obtains colo(u)rant dispersion resist (colored resist).On the 1mm heavy sheet glass, use the spin coater coating pigment to disperse resist, so that utilize spectrophotometer MCPD-3000 that great mound electronics (strain) manufactures, by the colour examining of C2 light source, calculate tristimulus coordinates x value for x=0.64, thereafter dry 5 minutes of 60 ℃ of preparations and formation is filmed.Then after photomask carries out UV-induced pattern exposure, after unexposed portion is cleaned in 0.5% aqueous sodium carbonate, clean with pure water again, then by the filming 230 ℃ of heat treated 15 minutes and cured coating film of gained, thereby form colour filter.The viscosity of the dispersible pigment dispersion so obtained (5) and the briliancy of color filter pixel section, contrast gradient are estimated by following method, and are recorded in table 6.

The making of<embodiment 6 dispersible pigment dispersions (6) and colour filter >

Add 65 parts of zirconium oxide beads that are dissolved in 26.8 parts of solution that obtain of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) and 0.5mm by 1.5 parts of (6) 5 parts of modified pigments by obtaining in modification example 6 and Ajisper PB-821 (pigment dispersing agent that aginomoto fine chemistry Co., Ltd. manufactures) in the polyethylene wide-necked bottle, paint after wobbler (Japan essence machine Co., Ltd.) carries out disperseing in 2 hours, thereby remove zirconium oxide bead, obtain dispersible pigment dispersion (6).Pass through dispersator, 13.5 parts of 75.00 parts of dispersible pigment dispersions and 5.50 parts of polyester acrylate resins (ARONIX M7100, East Asia synthetic chemical industry Co., Ltd. manufacture), 5.00 parts of dipentaerythritol acrylates (KAYARADDPHA, Nippon Kayaku K. K manufacture), 1.00 parts of benzophenone (KAYACURE BP-100, Nippon Kayaku K. K manufacture), UCAResterEFP are stirred, strainer by aperture 1.0 μ m is filtered, and obtains colo(u)rant dispersion resist (colored resist).On the 1mm heavy sheet glass, use the spin coater coating pigment to disperse resist, so that utilize spectrophotometer MCPD-3000 that great mound electronics (strain) manufactures, by the colour examining of C2 light source, calculate tristimulus coordinates x value for x=0.45, thereafter dry 5 minutes of 60 ℃ of preparations and formation is filmed.Then after photomask carries out UV-induced pattern exposure, after unexposed portion is cleaned in 0.5% aqueous sodium carbonate, clean with pure water again, then by the filming 230 ℃ of heat treated 15 minutes and cured coating film of gained, thereby form colour filter.The viscosity of the dispersible pigment dispersion so obtained (6) and the briliancy of color filter pixel section, contrast gradient are estimated by following method, and are recorded in table 6.

Except change like that modified pigment (1) according to table 7, by method similarly to Example 1, carry out colo(u)rant dispersion, application, evaluation.

Except change like that modified pigment (4) according to table 7, by method similarly to Example 4, carry out colo(u)rant dispersion, application, evaluation.

Except change like that modified pigment (5) according to table 7, by method similarly to Example 5, carry out colo(u)rant dispersion, application, evaluation.

Except change like that modified pigment (6) according to table 7, by method similarly to Example 6, carry out colo(u)rant dispersion, application, evaluation.

Table 6

Table 6	Pigment	The viscosity of dispersion liquid (mPas)	Briliancy	Contrast gradient
					Embodiment 1	Modified pigment (1)	7.9	61.1	7700
Embodiment 2	Modified pigment (2)	8.1	61.2	7800
					Embodiment 3	Modified pigment (3)	8.0	61.0	8100
Embodiment 4	Modified pigment (4)	8.9	23.8	1500
					Embodiment 5	Modified pigment (5)	7.8	12.0	5300
Embodiment 6	Modified pigment (6)	8.0	88.0	5000
					Embodiment 7	Modified pigment (7)	15.5	60.9	8000
Embodiment 8	Modified pigment (8)	13.4	61.1	8100
					Embodiment 9	Modified pigment (9)	7.8	61.2	7800
Embodiment 10	Modified pigment (10)	8.2	60.9	7600

Table 7

Table 7	Pigment	The viscosity of dispersion liquid (mPas)	Briliancy	Contrast gradient
					Embodiment 11	Modified pigment (11)	16.0	61.0	8000
Embodiment 12	Modified pigment (12)	13.7	61.1	8100
					Embodiment 13	Modified pigment (13)	8.2	60.9	8200
Embodiment 14	Modified pigment (14)	8.1	61.1	7800
					Embodiment 15	Modified pigment (15)	8.0	61.0	8200
Embodiment 16	Modified pigment (16)	8.5	61.0	7600
					Embodiment 17	Modified pigment (17)	7.9	61.0	7700
Embodiment 18	Modified pigment (18)	7.9	61.0	7550
					Embodiment 19	Modified pigment (19)	7.8	61.1	8000
Embodiment 20	Modified pigment (20)	7.9	61.2	7900
					Embodiment 21	Modified pigment (21)	8.0	61.0	7700
Comparative example 1	C.I. Pigment green 58	7.0	61.0	7000
					Comparative example 2	C.I. Pigment red 254	8.7	23.5	1300
Comparative example 3	C.I. pigment Blue 15: 6	6.8	11.9	4800
					Comparative example 4	C.I. Pigment Yellow 73 150	7.4	87.6	4500
Comparative example 5	Compare modified pigment (1)	8.1	61.0	7500

(mensuration of length of delay)

Measure the length of delay of the colour filter of gained in embodiment 19～21.With regard to length of delay, the input angle that the light splitting ellipsometer " M-2000X " that uses J.A.Woollam company to manufacture is measured this color filter pixel section is wavelength amplitude ψ and the phase difference between 245～1000nm of 0 degree and 45 while spending.Length of delay Rth while calculating 550nm, record is converted into the value of thickness 2 μ m.

Table 8

Table 8	Pigment	Length of delay (Rth/2 μ m)
			Embodiment 19	Modified pigment (19)	-9.2
Embodiment 20	Modified pigment (20)	-7.0
			Embodiment 21	Modified pigment (21)	-10.3
Comparative example 1	C.I. Pigment green 58	-0.2

From above result, used the briliancy, contrast gradient of the color filter pixel section of modified pigment (1)～(21) than comparative example 1～4 height that has used unmodified pigment.In addition, comparative example 5 is to have used pigment C.I. Pigment green 58 similarly to Example 1 and used the polymkeric substance that contains the polymerizability unsaturated group that the dissolves in non-aqueous solvent example as modified pigment, but the colour filter of embodiment 1 has higher contrast gradient.

In addition, use the colour filter of modified pigment (19)～(21) to compare with the comparative example 1 that has used unmodified pigment, can greatly reduce length of delay.

Claims

1. a pigment dispersing composition for color filters, it is for containing tinting material, resin and the pigment dispersing composition for color filters that can dissolve the organic solvent of this resin, it is characterized in that, use modified pigment (D) as described tinting material, described modified pigment (D) is to have the modified pigment of modified polyamine (B) and polymkeric substance (P) on pigment (A) surface, described modified polyamine (B) reacts and forms by the amino that makes to have the ethylenic copolymer (B-1) that can react with amino the functional group that forms amido linkage and a polyamine at an end, described polymkeric substance (P) dissolves in non-aqueous solvent by least one and becomes polymerizability unsaturated monomer (C) polymerization of insoluble or indissoluble and obtain after polymerization, described polyamine is for selecting free PAH, at least one in the group that polyvinylamine and polymine form.

2. pigment dispersing composition for color filters as claimed in claim 1, wherein, described polyamine is PAH.

3. pigment dispersing composition for color filters as claimed in claim 1 or 2, wherein, described pigment (A) is C.I. Pigment green 58.

4. a colour filter, is characterized in that, right to use requires 1～3 the described pigment dispersing composition for color filters of any one.