CN102031015A

CN102031015A - Pigment particle dispersion, light-cured composition using same, color filter, and method of making pigment particle dispersion

Info

Publication number: CN102031015A
Application number: CN2010102942983A
Authority: CN
Inventors: 神田博美; 佐佐木大辅; 中平真一
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2009-09-24
Filing date: 2010-09-21
Publication date: 2011-04-27
Also published as: JP2011089109A; KR20110033044A; TW201127910A; JP5739126B2

Abstract

The invention discloses a pigment particle dispersion whereof the particle is characterized by small grain diameter and pointed particle size distribution peak. The pigment particle dispersion herein is especially applicable to serving as pigment for color filter, can explicitly increase contrast, and displays efficient dispersion. The pigment particle dispersion herein comprises pigment particles and a compound expressed by the following general formula (1) whereof X1 and X2 each independently represents hydrogen atom, halogen atom, alkyl in replacement or non-replacement, or aromatic group in replacement or non-replacement; R 1 and R2 each independently represents hydrogen atom, or alkyl in replacement or non-replacement; wherein at least one of R1 and R2 represents alkyl in replacement or non-replacement with a carbon atomicity of 2. The general formula (1).

Description

The manufacture method of pigment particle dispersion, the Photocurable composition that uses it, colour filter and pigment particle dispersion

Technical field

The present invention relates to be particularly suitable as the manufacture method of pigment particle dispersion, the Photocurable composition that uses it, colour filter and pigment particle dispersion of purposes of the colorant of colour filter etc.

Background technology

For colour filter, require high-performance and high-quality, attempting the improvement of the pigment dyestuff of use in its making.Specifically, in the modulation of pigment dispersion, need its storage stability excellence, used the contrast gradient excellence of filming etc. of the colour filter colored pixels portion of pigment dispersion.In order to satisfy these needs, for example effectively carried out the scope of pigment particles small-sized to 10～100nm and made the research of its decentralized stabilization.Thus, can utilize by making nano-scale the action effect of finding first, and might bring into play the new features that in the past do not reckon with effectively.Just much less the purposes of above-mentioned colour filter is for example also carrying out its research and development in coating, printing-ink, electrophoto-graphic toner, jetted ink etc.Particularly, for above-mentioned colour filter or jetted ink, efforts be made so that the high performance of having used the precision chemical technology, and expect its achievement.

Here, dispersing method for pigment dyestuff, although various polishings such as microballon polishing or salt mill method (the broken method of grinding) or liquid phase method etc. are arranged, but consider that reaching nano level needs too much labour and time etc., in above-mentioned polishing, with pigment dyestuff miniaturization and be dispersed in the composition and be and unpractiaca (referring to Patent Document 1) fully.And inevitably sneaking into of abrasive substance also is difficult to avoid.Liquid phase method is applicable to and obtains fine pigment particles, specifically, following method has been proposed, promptly, mixing in good solvent (the 1st solvent) and pigment solution that obtains and bad solvent (the 2nd solvent) and nanoparticle is separated out, and is added the macromolecular compound or the dispersing auxiliary (referring to Patent Document 2～5) of regulation with pigment dissolved.If consider the high-performance of particularly recently desired colorant as colour filter, then expectation makes the further exploitation that each characteristic improves.

[patent documentation 1] TOHKEMY 2007-31539 communique

[patent documentation 2] international WO2006/121016 brochure that discloses

[patent documentation 3] TOHKEMY 2004-43776 communique

[patent documentation 4] TOHKEMY 2007-119586 communique

[patent documentation 5] TOHKEMY 2009-84417 communique

Summary of the invention

The object of the present invention is to provide the pigment particle dispersion, use its Photocurable composition, colour filter and the good manufacture method of its efficient, the particle diameter of the pigment particle of this pigment particle dispersion is little, and the size-grade distribution peak is sharp-pointed, and be particularly suitable as the colorant that the colour filter that is used to demonstrate good dispersiveness is used, when using this pigment particle dispersion to form the pixel of colour filter, can improve its contrast gradient and each characteristic and make suitable property.

Above-mentioned problem solves by following means.

(1) a kind of pigment particle dispersion is characterized in that, it contains the compound of pigment particle and following general formula (1) expression,

General formula (1)

(in the formula, X ¹And X ²Represent hydrogen atom, halogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aromatic group independently of one another; R ¹And R ²Represent hydrogen atom or replacement or unsubstituted alkyl independently of one another; Wherein, R ¹And R ²In one of at least be to replace or unsubstituted carbonatoms is a alkyl more than 2.)

(2) according to the pigment particle dispersion of (1) record, it is characterized in that, be mixed with the compound of above-mentioned general formula (1) expression in the above-mentioned pigment particle.

(3) the pigment particle dispersion of putting down in writing according to (1) or (2), it is characterized in that above-mentioned pigment particle is to mix with the medium that is bad solvent by the lysate that the common dissolving of compound with above-mentioned pigment and above-mentioned general formula (1) expression obtains to generate with respect to this lysate.

(4) according to the pigment particle dispersion of each record in (1)～(3), it is characterized in that above-mentioned R ¹And R ²In one of at least be substituting group with any one expression in the following general formula (R-1)～(R-4),

(in the above-mentioned general formula, Q ¹Expression alkyl or aromatic group; Q ²Expression annular aliphatic or aromatic group; Q ³Expression alkyl or aromatic group; Q4 represents aromatic group; P represents integer; * represent bonding position with nitrogen-atoms.)

(5) according to the pigment particle dispersion of each record in (1)～(4), it is characterized in that above-mentioned X ¹And X ²Be that hydrogen atom, chlorine atom, phenyl or carbonatoms are 1～4 alkyl independently of one another.

(6) according to the pigment particle dispersion of each record in (1)～(5), it is characterized in that above-mentioned pigment is the pyrrolopyrrole derovatives.

(7) according to the pigment particle dispersion of each record in (1)～(6), it is characterized in that it further contains the dispersion agent with polycaprolactone structure.

(8) the pigment particle dispersion of each record in basis (1)～(7), it is characterized in that, it further contains macromolecular compound, this macromolecular compound comprise be selected from following general formula (I) and (II) in the repeating unit of any one expression at least a repeating unit

(above-mentioned general formula (I) and (II) in, R ¹¹～R ¹⁶The organic group of representing hydrogen atom or 1 valency independently of one another; X ¹¹And X ¹²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene; L ¹And L ²Organic binding group of representing singly-bound or divalent independently of one another; A ¹And A ²The organic group of representing 1 valency independently of one another; M and n represent 2～8 integer independently of one another; P and q represent 1～100 integer independently of one another.)

(9) according to the pigment particle dispersion of each record in (1)～(8), it is the colour filter colorant.

(10) a kind of Photocurable composition, it contains dispersion, polymerizable compound and the Photoepolymerizationinitiater initiater of each record in (1)～(9).

(11) a kind of colour filter, the pixel that it has is solidified to form (10) middle Photocurable composition of putting down in writing.

(12) a kind of manufacture method of pigment particle dispersion, it is characterized in that, modulation makes the lysate of pigment dissolved in good solvent, and with this lysate be bad solvent with respect to above-mentioned pigment and mix with medium that good solvent mixes, when above-mentioned pigment particle was generated, it was under the coexistence of the compound of following general formula (1) expression described pigment particle to be generated.

General formula (1)

The particle diameter of the particulate that pigment particle dispersion of the present invention is contained is little, and the size-grade distribution peak is sharp-pointed, and be particularly suitable as the colorant that the colour filter that is used to demonstrate good dispersiveness (character that is difficult to secondary aggregation) is used, when using its pixel that forms colour filter, given play to and to have improved its contrast gradient and thermotolerance and demonstrate these excellent action effects of good development.

And, use the colour filter of above-mentioned pigment particle dispersion making, the colour filter of particularly making to realize extremely high contrast gradient by the Photocurable composition that has used above-mentioned pigment particle dispersion, and demonstrate good development, and can bring into play high heat resistance.

Moreover manufacturing method according to the invention can be made the pigment particle dispersion of above-mentioned excellence effectively, and can suitably tackle plant-scale production.

Embodiment

Pigment particle dispersion of the present invention is characterised in that it contains the compound of pigment particle and above-mentioned general formula (1) expression.Both are not particularly limited by the coexisting state in dispersion, preferably by coprecipitation method described later pigment particle are dispersed in the medium with the state that is mixed with above-claimed cpd.

According to an embodiment of the invention, the compound of general formula (1) expression has the parent nucleus of pyrrolopyrrole diketone, therefore, when carrying out crystalline growth by gathering (buildup) method, pigment when generating, above-mentioned parent nucleus is attached together with pigment molecule strongly by stronger interaction.It is believed that, at this moment, on the parent nucleus of above-mentioned pyrrolopyrrole diketone, import distinctive substituent R ¹And R ², on the other hand, import sulfonic group as required, therefore can suppress the crystalline growth of pigment molecule with suitable degree.It is believed that, can form the fine pigment of desirable particle diameter thus, for example, when using this dispersion to make colour filter, can realize extremely high contrast gradient.

And, according to an embodiment of the invention, the compound of above-mentioned general formula (1) expression is brought into play the effect of synergistic agent (synergist) effectively and is attached together strongly with pigment, has the effect that suppresses the cohesion between the pigment thus, demonstrate the distillation of the pigment self that inhibition causes because of thermal conductance or the effect of cohesion, for example can improve thermotolerance or quality in the pixel of colour filter.

[compound of general formula (1) expression]

General formula (1)

In the above-mentioned general formula (1), X ¹And X ²Represent hydrogen atom, halogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aromatic group independently of one another.R ¹And R ²Represent hydrogen atom or replacement or unsubstituted alkyl independently of one another.Wherein, R ¹And R ²In one of at least expression replace or unsubstituted carbonatoms is a alkyl more than 2.

At X ¹And X ²In, as halogen atom, can list fluorine atom, chlorine atom, bromine atoms, iodine atom, be preferably the chlorine atom.

At X ¹And X ²In, alkyl is that carbonatoms is preferably 1～6, more preferably 1～4 alkyl, can be in straight chain shape, chain, the ring-type any.As concrete group, for example can list methyl, butyl, the tertiary butyl, be preferably methyl.

When alkyl has substituting group,, can list hydroxyl, alkoxyl group, alkyl-carbonyl, alkyl carbonyl oxy, aromatic group as substituting group.

At X ¹And X ²In, as aromatic group, can list phenyl, naphthyl, xenyl, be preferably phenyl.

When aromatic group has substituting group,, can list hydroxyl, alkoxyl group, alkyl-carbonyl, alkyl carbonyl oxy, aromatic group as substituting group.

X ¹And X ²Be preferably hydrogen atom, chlorine atom, methyl, the tertiary butyl, phenyl, more preferably hydrogen atom, chlorine atom.X ¹With X ²Can be the same or different, but be preferably identical group.

At R ¹And R ²In, alkyl is that carbonatoms is preferably 2～10, more preferably 2～5 alkyl, can be in straight chain shape, chain, the ring-type any.As concrete group, for example can list ethyl, propyl group, butyl, amyl group, hexyl, sec.-propyl, isobutyl-, be preferably ethyl, propyl group, amyl group.R ¹And R ²Both all are not methyl.

When alkyl has substituting group; as substituting group; can list halogen atom; alkenyl (comprises cycloalkenyl; bicyclic alkenyl); aryl; heterocyclic radical; cyano group; hydroxyl; nitro; carboxyl; alkoxyl group; aryloxy; silyl oxygen base; heterocyclic oxy group; acyloxy; formamyl oxygen base; alkoxyl group carbonyl oxygen base; aryloxy carbonyl oxygen base; amino (comprising anilino); amido; amino carbonyl amino; alkoxycarbonyl amino; aryloxycarbonyl amino; sulfamyl amino; alkyl sulfonyl-amino and arlysulfonylamino; sulfydryl; alkylthio; arylthio; the heterocycle sulfenyl; sulfamyl; sulfo group; alkyl sulfinyl and aryl sulfinyl; alkyl sulphonyl and aryl sulfonyl; acyl group; aryloxycarbonyl; alkoxy carbonyl; formamyl; arylazo base and heterocycle azo base; imide; phosphino-; phosphinyl; phosphinyl oxygen base; phosphinyl amino; silyl is preferably halogen atom; aryl; heterocyclic radical; cyano group; carboxyl; alkoxyl group; aryloxy; acyloxy; formamyl oxygen base; alkoxyl group carbonyl oxygen base; aryloxy carbonyl oxygen base; amino (comprising anilino); amido; amino carbonyl amino; alkoxycarbonyl amino; aryloxycarbonyl amino; sulfamyl amino; alkyl sulfonyl-amino and arlysulfonylamino; alkylthio; arylthio; the heterocycle sulfenyl; sulfamyl; alkyl sulfinyl and aryl sulfinyl; alkyl sulphonyl and aryl sulfonyl; acyl group; aryloxycarbonyl; alkoxy carbonyl; formamyl; arylazo base and heterocycle azo base; imide or their combination.

As the substituting group of alkyl, be preferably aryl, heterocyclic radical, cyano group, carboxyl, alkoxyl group, aryloxy, acyloxy, formamyl oxygen base, amino (comprising anilino), amido, sulfamyl amino, alkyl sulfonyl-amino and arlysulfonylamino, sulfamyl, acyl group base, aryloxycarbonyl, alkoxy carbonyl, formamyl, imide or their combination especially.

R ¹And R ²Be preferably the substituting group of any one expression in the above-mentioned general formula (R-1)～(R-4).Be preferably the substituting group of any one expression in the general formula (R-2)～(R-4) especially.

In the formula:

Q ¹Be alkyl or aromatic group (comprising aryl).Be preferably ethyl, hexyl, cyclohexyl, 2-ethylhexyl, phenyl, naphthyl, xenyl, more preferably ethyl, cyclohexyl, phenyl, naphthyl are preferably phenyl especially.

Q ²Be cyclic aliphatic group or aromatic group (comprising aryl).Be preferably cyclohexyl, norbornene, phenyl, naphthyl, two pyridyl, pyridyl, quino-base, more preferably phenyl.

Q ³Be alkyl or aromatic group (comprising aryl).Be preferably methyl, ethyl, propyl group, sec.-propyl, amyl group, hexyl, phenyl, naphthyl, anthryl, pyridyl, quino-base, more preferably ethyl, propyl group, phenyl.

Q ⁴It is aromatic group (comprising aryl).Be preferably phenyl, naphthyl, anthryl, xenyl, pyridyl, quino-base, carbazyl, more preferably phenyl, naphthyl, pyridyl are preferably phenyl especially.

Alkyl, aromatic series and narrate previously identical.P represents integer, is preferably 1～3.

Below, enumerate R ¹And R ²Concrete example.* be meant bonding position.

Below enumerate the concrete example of the compound of general formula (1) expression, but the present invention is not explained limitedly by it.

In pigment particle dispersion of the present invention, the content of the compound of above-mentioned general formula (1) expression is not particularly limited, and with respect to pigment 100 mass parts, is preferably 0.1～100 mass parts, more preferably 1～50 mass parts.By being set at more than the above-mentioned lower value, can suppress the crystalline growth of pigment molecule effectively, and, by being set at below the above-mentioned higher limit tone of the color pigments of can remaining valid.

In an embodiment of the invention, in the generative process of above-mentioned pigment particle, preferably do not use other additive ground to carry out.Particularly, by reducing the amount of additive, can make pigment abundanter according to the relation of the total amount that is allowed with constituent (solids component) in colour filter.Recently, the requirement of colour filter that color depth is high or raising optical concentration (OD value) is improving always, according to a preferred embodiment of the invention, can improve the concentration of coloring components as described above, is favourable therefore.

The compound of above-mentioned general formula (1) expression can synthesize by ordinary method, for example can be with reference to Japanese kokai publication sho 60-35056 communique (though disclose the compound that general formula (1) is comprised in this communique, but it uses as the dyestuff at the macromolecular material of stipulating, does not have the combination of open and pigment particle.)。In embodiment described later, represent its synthesis example in detail.

In addition, in the record of the group in this specification sheets, replacement of note do and unsubstituted record are not meant, comprise not having substituent situation and have substituent situation.For example " alkyl " this record not only comprises not having substituent alkyl (not substituted alkyl), but also comprises having substituent alkyl (substituted alkyl).

[pigment dyestuff]

Pigment dyestuff does not limit aspect tone, for example can Lie Ju Chu perylene, purple cyclic ketones, quinoline a word used for translation ketone, quinoline a word used for translation ketone quinone, anthraquinone, anthracene form anthrone, benzoglyoxaline alkane ketone, disazo condensation, tetrazo, azo, indanthrone, phthalocyanine, triaryl carbon

, two

Piperazine, aminoanthraquinone, pyrrolopyrrole diketone (being also referred to as diketopyrrolo-pyrrole), thioindigo, isoindoline, isoindolone, pyrene anthrone, iso-violanthrone pigment or their mixture etc.In the present invention, also the sosoloid combination back of above-mentioned pigment dyestuff or pigment dyestuff can be used.And, can form with the combination of other compound after matrix material.

In the present invention, especially preferably use pyrrolopyrrole diketone pigment.Be the absorption region that the pyrrolopyrrole dione compounds pigment of representative has the purity of color that is fit to improve the red pixel that constitutes colour filter with C.I.P.R.254, and can enlarge the color reproduction zone, so attempting the utilization in this colour filter.But, for for example migrating ink for inking or utilize chemical paste (acid paste) method, microballon to disperse or the resulting pigment of method of salt mill method etc., it is difficult to tackle the requirement to purity of color and contrast gradient etc., and is difficult to obtain fully good colour filter.To this, according to a preferred embodiment of the invention, can under the sharp-pointed state of size distribution, generate the pyrrolopyrrole dione compounds pigment particle of nano-scale.And, when the dispersion thing of this pigment particle is used for the manufacturing of colour filter, can take into account desirable purity of color and high-contrast.And, the liquid crystal watch showing device that possesses this colour filter the dense degree of black (? まり) and the red power of describing aspect excellence, can suppress to show inequality.

In the above-mentioned pyrrolopyrrole dione compounds pigment, preferred especially C.I.P.R.254 (compound of following formula (Z) expression), 255 (compounds of following formula (W) expression), 264 (compounds that following formula V is represented), from the viewpoint of absorption spectrum, C.I.P.R.254 is preferred.In addition, as C.I.P.R.254, can use commercially available all those such as Irgaphor Red B-CF, Irgaphor Red BT-CF, CromophtalDPP Red BO, Irgazin DPP Red BO, Microlen DPP RED BP (be trade(brand)name, Ciba Specialty Chemicals company makes).As C.I.P.R.255, can use Cromophtal Coral Red C, Irgazin DPP Red 5G (being trade(brand)name, the manufacturing of CibaSpecialty Chemicals company) etc.As C.I.P.R.264, can use Irgazin DPPRubin TR (trade(brand)name, Ciba Specialty Chemicals company make) etc.

Formula (Z)

Formula (W)

Formula V

In pigment particle dispersion of the present invention, the content of pigment particle is not particularly limited, and when being considered as the colorant that colour filter uses, its concentration that contains in the pigment particle dispersion is preferably 1～40 quality %, more preferably 5～20 quality %.

[reprecipitation method]

In pigment particle dispersion of the present invention, the organic pigment particles that wherein contains preferably obtains by following method, promptly, the lysate of the pigment dyestuff that obtains organic materials being dissolved in good solvent (following the 1st solvent that is referred to as sometimes) and have intermiscibility with above-mentioned good solvent and be that the solvent of bad solvent (following the 2nd solvent that is referred to as sometimes) mixes with respect to pigment dyestuff generates organic pigment particles thus.Below, also this method is called " reprecipitation method " sometimes, also the dispersion liquid that contains organic pigment particles that obtains this moment is called " pigment redeposition liquid " sometimes.Moreover, especially distinguish mutually for the method for carrying out reprecipitation method after the common dissolving of compound and dispersion agent that will in the lysate of above-mentioned pigment dyestuff, make above-mentioned general formula (1) expression with reprecipitation method, sometimes it is called especially " coprecipitation method ".

1, bad solvent

At first, the bad solvent to pigment dyestuff describes.Bad solvent is so long as mix or can mix equably and get final product with the good solvent of dissolving pigment dyestuff, and there is no particular limitation.As bad solvent, the solubleness of pigment dyestuff is preferably below the 0.02 quality %, more preferably below the 0.01 quality %.For the solubleness of pigment dyestuff in bad solvent, there is not special lower limit, if but consider normally used pigment dyestuff, actual lower limit is more than the 0.000001 quality %.This solubleness can be the solubleness in the presence of acid or alkali, and particularly, when being the pigment kind of solubleness noticeable change along with hydrogen ion concentration (pH), it is preferred that acid or alkali are mixed with suitable bad solvent that the back uses.

Good solvent is preferably more than the 30 quality % with respect to the meltage of bad solvent, more preferably more than the 50 quality %.Good solvent does not have the special upper limit with respect to the meltage of bad solvent, in the reality with mixed arbitrarily.

As bad solvent, can list aqueous vehicles (for example water or hydrochloric acid, aqueous sodium hydroxide solution), the alkylol cpd solvent, the ketone compound solvent, the ether compound solvent, the aromatics solvent, the dithiocarbonic anhydride solvent, the fatty compounds solvent, the nitrile compound solvent, the halogen compounds solvent, the ester cpds solvent, ionic liquid, their mixed solvent etc., be preferably aqueous vehicles, the alkylol cpd solvent, the ketone compound solvent, the ether compound solvent, ester cpds solvent or their mixture, more preferably aqueous vehicles, alkylol cpd solvent or ester cpds solvent.

As the alkylol cpd solvent, can list for example methyl alcohol, ethanol, Virahol, n-propyl alcohol, 1-methoxyl group-2-propyl alcohol etc.As the ketone compound solvent, can list for example acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone.As the ether compound solvent, can list for example dimethyl ether, Anaesthetie Ether, tetrahydrofuran (THF) etc.As the aromatics solvent, can list for example benzene, toluene etc.As the fatty compounds solvent, can list for example hexane etc.As the nitrile compound solvent, can list for example acetonitrile etc.As the halogen compounds solvent, can list for example methylene dichloride, trieline etc.As the ester cpds solvent, can list for example ethyl acetate, ethyl lactate, propylene glycol monomethyl ether (MMPGAc) etc.As ionic liquid, can list for example 1-butyl-3-Methylimidazole With salt of PF6-etc.

Bad solvent can will be multiple solvent mix the back and use, use after also can mixing good solvent according to system.But, in this case, must in can not hindering the scope with miniaturization, crystallization separated out of pigment particles, mix.

2, good solvent

Then, the good solvent to the dissolving pigment dyestuff describes.Good solvent can dissolve employed pigment, gets final product so long as mix or mixes equably with above-mentioned bad solvent, with regard to there is no particular limitation.The solubleness of pigment dyestuff in good solvent is preferably more than the 0.2 quality %, more preferably more than the 0.5 quality %.Solubleness does not have the special upper limit, if but consider common employed pigment dyestuff, then be below the 50 quality % in the reality.This solubleness also can be the solubleness in when dissolving in the presence of acid or alkali.The solubleness of bad solvent and good solvent or the preferred range of intermiscibility are described as described above.

As good solvent, for example can list aqueous vehicles (for example water or hydrochloric acid, aqueous sodium hydroxide solution), the alkylol cpd solvent, the amide compound solvent, the ketone compound solvent, the ether compound solvent, the aromatics solvent, the dithiocarbonic anhydride solvent, the fatty compounds solvent, the nitrile compound solvent, the sulfoxide compound solvent, the halogen compounds solvent, the ester cpds solvent, ionic liquid, their mixed solvent etc., preferred aqueous vehicles, the alkylol cpd solvent, the ketone compound solvent, the ether compound solvent, the sulfoxide compound solvent, the ester cpds solvent, amide compound solvent or their mixture, more preferably aqueous vehicles, the alkylol cpd solvent, the ester cpds solvent, sulfoxide compound solvent or amide compound solvent, further preferred aqueous vehicles, sulfoxide compound solvent or amide compound solvent, preferred especially sulfoxide compound solvent or amide compound solvent.

As the sulfoxide compound solvent, for example can list dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexa-methylene sulfoxide, tetramethylene sulfone etc.As the amide compound solvent, for example can list N, dinethylformamide, 1-Methyl-2-Pyrrolidone (pyrrolidon), 2-Pyrrolidone (pyrrolidinone), 1,3-dimethyl-2-imidazolone, 2-Pyrrolidone, ε-Ji Neixianan, methane amide, N-methylformamide, ethanamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl propanamide, HMPA etc.

And, for pigment dyestuff being dissolved in the good solvent and the concentration of the pigment dyestuff solution that obtains, preferably under the condition when dissolving pigment dyestuff with respect to about 1/100 scope of saturation concentration～this saturation concentration of good solvent.Modulation condition to pigment dyestuff solution is not particularly limited, and can select to the scope of subcritical, super critical condition at normal pressure.Temperature under the preferred normal pressure is-10～150 ℃, more preferably-5～130 ℃, is preferably 0～100 ℃ especially.

Pigment dyestuff among the present invention also can be with acid or alkalescence dissolving in good solvent.In general, under intramolecularly has situation at pigment that can dissociated group under the alkalescence, dissolve with alkalescence; There is not under the alkalescence dissociated group and when intramolecularly has the nitrogen-atoms of the easy addition of proton morely, with acidic leach.For example quinoline a word used for translation ketone, pyrrolopyrrole diketone, disazo condensation compound pigment are that phthalocyanine compound pigment is with acidic leach with the alkalescence dissolving.

Employed alkali when dissolving with alkalescence has mineral alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or hydrated barta, or organic bases such as trialkylamine, diazabicyclo hendecene (DBU), metal alkoxide, but is preferably organic bases.The amount of employed alkali be can uniform dissolution pigment amount, there is no particular limitation, but when being mineral alkali, be 1.0～30 molar equivalents with respect to pigment dyestuff preferably, more preferably 1.0～25 molar equivalents, more preferably 1.0～20 molar equivalents.When being organic bases, be 1.0～100 molar equivalents preferably with respect to pigment dyestuff, more preferably 1.0～50 molar equivalents, more preferably 1.0～20 molar equivalents.

Employed acid as with acidic leach the time has mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, perhaps organic acids such as acetate, trifluoroacetic acid, oxalic acid, methylsulfonic acid or trifluoromethanesulfonic acid, but be preferably mineral acid.Be preferably sulfuric acid especially.The amount of employed acid be can the uniform dissolution pigment dyestuff amount, there is no particular limitation, but compare with alkali, usually excessively uses.No matter being mineral acid or organic acid, is 3～500 molar equivalents with respect to pigment dyestuff preferably, more preferably 10～500 molar equivalents, more preferably 30～200 molar equivalents.

When with alkali or acid mixes with organic solvent and when using as the good solvent of pigment dyestuff, dissolve fully in order to make alkali or acid, can also in organic solvent, add a little water or lower alcohol etc. with respect to alkali or sour solvent with high-dissolvability.The amount of water or lower alcohol is below the 50 quality % with respect to pigment dyestuff solution total amount preferably, more preferably below the 30 quality %.Particularly, can make water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols etc.

3, mixing condition

When organic filler is made, be about to that organic filler is separated out, the working conditions of the bad solvent when forming, be not particularly limited, can to the scope of subcritical, super critical condition, select at normal pressure.Temperature under the normal pressure be preferably-30～100 ℃, more preferably-10～60 ℃, be preferably 0～30 ℃ especially.

The ratio of mixture of pigment solution and bad solvent (the good solvent in the redeposition liquid/bad solvent than) is preferably 1/50～1/1 in volume ratio, and more preferably 1/40～1/1, be preferably 1/10～1/1 especially.Its volume flow ratio with pigment solution in the stream of movable reactor and bad solvent can be identical, also can be different.For example ratio of mixture is set at 1/2 o'clock,, can lists following method as concrete example.

(I) volume flow ratio with good solvent and bad solvent is made as 1/2.

(II) use the solvent A that in bad solvent, obtains with the good solvent of mixed of (volume ratio of good solvent/bad solvent)=(1/4) in advance, the volume flow ratio of pigment solution and solvent A is made as 1/5.At this moment, the good solvent in the pigment solution and the amount of the good solvent addition among the solvent A are 1+1=2, and the bad solvent amount among the solvent A is 4, and the final ratio of mixture of therefore good solvent and bad solvent is 1/2.

Pigment concentration in the pigment redeposition liquid so long as can generate pigment particles, just is not particularly limited, but with respect to redeposition liquid 1000ml, pigment particles is the scope of 10～40000mg, and the scope of 20～30000mg more preferably is preferably the scope of 40～25000mg especially.

In the present invention, preferably promptly carry out the mixing of pigment solution and bad solvent, be preferably promotion blended means in this part especially.As one of its method, can consider by the mixing field turbulent flowization is promoted the blended gimmick, for example, it is collided in narrow space at the dirty high speed fluid of crossing of the state of convection current.But hybrid mode is not limited to the turbulent flow domination down, also can consider following gimmick, promptly, for example shown in the TOHKEMY 2006-104448 communique like that, the intersection point of the stream by forming Y-shaped contacts with each other fluid under laminar flow regime, and realizes mixing by molecular diffusion.For example when being as shown in Figure 1 reactor, can take to utilize streamlined hybrid mode thus by flowing through pigment solution, flow through bad solvent with low discharge with low discharge from stream 12 and 16 from stream 13,14 and 15.

In the present invention, judge that the fluidic flow state is that turbulent flow or laminar flow are to be undertaken by the pipe Reynolds number.That is, will manage characteristic length (be called in the present invention and represent diameter) and be made as D[m], the linear flow speed of liquid of circulation is made as u[m/s] (definition aftermentioned), density of liquid and viscosity are made as ρ [kg/m respectively ³], during η [Pas], pipe reynolds number Re [-] defines by Re=Du ρ/η.In the present invention, be that state more than 1000 is made as turbulent flow, is to be made as transitional region, Re is made as laminar flow for the state less than 100 more than 100 and less than 1000 state with Re with Re.

The characteristic length D of following formula refers to that when being cylindrical duct, characteristic length D is its diameter, when being not cylindrical duct, defines by following formula to the rerum natura of the mobile pipe that exerts an influence most in managing.

D＝4A/P

Wherein, A[m ²] be sectional area, the P[m of stream] be length (wetted perimeter) in stream inner fluid and the contacted part of tube wall.

Use this D, and be defined as aforesaid linear flow speed u so following.

u＝Q/{(D/2) ²×π}

Wherein, Q is the fluidic volumetric flow rate [m that flows through the stream of definition wires flow velocity ³]

Cross-sectional shape after representative diameter when changing diameter or cross-sectional shape in stream way changes according to it is calculated, and represent diameter (representative diameter) to obtain the fast and Reynolds number of linear flow according to it and gets final product.

In addition, in the present invention, the flow state of mixing field is important, but the state of suitably measuring mixing field is difficult, and therefore, when satisfying 2 following conditions at the same time, then the condition estimating with mixing field be that turbulent flow is arranged.

(i) will mix pipe reynolds number Re before according to each mixed fluidic, the flow state in the stream that can be connected with mixing field at least can be considered to turbulent flow.

Pipe reynolds number Re after (ii) just having mixed according to mixed fluidic, the flow state after just having mixed can be considered to turbulent flow.

Form in the operation at above-mentioned particle, the median size of the pigment particles of separating out for making reaches desirable scope, preferably adjusts the representative diameter, flow of reactor etc.For the employed reactor of present embodiment, can increase the flow of each stream relatively, and, can think that the admixture of formed mixing field this moment is fit to the formation of pigment particles.Each raw material supplying of reactor is preferably 1～30m/s with the linear flow speed of pigment solution in the stream and bad solvent.

[dispersion agent that uses in the reprecipitation method]

In the present invention, make pigment dissolved when good solvent, pigment dispersing agent or pigment derivative can be dissolved together.In organic solvent, guarantee dispersed viewpoint from the repulsive interaction of the entropy repulsion that utilized molecular chain, preferably use macromolecule dispersing agent as dispersion agent.Use according to pigment derivative also can be carried out the modification of particle surface, particularly from improving and other the interaction force of dispersion agent or the viewpoint of control solvability of particle or crystallization crystal formation etc., also preferred compound or the pigment derivative different of using above-mentioned general formula (1) expression with it.

As operable dispersion agent, for example can use the low molecule or the macromolecule dispersing agent of anionic property, cationic, zwitter-ion, nonionic or pigment derivative.In addition, the molecular weight of macromolecule dispersing agent so long as can be dissolved in the solution equably gets final product, and can hard-corely use, preferred molecular weight is 1,000～2,000,000, more preferably 5,000～1,000,000, more preferably 10,000～500,000, be preferably 10 especially, 000～100,000.And, as macromolecule dispersing agent, can list among dispersant A described later and the B illustrated those etc.

As anionic property dispersion agent (anionic surfactant), can list N-acyl-N-alkyltaurate, soap, alkyl sulfuric ester salt, alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl sulfosuccinate succinate, alkyl phosphate salt, naphthalene sulfonic acidformaldehyde condensation product, polyxyethylated sulfuric acid etc.These anionic property dispersion agents can use separately also and can be used in combination more than 2 kinds.

Cationic dispersion agent (cationic surfactant) comprises the poly-glycol ether of quaternary ammonium salt, alkoxylate polyamines, fatty amine, fatty amine, by fatty amine and fatty alcohol deutero-diamines and polyamines, by the tetrahydroglyoxaline of fatty acid derived and the salt of their cationic material.These cationic dispersion agents can use separately also and can be used in combination more than 2 kinds.

The zwitter-ion dispersion agent be intramolecularly have simultaneously above-mentioned anionic property dispersion agent at anionic group that intramolecularly had part and cationic dispersion agent at cation group dispersion agent partly that intramolecularly had.As nonionic dispersion agent (nonionic surfactant), can list Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amine, glycerol fatty acid ester etc.These nonionic dispersion agents can use separately also and can be used in combination more than 2 kinds.

Pigment derivative type dispersion agent is defined as: from deriving as the pigment dyestuff of parent material and by its precursor structure being carried out the pigment derivative type dispersion agent that chemically modified is made, or the pigment derivative type dispersion agent that obtains by the pigmenting reaction through the pigment precursors of chemically modified.The pigment derivative type dispersion agent that contains sugar is for example arranged, the pigment derivative type dispersion agent that contains piperidyl, naphthalene or the perylene pigment derivative type dispersion agent of deriving, pigment derivative type dispersion agent with the functional group that is connected with the pigment matrix structure by methylene radical, be aggregated the pigment matrix structure that the thing chemistry is modified, has sulfonic pigment derivative type dispersion agent, pigment derivative type dispersion agent with sulfoamido, have the pigment derivative type dispersion agent of ether or have the carboxylic acid group, the pigment derivative type dispersion agent of carboxylic acid ester groups or carboxamide groups etc.

[pigment particle]

Particle diameter about particulate, have by the quantize method of the mean size that shows group of instrumentation method, but as the method for often using, the intermediate value footpath of the median that peaked mode footpath (modediameter) that expression distributes is arranged, is equivalent to integral distribution curve, various average diameter (number average, length is average, area is average, quality is average, volume averaging etc.) etc., in the present invention, short of special explanation, median size is meant number average diameter.The median size of the particulate in the dispersion of the present invention (primary particle) is preferably below the 100nm, more preferably below the 75nm, is preferably especially below the 50nm, is preferably below the 50nm especially.Particulate in the dispersion of the present invention can be this big or small monocrystalline or polycrystalline, aggregate, also can be the particulate that contains these monocrystalline or polycrystalline, aggregate.

As the index of the homogeneity (monodispersity) of representing particle, in the present invention, if not special explanation, the ratio (Mv/Mn) of use volume average particle size (Mv) and number average bead diameter (Mn).(in the present invention, monodispersity is meant the degree of particle diameter unanimity to the monodispersity of organic nano particle of the present invention (primary particle).), be that Mv/Mn is preferably 1.0～2.0, more preferably 1.0～1.8, be preferably 1.0～1.5 especially.

As the measuring method of the particle diameter of organic filler, can list microscopy, mass method, light scattering method, light blocking method, electrical resistance method, sound equipment method, dynamic light scattering method, be preferably microscopy, dynamic light scattering method especially.As the microscope that uses in the microscopy, for example can list scanning electron microscope, transmission electron microscope etc.As the particle assay device of dynamic light scattering method, for example can list day ダイ Na ミ Star Network light-scattering photometer DLS-7000 series (being trade(brand)name) of the Na ノトラ Star Network UPA-EX150, Da mound electronics corporation system of machine dress corporate system etc.In the present invention, about the value of particle diameter, if not special explanation is meant the value of measuring with the method that is adopted among the embodiment.

For the particulate in the dispersion liquid of the present invention, preferably the degree of crystallinity of the particulate in dispersion medium is more than 65%, and its degree of crystallinity is preferably 80～100%, more preferably 90～100%.The crystallite diameter of the particulate in the dispersion liquid of the present invention is not particularly limited, and is preferably 20～500 dusts, more preferably 20～200 dusts.

For particulate of the present invention, when particulate formed, preferably the compound of input above-mentioned general formula (1) expression was impregnated in (sneaking into) in particulate in system.At this moment, with respect to the quality (A) of the compound that is added, the ratio per-cent of the quality of being mixed in the particle (B) ((B)/(A) * 100) (followingly is called " incorporation efficiency " with this ratio sometimes.) be preferably more than the 10 quality %, more preferably more than the 20 quality %, be preferably especially more than the 30 quality %.Although there is not the upper limit of disperseing incorporation efficiency especially, the upper limit of calculating is 100 quality %, is below the 98 quality % in the reality.

(followingly sometimes this ratio is called " embedding rate " as the quality (X) of the above-mentioned compound that is mixed with respect to the per-cent ((X)/(Y) * 100) of the ratio of the quality (Y) of the pigment composition except that this compound in the particulate.), be preferably 5～200 quality % In, more preferably 8～160 quality %.

In addition, the state that is incorporated in the particulate of the compound of general formula (1) expression can be measured, estimate according to following.

(evaluation of mixing of compound)

Use solid ¹³C CP/MAS NMR measures (Block Le power one バイオスピ Application company makes AVANCE DSX-300 optical splitter and 4mm Ф HFX CP/MAS probe) and confirms whether specific compound is incorporated in the particle.Solid ¹³C CP/MAS NMR measures and can followingly carry out.

Use the membrane filter (cut-off size (cut size) that MILLIPORE makes: 0.05 μ m) attract to filter the pigment particle dispersion, make concentrating paste respectively.Above-mentioned concentrated paste is fixed to solid ¹³On the test portion platform of CCP/MAS NMR, based on Goldman-shen spike train, will ¹H90 ° of pulse be wide to be set at 4.5 μ s, will be used for waiting time that the solvent at initial stage selects is set at 200 μ s, CP is set at 1ms duration of contact, spin is changed in 0.5～200ms diffusion time, thereby measure.Cumulative number is 4096 times, with test portion ¹5 times of the H longitudinal relaxation time as benchmark, will be set at 3～10 seconds the repetition time.The rotating speed of evil spirit angle spin (Magic Angle Spinning) is set at 8000～10000Hz according to test portion.

Separate the peak area of calculating pigment and dispersion agent by the spectrogram in each spin diffusion hour is carried out the peak, supposed that the diffusion length L of one dimension diffusion model has L=1.1 (tm) with respect to spin tm diffusion time ^1/2Relation, use this relation, judge particle structure according to peak area with respect to marking on a map of distance from the solvent molecule.

[concentrating and redispersion]

1, dispersion concentrates

As the operation of removing of removing vehicle components the mixed solution after the pigment dyestuff particulate is separated out, there is no particular limitation, carries out filtering method, makes the sedimentation of pigment dyestuff particulate and spissated method etc. by centrifugation but for example can list by strainer etc.The filtering device of strainer for example can use decompression or the such device of pressure filtration.As preferred strainer, can list filter paper, nanofilter, microfilter etc.Separating centrifuge can use device arbitrarily so long as can make the sedimentation of water-insoluble compound particulate.For example can list except that general device, have the device of skimming aerosol function (attract the upper strata clear layer in the rotation, and be discharged to the outer function of system), the continuous centrifuge of continuously solid substance being discharged etc.As the centrifugation condition, be preferably 50～10000 in centrifugal force (expression has applied the value of several times the centrifugal acceleration that is equivalent to universal gravity constant), more preferably 100～8000, be preferably 150～6000 especially.Temperature during centrifugation depends on the solvent species of dispersion liquid, is preferably-10～80 ℃, more preferably-5～70 ℃, is preferably 0～60 ℃ especially.And, as the operation of removing of vehicle components, can also use by vacuum lyophilization make solvent distillation and spissated method, utilize heating or decompression make the dry and spissated method of solvent, with the method for these methods combinations etc.

2, redispersion

The pigment dyestuff particulate can be with for example dispersive state use in color spreading agent.Above-mentioned color spreading agent is meant, with coating, be the part that for liquid state the time, makes pigment dyestuff dispersive medium, comprise when aqueous and to combine with above-mentioned water-insoluble compound and make the part (tackiness agent) of solidifying and of filming the composition (organic solvent) of its dissolved dilution.In addition, in the present invention, the pigment dyestuff dispersion agent that uses in macromolecular compound that will use when particulate forms and/or the redispersion is generically and collectively referred to as tackiness agent.

The particulate loading of particulate after the redispersionization in dispersion can suitably determine that with respect to the dispersion total amount, preferred particulate is 2～30 quality % according to purpose, and more preferably 4～20 quality % are preferably 5～15 quality % especially.When in above-mentioned such color spreading agent, disperseing, the amount of tackiness agent and dissolved dilution composition can determine that suitably with respect to the dispersion total amount, tackiness agent is preferably 1～30 quality % according to the kind of water-insoluble compound etc., more preferably 3～20 quality % are preferably 5～15 quality % especially.The dissolved dilution composition is preferably 5～80 quality %, more preferably 10～70 quality %.

Can with pigment dyestuff particulate redispersion in the organic solvent identical as the employed solvent of bad solvent liquid in, also can add other dispersion agent etc., the state of aggregation that preferably has a pigment dyestuff particulate in the organic solvent identical with bad solvent is spontaneously untied and is dispersed in character in the medium, will have this character and be called " can from disperseing " or " having from dispersed ".But in the present invention,, when the redispersion of particulate, also can add pigment dispersing agent etc. in order further to improve redispersibility.From this viewpoint, divide into the cohesion (aggregate) that is difficult to redispersion and redispersible soft cohesion (agglomerate) sometimes.

Carry out the method for redispersion as the particulate that will be in so soft state of aggregation (agglomerate), for example can list the method for utilizing hyperacoustic dispersing method or applying physical energy of using.Operable ultrasonic irradiation device preferably has can apply the above hyperacoustic function of 10kHz, for example can list ultrasonic homogenizer, sono-cleaner etc.If the liquid temperature rises in ultrasonic irradiation, then therefore nanoparticle generation heat-coagulation preferably is set at 1～100 ℃ with the liquid temperature, more preferably 5～60 ℃.The temperature controlling method can be carried out temperature control of temperature controlled temperature adjustment layer etc. by the dispersion liquid temperature controlling, to dispersion liquid and be carried out.Employed dispersion machine when applying physical energy the pigment nanoparticle is disperseed, have no particular limits, for example can list dispersion machines such as kneader, roller mill, attritor, super grinding machine (supermill), dissolver, intimate mixing machine, sand mill.In addition, the dispersing method of high pressure dispersion method or use fine particle microballon also can be used as preferable methods and enumerates.

[macromolecule dispersing agent]

In the present invention, preferably to removing by the vehicle components in the water system of the synthetic dispersion of aforesaid reprecipitation method.Preferably after removing the operation of above-mentioned water, do not have drying process.Under the situation of harmless effect of the present invention, also can add dispersion agents such as specific pigment dispersing agent or tensio-active agent etc. in order further to improve dispersing of pigments this moment.In addition, also can in the reprecipitation method of narrating before, use dispersion agent used herein, for example when the separating out of pigment particle, make its coexistence.In addition, as following dispersion agent, main illustration macromolecular compound, but in the present invention, when mentioning molecular weight, if not special explanation is meant the matter average molecular weight, molecular weight and dispersity are meant the value of measuring by following measuring method.

[molecular weight of macromolecular compound, the measuring method of dispersity]

For molecular weight and dispersity, if not special explanation uses GPC (gel permeation chromatography) method to measure.The gel that is filled in the analytical column that uses in the GPC method is preferably the gel that has aromatics in repeating unit, for example can list the gel that is made of styrene diethylene benzene copoly mer.Analytical column preferably connects with 2～6 and uses.It is that acid amides such as solvent, N-Methyl pyrrolidone are solvent that employed solvent can list ethers such as tetrahydrofuran (THF), is solvent but be preferably ethers such as tetrahydrofuran (THF).Carry out in the scope that the preferred flow velocity at solvent of mensuration is 0.1～2mL/min, most preferably in the scope of 0.5～1.5mL/min, carry out.By in this scope, measuring, can more effectively measure not to the device applying load.Measure temperature and preferably under 10～50 ℃, carry out, most preferably under 20～40 ℃, carry out.

The actual conditions of below representing molecular weight determination.

Device: HLC-8220GPC (East ソ one (Co., Ltd.) system)

Analyzer: differential refractometer (RI analyzer)

Preanalysis post (precolumn): TSKGUARDCOLUMN MP (XL)

6mm * 40mm (East ソ one (Co., Ltd.) system)

Sample side analytical column: directly connect following 2 (Jun Wei East ソ one (Co., Ltd.) system)

·TSK-GEL?Multipore-HXL-M?7.8mm×300mm

With reference to the side analytical column: identical with sample side analytical column

Thermostatic bath temperature: 40 ℃

Mobile layer: tetrahydrofuran (THF)

Sample side shifting laminar flow amount: 1.0mL/ minute

Control sides mobile layer flow: 0.3mL/ minute

Sample solution concentration: 0.1 weight %

Test portion injection rate: 100 μ L

Data acquisition time: test portion injected back 16 minutes～46 minutes

Sampling interval: 300msec

1, dispersant A

In pigment dispersion of the present invention,, also can add dispersion agents such as pigment dispersing agent or tensio-active agent in order further to improve the dispersiveness of processed pigment.As dispersion agent (pigment dispersing agent), can list macromolecule dispersing agent (for example daiamid and its salt, poly carboxylic acid and its salt, high molecular unsaturated acid ester, modified polyurethane, modified poly ester, poly-(methyl) acrylate of modification, (methyl) acrylic copolymer, naphthalene sulfonic acidformaldehyde condensation product) and polyxyethylated phosphoric acid ester, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc.As macromolecule dispersing agent, can further be categorized as straight chain shape polymer, terminal-modified type polymer, graft type polymer, block type polymer according to its structure.

Macromolecule dispersing agent is adsorbed on the surface of pigment, plays the effect of condensing again of preventing.Therefore, as its preferred construction, can list terminal-modified type polymer, graft type polymer, the block type polymer at anchoring position with the surface of pigments of being anchored at.On the other hand, pigment derivative has the effect of the absorption that promotes macromolecule dispersing agent by surface of pigments is carried out upgrading.For above-mentioned macromolecule dispersing agent, in dispersion step, it is adsorbed on the surface of pigment, and plays the effect of condensing again of preventing.Therefore, as preferred construction, can list block type polymer, graft type polymer, the terminal-modified type polymer at anchoring position with the surface of pigments of being anchored at.On the other hand, pigment derivative is by carrying out upgrading to surface of pigments, has the effect of the absorption that promotes macromolecule dispersing agent.

(graft type polymer)

For the graft type polymer, be not particularly limited, preferably list Japanese kokai publication sho 54-37082 communique, record polyalkyleneimine and petchem are reacted in the Japanese kokai publication sho 61-174939 communique etc. and the compound that obtains, that puts down in writing in the Japanese kokai publication hei 9-169821 communique modifies the amino of the side chain of PAH and the compound that obtains with polyester, the polyester polyol of putting down in writing in the Japanese kokai publication sho 60-166318 communique adds generating polyurethane etc., in addition, also can preferably list with the graft type polymer of such as those polymerizability oligomers (hereinafter referred to as macromonomer) in Japanese kokai publication hei 9-171253 communique or " マ Network ロモノマ one chemical と industry " (アイピ one シ one publishing department, 1989) etc. as copolymer composition.And, give the viewpoint of good dispersiveness from adsorption pigment, be preferably the graft type polymer of putting down in writing among the TOHKEMY 2003-238837 with organic pigment part.As the high molecular branch of graft type portion, can preferably list polystyrene, polyethylene oxide, poly(propylene oxide), poly-(methyl) acrylate, polycaprolactone etc., more preferably have the graft type polymer of polycaprolactone chain.As the high molecular commercially available product of above-mentioned graft type, can list SOLSPERSE 24000, SOLSPERSE 28000, SOLSPERSE 32000, SOLSPERSE 38500, SOLSPERSE 39000, SOLSPERSE 55000 (above), Disperbyk-161, Disperbyk-171, Disperbyk-174 (being trade(brand)name) such as (above) by the manufacturing of BYK Chemie company by the manufacturing of Lubrizol company.

(terminal-modified type polymer)

As terminal-modified type polymer, the end at polymkeric substance that for example can list record in Japanese kokai publication hei 9-77994 communique, TOHKEMY 2002-273191 communique, TOHKEMY 2007-277514 communique, the TOHKEMY 2007-140487 communique etc. has the polymer of functional group.

(block type polymer)

As block type polymer, there is no particular limitation, can list by pigment adsorption block and the block type polymer that constitutes of adsorption pigment block not.Monomer as constituting the pigment adsorption block is not particularly limited, and for example can list the monomer of the functional group with adsorbable pigment.Specifically, have organic pigment structure or heterocycle structure monomer, have acidic groups monomer, have the monomer of basic nitrogen atom etc.As monomer, for example can list the organic pigment skeleton put down in writing among the TOHKEMY 2003-238837 or maleimide derivatives etc. with organic pigment structure or heterocycle structure.As block type polymer, also can utilize commercially available product.As concrete example, can list Disperbyk-2000, Disperbyk-2001 (above), EFKA4330, EFKA4340 (being trade(brand)name) such as (above) by the manufacturing of EFKA company by the manufacturing of BYK Chemie company.

The usage quantity of the dispersant A in the dispersion is not particularly limited, if be considered as the utilization of the colorant of colour filter, for example, with respect to pigment 100 mass parts, is preferably 10～400 mass parts, more preferably 20～200 mass parts.

2, dispersant B

In the present invention, preferably contain be selected from following general formula (I) and (II) in the repeating unit of any one expression in the macromolecular compound (below be sometimes referred to as " dispersant B ") of at least a kind of repeating unit.

Above-mentioned general formula (I) and (II) in, R ¹¹～R ¹⁶The organic group of representing hydrogen atom or 1 valency independently of one another, X ¹¹And X ¹²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, L ¹And L ²Organic binding group of representing singly-bound or divalent independently of one another, A ¹And A ²The organic group of representing 1 valency independently of one another, m and n represent 2～8 integer independently of one another, p and q represent 1～100 integer independently of one another.

R ¹¹～R ¹⁶The organic group of independent separately expression hydrogen atom or 1 valency.As the organic group of 1 valency, be preferably replacement or unsubstituted alkyl.As alkyl, preferred carbonatoms is 1～12 alkyl, and more preferably carbonatoms is 1～8 alkyl, and preferred especially carbonatoms is 1～4 alkyl.When alkyl had substituting group, as this substituting group, (preferred carbonatoms was 1～5, more preferably carbonatoms is 1～3 for example can to list hydroxyl, alkoxyl group.), methoxyl group, oxyethyl group, cyclohexyloxy etc.As preferred alkyl, specifically, for example can list methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl.As R ¹¹, R ¹², R ¹⁴And R ¹⁵, be preferably hydrogen atom, as R ¹³And R ¹⁶, the viewpoint from the adsorption efficiency of surface of pigments most preferably is hydrogen atom or methyl.

X ¹¹And X ¹²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.Wherein, the viewpoint to the adsorptivity of pigment, be preferably-C (=O) O-,-CONH-, phenylene, most preferably be-C (=O) O-.

L ¹And L ²Organic binding group of representing singly-bound or divalent independently of one another.As organic binding group of divalent, be preferably replace or unsubstituted alkylidene group, by this alkylidene group and heteroatoms or contain organic binding group of the divalent that heteroatomic part-structure constitutes.Wherein, as alkylidene group, preferred carbonatoms is 1～12 alkylidene group, and more preferably carbonatoms is 1～8 alkylidene group, and preferred especially carbonatoms is 1～4 alkylidene group.And, as the heteroatoms that contains in the heteroatomic part-structure, for example can list Sauerstoffatom, nitrogen-atoms, sulphur atom, especially be preferably Sauerstoffatom, nitrogen-atoms.As preferred alkylidene group, specifically, for example can list methylene radical, ethylidene, propylidene, trimethylene, tetramethylene.When alkylidene group has substituting group,, for example can list hydroxyl etc. as this substituting group.Organic binding group as divalent, from viewpoint to the adsorptivity of pigment, be preferably end at above-mentioned alkylidene group have be selected from-C (=O)-,-OC (=O)-,-NHC (=O)-in heteroatoms or comprise heteroatomic part-structure and by this heteroatoms or contain heteroatomic part-structure and organic binding group of the divalent that adjacent Sauerstoffatom is formed by connecting.Wherein, adjacent Sauerstoffatom is meant the L in side chain terminal side and general formula (I) ¹, and general formula (II) in L ²The Sauerstoffatom of bonding.

As A ¹And A ²Viewpoint from dispersion stabilization, development, being preferably and being selected from carbonatoms is that 1～20 straight chain shape, carbonatoms are that 3～20 chain and carbonatoms are the group in 5～20 the cyclic alkyl, more preferably be selected from carbonatoms and be 4～15 straight chain shape, carbonatoms and be 4～15 chain and carbonatoms and be the group in 6～10 the cyclic alkyl, more preferably be selected from carbonatoms and be 6～10 straight chain shape and carbonatoms and be the group in 6～12 the catenate alkyl.

M and n represent 2～8 integer independently of one another.From the viewpoint of dispersion stabilization, development, be preferably 4～6, be preferably 5 especially.

P and q represent 1～100 integer independently of one another.P is that situation, the q of different integers is that different integer situations also can be mixed more than 2 kinds.For p and q, from the viewpoint of dispersion stabilization, development, be preferably 5～60, more preferably 5～40, more preferably 5～20.

As the dispersant B in the present embodiment,, preferably contain the dispersion agent of the repeating unit of above-mentioned general formula (I) expression from the viewpoint of dispersion stabilization.

And, as the repeating unit of general formula (I) expression, the repeating unit of more preferably following general formula (I)-2 expression.

In the above-mentioned general formula (I)-2, R ¹¹～R ¹³The organic group of representing hydrogen atom or 1 valency independently of one another, La represent that carbonatoms is 2～10 alkylidene group, Lb represents-C (=O)-or-NHC (=O)-, A ¹The organic group of representing 1 valency, m are represented 2～8 integer, and P represents 1～100 integer.

For general formula (I), (II) or (I)-2 repeating unit of expression, respectively by polymerization or the following general formula of copolymerization (i), (ii) or the monomer of (i)-2 expression, with its repeating unit importing as macromolecular compound.

Above-mentioned general formula (i), (ii) or (i)-2, R ¹¹～R ¹⁶The organic group of representing hydrogen atom or 1 valency independently of one another, X ¹¹And X ¹²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, L ¹And L ²Organic binding group of representing singly-bound or divalent independently of one another, La represent that carbonatoms is 2～10 alkylidene group, Lb represents-C (=O)-or-NHC (=O)-, A ¹And A ²The organic group of representing 1 valency independently of one another, m and n represent 2～8 integer independently of one another, p and q represent 1～100 integer independently of one another.

Below, enumerate general formula (i), (ii) or (i)-2 monomeric preferred concrete example (monomer (A-1)～(A-23)) of expression following, but the present invention is not subjected to their restriction.

Dispersant B in the present embodiment can contain be selected from general formula (I) and (II) in the repeating unit of any one expression at least a repeating unit, also can also can contain more than 2 kinds for only containing a kind.

And, in dispersant B, formula (I) and (II) in the content of repeating unit of any one expression be not particularly limited, the whole repeating units that contained in polymkeric substance are during as 100 quality %, preferably contain the above formula (I) of 5 quality % and (II) in the repeating unit of any one expression, more preferably contain 50 quality %, further contain 50 quality %～80 quality %.

As the dispersant B in the present embodiment, in order to improve absorption to pigment, be preferably with have the monomer of functional group of adsorbable pigment and aforesaid general formula (i), (ii) or the monomer of (i)-2 expression carry out copolymerization and the macromolecular compound that obtains.As the monomer of functional group, specifically, can list monomer, monomer, monomer, have the monomer of ionic group etc. with basic nitrogen atom with acidic groups with organic pigment structure or heterocycle structure with adsorbable pigment.Viewpoint to the adsorptive power of pigment especially is preferably the monomer with organic pigment structure or heterocycle structure.

As monomer, be preferably a kind in monomer, maleimide and the maleimide derivatives that is selected from following general formula (11) expression with organic pigment structure or heterocycle structure.Especially especially be preferably the monomer of following general formula (11) expression.

General formula (11)

In the above-mentioned general formula (11), R ²¹Expression hydrogen atom or alkyl.R ²²The binding group of expression singly-bound or divalent.Y represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.Z represents to have the group of nitrogen heterocycle.

As the R in the general formula (11) ²¹The alkyl of expression, preferred carbonatoms is 1～12 alkyl, and more preferably carbonatoms is 1～8 alkyl, and preferred especially carbonatoms is 1～4 alkyl.R ²¹When the alkyl of expression has substituting group,, for example be preferably alkoxyl groups such as hydroxyl, methoxyl group, oxyethyl group, cyclohexyloxy as this substituting group.As this alkoxyl group, preferred carbonatoms is 1～5 alkoxyl group, and more preferably carbonatoms is 1～3 alkoxyl group.

As the R in the general formula (11) ²¹The preferred alkyl of expression specifically, for example can list methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl.Wherein, as R ¹, most preferably be hydrogen atom or methyl.

As the R in the general formula (11) ²²The binding group of divalent of expression, preferred alkylidene group or comprise the group of the divalent of alkylidene group.As this alkylidene group, preferred carbonatoms is 1～12 alkylidene group, and more preferably carbonatoms is 1～12 alkylidene group, and further preferred carbonatoms is 1～8 alkylidene group, and preferred especially carbonatoms is 1～4 alkylidene group.And this alkylidene group as this substituting group, for example can list hydroxyl etc. when having substituting group.As R ²²The preferred alkylidene group of expression specifically, for example can list methylene radical, ethylidene, propylidene, trimethylene, tetramethylene.

As the R in the general formula (11) ²²The group of the divalent that comprises alkylidene group of expression can connect the group that obtains more than 2 for above-mentioned alkylidene group by heteroatoms (for example Sauerstoffatom, nitrogen-atoms or sulphur atom).And, R ²²The group of the divalent that comprises alkylidene group of expression, can in above-mentioned alkylidene group have with the terminal bonding Z bonding be selected from-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-and-heteroatoms among the NHCO-or comprise the group of the divalent of heteroatomic part-structure.

The nitrogen heterocyclic ring structure of the formation nitrogen heterocycle of representing as the Z in the general formula (11), specifically, for example can list pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, thiodiphenylamine ring, fen

Piperazine ring, dihydroketoacridine ring, anthraquinone ring, has the nitrogen heterocyclic ring structure of benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure and cyclic imide structure.These nitrogen heterocyclic ring structures can have substituting group, as this substituting group, for example can list alkyl, alkoxyl group, halogen atom, aliphatics ester group, aromatic series ester group, alkoxy carbonyl etc.

The nitrogen heterocycle that Z represents especially more preferably carbonatoms is the group with nitrogen heterocyclic ring structure more than 6, and preferred especially carbonatoms is 6～12 the group with nitrogen heterocyclic ring structure.As carbonatoms is nitrogen heterocyclic ring structure more than 6, specifically, is preferably thiodiphenylamine ring, fen

Piperazine ring, dihydroketoacridine ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure and cyclic imide structure are preferably the structure of following general formula (12), (13) or (14) expression especially.

General formula (12) general formula (13) general formula (14)

In the general formula (12), X be selected from singly-bound, alkylidene group (for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene etc.) ,-O-,-S-,-NR ^A-and-C (=O)-in any one.Wherein, R ^AExpression hydrogen atom or alkyl.R ^AThe alkyl preferred carbonatoms of expression during alkyl is 1～18 alkyl, more preferably carbonatoms is 1～6 alkyl, for example can list methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, Octadecane base etc.Among above-mentioned, as the X in the general formula (12), be preferably singly-bound, methylene radical ,-O-or-C (=O)-, be preferably especially-C (=O)-.

In the general formula (14), Y and Z represent independently of one another-N=,-NH-,-N (R ^B)-,-S-or-O-.R ^BThe expression alkyl, the preferred carbonatoms of this alkyl is 1～18 alkyl, more preferably carbonatoms is 1～6 alkyl, for example can list methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, Octadecane base etc.Among above-mentioned, Y and Z as in the general formula (14), be preferably especially-N=,-NH-and-N (R ^B)-.As the combination of Y and Z, any one that can preferably list among Y and the Z is-N=, another person combination (imidazolyl) for-NH-.

In general formula (12), (13) or (14), ring A, ring B, ring C and ring D represent aromatic nucleus independently of one another.As this aromatic nucleus, for example can list phenyl ring, naphthalene nucleus, indenes ring, azulene, fluorenes ring, anthracene nucleus, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, thiodiphenylamine ring, fen

Piperazine ring, dihydroketoacridine ring, anthraquinone ring etc. especially are preferably phenyl ring, naphthalene nucleus, anthracene nucleus, pyridine ring, fen

Piperazine ring, acridine ring, thiodiphenylamine ring, fen

Piperazine ring, dihydroketoacridine ring, anthraquinone ring are preferably phenyl ring, naphthalene nucleus, pyridine ring especially.

Specifically, as ring A in the general formula (12) and ring B, for example can list phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.As the ring C in the general formula (13), for example can list phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.As the ring C in the general formula (14), for example can list phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.Among the structure of general formula (12), (13) or (14) expression, from the viewpoint of the ageing stability of dispersed, dispersion liquid, more preferably phenyl ring, naphthalene nucleus, in general formula (12) or (14), phenyl ring more preferably, in general formula (13), naphthalene nucleus more preferably.

And the maleimide derivatives among the present invention is meant, the maleimide that the N position is replaced by substituting groups such as alkyl or aryls.

Below, below enumerate the preferred concrete example (monomer M-1～M-33), but the present invention is not subjected to their restriction of monomer, maleimide and the maleimide derivatives of general formula (11) expression.

Dispersant B in the present embodiment can only contain a kind of a kind of monomeric repeating unit that comes from monomer, maleimide and the maleimide derivatives that is selected from general formula (11) expression, and this repeating unit also can contain more than 2 kinds.

In the dispersant B in the present embodiment, the content that comes from a kind of monomeric repeating unit in monomer, maleimide and the maleimide derivatives that is selected from general formula (11) expression is, when whole repeating units that polymkeric substance contained are 100 quality %, preferably contain more than the 5 quality %, more preferably contain 10 quality %～50 quality %.Promptly, in order to suppress as the generation of 2 aggregates of the aggregate of 1 particle of pigment effectively or to weaken the cohesive force of 2 aggregates effectively, the content that comes from a kind of monomeric polymerized unit in monomer, maleimide and the maleimide derivatives that is selected from general formula (11) expression is preferably more than the 5 quality %.And, the viewpoint of the development when making colour filter by the coloring photosensitive combination that contains pigment dispersion, the content that comes from a kind of monomeric polymerized unit in monomer, maleimide and the maleimide derivatives that is selected from general formula (1) expression is preferably below the 50 quality %.

As monomeric example, can list vinyl monomer or have sulfonic vinyl monomer with carboxyl with acidic groups.As vinyl monomer, can list (methyl) vinylformic acid, vinyl benzoic acid, toxilic acid, maleic acid mono alkyl ester, fumaric acid, methylene-succinic acid, Ba Dousuan, TRANSCINNAMIC ACID, acrylic acid dimer etc. with carboxyl.And, also can utilize 2-hydroxyethyl (methyl) acrylate etc. to have adduct, ω-carboxyl-polycaprolactone list (methyl) acrylate of the such cyclic acid anhydride of the monomer of hydroxyl and maleic anhydride or Tetra hydro Phthalic anhydride, cyclohexane dicarboxylic acid acid anhydride etc.And, as the precursor of carboxyl, can use maleic anhydride, itaconic anhydride, citraconic anhydride etc. to contain the monomer of acid anhydrides.In addition, among them, the viewpoint from copolymerization or cost, solvability etc. is preferably (methyl) vinylformic acid especially.

And, as having sulfonic vinyl monomer, 2-acrylamide-2-methyl propane sulfonic acid etc. can be listed,, mono phosphoric acid ester (2-acryloxy ethyl ester), mono phosphoric acid ester (1-methyl-2-acryloxy ethyl ester) etc. can be listed as vinyl monomer with phosphate.

Dispersant B in the present embodiment is preferably to contain and comes from the monomeric repeating unit with above-mentioned acidic groups.By containing such repeating unit, when pigment dispersion of the present invention is used for coloring photosensitive combination, removing property of the development excellence of unexposed portion.

Dispersant B in the present embodiment can only contain a kind and come from the monomeric repeating unit with acidic groups, also can contain more than 2 kinds.In dispersant B, the content that comes from the monomeric repeating unit with acidic groups is preferably more than the 50mgKOH/g, is preferably 50mgKOH/g～200mgKOH/g especially.That is, the viewpoint that the generation of the precipitate from developing solution suppresses, the content that comes from the monomeric repeating unit with acidic groups is preferably more than the 50mgKOH/g.In order to suppress as the generation of 2 aggregates of the aggregate of 1 particle of pigment effectively or to weaken the cohesive force of 2 aggregates effectively, the content that comes from the monomeric repeating unit with acidic groups is preferably 50mgKOH/g～200mgKOH/g.

For monomer with basic nitrogen atom, as (methyl) acrylate, can list (methyl) vinylformic acid N, the N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid 1-(N, the N-dimethylamino)-1,1-dimethyl methyl esters, (methyl) vinylformic acid N, the own ester of N-dimethylamino, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, N-diisopropylaminoethyl ethyl ester, (methyl) vinylformic acid N, N-di-n-butyl amino ethyl ester, (methyl) vinylformic acid N, N-Di-Isobutyl amino ethyl ester, (methyl) vinylformic acid morpholinyl ethyl ester, (methyl) vinylformic acid piperidyl ethyl ester, (methyl) vinylformic acid 1-pyrrolidyl (Pyrrolidino) ethyl ester, (methyl) vinylformic acid N, N-methyl-2-pyrrolidyl (pyrrolidyl) amino ethyl ester and (methyl) vinylformic acid N, N-aminomethyl phenyl amino ethyl ester etc.; As (methyl) acrylic amide, can list N-(N ', N '-dimethyl aminoethyl) acrylamide, N-(N ', N '-dimethyl aminoethyl) Methacrylamide, N-(N ', N '-diethylamino ethyl) acrylamide, N-(N ', N '-diethylamino ethyl) Methacrylamide, N-(N ', N '-dimethylaminopropyl) acrylamide, N-(N ', N '-dimethylaminopropyl) Methacrylamide, N-(N ', N '-diethylamino propyl group) acrylamide, N-(N ', N '-diethylamino propyl group) Methacrylamide, 2-(N, the N-dimethylamino) ethyl (methyl) acrylamide, 2-(N, the N-diethylamino) ethyl (methyl) acrylamide, 3-(N, the N-diethylamino) propyl group (methyl) acrylamide, 3-(N, the N-dimethylamino) propyl group (methyl) acrylamide, 1-(N, the N-dimethylamino)-1,1-dimethyl methyl (methyl) acrylamide and 6-(N, N-diethylamino) hexyl (methyl) acrylamide, morpholinyl (methyl) acrylamide, piperidyl (methyl) acrylamide, N-methyl-2-pyrrolidyl (methyl) acrylamide etc.; As styrenic, can list N, N-dimethylamino vinylbenzene, N, N-dimethylaminomethyl vinylbenzene etc.

And also can use the carbonatoms that has urea groups, carbamate groups, has a coordination Sauerstoffatom is alkyl, alkoxysilyl, epoxy group(ing), the isocyanate group more than 4, the monomer of hydroxyl.Specifically, for example can list the monomer of following structure.

As the monomer of ionic group, can list vinyl monomer (anionic property vinyl monomer, cationic vinyl monomer) with ionic group.For this example, as the anionic property vinyl monomer, can list the vinyl monomer with above-mentioned acidic groups an alkali metal salt or with salt of organic amine (for example tertiary amine such as triethylamine, dimethylaminoethanol) etc.; As the cationic vinyl monomer, can list above-mentioned nitrogenous vinyl monomer haloalkyl (alkyl: C1～18, halogen atom: chlorine atom, bromine atoms or iodine atom), halogeno-benzyl such as benzyl chloride, bromotoluene, alkyl sulfonic esters such as methylsulfonic acid (alkyl: C1～18), aryl sulfonic acid such as Phenylsulfonic acid, toluenesulphonic acids alkyl ester (alkyl: C1～18), sulfuric acid dialkyl (alkyl: C1～4) etc. carries out quaternary ammoniated and product that obtain; Perhaps dialkyldiallyl ammonium salt etc.

For the monomer of functional group with adsorbable pigment, can suitably select according to the kind of institute's dispersive pigment, they can use separately, and also two or more kinds may be used.

For the dispersant B in the present embodiment, in the scope of not damaging its effect, but can further contain the repeating unit of the vinyl monomer that comes from copolymerization.

As operable vinyl monomer here, be not particularly limited, for example be preferably ester class, styrenic, (methyl) vinyl cyanide of (methyl) esters of acrylic acid, crotonate class, vinyl ester, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol etc.As the concrete example of such vinyl monomer, for example can list following compound.In addition, in this manual, when any one in expression " vinylformic acid, methacrylic acid " or both sides, be recited as " (methyl) vinylformic acid " sometimes.

The preferred mode of the dispersant B in the present embodiment is that the monomer to major general's general formula (i), (i i) or (i)-2 expression carries out copolymerization with the monomer with organic pigment structure or heterocycle structure and the dispersion agent that obtains, more preferably carries out copolymerization and the dispersion agent that obtains to the monomer of the monomer of the aforesaid general formula of major general (I)-2 expression, aforesaid general formula (11) expression, monomer with acidic group.Thus, can be provided in the pigment dispersion of pigment adsorption aspect excellence and development excellence.

In the present embodiment, the preferred molecular weight of dispersant B is counted 1,000～100,000 scope, counted 400～50,000 scope with number-average molecular weight (Mn) with matter average molecular weight (Mw) is preferred.It is preferred counting 5,000～50,000 scope, count 2,000～30,000 scope with number-average molecular weight (Mn) with matter average molecular weight (Mw).Especially, it is most preferred counting 8,000～30,000 scope, count 4,000～12,000 scope with number-average molecular weight (Mn) with matter average molecular weight (Mw).From in order to untie as 2 aggregates of the aggregate of 1 particle of pigment effectively or to weaken the viewpoint of cohesion more effectively, the matter average molecular weight (Mw) of dispersant B is preferably more than 1000.And, the viewpoint of the development when making colour filter by the coloring photosensitive combination that contains pigment dispersion, the matter average molecular weight (Mw) of dispersant B is preferably below 30000.

Dispersant B in the present embodiment can be by following manufacturing, promptly, use the monomer of for example following general formula (i), (ii) or (i)-2 expression and other free-radical polymerised compound (foregoing various monomers), make by common radical polymerization as copolymer composition.Generally speaking, use suspension polymerization or solution polymerization process etc.The solvent that uses during as synthetic such dispersant B, for example can list ethylene dichloride, pimelinketone, methylethylketone, acetone, methyl alcohol, ethanol, propyl alcohol, butanols, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, 2-methoxy ethyl acetic ester, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl-acetic acid ester, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, ethyl acetate, methyl lactate, ethyl lactate etc.These solvents can use separately or mix the back more than 2 kinds and use.In addition, radical polymerization is fashionable, can use radical polymerization initiator to use, and, can further use chain-transfer agent (for example 2 mercapto ethanol and lauryl mercaptan.

In the pigment dispersion of present embodiment,, by quality ratio, be preferably pigment: dispersant B=1: 0.1～1: 2, more preferably 1: 0.2～1: 1, more preferably 1: 0.4～1: 0.7 as the content of dispersant B.

And, in the scope of the effect that can't harm present embodiment, as required, except above-mentioned specific copolymer, can also use other macromolecular compounds simultaneously.As other macromolecular compounds, synthetic resins that can use natural resin, modified natural resin, synthetic resins, obtains etc. with the natural resin modification.As natural resin, be representative with rosin; As modified natural resin, can list rosin derivative, derivatived cellulose, rubber derivative, protein derivatives and their oligopolymer.As synthetic resins, can list Resins, epoxy, acrylic resin, maleic acid resin, butyral resin, vibrin, melmac, phenol resins, urethane resin etc.As the synthetic resins that obtains with the natural resin modification, can list Abietyl modified maleic acid resin, Abietyl modified phenol resins etc.As synthetic resins, can list daiamid and salt thereof, poly carboxylic acid and salt thereof, high molecular unsaturated acid ester, urethane, polyester, poly-(methyl) acrylate, (methyl) acrylic copolymer, naphthalene sulfonic acidformaldehyde condensation product.

[Photocurable composition]

Photocurable composition contains dispersion, optical polymerism compound and the Photoepolymerizationinitiater initiater of above-mentioned pigment particle, preferably further contains alkali soluble resin.The method of pigment dyestuff particulate and this dispersion of making is narrated in detail.As the content of the particulate in the Photocurable composition, (in the present invention, all solids composition is meant the total of the composition except that organic solvent with respect to all solids composition.), be preferably 3～90 quality %, more preferably 20～80 quality %, more preferably 25～60 quality %.If this content is too much, then the viscosity of dispersion liquid rises, and is having problems aspect the suitable property of manufacturing sometimes.If very few, then tinting strength is insufficient.And, in order to mix colours, also can use with common pigment combinations.Pigment can use those of above-mentioned narration.

As optical polymerism compound (below be sometimes referred to as polymerizable monomer or polyreactive oligomers), be preferably ethylenic unsaturated double-bond that has more than 2 and the polyfunctional monomer that carries out addition polymerization by the irradiation of light.As such optical polymerism compound, under the normal pressure be compound more than 100 ℃ but can be set forth in the ethylenic unsaturated group that has at least 1 addition polymerization in the molecule and boiling point.As this example, can list monofunctional acrylate or simple function methacrylic esters such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate and phenoxy group ethyl (methyl) acrylate; Polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate; TriMethylolPropane(TMP) or glycerine etc. in addition on the polyfunctional alcohol carry out the polyfunctional acrylic ester or the multifunctional methacrylic esters such as compound of (methyl) acroleic acid esterification behind oxyethane or the propylene oxide.And, can preferably list: in the Japanese kokai publication hei 10-62986 communique as putting down in writing in general formula (1) and (2), in addition on the polyfunctional alcohol carried out the compound of (methyl) acroleic acid esterification behind oxyethane or the propylene oxide.

Further can list the urethane acrylate class of putting down in writing in Japanese Patent Publication 48-41708 communique, Japanese Patent Publication 50-6034 communique and the Japanese kokai publication sho 51-37193 communique; The polyester acrylate class of putting down in writing in Japanese kokai publication sho 48-64183 communique, Japanese Patent Publication 49-43191 communique and the Japanese Patent Publication 52-30490 communique; As polyfunctional acrylic ester or the methacrylic esters such as epoxy acrylate class of Resins, epoxy with (methyl) acrylic acid reaction product.

Among them, be preferably trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate.

And, can preferably list " the polymerizable compound B " that put down in writing in the Japanese kokai publication hei 11-133600 communique in addition.

The optical polymerism compound can use separately, also can mix more than 2 kinds the back and use, and is generally 5～50 quality % with respect to the content of all solids composition of Photocurable composition, is preferably 10～40 quality %.If this content is too much, the control difficulty of development property then, thereby problem is being arranged aspect the suitable property making.If very few, the curing power when then exposing is insufficient.

As Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater is that (in the present invention, Photoepolymerizationinitiater initiater system is meant by making up multiple compound and embodies the mixture that photopolymerization causes function.), can list disclosed vicinal polyketaldonyl compound in No. 2367660 specification sheets of United States Patent (USP), the acyloin ether compound of putting down in writing in No. 2448828 specification sheets of United States Patent (USP), the aromatic series acyloin compound of putting down in writing in No. 2722512 specification sheets of United States Patent (USP) with α-hydrocarbon replacement, the multinuclear naphtoquinone compounds of putting down in writing in No. 3046127 specification sheets of United States Patent (USP) and No. 2951758 specification sheets of United States Patent (USP), the triarylimidazoles dipolymer of putting down in writing in No. 3549367 specification sheets of United States Patent (USP) with to the combination of keto-amine, benzothiazole compound of putting down in writing in the Japanese Patent Publication 51-48516 communique and trihalomethyl group-s-triaizine compounds, trihalomethyl group-triaizine compounds of putting down in writing in No. 4239850 specification sheets of United States Patent (USP), the trihalomethyl group of putting down in writing in No. 4212976 specification sheets of United States Patent (USP) Diazole compounds etc.Be preferably trihalomethyl group-s-triazine, trihalomethyl group especially

Diazole and triarylimidazoles dipolymer.

And; in addition; as " the polymerization starter C " that put down in writing in the Japanese kokai publication hei 11-133600 communique or oxime system; can also list 1-phenyl-1; 2-propanedione-2-(adjacent ethoxy carbonyl) oxime, O-benzoyl-4 '-(benzo sulfydryl) benzoyl-hexyl-ketoxime, 2; 4,6-trimethylphenyl carbonyl-diphenylphosphine acyl-oxygen, hexafluoro idol phosphorus-trialkyl Ben Ji Phosphonium

Salt etc.

Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system can use separately, also can mix back use more than 2 kinds, especially preferably use more than 2 kinds.If use at least 2 kinds Photoepolymerizationinitiater initiater, then display characteristic, particularly show inhomogeneous can the minimizing.With respect to all solids composition of Photocurable composition, the content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system is generally 0.5～20 quality %, is preferably 1～15 quality %.If this content is too much, then sensitivity becomes too high, thereby control becomes difficult.If very few, then exposure sensitivity became low.

As alkali soluble resin, can also add during with the modulation of jetted ink at Photocurable composition or colour filter, but also preferably interpolation when making the dispersion of above-mentioned particulate or when particulate forms.Also alkali soluble resin can be added on the solution of water-insoluble compound and be used for generating two sides or a side among the bad solvent of particulate of water-insoluble compound by the solution that adds water-insoluble compound.Perhaps also preferably alkali soluble resin solution is added when the particulate of water-insoluble compound forms with the form of other systems.

As alkali soluble resin, preferably have the tackiness agent of acidic groups, be preferably the polymkeric substance of the alkali-soluble that on side chain, has carboxylic acid group or carboxylate salt isopolarity group.As its example, can list the Sipacril 2739OF put down in writing in Japanese kokai publication sho 59-44615 communique, Japanese Patent Publication 54-34327 communique, Japanese Patent Publication 58-12577 communique, Japanese Patent Publication 54-25957 communique, Japanese kokai publication sho 59-53836 communique and the Japanese kokai publication sho 59-71048 communique, acrylic copolymer, itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, partial esterification maleic acid etc.In addition, can also list the derivatived cellulose that on side chain, has carboxylic acid group or carboxylate salt etc., in addition, can also preferably use at the product of cyclic acid anhydride that had on the polymkeric substance of hydroxyl addition.And, as more preferred example, can list United States Patent (USP) the 4th, 139, (methyl) vinylformic acid benzyl ester of putting down in writing in No. 391 specification sheetss and (methyl) acrylic acid multipolymer or (methyl) vinylformic acid benzyl ester and (methyl) vinylformic acid and other monomeric multiple copolymers.

Alkali soluble resin can use separately, perhaps use with the state that forms the composition of property polymkeric substance and usefulness with common film, addition with respect to particulate 100 mass parts of water-insoluble compound is generally 10～200 mass parts, is preferably 25～100 mass parts.

In addition, in order to improve cross-linking efficiency, also can have polymerizable group on the side chain of alkali soluble resin, UV curable resin or heat-curing resin etc. also are useful.And then, as alkali soluble resin, also can use the resin that has water-soluble atomic group in the part of side chain.For the content of organic solvent,, be preferably 10～95 quality % with respect to the Photocurable composition total amount.And, can make and contain suitable tensio-active agent, thermopolymerization in the Photocurable composition and prevent drug, UV light absorber, bonding auxiliary agent, other additive etc.

Photocurable composition can be made jetted ink by regulating its composition aptly.As jetted ink, except being used for colour filter, also can making to print and common jetted ink such as use, but especially preferably make the colour filter jetted ink.

As long as jetted ink contains above-mentioned water-insoluble compound particulate, preferably in the solvent that contains polymerizable monomer and/or polyreactive oligomers, contain above-mentioned water-insoluble compound particulate.Wherein, can use those that the front illustrated as polymerizable monomer and/or polyreactive oligomers in " Photocurable composition ".

At this moment, ink characteristics, printing ink during for use ejaculation blow pattern form of method, ink gun form or colour filter and forming method thereof, and with disclosed identical in the TOHKEMY 2008-138194 communique, its preferred range is also identical.

For the composition that contains in the coated film of having used Photocurable composition, with did record those are identical.And for the proterties of the coated film of having used Photocurable composition, to the coating process of substrate, identical with those disclosed in the TOHKEMY 2008-138194 communique, its preferred range is also identical.

[colour filter]

The pixel of colour filter of the present invention is preferably to be used above-mentioned pigment particle dispersion or has changed the redispersion body of its solvent and the pixel that forms, and preferred contrast gradient excellence.In the present invention, contrast gradient is represented: the ratio of the transmission light quantity between 2 polaroids, when polarization axle is parallel when vertical (with reference to " nineteen ninety the 7th color reversion glory learn コ Application Off アレ Application ス, 512 colour specifications 10.4 " サイズ TFT-LCD with カラ one Off イ Le タ,

Wood, Xiao Seki, good fortune forever, in the mountain " etc.)。The contrast gradient height of colour filter means that it is big that the difference of the light and shade when making up with liquid crystal becomes, and this is very important performance concerning liquid-crystal display replaces CRT.

Colour filter is when being used for the TV purposes, whole each the unicolor colourity of red (R) of F10 light source, green (G) and blue (B) preferably with the value of following table record (below, be called " target colourity " in the present invention) poor (Δ E) 5 with interior scope, more preferably in 3, be preferably in 2 especially.

Chrominance passband among the present invention is crossed microspectrophotometer (Olympus Optical Co Ltd.'s system, OSP100 or 200) and is measured, as result's calculating of the F10 light source visual field 2 degree, with the xyY value representation of xyz chromaticity diagram.In addition, with the difference of target colourity with La ^*b ^*The aberration of chromaticity diagram is represented.

Possessed the contrast of LCD degree height of colour filter, it is good that the dense degree of black etc. is described power, is preferably the VA mode especially.Also be suitable as notebook computer with the liquid crystal indicator of big picture such as indicating meter or TV monitor etc.In addition, above-mentioned colour filter can be used for CCD equipment, brings into play good performance.

Embodiment

Below based on embodiment to further detailed describing of the present invention, but the present invention is not subjected to its determinate explanation.In addition, in the present embodiment, " part " and " % " is quality criteria unless otherwise specified.

(synthesis example 1) above-mentioned exemplary compounds a-1's is synthetic

At volume is in the there-necked flask of 1000mL, drop into PR255 (Cromophtal DPP CoralRed C[trade(brand)name], Ciba Specialty Chemicals (Co., Ltd.) system, also identical in following synthesis example) 20g, dimethyl sulfoxide (DMSO) 300mL, potassium tert.-butoxide 7.8g, carry out stirring and dissolving for pigment of the same race.In this liquid, in 30 minutes, drip the mixed solution of bromotoluene 15g and dimethyl sulfoxide (DMSO) 100mL, stirred 4 hours down at 60 ℃.Reaction solution is thrown in the 1.5L frozen water so that solid is separated out.With the water washing of precipitate, obtain target compound with 4L.Be confirmed to be target compound by H-NMR, MS.By H-NMR, confirmed PR255: compound 1-1: compound 1-2=22: 45: 55.Below this compound test portion is called compound 1.

[compound 1]

Compound 1-1 compound 1-2

(synthesis example 2) above-mentioned exemplary compounds a-2's is synthetic

Dropping into PR254 in the there-necked flask of 1L is 20g, dimethyl sulfoxide (DMSO) 400mL, potassium tert.-butoxide 11.0g, carries out stirring and dissolving.In this liquid, drop into potassiumiodide 2.0g and chloracetanilide 19g, under 60 ℃, stirred 4 hours.Reaction solution is thrown in the 1.5L frozen water so that solid is separated out.With the water washing of precipitate, obtain target compound with 3L.Be confirmed to be target compound by H-NMR, MS.Confirmed by H-NMR: PR254: compound 1-1: compound 1-2=0: 18: 82.Below this compound test portion is called compound 2.

[compound 2]

Compound 2-1 compound 2-2

Following compound test portion 3 (PR254 of the present invention have similarly been synthesized, compound 3-1,3-2), compound test portion 4 (PR254, compound 4-1,4-2), compound test portion 5 (PR254, compound 5-1,5-2), compound test portion 6 (PR254, compound 6-1,6-2), compound test portion 7 (PR254, compound 7-1,7-2).And, prepared the relatively compound test portion of usefulness (comparative compound 1).

[compound 3,4]

Compound 3-1 compound 3-2 PR254: compound 3-1: 3-2=50: 32: 18

Compound 4-1 compound 4-2 PR254: compound 4-1: 4-2=44: 30: 26

[compound 5～7]

Compound 5-1 compound 5-2 PR254: compound 5-1: 5-2=42: 32: 24

Compound 6-1 compound 6-2 PR254: compound 6-1: 6-2=55: 43: 2

Compound 7-1 compound 7-2 PR254: compound 7-1: 7-2=0: 92: 8

[compound 8～10]

Compound 8-1 compound 8-2 PR254: compound 8-1: compound 8-2=10: 85: 5

Compound 9-1 compound 9-2 PR254: compound 9-1: compound 9-2=30: 60: 10

Compound 10-1 compound 10-2 PR254: compound 10-1: compound 10-2=15: 45: 40

[compound 11]

Compound 11-1 compound 11-2 PR254: compound 11-1: compound 11-2=45: 50: 5

Comparative compound 1

(example I, Comparative Example I)

(embodiment 1)

The modulation of＜organic pigment nano particle dispersion liquid 〉

With dimethyl sulfoxide (DMSO) (making) with the pure medicine of light company as good solvent, in the good solvent of 1000g, disperse 50g pigment C.I. Pigment red 254 (Irgaphor Red Irgazin Red, trade(brand)name, CibaSpecialty Chemicals (Co., Ltd.) system), add the above-mentioned exemplary compounds a-1 of 5g (compound 1), to the methanol solution of the Tetramethylammonium hydroxide 25% of Dropwise 5 2.3g wherein, modulated pigment solution.For this pigment solution, use Viscometer VM-10A-L (trade(brand)name, CBC materials company make) to measure viscosity, its result is that the viscosity when the liquid temperature of pigment solution is 24.5 ℃ is 14.3mPas.As the bad solvent different, prepared to contain the propylene glycol monomethyl ether of 1000ml of the 1mol/l aqueous hydrochloric acid (making) of 19g with the pure medicine of light company with it.

At this, temperature is controlled to 10 ℃, to passing through GK-0222-10 type Ramond stirrer (trade(brand)name, Fujisawa Pharmaceutical makes), rotating speed with 500rpm stirs among the bad solvent 1000ml afterwards, with the non-jerk pump of NP-KX-500 type large vol (non-pulsation pumps) (trade(brand)name, Japan's precision chemical corporate system) from the stream diameter is the flow velocity injection pigment solution 100ml of the liquor charging pipe arrangement of 1.1mm with 400ml/min, form the organic pigment particles of the median size of following table 1 thus, thereby modulated the dispersion liquid (dispersion 1) of crystallinity organic pigment nano particle.The temperature of above-mentioned organic pigment nano particle dispersion liquid (dispersion 1) is controlled to 5 ℃, stirred 2 hours.

The modulation of＜pigment dyestuff powder 〉

To use H-112 type (trade(brand)name, (Co., Ltd.) Kokusan company make) centrifugal filter and P89C type (trade(brand)name, Shikishima Canvas (Co., Ltd.) company make) filter cloth, concentrate 90 minutes according to the synthetic organic pigment nano particle dispersion liquid of above-mentioned step (dispersion 1) with the rotating speed of 5000rpm, then add ion exchanged water 1100g, mix, similarly carried out centrifuging.Add ion exchanged water 1100g once more, mix and carried out centrifuging.Reclaim resulting organic pigment nano particle and concentrate paste 1.

Utilize baking oven that above-mentioned organic pigment nano particle is concentrated paste and descended dry 2 hours at 100 ℃, having obtained median size thus is the pigment dyestuff powder 1 of 15-20nm.

The modulation of＜pigment dyestuff dispersive composition 〉

After being crushed to above-mentioned pigment dyestuff powder 1 usefulness mortar below the 180 μ m, making the pigment dyestuff dispersive composition 1 of following composition, and mix equably.

Above-mentioned pigment dyestuff powder 19.7g

Pigment derivative 12.0g

Pigment derivative 22.3g

The dispersion resin 11.3g that puts down in writing in the table

Propylene glycol monomethyl ether 24.7g

Comparative compound 1

With the pigment dyestuff dispersive composition 1 usefulness Sand grinder mill BSG-01 of above-mentioned composition (trade(brand)name, AIMEX company make) and uses diameter as the zirconium white microballon of 0.5mm with the rotating speed dispersion of 1500rpm 1 hour, then use diameter to disperse 2 hours, obtained pigment dyestuff dispersive composition 1A as the zirconium white microballon of 0.05mm rotating speed with 2500rpm.

(embodiment 2～8, comparative example 1,2,3)

Except the compound that will add in the pigment solution changes to shown in following table 1 like that by exemplary compounds a-1 (compound 1),, dispersible pigment dispersion (dispersion 2～8, c1～c3) have been modulated according to the step identical with embodiment 1.In addition, use dispersion test portion separately, modulated base-material, powder and pigment dyestuff dispersive composition 1A～4A, c1A, c2A, c3A.In addition, in table 1, c2 is meant about dispersion, the modulation of not using exemplary compounds a-1 to be carried out.

(reference example)

40 mass parts (median size 60nm) C.I. Pigment red 254 (Irgaphor Red Irgazin Red, trade(brand)name, Ciba Specialty Chemicals (Co., Ltd.) system) and the above-mentioned exemplary compounds a-1 of 4g (compound test portion 1) are mixed in the 500g propylene glycol monomethyl ether, this mixed solution is carried out 3 hours mixing and dispersion with ball mill (zirconium white microballon 0.3mm), modulated dispersible pigment dispersion (dispersion s).Then, according to the step identical, powder and pigment dyestuff dispersive composition sA have been modulated with embodiment 1.

The evaluation of＜pigment dispensing composition 〉

Each test portion for resulting pigment dispensing composition carries out following evaluation.The result is shown in Table 1 in the lump.

The mensuration of the size distribution of zero pigment particle, number average primary particle size (Dp)

According to the size distribution of the pigment particles that is contained in the following condition mensuration dispersion liquid, calculating particle diameter is the ratio P and the number average primary particle size Dp of the population of 20nm～30nm.

＜TEM photography 〉

Device: Hitachi's system, H-7650 electron microscope (trade(brand)name)

Acceleration voltage: 110kV

(carry out tomography and observe, take out from the 3D playing data for broadcasting and overlap few face between the particle, obtain the shadow area of particle.)

＜image instrumentation 〉

Device: Carl Zeiss company makes, KS-400 (trade(brand)name)

(the TEM image of optional 5000 pigment particles of instrumentation, and calculate diameter of equivalent circle from shadow area, thus calculate above-mentioned ratio P and Dp.)

The mensuration of zero viscosity, evaluation

For resulting pigment dispensing composition, use E type viscometer (eastern machine industry (Co., Ltd.) company makes, the RE-85L[trade(brand)name], measure 25 ℃ of temperature), measure the pigment dispensing composition after just disperseing viscosities il 1 and after the dispersion under room temperature through the viscosities il 2 of the pigment dispensing composition after 1 week, the degree of evaluation thickening.Here, the low expression of viscosity: the viscosity that can suppress to be caused by dispersion agent rises, and dispersing of pigments and dispersion stabilization are good.

The mensuration of zero contrast gradient, evaluation

Resulting pigment dispensing composition is applied on the glass substrate, is that the mode of 1 μ m has been made sample with the thickness of dried coated film.Between 2 polaroids, place this sample, when to measure polarization axle be parallel with transmission light quantity when vertical, its ratio is spent as a comparison (this evaluation assessment with reference to " nineteen ninety the 7th color reversion glory learn コ Application Off アレ Application ス, 512 colour specifications 10.4 " サイズ TFT-LCD with カラ one Off イ Le タ,

Wood, Xiao Seki, good fortune forever, in the mountain " etc.)。Here, the high expression of contrast gradient: owing to pigment is disperseed under the state of height miniaturization equably, so transmissivity is the tinting strength height.

Table 1

Contrast gradient (1): the contrast gradient of composition

Contrast gradient (2): the contrast gradient of colour filter

Resin 1:Dysperbyk-161

Resin 2: the multipolymer of above-mentioned repeating unit (M-11)/(A-5)/methacrylic acid (Mw 20,000, ratio of components (wt%) 10/60/30)

By the result shown in the last table as can be known, used the extremely little and particle diameter unanimity of median size of dispersion of the compound of general formula of the present invention (1) expression, viscosity is suppressed to lower, the thermotolerance height, and have the high good properties of contrast gradient.In addition, compound 11 has also been carried out identical evaluation, and confirmed that it also can obtain good performance.

(example II, Comparative Example I I)

The modulation of＜coloring photosensitive combination 〉

Use above-mentioned pigment dispensing composition to modulate following coloring photosensitive combination respectively.

2000 parts of pigment dispensing compositions

100 parts of Dipentaerythritol five/six acrylate (optical polymerism compound)

4-[o-bromo-p-N, N-two (ethoxy carbonyl) aminophenyl]-2,30 parts of 6-two (trichloromethyl)-s-triazine (Photoepolymerizationinitiater initiater)

Methacrylic acid benzyl ester/methacrylic acid (=75/25[mass ratio]) multipolymer (weight-average molecular weight: propylene glycol 12,000)

Monomethyl ether acetate solution (solids component 30%)

(alkali soluble resin) 400 parts

390 parts of 1-methoxyl groups-2-propyl-acetic acid ester (solvent)

＜used the making of the colour filter of coloring photosensitive combination 〉

With synthetic coloring photosensitive combination (colored resist liquid) be applied on the glass substrate (1737, Corning company make) of 100mm * 100mm, so that reach 0.650, dry 60 seconds (prebake) in 90 ℃ baking oven as the x value of the index of depth of shade.Then, on whole of coated film with 200mJ/cm ²(illumination is 20mW/cm ²) expose, the coated film after the exposure is full of 1% aqueous solution of alkaline developer CDK-1 (FUJIFILM Electronic Materials (Co., Ltd.) system), static 60 seconds.After static, pure water is the shower shape to be scattered, developing solution is washed, then, by above-mentioned such, with the coated film heat treated 1 hour (main cure) of 220 ℃ baking ovens to having implemented exposure and having developed, on glass substrate, formed the colored pattern that colour filter is used (painted areas), made painted filter substrate (colour filter).

The evaluation of＜coloring photosensitive combination and colour filter 〉

For the coloring photosensitive combination and the painted filter substrate (colour filter) of made, estimate according to following, the result is shown in the above-mentioned table in the lump.

The contrast gradient of zero colour filter (CF)

On the colored substrate of colour filter, place polaroid, sandwich colored substrate, the resulting value of brightness during divided by quadrature of the brightness of the brightness that the BM-5 (trade(brand)name) that uses TOPCON company to make measures polaroid when being parallel with as quadrature time the, the brightness when parallel (brightness during=brightness when parallel/orthogonal) is as the index that is used to estimate contrast gradient.It is high more to be worth big more expression contrast gradient.

Zero stable on heating evaluation

The colour filter of made is carried out 1 hour heat treated forcibly in 250 ℃ baking oven, estimate the contrast gradient conservation rate before and after handling.

Zero development

In exposure process, observe the having or not of residue of not zone of irradiates light (unexposed portion), estimate development.

-metewand-

3: in unexposed portion, the complete residue that has unconfirmed.

2: although confirm to have residue a little in unexposed portion, no problem degree in practicality.

1:, confirm to have residue significantly in unexposed portion.

According to the result of each embodiment shown in the last table and comparative example as can be known, use the contrast gradient of the colour filter that the dispersion that contains the compound of general formula (1) expression of the present invention is made extremely high, bringing into play excellent performance aspect thermotolerance, the development.And, can confirm that the R of the resulting colour filter of the present invention of the foregoing description (red) pixel is all within the scope of target colourity.

Claims

1. a pigment particle dispersion is characterized in that, it contains the compound of pigment particle and following general formula (1) expression,

General formula (1)

In the formula, X ¹And X ²Represent hydrogen atom, halogen atom, replacement or unsubstituted alkyl or replacement or unsubstituted aromatic group independently of one another; R ¹And R ²Represent hydrogen atom or replacement or unsubstituted alkyl independently of one another; Wherein, R ¹And R ²In one of at least be to replace or unsubstituted carbonatoms is a alkyl more than 2.

2. according to the pigment particle dispersion of claim 1 record, it is characterized in that, be mixed with the compound of described general formula (1) expression in the described pigment particle.

3. according to claim 1 or the 2 pigment particle dispersions of putting down in writing, it is characterized in that described pigment particle is to mix with the medium that is bad solvent by the lysate that the common dissolving of compound with described pigment and described general formula (1) expression obtains to generate with respect to this lysate.

4. according to the pigment particle dispersion of each record in the claim 1～3, it is characterized in that described R ¹And R ²In one of at least be substituting group with any one expression in the following general formula (R-1)～(R-4),

In the above-mentioned general formula, Q ¹Expression alkyl or aromatic group; Q ²Expression annular aliphatic or aromatic group; Q ³Expression alkyl or aromatic group; Q4 represents aromatic group; P represents integer; * represent bonding position with nitrogen-atoms.

5. according to the pigment particle dispersion of each record in the claim 1～4, it is characterized in that described X ¹And X ²Be that hydrogen atom, chlorine atom, phenyl or carbonatoms are 1～4 alkyl independently of one another.

6. according to the pigment particle dispersion of each record in the claim 1～5, it is characterized in that described pigment is the pyrrolopyrrole derovatives.

7. according to the pigment particle dispersion of each record in the claim 1～6, it is characterized in that it further contains the dispersion agent with polycaprolactone structure.

8. according to the pigment particle dispersion of each record in the claim 1～7, it is characterized in that, it further contains macromolecular compound, described macromolecular compound comprise be selected from following general formula (I) and (II) in the repeating unit of any one expression at least a repeating unit

Described general formula (I) and (II) in, R ¹¹～R ¹⁶The organic group of representing hydrogen atom or 1 valency independently of one another; X ¹¹And X ¹²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene; L ¹And L ²Organic binding group of representing singly-bound or divalent independently of one another; A ¹And A ²The organic group of representing 1 valency independently of one another; M and n represent 2～8 integer independently of one another; P and q represent 1～100 integer independently of one another.

9. according to the pigment particle dispersion of each record in the claim 1～8, it is the colour filter colorant.

10. Photocurable composition, it contains dispersion, polymerizable compound and the Photoepolymerizationinitiater initiater of each record in the claim 1～9.

11. a colour filter, the pixel that its Photocurable composition with the record of making in the claim 10 is solidified to form.

12. the manufacture method of a pigment particle dispersion, it is characterized in that, modulation makes the lysate of pigment dissolved in good solvent, and with this lysate be bad solvent with respect to described pigment and mix with medium that good solvent mixes, when described pigment particle is generated, it is under the coexistence of the compound of following general formula (1) expression described pigment particle to be generated

General formula (1)