CN102134403A

CN102134403A - Pigment particle dispersion, light-cured composition, color filter, pigment derivative compound and the preparing method of the pigment derivative compound

Info

Publication number: CN102134403A
Application number: CN2010105784623A
Authority: CN
Inventors: 佐佐木大辅; 中尾真人
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2009-12-04
Filing date: 2010-12-03
Publication date: 2011-07-27
Also published as: JP2011137142A; TW201129640A; KR20110063333A

Abstract

The invention aims to provide pigment particle dispersion, a light-cured composition, a color filter using the dispersion, a pigment derivative compound applied in the formation of the dispersion and the preparing method of the pigment derivative compound. The pigment particle dispersion has small particle-sized pigment particles with a sharp particle size distribution. The color filter thus resulted has an upgraded pixel with higher contrast ratio, higher heat resistance and higher light resistance. The pigment particle dispersion comprises pigment derivative compound and pigment particles, wherein, the pigment derivative compound is obtained through a reaction of the pigment, the compound shown in the following formula (1) and the compound shown in the following formula (2) in an acidic solvent. In the formula (1), Q represents aromatic alkyl with a substituent while n represents an integer between 1 and 4. In formula (2), R1 and R2 independently represent hydrogen atoms or alkyl respectively.

Description

Pigment particle dispersion, Photocurable composition and colour filter and pigment derivative compound and manufacture method thereof

Technical field

The present invention relates to particularly suitable and make pigment derivative compound and the manufacture method thereof used in pigment particle dispersion, the colour filter that has used this dispersion and this dispersion of tinting material of colour filter etc.

Background technology

Colour filter requires to have high-performance, high-quality, this has been attempted the pigment dyestuff that uses in its making is improved.Particularly, require pigment dyestuff storage stability excellence and used the contrast gradient excellence of filming etc. of the colour filter colored pixels portion of this pigment dispersion in the preparation of pigment dispersion.In order to satisfy this demand, carried out the research that for example makes the scope of pigment particles small-sized to 10～100nm and make its stably dispersing energetically.Thus, reach nano-scale, thereby effectively utilized the action effect of first discovery, make that the unexpected in the past new characteristic of performance becomes possibility effectively by making it.Above-mentioned colour filter purposes just much less, even for example coating, printing-ink, electronic photo with toning agent, ink for inking etc. in, its research and development have also obtained progress.Particularly for above-mentioned colour filter and ink for inking, be devoted to realize using the high performance of precision chemical technology, its achievement also enjoys expectation.

Here, about the dispersing method of pigment dyestuff, various polishings (crush method) such as pearl mill method, salt mill method and liquid phase method etc. are arranged.Be applied to document in the printing ink etc. as disclosing the pigment particle that will utilize crush method preparation, patent documentation 1 and 2 etc. are arranged.Disclose particularly in the patent documentation 1 that the group that will have three zin residues imports pigment molecule and the pigment derivative that obtains, and proposed this derivative is applied in the dispersion liquid of broken pigment particles, thereby reduced viscosity and improve the glossy scheme of printing ink.Proposed in the patent documentation 2 sulfonic group to be imported the pigment derivative that pigment molecule obtains, thereby improved the scheme of the luminance brightness of red ink by using.

In addition, liquid phase method is suitable for obtaining fine pigment particles, particularly, have by pigment dissolved is mixed with bad solvent (the 2nd solvent) in the pigment solution that good solvent (the 1st solvent) obtains, thus the reprecipitation method that nanoparticle is separated out.Recently, proposed in the dispersion liquid that obtains by this reprecipitation method to add the scheme (with reference to patent documentation 3～6) of the macromolecular compound etc. of regulation as dispersion agent.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-186681 communique

Patent documentation 2: TOHKEMY 2000-160084 communique

Patent documentation 3: the international WO2006/121016 brochure that discloses

Patent documentation 4: TOHKEMY 2004-43776 communique

Patent documentation 5: TOHKEMY 2007-119586 communique

Patent documentation 6: TOHKEMY 2007-23169 communique

Summary of the invention

The object of the present invention is to provide a kind of pigment particle dispersion and Photocurable composition, used pigment derivative compound and the manufacture method thereof used in the colour filter of this dispersion and this dispersion, described pigment particle dispersion is because the particle diameter of pigment particle is little and the size-grade distribution peak is sharp-pointed and show good dispersiveness and tinting material that particularly suitable is used as colour filter, when using this dispersion to form the pixel of colour filter, its contrast gradient can be improved, and high thermotolerance and photostabilization can be brought into play.

Above-mentioned problem solves by following means.

(1) a kind of pigment particle dispersion, it is characterized in that, it contains pigment derivative compound and pigment particle, and described pigment derivative compound is the compound that the compound reaction by compound that makes the expression of pigment, following general formula (1) in acid solvent and following general formula (2) expression obtains.

General formula (1) general formula (2)

(in the general formula (1), Q represents to have substituent aromatic hydrocarbyl.N represents 1～4 integer.In the general formula (2), R ¹And R ²Represent hydrogen atom or alkyl independently of one another.)

(2) according to (1) described pigment particle dispersion, wherein, described pigment derivative compound is the compound that further obtains by the compound reaction that makes following general formula (3) expression.

General formula (3)

(in the general formula (3), T represents the univalent organic group.K represents 0～4 integer.R ³Expression hydrogen atom or methylol.)

(3) according to (1) described pigment particle dispersion, it is characterized in that, be the diketopyrrolo-pyrrole pigment compound as the pigment of the matrix of described pigment derivative compound.

(4), it is characterized in that described pigment particle is by making lysate that pigment dissolved obtains in good solvent and mixing with described good solvent and generate for the medium of the bad solvent of described pigment mixes according to (1) described pigment particle dispersion.

(5) according to (1) described pigment particle dispersion, it is characterized in that the pigment that constitutes described pigment particle is at least a kind that is selected from diketopyrrolo-pyrrole pigment, quinoline a word used for translation ketone pigment, anthraquinone pigment and the azo pigment.

(6) according to (1) described pigment particle dispersion, it is characterized in that, further contain dispersion agent with polycaprolactone structure.

(7) according to (1) described pigment particle dispersion, it is characterized in that it further contains the macromolecular compound that comprises at least a kind of repeating unit in the repeating unit that is selected from following general formula (I) and any expression (II).

(general formula (I) and (II) in, R ²¹～R ²⁶Represent hydrogen atom or univalent organic group independently of one another, X ²¹And X ²²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, L ²¹And L ²²Organic linking group of representing singly-bound or divalence independently of one another, A ²¹And A ²²Represent the univalent organic group independently of one another, ma and na represent 2～8 integer independently of one another, and p and q represent 1～100 integer independently of one another.)

(8) according to (1) described pigment particle dispersion, it is the colour filter tinting material.

(9) a kind of Photocurable composition, it contains each described dispersion, polymerizable compound and Photoepolymerizationinitiater initiater in (1)～(8).

(10) a kind of colour filter, the pixel that it has is solidified to form (9) described Photocurable composition.

(11) a kind of pigment derivative compound, it is that compound by compound that makes the expression of pigment, following general formula (1) and following general formula (2) expression reacts in acid solvent and obtains, and is made of the residue of described each matrix.

General formula (1) general formula (2)

(12) according to (11) described pigment derivative compound, it is further to obtain by the compound reaction that makes following general formula (3) expression, and has its residue.

General formula (3)

(13) according to the manufacture method of (11) described pigment derivative compound, it is characterized in that, the compound of described pigment, described general formula (1) expression and the compound of described general formula (2) expression are reacted in acid solvent.

Pigment particle dispersion of the present invention and the action effect that has used the Photocurable composition of this dispersion to have following excellence: because the particle diameter of the particulate that it contained is little and the size-grade distribution peak sharp-pointed and show good dispersiveness (character that is difficult to 2 cohesions), therefore the tinting material used as colour filter of particularly suitable, when using this dispersion to form the pixel of colour filter, its contrast gradient be can improve, and high thermotolerance and photostabilization brought into play.

Crystal growth inhibitor or the dispersing auxiliary in the pigment dispersion when in addition, pigment derivative compound of the present invention forms as pigment particle are useful.

Embodiment

Pigment particle dispersion of the present invention is characterised in that particulate that contains pigment and the pigment derivative compound of making by specific manufacture method.

[pigment derivative compound]

(A) pigment

The pigment that reacts in acid solvent is pigment dyestuff, and the concrete face of land shows that perylene dye, purple cyclic ketones pigment, quinoline a word used for translation ketone pigment, quinoline a word used for translation ketone quinone pigments, anthraquinone pigment, anthracene form anthrone pigment, benzimidazolone pigment, disazo pigment, azo pigment, indanthrone pigment, phthalocyanine pigment, triaryl carbon pigment, triazine dioxin pigment, aminoanthraquinone pigment, diketopyrrolo-pyrrole pigment, indigo pigment, thioindigo pigment, isoindoline pigment, isoindoline ketone pigment, pyrene anthrone pigment or iso-violanthrone pigment.Wherein, be preferably quinoline a word used for translation ketone pigment, anthraquinone pigment, diketopyrrolo-pyrrole pigment, benzimidazolone pigment, phthalocyanine pigment, azo pigment, triazine dioxin pigment, isoindoline pigment, more preferably quinoline a word used for translation ketone pigment, anthraquinone pigment, diketopyrrolo-pyrrole pigment are preferably diketopyrrolo-pyrrole pigment especially.Need to prove,, also be referred to as " pigment matrix " sometimes for the pigment difference of pigment used herein with hereinafter described formation pigment particle.

(B) compound of general formula (1) expression

General formula (1)

In the formula, Q represents to have substituent aromatic hydrocarbyl.As this moment of substituting group arbitrarily, can list halogen (F ,-Br ,-Cl ,-I), alkyl, hydroxyl, alkoxyl group, nitro etc.Wherein, be preferably alkyl, hydroxyl, nothing replacement (hydrogen).Alkyl is represented the alkyl of straight or branched, and carbonatoms is preferably 1～6, more preferably 1～3.As aromatic hydrocarbyl, particularly, can list benzene, naphthalene, anthracene, pyrene, Azulene, 1,2-benzophenanthrene, kekulene, coronene etc.Wherein, be preferably benzene, naphthalene, anthracene, more preferably benzene, naphthalene are preferably benzene especially.

N represents any integer in 1～4, is preferably any integer in 1～2, most preferably is 1.

(C) compound of general formula (2) expression

General formula (2)

In the formula, R ¹And R ²Represent hydrogen atom or alkyl independently of one another.R ¹With R ²Can be the same or different.Alkyl is represented the alkyl of straight or branched, and carbonatoms is preferably 1～6, more preferably 1～3.About R ¹And R ², wherein more preferably hydrogen atom, methyl, preferred especially R ¹, R ²Be hydrogen atom.

(D) compound of general formula (3) expression

General formula (3)

The univalent organic group of representing as T; can list alkyl; hydroxyl; alkoxyl group; aryloxy; sulfydryl; cyano group; nitro; amide group; sulfahydantoin; the alkyl sulfenyl; artyl sulfo; the alkyl disulfide group; the aryl disulfide group; amino; the N-alkylamino; N; the N-dialkyl amido; the N-arylamino; N; the N-ammonia diaryl base; N-alkyl-N-arylamino; acyloxy; formamyl oxygen base; N-alkyl-carbamoyl oxygen base; N-aryl-amino-carbonyl oxygen base; N; N-dialkyl amido formyl radical oxygen base; N; N-ammonia diaryl base formyl radical oxygen base; N-alkyl-N-aryl-amino-carbonyl oxygen base; alkyl sulphonyl; aryl sulfonyl; acyl mercapto; acyl amino; N-alkyl acyl amino; N-aryl-acyl amino; carbamate groups; urea groups; N '-alkyl urea groups; N '; N '-dialkyl group urea groups; N '-aryl-ureido; N '; N '-diaryl urea groups; N '-alkyl-N '-aryl-ureido; N-alkyl urea groups; the N-aryl-ureido; N '-alkyl-N-alkyl urea groups; N '-alkyl-N-aryl-ureido; N '; N '-dialkyl group-N-alkyl urea groups; N '; N '-dialkyl group-N-aryl-ureido; N '-aryl-N-alkyl urea groups; N '-aryl-N-aryl-ureido; N '; N '-diaryl-N-alkyl urea groups; N '; N '-diaryl-N-aryl-ureido; N '-alkyl-N '-aryl-N-alkyl urea groups; N '-alkyl-N '-aryl-N-aryl-ureido; alkoxycarbonyl amino; aryloxycarbonyl amino; N-alkyl-N-alkoxycarbonyl amino; N-alkyl-N-aryloxycarbonyl amino; N-aryl-N-alkoxycarbonyl amino; N-aryl-N-aryloxycarbonyl amino; formyl radical; acyl group; carboxyl and conjugation base thereof (hereinafter referred to as the carboxylic acid foundation); ester group; alkoxy carbonyl; aryloxycarbonyl; formamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formyl radical; N-aryl-amino-carbonyl; N, N-ammonia diaryl base formyl radical; N-alkyl-N-aryl-amino-carbonyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfonic group (SO ₃H) and conjugation base (hereinafter referred to as sulfonic acid foundation (sulfonato)); the alkoxyl group alkylsulfonyl; aryloxy sulfonyl; the amine sulfinyl; N-alkylamine sulfinyl; N; N-dialkylamine sulfinyl; N-arylamines sulfinyl; N; N-diarylamine sulfinyl; N-alkyl-N-arylamines sulfinyl; sulfamic; N-alkylamine alkylsulfonyl; N; N-dialkylamine alkylsulfonyl; N-arylamines alkylsulfonyl; N, N-diarylamine alkylsulfonyl; N-alkyl-N-arylamines alkylsulfonyl; N-acyl amine alkylsulfonyl and conjugation base thereof; N-alkyl sulphonyl sulfamic (SO ₂NHSO ₂) and conjugation base, N-aryl sulfonyl sulfamic (SO ₂NHSO ₂And conjugation base, N-alkyl sulfonyl-amino formyl radical (CONHSO (allyl)) ₂And conjugation base, N-aryl-sulfonyl-amino-carbonyl (CONHSO (alkyl)) ₂And conjugation base, alkoxysilyl (Si (Oalkyl) (allyl)) ₃), aryloxymethyl silylation (Si (Oallyl) ₃), hydroxyl silyl (Si (OH) ₃) and conjugation base, phosphono (PO ₃H ₂) and conjugation base (hereinafter referred to as phosphono foundation (phosphonato)), dialkyl phosphine acyl group (PO ₃(alkyl) ₂), diaryl phosphono (PO ₃(aryl) ₂), alkylaryl phosphono (PO ₃(alkyl) (aryl)), monoalkyl phosphono (PO ₃H (alkyl)) and conjugation base (being called alkyl phosphono foundation later on), single aryl phosphine acyl group (PO ₃H (aryl)) and conjugation base (being called aryl phosphono foundation later on), phosphono oxygen base (OPO ₃H ₂) and conjugation base (being called phosphono foundation oxygen base later on), dialkyl phosphine acyloxy (OPO ₃(alkyl) ₂), diaryl phosphono oxygen base (OPO ₃(aryl) ₂), alkylaryl phosphono oxygen base (OPO ₃(alkyl) (aryl)), monoalkyl phosphono oxygen base (OPO ₃H (alkyl)) and conjugation base (being called alkyl phosphono foundation oxygen base later on), single aryl phosphine acyloxy (OPO ₃H (aryl)) and conjugation base (being called aryl phosphono foundation oxygen base later on).Wherein, as preferred substituted, can list halogen, alkyl, alkoxyl group, amino, carboxyl, cyano group, nitro, amide group, sulfahydantoin, ester group, carbamate groups, urea groups, sulfonic group, phosphono.From the viewpoint of carbonatoms, the carbonatoms of substituting group T is preferably 1～8, more preferably 1～6.

K represents 0～4 integer, be preferably 0～2 integer, more preferably 0 or 1.

R ³Expression hydrogen atom or methylol.

(acid solvent)

The acid solvent that uses when making paints derivative can list organic acids such as mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid or acetate, trifluoroacetic acid, oxalic acid, methylsulfonic acid, trifluoromethanesulfonic acid.Wherein, preferably sulfuric acid, hydrochloric acid, phosphoric acid, trifluoroacetic acid, Tripyrophosphoric acid, methylsulfonic acid, trifluoromethanesulfonic acid, from the viewpoint of pigment dissolved, more preferably sulfuric acid, methylsulfonic acid, trifluoromethanesulfonic acid.In order in sulfuric acid, to make its reaction and yield obtain pigment derivative well, special preferably sulfuric acid.

(reaction conditions)

The preferred reaction conditions of above-mentioned each matrix that is used for synthetic pigment derivative compound of the present invention is as follows.At first, in acid solvents such as sulfuric acid, add pigment matrix (A).At this moment, pigment matrix (A) can dissolve fully also and can not dissolve fully.At this moment, temperature of reaction is preferably 0 ℃～100 ℃, more preferably 0 ℃～60 ℃, is preferably 0 ℃～40 ℃ especially.Then, add (B) by the compound of general formula (1) expression and the compound of (C) representing by general formula (2).At this moment, can also further add (D) compound by general formula (3) expression.In addition, the order that adds matrix compounds (B), (C), (D) can be that whatsoever the order of sample all can simultaneously.And can be that once all the interpolation of amount ground also can the gradation interpolation.After adding end, by under above-mentioned temperature of reaction, stirring 30 minutes～10 hours the synthetic dyestuff derivative.

Amount in the response matrix system does not have particular determination, but if consider typical condition, then can list pigment matrix (A) is 1～50 quality % in reaction medium.For the compound (B) of general formula (1) expression, can list with respect to pigment matrix (A) 1 equivalent is 0.1～10 equivalent.For the compound (C) of general formula (2) expression, can list with respect to pigment matrix (A) 1 equivalent is 0.1～30 equivalent.For the compound (D) of general formula (3) expression, can list with respect to pigment matrix (A) 1 equivalent is 0.1～10 equivalent.

Here, enumerate the matrix of above-mentioned building-up reactions and the example of action solvent, but the present invention is not subjected to the limited interpretation of these examples.

Table 1

The pigment derivative compound of the present invention of the above-mentioned building-up reactions of process is made of the residue of above-mentioned each matrix.That is, above-mentioned pigment derivative compound has the molecular structure of the residue be combined into of the residue of compound (C) of residue, above-mentioned general formula (2) expression of the compound (B) of the residue of pigment matrix (A), above-mentioned general formula (1) expression and the compound (D) that above-mentioned general formula (3) is as required represented.

As the example of the compound that obtains by above-mentioned reaction, can list the structure that the aromatic hydrocarbyl Q that represents as pigment Pig and the general formula (1) of following A-1 passes through the methylene radical be combined into.

Formula A-1

N represents that 0～4 integer, n1, m1 represent 1～4 integer independently of one another.

In addition, when the pigment derivative compound with above-mentioned general formula (3) expression uses as raw material, when explaining accordingly, can list the structure of following formula A-2 with above-mentioned formula A-1.The same meaning of n in the formula, n1, m1 and formula A-1, the integer of 11 expressions 1～4.

Formula A-2

In pigment particle dispersion of the present invention, the content of the pigment derivative by described manufacture method manufacturing is not particularly limited, and is preferably 1～100 mass parts, 10～50 mass parts more preferably with respect to pigment 100 mass parts.By being set in more than the above-mentioned lower value, can make through miniaturization and pigment particle stable dispersion that surface-area increases, by being set in below the above-mentioned higher limit, can prevent that the excessive interpolation of pigment derivative from adding look energy (color valency) reduction that is caused.

Can will add to by the pigment derivative of described manufacture method manufacturing in the dispersion of pigment particle in any stage, for example in reprecipitation method described later, can add in advance in good solvent or the bad solvent, or after pigment particle is separated out, perhaps concentrating thereafter or adding during redispersion.In the present invention, when considering to make the dispersion of the non-water system that colour filter uses, preferably dispersion liquid is concentrated or powdered after when carrying out redispersion, add as dispersing auxiliary with the dispersion agent that is applicable to the Photocurable composition that colour filter is used.

According to an embodiment of the invention, because above-mentioned pigment derivative compound has the pigment mother nucleus structure, this parent nucleus is adsorbed in pigment molecule consumingly by strong interaction.At this moment, consider therefore to have suppressed the cohesion of pigment particles owing to acidic-group (sulfonic group) is arranged by specific linking group importing.Thus, though detailed reason and unclear for example when using its dispersion to make colour filter, makes and takes into account high contrast gradient and high-light-fastness becomes possibility.In addition, though also have unclear place about its mechanism of action, can't obtain and the distinctive condition of surface of compound (build up) particulate of obtaining by reprecipitation method is particularly suitable for acting on described pigment derivative compound by crush method, by with they combinations, can bring into play above-mentioned effect with higher level.

Need to prove that in the statement of the group in this specification sheets, expression replaces and the statement of not having a replacement is meant to comprise not have substituent group, also comprise and have substituent group.For example, the statement of " alkyl " not only refers to not have substituent alkyl (no substituted alkyl), and comprises and have substituent alkyl (substituted alkyl).

[pigment dyestuff]

The particulate that also contains pigment (below be sometimes referred to as " pigment E ") in the pigment particle dispersion of the present invention with above-mentioned pigment derivative compound.

Pigment E is a pigment dyestuff, it is not subjected to the qualification of tone, can list Li such as perylene dye, purple cyclic ketones pigment, quinoline a word used for translation ketone pigment, quinoline a word used for translation ketone quinone pigments, anthraquinone pigment, anthracene is formed anthrone pigment, benzimidazolone pigment, disazo condensation pigment, disazo pigment, azo pigment, indanthrone pigment, phthalocyanine pigment, triaryl carbon pigment, triazine dioxin pigment, aminoanthraquinone pigment, diketopyrrolo-pyrrole pigment, thioindigo pigment, isoindoline pigment, isoindoline ketone pigment, pyrene anthrone pigment or iso-violanthrone pigment or their mixture etc.Wherein, be preferably quinoline a word used for translation ketone pigment, anthraquinone pigment, benzimidazolone pigment, phthalocyanine pigment, azo pigment, triazine dioxin pigment, isoindoline pigment, more preferably quinoline a word used for translation ketone pigment, anthraquinone pigment, diketopyrrolo-pyrrole pigment, azo pigment are preferably diketopyrrolo-pyrrole pigment especially.

In the present invention, can also be used in combination the above-mentioned pigment dyestuff or the Solid solution of pigment dyestuff.In addition, can also make the matrix material that combines with other compounds.

In addition, pigment E can with the pigment matrix that when making paints derivative, uses (A) as identical type or for different kinds, wherein be preferably on the structure similarly pigment.As similar pigment compound on the structure, can list the identical pigment compound of unity structure that for example develops the color.Even under the pigment E situation different with pigment matrix (A), the tinting material that pigment particle dispersion of the present invention is used as colour filter also can be taken into account the purity of color of expectation and high contrast gradient, but similar pigment or the identical easier color adaptation of carrying out of pigment on the utilization structure are therefore preferred.

In pigment particle dispersion of the present invention, the content of pigment particle is not particularly limited, and when considering to make the tinting material that colour filter uses, the concentration that contains in the pigment particle dispersion is preferably 1～40 quality %, 5～20 quality % more preferably.

[comminuting method]

The pigment particle that uses among the present invention can be the pigment particle by the preparation of crush method such as comminuting method.At this moment, mixing such as all kinds of SOLVENTS that can be by will be as required, resin, varnish utilize desk-top sand mill, vertical grinding machine, ring-type type ball mill, masher etc. to disperse and obtain.Hereinafter described specific macromolecular compound (particular polymers) or other pigment dispersing agent can disperse after whole compositions mixes, also can first dispersed color and specific macromolecular compound (particular polymers) etc., only pigment or only pigment and pigment dispersing agent, add other compositions then and disperse once more.

In addition, utilizing before desk-top sand mill, vertical grinding machine, ring-type type ball mill, masher etc. disperse, the preceding dispersion of putty-chaser-type mixers such as kneader, triple-roller mill be can also use, the solid-state dispersion of two roller mills etc. or the Synergist that pigment is carried out and/or the processing of dispersion agent utilized with basic group.In addition, can also use dispersion machine or mixing machines such as high speed agitator, clarifixator, ball mill, roller mill, stone mortar formula grinding machine, ultra-sonic dispersion machine.

[reprecipitation method]

In pigment particle dispersion of the present invention, the organic pigment particles that the is contained particle of following generation preferably wherein: will make organic materials be dissolved in good solvent (following be referred to as sometimes " the 1st solvent ") and the lysate of the pigment dyestuff that obtains and have intermiscibility with described good solvent and generate for the solvent of the bad solvent of pigment dyestuff (following be referred to as sometimes " the 2nd solvent ") mixes.Below sometimes this method is called " reprecipitation method ", the dispersion liquid that contains organic pigment particles that obtained this moment is called " pigment redeposition liquid ".In addition, reprecipitation method and the difference of the additive method in the reprecipitation method carried out in order to make the common dissolving of above-mentioned pigment derivative compound and dispersion agent in the lysate of above-mentioned pigment dyestuff are referred to as " coprecipitation method " sometimes especially.

1. bad solvent (the 2nd medium)

The bad solvent of pigment dyestuff at first, is described.About bad solvent,, then there is not particular determination so long as can mix with the good solvent of dissolving pigment dyestuff or can mixed uniformly solvent.As bad solvent, the solubleness of preferred pigment dyestuff is below the 0.02 quality %, more preferably below the 0.01 quality %.The solubleness of pigment dyestuff in bad solvent is not had special lower limit,, be actually more than the 0.000001 quality % if consider normally used pigment dyestuff.This solubleness can be the solubleness in the presence of acid or alkali, especially under the situation along with the pigment type of the variation solubleness generation noticeable change of hydrogen ion concentration (pH), preferably acid or alkali suitably is mixed in the bad solvent and uses.

Preferred good solvent is more than the 30 quality %, more preferably more than the 50 quality % with respect to the meltage of bad solvent.Good solvent does not have the special upper limit with respect to the meltage of bad solvent, in fact mixes mutually with ratio arbitrarily.

As bad solvent, can list aqueous vehicles (water for example, hydrochloric acid or 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., preferred 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, 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 and PF ₆ ^-Salt etc.

Bad solvent can mix use by multiple solvent, also can mix good solvent according to classification and use.But this moment, need mix can not hinder separating out of pigment particles with the scope of miniaturization, crystallization.

2. good solvent (the 1st medium)

The good solvent of dissolving pigment dyestuff then, is described.Good solvent can dissolve the pigment of use, so long as mix or mixed uniformly solvent with described bad solvent, does not then have particular determination.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, when considering normally used pigment dyestuff, then is actually below the 50 quality %.This solubleness can be the solubleness in when dissolving in the presence of acid or alkali.The solubleness of bad solvent and good solvent or the preferable range of intermiscibility are as mentioned before.

As good solvent, for example can list aqueous vehicles (water for example, hydrochloric acid or 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, can list for example dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexa-methylene sulfoxide, tetramethylene sulfone etc.As the amide compound solvent, can list for example N, dinethylformamide, 1-Methyl-2-Pyrrolidone, 2-Pyrrolidone, 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.

In addition, the concentration of the pigment dyestuff solution that obtains as pigment dyestuff is dissolved in good solvent under the condition in when dissolving, preferably is about 1/ 100 scope of saturation concentration or it with respect to the good solvent of pigment dyestuff.Preparation condition to pigment dyestuff solution is not particularly limited, and can select in the scope from normal pressure to subcritical, super critical condition.Preferred normal pressure temperature down be-10～150 ℃, more preferably-5～130 ℃, be preferably 0～100 ℃ especially.

In the present invention, pigment dyestuff also can be dissolved in good solvent under acidity or alkalescence.In general, under intramolecularly has situation at pigment that can dissociated group under the alkalescence, use alkalescence, do not exist in dissociated group under the alkalescence and intramolecularly have use under the situation of nitrogen-atoms that a plurality of protons are easy to addition acid.For example quinoline a word used for translation ketone, diketopyrrolo-pyrrole, disazo condensation compound pigment dissolve under alkalescence, phthalocyanine compound pigment dissolves under acidity.

Being used for making under alkalescence pigment dyestuff dissolved alkali is mineral alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or hydrated barta, and perhaps organic basess such as trialkylamine, diazabicyclo hendecene (DBU) or metal alkoxide are preferably organic bases.The amount of employed alkali is can be with the amount of pigment uniform dissolution, there is not particular determination, under the situation of mineral alkali, be 1.0～30 molar equivalents, more preferably 1.0～25 molar equivalents, 1.0～20 molar equivalents more preferably preferably with respect to pigment dyestuff.Under the situation of organic bases, be 1.0～100 molar equivalents, more preferably 1.0～50 molar equivalents, 1.0～20 molar equivalents more preferably preferably with respect to pigment dyestuff.

Be used for making under acidity the acid of pigment dyestuff dissolved to be 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 are preferably mineral acid.Be preferably sulfuric acid especially.The amount of employed acid is the amount of pigment dyestuff uniform dissolution can not to be had particular determination, usually compares with alkali excessively and uses.No matter being mineral acid or organic acid, is 3～500 molar equivalents, more preferably 10～500 molar equivalents, 30～200 molar equivalents more preferably with respect to pigment dyestuff preferably.

When the good solvent that alkali or acid and organic solvent are mixed and made into pigment dyestuff uses, fully dissolve, can in organic solvent, add a little water or lower alcohol etc. alkali or sour solvent with high solubleness in order to make alkali or acid.The amount of water or lower alcohol with respect to pigment dyestuff solution total amount be preferably below the 50 quality %, more preferably below the 30 quality %.Particularly, can make water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols etc.

3. mixing condition

Separate out when organic filler is made, the working conditions of the bad solvent when forming organic filler is not particularly limited, can select in the scope from normal pressure to subcritical, super critical condition.Preferred normal pressure temperature down be-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 ratio) is preferably 1/50～1/1, more preferably 1/40～1/1, is preferably 1/10～1/1 especially in volume ratio.It can be identical with the volume flow ratio of pigment solution in the stream of flow reactor and bad solvent also can be different.For example, ratio of mixture being set under 1/2 the situation,, can take following method as object lesson.

(i) volume flow ratio with good solvent and bad solvent is set at 1/2

(ii) use in advance with good solvent with the mixed of (volume ratio of good solvent/bad solvent)=(1/4) in bad solvent and the solvent A that obtains, the volume flow ratio of pigment solution and solvent A is set at 1/5.Under this situation, the good solvent in the pigment solution and the total amount of the good solvent among the solvent A are 1+1=2, and because the bad solvent amount among the solvent A is 4, the final ratio of mixture of therefore good solvent and bad solvent is 1/2.

As long as the pigment concentration in the pigment redeposition liquid can generate pigment particles, then be not particularly limited, with respect to redeposition liquid 1000ml, pigment particles be preferably the scope of 10～40000mg, more preferably 20～30000mg scope, be preferably the scope of 40～25000mg especially.

In the present invention, preferably carry out mixing of pigment solution and bad solvent rapidly, particularly preferably in adopting promotion blended means in this part.As one of wherein method, consider for example to make the high speed fluid flow the method that it is clashed in narrow space with the state of adverse current by making mixing space generation turbulent flow promote to mix.Wherein, mixed pattern is not defined as the mixing under the turbulent flow domination, for example it is also conceivable that intersection point, make between the fluid to contact, carry out the blended method by molecular diffusion with laminar flow regime by the stream that forms the Y-shaped as shown in TOHKEMY 2006-104448 communique.

In the present invention, be that turbulent flow or streamlined judgement use the pipe Reynolds number to carry out about the fluidic flow state.That is, represent length (be called in the present invention represent footpath) to be designated as D[m when managing], the linear flow shorthand of the liquid of circulation is u[m/s] (literary composition is seen below in definition), density of liquid and viscosity are designated as ρ [kg/m respectively ³], during η [Pas], pipe reynolds number Re [-] defines by following formula.

Re＝Duρ/η

In the present invention, Re is decided to be turbulent flow at the state more than 1000,, will be lower than 100 state and be decided to be laminar flow more than 100 and be lower than 1000 state and be decided to be the transition territory.

The representative length D of following formula is the rerum natura to the pipe of the mobile tool influence in managing, and be its diameter under the situation of cylindrical duct, is defined by following formula under the situation that is not cylindrical duct.

D＝4A/p

Here, A[m ²] be the sectional area of stream, p[m] be the length (soaking the length of side) of the part that contacts with wall at the stream inner fluid.

Use this D that linear flow speed u mentioned above is defined as follows.

u＝Q/{(D/2) ²×π}

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

In the stream way, the cross-sectional shape after the representative footpath when diameter or cross-sectional shape change changes according to it is calculated, and represents the footpath can obtain linear flow speed and Reynolds number according to it.

In addition, in the present invention, the flow state of mixing space is very important, because the state of measuring mixing space exactly difficulty relatively, therefore when satisfying 2 following conditions simultaneously, be turbulent the domination with the condition estimating of mixing space.

(i) according to the blended fluid pipe reynolds number Re before be about to mixing separately, the flow state in the stream that is connected with mixing space at least is judged to be turbulent flow.

(ii) according to mixed fluid at firm mixed pipe reynolds number Re, firm mixed flow state is judged to be turbulent flow.

Form in the operation at above-mentioned particle, the representative footpath of preferred conditioned reaction device, flow etc. are so that the median size of the pigment particles of separating out reaches the scope of expectation.Think in the present embodiment in the reactor that uses, can must be bigger with the flow set of each stream, and the admixture of the mixing space that forms this moment is suitable for 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, when pigment dissolved in good solvent the time, can be dissolved pigment dispersing agent and pigment derivative together.In the organic solvent, guarantee dispersed viewpoint, preferably use macromolecule dispersing agent as dispersion agent from the repulsive interaction of the entropy repulsion by having utilized molecular chain.According to the purposes of pigment derivative, can also carry out the modification of particle surface, especially from improving these viewpoints with the solvability of the interaction force of other dispersion agents or control particle and crystal formation etc., the also preferred pigment derivative of using.

As the dispersion agent that can use, can use for example low molecule or the macromolecule dispersing agent of anionic property, cationic, zwitter-ion, nonionic or pigment derivative.Wherein, if the molecular weight of macromolecule dispersing agent can be in solution uniform dissolution, then can use ad lib, preferred molecular weight is 1,000～2,000,000, more preferably 5,000～1,000,000, more preferably 10,000～500,000, is preferably 10,000～100,000 especially.In addition, as macromolecule dispersing agent, can list illustrative dispersion agent among described later dispersant A and the B.

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 may be used alone, two or more kinds can also be used in combination.

Comprise quaternary ammonium salt, alkoxylate polyamines, fatty amine Soxylat A 25-7, fatty amine in the cationic dispersion agent (cationic surfactant), 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 may be used alone, two or more kinds can also be used in combination.

The zwitter-ion dispersion agent for have simultaneously at intramolecularly described 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 may be used alone, two or more kinds can also be used in combination.

Pigment derivative type dispersion agent is defined as by 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, perhaps 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 Nai Huo perylene deutero-pigment derivative type dispersion agent that contains piperidyl, has the pigment derivative type dispersion agent that is connected to the structural functional group of pigment matrix by methylene radical, be aggregated the pigment matrix structure that the thing chemistry is modified, has sulfonic pigment derivative type dispersion agent, has sulfa pigment derivative type dispersion agent, pigment derivative type dispersion agent with ether, perhaps has the carboxylic acid group, the pigment derivative type dispersion agent of carboxylic acid ester groups or formamido-etc.

In the present invention, preferably use the compound of following general formula (1) expression.

General formula (1)

In the described general formula (1), X ¹And X ²Represent hydrogen atom, halogen atom independently of one another, replace or do not have the alkyl or the replacement of replacement or do not have the aromatic group of replacement.R ¹And R ²Represent hydrogen atom independently of one another or replace or do not have the alkyl of replacement.Wherein, R ¹And R ²In at least one expression replace or do not have alkyl of replacement.

At X ¹And X ²In, as halogen atom, can list fluorine atom, chlorine atom, bromine atoms, iodine atom, preferred 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, a chain, the ring-type any.As concrete group, can list for example methyl, butyl, the tertiary butyl, preferable methyl.

Have under the substituent situation at alkyl,, can list hydroxyl, alkoxyl group, alkyl-carbonyl, alkyl-carbonyl oxygen base, aromatic group as substituting group.

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

Have under the substituent situation at aromatic group,, can list hydroxyl, alkoxyl group, alkyl-carbonyl, alkyl-carbonyl oxygen base, 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 ¹And X ²Can be the same or different, be preferably identical group.

At R ¹And R ²In, alkyl is that carbonatoms is preferably 1～10, more preferably 1～5 alkyl, can be in straight chain shape, chain, the ring-type any.As concrete group, can list for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, sec.-propyl, isobutyl-, preferable methyl, ethyl, propyl group, amyl group.

Have under the substituent situation at alkyl; 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; alkoxy-carbonyl oxy; aryloxy ketonic oxygen base; amino (comprising anilino); acyl amino; amino carbonyl amino; alkoxycarbonyl amino; the aryloxy carbonylamino; sulfamyl amino; alkyl and arlysulfonylamino; sulfydryl; the alkyl sulfenyl; artyl sulfo; the heterocycle sulfenyl; sulfamic; sulfonic group; alkyl and aryl sulfonyl kia; alkyl and aryl sulfonyl; acyl group; the aryloxy carbonyl; alkoxy carbonyl; formamyl; aryl 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; alkoxy-carbonyl oxy; aryloxy ketonic oxygen base; amino (comprising anilino); acyl amino; amino carbonyl amino; alkoxycarbonyl amino; the aryloxy carbonylamino; sulfamyl amino; alkyl and arlysulfonylamino; the alkyl sulfenyl; artyl sulfo; the heterocycle sulfenyl; sulfamic; alkyl and aryl sulfonyl kia; alkyl and aryl sulfonyl; acyl group; the aryloxy carbonyl; alkoxy carbonyl; formamyl; aryl and heterocycle azo base; imide or their combination.

R ¹And R ²Be preferably following structure.

Q ₁Be alkyl, aromatic series (comprising aryl).Q ₂Be annular aliphatic, aromatic series (comprising aryl).Q ₃Be alkyl, aromatic series (comprising aryl), Q ₄Be aromatic series (comprising aryl).Alkyl, aromatic series are identical with alkyl, aromatic series mentioned above.

Below enumerate R ¹, R ²Object lesson.

Below enumerated the object lesson of the compound of general formula (1) expression, but the present invention is not subjected to the limited interpretation of these examples.

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

Need to prove that in the statement of group in this manual, expression replaces and the statement of not having a replacement is meant to comprise not have substituent group, also comprise and have substituent group.For example, the statement of " alkyl " not only refers to not have substituent alkyl (no substituted alkyl), and comprises and have substituent alkyl (substituted alkyl).

[pigment particle]

Particle diameter about particulate, utilize method of masurement that it is quantized, thereby the method for the mean size of reflection group, as method commonly used, the peaked mode particle diameter that expression distributes, the median diameter that is equivalent to the median of integral distribution curve, various median size (number is average, length is average, area is average, quality is average, volume averaging etc.) etc. are arranged, in the present invention, unless otherwise specified, then median size is meant number average bead diameter.The median size of the particulate in the dispersion of the present invention (primary particle) be preferably 100nm following, more preferably 75nm following, be preferably 5nm～50nm especially.Particulate in the dispersion of the present invention is preferably monocrystalline, polycrystalline or the associated complex of such size.

As the index of the homogeneity (monodispersity) of representing particle, in the present invention, unless otherwise specified, use the ratio (Mv/Mn) of 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).), promptly Mv/Mn is preferably 1.0～2.0, more preferably 1.0～1.8, is preferably 1.0～1.5 especially.

Measuring method as the particle diameter of organic filler can list microscopy, mass method, light scattering method, light shield method, electrical resistance method, acoustic method, dynamic light scattering method, preferred especially microscopy, dynamic light scattering method.As the microscope that uses in the microscopy, can list for example scanning electron microscope, transmission electron microscope etc.As the particle assay device that utilizes dynamic light scattering method, for example can list day machine dress corporate system Nano Trak UPA-EX150, Da mound electronics corporation's braking attitude light-scattering photometer DLS-7000 series (being trade(brand)name) etc.In the present invention, about the value of particle diameter, unless otherwise specified, be meant the value of measuring by the method that adopts among the embodiment.

The degree of crystallinity of the particulate of the particulate in the dispersion liquid of the present invention in dispersion medium is preferably more than 65%, and this degree of crystallinity is preferably 80～100%, more preferably 90～100%.The crystal grain diameter of the particulate in the dispersion liquid of the present invention is not particularly limited, and is preferably 20～500 dusts, 20～200 dusts more preferably.In the present invention, degree of crystallinity and crystal grain diameter are meant the value of following mensuration unless otherwise specified.

(evaluation of degree of crystallinity)

As the representational index of obtaining degree of crystallinity is the method for α degree of crystallinity, can be according to i.e. 28 ± 0.5 ° the peak intensity I of the distinctive Bragg angle (2 θ) of alpha type crystal _αWith i.e. 27 ° the peak intensity I of the distinctive Bragg angle (2 θ) of β N-type waferN _βCalculate by following formula.

(α degree of crystallinity)=(I _α)/(I _α+ I _β)

The distinctive Bragg angle of alpha type crystal (2 θ) i.e. is 28 ± 0.5 ° peak intensity I _αWith i.e. 27 ° the peak intensity I of the distinctive Bragg angle (2 θ) of β N-type waferN _βFollowing obtaining.Remove background as follows according to measuring the diffraction pattern that obtains by X-ray diffraction.Draw near 23 ° of lower end of low angle side of a Bragg angle that connects alpha type crystal and 30 ° of the lower end of high angle side near straight line, this straight line is removed as a setting.According to the diffraction pattern of having removed background, obtain peak intensity I _αWith I _β, calculate α degree of crystallinity by following formula.

(mensuration of crystal grain diameter)

Used the X-ray diffraction analysis of Cu-K α 1 line.Thereafter, in the scope of 2 θ=4deg～70deg, measuring the peak of expression maximum strength or expression can be wide with the half value at the peak of the isolating enough big intensity in contiguous peak, calculates crystal grain diameter by the formula of following Sherrer:

The formula of D=K * λ/(β * cos θ) Scherrer

[D: crystal grain diameter (

, crystal grain size), λ: measure the X ray wavelength (

), β: the width (radian) of the diffracted ray that the crystalline size is caused, θ: the Bragg angle of diffracted ray (radian), K: constant (β is different with the constant of D)]

In general, when known β uses the wide β 1/2 of half value, K=0.9.And the wavelength of Cu-K α 1 line is 1.54050

, so the crystal grain diameter D among the present invention calculates based on following formula:

D＝0.9×1.54050/(β1/2×cosθ)

Here, by the spectrographic peak width that mensuration obtains, under the wide situation of the half value that can't differentiate described peak, infer crystal grain diameter less than 20

Or be amorphous (amorphousness).

[concentrating and redispersion]

1. dispersion concentrates

The operation of removing as removing the solvent composition the mixed solution after the pigment dyestuff particulate is separated out does not have particular determination, can list for example to utilize strainer etc. to carry out filtering method, utilize centrifugation to make the sedimentation of pigment dyestuff particulate carry out spissated method etc.About the filtering device of strainer, can use the device of for example decompression or pressure filtration.As preferred strainer, can list filter paper, nanofilter, ultra-fine filter etc.Separating centrifuge is so long as can make the sedimentation of water-insoluble compound particulate, and then any device can use.For example except general device, can list and have the separating centrifuge of getting rid of function (attracting supernatant layer and the outer function of discharge system in the rotation), or the continuous centrifuge of continuously solid matter being discharged etc.About the centrifugation condition, be preferably 50～10000, more preferably 100～8000, be preferably 150～6000 especially in centrifugal force (value of several times centrifugal acceleration of expression weight application acceleration).Though the temperature during centrifugation according to the difference of the solvent species of dispersion liquid and difference, be preferably-10～80 ℃, more preferably-5～70 ℃, be preferably 0～60 ℃ especially.In addition, as the operation of removing of solvent composition, can also use by vacuum lyophilization to make solvent distillation carry out spissated method, make the solvent drying carry out spissated method, their combined method etc. by heating or decompression.

2. redispersion

The particulate of pigment dyestuff for example can use with dispersive state in vehicle.Described vehicle is that example is meant with coating, make the part of pigment dyestuff dispersive medium when being in liquid state, it is included as aqueous and combines the part (tackiness agent) of filming with reinforcing with described water-insoluble compound and the composition (organic solvent) of this part of dissolved dilution.Wherein, in the present invention, the pigment dyestuff dispersion agent that uses in macromolecular compound that uses when particulate is formed and/or the redispersionization is referred to as tackiness agent.

The particulate loading of the dispersion of the particulate after the redispersionization can suitably determine according to purpose, but preferably with respect to dispersion total amount particulate be preferably 2～30 quality %, more preferably 4～20 quality %, be preferably 5～15 quality % especially.Under the situation in being distributed to above-mentioned vehicle, the amount of tackiness agent and dissolved dilution composition can wait suitably according to the kind of water-insoluble compound to be determined, with respect to the dispersion total amount, tackiness agent be preferably 1～30 quality %, more preferably 3～20 quality %, be preferably 5～15 quality % especially.The dissolved dilution composition is preferably 5～80 quality %, 10～70 quality % more preferably.

Can be in the organic solvent identical with the used solvent of bad solvent liquid with the particulate redispersion of pigment dyestuff, also can add other dispersion agent etc., thereby the state of aggregation that preferably has pigment dyestuff particulate in the organic solvent identical with bad solvent is spontaneously untied the character that is distributed in the medium, and the phenomenon of this character that will have is called " can self-ly disperse " or " it is dispersed to have the oneself ".Wherein, in the present invention,, can also when the particulate redispersion, add pigment dispersing agent etc. in order further to improve redispersibility.From this viewpoint, the cohesion (aggregate) that will be difficult to redispersion sometimes and soft cohesion (agglomerate) or slowly cohesion (Flocculate) difference expression again that can redispersion.About their the cohesion form etc. of particulate, can be with reference to Japanese painting as the little Fineization と of Hui Chi “ You Machine pigment Fen San Ji Intraoperative " Chu Ye Expensive, the 45th volume, No. 5,2006,12-21 Page.

As the method that makes the particulate redispersion that is in this soft state of aggregation (agglomerate), can use the method for for example utilizing ultransonic dispersing method or applying physical energy.Employed ultrasonic irradiation device preferably has can apply the above ultransonic function of 10kHz, can list for example ultrasonic refiner, ultrasonic washing machine etc.Because when fluid temperature rose in ultrasonic irradiation, heat-coagulation can take place nanoparticle, therefore preferably fluid temperature is set at 1～100 ℃, more preferably is set at 5～60 ℃.The temperature control that the temperature controlling method can be carried out temperature controlled temperature regulation layer by the dispersion liquid temperature controlling, to dispersion liquid waits to be carried out.As by applying the dispersion machine that uses when physical energy disperses the pigment nanoparticle, be not particularly limited, can list for example dispersion machines such as kneader, roller mill, masher, super mill (Super mill), dissolver, clarifixator, sand mill.In addition, as preferred dispersing method, also can list the dispersing method of high pressure dispersion method, use fine particle bead.

[macromolecule dispersing agent]

In the present invention, preferably remove as mentioned above solvent composition in the water system of the dispersion by the reprecipitation method preparation.After the operation of removing above-mentioned water, preferably do not have drying process.At this moment, in order further to improve dispersing of pigments, only otherwise damage effect of the present invention, can also add dispersion agents such as specific pigment dispersing agent or tensio-active agent etc.Wherein, in reprecipitation method mentioned above, use dispersion agent used herein, for example can make its coexistence when the separating out of pigment particle.In addition, as following dispersion agent, main example illustrates macromolecular compound, among the present invention, when mentioning molecular weight, unless otherwise specified, then represents weight-average molecular weight, and molecular weight and dispersity are meant the value of measuring by following measuring method.

[measuring method of molecular weight, dispersity]

About molecular weight and dispersity, unless otherwise specified, then use GPC (gel permeation chromatography) method to measure.The gel that is filled in the post that uses in the GPC method is preferably the gel that has aromatics in repeating unit, can list the gel that for example is made of styrene diethylene benzene copoly mer.Preferred 2～6 of post connects use.It is that acid amides such as solvent, N-Methyl pyrrolidone are solvent that the solvent that uses can list ether such as tetrahydrofuran (THF), and ethers such as preferred tetrahydrofuran (THF) are solvent.Carry out, most preferably carry out in the scope at 0.5～1.5mL/min in the scope that the preferred flow velocity at solvent of mensuration is 0.1～2mL/min.By in this scope, measuring, can not increase the load of device, and then can measure efficiently.Measuring temperature is preferably carrying out under 10～50 ℃, is most preferably carrying out under 20～40 ℃.

The actual conditions of molecular weight determination below is shown.

Device: HLC-8220GPC (TOSOH (strain) system)

Detector: differential refractometer (RI detector)

Pre-column: TSKGUARDCOLUMN MP (XL) 6mm * 40mm (TOSOH (strain) system)

Sample lateral column: following 2 post series connection (being TOSOH (strain) system)

·TSK-GEL?Multipore-HXL-M?7.8mm×300mm

With reference to lateral column: identical with the sample lateral column

Thermostatic bath temperature: 40 ℃

Fluidised bed: tetrahydrofuran (THF)

Sample side flow laminar flow amount: 1.0mL/ minute

With reference to side flow laminar flow amount: 0.3mL/ minute

Sample solution concentration: 0.1 weight %

Sample injection rate: 100 μ L

Data are taked the time: sample injected back 16 minutes～46 minutes

Sampling interval: 300msec

1. dispersant A

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

Macromolecule dispersing agent is adsorbed in the surface of pigment, plays a role according to the mode that prevents to condense again.Therefore, can list the terminal-modified type polymer, graft type polymer, block type polymer at position as preferred construction with the surface of pigments of anchoring to.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.Described macromolecule dispersing agent is adsorbed onto the surface of pigment in dispersion step, and plays a role according to the mode that prevents to condense again.Therefore, can list the block type polymer, graft type polymer, terminal-modified type polymer at position as preferred construction with the surface of pigments of anchoring to.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.By above-mentioned pigment derivative of the present invention and following macromolecule dispersing agent with ad hoc structure are used in combination, can further improve the interaction between the dispersed effect of above-mentioned surfaction effect and raising, therefore preferred.

(graft type polymer)

About the graft type polymer, be not particularly limited, preferably can list Japanese kokai publication sho 54-37082 communique, record poly-alkylene imines and petchem are reacted in the Japanese kokai publication sho 61-174939 communique etc. and the compound that obtains, the amino of the side chain of the polyallylamine of putting down in writing in the Japanese kokai publication hei 9-169821 communique is modified by polyester and the compound that obtains, the polyester polyol of putting down in writing in the Japanese kokai publication sho 60-166318 communique adds generating polyurethane etc., in addition, also preferably can list as Japanese kokai publication hei 9-171253 communique, マ Network ロモノマ one chemical と industry (ァィピ one シ one publishing department, 1989) etc. in the record with the graft type polymer of polymerizability oligomer (hereinafter referred to as macromonomer) as copolymer composition.In addition, from being adsorbed in pigment and giving the angle of good dispersiveness, the graft type polymer of putting down in writing among the preferred TOHKEMY 2003-238837 with organic pigment part.About the high molecular branch of graft type portion, preferably can 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 described graft type, can list SOLSPERSE 24000, SOLSPERSE 28000, SOLSPERSE 32000, SOLSPERSE38500, SOLSPERSE 39000, SOLSPERSE 55000 (above is the Lubrizol corporate system), Disperbyk-161, Disperbyk-171, Disperbyk-174 [being trade(brand)name] such as (above are BYK Chemie corporate system).

(terminal-modified type polymer)

As terminal-modified type polymer, the end at polymkeric substance that can list record in Japanese kokai publication hei 9-77994 communique for example or 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 not particular determination, can list by the pigment adsorption block and be not adsorbed in the block type polymer that the block of pigment constitutes.Monomer as constituting the pigment adsorption block is not particularly limited, and can list the monomer that for example has adsorbable functional group in pigment.Particularly, can list monomer, monomer with organic pigment structure or heterocycle structure with acidic-group, have the monomer of basic nitrogen atom etc.As monomer, can list the organic pigment bone lattice put down in writing among the TOHKEMY 2003-238837 for example or maleimide derivatives etc. with organic pigment structure or heterocycle structure.As block type polymer, can utilize commercially available product.As concrete example, can list Disperbyk-2000, Disperbyk-2001 (above is BYK Chemie corporate system), EFKA4330, EFKA4340 [being trade(brand)name] such as (above are the EFKA corporate system).

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

2. dispersant B

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

Above-mentioned general formula (I) and (II) in, R ²¹～R ²⁶Represent hydrogen atom or univalent organic group independently of one another, X ²¹And X ²²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, L ²¹And L ²²Organic linking group of representing singly-bound or divalence independently of one another, A ²¹And A ²²Represent the univalent organic group independently of one another, ma and na represent 2～8 integer independently of one another, and p and q represent 1～100 integer independently of one another.

R ²¹～R ²⁶Represent hydrogen atom or univalent organic group independently of one another.As the univalent organic group, preferably replace or do not have the alkyl of replacement.As alkyl, be preferably carbonatoms and be 1～12 alkyl, more preferably carbonatoms is 1～8 alkyl, to be preferably carbonatoms especially be 1～4 alkyl.Have under the substituent situation at alkyl, as this substituting group, for example can list hydroxyl, (preferred carbonatoms is 1～5 to alkoxyl group, more preferably carbonatoms is 1～3.) methoxyl group, oxyethyl group, cyclohexyloxy etc.As preferred alkyl, particularly, can list for example methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl.As R ²¹, R ²², R ²⁴And R ²⁵, preferred hydrogen atom is as R ²³And R ²⁶, from the angle to the adsorption efficiency of surface of pigments, most preferably hydrogen atom or methyl.

X ²¹And X ²²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.Wherein, from viewpoint to the adsorptivity of pigment, preferred-C (=O) O-,-CONH-, phenylene, most preferably-C (=O) O-.

L ²¹And L ²²Organic linking group of representing singly-bound or divalence independently of one another.As organic linking group of divalence, preferably replace or do not have the alkylidene group of replacement or by this alkylidene group and heteroatoms or contain organic linking group of the divalence that heteroatomic part-structure constitutes.Here, as alkylidene group, preferred carbonatoms is that 1～12 alkylidene group, further preferred carbonatoms are that 1～8 alkylidene group, preferred especially carbonatoms are 1～4 alkylidene group.In addition,, can list for example Sauerstoffatom, nitrogen-atoms, sulphur atom as the heteroatoms that contains in the heteroatomic part-structure, wherein, preferred oxygen atom, nitrogen-atoms.As preferred alkylidene group, particularly, can list for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene.Have under the substituent situation at alkylidene group,, can list for example hydroxyl etc. as this substituting group.Organic linking group as divalence, from angle to the adsorptivity of pigment, preferably have at the end of above-mentioned alkylidene group be selected from-C (=O)-,-OC (=O)-,-NHC (=O)-in heteroatoms or contain heteroatomic part-structure, by this heteroatoms or contain heteroatomic part-structure and be connected the group that obtains with the Sauerstoffatom of adjacency.Here, the Sauerstoffatom of adjacency be meant with general formula (I) in L ²¹, and general formula (II) in L ²²Relatively at side chain terminal side bonded Sauerstoffatom.

As A ²¹And A ²²Angle from dispersion stabilization, development, be preferably selected from carbonatoms and be 1～20 straight chain shape, carbonatoms and be 3～20 chain and carbonatoms and be 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, further be preferably selected from carbonatoms and be 6～10 straight chain shape and carbonatoms and be the group in 6～12 the catenate alkyl.

Ma and na represent 2～8 integer independently of one another.From the angle of dispersion stabilization, development, be preferably 4～6, be preferably 5 especially.

P and q represent 1～100 integer independently of one another.Can mix the different repeating unit of repeating unit, q that p is different more than 2 kinds.P and q are preferably 5～60, more preferably 5～40, more preferably 5～20 from the angle of dispersion stabilization, development.

As the dispersant B in the present embodiment,, preferably contain the repeating unit of described general formula (I) expression from the angle of dispersion stabilization.

In addition, 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 ²¹～R ²³Represent hydrogen atom or univalent organic group independently of one another, La represents that carbonatoms is 2～10 alkylidene group, Lb represents-C (=O)-or-NHC (=O)-, A ²¹Expression univalent organic group, ma represents that 2～8 integer, p represent 1～100 integer.The preferable range of ma and p is identical with the definition of general formula (I).

The repeating unit of general formula (I), (II) or (I)-2 expression respectively by make following general formula (i), (ii) or the monomer polymerization of (i)-2 expression or copolymerization import the repeating unit that is used as macromolecular compound.

Above-mentioned general formula (i), (ii) and (i)-2, R ²¹～R ²⁶Represent hydrogen atom or univalent organic group independently of one another, X ²¹And X ²²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, L ²¹And L ²²Organic linking group of representing singly-bound or divalence independently of one another, La represent that carbonatoms is 2～10 alkylidene group, Lb represents-C (=O)-or-NHC (=O)-, A ²¹And A ²²Represent the univalent organic group independently of one another, ma and na represent 2～8 integer independently of one another, and p and q represent 1～100 integer independently of one another.The preferred range of ma, na and p, q is identical with the definition among general formula (I), (II).

Below enumerate general formula (i), (ii) or (i)-2 monomeric preferred object lesson (monomer (A-1)～(A-23)) of expression, but the present invention and be limited to these examples.

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

In addition, in dispersant B, the content of the repeating unit of general formula (I) and any expression (II) does not have particular restriction, the total repetition unit that contains in polymkeric substance is during as 100 quality %, preferably contain the repeating unit of the above general formula (I) of 5 quality % and any expression (II), more preferably contain 50 quality %, further preferably contain 50 quality %～80 quality %.

In order to improve absorption to pigment, the dispersant B in the present embodiment be preferably monomer with adsorbable functional group in pigment and general formula (i) mentioned above, (ii), the monomer copolymerization of (i)-2 expression and the macromolecular compound that obtains.As monomer, particularly, can list monomer, monomer, monomer, have the monomer of ionic group etc. with basic nitrogen atom with acidic-group with organic pigment structure or heterocycle structure with adsorbable functional group in pigment.Wherein, from angle, preferably has the monomer of organic pigment structure or heterocycle structure to the adsorptive power of pigment.

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.Wherein, be preferably the monomer of following general formula (11) expression especially.

General formula (11)

In the above-mentioned general formula (11), R ¹¹Expression hydrogen atom or alkyl.R ¹²Expression singly-bound or divalent linking group.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) ¹¹The alkyl of expression, preferred carbonatoms are 1～12 alkyl, more preferably carbonatoms is that 1～8 alkyl, preferred especially carbonatoms are 1～4 alkyl.At R ¹¹The alkyl of expression has under the substituent situation, as this substituting group, and alkoxyl groups such as preference such as hydroxyl, methoxyl group, oxyethyl group or cyclohexyloxy.As this alkoxyl group, preferred carbonatoms is 1～5, more preferably carbonatoms is 1～3.

As the R in the general formula (11) ¹¹The preferred alkyl of expression particularly, can list for example 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 hydrogen atom or methyl.

As the R in the general formula (11) ¹²The divalent linking group of expression, preferred alkylidene group or contain the group of the divalence of alkylidene group.As this alkylidene group, preferred carbonatoms is 1～12 alkylidene group, more preferably carbonatoms is that 1～12 alkylidene group, further preferred carbonatoms are that 1～8 alkylidene group, preferred especially carbonatoms are 1～4 alkylidene group.In addition, have under the substituent situation,, can list for example hydroxyl etc. as this substituting group at this alkylidene group.As R ¹²The preferred alkylidene group of expression particularly, can list for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene.

As the R in the general formula (11) ¹²The group of the divalence that contains alkylidene group of expression can be the group that the above-mentioned alkylidene group more than 2 is formed by connecting by heteroatoms (for example Sauerstoffatom, nitrogen-atoms or sulphur atom).In addition, as R ¹²The group of the divalence that contains alkylidene group of expression, also can be combined with for one side's of the Z in being incorporated into above-mentioned alkylidene group end 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 contain the group of heteroatomic part-structure.

The nitrogen heterocyclic ring structure of the nitrogen heterocycle of representing as the Z that constitutes in the general formula (11), particularly, can list for example have pyridine ring, the structure of pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure and cyclic imide structure.Their nitrogen heterocyclic ring structure can have substituting group, as this substituting group, can list for example alkyl, alkoxyl group, halogen atom, aliphatics ester group, aromatic series ester group, alkoxy carbonyl etc.

The nitrogen heterocycle that Z represents more preferably has the group that carbonatoms is the nitrogen heterocyclic ring structure more than 6, is preferably especially to have the group that carbonatoms is 6～12 nitrogen heterocyclic ring structure.As carbonatoms is nitrogen heterocyclic ring structure more than 6, particularly, preferred thiodiphenylamine ring, phenoxazine 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 for 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.Here, R ^AExpression hydrogen atom or alkyl.R ^AThe alkyl of expression during alkyl is preferably that carbonatoms is 1～18 alkyl, more preferably carbonatoms is 1～6 alkyl, can list for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, Octadecane base etc.In the above-mentioned group, as the X in the general formula (12), preferred singly-bound, methylene radical ,-O-or-C (=O)-, especially preferred-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, this alkyl is preferably that carbonatoms is 1～18 alkyl, more preferably carbonatoms is 1～6 alkyl, can list for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, Octadecane base etc.In the above-mentioned group, as Y and the Z in the general formula (14), preferred especially-N=,-NH-and-N (R ^B)-.As the combination of Y and Z, can list among Y and the Z any for-N=, another for the combination (imidazolyl) of-NH-as preferably combination.

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, can list for example phenyl ring, naphthalene nucleus, indenes ring, Azulene ring, fluorenes ring, anthracene nucleus, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring etc., wherein, preferred phenyl ring, naphthalene nucleus, anthracene nucleus, pyridine ring, phenoxazine ring, acridine ring, thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring, preferred especially phenyl ring, naphthalene nucleus, pyridine ring.

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

In addition, 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 list preferred object lesson (monomer M-1～M-33), but the present invention and be limited to these examples of monomer, maleimide and the maleimide derivatives of general formula (11) expression.

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

In the dispersant B in the present embodiment, content about the repeating unit in a kind of monomer source in the monomer, maleimide and the maleimide derivatives that are selected from general formula (11) expression, the total repetition unit that contains in polymkeric substance is during as 100 quality %, preferably contain 5 quality % above, more preferably contain 10 quality %～50 quality %.Promptly, in order to suppress as the generation of the secondary aggregation body of the aggregate of the primary particle of pigment effectively or to weaken the cohesive force of secondary aggregation body effectively, the content that is selected from the polymerized unit in a kind of monomer source in monomer, maleimide and the maleimide derivatives of general formula (11) expression is preferably more than the 5 quality %.In addition, the viewpoint of the development the when coloring photosensitive combination that contains pigment dispersion from utilization is made colour filter, the content that is selected from the polymerized unit in a kind of monomer source in monomer, maleimide and the maleimide derivatives of 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-group.As vinyl monomer, can list (methyl) vinylformic acid, vinyl benzoate, toxilic acid, maleic acid mono alkyl ester, fumaric acid, methylene-succinic acid, Ba Dousuan, styracin, acrylic acid dimer etc. with carboxyl.In addition, can also utilize monomer that (methyl) vinylformic acid 2-hydroxy methacrylate etc. has a hydroxyl with as the addition reaction of cyclic acid anhydrides such as maleic anhydride, Tetra hydro Phthalic anhydride or cyclohexane dicarboxylic acid acid anhydrides, ω-carboxyl-polycaprolactone list (methyl) acrylate etc.In addition, as the precursor of carboxyl, can also use maleic anhydride, itaconic anhydride, citraconic anhydride etc. to contain the monomer of acid anhydrides.In addition, wherein, from the viewpoint of copolymerization, cost or solvability etc., preferred especially (methyl) vinylformic acid.

In addition, as having sulfonic vinyl monomer, can list 2-acrylamide-2-methyl propane sulfonic acid etc.; As vinyl monomer, can list mono phosphoric acid ester (2-acryloxy ethyl ester), mono phosphoric acid ester (1-methyl-2-acryloxy ethyl ester) etc. with phosphate.

Dispersant B in the present embodiment preferably contains the repeating unit in the above-mentioned monomer source with acidic-group.By containing such repeating unit, when being applied to pigment dispersion of the present invention in the coloring photosensitive combination, removing property of the development excellence of unexposed portion.

Dispersant B in the present embodiment can only contain a kind of repeating unit that also can contain the monomer source with acidic-group more than 2 kinds.In dispersant B, the content of repeating unit with monomer source of acidic-group be preferably 50mgKOH/g above, be preferably 50mgKOH/g～200mgKOH/g especially.That is, the angle that the generation of the precipitate from developing solution suppresses, the content of repeating unit with monomer source of acidic-group is preferably more than the 50mgKOH/g.In order to suppress as the generation of the secondary aggregation body of the aggregate of the primary particle of pigment effectively or to weaken the cohesive force of secondary aggregation body effectively, the content of repeating unit with monomer source of acidic-group is preferably 50mgKOH/g～200mgKOH/g.

About having the monomer of 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-pyrroles piperazine base ethyl ester, (methyl) vinylformic acid N, N-methyl-2-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.

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

As monomer, can list vinyl monomer (anionic property vinyl monomer, cationic vinyl monomer) with ionic group with ionic group.About its example,, can list an alkali metal salt of described vinyl monomer with acidic-group or the salt that forms with organic amine (for example tertiary amine such as triethylamine, dimethylaminoethanol) etc. as the anionic property vinyl monomer; As the cationic vinyl monomer, can list described nitrogenous vinyl monomer alkyl halide (alkyl: C1～18, halogen atom: chlorine atom, bromine atoms or iodine atom), benzyl such as benzyl chloride, bromotoluene halogenide, the alkyl sulfonic ester of methylsulfonic acid etc. (alkyl: C1～18), aryl sulfonic acid such as Phenylsulfonic acid, toluenesulphonic acids alkyl ester (alkyl: C1～18), sulfuric acid dialkyls (alkyl: C1～4) etc. are quaternized and the monomer that obtains can list dialkyldiallyl ammonium salt etc.

Monomer with adsorbable functional group in pigment can suitably be selected according to the kind of carrying out dispersive pigment, and they can be suitable for separately, also can more than 2 kinds and use.

Dispersant B in the present embodiment in the scope of not damaging its effect, but can also further contain the repeating unit in the vinyl monomer source of copolymerization.

Here, as spendable vinyl monomer, be not particularly limited, preference is as the ester class 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, styrenic, (methyl) vinyl cyanide etc.As the object lesson of such vinyl monomer, can list for example following compound.Need to prove, in this manual, when any in will representing " propenyl, methylpropenyl " or both, sometimes it is designated as " (methyl) propenyl ".

The preferred mode of the dispersant B in the present embodiment for general formula (i) at least, (ii) or the compound that obtains of the monomer of (i)-2 expression and monomer copolymerization copolymerization with organic pigment structure or heterocycle structure, the compound that the monomer and the monomer copolymerization with acidic group of the monomer of general formula (i)-2 expression more preferably mentioned above at least, general formula (11) expression mentioned above obtains.Can access the pigment dispersion of pigment adsorption excellence and development excellence thus.

About the preferred molecular weight of dispersant B in the present embodiment, preferably count 1,000～100,000 scope, count 400～50,000 scope with number-average molecular weight (Mn) with weight-average molecular weight (Mw).More preferably count 5,000～50,000 scope, count 2,000～30,000 scope with number-average molecular weight (Mn) with weight-average molecular weight (Mw).Particularly, most preferably count 8,000～30,000 scope, count 4,000～12,000 scope with number-average molecular weight (Mn) with weight-average molecular weight (Mw).From untiing as the secondary aggregation body of the aggregate of the primary particle of pigment effectively or weakening the viewpoint of cohesion more effectively, the weight-average molecular weight of preferred dispersants B (Mw) is more than 1000.In addition, the viewpoint of the development the when coloring photosensitive combination that contains pigment dispersion from utilization is made colour filter, the weight-average molecular weight of dispersant B (Mw) is preferably below 30000.

Dispersant B in the present embodiment can use the monomer of for example following general formula (i), (ii) or (i)-2 expression and as other free-radical polymerised compound (various monomers as indicated above) of copolymer composition, make by common radical polymerization.In general, use suspension polymerization or solution polymerization process etc.The solvent that uses during as synthetic such dispersant B, can list for example 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 also can mix use more than 2 kinds.In addition, radical polymerization is fashionable, can also use radical polymerization initiator; In addition, can also further use chain-transfer agent (for example 2 mercapto ethanol and lauryl mercaptan).

In the pigment dispersion of present embodiment,, be preferably pigment by quality ratio: 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.

In addition, in the scope of the effect of not damaging present embodiment, as required, except above-mentioned specific copolymer, can also use other macromolecular compound simultaneously.As other macromolecular compound, can use with natural resin, modified natural resin, synthetic resins, natural resin and carry out modification and synthetic resins of obtaining etc.As natural resin, representational have rosin; As modified natural resin, can list rosin derivative, derivatived cellulose, rubber derivative, protein derivatives and their oligomer.As synthetic resins, can list Resins, epoxy, propylene ester resin, maleic acid resin, butyral resin, vibrin, melamine resin, resol, urethane resin etc.The synthetic resins that obtains as carrying out modification with natural resin can list Abietyl modified maleic acid resin, rosin modified phenolic resin 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 comprises dispersion, optical polymerism compound and the Photoepolymerizationinitiater initiater of described pigment particle, preferably further comprises alkali soluble resin.Be described in detail about the method for making organic pigment particle and dispersion thereof.(in the present invention, the total solids composition is meant and does not comprise the total of organic solvent at interior composition the content of the particulate in the Photocurable composition with respect to the total solids composition.) be preferably 3～90 quality %, more preferably 20～80 quality %, further preferred 25～60 quality %.If this amount too much, then the viscosity of dispersion liquid rises, sometimes existing problems aspect manufacturing adaptability.If this amount is very few, then tinting strength is abundant inadequately.In addition, in order to mix colours, can also use with common pigment combinations.Pigment can use the pigment of above recording and narrating.

As optical polymerism compound (following polymerizable monomer or the polymerizability oligomer of being also referred to as sometimes), preferably have more than 2 the ethylenic unsaturated double-bond and for the polyfunctional monomer of addition polymerization takes place under the irradiation of light.As such optical polymerism compound, under normal pressure compound more than 100 ℃ but can list the ethylenic unsaturated group that in molecule, has at least 1 addition polymerization and boiling point.As its 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) isocyanic ester, three (acryloxy ethyl) cyanate, glycerine three (methyl) acrylate; Polyfunctional acrylic ester or the multifunctional methacrylic esters such as compound that behind addition of ethylene oxide or propylene oxide on the polyfunctional alcohols such as TriMethylolPropane(TMP) or glycerine, carry out (methyl) acroleic acid esterification and obtain.In addition, also can list as what put down in writing in the general formula (1) in the Japanese kokai publication hei 10-62986 communique and (2), behind addition of ethylene oxide on the polyfunctional alcohol or propylene oxide, carry out (methyl) acroleic acid esterification and the compound that obtains as preferred compound.

In addition, also 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; Polyfunctional acrylic ester or the methacrylic esters such as epoxy acrylate class that belong to Resins, epoxy and (methyl) acrylic acid resultant of reaction.

Wherein, preferred trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate.

In addition, other also can list " the polymerizable compound B " that put down in writing in the Japanese kokai publication hei 11-133600 communique as preferred compound.

The optical polymerism compound can use separately, also can mix use more than two kinds, is generally 5～50 quality %, is preferably 10～40 quality % with respect to the content of the total solids composition of Photocurable composition.As if this amount too much, then the control of development property becomes difficult, has problems on manufacturing adaptability.If this amount is very few, the curing power when then exposing is abundant inadequately.

(in the present invention, the Photoepolymerizationinitiater initiater system is meant with a plurality of combination of compounds and brings into play the mixture that photopolymerization causes function as Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.), 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) that is replaced by α-hydrocarbon, many 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 dimer 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 trihalogenmethyl-s-triaizine compounds, trihalogenmethyl-triaizine compounds of putting down in writing in No. 4239850 specification sheets of United States Patent (USP), the San halogen Jia oxadiazole compound of putting down in writing in No. 4212976 specification sheets of United States Patent (USP) etc.Preferred especially trihalogenmethyl-s-triazine, San halogen Jia oxadiazole and triarylimidazoles dimer.

In addition; other; as " the polymerization starter C " that put down in writing in the Japanese kokai publication hei 11-133600 communique or oxime system; also can 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 group oxide compound, phosphorus hexafluoride-trialkyl Ben Ji phosphonium salt etc. are as preferred compound.

Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system may be used alone, can also be two or more kinds in combination, preferred especially use more than 2 kinds.If use at least 2 kinds of Photoepolymerizationinitiater initiaters, then the inequality of display characteristic, particularly demonstration can reduce.With respect to the total 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 amount too much, then sensitivity is too high, becomes to be difficult to control.If this amount is very few, the sensitivity of then exposing became low.

As alkali soluble resin, can add in the Photocurable composition or when preparing colour filter and add with ink for inking, preferably when making the dispersion of described particulate or when particulate forms, add.Thereby the solution of can be at the solution of water-insoluble compound and being used for adding water-insoluble compound generates the bad solvent of particulate of water-insoluble compound or one of them adds alkali soluble resin.Perhaps also preferably alkali soluble resin solution is added when the particulate of water-insoluble compound forms by other system.

As alkali soluble resin, preferably have the tackiness agent of acidic-group, preferably have the polymkeric substance of the alkali-soluble of carboxylic acid group or carboxylic acid foundation isopolarity group at side chain.As its example, can list as 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, also can list the derivatived cellulose that has carboxylic acid group or carboxylate salt etc. at side chain, in addition, in addition, also can preferably use having to add the compound that acid anhydrides circlewise forms on the polymkeric substance of hydroxyl.In addition, as more preferred example, can list United States Patent (USP) the 4th, 139, (methyl) benzyl acrylate of putting down in writing in No. 391 specification sheetss and (methyl) acrylic acid multipolymer or (methyl) benzyl acrylate, (methyl) vinylformic acid and other monomeric multiple copolymers.

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

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

Photocurable composition can also be made ink for inking by suitably regulating its composition.As ink for inking, except colour filter with, can also make lettering and common ink for inking such as use, wherein preferably make the colour filter ink for inking.

As long as ink for inking comprises above-mentioned water-insoluble compound particulate, preferably in the medium that contains polymerizable monomer and/or polymerizability oligomer, contain described water-insoluble compound particulate.Here, as polymerizable monomer and/or polymerizability oligomer, the compound that in Photocurable composition, has illustrated before can using.

At this moment, pattern form of the ink characteristics during about employed injection the, printing ink spraying method, ink gun form, colour filter and forming method thereof, identical with disclosed content in the TOHKEMY 2008-138194 communique, preferred range is also identical.

About the composition that contains in the coated film of having used Photocurable composition, with the composition of having put down in writing be same.In addition, about the proterties of the coated film of having used Photocurable composition, to the coating process of substrate, identical with disclosed content in the TOHKEMY 2008-138194 communique, preferred range is also identical.

[colour filter]

The pixel of colour filter of the present invention is preferably used above-mentioned pigment particle dispersion or has been replaced that the redispersion body of its solvent forms, and preferred contrast gradient excellence.In the present invention, contrast gradient is illustrated between 2 polaroids, the ratio of the light transmission capacity when polarizing axis is parallel when vertical (" nineteen ninety the 7th color reversion glory learn コ Application Off ァレ Application ス, 512 colour specifications 10.4 " サィズ T F T-L C D with カラ one Off ィ Le タ, plant

Wood, Xiao Seki, good fortune forever, in the mountain " etc. reference.)。The contrast gradient height of colour filter means that the difference of the light and shade when making up with liquid crystal can be bigger, and it is very important performance for liquid-crystal display being replaced to CRT.

Colour filter is being used as under the situation of TV, and the value of putting down in writing in unicolor colourity that the redness (R) that the F10 light source is sent, green (G) and blueness (B) are all separately and the following table (in the present invention following, be called " target colourity ".) poor (Δ E) be preferably 5 with interior scope, more preferably 3 with interior, be preferably in 2 especially.

In the present invention, colourity is utilized microspectrophotometer (Olympus Optical Co Ltd.'s system; OSP100 or 200) measures, calculate the result of the F10 light source visual field 2 degree, with the xyY value representation of xyz chromaticity diagram.In addition, with the difference La of target colourity ^*b ^*The aberration of chromaticity diagram is represented.

Contrast of LCD degree height, the dense degree of black that possesses colour filter etc. described the power excellence, is preferably the VA mode especially.Also can be preferably as the uses such as liquid crystal indicator of notebook computer with big picture such as indicating meter or TV monitor.In addition, above-mentioned colour filter also can be used in the CCD device, and the excellent performance of performance.

Embodiment

Below, based on embodiment the present invention is further described in detail, but the present invention is not subjected to its limited interpretation.Need to prove that in the present embodiment, " part " and " % " is quality criteria unless otherwise specified.

The inventive embodiment of (Production Example) pigment derivative compound

(Production Example 1) pigment derivative a's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, when wherein temperature surpasses 35 ℃ in attention does not make, add tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts.After the interpolation, be 20 ℃ in interior temperature and stirred 10 minutes down, then add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts then, under 30 ℃, carry out 4 hours heated and stirred.After the heated and stirred, reaction solution is injected frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative a of 39.18 mass parts.

(Production Example 2) pigment derivative b's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, to wherein adding tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts, stirred 10 minutes down for 20 ℃ in interior temperature.Then, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.Then, add hydroxymethyl phthalic imidine (with the pure medicine corporate system of light) 18.43 mass parts, under 30 ℃, carry out 2 hours heated and stirred.After the heated and stirred, reaction solution is injected in frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative b of 27.5 mass parts.

(Production Example 3) pigment derivative c's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, to wherein adding tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts, stirred 10 minutes down for 20 ℃ in interior temperature.Then, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.Then, add phthalic imidine (with the pure medicine corporate system of light) 15.31 mass parts, after 10 minutes, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.After the heated and stirred, reaction solution is injected in frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative c of 26.8 mass parts.

(Production Example 4) pigment derivative d's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, add hydroxymethyl phthalic imidine (with the pure medicine corporate system of light) 18.43 mass parts, under 30 ℃, carry out 2 hours heated and stirred.Then,, after 10 minutes, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred to wherein adding tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts.After the heated and stirred, reaction solution is injected in frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative d of 29.4 mass parts.

(Production Example 5) pigment derivative e's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, when wherein temperature surpasses 35 ℃ in attention does not make, add Phenylsulfonic acid 1 hydrate (Tokyo changes into corporate system) 18.32 mass parts.After the interpolation, be 20 ℃ in interior temperature and stirred 10 minutes down, then add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts then, under 30 ℃, carry out 4 hours heated and stirred.After the heated and stirred, reaction solution is injected in frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative e of 37.1 mass parts.

(Production Example 6) pigment derivative f's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, to wherein adding tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts, be 20 ℃ in interior temperature and stirred 10 minutes down.Then, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.Then, add 4-nitro phthalic imidine 19.98 mass parts, after 10 minutes, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.After the heated and stirred, reaction solution is injected in frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative f of 29.2 mass parts.

(Production Example 7) pigment derivative g's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, to wherein adding tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts, be 20 ℃ in interior temperature and stirred 10 minutes down.Then, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.Then, add 4-methyl phthalimide 16.76 mass parts, after 10 minutes, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.After the heated and stirred, reaction solution is injected in frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative g of 27.6 mass parts.

(Production Example 8) pigment derivative h's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, to wherein adding tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts, be 20 ℃ in interior temperature and stirred 10 minutes down.Then, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.Then, add 4-bromine phthalic imidine 23.51 mass parts, after 10 minutes, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.After the heated and stirred, reaction solution is injected in frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative h of 31.2 mass parts.

(Production Example 9) pigment derivative i's is synthetic

PR255 (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 30 mass parts are dissolved in sulfuric acid 450 mass parts, stir down at 20 ℃ and made its dissolving in 30 minutes.Then, to wherein adding tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts, be 20 ℃ in interior temperature and stirred 10 minutes down.Then, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.Then, add 4-carboxyl phthalic imidine 19.88 mass parts, after 10 minutes, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 30 ℃, carry out 2 hours heated and stirred.After the heated and stirred, reaction solution is injected in frozen water 1800 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative i of 28.6 mass parts.

(Production Example 10) pigment derivative j's is synthetic

PR122 (cromophtal Pink PT[trade(brand)name], Ciba Specialty Chemicals corporate system) (Cromophtal DPP Coral Red C[trade(brand)name], Ciba Specialty Chemicals corporate system) 35.4 mass parts are dissolved in sulfuric acid 220 mass parts, stir down at 60 ℃ and made its dissolving in 30 minutes.Then, to wherein adding tosic acid 1 hydrate (with the pure medicine corporate system of light) 19.8 mass parts, be 60 ℃ in interior temperature and stirred 10 minutes down.Then, add Paraformaldehyde 96 (Tokyo changes into corporate system) 3.82 mass parts, under 60 ℃, carry out 2 hours heated and stirred.Then, add hydroxymethyl phthalic imidine (with the pure medicine corporate system of light) 18.43 mass parts, under 60 ℃, carry out 2 hours heated and stirred.After the heated and stirred, reaction solution is injected in frozen water 1100 mass parts while stirring, the precipitate that obtains is filtered, washs, obtain the pigment derivative j of 38.7 mass parts.

(example I, Comparative Example I)

(embodiment 1)

The preparation of＜organic pigment nano particle dispersion liquid 〉

In the SUS304 of 10L capacity system jar (jar diameter is 210mm), drop into the dimethyl sulfoxide (DMSO) (manufacturers: Wako), utilize of 4000g

3 pinniform blades carry out vane-type with 600rpm and stir, drop into lentamente the PR254IRGAZIN powder (manufacturers: 300g Ciba Specialty Chemicals), make the slurry of pigment.Then, in order to make the pigment dissolved in the above-mentioned slurry arrive molecular level, make with 25% tetramethylammonium hydroxide aqueous solution (manufacturers: the Wako) liquid that obtains with dimethyl sulfoxide (DMSO) 950g dilution of 310g, it is made Chemical Gear Pump with Iwaki puts in the slurry with the flow of 2L/min.The stirring of the slurry of this moment is stirred 600rpm with adopting vane-type before in the same manner.After just dropping into, with spectrophotometer (manufacturers: Agilent Technologies, model: 8453) measure absorbancy, confirm that the absorbance A bs at 750nm, 800nm place is below 0.005.Then, transfer liquid differently to make the slurry of pigment derivative again with above-mentioned pigment.In the 3L of SUS304 volumetrical jar, add dimethyl sulfoxide (DMSO) 1300g in advance, have making

The high-speed stirring dispersion machine (power consumption is 1Kw) of Scroll-type blade the time with the 600rpm stirring at low speed, drop into pigment derivative 60g lentamente.At this moment,, therefore make the rotating speed of this dissolver wing rise to 6000rpm, carry out 2 minutes high-speed stirring, make uniform sizing material because slurry does not evenly suspend.Then, join once in the IRGAZIN lysate of semi-finished above-mentioned slurry.Then, with this lysate with the 600rpm stirring at low speed, the liquid that has obtained to wherein 25% tetramethylammonium hydroxide aqueous solution 95g having been diluted with dimethyl sulfoxide (DMSO) 300g with the flow input of 0.2L/min with Iwaki system Chemical Gear Pump.So finish the liquid preparation manipulation.Measure absorbancy once more, confirm that the Abs of 750nm, 800nm is below 0.005.In addition, confirming that the Abs that is about to the liquid before the reactor mixing use also uses in back below 0.005.

Measure the viscosity of this pigment solution with Viscometers VM-10A-L (trade(brand)name, CBC materials corporate system), the viscosity of the fluid temperature of pigment solution in the time of 24.5 ℃ is 14.3mPas as a result.As different therewith bad solvents, prepare to contain the ion exchanged water 2000ml of 1mol/l aqueous hydrochloric acid (with the pure medicine corporate system of light) 38g.

Here, temperature is controlled to 10 ℃, in the bad solvent 1000ml that stirs with 500rpm with GK-0222-10 type Ramond Stirrer (trade(brand)name, Fujisawa Pharmaceutical's system), is that the liquor charging pipe arrangement of 1.1mm is the pigment solution that 400ml/min injects 200ml with the flow velocity with NP-KX-500 type large vol pulse-free pump (trade(brand)name, Japanese precision chemical corporate system) from the stream diameter, thereby forms the organic pigment particles of the median size of following table 2.

The preparation of＜pigment dyestuff powder 〉

Use diameter as the Nutsche of 9cm and filter paper (Advantech corporate system, No.2 (trade(brand)name)), will obtain containing the mashed prod of particulate coloring matter according to the dispersible pigment dispersion filtration under diminished pressure of said sequence preparation with vent fan.The mashed prod that repeats to obtain is distributed in the ion exchanged water once more, carries out once more filtering operation, thus mashed prod is washed, to remove good solvent and water soluble ion.Repeat the washing of mashed prod, when the mode that reaches 5% according to pigment concentration was disperseed mashed prod, its conductance reached below the 1ms/m.

With respect to above-mentioned water mashed prod 30 mass parts, add propylene glycol monomethyl ether 189 mass parts, under 25 ℃ temperature, use GK-0222-10 type Ramond Stirrer (trade(brand)name, Fujisawa Pharmaceutical's system) to stir 3 hours, to carry out crystal conversion.Then, utilizing Nutsche to filter to concentrate and then add ion exchanged water washes and filters once more, repeat 2 times, thereby solvent is replaced to water, thereby after the over-drastic that stops crystal conversion carrying out, concentrate by utilizing Nutsche to filter once more, the solid component concentration that contains the dichloro diketopyrrolo-pyrrole pigment that obtains the process crystal conversion is 30% water mashed prod.The water mashed prod that obtains was descended freezing 2 hours at-20 ℃, carry out drying, obtain pigment dyestuff powder 1 with freeze drier.

The preparation of＜pigment dyestuff dispersive composition 〉

Described pigment dyestuff powder 1 usefulness mortar is crushed to below the 180 μ m, makes the pigment dyestuff dispersive composition 1 of following composition then, evenly mix.

Described pigment dyestuff powder 19.7g

Pigment derivative 12.0g

Pigment derivative 22.3g

The dispersion resin 12.1g that puts down in writing in the table

Propylene glycol monomethyl ether 112.7g

Described pigment derivative a 3.5g

N=1 or 2 n=1 or 2

Pigment derivative 1 pigment derivative 2

With the pigment dyestuff dispersive composition 1 of above-mentioned composition in sand mill BSG-01 (trade(brand)name, AIMEX corporate system), use diameter as the zirconium white bead of 0.5mm with 1500rpm disperse 1 hour, then with diameter as the zirconium white bead of 0.05mm with 2500rpm dispersion 2 hours, obtain pigment dispensing composition 1.

(embodiment 2～10, comparative example 1～2)

Except the compound that will be in the pigment dyestuff dispersive composition 1 adds be pigment derivative a according to changing shown in the following table 2, prepare pigment dyestuff dispersive composition 2～10 (pigment dispensing composition 2～10, c1～c2) similarly to Example 1.In addition, about the dispersion c2 in the table 2, expression does not use pigment derivative a to be prepared.In addition, about dispersion c 1, expression replaces pigment derivative a to use following compound.

(embodiment 11)

The preparation of＜organic pigment nano particle dispersion liquid 〉

3 pinniform blades carry out vane-type with 600rpm and stir, Ciba Specialty Chemicals), the pigment derivative 2 of 15g and the pigment derivative 3 of 45g slowly drop into the PR254IRGAZIN powder (manufacturers:, make the slurry of pigment of 300g.Then, in order to make pigment dissolved in the above-mentioned slurry to molecular level, make with 25% tetramethylammonium hydroxide aqueous solution (manufacturers: the Wako) liquid that obtains with dimethyl sulfoxide (DMSO) 950g dilution of 372g, utilize Iwaki to make Chemical Gear Pump it and put in the slurry with the flow of 2L/min.The stirring of the slurry of this moment with carry out vane-type before in the same manner and stir 600rpm.After just dropping into, with spectrophotometer (manufacturers: Agilent Technologies, model: 8453) measure absorbancy, confirm that the absorbance A bs at 750nm, 800nm place is below 0.005.Then, transfer liquid differently to make the slurry of pigment derivative again with above-mentioned pigment.In the 3L of SUS304 volumetrical jar, add dimethyl sulfoxide (DMSO) 1300g in advance, have making

The high-speed stirring dispersion machine (power consumption is 1Kw) of Scroll-type blade the time with the 600rpm stirring at low speed, slowly drop into pigment derivative 60g.At this moment,, therefore make the rotating speed of this dissolver wing rise to 6000rpm, high-speed stirring 2 minutes, make uniform sizing material because slurry can evenly not suspend.Then, above-mentioned slurry is put into once before in the semi-finished IRGAZIN lysate.Then, with this lysate with the 600rpm stirring at low speed, the liquid that has obtained to wherein 25% tetramethylammonium hydroxide aqueous solution 95g having been diluted with dimethyl sulfoxide (DMSO) 300g with the flow input of 0.2L/min with Iwaki system Chemical Gear Pump.So finish the liquid preparation manipulation.Measure absorbancy once more, confirm that the Abs at 750nm, 800nm place is below 0.005.In addition, confirming that the Abs that is about to the liquid before the reactor mixing use also uses in back below 0.005.

Measure the viscosity of this pigment solution with viscometers VM-10A-L (trade(brand)name, CBC materials corporate system), the viscosity the when fluid temperature of pigment solution is 24.5 ℃ as a result is 16.1mPas.As different therewith bad solvents, prepare to contain the ion exchanged water 2000ml of 1mol/l aqueous hydrochloric acid (with the pure medicine corporate system of light) 57g.

Here, temperature is controlled to 10 ℃, in the bad solvent 1000ml that stirs with 500rpm with GK-0222-10 type Ramond Stirrer (trade(brand)name, Fujisawa Pharmaceutical's system), use NP-KX-500 type large vol pulse-free pump (trade(brand)name, Japanese precision chemical corporate system) to inject the pigment solution of 200ml, preparation dispersible pigment dispersion with flow velocity as 400ml/min as the liquor charging pipe arrangement of 1.1mm from the stream diameter.

Use diameter as the Nutsche of 9cm and filter paper (Advantech corporate system, No.2 (trade(brand)name)), the dispersible pigment dispersion according to the said sequence preparation is carried out filtration under diminished pressure, obtain containing the mashed prod of particulate coloring matter with vent fan.The mashed prod that repeats to obtain is distributed in the ion exchanged water once more, carries out once more filtering operation, carries out the washing of mashed prod thus, to remove good solvent and water soluble ion.Repeat the washing of mashed prod, when the mode that reaches 5% according to pigment concentration was disperseed mashed prod, its conductance reached below the 1ms/m.

With respect to above-mentioned water mashed prod 30 mass parts, add propylene glycol monomethyl ether 189 mass parts, under 25 ℃ temperature, use GK-0222-10 type Ramond Stirrer (trade(brand)name, Fujisawa Pharmaceutical's system) to stir 3 hours, to carry out crystal conversion.Then, utilizing Nutsche to filter to concentrate and then add ion exchanged water washes and filters once more, repeat 2 times, thereby solvent is replaced to water, thereby after stopping excessively the carrying out of crystal conversion, concentrate by utilizing Nutsche to filter once more, the solid component concentration that contains the dichloro diketopyrrolo-pyrrole pigment that obtains the process crystal conversion is 30% water mashed prod.The water mashed prod that obtains was descended freezing 2 hours at-20 ℃, carry out drying, obtain pigment dyestuff powder 2 with freeze drier.

Derivative 3-1 derivative 3-2

Derivative 3=(PR254: compound 3-1: compound 3-2=10: 89: 1)

The preparation of＜pigment dyestuff dispersive composition 〉

After in mortar, being crushed to described pigment dyestuff powder 2 below the 180 μ m, make the pigment dyestuff dispersive composition 11 of following composition, mix equably.

Described pigment dyestuff powder 29.7g

The dispersion resin 8.55g that puts down in writing in the table

Propylene glycol monomethyl ether 79.9g

Described pigment derivative a 2.7g

With the pigment dyestuff dispersive composition 11 of above-mentioned composition in sand mill BSG-01 (trade(brand)name, AIMEX corporate system) with diameter be 0.5mm the zirconium white bead with 1500rpm disperse 1 hour, then use diameter to disperse 2 hours with 2500rpm as the zirconium white bead of 0.05mm, obtain pigment dispensing composition 11.

(embodiment 12～20, comparative example 3～4)

Except the compound pigment derivative a that will be in the pigment dyestuff dispersive composition 11 adds according to changing shown in the following table 2, prepare pigment dyestuff dispersive composition 12～20 (pigment dispensing composition 12～20, c3～c4) similarly to Example 11.

(embodiment 21)

C.I. Pigment red 254 (Irgaphor Red BT-CF with 9.7g, trade(brand)name, Ciba Specialty Chemicals (strain) system) (median size is 60nm), the pigment derivative 1 of 2g, 2.3g pigment derivative 2,11.3g dispersant resin, 24.7g propylene glycol monomethyl ether, 3.5g pigment derivative a mix, with this mixed solution in sand mill BSG-01 (trade(brand)name, the AIMEX corporate system) use diameter to disperse 1 hour with 1500rpm in as the zirconium white bead of 0.5mm, then with diameter be the zirconium white bead of 0.05mm with 2500rpm dispersion 2 hours, obtain pigment dispensing composition 21.

The evaluation of＜pigment dispensing composition 〉

Each sample to the pigment dispensing composition that obtains carries out following evaluation.The result is shown in Table 2 in the lump.

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

Measure the size distribution of pigment particles contained in the dispersion liquid under the following conditions, calculating particle diameter is the ratio P and the number average primary particle diameter Dp of the population of 20nm～30nm.

＜TEM takes 〉

Device: Hitachi's system, H-7650 electricity show (trade(brand)name)

Acceleration voltage: 110kV

(observe by tomography, obtain overlapping few face between the particle, obtain the shadow area of particle according to the 3D reconstruct data.)

＜image measurement 〉

Device: Carl Zeiss corporate system, KS-400 (trade(brand)name)

(measure the TEM image of 5000 pigment particles selecting at random, calculate quite footpath of ball, calculate above-mentioned ratio P and Dp according to shadow area.)

The mensuration of zero viscosity, evaluation

For the pigment dispensing composition that obtains, use E type viscometer (eastern machine industry (strain) corporate system, RE-85L[trade(brand)name], measure temperature be 25 ℃) measure the viscosities il 1 of the pigment dispensing composition after just disperseing and disperse after at room temperature through the viscosities il 2 of the pigment dispensing composition after 1 week, the degree of tackify is estimated.Here, the rising of the caused viscosity of viscosity low expression dispersion agent is inhibited, and dispersing of pigments and dispersion stabilization are good.

The mensuration of zero contrast gradient, evaluation

The pigment dispensing composition that obtains is applied on the glass substrate, and the mode that reaches 1 μ m according to the thickness of dried coated film is made sample.This sample is placed between 2 polaroids, measure polarizing axis when parallel and the light transmission capacity when vertical, with they liken to for contrast gradient (this evaluation assessment with reference to " nineteen ninety the 7th color reversion glory コ Application Off ァレ Application ス, 512 colour specifications 10.4 " サィズ T F T-L C D usefulness カラ one Off ィ Le タ one,

Wood, Xiao Seki, good fortune forever, in the mountain ").Here, the high expression of contrast gradient is owing to the state homodisperse of pigment with the height miniaturization, so transmissivity is the tinting strength height.

Table 2

The sample name is represented typically with the numbering of dispersion, puts down in writing as this paper respectively as the sample that determination object uses.

Resin 1:Disperbyk-161

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

Resin 3: the graft resin of following structure (main chain Mn:600, grafting amount 9.3mol% (the total amine of vs.), acid number 10mgKOH/g, Mw:10000

Ra:-CO-nC ₇H ₁₅Or hydrogen atom, v:40, w:5, x:10, y+z:45)

From the result shown in the last table as can be known, when disperseing, add the pigment dispensing composition that pigment derivative compound of the present invention obtains and compare, show much better dispersing characteristic with comparative example.In addition, in the reprecipitation method, used the median size of pigment dispensing composition of pigment derivative minimum and particle diameter is consistent, compared with the composition of comparative example in addition to have good properties.

(example II, Comparative Example I I)

The preparation of＜coloring photosensitive combination 〉

Use above-mentioned pigment dispensing composition (1A～11A, c1A～c2A), prepare following coloring photosensitive combination respectively.

2000 parts of pigment dispensing compositions

100 parts of dipentaerythritol acrylates (optical polymerism compound)

The adjacent bromo-of 4-[is right-N, and N-two (ethoxy carbonyl) aminophenyl]-2,30 parts of 6-two (trichloromethyl)-S-triazine (Photoepolymerizationinitiater initiater)

Benzyl methacrylate/methacrylic acid (=75/25[mass ratio]) multipolymer (weight-average molecular weight: propylene glycol monomethyl ether solution 12,000) (solids component is 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 〉

0.650 the mode of reaching according to the x value as the depth of shade index is applied to the coloring photosensitive combination (painted resist liquid) of preparation on the glass substrate (1737, Corning corporate system) of 100mm * 100mm, with 90 ℃ oven dryings 60 seconds (prebake conditions).Thereafter, whole to coated film uses 200mJ/cm ²(illumination is 20mW/cm ²) expose, with 1% aqueous solution covering of the coated film after the exposure with alkaline developer CDK-1 (Fujifilm Electronic materials (strain) system), static 60 seconds.After static, pure water is scattered with wash-out developer with the shower shape.Then, will handle 1 hour (back baking) with 220 ℃ baking oven for heating, on glass substrate, form the colored pattern (painted areas) that colour filter is used, make painted filter substrate (colour filter) as the coated film of having bestowed exposure and having developed above-mentionedly.

The evaluation of＜coloring photosensitive combination and colour filter 〉

The coloring photosensitive combination of following evaluation made and painted filter substrate (colour filter).The result is shown in the above-mentioned table in the lump.

The contrast gradient of zero colour filter (CF)

On the colored pattern of colour filter, place polaroid and clamp colored pattern, measure the brightness of polaroid when parallel and the brightness when vertical with the BM-5 (trade(brand)name) of TOPCON corporate system, the value that the brightness of the brightness when parallel divided by vertically the time obtains (brightness during=brightness when parallel/vertically) is as the index that is used to estimate contrast gradient.It is high more to be worth big more expression contrast gradient.

Zero sunproof mensuration

The sample 90mW/cm that uses in the mensuration with above-mentioned contrast gradient ²High voltage mercury lamp radiation 24 hours, measure the aberration behind the pre-irradiation, as sunproof index.Wherein, colourity is utilized microspectrophotometer (Olympus Optical Co Ltd.'s system; OSP100 or 200) measures, calculate the result of the F10 light source visual field 2 degree, with the xyY value representation of xyz chromaticity diagram.In addition, the difference La of colourity ^*b ^*The aberration of chromaticity diagram is represented.The more little expression photostabilization of this aberration is high more.

Zero stable on heating evaluation

The colour filter of made was handled 1 hour with 250 ℃ baking oven for heating forcibly, estimated the contrast gradient conservation rate before and after handling.

According to the result shown in the last table, employing has used the contrast gradient of pixel of the colour filter that the dispersion of pigment derivative compound of the present invention makes high, and show high photostabilization, dense degree excellence of the black of the pixel of colour filter of the present invention and color and luster are extremely good.

Claims

1. pigment particle dispersion, it is characterized in that, it contains pigment derivative compound and pigment particle, and described pigment derivative compound is that the compound that compound and the following general formula (2) by making the expression of pigment, following general formula (1) represented reacts the compound that obtains in acid solvent;

General formula (1) general formula (2)

In the general formula (1), Q represents to have substituent aromatic hydrocarbyl, and n represents 1～4 integer; In the general formula (2), R ¹And R ²Represent hydrogen atom or alkyl independently of one another.

2. pigment particle dispersion according to claim 1, wherein, described pigment derivative compound is further to make the compound reaction of following general formula (3) expression and the compound that obtains;

General formula (3)

In the general formula (3), T represents the univalent organic group, and k represents 0～4 integer, and R3 represents hydrogen atom or methylol.

3. pigment particle dispersion according to claim 1 is characterized in that, is the diketopyrrolo-pyrrole pigment compound as the pigment of the matrix of described pigment derivative compound.

4. pigment particle dispersion according to claim 1 is characterized in that, described pigment particle is by making lysate that pigment dissolved obtains in good solvent and mixing with described good solvent and generate for the medium of the bad solvent of described pigment mixes.

5. pigment particle dispersion according to claim 1 is characterized in that, the pigment that constitutes described pigment particle is at least a kind that is selected from diketopyrrolo-pyrrole pigment, quinoline a word used for translation ketone pigment, anthraquinone pigment and the azo pigment.

6. pigment particle dispersion according to claim 1 is characterized in that it further contains the dispersion agent with polycaprolactone structure.

7. pigment particle dispersion according to claim 1 is characterized in that, it further contains the macromolecular compound that comprises at least a kind of repeating unit in the repeating unit that is selected from following general formula (I) and any expression (II);

General formula (I) and (II) in, R ²¹～R ²⁶Represent hydrogen atom or univalent organic group independently of one another, X ²¹And X ²²Independently of one another expression-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, L ²¹And L ²²Organic linking group of representing singly-bound or divalence independently of one another, A ²¹And A ²²Represent the univalent organic group independently of one another, ma and na represent 2～8 integer independently of one another, and p and q represent 1～100 integer independently of one another.

8. pigment particle dispersion according to claim 1, it is the colour filter tinting material.

9. Photocurable composition, it contains each described dispersion, polymerizable compound and Photoepolymerizationinitiater initiater in the claim 1～8.

10. colour filter, it has the pixel by the described Photocurable composition of claim 9 is solidified to form.

11. a pigment derivative compound, the compound of its compound by making the expression of pigment, following general formula (1) and following general formula (2) expression reacts in acid solvent and obtains, and is made of the residue of described each matrix;

General formula (1) general formula (2)

12. pigment derivative compound according to claim 11, it is further to obtain by the compound reaction that makes following general formula (3) expression, and has its residue;

General formula (3)

In the general formula (3), T represents the univalent organic group, and k represents 0～4 integer, R ³Expression hydrogen atom or methylol.

13. the manufacture method of pigment derivative compound according to claim 11 is characterized in that, the compound of described pigment, described general formula (1) expression and the compound of described general formula (2) expression are reacted in acid solvent.