CN101676339A

CN101676339A - Microparticles of water-insoluble compound and disperser thereof, their preparation method, and color filter

Info

Publication number: CN101676339A
Application number: CN200910177802A
Authority: CN
Inventors: 两角一真; 藤村秀俊; 相见敬太郎; 宫下阳介; 佐佐木大辅; 汤本真敏
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2008-09-19
Filing date: 2009-09-21
Publication date: 2010-03-24
Also published as: KR20100033344A; JP5438942B2; TW201022372A; JP2010070694A; TWI481673B

Abstract

The present invention provides microparticles of a water-insoluble compound having excellent stability and firm performance, and their effective preparation methods. The microparticles of the water-insoluble compound is embedded with a dispersant, and is prepared by mixing a solution formed by dissolving the water-insoluble compound in a good solvent into a poor solvent, wherein the mixing mode isthat (i) adding the disperser in the good solvent and/or poor solvent, then mixing two obtained liquids; or (ii) furthermore, preparing the solution formed by dissolving the disperser in the good solvent, then dissolving the solution and the water-insoluble compound in the good solvent to form a solution, and mixing the solution with the poor solvent; wherein at least 10% by weight of the dissolved disperser is imbedded in the microparticles, and a degree of crystallinity of the microparticles is more than 65% in a disperse medium.

Description

The particulate of water-insoluble compound and dispersion thing thereof, their method for making and colour filter

Technical field

The present invention relates to a kind of particulate of water-insoluble compound and disperse thing, described particulate and the preparation method of dispersion thing and the colour filter that has used them.

Background technology

In recent years, just promptly developed about the extension of high-qualityization of the precision machinery relevant of color image sensor, color liquid crystal display arrangement and so on and purposes with image.Corresponding to this, for colour filter, people are the high quality of its display performance of strong request also.With regard to the look material of colour filter, pigment dyestuff is used to replace dyestuff gradually, recently, the stable pigment nano particle that people's demand is such, it is a nano level, and is monodispersity.So people study the manufacture method of the New Color Filter Used of utilizing ink-jet technology.By this research, expectation is significantly improved the freedom of design and cost is significantly reduced, however the dispersion thing of present pigment particle that also be not applicable to this, that performance can be not fully exerted.

If mention the manufacture method of organic pigment particle, generally be meant comminuting methods such as microballon polishing and salt mill method herein.When adopting above-mentioned polishing, thereby, need a large amount of time and energy for the abundant miniaturization of pigment dyestuff is dispersed in the composition.In addition, the pigment type that can use also is limited.And along with the miniaturization of pigment, this dispersive composition demonstrates high viscosity sometimes, and gelation can take place this dispersive composition in storage process in some cases, thereby can't use.

Someone points out, adopts the composition that utilizes above-mentioned liquid phase method and prepare, and can make the colour filter (referring to patent documentation 1) of high-contrast.Even obtained to realize the pigment dyestuff particulate of above-mentioned high-contrast, but for used as the various industrial materials such as colored resist etc., usually after the preparation particle, be necessary its dispersion or redispersion in desirable solvent.Therefore, what for example adopt now is such method: in case after the dried powder of preparation pigment, with microballon pulverizer etc. with its dispersion or redispersion in desirable solvent.But when adopting the method for this dried powder of process, dry needed burden and the needed burden of redispersion are big, operation becomes loaded down with trivial details, and sometimes because dispersion is bad, the result causes contrast gradient to reduce.

There are various crystalline forms in pigment dyestuff, according to the difference of its crystalline form, and tinting strength, distinctiveness, form and aspect, stability difference.Therefore, when the colo(u)rant dispersion thing is used for the purposes of colour filter or ink for inkjet recording etc., need to use the colo(u)rant dispersion thing that has desirable crystalline form and have high crystalline.About being converted to the method for desirable crystalline form, will be handled the method that changes crystalline form with the polar solvent after heating by the ground diketo pyrrolo-pyrrole pigment(DPP pigment) in advance thereby for example in patent documentation 2, disclose.In addition, in patent documentation 3, pigment dyestuff coarse fodders such as copper phthalocyanine are mixed the method that changes crystalline form that stirs in the presence of organic solvent thereby disclose.Similarly, as shown in patent documentation 4, under the situation in pigment dyestuff being applied to electronic photo usefulness photoreceptor, according to the difference of crystalline form, there are very big-difference in charging property, dark decay, sensitivity etc., therefore are necessary to control crystalline form.Usually, if carry out crystal phase transition, crystallization also increases thereupon easily, and therefore, the particle diameter chap is big.Increase in order to suppress crystalline, present method is the pigment derivative of adding shown in patent documentation 5.But still there is not the two method of the dispersiveness of taking into account organic fine particles simultaneously and crystallinity.

[patent documentation 1] international WO2006/121016 brochure that discloses

[patent documentation 2] Japanese kokai publication hei 5-222314 communique

[patent documentation 3] TOHKEMY 2002-88269 communique

[patent documentation 4] TOHKEMY 2000-22174 communique

[patent documentation 5] TOHKEMY 2000-7677 communique

Summary of the invention

The problem that invention will solve

The purpose of this invention is to provide a kind of time stability and stability excellence water-insoluble compound particulate and disperse thing, its effective preparation method, the particulate that a kind of employing has above-mentioned characteristic also is provided and disperses thing and the colour filter made, also can realize high-contrast even this colour filter has passed through the change or the redispersion operation of solvent.

The means of dealing with problems

Above-mentioned problem reaches by following means:

(1) a kind of particulate of water-insoluble compound, be characterised in that, this particulate is embedded with dispersion agent, and this particulate is by mixing with poor solvent and generate water-insoluble compound being dissolved in the solution that forms in the good solvent, described hybrid mode is: (i) add dispersion agent in described good solvent and/or poor solvent, then with resulting two kinds of liquid mixing; Perhaps (ii) prepare in addition dispersion agent is dissolved in the good solvent and the solution that forms, the solution and the described poor solvent of formation are mixed together with above-mentioned water-insoluble compound is dissolved in the good solvent this solution then; Wherein, at least 10 quality % of the described dispersion agent of dissolved are embedded in the described particulate, and the degree of crystallinity of described particulate in dispersion medium is more than 65%.

As above-mentioned (1) described particulate, it is characterized in that (2) its median size is below the 100nm.

As above-mentioned (1) or (2) described particulate, it is characterized in that (3) the crystallization particle diameter of the crystallising part of described particulate is 2～50nm.

As above-mentioned (1) or (2) described particulate, it is characterized in that (4) described dispersion agent is that the matter average molecular weight is the macromolecule dispersing agent more than 1000.

As above-mentioned (1) or (2) described particulate, it is characterized in that (5) described dispersion agent is the macromolecule dispersing agent that intramolecularly contains a heterocycle alkyl at least.

(6) as above-mentioned (1) or (2) described particulate, it is characterized in that, described dispersion agent is the macromolecule dispersing agent with the structure division that is made of aromatic nucleus and nitrogenous cyclic hydrocarbon radical and/or quaternary ammonium group, and this structure division can interact with described water-insoluble compound.

As above-mentioned (1) or (2) described particulate, it is characterized in that (7) described water-insoluble compound is a pigment dyestuff.

(8) a kind of microparticulate thing, it is characterized in that, its main component for above-mentioned (1) or (2) described microparticulate in the material that is selected from the organic solvent that is selected from by (a) aqueous medium, (b) in ester cpds solvent, ketone compound solvent and the alkylol cpd and (c) obtains at least a solvent in the group that reactive diluent constituted.

As above-mentioned (8) described microparticulate thing, it is characterized in that (9) this dispersion thing is used to prepare resist or the ink that forms on base material.

(10) a kind of colour filter, it is to use as above-mentioned (8) described microparticulate thing and makes.

(11) a kind of preparation method who is embedded with dispersion agent and crystallized particulate is characterized in that,

This particulate is by mixing with poor solvent and generate water-insoluble compound being dissolved in the solution that forms in the good solvent, described hybrid mode is: (i) add dispersion agent in described good solvent and/or poor solvent, then with resulting two kinds of liquid mixing; Perhaps (ii) prepare in addition dispersion agent is dissolved in the good solvent and the solution that forms, the solution and the described poor solvent of formation are mixed together with above-mentioned water-insoluble compound is dissolved in the good solvent this solution then; Wherein, at least 10 quality % of the described dispersion agent of dissolved are embedded in this particulate,

Then,, described particulate is contacted with the crystallization solvent, the degree of crystallinity of this particulate is brought up to more than 65% by gas phase.

(12) a kind of method for preparing the microparticulate thing is characterized in that, obtains the particulate of crystallization according to above-mentioned (11) described preparation method, and with the microparticulate of this crystallization in medium.

The invention effect

The particulate of water-insoluble compound of the present invention and dispersion thing thereof have excellent ageing stability and stability, use the colour filter of their manufacturings, even also can realize high-contrast through the change and the redispersion operation of solvent.

In addition, adopt manufacture method of the present invention, can be effectively, can and disperse thing with the particulate of the above-mentioned water-insoluble compound of technical scale mass production in case of necessity with excellent specific property.

Description of drawings

[Fig. 1] is the sectional view that medelling illustrates water-insoluble compound particulate in the preferred embodiments of the invention.

[Fig. 2] is the device explanatory view that medelling illustrates the employed preferred embodiment of operation that is used for improving degree of crystallinity in the manufacture method of the present invention.

[explanation of symbol]

1 water-insoluble compound

2 embedding dispersion agents

The particulate of 10 water-insoluble compounds

11 closed pressure containers

12 loam cakes

13 pedestals

14 crystallization solvents (acetone)

15 fine-particle powder samples

100 reactors

Preferred forms of the present invention

Below, the preferred embodiments of the invention are described, but the present invention can not be interpreted as being confined to these embodiments.

Particulate of the present invention is embedded with dispersion agent.Herein, embedding be meant dispersant molecule part or all be embedded to state in the particulate.For example, based on Fig. 1, the state that dispersion agent all is embedded in, all molecules that are meant the dispersion agent that is added are encased the state (referring to interior embedding dispersion agent 2b) in the particulate 10; The state that a dispersion agent part is embedded in is meant that the part of the dispersion agent that is added or functional group are encased in the particle and its remainder extends in the state (referring to outer embedding dispersion agent 2a) of particle outside, when referring to embedding, comprises the two.

Particulate of the present invention is preferably such particulate, promptly, specific dispersion agent is coexisted as at least one of good solvent or poor solvent, meanwhile or in addition water-insoluble compound is dissolved in the good solvent, then it is mixed with the liquid of above-mentioned good solvent and the liquid of poor solvent, thereby dispersion agent is encapsulated into intragranular aggegation particulate.It is macromolecule dispersing agent more than 1000 that above-mentioned dispersion agent is preferably the matter average molecular weight, and the macromolecule dispersing agent with specific structure position more preferably as mentioned below.

In the present invention, part or all dispersion agent that is embedded to granule interior has such feature: it be not as traditional dispersion agent (for example) only physical adsorption in the particulate surface, but irreversibly be embedded in the particle and immobilization, therefore, as long as particulate is not destroyed or is not dissolved, in dispersion medium and/or composition solvent, can not take place usually to separate or break away from.Therefore, be embedded with the particulate of dispersion agent, the persistence height of the dispersion effect that the cohesion between the inhibition particle is such, thus even the usage quantity of dispersion agent is less, dispersion stabilization is also very high.For example, promptly use the solvent of solubilized dispersion agent to wash repeatedly, dispersion agent can not break away from and measure this amount yet, can confirm the characteristic that is embedded with the particulate of dispersion agent of the present invention thus.

There is no particular limitation for making dispersion agent be embedded in intragranular method effectively, still, for example can select to use specific dispersion agent or can regulate processing condition of fluid passage hybrid system etc. etc.Below, be described in detail making dispersion agent be embedded into intragranular preferred embodiment.

In order to adopt common reprecipitation method that dispersion agent is embedded in the particle, preferably use specific dispersion agent.At this moment, if whole dispersant molecules is encased in the particle, even needed functional group also all is encased in the particle when disperseing, and then can not give full play to the dispersed effect of giving of dispersion agent sometimes.For this reason, preferably, needed functional group is not encased in the particle all when making above-mentioned dispersion.In order to make dispersion agent suitably be encased in the particulate and to give dispersion stabilization, the preferred dispersion agent that satisfies following prerequisite that uses.That is, by reaching following prerequisite, above-mentioned dispersion agent effectively and suitably is encased in the particle, described prerequisite is:

(1) medium of the water-insoluble compound that is used in combination of the medium of solubilized dispersion agent and solubilized has compatibility,

(2) dispersion agent is that the matter average molecular weight is the macromolecule dispersing agent more than 1000,

(3) though dispersion agent is separated out owing to mixing with poor solvent, and the speed of separating out of dispersion agent is slower than the speed of separating out of water-insoluble compound,

(4) dispersion agent contains one at least has the functional group of interaction with water-insoluble compound.

Can be used for of the present inventionly above-mentionedly preferably in following solvent, being dissolved by the dispersion agent of embedding and using: be dissolved with the good solvent of water-insoluble compound, good solvent or the poor solvent of preparing in addition.As the dissolving and the blended preferred embodiment of above-mentioned dispersion agent, can enumerate following method.

(1) dispersion agent is dissolved in the good solvent altogether with water-insoluble compound, contacts with poor solvent then, thus the method for separating out

(2) prepare water-insoluble compound lysate and dispersion agent lysate respectively, contact with poor solvent then, thus the method for separating out

(3) dispersion agent is dissolved in respectively in water-insoluble compound lysate and the poor solvent, the liquid that obtains is contacted with each other, thus the method for separating out etc.

Though adopt any method wherein all can make particulate of the present invention, preferably, dispersion agent lysate and water-insoluble compound lysate have compatibility.If dispersion agent lysate and water-insoluble compound lysate are immiscible, then sometimes can not be by being embedded in the particle fully with the dispersion agent that mixes, makes of poor solvent.In above-mentioned method, the preferred especially method of using above-mentioned (1), (2).

In the present invention, for dispersion agent is embedded in the particle, the matter average molecular weight of preferred dispersants is the macromolecule dispersing agent more than 1000, and more preferably the matter average molecular weight of dispersion agent is more than 3000, below 300,000, and the matter average molecular weight of special preferred dispersants is more than 5000, below 100,000.If the molecular weight of dispersion agent is low excessively, then dispersion agent is embedded to intragranular ratio and can reduces sometimes; If the molecular weight of dispersion agent is excessive, then the aggegation of dispersion agent increases sometimes, thereby redispersibility can worsen.Preferably, the dispersity of employed dispersion agent is narrow,, is the dispersion agent of monodispersity that is.The dispersity of dispersion agent is represented with the ratio of number-average molecular weight and matter average molecular weight, preferably uses the dispersion agent of dispersity in 1.0～5.0 scopes, especially preferably uses the dispersion agent of dispersity in 1.0～4.0 scopes.In the present invention, if not special explanation, then molecular weight and dispersity adopt the measuring method among the embodiment.

The employed dispersion agent in the particulate (below, be referred to as " embedding dispersion agent " sometimes, to differentiate with simple dispersion agent) that is embedded in can be dissolved in the solvent in advance among the present invention, thereby separates out by mixing with poor solvent then.Equally, also can be by water-insoluble compound is dissolved in the good solvent, contact with poor solvent then separating out, thereby form particulate.In the stage of this formation particulate, when the speed of separating out of dispersion agent was faster than the speed of separating out of water-insoluble compound, dispersion agent was just separated out before fully being embedded in the particle, so dispersion agent is difficult to be embedded in the particle.For dispersion agent is embedded in the particle fully, preferably, the speed of separating out of dispersion agent is slower than the speed of separating out of water-insoluble compound.And, as required,, can control the state that this dispersion agent is embedded in the particulate by the speed of separating out of such adjusting embedding dispersion agent.Consider from separating out to form eutectiferous viewpoint, preferably, the speed of separating out of embedding dispersion agent is slower than the speed of separating out of water-insoluble compound, its suitable speed of separating out depends on the solvent affinity etc. of structure, good solvent and poor solvent of speed of separating out, the dispersion agent of affinity, the water-insoluble compound of kind, water-insoluble compound and the dispersion agent of water-insoluble compound, preferably, decide the speed of separating out ratio of water-insoluble compound and dispersion agent according to each particulate formation condition.

Then, structure and the effect thereof to preferred dispersing agent describes preferred such dispersion agent: the embedding dispersion agent is embedded in the particle, and in dispersion medium or composition medium, is not dissociated by the dispersion agent of embedding.

For the embedding dispersion agent is encapsulated in the particle, the embedding dispersion agent chemical structure that preferred design is such: in the stage of separating out behind this dispersion agent and water-insoluble compound process mixed processes, the two demonstrates the interaction that attracts each other.In the present invention, though preferably the embedding dispersion agent is mixed mutually with water-insoluble compound with the state that is dissolved in the solvent, but this moment, if the above-mentioned interaction of this dispersion agent and water-insoluble compound is little, then sometimes dispersion agent to be embedded to intragranular ratio too small, perhaps taken place easily to dissociate in dispersion medium or composition medium by the dispersion agent of embedding, perhaps dispersion stabilization worsens.Therefore, the preferred dispersion agent that has the structure position of intensive adelphotaxy with water-insoluble compound that uses preferably, strengthens this interaction and dispersion agent is securely fixed in the particle.

In particulate of the present invention, preferably, when forming particulate, more than the 10 quality % of the embedding dispersion agent that in system, drops into by embedding.Promptly, quality (A) with respect to the embedding dispersion agent that is added, be embedded in the particle and the ratio percentage ((B)/(A) * 100) of the quality (B) of this dispersion agent of embedding (below, this ratio is called " dispersion agent is imbedded rate ") is preferably more than the 10 quality %.If it is too small that above-mentioned dispersion agent is imbedded rate, then sometimes initial stage dispersiveness or dispersion stabilization are insufficient.In addition, above-mentioned dispersion agent is imbedded rate ((B)/(A)) and is preferably more than the 20 quality %, is preferably especially more than the 30 quality %.Dispersion agent is imbedded the upper limit of rate, and there is no particular limitation, but on calculating on be limited to 100 quality %, be actually below 98%.In the present invention, if do not particularly point out, then above-mentioned dispersion agent is imbedded rate and is calculated according to the method described in following examples.

The ratio of the quality of the amount of the above-mentioned embedding dispersion agent that is embedded in and other composition except this dispersion agent of particulate, promptly, when particulate being regarded as when constituting by formed external phases such as embedding dispersion agent that forms disperse phase and water-insoluble compounds, quality (Y) with respect to the external phase of particulate, the ratio percentage ((X)/(Y) * 100) of the quality (X) of the embedding dispersion agent of above-mentioned formation disperse phase (below, this ratio is called " dispersion agent embedding rate "), be 5～200 quality %, 8～160 quality % more preferably.If do not particularly point out, the mensuration and the calculating of then being somebody's turn to do " dispersion agent embedding rate " are carried out according to the method described in following examples.

As above-mentioned embedding dispersion agent or its structure position, the effect that preferably has and water-insoluble compound attracts each other is meant adsorptivity between intermolecular or its structure position or the interaction in the affinity.There are interaction of hydrogen bond, π-π interaction, interionic interaction, dipolar interaction, london dispersion force (Van der Waals force), charge transfer to interact specifically.In addition, can enumerate hydrophobic interaction based on the thermodynamics key element etc.There is no particular limitation to interaction that above-mentioned dispersion agent or its structure position and water-insoluble compound are attracted each other, can utilize above-mentioned any interaction, but interaction of hydrogen bond, π-π interaction and interionic interaction are effective.Therefore, as the part-structure of embedding dispersion agent, preferred introducing demonstrates above-mentioned interactional position strongly, thereby this dispersion agent is embedded to the easy suitably state of embedding of quilt that forms in the particle thus.

Below, enumerate interaction of hydrogen bond, π-π interaction, the interactional embodiment of interionic, molecular structure and the design thereof that is of value to the dispersion agent of giving these interactions described.

Interaction of hydrogen bond is to take place in the molecule of high atom of electronegativity such as fluorine, oxygen or nitrogen and hydrogen evolution covalent linkage, in this case, and the polarization molecule.At this moment, hydrogen atom has than 1 also little positive charge, and consequently, thereby the electronegative atoms such as oxygen that comprise in nigh another molecule of absorption produce interaction.As a result, produced and made two keys that the molecule bonded is stable.For example, if adopt such dispersion agent, it has by hydrogen bond and the above-mentioned interactional functional group of the easy formation of water-insoluble compound, then can improve dispersion agent and be embedded to the interior rate of imbedding of particulate.

It is the dispersion force that works between the aromatic nucleus of organic compound molecule that π-π interacts, and is also referred to as the accumulative facies mutual effect.For example, aromatics has firm two dimensional structure, because the πDian Zi system, therefore the delocalized electron enrichment shows london dispersion force especially consumingly.Therefore, πDian Zi increases more, and the power of attracting each other is got over grow.For example, if adopt such dispersion agent, it has with water-insoluble compound and forms the interactional functional group of π-π easily, then can improve dispersion agent and be embedded to the ratio of imbedding in the particulate.

The interaction that interionic interacts and to be between charged ion to be produced.For example, because different electric charges is attracted each other, in dispersion medium, if design molecule like this, make dispersion agent have and the different electric charge of water-insoluble object material, then the adelphotaxy of dispersion agent and water-insoluble compound is strengthened, and can improve dispersion agent and be embedded to the ratio of imbedding in the particulate.

In the present invention, embedding dispersion agent and water-insoluble compound preferably use the molecule of such design, make to demonstrate above-mentioned multiple interaction.The preferred molecular structure of this dispersion agent is according to as the kind of the water-insoluble compound of object and difference, but, be under the situation of pigment dyestuff for example at water-insoluble compound, in order to give interaction of hydrogen bond, can preferably use macromolecular compound, be preferably macromolecular compound especially with nitrogen heterocyclic ring position with heterocycle position.In addition, have the dispersion agent of aromatic nucleus in order to give π-π interaction or hydrophobic interaction, to be preferably as part-structure.In addition, particularly preferably be the dispersion agent that has heterocycle and aromatic nucleus in the same molecular skeleton simultaneously.

The object lesson of the heterocyclic moiety structure of, preferred dispersing agent of the present invention as can be used for, can enumerate the following position that illustrates (I-1) to organic pigment structures such as (I-29) and phthalocyanines, insoluble azo class, azo lake class, anthraquinone class, quinoline a word used for translation ketone, dioxazines, diketopyrrolopyrroles, anthracene pyridines, anthanthrene two ketones, indanthrone class, flavanthrones, perylene ketone, perylene class, thioindigo classes, but the present invention is not confined to these especially.The unit of being introduced with these positions preferably accounts for 1.0～99.0 moles of % of the population of cells that constitutes macromolecular compound, more preferably accounts for 3.0～95.0 moles of %, especially preferably accounts for 5.0～90.0 moles of %.

[formula 1]

[formula 2]

In addition, interact, can be used for dispersion agent of the present invention, also can adopt to have the dispersion agent of the following position that illustrates (II-1), but not be confined to these especially to (II-4) in order to obtain interionic.The unit of being introduced with these positions preferably accounts for 1.0～99.0 moles of % of the population of cells that constitutes macromolecular compound, more preferably accounts for 3.0～95.0 moles of %, especially preferably accounts for 5.0～90.0 moles of %.

[formula 3]

Above-mentioned embedding dispersion agent, be preferably the macromolecular compound that has above-mentioned interaction group in the part-structure, can suitably enumerate organic solvent class medium in addition, alcoholic solvent for example, ketones solvent, ether solvent, sulfoxide kind solvent, esters solvent, amide solvent, aromatic hydrocarbon solvent, fat hydrocarbon, nitrile solvents or their mixture etc., wherein more preferably ketones solvent, ether solvent, esters solvent, aromatic hydrocarbon solvent, fat hydrocarbon solvent or their mixture etc.

As ketones solvent, can enumerate as methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, 2-heptanone etc.As ether solvent, can enumerate as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate etc.As esters solvent, can enumerate as 1,3 butylene glycol diacetate esters, 3-methoxypropionic acid methyl esters, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, acetate ethyl cellosolve, ethyl lactate, N-BUTYL ACETATE, ethyl carbitol acetic ester, acetate of butyl carbitol etc.As aromatic hydrocarbon solvent, can enumerate as toluene, dimethylbenzene etc.As fat hydrocarbon solvent, can enumerate as hexanaphthene, octane etc.

These solvents can use separately or can be used in combination.In addition, can use boiling point in case of necessity is 180 ℃～250 ℃ solvent.Total amount with respect to Photocurable composition; the content of organic solvent is preferably 10～95 quality %, perhaps preferably has the reactive diluent part-structures high to the dispersion medium affinity such as (for example polymerizable compounds such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid ethoxyl phenenyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid phenoxy ethyl, (methyl) vinylformic acid phenoxy group TEG ester, N-vinyl-2-Pyrrolidone, N-acryloyl morpholine).Because the position of steric repulsion has affinity to dispersion medium,, can in dispersion medium, give dispersiveness by the part (2o position among Fig. 1) outside particle exposed of embedding dispersion agent.

As the above-mentioned position that has affinity with dispersion medium, there is no particular limitation to it, but, can enumerate as (methyl) esters of acrylic acid, crotonate class, vinyl ester, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, styrenic, vinyl ethers, vinyl ketones, olefines, maleimide, (methyl) vinyl cyanide etc. as preferred example.

Example as (methyl) esters of acrylic acid, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) vinylformic acid 3-phenoxy group-2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-chloroethene ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters, (methyl) vinyl acrylate, (methyl) vinylformic acid 2-phenyl vinyl acetate, (methyl) vinylformic acid 1-propylene ester, (methyl) allyl acrylate, (methyl) vinylformic acid 2-allyloxy ethyl ester, (methyl) vinylformic acid alkynes propyl ester, (methyl) vinylformic acid benzyl ester, diethylene glycol monomethyl ether (methyl) acrylate, TC (methyl) acrylate, triethylene glycol monomethyl ether (methyl) acrylate, triethylene glycol list ethyl ether (methyl) acrylate, polyoxyethylene glycol monomethyl ether (methyl) acrylate, polyethyleneglycol ethyl ether (methyl) acrylate, (methyl) vinylformic acid beta-phenoxy ethoxy ethyl ester, (methyl) vinylformic acid Nonylphenoxy macrogol ester, (methyl) vinylformic acid dicyclopentenyloxyethyl methacrylate, (methyl) vinylformic acid double cyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid tribromophenyl, (methyl) vinylformic acid tribromophenoxy ethyl ester, (methyl) vinylformic acid gamma-butyrolactone etc.

As the example of crotonate class, can enumerate butyl crotonate and the own ester of Ba Dousuan etc.

As the example of vinyl ester, can enumerate vinyl-acetic ester, vinyl chloroacetate, propionate, vinyl butyrate, methoxyacetic acid vinyl acetate and vinyl benzoate etc.

As the example of maleic acid diester class, can enumerate dimethyl maleate, ethyl maleate and dibutyl maleinate etc.

As the example of dimethyl ester class, can enumerate dimethyl fumarate, DEF and dibutyl fumarate etc.

As the example of methylene-succinic acid diester class, can enumerate dimethyl itaconate, diethyl itaconate and dibutyl itaconate etc.

As (methyl) acrylic amide; can enumerate (methyl) acrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-propyl group (methyl) acrylamide; N-sec.-propyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tertiary butyl (methyl) acrylamide; N-cyclohexyl (methyl) acrylamide; N-(2-methoxy ethyl) (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N; N-diethyl (methyl) acrylamide; N-phenyl (methyl) acrylamide; N-nitrophenyl acrylamide; N-ethyl-N phenyl acrylamide; N-benzyl (methyl) acrylamide; (methyl) acryloyl morpholine; diacetone-acryloamide(DAA); N hydroxymethyl acrylamide; N-hydroxyethyl acrylamide; vinyl (methyl) acrylamide; N, N-diallyl (methyl) acrylamide; N-allyl group (methyl) acrylamide etc.

As the example of styrenic, can enumerate vinylbenzene, vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, isopropyl benzene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chloro-styrene, dichlorostyrene, bromstyrol, 1-chloro-4-methyl-benzene, by can be by acidic substance and hydroxy styrenes, vinyl benzoic acid methyl esters and the alpha-methyl styrene etc. of the group of deprotection (for example t-Boc etc.) protection.

As the example of vinyl ethers, can enumerate methylvinylether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl group vinyl ether, methoxy ethyl vinyl ether and Vinyl phenyl ether etc.

As the example of vinyl ketones, can enumerate methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone etc.

As the example of olefines, can enumerate ethene, propylene, iso-butylene, divinyl, isoprene etc.

As the example of maleimide, can enumerate maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide etc.

Can also use (methyl) vinyl cyanide, N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, vinyl caprolactone etc.

As mentioned above, can be used for embedding dispersion agent of the present invention, be preferably such macromolecule dispersing agent, it has the structure division that is made of aromatic nucleus and nitrogenous cyclic hydrocarbon radical and/or quaternary ammonium group, and this structure division can demonstrate adelphotaxy with above-mentioned water-insoluble compound.At this moment, preferably, aromatic nucleus and nitrogenous cyclic hydrocarbon radical and/or quaternary ammonium group are positioned on the identical structure position, and they also can interconnect and form ring.

Except above-mentioned having the group of adelphotaxy, can be used for to introduce various functional groups in the dispersion agent of the present invention with water-insoluble compound.According to the kind of dispersion medium or composition medium or the purposes of composition,, can introduce hydrophobic grouping, acidic-group, basic group, crosslinked group, optical polymerism group, thermopolymerization group etc. as the example of functional group.The unit of being introduced with these functional groups, 95 moles that preferably account for the population of cells that constitutes macromolecular compound below the %, more preferably account for 90.0 moles below the %, especially preferably account for 85 moles below the %.In addition, above-mentioned embedding dispersion agent is preferably non-water-soluble macromolecular compound.If this macromolecular compound is water miscible words, then when contacting with the poor solvent that with water is main component, sometimes dispersion agent is difficult to be embedded in the particulate.

As above-mentioned acidic-group, can enumerate (methyl) vinylformic acid, vinyl benzoic acid, toxilic acid, maleic acid mono alkyl ester, fumaric acid, methylene-succinic acid, Ba Dousuan, TRANSCINNAMIC ACID, acrylic acid dimer etc.In addition, can also utilize addition reaction that the monomer with hydroxyl and cyclic acid anhydride such as maleic anhydride or Tetra hydro Phthalic anhydride, cyclohexane dicarboxylic acid acid anhydride such as (methyl) vinylformic acid 2-hydroxyl ethyl ester form, (methyl) vinylformic acid ω-carboxyl-polycaprolactone etc.In addition, as the precursor of carboxyl, can enumerate maleic anhydride, itaconic anhydride, citraconic anhydride etc. and contain monomer of acid anhydrides etc.In addition, as vinyl monomer with sulfonic acid group, 2-acrylamide-2-methyl propane sulfonic acid etc. can be enumerated,, mono phosphoric acid ester (2-acryloxy ethyl ester), mono phosphoric acid ester (1-methyl-2-acryloxy ethyl ester) etc. can be enumerated as vinyl monomer with phosphate group.

As basic group, can enumerate (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-diisobutyl amino ethyl ester, (methyl) vinylformic acid morpholinyl ethyl ester, (methyl) vinylformic acid piperidyl ethyl ester, (methyl) vinylformic acid 1-pyrrolidino 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 enumerate 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, the N-diethylamino) hexyl (methyl) acrylamide, morpholinyl (methyl) acrylamide, piperidyl (methyl) acrylamide, N-methyl-2-pyrrolidyl (methyl) acrylamide etc., as styrenic, can enumerate N, N-dimethylamino vinylbenzene, N, N-dimethylaminomethyl vinylbenzene etc.

In addition, can also use the group, the carbon number that have urea groups, urethano, have the coordination Sauerstoffatom is the monomer of alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and hydroxyl more than 4.Specifically, can enumerate as (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid uncle monooctyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid octadecane ester, (methyl) stearyl acrylate acyl ester, (methyl) vinylformic acid oil base ester, (methyl) vinylformic acid diamantane ester, and monomer with following structure.

Wherein, as above-mentioned other functional groups, particularly more preferably have polymer of vinyl monomer or multipolymer that carbon number is the alkyl more than 4, further be preferably especially and have polymer of monomers or the multipolymer that carbon number is the alkyl more than 6, below 24.

In addition, can also utilize the monomer that contains ionic functional group.In ionic vinyl monomer (comprising anionic property vinyl monomer and cationic vinyl monomer), as the anionic property vinyl monomer, can enumerate an alkali metal salt of vinyl monomer with above-mentioned acidic-group, or with organic amine (triethylamine for example, tertiary amines such as dimethylaminoethanol) salt of Xing Chenging etc., as the cationic vinyl monomer, can enumerate above-mentioned nitrogenous vinyl monomer haloalkyl (alkyl: C1～18, halogen atom: chlorine atom, bromine atoms or iodine atom): halogeno-benzyl (chloro benzyl for example, benzyl bromide etc.), the ester of alkylsulphonic acids such as methylsulfonic acid (alkyl: C1～18), Phenylsulfonic acid, the alkyl ester of aryl sulfonic acids such as toluenesulphonic acids (alkyl: C1～18), sulfuric acid dialkyl (alkyl: C1～4) etc. carries out quaternized and compound that form; Dialkyldiallyl ammonium salt etc.

Particulate of the present invention also can be used as the tinting material that inkjet recording ink is used.In this case, the main component of dispersion medium and/or composition medium is an aqueous solvent, for example, and water and water/water-miscible organic solvent mixed solution.Example as water-miscible organic solvent, can enumerate alkyl diol (polyalcohols), for example glycerine, 1,2,6-hexanetriol, TriMethylolPropane(TMP), ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, TEG, five ethylene glycol, dipropylene glycol, 2-butylene-1,4-glycol, 2-ethyl-1,3-hexylene glycol, 2-methyl-2,4-pentanediol, 1,2-ethohexadiol, 1,2-hexylene glycol, 1,2-pentanediol, 4-methyl isophthalic acid, 2-pentanediol etc.; Carbohydrate, for example glucose, seminose, fructose, ribose, wood sugar, pectinose, semi-lactosi, glyconic acid, sorbitol, maltose, cellobiose, lactose, sucrose, trehalose, trisaccharide maltose etc.; Glycitols; The hyaluronic acids; So-called solid wetting agents such as urea class; Carbon number is 1～4 alkyl alcohols, for example ethanol, methyl alcohol, butanols, propyl alcohol, Virahol etc.; Glycol ethers, for example glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, the ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, TC, Diethylene Glycol list n-propyl ether, the glycol monomethyl isopropyl ether, the Diethylene Glycol monoisopropyl ether, the glycol monomethyl n-butyl ether, the glycol monomethyl tertbutyl ether, Diethylene Glycol list tertbutyl ether, 1-methyl isophthalic acid-methoxybutanol, propylene glycol monomethyl ether, propylene glycol list ethyl ether, propylene glycol list tertbutyl ether, propylene glycol list n-propyl ether, the propylene glycol monoisopropyl ether, DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list n-propyl ether, dipropylene glycol monoisopropyl ether etc.; 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl-2-imidazolidone, methane amide, ethanamide, dimethyl sulfoxide (DMSO), Sorbitol Powder, anhydrosorbitol, acetin, glyceryl diacetate, triactin, tetramethylene sulfone etc. can use wherein one or more.

In order to be used as antidesiccant and wetting agent, polyalcohols is effective, can enumerate for example glycerine, ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butyleneglycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 3-methyl isophthalic acid, 3-butyleneglycol, 1,5-pentanediol, TEG, 1,6-hexylene glycol, 2-methyl-2,4-pentanediol, polyoxyethylene glycol, 1,2,4-trihydroxybutane, 1,2,6-hexanetriol etc.They can be used alone, and also can two or more merging use.When polyalcohols has the Coulomb repulsion group, by the Coulomb repulsion effect, can suppress the aggegation between particulate, and, can be dispersed in the dispersion medium by introducing above-mentioned acidic-group, basic group, ionic functional group.

To having above-mentioned interaction group, steric repulsion dispersion group, there is no particular limitation for the polymeric species of the embedding dispersion agent of various functional groups, but can enumerate: unit with above-mentioned interaction group, unit with steric repulsion dispersion group, (for example have unitary each polymer of vinyl monomer of various functional groups or multipolymer, the homopolymer of alkyl methacrylate, the homopolymer of styrenic, the multipolymer of alkyl methacrylate/styrenic, polyvinyl butyral acetal etc.), esters polymer (for example, polycaprolactone etc.), ether polymer (for example, polytetramethylene oxide compound etc.), the ammonia esters polymer (for example, urethane that constitutes by butyleneglycol and hexamethylene diisocyanate etc.), acylamide polymer (for example, polyamide 6, polyamide 66 etc.), silicone based polymkeric substance (for example, polydimethylsiloxane etc.), carbonates polymkeric substance (for example, by dihydroxyphenyl propane and carbonyl chloride synthetic polycarbonate etc.) etc.

Wherein, as above-mentioned macromolecular compound, be preferably each polymer of vinyl monomer or multipolymer, esters polymer, ether polymer and their modifier or multipolymer especially.From the solvability adjusting solvent, cost, synthetic easy degree equal angles,, most preferably be each polymer of vinyl monomer or multipolymer as above-mentioned macromolecular compound.

The preparation of each polymer of vinyl monomer or multipolymer for example can be used the method for radical polymerization.For a person skilled in the art, the kind and the polymerizing conditions such as amount, solvent types thereof of temperature when adopting radical polymerization to prepare polymer of vinyl monomer or multipolymer, pressure, radical initiator can be easily be set in, also this condition can be determined experimentally.

Macromolecule dispersing agent as above-mentioned embedding dispersion agent can adopt any combining form.Specifically, any multipolymer in random (being total to) polymers, block (being total to) polymers, grafting (being total to) polymers be can use, but block (being total to) polymers, grafting (being total to) polymers are preferably especially.

Preferably, the particulate of water-insoluble compound of the present invention mainly uses the embedding dispersion agent with above-mentioned ad hoc structure position, and this dispersion agent is encapsulated in the particulate, but also can and use not by the dispersion agent of embedding.For example in order to modulate the viscosity of disperseing thing, give, give, to give, particle deagglomeration, the size of regulating particulate, the affinity of regulating good solvent and poor solvent that make in poor solvent to be separated out, giving the affinity with dispersion medium, can use and the dispersion agent of usefulness with the affinity of dispersion medium with the interaction of above-mentioned embedding dispersion agent with the reactivity of above-mentioned embedding dispersion agent.Can and use common dispersion agents such as tensio-active agent, low dispersal agent molecule, macromolecule dispersing agent.To and the usage ratio of the dispersion agent of usefulness there is no particular limitation, still, with respect to the above-mentioned embedding dispersion agent of 1 mass parts, its consumption is preferably 0.01～1 mass parts, its consumption is more preferably below 0.05～0.5 mass parts.

As and the dispersion agent of usefulness, can use macromolecular compound, specifically can enumerate by being selected from vinylbenzene, styrene derivatives, vinylnaphthalene, the vinylnaphthalene derivative, α, the aliphatics alcohol ester of β-ethylenic unsaturated carboxylic acid etc., vinylformic acid, acrylic acid derivative, methacrylic acid, methacrylic acid derivative, toxilic acid, maleic acid derivatives, olefin sulfonic acid, vinyl-amine, allyl amine, methylene-succinic acid, derivatives from itaconic acid, fumaric acid, fumaric acid derivatives, vinyl acetate, vinyl phosphonate, vinyl pyrrolidone, acrylamide, the N-vinyl acetamide, (wherein at least a be to have hydroxy-acid group to two or more at least monomers in N-vinyl formamide and the derivative thereof etc., sulfonic acid group, phosphate group, hydroxyl, the monomer of any one functional group in the epoxy alkane) segmented copolymer of Gou Chenging, or random copolymers, graft copolymer, or their modifier, and their salt etc.Perhaps, also can and use natural high moleculer eompound and their modifiers such as albumin, gelatin, rosin, shellac, starch, gum arabic, sodium alginate.

There is no particular limitation to can be used for water-insoluble compound of the present invention, specifically can enumerate the particle that waits formation as polymer organic materialss such as organic pigment, organic pigment, soccerballene, polydiacetylene, polyimide, by aromatic hydrocarbons or aliphatic hydrocarbon (for example having the aromatic hydrocarbons or the aliphatic hydrocarbon of orientation characteristic or aromatic hydrocarbons or aliphatic hydrocarbon) with distillation characteristic, be preferably pigment dyestuff, organic pigment or macromolecule organic material, be preferably pigment dyestuff especially.In addition, organic granular can use separately, also can use multiplely, they can also be used in combination, and can use multiple water-insoluble compound and forms the multilayer particle structure.

Can be used for the restriction that pigment dyestuff of the present invention is not subjected to form and aspect, for example can Lie Ju perylene compound pigment perylene ketone compound pigment, quinoline a word used for translation ketone compound pigment, quinoline a word used for translation ketone naphtoquinone compounds pigment, anthraquinone compounds pigment, three benzopyrene dione compounds pigment, benzimidazolone compound pigment, disazo condensation compound pigment, tetrazo compound pigment, azo-compound pigment, indanthrone compound pigment, phthalocyanine compound pigment, triaryl carbonium compound pigment dioxazine compound pigment, aminoanthraquinone compound pigment, Diketopyrrolo-pyrrole compounds pigment, thioindigo compound pigment, isoindoline compounds pigment, isoindoline ketone compound pigment, pyranthrone compound pigment, isoviolanthrone compound pigment, their mixture etc.

Wherein, You Xuan Wei perylene compound pigment, quinoline a word used for translation ketone compound pigment, anthraquinone compounds pigment, Diketopyrrolo-pyrrole compounds pigment, aminoanthraquinone compound pigment, dioxazine compound pigment, phthalocyanine compound pigment or azo-compound pigment, more preferably Diketopyrrolo-pyrrole compounds pigment, aminoanthraquinone compound pigment, phthalocyanine compound pigment, dioxazine compound pigment or azo-compound pigment.

Particulate of the present invention or its disperse in the thing, can be used in combination two or more water-insoluble compounds or its solid solution or also can use with general dye combinations.In containing the dispersion thing of particulate of the present invention, there is no particular limitation to the content of water-insoluble compound, but be preferably 1～60 quality %, more preferably 2～50 quality %.

The preferably water-fast compound of the particulate that obtains among the present invention and in dispersion medium, can stably disperseing.Particle diameter about particulate, thereby have by the quantize method of expression group mean sizes of assay method, particle diameter as frequent use, performance distribute peaked particle diameter the most frequently, the meta particle diameter that is equivalent to the integral distribution curve central value, various median size (number average, length is average, area is average, matter is equal, volume averaging etc.) etc. are arranged, in the present invention, if do not particularly point out, then median size is meant number average bead diameter.The median size of particulate of the present invention (primary granule) is preferably below the 100nm, more preferably below the 75nm, is preferably below the 50nm especially.There is no particular limitation to the lower limit of median size, is actually more than the 5nm.Particulate of the present invention is the single crystal of like this size or polycrystal, aggregate, and this particulate can be a crystal grain, also can be the particle that contains noncrystal part, or their mixture.

If particulate medelling of the present invention is described, can be as shown in Figure 1, water-insoluble compound 1 as external phase and the specific dispersion agent 2 of institute's embedding as disperse phase, but also can imbed or be adsorbed with other one-tenth and grade.At this moment, as by the dispersion agent 2 of embedding, show as all interior embedding dispersion agent 2b that is all wrapped into of its molecule and its part and extend outside outer embedding dispersion agent 2a.The outside extension 2o that is somebody's turn to do outer embedding dispersion agent 2a is connected with the inherent 2i of portion, and preferably, this outside extension 2o has the steric repulsion position, and the inherent 2i of portion has the position that demonstrates the effect that attracts each other with the water-insoluble coloured material.About the embodiment of the preferred molecular structure of the dispersion agent that forms this embedding state and design thereof as mentioned above.

As the expression particle homogeneity (monodispersity) index, in the present invention, short of specifying, use be the ratio (Mv/Mn) of volume average particle size (Mv) and number average bead diameter (Mn).The monodispersity of organic nanometer granule of the present invention (primary granule) (in the present invention, monodispersity is meant the degree of particle diameter unanimity), promptly Mv/Mn is preferably 1.0～2.0, and more preferably 1.0～1.8, be preferably 1.0～1.5 especially.

As the particle size determination method of organic granular, can enumerate microscopy, mass method, light scattering method, light and block method, electrical resistance method, sound equipment method, dynamic light scattering method, preferred especially microscopy, dynamic light scattering method.As the microscope that uses in the microscopy, can enumerate for example scanning electronic microscope, transmission electron microscope etc.As the particle determinator that utilizes dynamic light scattering method, can enumerate the ダイ Na ミ Star Network light-scattering photometer DLS-7000 series (being trade(brand)name) of for example day Na ノトラ Star Network UPA-EX150 ， Da mound electronics society manufacturing that machine dress society makes etc.

Herein, the crystallization to the particulate among the present invention describes.

About reprecipitation method (it is as the preferred embodiment of the manufacture method of the particulate of water-insoluble compound), will further set forth in the back, but preferably, particulate of the present invention is the particulate after the degree of crystallinity of the particulate that obtains of reprecipitation method improves.Address before making desirable dispersion agent be embedded in preferred embodiment in the particulate, still, the particulate that is embedded with dispersion agent of Huo Deing is generally noncrystal (for example degree of crystallinity is about 0～50%) before dispersion treatment like this.Therefore, preferably, before dispersion, noncrystal particle is carried out crystallization and handle.Handle as crystallization, known have contact, apply machinery with solvent and grind power, heating or their methods such as combination.In addition, when forming particle,, can obtain crystallization and obtain promoted particle by using crystal seed.In the present invention, there is no particular limitation to the method for crystallization, but preferably, use crystallization solvent described as follows, promotes crystallization thereby it is contacted with noncrystal particle, particularly preferably is, and by gas phase, it contacted with noncrystal particle.If this crystallization solvent is contacted in (for example) liquid phase, then may be broken away from by the dispersion agent of embedding, and as mentioned above, gas phase contact by the crystallization solvent, the degree of crystallinity of particulate can be improved, thereby the degree of crystallinity that good dispersant embedding dispersion state improves particulate can be kept thus.Specifically, by being placed on, noncrystal particle realizes contact in the atmosphere after the above-mentioned crystallization solvent evaporates.In addition, when contacting,, in addition, can also there be gas after liquid such as water or its volatilize etc. as long as the crystallization solvent contacts with the gas of microparticle surfaces by this solvent molecule by above-mentioned gas phase.

As the crystallization solvent, can enumerate part alkylol cpd solvent (for example ethanol, Virahol, n-propyl alcohol, butanols etc.), ketone compound solvent (for example acetone, methylethylketone etc.), ester cpds solvent (for example vinyl acetic monomer etc.), nitrile compound solvent (for example acetonitrile etc.), the mixed solvent that they can use or can use itself and water separately can also use their mixed solvent.

Wherein, be preferably ketone compound solvent or nitrile compound solvent, more preferably acetone, methylethylketone, acetonitrile.

If represent the crystallization state of particulate of the present invention with medelling, particulate 10 as shown in Figure 1, in the water-insoluble compound 1 that constitutes crystalline external phase, crystallization part (crystal portion) 1b and not crystallization partly (amorphous body) 1a be admixture.At this moment, the 1b of crystal portion can exist in the part, many places as shown in the figure, also can exist in place gathering.There is no particular limitation to the shape of the 1b of crystal portion, and much less, its section needs not to be such as shown in the figure circle.

The degree of crystallinity of particulate of the present invention particulate in dispersion medium is more than 65%, and this degree of crystallinity is preferably 80～100%, more preferably 90～100%.There is no particular limitation to the crystal particle diameter (coming word by Fig. 1, is the diameter of a 1b of crystal portion) of particulate of the present invention, but be preferably 20～500 dusts, more preferably 20～200 dusts.In the present invention, if do not particularly point out, then the degree of crystallinity of particulate and crystal particle diameter are to measure according to measuring method used among the embodiment described later.

As above-mentioned embedding dispersion agent, the following macromolecular compound of also preferred use.

There is no particular limitation to above-mentioned macromolecular compound, (for example can enumerate polymer of vinyl monomer or multipolymer, the homopolymer of alkyl methacrylate, the homopolymer of styrenic, the multipolymer of alkyl methacrylate/styrenic, polyvinyl butyral acetal etc.), esters polymer (for example, polycaprolactone etc.), ether polymer (for example, polytetramethylene oxide compound etc.), the ammonia esters polymer (for example, urethane that constitutes by butyleneglycol and hexamethylene diisocyanate etc.), acylamide polymer (for example, polyamide 6, polyamide 66 etc.), silicone based polymkeric substance (for example, polydimethylsiloxane etc.), carbonates polymkeric substance (for example, by dihydroxyphenyl propane and carbonyl chloride synthetic polycarbonate etc.) etc.

Wherein, as above-mentioned macromolecular compound, particularly be preferably polymer of vinyl monomer or multipolymer, esters polymer, ether polymer and their modifier or multipolymer.Angle from the solvability adjusting solvent, cost, synthetic easy degree as above-mentioned macromolecular compound, is preferably polymer of vinyl monomer or multipolymer especially.

There is no particular limitation to above-mentioned vinyl monomer, for example can enumerate (methyl) esters of acrylic acid, crotonate class, vinyl ester, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, styrenic, vinyl ethers, vinyl ketones, olefines, maleimide, (methyl) vinyl cyanide etc. as preferred example.

Example as (methyl) esters of acrylic acid, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) 2-EHA, (methyl) vinylformic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 3-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(2-methoxyethoxy) ethyl ester, (methyl) vinylformic acid 3-phenoxy group-2-hydroxypropyl acrylate, (methyl) vinylformic acid 2-chloroethene ester, (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters, (methyl) vinyl acrylate, (methyl) vinylformic acid 2-phenyl vinyl acetate, (methyl) vinylformic acid 1-propylene ester, (methyl) allyl acrylate, (methyl) vinylformic acid 2-allyloxy ethyl ester, (methyl) vinylformic acid alkynes propyl ester, (methyl) vinylformic acid benzyl ester, diethylene glycol monomethyl ether (methyl) acrylate, TC (methyl) acrylate, triethylene glycol monomethyl ether (methyl) acrylate, triethylene glycol list ethyl ether (methyl) acrylate, polyoxyethylene glycol monomethyl ether (methyl) acrylate, polyethyleneglycol ethyl ether (methyl) acrylate, (methyl) vinylformic acid beta-phenoxy ethoxy ethyl ester, (methyl) vinylformic acid Nonylphenoxy macrogol ester, (methyl) vinylformic acid dicyclopentenyloxyethyl methacrylate, (methyl) vinylformic acid double cyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid two ring pentyl esters, (methyl) vinylformic acid tribromophenyl, (methyl) vinylformic acid tribromophenoxy ethyl ester, (methyl) vinylformic acid gamma-butyrolactone etc.

Example as (methyl) acrylic amide; can enumerate (methyl) acrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-propyl group (methyl) acrylamide; N-sec.-propyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tertiary butyl (methyl) acrylamide; N-cyclohexyl (methyl) acrylamide; N-(2-methoxy ethyl) (methyl) acrylamide; N; N-dimethyl (methyl) acrylamide; N; N-diethyl (methyl) acrylamide; N-phenyl (methyl) acrylamide; N-nitrophenyl acrylamide; N-ethyl-N phenyl acrylamide; N-benzyl (methyl) acrylamide; (methyl) acryloyl morpholine; diacetone-acryloamide(DAA); N hydroxymethyl acrylamide; N-hydroxyethyl acrylamide; vinyl (methyl) acrylamide; N, N-diallyl (methyl) acrylamide; N-allyl group (methyl) acrylamide etc.

As maleimide, can enumerate maleimide, butyl maleimide, cyclohexyl maleimide, phenyl maleimide etc.

Wherein, above-mentioned macromolecular compound particularly more preferably has polymer of vinyl monomer or multipolymer that carbon number is the alkyl more than 4, further is preferably especially to have polymer of monomers or the multipolymer that carbon number is the alkyl more than 6, below 24.As an example, can enumerate (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) vinylformic acid uncle monooctyl ester, (methyl) isobornyl acrylate, (methyl) vinylformic acid dodecane ester, (methyl) vinylformic acid octadecane ester, (methyl) stearyl acrylate acyl ester, (methyl) vinylformic acid oil base ester, (methyl) vinylformic acid diamantane ester etc.

In addition, except above-mentioned,, can also enumerate the vinyl monomer with acidic-group, vinyl monomer etc. with basic group as the example of preferred vinyl monomer.

Example as above-mentioned vinyl monomer with acidic-group, can enumerate vinyl monomer, for example (methyl) vinylformic acid, vinyl benzoic acid, toxilic acid, maleic acid mono alkyl ester, fumaric acid, methylene-succinic acid, Ba Dousuan, TRANSCINNAMIC ACID, acrylic acid dimer etc. with carboxyl.In addition, can also utilize addition reaction that the monomer with hydroxyl and cyclic acid anhydride such as maleic anhydride or Tetra hydro Phthalic anhydride, cyclohexane dicarboxylic acid acid anhydride such as (methyl) vinylformic acid 2-hydroxyl ethyl ester etc. form, (methyl) vinylformic acid ω-carboxyl-polycaprolactone etc.In addition, as the precursor of carboxyl, can enumerate maleic anhydride, itaconic anhydride, citraconic anhydride etc. and contain monomer of acid anhydrides etc.In addition, as vinyl monomer with sulfonic acid group, 2-acrylamide-2-methyl propane sulfonic acid etc. can be enumerated,, mono phosphoric acid ester (2-acryloxy ethyl ester), mono phosphoric acid ester (1-methyl-2-acryloxy ethyl ester) etc. can be enumerated as vinyl monomer with phosphate group.

As vinyl monomer with basic nitrogen atom, as its (methyl) acrylate, can enumerate (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-diisobutyl amino ethyl ester, (methyl) vinylformic acid morpholinyl ethyl ester, (methyl) vinylformic acid piperidyl ethyl ester, (methyl) vinylformic acid 1-pyrrolidino 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 its (methyl) acrylic amide, can enumerate 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 enumerate N, N-dimethylamino vinylbenzene, N, N-dimethylaminomethyl vinylbenzene etc.

In addition, can also use the group, the carbon number that have urea groups, urethano, have the coordination Sauerstoffatom is alkyl, alkoxysilyl, epoxy group(ing), the isocyanate group more than 4, the monomer of hydroxyl.Specifically, can enumerate the monomer that for example has following structure.

[formula 4]

In addition, can also utilize the monomer that contains ionic functional group.(comprise the anionic property vinyl monomer at ionic vinyl monomer, the cationic vinyl monomer) in, as the anionic property vinyl monomer, can enumerate an alkali metal salt of vinyl monomer with above-mentioned acidic-group, and with organic amine (triethylamine for example, tertiary amines such as dimethylaminoethanol) salt of Xing Chenging etc., as the cationic vinyl monomer, can enumerate above-mentioned nitrogenous vinyl monomer haloalkyl (alkyl: C1～18, halogen atom: chlorine atom, bromine atoms or iodine atom): halogeno-benzyl (chloro benzyl for example, benzyl bromide etc.), the ester of alkylsulphonic acids such as methylsulfonic acid (alkyl: C1～18), Phenylsulfonic acid, the alkyl ester of aryl sulfonic acids such as toluenesulphonic acids (alkyl: C1～18), sulfuric acid dialkyl group quaternised compounds such as (alkyl: C1～4); Dialkyldiallyl ammonium salt etc.

Above-mentioned macromolecular compound is preferably the monomer with organic pigment structure or heterocycle structure.As monomer, can enumerate and have the pigment structure (phthalocyanines for example with organic pigment structure or heterocycle structure, insoluble azo class, the azo lake class, the anthraquinone class, quinoline a word used for translation ketone dioxazines, diketopyrrolopyrroles, the anthracene pyridines, anthanthrene two ketones, the indanthrone class, flavanthrones perylene ketone perylene class, thioindigo class etc.), or heterocycle structure (thiophene for example, furans, xanthene, the pyrroles, pyrroline, tetramethyleneimine, dioxolane, pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithian, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, anthraquinone etc.) monomer.

More particularly, have in the monomer of organic pigment structure or heterocycle structure at these, above-mentioned macromolecular compound is preferably general formula (1) represented polymer of monomers or multipolymer.In addition, in the present invention, when representing macromolecular compound,, for example, can only be hydrogen atom, stopper residue etc. as long as end group is atom or group arbitrarily arbitrarily with the repeat unit structure formula.

[formula 5]

General formula (1)

In the formula, R ¹Expression hydrogen atom or methyl.J represents-CO-,-COO-,-CONR ⁶-,-OCO-, phenylene or-C ₆H ₄The CO-base, R ⁶Expression hydrogen atom, alkyl, aryl or aralkyl.W ¹Expression singly-bound, straight chain, side chain or cyclic alkylidene group or inferior aralkyl.P represents heterocyclic radical.

In the formula (1), J is preferably-CO-, phenylene, benzoyl.R ⁶Expression hydrogen atom, alkyl (for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, n-hexyl, n-octyl, 2-hydroxyethyl etc.), aryl (for example phenyl) are preferably hydrogen atom, methyl, ethyl.

As above-mentioned W ¹The alkylidene group of expression is preferably carbon number and is 1～10 alkylidene group, and more preferably carbon number is 1～4 alkylidene group.Can enumerate as methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, octylene, inferior decyl etc., wherein be preferably methylene radical, ethylidene or propylidene.As above-mentioned W ¹The inferior aralkyl of expression is preferably carbon number and is 7～13 inferior aralkyl, can enumerate as benzylidene, inferior cassia bark base etc.As above-mentioned W ¹The arylidene of expression is preferably carbon number and is 6～12 arylidene, can enumerate as phenylene, inferior cumenyl, sym-trimethylbenzene base, tolylene, xylylene etc., wherein is preferably phenylene especially.

In addition, at W ¹In straight chain, side chain or cyclic alkylidene group, the inferior aralkyl of expression, also can exist as conjugated group-NR ³²-,-NR ³²R ³³-,-COO-,-OCO-,-O-,-SO ₂NH-,-NHSO ₂-,-NHCOO-,-OCONH-or by the group of heterocyclic derivatives.Above-mentioned R ³², R ³³Represent hydrogen or alkyl independently of one another, can suitably enumerate hydrogen, methyl, ethyl, propyl group etc.

By W ¹In the linking group of expression, be preferably singly-bound or alkylidene group, more preferably methylene radical, ethylidene or 2-hydroxyl propylidene.

In the formula (1), P represents heterocyclic radical, wherein be preferably the heterocyclic radical that constitutes pigment dyestuff, can enumerate the heterocyclic radical that forms phthalocyanines, insoluble azo class, azo lake class, anthraquinone class, quinoline a word used for translation ketone, dioxazines, diketopyrrolopyrroles, anthracene pyridines, anthanthrene two ketones, indanthrone class, flavanthrones, perylene ketone, perylene class, thioindigo class, quinophthalone class pigment.As this heterocyclic radical, can enumerate thiophene, furans, xanthene, the pyrroles, pyrroline, tetramethyleneimine, dioxolane, pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithian, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, veronal, the sulfo-veronal, carbazole, acridine, dihydroketoacridine, quinoline a word used for translation ketone, anthraquinone, phthalic imidine, adjacent toluquinoline, quinophthalone, be preferably thiophene, furans, xanthene, the pyrroles, imidazoles, isoindoline, isoindolinone, benzimidazolone, indoles, quinoline, carbazole, acridine, dihydroketoacridine, quinoline a word used for translation ketone, anthraquinone, phthalic imidine, adjacent toluquinoline, quinophthalones etc. are preferably benzimidazolone especially, indoles, quinoline, veronal, the sulfo-veronal, carbazole, acridine, dihydroketoacridine, anthraquinone, and phthalic imidine.According to the structure or the electronic property of employed pigment, can suitably select these heterocyclic radicals.

Wherein, the repeating unit of general formula (1) expression is preferably the unit of general formula (2), (3) expression.

General formula (2) general formula (3)

R ¹Expression hydrogen atom or methyl.Y represents-NH-,-O-or-S-.W ²Expression singly-bound or divalent linker are preferably singly-bound, straight chain, side chain or cyclic alkylidene group or inferior aralkyl.P represents heterocyclic radical.In the following formula, W ²Preferable range and the W in the general formula (1) ¹Identical.P in the following formula is identical with P in the general formula (1).

The preferred object lesson of the structure that following enumerative (1), (2) and (3) are represented.But the present invention is not limited to these.

[formula 7]

[formula 8]

In addition, except above-mentioned shown structure, the P in the repeating unit of above-mentioned general formula (1), (2) and (3) expression preferably uses following general formula (4) or its tautomerism body structure to represent.

[formula 9]

General formula (4)

R ²The expression hydrogen atom, be substituted or unsubstituted alkyl or be substituted or unsubstituted aryl.R ³Expression hydrogen atom, alkyl, aryl, halogen atom or azo-group.

Herein, tautomerism is described.Tautomerism is meant that the reversible that takes place between the isomer changes mutually, is mainly prototropy, that is, and and the phenomenon that hydrogen atom shifts mutually.In addition, tautomer is meant that the isomerization speed of conversion is fast mutually between the constitutional isomer that can change mutually, and any one isomer can reach the equilibrium state of coexistence.As the example of generally seeing, tautomer is the conversion that is accompanied by singly-bound and two keys, and hydrogen atom (being proton) shift reaction takes place takes place.According to temperature, pH, liquid phase or solid phase or solvent types (under the situation that is solution), isomerized speed and equilibrium ratio also change.Also often be called tautomer when being a few hours to a couple of days when reaching the required time of balance.

In macromolecular compound of the present invention, the chemical structure (part) that shows above-mentioned tautomerism is called tautomerism body structure (part), and the chemical structure (tautomerism body structure) that obtains by the reaction of the tautomerization in the repeating unit of general formula (4) expression is as shown in the formula shown in (a)～(h).

[formula 10]

Work as R ²During for the group beyond the hydrogen atom

Work as R ²During for hydrogen atom

Wherein, R ²Be preferably hydrogen atom, methyl, ethyl, 2-ethylhexyl or phenyl.

Wherein, R ³The substituting group of expression preferably has the azo structure of following general formula (7) expression.

[formula 11]

General formula (7)

-N＝N-R ²³

R ²³Expression is substituted or unsubstituted, aromatic nucleus or contain the heterocycle of heteroatoms (for example Sauerstoffatom, sulphur atom, nitrogen-atoms etc.).Wherein, as this aromatic nucleus and heterocyclic structure, be preferably the monocycle or two fused rings of～6 yuan of rings of 5 yuan of rings.Wherein, be preferably phenyl ring, pyridine ring, pyrimidine ring, imidazole ring, isoxazole ring, oxazole ring, thiazole ring, pyrazoles ring, triazole ring, tetrazole ring, benzoglyoxaline ring, benzothiazole ring, benzoxazole ring, benzoisoxazole ring, benzothiazole ring, thiadiazoles ring.

Below, enumerate and have, but the present invention is not limited to these the group of above-mentioned general formula (4) expression preferred example as the repeating unit of heterocyclic radical P.In addition, the structure of enumerating in this object lesson is an example in the tautomerism body structure that can consider, also can take other tautomerism body structure.

[formula 12]

[formula 13]

In addition, above-mentioned macromolecular compound is preferably the graft copolymer with such repeating unit, and the polyreactive oligomers copolymerization that this repeating unit end has the ethylenic unsaturated double-bond forms.The polyreactive oligomers that this end has the ethylenic unsaturated double-bond is the compound with molecular weight of regulation, therefore it is also referred to as big monomer.The polyreactive oligomers that this is specific preferably is made of polymer chain part and the terminal polymerisable functional moieties with ethylenic unsaturated double-bond.From obtaining the angle of desirable graftomer, preferably, only an end at polymer chain has this group that contains the ethylenic unsaturated double-bond.Group as containing the ethylenic unsaturated double-bond is preferably (methyl) acryl, vinyl, is preferably (methyl) acryl especially.

In addition, this big monomeric number-average molecular weight through polystyrene conversion (Mn) is preferably in 1000～20000 scope, in 2000～10000 scope.

Usually, above-mentioned polymer chain is partly served as reasons and is selected from homopolymer that at least a monomer in the group that is made of (methyl) alkyl acrylate, vinylbenzene and derivative thereof, vinyl cyanide, vinyl acetate and divinyl forms or multipolymer or polyethylene oxide, poly(propylene oxide), polycaprolactone.

Above-mentioned polyreactive oligomers is preferably the oligopolymer that following general formula (5) is represented.

[formula 14]

General formula (5)

But, R ⁹And R ¹¹Represent hydrogen atom or methyl independently of one another, R ¹⁰The expression carbonatoms is that 1～12 alkylidene group (is preferably carbonatoms and is 2～4 alkylidene group, can have substituting group (for example hydroxyl), can also connect by ester bond, ehter bond, amido linkage etc.), Z represents phenyl, have phenyl that carbonatoms is 1～4 alkyl or-COOR ¹²(still, R ¹²The expression carbonatoms is that 1～6 alkyl, phenyl or carbonatoms are 7～10 aralkyl), and q is 20～200.Z be preferably phenyl or-COOR ¹²(still, R ¹²The expression carbonatoms is 1～12 alkyl).

As the preferred example of above-mentioned polyreactive oligomers (big monomer), can enumerate the polymkeric substance that is combined with (methyl) acryl on the end of poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, poly-(methyl) isobutyl acrylate and polystyrene molecule.As the commercially available this polyreactive oligomers that gets; can enumerate single terminal methyl group acryl polystyrene oligopolymer (Mn=6000; trade(brand)name: AS-6; the manufacturing of East Asia synthetic chemical industry (strain) society), single terminal methyl group acryl polymethyl methacrylate oligomer (Mn=6000; trade(brand)name: AA-6; East Asia synthetic chemical industry (strain) society makes) and single terminal methyl group acryl Vinalac 5920 oligopolymer (Mn=6000; trade(brand)name: AB-6, East Asia synthetic chemical industry (strain) society makes).

Above-mentioned polyreactive oligomers not only is the polyreactive oligomers of above-mentioned general formula (5) expression, also is preferably the polyreactive oligomers of following general formula (6) expression.

[formula 15]

General formula (6)

In the above-mentioned general formula (6), R ¹³Expression hydrogen atom or methyl, R ¹⁴The expression carbon number is 1～8 alkylidene group.Q represents-OR ¹⁵Or-OCOR ¹⁶Herein, R ¹⁵, R ¹⁶Expression hydrogen atom, alkyl or aryl.N represents 2～200.

In the above-mentioned general formula (6), R ¹³Expression hydrogen atom or methyl.R ¹⁴The expression carbon number is 1～8 alkylidene group, wherein is preferably carbon number and is 1～6 alkylidene group, and more preferably carbon number is 2～3 alkylidene group.Q represents-OR ¹⁵Or-OCOR ¹⁶Herein, R ¹⁵Expression hydrogen atom, carbon number are 1～18 alkyl, phenyl or are the phenyl that 1～18 alkyl replaces by carbon number.R ¹⁶The expression carbon number is 1～18 alkyl.In addition, n represents 2～200, is preferably 5～100, is preferably 10～100 especially.

Polyreactive oligomers as general formula (6) expression, can enumerate as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, polytetramethylene glycol monomethacrylates etc., they can be the commercially available prod, also can be suitable synthetic.

As mentioned above, polyreactive oligomers as general formula (6) expression, can be used as the commercially available prod and obtain, as the commercially available prod, can enumerate methoxy polyethylene glycol methacrylate-styrene polymer (trade(brand)name: NK エステ Le M-40G, M-90G, M-230G (above) by Xin Zhong village chemical industry (strain) society system; Trade(brand)name: Block レ Application マ one PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (above) by Japanese grease (strain) society system, polyethylene glycol monomethacrylate (trade(brand)name: Block レ Application マ one PE-90, PE-200, PE-350, Japan grease (strain) society system), polypropylene glycol monomethacrylate (trade(brand)name: Block レ Application マ one PP-500, PP-800, PP-1000, Japan grease (strain) society system), polyoxyethylene glycol polypropylene glycol monomethacrylate (trade(brand)name: Block レ Application マ one 70PEP-350B, Japan grease (strain) society system), polyoxyethylene glycol polytetramethylene glycol monomethacrylates (trade(brand)name: Block レ Application マ one 55PET-800, Japan grease (strain) society system), polypropylene glycol polytetramethylene glycol monomethacrylates (trade(brand)name: Block レ Application マ one NHK-5050, Japanese grease (strain) society system) etc.

In addition, except the polyreactive oligomers of above-mentioned general formula (5) and (6), also be preferably the polycaprolactone monomer, as the commercially available prod, can enumerate polycaprolactone monomethacrylates (trade(brand)name: プラ Network セ Le FM2D, FM3, FM5, FA1DDM, FA2D, ダイセ Le chemical industry (strain) society system) etc.

When preparation polymer of vinyl monomer or multipolymer, for example can use method according to radical polymerization.For a person skilled in the art, the easily kind and the polymerizing conditions such as amount, solvent types thereof of design temperature, pressure, radical initiator when utilizing radical polymerization to prepare polymer of vinyl monomer or multipolymer also can determine this condition experimentally.

Above-mentioned polymer of vinyl monomer or multipolymer can be the macromolecular compounds that end has functional group.As this functional group, be preferably the functional group that the pigment of being separated out is had excellent adsorptivity.

For example, the chain-transfer agent that contains functional group according to use carry out radical polymerization method, use the polymerization starter that contains functional group (for example to carry out the polymeric method, radical polymerization, cationoid polymerisation, anionoid polymerization etc.), can synthesize the macromolecular compound that end has functional group.

As the chain-transfer agent that functional group can be incorporated into the macromolecular compound end; can enumerate as sulfhydryl compound (for example mercaptoethanol acid; mercaptosuccinic acid; thiosalicylic acid; 2 mercaptopropionic acid; the 3-thiohydracrylic acid; 3-sulfydryl butyric acid; N-(2-mercapto radical propionyl group) glycine; 2-sulfydryl nicotinic acid; 3-[N-(2-mercaptoethyl) formamyl] propionic acid; 3-[N-(2-mercaptoethyl) amino] propionic acid; N-(3-mercapto radical propionyl group) L-Ala; mistabrom; 3-sulfydryl propanesulfonic acid; 4-sulfydryl fourth sulfonic acid; 2 mercapto ethanol; 3-sulfydryl-1; the 2-propylene glycol; 1-sulfydryl-2-propyl alcohol; 3-sulfydryl-2-butanols; mercapto-phenol; the 2-mercaptoethylamine; the 2-mercaptoimidazole; 2-sulfydryl-3-pyridol; thiophenol; thiocresol; the sulfydryl methyl phenyl ketone; naphthyl mercaptan; naphthalene thiomethyl alcohol etc.) or as the di-sulphide compounds of the oxide compound of these sulfhydryl compounds; and halogenated compound (for example, 2-iodine ethyl sulfonic acid; 3-iodine propanesulfonic acid etc.).

In addition, as the polymerization starter that functional group can be incorporated into the macromolecular compound end, can enumerate as 2,2 '-azo two (2-cyano group propyl alcohol), 2,2 '-azo two (2-cyano group amylalcohol), 4,4 '-azo two (4-cyanopentanoic acid), 4,4 '-azo two (4-cyano group valeryl chloride), 2,2 '-azo two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane], 2,2 '-azo two [2-(2-tetrahydroglyoxaline-2-yl) propane], 2, [2-(3 for 2 '-azo two, 4,5,6-tetrahydropyrimidine-2-yl) propane], 2,2 '-azo two 2-[1-(2-hydroxyethyl)-2-tetrahydroglyoxaline-2-yl] propane }, 2,2 '-azo two [2-methyl-N-(2-hydroxyethyl)-propionic acid amide] etc. or their derivative etc.

The particulate of water-insoluble compound of the present invention is preferably such aggegation particulate, promptly, when the solution that above-mentioned water-insoluble compound is dissolved in the good solvent and forms is carried out mixing of following mode with poor solvent, the aggegation particulate that is embedded with above-mentioned dispersion agent that generates, wherein said being mixed into: (i) in good solvent and/or poor solvent, add above-mentioned dispersion agent, then with resulting two kinds of liquid mixing; Perhaps (ii) prepare in addition above-mentioned dispersion agent is dissolved in the good solvent and the solution that forms, the solution and the described poor solvent of formation are mixed together with above-mentioned water-insoluble compound is dissolved in the good solvent this solution then.

There is no particular limitation to the consumption of above-mentioned embedding dispersion agent, but when the particulate that makes water-insoluble compound is separated out, as the amount of in system, adding, water-insoluble compound with respect to 100 mass parts, be preferably the scope of 10～300 mass parts, the scope of 10～120 mass parts more preferably is preferably the scope of 20～100 mass parts especially.As mentioned above, in particulate of the present invention, preferred package is embedded with more than the 10 quality % of the embedding dispersion agent that adds in above-mentioned reprecipitation method.Above-mentioned embedding dispersion agent can be used alone, also can be also with two or more.There is no particular limitation to the content of the embedding dispersion agent in the dispersion thing of the present invention, but in fact its higher limit is the amount of being added in above-mentioned system, and lower value is the amount of institute's embedding in the particulate, specifically, be preferably 1～294 quality %, more preferably 2～99 quality %.

The example that can be used as the macromolecular compound of embedding dispersion agent among the present invention below is shown, but the present invention is not limited to these.

(1) polymethylmethacrylate

(2) polypropylene glycol

(3) poly-epsilon-caprolactone

(4) methyl methacrylate/cinnamic multipolymer

(5) methacrylic acid benzyl ester/acrylic acid multipolymer

(6) multipolymer of methyl methacrylate/dimethylaminopropyl acrylamide

(7) methyl methacrylate/the give monomeric multipolymer of above-mentioned moiety Q-17

(8) methyl methacrylate/the give multipolymer of monomer/terminal methyl group propylene acidylate polymethylmethacrylate of above-mentioned moiety Q-17

(9) give the multipolymer of monomer/styrene/methacrylic acid of above-mentioned moiety M-1

(10) give monomer/terminal methyl group propylene acidylate polymethylmethacrylate/Sipacril 2739OF of above-mentioned moiety M-1

(11) give the multipolymer of monomer/terminal methyl group propylene acidylate polymethylmethacrylate/dimethylaminopropyl acrylamide of above-mentioned moiety M-1

(12) give the multipolymer of monomer/terminal methyl group propylene acidylate polystyrene/methacrylic acid of above-mentioned moiety Q-22

(13) give the multipolymer of monomer/terminal methyl group propylene acidylate poly-n-butyl methacrylate/methacrylic acid of above-mentioned moiety Q-10

(14) give the multipolymer of monomer/end (methyl) acryloyl polyethylene glycol polypropylene glycol/methacrylic acid of above-mentioned moiety M-1

(15) give the multipolymer of monomer/end (methyl) acryloyl polyethylene glycol/methacrylic acid of above-mentioned moiety Q-4

(16) give the multipolymer of monomer/end (methyl) propylene acidylate polypropylene glycol/methacrylic acid of above-mentioned moiety Q-1

(17) give the multipolymer of monomer/terminal methyl group propylene acidylate polycaprolactone/methacrylic acid of above-mentioned moiety M-1

(18) give the multipolymer of monomer/terminal methyl group propylene acidylate polystyrene/methacrylic acid/dimethylaminopropyl acrylamide of above-mentioned moiety Q-21

(19) give the multipolymer of monomer/terminal methyl group propylene acidylate polymethylmethacrylate of above-mentioned moiety M-1

(20) give the multipolymer of monomer/vinylbenzene/dimethylaminopropyl acrylamide of above-mentioned moiety Q-22

(21) give monomer/N of above-mentioned moiety M-1, the multipolymer of N-dimethyl-4-vinyl benzene methane amide/methacrylic acid

(22) give the multipolymer of monomer/4-t-butyl styrene/methacrylic acid of above-mentioned moiety Q-23

(23) give the multipolymer of monomer/methacrylic acid/terminal methyl group propylene acidylate polymethylmethacrylate of above-mentioned moiety M-3

(24) give the multipolymer of monomer/methacrylic acid/terminal methyl group propylene acidylate polycaprolactone of above-mentioned moiety Q-24

(25) give the multipolymer of monomer/terminal methyl group propylene acidylate polymethylmethacrylate/end (methyl) acryloyl polyethylene glycol polypropylene glycol of above-mentioned moiety M-2

(26) give the multipolymer of monomer/methacrylic acid/terminal methyl group propylene acidylate polymethylmethacrylate/polyethyleneglycol (methyl) acrylate of above-mentioned moiety M-7

(27) give the multipolymer of monomer/4-vinylpridine/terminal methyl group propylene acidylate polymethylmethacrylate of above-mentioned moiety Q-9

(28) give the multipolymer of monomer/terminal methyl group propylene acidylate poly-n-butyl methacrylate/N-vinyl imidazole of above-mentioned moiety M-10

(29) give the multipolymer of monomer/methacrylic acid/terminal methyl group propylene acidylate Vinalac 5920/terminal methyl group propylene acidylate polymethylmethacrylate of above-mentioned moiety M-1

(30) give the multipolymer of monomer/acrylic/terminal methyl group propylene acidylate polymethylmethacrylate of above-mentioned moiety Q-4

(31) give the multipolymer of monomer/styrene/methacrylic acid of above-mentioned moiety M-13

(32) give the multipolymer of monomer/methacrylic acid/terminal methyl group propylene acidylate polymethylmethacrylate/methacrylic acid dodecane ester of above-mentioned moiety M-1

(33) give the multipolymer of monomer/methacrylic acid/terminal methyl group propylene acidylate polystyrene/methacrylic acid stearyl ester of above-mentioned moiety Q-1

(34) multipolymer of methacrylic acid/terminal methyl group propylene acidylate polymethylmethacrylate/isobornyl methacrylate

(35) multipolymer of cyclohexyl methacrylate/4-vinylpridine

(36) give the multipolymer of monomer/butyl methacrylate of above-mentioned moiety Q-1

(37) give the multipolymer of monomer/styrene/methacrylic acid/methyl methacrylate of above-mentioned moiety M-1

(38) give the multipolymer of monomer/styrene/methacrylic acid butyl ester of above-mentioned moiety M-2

(39) give the multipolymer of monomer/methacrylic tert-butyl acrylate/methacrylic acid of above-mentioned moiety Q-21

(40) give the multipolymer of monomer/vinylbenzene/butyl acrylamide of above-mentioned moiety Q-10

(41) multipolymer of methyl methacrylate/methacrylic acid

In addition, except above-claimed cpd, can also use commercially available macromolecular compound.As commercially available block type polymer, can enumerate " Disperbyk-2000,2001 " of BYK Chemie society manufacturing, " EFKA4330,4340 " that EFKA society makes etc.As commercially available graft type polymer, can enumerate " ソ Le スパ one ス 24000,28000,32000,38500,39000,55000 " of Le one Block リゾ one Le society manufacturing, " Disperbyk-161,171,174 " that BYK Chemie society makes etc.As commercially available terminal-modified type polymer, can enumerate (commercially available polymkeric substance are trade(brand)name) such as " ソ Le スパ one ス 3000,17000,27000 " that Ha one Block リゾ one Le society makes.

Good solvent is had no particular limits,, and can miscible with poor solvent (uniform mixing) get final product as long as it can dissolve above-mentioned water-insoluble compound and/or embedding dispersion agent.The solubleness of water-insoluble coloured material in good solvent is preferably more than the 0.2 quality %, more preferably more than the 0.5 quality %.This solubleness does not have specific upper limit, but considers the water-insoluble coloured material of common employing, is actually below the 50 quality %.In addition, the solubleness of embedding dispersion agent in good solvent is preferably more than the 4.0 quality %, more preferably more than the 10.0 quality %.This solubleness does not have specific upper limit, but considers the macromolecular compound of common employing, is actually below the 70 quality %.

For the compatibility of good solvent and poor solvent, the preferred meltage of good solvent in poor solvent is more than the 30 quality %, more preferably more than the 50 quality %.The meltage of good solvent in poor solvent do not have specific upper limit, in fact can mix with arbitrary proportion.In addition, when the solution of the solution of preparing water-insoluble compound respectively and embedding dispersion agent, preferably, be subordinated to select in the water of above-mentioned good solvent scope dissolving both the time employed solution, and preferably, two solvents are with a kind of solvent.

There is no particular limitation to good solvent, can (for example suitably enumerate organic acid, formic acid, dichloroacetic acid, methylsulfonic acid etc.), organic bases (for example, diazabicyclo hendecene (DBU), TBAH, sodium methylate etc.), aqueous solvent (for example, water, or hydrochloric acid, aqueous sodium hydroxide solution), alcoholic solvent (for example, methyl alcohol, ethanol, n-propyl alcohol etc.), ketones solvent (for example, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.), ether solvent (for example, tetrahydrofuran (THF), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate etc.), the sulfoxide kind solvent (for example, dimethyl sulfoxide (DMSO), the hexamethylene sulfone, tetramethylene sulfone etc.), esters solvent (for example, vinyl acetic monomer, n-butyl acetate, ethyl lactate etc.), amide solvent (for example, N, dinethylformamide, 1-Methyl-2-Pyrrolidone etc.), aromatic hydrocarbon solvent (for example, toluene, dimethylbenzene etc.), fat hydrocarbon solvent (for example, octane etc.), nitrile solvents (for example, acetonitrile etc.), halogen-containing kind solvent (for example, tetracol phenixin, methylene dichloride etc.), ionic liquid (for example, 1-ethyl-3-methyl imidazolium tetrafluoroborate etc.), the dithiocarbonic anhydride solvent, perhaps their mixture etc.

Wherein, more preferably organic acid, organic bases, aqueous solvent, alcoholic solvent, ketones solvent, ether solvent, sulfoxide kind solvent, esters solvent, amide solvent or their mixture are preferably organic acid, organic bases, sulfoxide kind solvent, amide solvent or their mixture especially.

As organic acid, can enumerate as sulfoacid compound, carboxylic acid cpd, anhydride compound etc., but be not limited to these.

As above-mentioned sulfoacid compound, can enumerate alkylsulphonic acid, haloalkyl sulfonic acid, aromatic sulphonic acid etc., alkyl chain and aromatic nucleus can not be substituted, and also can be substituted basic T and replace.As long as can form replacement in sulfoacid compound, substituting group T described herein can be any substituting group.

As substituting group T, can enumerate for example aliphatic group; aryl; heterocyclic radical; acyl group; nitro; amino; acyloxy; acyl amino; aliphatics oxygen base; aryloxy; heterocyclic oxy group; aliphatics oxygen base carbonyl; aryloxycarbonyl; the heterocyclic oxy group carbonyl; formamyl; the aliphatics alkylsulfonyl; aryl sulfonyl; the heterocycle alkylsulfonyl; aliphatics alkylsulfonyl oxygen base; aryl sulfonyl oxygen base; heterocycle alkylsulfonyl oxygen base; sulfamyl; the aliphatics sulfoamido; aryl-sulfonyl amino; the heterocyclic sulfonamide base; amino; aliphatics amino; arylamino; heterocyclic amino group; aliphatics oxygen base carbonylamino; aryloxycarbonyl amino; the heterocyclic oxy group carbonylamino; the aliphatics sulfinyl; aryl sulfonyl kia; the aliphatics sulfenyl; artyl sulfo; hydroxyl; cyano group; sulfo group; carboxyl; aliphatics oxygen base amino; aryloxy amino; formamyl amino; sulfamyl amino; halogen atom; the sulfamyl formamyl; the formamyl sulfamyl; two aliphatics oxygen base phosphinyls; diaryl oxygen base phosphinyl etc.

As can be used for sulfoacid compound of the present invention, specifically can enumerate methylsulfonic acid, ethyl sulfonic acid, propanesulfonic acid, fourth sulfonic acid, trifluoromethanesulfonic acid, five fluorine ethyl sulfonic acids, seven fluorine propanesulfonic acid, nine fluorine fourth sulfonic acid, Phenylsulfonic acid, toluenesulphonic acids, xylene monosulfonic acid, Witco 1298 Soft Acid, naphthene sulfonic acid, chlorobenzenesulfonic acid, aniline sulfonic acid, 1,5-naphthalene disulfonic acid tetrahydrate etc.

As above-mentioned carboxylic acid cpd, can enumerate alkyl carboxylic acid, haloalkyl carboxylic acid, aromatic carboxylic acid etc., alkyl chain and aromatic nucleus can not be substituted, and also can be replaced by above-mentioned substituting group T.As carboxylic acid cpd; specifically can enumerate formic acid; acetate; propionic acid; butyric acid; trifluoroacetic acid; trichoroacetic acid(TCA); tribromoacetic acid; difluoroacetic acid; dichloro acetic acid; dibromoacetic acid; gifblaar poison; Mono Chloro Acetic Acid; bromoacetic acid; the chlorine difluoroacetic acid; cyanoacetic acid; phenylium; diphenyl acetic acid; thioacetic acid; Thiovanic acid; thiohydracrylic acid; the 2-chloropropionic acid; 2; the 2-Tripon; the 3-chloropropionic acid; 2 bromopropionic acid; the 3-bromo-propionic acid; 2; the 3-dibromo-propionic acid; the 2-chloro-butyric acid; the 3-chloro-butyric acid; the 4-chloro-butyric acid; isopropylformic acid; the 2-isobutyl bromide; hexahydrobenzoic acid; nitroacetic acid; phosphine acyl acetic acid; pyruvic acid; oxalic acid; propynoic acid; the trimethylacetic acid ammonium; phenylformic acid; tetrafluorobenzoic aid; pentafluorobenzoic acid; the 2-chloro-benzoic acid; the 2-fluorobenzoic acid; benzoyl formic acid; benzoylbenzoic acid; the 2-dimethylaminobenzoic acid; 2, the 6-resorcylic acid; pyridine carboxylic acid; citric acid; halfcystine; Sulphanilic Acid; side's acid etc.

In the present invention, except carboxylic acid and sulfonic acid, can also use the acid anhydrides that forms above-mentioned acid, specifically can enumerate acid anhydrides such as acetic anhydride, propionic anhydride, trifluoromethanesulfanhydride anhydride, Tricholroacetic Acid acid anhydride.In addition, as organic acid in addition, can enumerate as p isopropylbenzoic acid ester, methyl orthophosphoric acid, phenyl-phosphonic acid, ethylenediamine tetraacetic phosphonic acids, 1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid, methylenediphosphonate (MDP).

Wherein, as organic acid, be preferably alkylsulphonic acid, alkyl carboxylic acid, haloalkyl carboxylic acid, aromatic carboxylic acid, more preferably methylsulfonic acid, trifluoromethanesulfonic acid, ethyl sulfonic acid, trifluoroacetic acid, dichloro acetic acid, Mono Chloro Acetic Acid, formic acid, toluenesulphonic acids, Witco 1298 Soft Acid.

Example as organic bases, can enumerate primary amine class, secondary amine class, tertiary amines, quaternary ammonium, phenyl amines, piperidines, piperazines, amidine class, formamidine, pyridines, guanidine class, morpholine class, nitrogen heterocyclic ring class, metal alkoxide class etc., but be not limited to these.Wherein, be preferably tertiary amines, quaternary ammonium, morpholine class, nitrogen heterocyclic ring class, metal alkoxide class etc.

Specifically can enumerate aniline, the 2-chloroaniline, the 3-fluoroaniline, 2, the 4-difluoroaniline, the 2-N-methyl-p-nitroaniline, N, the N-Diethyl Aniline, 2, the 6-Diethyl Aniline, 2, the 4-dimethoxyaniline, P-pHENYLENE dI AMINE, pyridine, the 2-aminopyridine, pyrimidine, pyridazine, pyrazine, 2, the 2-dipyridyl, tetramethyleneimine, piperidines, imidazoles, pyrazoles, thiazole, benzothiazole oxazole, the diazabicyclo hendecene, diazabicyclo-nonene, the diazabicyclo octane, the 1-dicyanodiamide, N, N '-diphenylguanidine, hexahydroaniline, butylamine, cyclopropylamine, TERTIARY BUTYL AMINE, benzyl amine, Diisopropylamine, Trimethylamine 99, triethylamine, Tributylamine, tetrahydroquinoline, the phenyl trimethylammonium hydroxide, benzyltrimethylammonium hydroxide, Tetramethylammonium hydroxide, TBAH, morpholine, thiomorpholine, N-methylmorpholine, hexamethylphosphoramide, 1-methyl-4-piperidone, N-(2-amino-ethyl) piperazine, quadrol, diethylenetriamine, two-(3-aminopropyl) ether, sodium methylate, sodium ethylate, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium tert.-butoxide etc.

Wherein, be preferably aniline, 2, the 4-difluoroaniline, pyridine, the diazabicyclo hendecene, diazabicyclo-nonene, the diazabicyclo octane, triethylamine, tetrahydroquinoline, the phenyl trimethylammonium hydroxide, benzyltrimethylammonium hydroxide, Tetramethylammonium hydroxide, TBAH, N-methylmorpholine, N-(2-amino-ethyl) piperazine, sodium methylate, sodium ethylate, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium tert.-butoxide, 2,4 difluorobenzene amine more preferably, the diazabicyclo hendecene, diazabicyclo-nonene, tetrahydroquinoline, the phenyl trimethylammonium hydroxide, Tetramethylammonium hydroxide, TBAH, N-methylmorpholine, sodium methylate, potassium tert.-butoxide.

As the sulfoxide kind solvent, more specifically can enumerate as dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexamethylene sulfone, tetramethylene sulfone etc.

As amide solvent, more specifically can enumerate as N, dinethylformamide, 1-Methyl-2-Pyrrolidone, 2-Pyrrolidone, 1,3-dimethyl-2-imidazolidone, 2-Pyrrolidone, ε-Ji Neixianan, methane amide, N-methylformamide, ethanamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl propanamide, HMPA etc.

Preparation condition to water-insoluble compound solution has no particular limits, and can select from normal pressure to scope subcritical, super critical condition.Temperature under the normal pressure is preferably-10～150 ℃, more preferably-5～130 ℃, is preferably 0～100 ℃ especially.

When in good solvent, dissolving water-insoluble compound equably, generally preferably, adopt intramolecularly have can be at dissociated group under the alkaline condition pigment the time, use alkaline condition, and intramolecularly uses acidic conditions when not existing in dissociated group under the alkaline condition and intramolecularly and having a plurality of nitrogen-atoms that is easy to the addition proton.For example, quinoline a word used for translation ketone pigment, diketopyrrolopyrroles pigment, disazo condensation thing class pigment dissolve under alkaline condition, and phthalocyanine pigment dissolves under acidic conditions.

Operable alkali when dissolving under alkaline condition except above-mentioned organic bases, can also use mineral alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, hydrated barta.Usage quantity to alkali has no particular limits, but under the situation of using mineral alkali, with respect to water-insoluble compound, is preferably 1.0～30 molar equivalents, and more preferably 1.0～25 molar equivalents are preferably 1.0～20 molar equivalents especially.Under the situation of using organic bases, with respect to water-insoluble compound, be preferably 1.0～100 molar equivalents, more preferably 5.0～100 molar equivalents are preferably 20～100 molar equivalents especially.

Operable acid when dissolving under acidic conditions except above-mentioned organic acid, can also be used mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid.Usage quantity to acid has no particular limits, but compares often excessive use with alkali, is preferably 3～500 molar equivalents with respect to water-insoluble compound, and more preferably 10～500 molar equivalents are preferably 30～200 molar equivalents especially.

Mineral alkali or mineral acid being mixed the back with organic solvent, when using, dissolving fully, can in organic solvent, add some water or lower alcohol etc. to alkali or sour solvent with high-dissolvability in order to make alkali or acid as the good solvent of water-insoluble compound.The amount of water or lower alcohol with respect to the total amount of water-insoluble compound solution, is preferably below the 50 quality %, more preferably below the 30 quality %.Specifically, can make water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols etc.

The viscosity of water-insoluble compound solution is preferably 0.5～100.0mPas, more preferably 1.0～50.0mPas.

There is no particular limitation to water-insoluble compound solution, gets final product so long as be dissolved with the solution of water-insoluble compound and (in case of necessity) macromolecular compound in good solvent, also can contain other compositions.

Other compositions are had no particular limits, can suitably enumerate the organic compound with acidic-group, organic compound etc. with basic group.When above-mentioned water-insoluble compound solution being mixed with above-mentioned poor solvent pigment is separated out, these compositions are adsorbed in rapidly on the pigment of separating out, and have the effect that surface of pigments is processed into acidity or alkalescence.The solvability of above-mentioned other compositions in above-mentioned poor solvent had no particular limits, but preferably, concerning above-mentioned other compositions, above-mentioned poor solvent also becomes the compound of poor solvent.

As can be used for the acidic-group with organic compound of acidic-group of the present invention, can enumerate hydroxy-acid group, sulfonic acid group,-sulfinic acid group, sulfenic acid group, phosphonyl group, hydroxyl, thioether group etc., but be not limited to these.In addition, intramolecularly can contain a kind of functional group separately, also can contain two or more identical or different functional groups.In addition, the organic compound with these acidic-groups can be used alone, also can be also with two or more.Wherein, be preferably have hydroxy-acid group, the compound of sulfonic acid group, phosphate group.

As organic compound with hydroxy-acid group; can enumerate as docosoic; the 13-Decosahedaenoic acid; oleic acid; linolic acid; stearic acid; Unimac 5680; the 2-hexyldecanoic acid; palmitinic acid; tetradecanoic acid; lauric acid; capric acid; sad; 3; 5; the 5-tri-methyl hexanoic acid; 1; 12-dodecyl dicarboxylic acid; sebacic acid; the 1-adamantanecarboxylic acid; the 1-naphthoic acid; the 2-naphthoic acid; Pyromellitic Acid; to the benzoyl-amido phenylformic acid; terephthalic acid; m-phthalic acid; phthalic acid; phenylformic acid; trimellitic acid; 1-hydroxyl-2-naphthoic acid; β-oxygen base naphthoic acid; to the octyloxy phenylformic acid; triphenylacetic acid; amygdalic acid; Perfluorocaprylic Acid; p-nitrobenzoic acid; the o-benzoyl yl benzoic acid; the 4-sulfamoylbenzoic acid; o-benzoyl base benzaminic acid; 2; dipicolimic acid 2; the tetrahydrofuran (THF) tetracarboxylic acid; quinaldinic acid; 4; the 4-biphenyl dicarboxylic acid; 4-xenol-3-carboxylic acid; the 2-naphthylacetic acid; 2; the 6-naphthalene dicarboxylic acids; 6-hydroxyl-2-naphthoic acid; 1; 4; 5; the 8-naphthalene tetracarboxylic acid; 1; the 8-naphthalic acid; 3; 4; 9; 10-perylene tetracarboxylic acid; indole-3-butyric acid; 3; 7-dicarboxylic acid phenyl ether tetrachlorophthalic acid; phthalandione; folic acid; benzilic acid; naphthenic acid; diphenyl acetic acid; 2,4 dichloro benzene formic acid etc.

As organic compound, can enumerate as beta-naphthalenesulfonic-acid, Witco 1298 Soft Acid, hexadecyl hydrosulfate, C acid, J acid, γ acid, diaminobenzil disulfonic acid, Phenylsulfonic acid, benzene disulfonic acid, naphthene sulfonic acid, naphthalene disulfonic acid, chlorobenzenesulfonic acid, naphthalidine-4-sulfonic acid (naphthionic acid), TOBIAS ACID 97MIN.﹠ 98MIN., Schollkopf acid, J acid, koch's acid, m-sulfanilic acid, toluenesulphonic acids, hot sulfonic acid etc. with sulfonic acid group.

As compound, can enumerate to toluenesulfinic acid, benzene sulfinic acid, to carboxyl benzene sulfinic acid, hot-sulfinic acid, ethyl sulfinic acid, 4-chloro-3-oil of mirbane-sulfinic acid, 4-kharophen benzene sulfinic acid, thiophene-2--sulfinic acid, methyl-sulfinic acid, isobutyl-sulfinic acid, hexadecyl-sulfinic acid, hydroxyl methyl-sulfinic acid etc. with-sulfinic acid group.

As the sulfenic acid compound, can enumerate the benzene sulfenic acid, to toluene sulfenic acid etc.

As phosphinic acid compounds, can enumerate stearyl phosphonic acids, lauryl phosphonic acids etc.

In the present invention, have the addition of the organic compound of acidic-group, be preferably the scope of 0.01～30 quality % with respect to water-insoluble compound, the scope of 0.05～20 quality % more preferably is preferably the scope of 0.05～15 quality % especially.

As organic compound with basic group, alkylamine, arylamines, aralkylamine, pyrazole derivatives, imdazole derivatives, triazole derivative, terazole derivatives, oxazole derivative, thiazole derivative, pyridine derivate, pyridazine derivatives, pyrimidine derivatives, pyrazines derivatives, pyrrolotriazine derivatives etc. can be enumerated, preferably alkylamine, arylamines, imdazole derivatives can be enumerated.

The carbon number of the above-mentioned organic compound with basic group is preferably more than 6, more preferably more than 8, more preferably more than 10.

In above-mentioned organic compound with basic group, as alkylamine, can enumerate as butylamine, amylamine, hexylamine, heptyl amice, octylame, 2 ethyl hexylamine, nonyl amine, decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine, pentadecyl amine, cetylamine, stearylamine, isobutylamine, TERTIARY BUTYL AMINE, the 1-methylbutylamine, the 1-ethyl butyl amine, uncle's amylamine, the amino heptane of 3-, tert-Octylamine, 1, the 4-diaminobutane, 1, the 6-hexanediamine, 1,8-diamino octane, 1, the 10-diamino decane, 1,12-diamino dodecane, dibutylamine, dihexylamine, Di-Octyl amine, two (2-ethylhexyl) amine, didecylamine, N-methyl stearylamine, triethylamine, tripropyl amine, N, the N-dimethyl butylamine, N-methyl dibutylamine, Tributylamine, triamylamine, N, the N-dimethylhexylamine, N, N-dimethyl octylame, the N-MDOA methyldioctylamine, trioctylamine, tri-iso-octylamine, N, N-dimethyl amino dodecane, tridodecylamine, N-methyl-N-octadecyl-1-stearylamine, N, N-dibutyl quadrol, N, N, N, ' N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetramethyl--1, the 6-hexanediamine, N-methylcyclohexylamine, N, N, N ', N ', N '-pentamethyl-diethylenetriamine, hexahydroaniline, cycloheptylamine, hexahydroaniline, the ring amino dodecane, 1-amantadine etc., preferably can enumerate octylame, 2 ethyl hexylamine, nonyl amine, decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine, stearylamine, tert-Octylamine, 1,8-diamino octane, 1, the 10-diamino decane, 1,12-diamino dodecane, Di-Octyl amine, two (2-ethylhexyl) amine, didecylamine, N-methyl stearylamine, N, N-dimethyl octylame, the N-MDOA methyldioctylamine, trioctylamine, tri-iso-octylamine, N, N-dimethyl amino dodecane, tridodecylamine, N-methyl-N-octadecyl-1-stearylamine, N, N-dibutyl quadrol, N, N, N ', N '-Tetramethyl Ethylene Diamine, N, N, N ', N '-tetramethyl--1, the 6-hexanediamine, N-methylcyclohexylamine, N, N, N ', N ' N '-pentamethyl-diethylenetriamine, the ring amino dodecane, 1-amantadine etc., further preferably can enumerate decyl amine, undecylamine, amino dodecane, tridecyl amine, tetradecy lamine, didecylamine, N-methyl stearylamine, N, N-dimethyl amino dodecane, tridodecylamine etc.In addition, also can suitably use PAH, polyvinylamine etc. to have the organic high molecular compound of basic group.

As arylamine, can enumerate as N, the N-dibutyl aniline, the 4-butylaniline, the 4-amylamine, the 4-hexylamine, 4-heptyl aniline, 4-octyl group aniline, 4-decyl aniline, the 4-dodecyl polyaniline, 4-tetradecyl aniline, 4-hexadecyl aniline, the 4-butoxy aniline, 4-pentyloxy aniline, 4-hexyloxy aniline, 4-hexyloxy aniline etc., preferably can enumerate 4-octyl group aniline, 4-decyl aniline, the 4-dodecyl polyaniline, 4-tetradecyl aniline, 4-hexadecyl aniline, 4-pentyloxy aniline, 4-hexyloxy aniline, 4-hexyloxy aniline etc. further preferably can be enumerated 4-decyl aniline, the 4-dodecyl polyaniline, 4-tetradecyl aniline, 4-hexadecyl aniline, 4-pentyloxy aniline, 4-hexyloxy aniline, 4-hexyloxy aniline etc.

As imdazole derivatives, can enumerate as 1-(10-hydroxyl decyl) imidazoles, 1-butyl imidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles etc.

Above-mentioned organic compound with basic group is preferably the scope of 0.01～30 quality % with respect to water-insoluble compound, and the scope of 0.05～20 quality % more preferably is preferably the scope of 0.05～15 quality % especially.

In addition, the also preferred organic compound that constitutes by basic group and heterocyclic group that adds.

As this organic compound, can enumerate aminopyridine as 2-, the 3-aminopyridine, 1-(2-aminophenyl) pyrroles, the 5-amino-pyrazol, the 3-amino-5-methylpyrazole, 5-amino-1-ethyl pyrazoles, the 3-aminotriazole, thiazolamine, the 5-amino indole, the 2-aminobenzothiazole, the amino benzoglyoxaline of 5-, N, the amino benzoglyoxaline of N-dimethyl-5-, phthalic imidine, the amino benzimidazolone of 5-, N, the amino benzimidazolone of N-dimethyl-5-, the 5-amino uracil, the 6-amino uracil, uridylic, thymus pyrimidine, VITAMIN B4, guanine, trimeric cyanamide, amino pyrazine, the 8-quinolylamine, the 3-quinolylamine, 9-aminoacridine, ASTRA indigo plant-6GLL (alkaline phthalocyanine derivates), the 2-aminoanthraquinone, the 3-aminoanthraquinone, dihydroketoacridine, the N-dihydroketoacridine, quinoline a word used for translation ketone, NILE is red, the purple naphthalimide of methylene radical etc.Preferably can enumerate the 2-aminobenzothiazole, the amino benzoglyoxaline of 5-, N, the amino benzoglyoxaline of N-dimethyl-5-, the amino benzimidazolone of 5-, N, the amino benzimidazolone of N-dimethyl-5-, the 5-amino uracil, the 6-amino uracil, uridylic, thymus pyrimidine, VITAMIN B4, guanine, trimeric cyanamide, the 8-quinolylamine, the 3-quinolylamine, 9-aminoacridine, ASTRA indigo plant-6GLL (alkaline phthalocyanine derivates), the 2-aminoanthraquinone, the 3-aminoanthraquinone, dihydroketoacridine, the N-dihydroketoacridine, quinoline a word used for translation ketone, NILE is red, the purple naphthalimide of methylene radical, more preferably can enumerate 9-aminoacridine, ASTRA indigo plant-6GLL (alkaline phthalocyanine derivates), the 2-aminoanthraquinone, the 3-aminoanthraquinone, dihydroketoacridine, the N-dihydroketoacridine, the amino benzoglyoxaline of 5-, N, the amino benzoglyoxaline of N-dimethyl-5-, the amino benzimidazolone of 5-, N, the amino benzimidazolone of N-dimethyl-5-, the 5-amino uracil, the 6-amino uracil, NILE is red, the purple naphthalimide of methylene radical.

The addition of the above-mentioned organic compound that is made of basic group and heterocyclic group is preferably the scope of 0.01～30 quality % with respect to water-insoluble compound, and the scope of 0.05～20 quality % more preferably is preferably the scope of 0.05～15 quality % especially.

Except the above-mentioned compound of enumerating, can also enumerate the pigment derivative of being put down in writing in TOHKEMY 2007-9096 communique and the Japanese kokai publication hei 7-331182 communique etc.Herein, so-called pigment derivative is meant by as the pigment dyestuff deutero-of parent material, by this precursor structure being carried out pigment derivative type compound that chemically modified prepares or the pigment derivative type compound that obtains by the reaction of the pigment precursors generation pigmenting after the chemically modified.As the commercially available prod, can enumerate " EFKA6745 (phthalocyanine derivates) " of for example EFKA society manufacturing, (being trade(brand)name) such as " ソ Le スパ one ス 5000 (phthalocyanine derivates) " that Le one Block リゾ one Le society makes.Using under the situation of pigment derivative, its consumption is preferably the scope of 0.5～30 quality % for pigment, and the scope of 3～20 quality % more preferably is preferably the scope of 5～15 quality % especially.

There is no particular limitation to poor solvent, but the solubleness of water-insoluble compound in poor solvent is preferably below the 0.02 quality %, more preferably below the 0.01 quality %.The solubleness of water-insoluble compound in poor solvent does not have specific lower limit, but considers normally used water-insoluble compound, is actually more than the 0.0001 quality %.In addition, the solubleness of above-mentioned automatic decentralized macromolecular compound in poor solvent is below the 2.0 quality % (insoluble), is preferably below the 1.0 quality %.The solubleness of water-insoluble compound in poor solvent does not have specific lower limit, but considers normally used macromolecular compound, is actually more than the 0.001 quality %.

There is no particular limitation to poor solvent, can (for example suitably enumerate aqueous solvent, water, or hydrochloric acid, aqueous sodium hydroxide solution), alcoholic solvent (for example, methyl alcohol, ethanol, n-propyl alcohol etc.), ketones solvent (for example, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.), ether solvent (for example, tetrahydrofuran (THF), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate etc.), the sulfoxide kind solvent (for example, dimethyl sulfoxide (DMSO), the hexamethylene sulfone, tetramethylene sulfone etc.), esters solvent (for example, vinyl acetic monomer, n-butyl acetate, ethyl lactate etc.), amide solvent (for example, N, dinethylformamide, 1-Methyl-2-Pyrrolidone etc.), aromatic hydrocarbon solvent (for example, toluene, dimethylbenzene etc.), fat hydrocarbon solvent (for example, octane etc.), nitrile solvents (for example, acetonitrile etc.), halogen-containing kind solvent (for example, tetracol phenixin, methylene dichloride etc.), ionic liquid (for example, 1-ethyl-3-methyl imidazolium tetrafluoroborate etc.), the dithiocarbonic anhydride solvent, perhaps their mixture etc.

Wherein, more preferably aqueous solvent, alcoholic solvent, ketones solvent, sulfoxide kind solvent, esters solvent, amide solvent, nitrile solvents or their mixture are preferably aqueous medium, alcoholic solvent or their mixture especially.

Aqueous medium is meant the lysate of independent water or water and water-soluble organic solvent or inorganic salt, can enumerate Ru Shui, hydrochloric acid, aqueous sodium hydroxide solution, potassium hydroxide aqueous solution etc.

As alcoholic solvent, can enumerate for example methyl alcohol, ethanol, Virahol, n-propyl alcohol, 1-methoxyl group-2-propyl alcohol etc.

As the object lesson of good solvent and though the solvent of enumerating has identical with the solvent of enumerating as poor solvent, but not being used in combination identical solvent also is fine as good solvent and poor solvent, as long as fastening with the pass of employed various water-insoluble compounds and macromolecular compound, these water-insoluble compounds and the macromolecular compound solubleness in good solvent gets final product greater than its solubleness in poor solvent fully, for water-insoluble compound, for example, the difference of its solubleness is preferably more than the 0.2 quality %, more preferably more than the 0.5 quality %.Do not have specific qualification for water-insoluble compound in the upper limit of the difference of good solvent and the solubleness in poor solvent, but consider normally used water-insoluble compound, be actually below the 50 quality %.For macromolecular compound, for example, the difference of its solubleness is preferably more than the 2.0 quality %, more preferably more than the 5.0 quality %.Do not have specific qualification for macromolecular compound in the upper limit of the difference of good solvent and the solubleness in poor solvent, but consider normally used macromolecular compound, be actually below the 70 quality %.

There is no particular limitation for the state of poor solvent, can select from normal pressure to scope subcritical, super critical condition.Temperature during normal pressure is preferably-30 ℃～100 ℃, more preferably-10 ℃～60 ℃, be preferably 0 ℃～30 ℃ especially.The viscosity of water-insoluble compound solution is preferably 0.5～100.0mPas, more preferably 1.0～50.0mPas.

When water-insoluble compound solution is mixed with poor solvent, can add any one among both and mix, but preferably water-insoluble compound solution is injected in the poor solvent and mixes, this moment, preferably poor solvent was in the state that is stirred.Stirring velocity is preferably 100～10000rpm, and more preferably 150～8000rpm is preferably 200～6000rpm especially.Can use equipment such as also can not using pump during interpolation.In addition, can in liquid, submergence add, also can outside liquid, add, but more preferably submergence interpolation in liquid.Also preferably use pump in liquid, to supply with continuously by supply-pipe.The internal diameter of supply-pipe is preferably 0.1～200mm, more preferably 0.2～100mm.The speed of supplying with to liquid from supply-pipe is preferably 1～10000ml/min, more preferably 5～5000ml/min.

When water-insoluble compound solution is mixed with poor solvent,, can control the particle diameter of the pigment nano particle of separating out generation by regulating Reynolds number.Herein, Reynolds number is the non-dimensional number of expression fluidic flow state, and it is represented by following formula.

Re=ρ UL/ μ ... mathematical expression (1)

In the mathematical expression (1), Re represents Reynolds number, and ρ represents the density [kg/m of water-insoluble compound solution ³], speed of relative movement [m/s] when U represents that water-insoluble compound solution and poor solvent converge, L represents that water-insoluble compound solution and poor solvent converge the fluid passage of part or the equivalent diameter [m] of supplying opening, and μ represents the coefficient of viscosity [Pas] of water-insoluble compound solution.

When equivalent diameter L is meant the aperture of the pipeline of arbitrary section shape or fluid passage is assumed to the pipe of equivalence, the diameter of this equivalence pipe.If the cross-sectional area of pipeline is represented with A the wetted perimeter (girth) of pipeline or the periphery of fluid channel are expressed as P, and then equivalent diameter L can be represented by following mathematical expression (2).

L=4A/p ... mathematical expression (2)

Preferably, by pipeline water-insoluble compound solution is injected into and forms particle in the poor solvent, when using pipe as pipeline, equivalent diameter is identical with the diameter of pipe.For example, can regulate equivalent diameter by the aperture that changes liquid supply port.There is no particular limitation to the value of equivalent diameter L, and for example its value with the preferred internal diameter of above-mentioned supplying opening is identical.

Speed of relative movement U when water-insoluble compound solution and poor solvent meet is defined as with respect to both meet speed of relative movement on the vertical direction of face of part.That is, for example in the immobilized poor solvent, inject water-insoluble compound solution and when mixing, the speed of injecting from supplying opening equals speed of relative movement U.There is no particular limitation to the value of speed of relative movement U, for example is preferably 0.5～100m/s, more preferably 1.0～50m/s.

The density p of water-insoluble compound solution is the value by the kind decision of selected material, but in fact (for example) is 0.8～2.0kg/m ³In addition, the coefficient of viscosity μ of water-insoluble compound solution also is the value by decision such as employed material or envrionment temperature, but its preferable range is identical with the scope of the preferred viscosities of above-mentioned water-insoluble compound solution.

The more little easy more formation laminar flow of the value of Reynolds number (Re), the big more easy more formation turbulent flow of its value.For example, by Reynolds number is adjusted to more than 60, the particle diameter of may command pigment nano particle, Reynolds number is preferably more than 100, more preferably more than 150.Reynolds number does not have specific upper limit, but preferably, for example by its adjusting being controlled at the scope below 100000, may command obtains excellent pigment nano particle.Perhaps, can take to improve the condition of Reynolds number, the median size that makes the nano particle that is obtained is below the 60nm.At this moment, in above-mentioned scope, general by improving Reynolds number, may command obtains the littler pigment nano particle of particle diameter.

The ratio of mixture of water-insoluble compound solution and poor solvent is preferably 1/50～2/3 by volume, and more preferably 1/40～1/2, be preferably 1/20～3/8 especially.Granule density when separating out organic fine particles in the liquid has no particular limits, but with respect to the 1000ml solvent, organic granular is preferably the scope of 10～40000mg, and the scope of 20～30000mg more preferably is preferably the scope of 50～25000mg especially.In addition, there is no particular limitation for the preparative-scale during to the generation particulate, and preferably, the combined amount of poor solvent is the preparative-scale of 10～2000L, more preferably the preparative-scale of 50～1000L.

When separating out the water-insoluble compound particulate and preparing dispersion liquid, can be at least one of water-insoluble compound solution and poor solvent, at least contain the compound that makes poor solvent become good solvent (its solubleness in poor solvent is more than the 4.0 quality %) (below, be called the particle size adjustment agent).

As the agent of polymer particle size adjustment, can enumerate as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyoxyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, the part formalizing thing of polyvinyl alcohol, the part butyralization thing of polyvinyl alcohol, vinyl pyrrolidone-vinyl acetate copolymer, the polyethylene oxide/propylene oxide segmented copolymer, polyacrylic acid, polyacrylic acid sodium salt, polyvinyl sulfuric acid salt, poly-(4-vinylpridine) salt, PAH, the PAH hydrochloride, the polyvinylamine hydrochloride, allylamine hydrochloride/diallyl amine hydrochlorate multipolymer, diallyl amine monomer/SO ₂Multipolymer, diallyl amine hydrochlorate/maleic acid, PDMA hydrochloride, diallyl dimethyl ammoniumchloride, diallyldimethylammonium chloride/acrylamide copolymer, naphthalenesulfonate condensation compound, derivatived cellulose, starch derivative etc.In addition, can also use natural polymer subclasses such as alginate, gelatin, albumin, casein, Sudan Gum-arabic, tragacanth gum, sulfonated lignin.Wherein, be preferably polyvinylpyrrolidone, polyacrylic acid, PAH, PAH hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride/diallyl amine hydrochlorate multipolymer, diallyl amine monomer/SO ₂Multipolymer etc.These particle size adjustment agent can be used alone, and perhaps also can be used in combination.

The matter average molecular weight is preferably 1,000～500, and 000, more preferably 10,000～500,000, be preferably 10,000～100,000 especially.

As anionic particle size adjustment agent (aniorfic surfactant), can enumerate N-acyl-N-alkyltaurate, soap, alkyl sulfuric ester salt, alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl group sulfonic group succinate, alkyl phosphate salt, naphthalene sulfonic acidformaldehyde condensation product, polyxyethylated sulfuric acid etc.Wherein, be preferably the N-acyl-N-alkyltaurate.As the N-acyl-N-alkyltaurate, be preferably the compound of in Japanese kokai publication hei 3-273067 specification sheets, being put down in writing.These anionic particle size adjustment agent may be used singly or in combination of two or more.

As cationic particle size adjustment agent (cationic surfactant), can enumerate quaternary ammonium salt, alkoxylate polyamines, fatty amine polyglycol ether, fatty amine, by fatty amine and fatty alcohol deutero-diamines and polyamines, by the salt of the cationic material of the tetrahydroglyoxaline of fatty acid derived.These cationic particle size adjustment agent can be used separately, perhaps are used in combination.

The agent of amphoteric ion type particle size adjustment is that intramolecularly has the cation group particle size adjustment agent partly that contains in the anionic group part that contains in the above-mentioned anionic particle size adjustment agent molecule and the cationic particle size adjustment agent molecule simultaneously.

As non-ionic type particle size adjustment agent (nonionic surface active agent), can enumerate Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty(acid)ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, glycerol fatty acid ester etc.Wherein, be preferably polyoxyethylene alkylaryl ether.These non-ionic type particle size adjustment agent can be used separately, also can be used in combination.

In order further to improve the particle diameter control of water-insoluble compound particulate, the content of particle size adjustment agent is the scope of 0.1～100 quality % with respect to pigment optimization, more preferably the scope of 0.1～50 quality %, the more preferably scope of 0.1～20 quality %.In addition, the particle size adjustment agent can be used separately, also can multiplely be used in combination.

When under the state that contains good solvent, poor solvent, carrying out the crystallization processing, can use the 3rd solvent to remove good solvent, poor solvent.There is no particular limitation to the 3rd solvent types, but be preferably organic solvent, for example be preferably ester cpds solvent, alkylol cpd solvent, aromatic compound solvent, fatty compounds solvent, more preferably ester cpds solvent, aromatic compound solvent or fatty compounds solvent are preferably the ester cpds solvent especially.In addition, the 3rd solvent can be the neat solvent that is made of above-mentioned solvent, also can be the mixed solvent that is made of multiple solvent.

In addition, in the present invention, with not only comprise above-mentioned the 3rd solvent also comprise the 4th solvent described later, as the medium of dispersive composition, with above-mentioned good solvent and above-mentioned poor solvent in any one all different solvents be generically and collectively referred to as " the 3rd solvent ".

As the ester cpds solvent, can enumerate as acetic acid 2-(1-methoxyl group) propyl ester, vinyl acetic monomer, ethyl lactate etc.As the alkylol cpd solvent, can enumerate as methyl alcohol, ethanol, propyl carbinol, isopropylcarbinol etc.As aromatic compound solvent, can enumerate as benzene,toluene,xylene etc.As the fatty compounds solvent, can enumerate as normal hexane, hexanaphthene etc.

Wherein, be preferably ethyl lactate, vinyl acetic monomer, ethanol, acetic acid 2-(1-methoxyl group) propyl ester, more preferably ethyl lactate, acetic acid 2-(1-methoxyl group) propyl ester.They can use a kind separately, also can two or more and usefulness.In addition, the 3rd solvent and good solvent or poor solvent are materials inequality.

There is no particular limitation opportunity to the interpolation of the 3rd solvent, so long as after separating out the water-insoluble compound particulate, get final product, can in separating out fine-grained mixed solution, add, add again after also a part of solvent composition of mixed solution can being removed, perhaps can remove interpolation again behind whole solvent composition (concentrating) of mixed solution in advance.

That is to say, use the 3rd solvent to use solvent, available the 3rd solvent to replace by separating out the solvent composition that good solvent in the fine-grained dispersion liquid and poor solvent constitute as displacement.

Perhaps, can after good solvent and poor solvent being removed fully (concentrating) and being taken out the granules of pigments powder, add the 3rd solvent again.

In addition, when preparation pigment dispensing composition described later, can after removing the operation (once removing) of solvent composition for the first time, add the 3rd solvent to carry out solvent exchange, and remove solvent composition, thereby form powder by the operation (secondary is removed) of removing for the second time solvent composition.And, add pigment dispersing agent and/or solvent afterwards, thereby can form desirable pigment dispensing composition.

Perhaps, can after good solvent and poor solvent be removed fully (concentrating) and being taken out the granules of pigments powder, add the 3rd solvent and/or pigment dispersing agent, thereby can form desirable pigment dispensing composition.

There is no particular limitation to the addition of the 3rd solvent, but with respect to the particulate of the water-insoluble coloured material of 100 mass parts, be preferably 100～300000 mass parts, more preferably 500～10000 mass parts.

There is no particular limitation to the operation of removing solvent composition the mixed solution after the water-insoluble compound particulate is separated out, thereby but can enumerate as the filter method that utilizes strainer etc., utilize centrifugation to make the spissated method of water-insoluble compound particulate sedimentation etc.

Utilize the filtering device of strainer, can use device as decompression or pressure filtration and so on.As preferred strainer, can enumerate filter paper, nanofilter, ultra-fine filter etc.

Separating centrifuge can use any device, as long as can make the sedimentation of water-insoluble compound particulate.For example, except multipurpose plant, the continuous centrifuge etc. that can also enumerate the whizzer of the skin function of taking (suction supernatant layer in rotation, and be discharged into system outer function with it) and discharge solid substance continuously.As the condition of centrifugation, centrifugal force (be expressed as need times over the value of the centrifugal acceleration of universal gravity constant) is preferably 50～10000, and more preferably 100～8000, be preferably 150～6000 especially.Temperature during centrifugation depends on the solvent species of dispersion liquid, but is preferably-10～80 ℃, more preferably-5～70 ℃, is preferably 0～60 ℃ especially.

In addition, as the operation of removing solvent composition, can use by vacuum lyophilization to make solvent distillation carry out spissated method, make solvent seasoning carry out method etc. after spissated method or their combinations by heating or decompression.

The particulate of water-insoluble compound can be scattered in the state in the carrier (vehicle) and uses with (for example).Above-mentioned carrier is meant, for coating, make water-insoluble compound dispersive medium part when being in liquid state, comprise that aqueous and above-mentioned water-insoluble compound combine and make the fixed part (binding agent) and it is carried out the composition (organic solvent) of dissolved dilution of filming.In addition, in the present invention, the water-insoluble compound dispersion agent that is adopted when macromolecular compound that is adopted during with the formation particulate and/or redispersion is generically and collectively referred to as binding agent.

Can come suitably to determine particulate loading in the microparticulate composition behind the redispersion according to purpose, but with respect to the total amount of dispersive composition, particulate is preferably 2～30 quality %, more preferably 4～20 quality % are preferably 5～15 quality % especially.Under the situation in being scattered in aforesaid carrier, the amount of binding agent and dissolved dilution composition can suitably be selected according to kind of water-insoluble compound etc., total amount with respect to dispersive composition, binding agent is preferably 1～30 quality %, more preferably 3～20 quality % are preferably 5～15 quality % especially.The dissolved dilution composition is preferably 5～80 quality %, more preferably 10～70 quality %.

When the particulate redispersion of water-insoluble compound of the present invention is in the 3rd solvent, preferably, even do not add other dispersion agent etc., also have such character: thus the state of aggregation of water-insoluble compound particulate in the 3rd solvent, automatically untied and be scattered in the medium, and the phenomenon that will have this character is called " can disperse automatically " or " having automatic dispersiveness ".Yet, in the present invention,, can when the redispersion of particulate, add pigment dispersing agent etc. in order further to improve redispersibility.

As the method for this particulate that is in state of aggregation being carried out redispersion, for example can adopt ultrasonic scattering method and apply the method for physical energy.Employed ultrasonic irradiation device preferably has can apply the above hyperacoustic function of 10kHz, can enumerate for example ultrasonic homogenizer, Ultrasonic Cleaners etc.If the liquid temperature rises during ultrasonic irradiation, then can cause the thermal thermocoagulation of nano particle, therefore preferred liquid temperature is 1～100 ℃, more preferably 5～60 ℃.As temperature-controlled process, can be by control dispersion liquid temperature, the temperature regulation layer of control dispersion liquid temperature is carried out temperature control wait and implement.

Thereby be not particularly limited for employed dispersion machine when applying physical energy and make the pigment nanoparticulate dispersed, can enumerate for example dispersion machines such as kneader, roll crusher, second reduction machine, high-speed grinder, dissolving machine, homo-mixer, sand mill.In addition, as suitable method, can also enumerate the high pressure dispersion method, use microgranular pearl to carry out the dispersive method.

In order further to improve dispersing of pigments, only otherwise damage effect of the present invention, also can in pigment dispensing composition, add dispersion agents such as known in the past pigment dispersing agent or tensio-active agent etc.

As pigment dispersing agent, (for example can enumerate macromolecule dispersing agent, straight chain polymer, block type polymer, graft type polymer, terminal-modified type polymer etc.), tensio-active agent (for example, polyxyethylated phosphoric acid ester, polyoxyethylene alkyl amine, alkanolamine etc.), pigment derivative etc.Thereby dispersant adsorption has the agglutinative effect again that prevents on the surface of pigment.Therefore, as preferred construction, can enumerate the block type polymer, graft type polymer, the terminal-modified type polymer that surface of pigments are had anchor site.On the other hand, by improving surface of pigments, pigment derivative has the effect of the absorption that promotes macromolecule dispersing agent.

As the example of macromolecular compound,, can enumerate " Disperbyk-2000,2001 " of BYK Chemie society manufacturing, " EFKA4330,4340 " that EFKA society makes etc. wherein as block type polymer.As the high molecular example of graft type, can enumerate " ソ Le スパ one ス 24000,28000,32000,38500,39000,55000 " of Le one Block リゾ one Le society manufacturing, " Disperbyk-161,171,174 " that BYK Chemie society makes etc.As the high molecular example of terminal-modified type, can enumerate (being trade(brand)name) such as " ソ Le スパ one ス 3000,17000,27000 " that Ha one Block リゾ one Le society makes.

In the present invention, pigment derivative (below, be also referred to as " pigment derivative type dispersion agent ") be defined as by as the pigment dyestuff deutero-of parent material, by this precursor structure being carried out the pigment derivative type dispersion agent that chemically modified prepares, or the pigment derivative type dispersion agent that forms through the pigmenting reaction by the pigment precursors after the chemically modified.Usually, be also referred to as synergy type dispersion agent.

There is no particular limitation to pigment derivative, can suitably use the pigment derivative of being put down in writing in for example TOHKEMY 2007-9096 communique, the Japanese kokai publication hei 7-331182 communique etc. with acidic-group, the pigment derivative with basic group, introduce pigment derivative that functional groups such as phthalimide methyl are arranged etc.

As the commercially available prod, can enumerate " EFKA6745 (phthalocyanine derivates), 6750 (azo pigment derivative) ", (being trade(brand)name) such as " ソ Le スパ one ス 5000 (phthalocyanine derivates), 22000 (azo pigment derivatives) " that Japanese Le one Block リゾ one Le society makes that EFKA society makes.

As linear macromolecule, can enumerate alkali soluble resins described later, preferably with above-mentioned pigment derivative and usefulness.

Pigment dispersing agent can only use a kind of, also can two or more and usefulness.

Photocurable composition contains microparticulate composition, optical polymerism compound and the Photoepolymerizationinitiater initiater (below, be also referred to as the Photoepolymerizationinitiater initiater system sometimes) of above-mentioned water-insoluble compound, preferably, also contains alkali soluble resins.Below, each composition of Photocurable composition is described.

Preparation method about water-insoluble compound particulate and dispersive composition thereof is described in detail.The content of particulate in the Photocurable composition, with respect to whole solid substances (in the present invention, all solid substance is meant the total of the composition except organic solvent), be preferably 3～90 quality %, more preferably 20～80 quality %, more preferably 25～60 quality %.If should measure too much, then the viscosity of dispersion liquid rises, and causes making the problem of adaptability aspect sometimes.If very few, tinting strength deficiency then.In addition, in order to mix colours, also can use with pigment combinations commonly used.The material that pigment can use above to be put down in writing.

As optical polymerism compound (below, be sometimes referred to as polymerizable monomer or polyreactive oligomers), be preferably ethylenic unsaturated double-bond that has more than 2 and the polyfunctional monomer that can carry out addition polymerization by illumination.As this optical polymerism compound, can enumerate and have at least one ethylenic unsaturated group that can carry out addition polymerization, the boiling point under the normal pressure in the molecule at the compound more than 100 ℃.As its example, can enumerate monofunctional acrylate or simple function methacrylic esters such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate and phenoxy group ethyl (methyl) acrylate; Polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanuric acid ester, three (acryloxy ethyl) cyanurate, glycerine three (methyl) acrylate; Polyfunctional alcohol such as TriMethylolPropane(TMP) or glycerine goes up polyfunctional acrylic ester or the multifunctional methacrylic esters such as compound that forms through (methyl) acroleic acid esterification again behind addition of ethylene oxide or the propylene oxide.In addition, the general formula (1) that can also enumerate as Japanese kokai publication hei 10-62986 communique reaches the suitable material of compound conduct the record, that form through (methyl) acroleic acid esterification again in (2) behind addition of ethylene oxide on the polyfunctional alcohol or propylene oxide.

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

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

In addition, in addition, can also enumerate the suitable compound of putting down in writing in the Japanese kokai publication hei 11-133600 communique of " polymerizable compound B " conduct.

The optical polymerism compound can use separately, also can two or more mixing use, and with respect to whole solid substances of Photocurable composition, its content is generally 5～50 quality %, is preferably 10～40 quality %.If should measure too much, then be difficult to control development, can on manufacturing adaptability, have problems.If very few, the curing power deficiency when then exposing.

As Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system (in the present invention, the Photoepolymerizationinitiater initiater system is meant to be combined by multiple compound and realizes that photopolymerization causes the mixture of function), can enumerate the even acyl ketone of disclosed neighbour (vicinalpolyketaldonyl) 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 that the α that puts down in writing in No. 2722512 specification sheets of United States Patent (USP)-hydrocarbon replaces, the polynucleation quinone compound of putting down in writing in No. 3046127 specification sheets of United States Patent (USP) and No. 2951758 specification sheets of United States Patent (USP), the triarylimidazoles dipolymer of putting down in writing in No. 3549367 specification sheets of United States Patent (USP) and 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 dipolymer.

In addition; in addition; can also enumerate " the polymerization starter C " that put down in writing in the Japanese kokai publication hei 11-133600 communique; and as the 1-phenyl-1 of oximes; 2-propanedione-2-(adjacent ethoxycarbonyl) oxime, O-benzoyl-4 '-(thiophenyl) benzoyl-hexyl-ketoxime, 2; 4,6-trimethylphenyl carbonyl-diphenylphosphine acyloxylation thing, phosphofluoric acid-trialkyl Ben phosphonium salt etc. are as preferred material.

Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system can be used separately, also can mix two or more uses, and preferred especially use is two or more.If use at least two kinds of Photoepolymerizationinitiater initiaters, then can reduce the demonstration non-uniform phenomenon in the display characteristic especially.With respect to whole solid substances of Photocurable composition, the content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system is generally 0.5～20 quality %, is preferably 1～15 quality %.If should measure too much, then susceptibility is too high, is difficult to control.If very few, then exposure sensitivity is low excessively.

Can when preparation Photocurable composition or ink-jet ink for color filter, add alkali soluble resins, also preferably when the above-mentioned microparticulate composition of preparation or when forming particulate, add.Alkali soluble resins can be added to the solution of water-insoluble compound and poor solvent (in this poor solvent, adding water-insoluble compound) to generate the particulate of insoluble compound both or one in.Perhaps also preferably, when forming the particulate of water-insoluble compound, add alkali soluble resins by other system.

As alkali soluble resins, preferably have the binding agent of acidic-group, more preferably on side chain, have the alkali-soluble polymer of hydroxy-acid group or carboxylate group isopolarity group.As its example, can be set forth in Japanese kokai publication sho 59-44615 communique, special public clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, spy and open clear 59-53836 communique and the special maleic acid of opening the Sipacril 2739OF put down in writing in the clear 59-71048 communique, acrylic copolymer, itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, partial esterification etc.In addition, can also be set forth in the derivatived cellulose that has carboxylic acid group or carboxylate salt etc. on the side chain, in addition, in addition, also can preferably use the material that forms having after addition has cyclic acid anhydride on the polymkeric substance of hydroxyl.And, as more preferred example, can be set forth in United States Patent (USP) the 4th, 139, (methyl) vinylformic acid benzyl ester of putting down in writing in No. 391 specification sheetss and (methyl) acrylic acid multipolymer, the perhaps multiple copolymer of (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid and the formation of other monomer.

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

In addition,, can on the side chain of alkali soluble resins, have polymerizable group, also can adopt ultraviolet curing type resin or thermosetting resin etc. in order to improve cross-linking efficiency.And, as alkali soluble resins, can also use the resin that has water-soluble atomic group in the part of side chain.

Except mentioned component, the organic solvent (the 4th solvent) that Photocurable composition can also use the preparation Photocurable composition to use.There is no particular limitation to the example of the 4th solvent, can suitably enumerate for example alcoholic solvent, ketones solvent, ether solvent, sulfoxide kind solvent, esters solvent, amide solvent, aromatic hydrocarbon solvent, fat hydrocarbon solvent, nitrile solvents or their mixture etc., wherein more preferably ketones solvent, ether solvent, esters solvent, aromatic hydrocarbon solvent, fat hydrocarbon solvent or their mixture etc.

These solvents can use separately or can be used in combination.In addition, can use boiling point in case of necessity is 180 ℃～250 ℃ solvent.With respect to the total amount of Photocurable composition, the content of organic solvent is preferably 10～95 quality %.

In addition, preferably in Photocurable composition, contain suitable tensio-active agent.As tensio-active agent, can enumerate TOHKEMY 2003-337424 communique, spy and open in the flat 11-133600 communique disclosed tensio-active agent as the tensio-active agent that is fit to.With respect to the total amount of Photocurable composition, the content of tensio-active agent is preferably below the 5 quality %.

Preferably contain thermopolymerization in the Photocurable composition and prevent agent.Prevent the example of agent as this thermopolymerization, can enumerate quinhydrones, Hydroquinone monomethylether, p methoxy phenol, ditertbutylparacresol, pyrogallol, tert-butyl catechol, benzoquinones, 4,4 '-thiobis (3 methy 6 tert butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole, thiodiphenylamine etc.With respect to the total amount of Photocurable composition, thermopolymerization prevents that the content of agent is preferably below the 1 quality %.

In case of necessity, in Photocurable composition, except above-mentioned tinting material (pigment), can also add tinting material (dyestuff, pigment).When using the pigment in the tinting material, preferably make it in Photocurable composition, reach homodisperse.As dyestuff or pigment, specifically, be fit to use the coloured material of putting down in writing in [0038]～[0040] section of TOHKEMY 2005-17716 communique as above-mentioned pigment, the spy opens the pigment of record in the section of 2005-361447 communique [0068]～[0072], and the special tinting material of putting down in writing in [0080]～[0088] section of 2005-17521 communique of opening.With respect to the total amount of Photocurable composition, the auxiliary dyestuff that uses or the content of pigment are preferably below the 5 quality %.

In case of necessity, can contain UV light absorber in the Photocurable composition.As UV light absorber, the compound of in Japanese kokai publication hei 5-72724 communique, putting down in writing, also can enumerate salicylate class, benzophenone, benzotriazole category, cyanoacrylate, nickel chelate class, hindered amines etc.With respect to the Photocurable composition total amount, the content of UV light absorber is preferably below the 5 quality %.

In addition, except that above-mentioned additive, can also contain " adhesive aid " put down in writing in the Japanese kokai publication hei 11-133600 communique and other additive etc. in the Photocurable composition.

By suitably regulating the composition of Photocurable composition, can be made into ink for ink-jet print.Ink for ink-jet print except can be used as ink-jet ink for color filter, also can be used as typewriting and common ink for ink-jet print such as using, and wherein is preferably used as ink-jet ink for color filter.

As long as ink for ink-jet print contains above-mentioned water-insoluble compound particulate, preferably in the medium that contains polymerizable monomer and/or polyreactive oligomers, contain above-mentioned water-insoluble compound particulate.Herein, as polymerizable monomer and/or polyreactive oligomers, can use at the material described in the Photocurable composition above.

At this moment, the temperature of preferably controlling ink makes the amplitude of fluctuation of viscosity in ± 5%.Viscosity during injection is preferably 5～25mPas, and more preferably 8～22mPas is preferably 10～20mPas (in the present invention, if not otherwise specified, viscosity is meant the value in the time of 25 ℃) especially.Except above-mentioned injection temperature is set, also can regulate viscosity by kind and the addition of regulating the composition that contains in the ink.Above-mentioned viscosity can be measured by common devices such as for example cone-plate type rotational viscosimeter or E type viscometers.

In addition, consider that from the angle of the flatness that improves pixel the surface tension of ink is preferably 15～40mN/m (in the present invention during injection, if not otherwise specified, surface tension is meant the value in the time of 23 ℃), more preferably 20～35mN/m most preferably is 25～30mN/m.Can come the reconciliation statement surface tension by interpolation tensio-active agent, change solvent types.(consonance interface science Co., Ltd. makes, and CBVP-Z), full automatic balance type electron surface tonometer ESB-V survey meters such as (consonance science Co., Ltd. make), measures above-mentioned surface tension according to platinum plate method for example can to use surface tension apparatus.

Injection method as ink-jet ink for color filter, can adopt the method for spraying charged ink continuously and utilizing electric field to control, the method of utilizing piezoelectric element intermittently to spray ink, and the whole bag of tricks such as method that ink is heated and utilizes the bubble that produces that ink is intermittently sprayed.

In addition, the ink jet method of using when forming each pixel can adopt the method that makes the ink thermofixation, makes the method for ink photocuring, forms the usual methods such as method that instil after the transparent image receiving layer in advance on substrate.

Inkjet head (following also abbreviate as " shower nozzle ") can use ink gun commonly used, can use continuous injection type, need based jet type (dot on demand).In the need based jet type, aspect the temperature-sensitive shower nozzle,, preferably has the sort of temperature-sensitive shower nozzle as the operating valve of being put down in writing in the Japanese kokai publication hei 9-323420 communique in order to spray ink.Aspect piezo jets, the shower nozzle of being put down in writing in for example can use European patent A 277, No. 703,278, No. 590 grades of European patent A.Shower nozzle preferably has temp regulating function, so that can control the temperature of ink.Set injection temperature so that the viscosity when spraying is 5～25mPas, preferably ink temperature is controlled so that the viscosity rangeability in ± 5%.In addition, preferably carry out work with the driving frequency of 1～500kHz.

In addition, after each pixel forms, the heating process of heat treated (so-called oven dry processing) can be set.That is, will have the substrate that photopolymerisable layer takes place by rayed is placed on and heats in electric furnace, the moisture eliminator etc. or shine with infrared lamp.The temperature and time of heating depends on the composition of photosensitivity heavy colour composition or the thickness of formed layer, in general consider from the aspect that can obtain sufficient solvent resistance, alkali resistance and ultraviolet radiation absorption degree, be preferably at about 120 ℃～about 250 ℃ and heated about 10 minutes～about 120 minutes down.

Pattern form to formed colour filter does not thus limit especially, its can for the bar shaped of general black matrix (black matrix) shape, also can be for grid, can also be the shape of rounded projections arranged.

Preferably, before forming the operation of pixel, make the next door in advance, in by the part that this next door surrounded, spray the such making method of ink with previously described ink-jet ink for color filter.Though described next door can be any material, when making colour filter, preferably, has the next door (following also abbreviate as " next door ") of the tool opacifying property of black matrix function.Can adopt with colour filter commonly used and make this next door with black matrix identical materials, method.For example the ink for ink-jet print of being put down in writing in [0009]～[0044] section in [0015]～[0020] section, TOHKEMY 2006-10875 communique in the black matrix described in [0012]～[0021] section or the TOHKEMY 2006-17980 communique in [0021]～[0074] section, TOHKEMY 2004-240039 communique in the TOHKEMY 2005-3861 communique is with black matrix etc.

With Photocurable composition form film in the composition that contained, identical with the composition of having put down in writing.In addition, the thickness of filming that forms with Photocurable composition can carry out suitably determining according to purposes, but is preferably 0.5～5.0 μ m, more preferably 1.0～3.0 μ m.Film for this that forms with Photocurable composition, make above-mentioned monomer or oligopolymer carry out the polymeric membrane that polymerization forms Photocurable composition, can make the colour filter (, hereinafter stating) that contains this film about the manufacturing of colour filter.The polymerization of optical polymerism compound can be undertaken by Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system are worked.

In addition, adopt common coating process to be coated with Photocurable composition and carry out drying, can form above-mentioned filming, in the present invention, the preferred slit-shaped nozzle that has the hole of slit-shaped in the hydrojet part that adopts is coated with.Specifically, can suitably use TOHKEMY 2004-89851 communique, spy to open 2004-17043 communique, spy opens 2003-170098 communique, spy and opens 2003-164787 communique, spy and open that 2003-10767 communique, spy are opened the 2002-79163 communique, the spy drives slit-shaped nozzle and the slot coated device described in 2001-310147 communique etc.

As the method that Photocurable composition is applied on the substrate, from can be equably and be coated with the aspect of the film of 1～3 μ m accurately, rotary coating be excellent, generally uses this method in the making of colour filter widely.But, in recent years, along with the maximization and the batch process of liquid crystal indicator, make efficient and save manufacturing cost in order further to improve, adopting slot coated in the making of colour filter, it is more suitable in the coating of the large-area substrates that carries out wide cut than the rotation coating.In addition, consider that slot coated is also excellent than the rotation coating, can be filmed uniformly with coating liquid measure still less from the viewpoint of saving liquid.

Slot coated is a kind of like this coating process, promptly, make the space (gap) between dispense tip (it is that tens of microns slit (gap) and its length is corresponding with the coating width of rectangular substrate that its front end has width) and the substrate remain tens of～hundreds of microns, make substrate and dispense tip keep the constant speed of relative movement simultaneously, will be coated on the substrate by the coating fluid that slit provides by predetermined glue spread.This slot coated have (1) compare with rotary coating liquid loss less, (2) coating fluid do not have and disperses, so reduced the time of dispersing in clean, (3) that liquid component can not sneaked in the coated film again, (4) do not rotate beginning and stop, therefore making and produce interval shortening, (5) easily to advantages such as large substrate are coated with.Owing to have these advantages, slot coated is suitable for the making of the liquid crystal indicator of large-scale picture with colour filter, also is expected to become favourable coating process with regard to the minimizing that is coated with liquid measure.

Also have, the coating in the above-mentioned making method can be adopted common apparatus for coating to wait to carry out, and in the present invention, preferred employing apparatus for coating (slot coated device) that illustrated, that used the slit-shaped nozzle is coated with.The preferred object lessons of slot coated device etc. as mentioned above.

Colour filter of the present invention preferably has excellent contrast gradient.In the present invention, what contrast gradient was represented is, between two polaroids, the ratio of the light transmission capacity the when light transmission capacity when polarizing axis is parallel is vertical with polarizing axis (referring to " nineteen ninety the 7th the color reversion glory learn コ Application Off アレ Application ス; 512 colour specifications 10.4 " サイズ TFT-LCD is with カラ-Off イ Le タ, plant wood, Xiao Guan, good fortune forever, in the mountain " etc.).

Light and shade difference when the contrast gradient height of colour filter is meant and makes up with liquid crystal can become big, and in order to replace CRT with liquid-crystal display, this is very important performance.

When colour filter is used with colour filter as TV, preferably under the F10 light source, all the monochromatic colourities of red (R), green (G) and blue (B) and following table record value (below, be called " standard chroma " in the present invention) poor (Δ E) all in 5, more preferably in 3, in 2.

Colourity among the present invention is to utilize microscope spectrophotometer (オリ Application パス optics society make, OSP100 or 200) to measure, and calculates as the results in the 2 degree visuals field under the F10 light source, represents with the xyY value of xyz coloring system.In addition, represent with the aberration of La*b* coloring system with the difference of standard chroma.

Preferably, contrast of LCD degree height, black density that possesses colour filter etc. described the power excellence, and particularly it is the VA standard.Also be suitable as notebook computer with the liquid crystal indicator of big picture such as indicating meter and TV monitor etc.In addition, above-mentioned colour filter can be used for the CCD device, and the excellent performance of performance.

[embodiment]

Below based on embodiment the present invention is described in more detail, but can not be interpreted as the present invention and be confined to this.In addition, if not special explanation, in the present embodiment, " part " and " % " is quality standard.

(synthesis example)

(synthesizing of monomer M-1)

45.28 parts 2-thiobarbituricacids, 13.82 parts dissolution of sodium hydroxide in 200 parts dimethyl sulfoxide (DMSO), are heated under 25 ℃.To the 1-chloro-4-methyl-benzene of 7.53 parts of Dropwise 5s wherein, 55 ℃ of further heated and stirred 5 hours down.After the heated and stirred, in this reaction solution, add 150 parts methyl alcohol, 150 parts distilled water and stirred 1 hour, then with this solution while stirring in the distilled water that is injected into 2000 parts, the precipitate that filter, washing is obtained, thus obtain 80.1 parts monomer M-1.

(synthesizing of polymer P-1)

Following monomer solution is joined in the there-necked flask after the nitrogen displacement, and with stirrer (new eastern science Co., Ltd.: スリ one ワ Application モ one タ) stir, carry out heat temperature raising to 78 ℃ while in flask, import nitrogen, and stirred 30 minutes.Then, in aforesaid liquid, add following initiator solution, and 78 ℃ of following heated and stirred 2 hours.After the heated and stirred, further add following initiator solution, and, repeat this operation totally 2 times 78 ℃ of following heated and stirred 2 hours.After last 2 hours stir, continued under 90 degree heated and stirred 2 hours.The reaction solution that obtained while stirring in the Virahol that is injected into 1500 parts, is filtered and collects the precipitation that is generated, heat drying, thus obtain graftomer P-1 (matter average molecular weight: 10000).

(monomer solution)

Monomer M-1 5.0 part

14.0 parts of vinylbenzene

2.0 parts of methacrylic acids

46.67 parts of 1-Methyl-2-Pyrrolidones

(initiator solution)

2,1.2 parts of 2 '-azo two (isopropylformic acid) dimethyl esters

(make with the pure medicine of light (strain) society, V-601)

2 parts of 1-Methyl-2-Pyrrolidones

MAA: methacrylic acid (making) with the pure medicine of light (strain) society

MMP:1-N-methyl-2-2-pyrrolidone N-(making) with the pure medicine of light (strain) society

[mensuration of molecular weight and dispersity]

Molecular weight and dispersity adopt GPC (gel filtration chromatography) to measure.

In general, the gel of filling in the used pillar of GPC method preferably has the gel of aromatics as repeating unit, for example can enumerate the gel that is made of styrene diethylene benzene copoly mer.Preferably 2～6 pillars are coupled together use.Used solvent can be enumerated amide solvents such as ether solvent, N-Methyl pyrrolidone such as tetrahydrofuran (THF), but ether solvents such as preferred tetrahydrofuran (THF).During mensuration, the flow velocity of solvent is preferably 0.1～2mL/min, most preferably is 0.5～1.5mL/min.By in this scope, measuring, can not cause load, thereby can measure more effectively to device.Measure temperature and be preferably 10～50 ℃, be preferably 20～40 ℃ especially.

The condition determination that below illustrates in the present embodiment to be adopted.

Device: HLC-8220GPC (East ソ one (strain) made)

Detector: differential refractometer (RI detector)

Pre-column: TSKGUARDCOLUMN MP (XL)

6mm * 40mm (East ソ one (strain) made)

The pillar that is used for sample: following 2 pillar (Jun You East ソ one (strains) are made) directly connects

TSK-GEL?Multipore-HXL-M?7.8mm×300mm

Be used for pillar: identical with the pillar that is used for sample with reference to product

Thermostatic bath temperature: 40 ℃

Moving phase: tetrahydrofuran (THF)

The flow rate of mobile phase that is used for sample: 1.0mL/ minute

Be used for flow rate of mobile phase: 0.3mL/ minute with reference to product

The concentration of sample: 0.1 weight %

The injection rate of sample: 100 μ L

Data acquisition time: sample injected back 16 minutes～46 minutes

Sampling interval: 300msec

(embodiment 1)

When solution (it is as good solvent (first the solvent)) 2500ml that 25% tetramethylammonium hydroxide aqueous solution of 70.5ml (making with the pure medicine of light society) is formed in the N-Methyl pyrrolidone of 1000ml heats under 80 ℃ to the pigment C.I. Pigment red 254 that wherein adds 50g (trade(brand)name: Irgaphor Red BT-CF, チバスペシヤ Le テイケミカ Le ズ (strain) society makes) and the graft copolymer P-1 of 30.0g, thereby pigment preparation solution 1.Use viscometer VM-10A-L (manufacturing of CBC マテリア Le ズ society) to measure the viscosity of this pigment solution 1, the result shows that the viscosity of pigment solution 1 when the liquid temperature is 25 ℃ is 13.3mPas.The water 1000ml of 1mol/L hydrochloric acid (making with the pure medicine of light society) for preparing to contain 16ml in addition is as poor solvent.

At this moment, temperature is controlled to be 15 ℃, to utilizing GK-0222-10 type ラモ Application De スタ-ラ-(trade(brand)name, rattan pool medicine Co., Ltd. makes) in second solvent that stirs with the rotating speed of 500rpm, inject pigment solution 1 with NP-KX-500 type large vol pulseless pump (trade(brand)name, Japanese precision chemical society makes).Be made as 2.2mm by fluid passage diameter and supplying opening diameter with the liquid-transport pipe-line of pigment solution 1, and its supplying opening is put in second solvent, the flow velocity of pressing 200ml/min injects 100ml, forms organic pigment particle thus, thus the preparation dispersible pigment dispersion.Use is diluted to the dispersion liquid sample of 0.5 quality %, adopt day Na ノトラ Star Network UPA-EX150 (trade(brand)name) of machine dress society manufacturing, measure the particle diameter of the pigment particle in the resulting dispersion liquid, the volume average particle size Mv that the result records is 23.0nm, and single dispersity (Mv/Mn) is 1.18.

The H-110A type centrifugal filter that utilizes the manufacturing of (strain) コ Network サ Application society is Ji the P89C type filter cloth that Fu Island カ Application バス (strain) society makes, to concentrate 90 minutes with 3000rpm by the prepared dispersible pigment dispersion of above-mentioned operation, from dispersible pigment dispersion, remove and deduct solvent composition (the first concentrated operation of removing), and 100 ℃ dry 12 hours down, thereby obtain the powder R-1 (pigment dyestuff content is 61.8 quality %) that the throw out (flock) by the pigment dyestuff particulate constitutes.

As shown in Figure 2, this powder R-1 (15) of 30g is placed on the pedestal (13), its acetone with 50g (14) is put in the closed pressure container (11).And, as shown in Figure 2, loam cake (12) is covered, be set in the reactor (100), and in 100 ℃ baking box, heated 8 hours, in acetone atmosphere (16), carry out crystallization thus.Take out pigment powder from container, drying is 4 hours under 100 ℃, thereby obtains pigment powder R-2 (pigment dyestuff content is 63.0%).

Use the powder R-2 of above-mentioned pigment dyestuff particulate, prepare following composition, utilizing electronic mill M-50 (manufacturing of アイガ one ジヤパ Application society) and use the zirconium white microballon of diameter as 0.65mm, is to disperse 8 hours under the condition of 9m/s in circumferential speed, prepares pigment dispensing composition 1 thus.At this moment, above-mentioned pigment dyestuff particulate demonstrates excellent automatic dispersiveness to acetate 1-methoxyl group-2-propyl ester.

The powder R-2 20.4g of above-mentioned pigment dyestuff particulate (pigment is 12.85g)

Acetate 1-methoxyl group-2-propyl ester 100.0g

[measuring method of contrast gradient]

Resulting pigment dispensing composition 1 separate application is made thickness on glass substrate be 2 μ m, made sample.As backlight assembly, use is provided with diffuser plate and the device that forms on three-wavelength cold-cathode tube light source (Toshiba's ライテ Star Network (strain) society make FWL 18EX-N), between two polaroids (the polaroid HLC2-2518 that (strain) サ Application リ Star society makes), place this sample, measure polarizing axis light transmission capacity when vertical when parallel, with its liken to into contrast gradient (referring to " and nineteen ninety the 7th the color reversion glory learn コ Application Off アレ Application ス; 512 colour specifications 10.4 " サイズ TFT-LCD is with カラ-Off イ Le タ, plant wood, Xiao Guan, good fortune forever, in the mountain " etc.).The position that is provided with about two polaroids, sample, color briliancy instrument, position at distance 13mm backlight is provided with polaroid, the cylinder of diameter 11mm, length 20mm is set in the position of 40mm～60mm, the rayed that wherein sees through is being arranged on the locational mensuration sample of 65mm, make to see through light and pass and be arranged at the locational polaroid of 100mm, measure by being arranged at the locational color briliancy of 400mm instrument.The mensuration angle of color briliancy instrument is set at 2 °.The setting of light quantity backlight will make that under the state that sample is not set the briliancy when two polaroids are be arranged in parallel is 1280cd/m ²

[through the time contrast gradient measuring method and evaluation method]

After disperseing 30 days, adopt method same as described above once more, the pigment dispensing composition 1 that coating is obtained, and measure contrast gradient.According to this through the time be coated with immediately after contrast gradient and the preparation just and survey periodic contrast gradient, calculate through the time contrast gradient velocity of variation.

[through the time contrast gradient velocity of variation]=[initial stage contrast gradient]/[through the time contrast gradient]

[mensuration and the evaluation method of the state that wraps into of dispersion agent]

Utilize solid ¹³C CP/MAS NMR measures (AVANCE DSX-300 spectrometer (trade(brand)name) and 4mm Φ HFX CP/MAS probe that Block Le カ one バイオスピ Application society makes), confirms whether dispersion agent is encased in the particle.Solid ¹³C CP/MAS NMR measuring method is as follows.

(MILLIPORE makes, the aperture: 0.05 μ m) come suction filtration pigment dispensing composition 1, stick with paste thereby preparation concentrates to utilize film filter.Above-mentioned concentrated paste is arranged on ¹³On the sample table of C CP/MASNMR, based on Goldman-shen pulse sequence, will ¹H90 ° of pulse width of cloth be decided to be 4.5 μ s, be used for the waiting time that initial solvent selects be decided to be 200 μ s, CP is decided to be 1ms duration of contact, make rotation be changed to 0.5～200ms diffusion time, thereby measure.Accumulative frequency is 4096 times, and the repetition time is with sample ¹5 times of the H rotation grid relaxation time is benchmark, is decided to be 3～10 seconds.Per sample, the revolution with the rotation of magic angle is decided to be 8000～10000Hz.

Carrying out the peak by the spectrum that each is rotated diffusion time separates, calculate the peak area of pigment and dispersion agent, utilize the diffusion length L of hypothesis one dimension diffusion model the relation shown in the following mathematical expression to be arranged with rotation tm diffusion time, and between the distance of solvent molecule and peak area, drawing, thereby judge the particulate structure.

[mathematical expression 1]

L = 1.1 \sqrt{t_{m}}

[dispersion agent is imbedded the mensuration and the evaluation method of rate]

(MILLIPORE makes to utilize film filter, aperture: 0.05 μ m) come suction filtration pigment dispensing composition 1, resulting filtering powder 1 is disperseed under the following conditions again, adopt method same as described above to carry out suction filtration, according to the amount of polymers of resulting filtering powder 2 and the amount of polymers of interpolation, estimate that dispersion agent wraps into rate.

[dispersion agent wraps into rate]=[filtering the amount of polymers that the back powder is contained]/[amount of polymers of interpolation] * 100

It the results are shown in table 2.

[mensuration of dispersion agent embedding rate and method of calculation]

Utilize the amount of polymers of above-mentioned filtering powder 2 and the amount of pigment of being added (total amount of the pigment that supposition is added all separate out and form micronize), estimate the dispersion agent embedding rate according to following formula.

(dispersion agent embedding rate)=(filtering the amount of polymers that back powder 2 is contained)/(amount of pigment of interpolation) * 100

It the results are shown in table 2 (unit in the table is quality %).

[observing the method for measuring median size according to transmission electron microscope (TEM)]

Observe by transmission electron microscope (TEM), the coating of particles of observing the water-insoluble coloured material that contains in the resulting colo(u)rant dispersion thing 1, and calculate its median size with following method.It is online that the dispersion thing (or dispersion liquid) that will contain the particulate of water-insoluble coloured material is diluted in the Cu200 that posts carbon film, and be placed on top and carry out drying, images according to TEM (1200EX that Jeol Ltd. makes) shooting under 100,000 times, measure 500 particle grain size, and obtain its mean value.At this moment, as mentioned above, because dispersion agent is carried out drying on the net at above-mentioned Cu200, though the water-insoluble coloured material is in good dispersion state in above-mentioned dispersion thing, but in drying process, form aggegation on the water-insoluble coloured material particle appearance, therefore be difficult to judicious particle diameter sometimes.In this case, measure the particle grain size of 500 nonoverlapping, Individual existences, and obtain its mean value.In addition, when the water-insoluble coloured material is not spherical in shape, measure particulate major diameter (diameter that particulate is the longest).

[mensuration and the evaluation method of the change of size rate that heat causes]

Resulting colo(u)rant dispersion thing 1 was kept 6 hours down at 80 ℃, then,, utilize TEM to calculate the median size of water-insoluble coloured material with the same before the heating.And, calculate the change of size rate that heat causes according to following formula.

[the change of size rate that heat causes]=([80 ℃ heating after median size]-[median size before the heating])/[median size before the heating] * 100

When the change of size rate that causes when this heat is high, under 230 ℃ the Heating temperature when making colour filter, observes contrast gradient and reduce, also can be observed the generation of precipitate when serious, so the change of size rate that this heat causes is preferably lower.

[measuring method of crystal particle diameter (its definition)]

To the mensuration of crystal particle diameter with calculate that there is no particular limitation, in the present invention, have crystalline structure and be meant when disperseing that contained water-insoluble coloured material carries out powder x-ray diffraction analysis in the thing, do not have following (i) and (ii) in any situation.

When (i) observing noncrystal distinctive halation.

(ii) by crystal particle diameter deficiency that following method determined

Or when being noncrystal shape.

In the present invention, measure and calculate crystal particle diameter according to following method.

At first, resulting colo(u)rant dispersion thing 1 is coated on the glass substrate, after at room temperature placement makes its drying, collected also and pulverize.Use Cu-K α 1 ray to carry out X-ray diffraction analysis to it.Then, in the scope of 20=4deg～70deg, measure the peak width at half height demonstrate the peak of maximum strength or to demonstrate and peak that intensity enough big indissociable, and, calculate crystal particle diameter according to following Scherrer formula with the peak that is close to.

D=K * λ/(β * cos θ) ... the Scherrer formula

[D: crystal particle diameter (

The crystalline size), λ: X ray is measured wavelength

β: the broadening of the diffracted ray that crystalline size causes (radian), θ: the Bragg angle of diffracted ray (radian), K: constant (constant according to β and D is different and different)

Usually, be known that when β uses peak width at half height β 1/2 K=0.9.

In addition, the wavelength of Cu-K α 1 ray is 1.54050

Therefore crystal particle diameter D of the present invention can calculate according to following formula:

D＝0.9×1.54050/(β1/2×cosθ)

When the peak width at half height of measuring resulting spectrographic peak broad and above-mentioned peak can not be distinguished, infer the crystal particle diameter deficiency herein, Or be noncrystal shape (noncrystal).

[measuring method of degree of crystallinity (its definition)]

To the mensuration of degree of crystallinity with calculate that there is no particular limitation, be defined as the value that obtains after the quality of crystal block section the quality in the present invention divided by the quality addition of the quality of crystal block section and noncrystal part.That is, can represent by following formula.

[degree of crystallinity]=[quality of crystal block section]/[quality of crystal block section]+[quality of noncrystal part]

[measuring method of degree of crystallinity (its analysis)]

In the present invention, utilize solid ¹³C CP/MAS NMR measures the mensuration of carrying out degree of crystallinity.Carry out solid ¹³C CP/MAS NMR has adopted Block Le カ one バイオスピ Application society to make when measuring AVANCE DSX-300 spectrometer and 4mm Φ HFX CP/MAS probe.

The xeraphium that use prepares in order to calculate crystal particle diameter, utilization is measured according to spin lock (Spin-locking) method ¹³The rotation grid relaxation time T of the rotating system of C nuclear _{1 ρ} ^c, estimate degree of crystallinity.Will ¹90 ° of pulse width of cloth of H are decided to be 4.5 μ s, CP and are decided to be 1ms duration of contact, and the spin lock time is decided to be 50 μ s～20ms, repetition time with sample ¹5 times of the H rotation grid relaxation time is benchmark, is decided to be 3～10 seconds.The rotation number of magic angle rotation is decided to be 14000Hz.

Spectrographic peak according to each rotation diffusion time separates the peak area of calculating pigment, decays with two component index functions and comes the match peak area with respect to the figure of spin lock time, its composition is likened to be degree of crystallinity.

Measurement result about the foregoing description in above-mentioned projects and following embodiment, comparative example, reference example is shown in Table 1.

(embodiment 2)

Adopt the method identical with embodiment 1, preparation pigment dispensing composition 2, difference is, the crystallization method that replaces embodiment 1 by following method, promptly, use dissolving machine, under the condition of 1500rpm, the powder R-1 of 30g and the acetone of 270g were stirred 60 minutes together, the H-112 type centrifugal filter that utilizes the manufacturing of (strain) コ Network サ Application society is Ji the P89C type filter cloth that Fu Island カ Application バス (strain) society makes, prepared pigment nanoparticulate dispersion A is concentrated 90 minutes with the rotating speed of 5000rpm, and reclaim resulting pigment nano particle and concentrate and stick with paste A, should concentrate and stick with paste A drying 4 hours under 100 ℃.

(embodiment 3)

Adopt the method identical with embodiment 1, preparation pigment dispensing composition 3, difference is, during with the pigment dispensing composition for preparing embodiment 1 in Crystallization Procedure employed solvent change to vinyl acetic monomer by acetone.

(embodiment 4)

Adopt the method identical with embodiment 1, preparation pigment dispensing composition 4, difference is, during with the pigment dispensing composition for preparing embodiment 1 in Crystallization Procedure employed solvent change to propylene glycol monomethyl ether by acetone.

(embodiment 5)

Adopt the method identical with embodiment 2, preparation pigment dispensing composition 5, difference is, during with the pigment dispensing composition of preparation embodiment 2 in Crystallization Procedure employed solvent change to ethyl lactate by acetone, and stir back stirring heating 3 hours in 60 ℃ hot water bath with dissolving machine.

(comparative example 1)

Adopt the method identical with embodiment 1, preparation pigment dispensing composition 6, difference is, during with the pigment dispensing composition for preparing embodiment 1 in Crystallization Procedure employed solvent change to methyl alcohol by acetone.

(comparative example 2)

To 1, pigment C.I. Pigment red 254 (the trade(brand)name Irgaphor Red BT-CF that adds sodium-chlor, 10g in the 3-butyleneglycol diacetate esters liquid, the manufacturing of チバスペシヤ Le テイケミカ Le ズ (strain) society) the graftomer P-1 of powder and 30.0g, then it is joined in the twin screw kneader, descended mixing 15 hours at 80 ℃.After mixing, said mixture is joined in 80 ℃ 1% aqueous hydrochloric acid of 700 mass parts, stir after 1 hour, filter hot wash, drying, pulverize, the ratio of adding the propylene glycol monomethyl ether acetate of 2.4g according to every 1g crushed material is added and is mixed then.Adopt electronic mill M-50 (manufacturing of アイガ one ジヤパ Application society) and use the zirconium white microballon of diameter, under the condition of circumferential speed 9m/s, above-mentioned color compositions was disperseed 10 hours, thereby obtain pigment dispensing composition 7 as 0.65mm.By the method identical with embodiment 1, measure the particle diameter of the pigment particle in the dispersion liquid that is obtained, the result, volume average particle size Mv is 24.2nm, single dispersity (Mv/Mn) is 1.31.

(comparative example 3)

Adopt the method identical, prepare pigment dispensing composition 8 with embodiment 1.Difference is, used graftomer P-1 changes to polyvinylpyrrolidone (K-30, the pure medicine of trade(brand)name and light society makes) during with the pigment dispensing composition of preparation embodiment 1.By adopting the method identical with embodiment 1, the particle diameter of the pigment particle in the dispersion liquid that mensuration is obtained, the result, volume average particle size Mv is 21.4nm, single dispersity (Mv/Mn) is 1.20.

(reference example 1)

Adopt the method identical, prepare pigment dispensing composition 9 with embodiment 1.Difference is, does not carry out Crystallization Procedure when the pigment dispensing composition of preparation embodiment 1.

[table 1]

As can be seen, use particulate of the present invention and the contrast gradient of the pigment dispensing composition that obtains, through the time contrast gradient, thermostability all excellent.

The making of＜liquid crystal indicator 〉

1. adopt ink jet method to make CF and the liquid crystal indicator that has used CF

(making of photosensitive transfer printing material)

At thickness is on the interim upholder of polyethylene terephthalate film of 75 μ m, is coated with the thermoplastic resin coating fluid that is made of following prescription H1 with the slit-shaped nozzle, and carries out drying.Then, the middle layer coating fluid that coating is made of following prescription P1, and carry out drying.Be coated with again by the resin combination K1 that forms that forms that puts down in writing among the following table 2-A with opacifying property; and carry out drying; thereby the thermoplastic resin that dry film thickness is 15 μ m is set on this interim upholder, middle layer, the dry film thickness that dry film thickness is 1.6 μ m is the resin layer with opacifying property of 2.4 μ m, and pressing protective membrane (thickness is the polypropylene screen of 12 μ m).

Make the photosensitive resin transfer material that forms one by interim upholder, thermoplastic resin, middle layer (oxygen barrier layers) and resin layer with opacifying property thus, the sample name is decided to be photosensitive resin transfer material K1.

* thermoplastic resin coating fluid: prescription H1

Methyl alcohol 11.1 mass parts

Propylene glycol monomethyl ether 6.4 mass parts

Methylethylketone 52.4 mass parts

The multipolymer of methyl methacrylate/2-EHA/benzyl methacrylate/methacrylic acid (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight=100,000, Tg: about 70 ℃) 5.83 mass parts

The multipolymer of styrene/acrylic (copolymerization ratio of components (mol ratio)=63/37, molecular weight: 10,000, Tg: about 100 ℃) 3.6 mass parts

2, two [4-(methacryloxy polyethoxye) phenyl] propane of 2-

(Xin Zhong village chemical industry (strain) manufacturing) 9.1 mass parts

Tensio-active agent 10.54 mass parts

＜tensio-active agent 1〉(メガ Off ア Star Network F-780-F (big Japanese ink chemical industry (strain) society make)) consist of:

C ₆F ₁₃CH ₂CH ₂OCOCH=CH ₂: 40 mass parts

H (OCH (CH ₃) CH ₂) ₇OCOCH=CH ₂: 55 mass parts and

H (OCH ₂CH ₂) ₇OCOCH=CH ₂: 5 mass parts

Multipolymer (molecular weight 30,000) 30 mass parts that form

Methylethylketone 70 mass parts

Fill a prescription with coating liquid in＜middle layer (oxygen barrier layers): P1 〉

Polyvinyl alcohol 32.2 mass parts

(PVA205 (saponification degree=88%); (strain) Network ラレ society makes)

Polyvinylpyrrolidone 14.9 mass parts

(PVP, K-30; アイエスピ-ジヤパ Application Co., Ltd. makes)

Methyl alcohol 429 mass parts

Distilled water 524 mass parts

[table 2-A]

Resin combination K1 with opacifying property obtains in the following manner, promptly, at first take by weighing K colo(u)rant dispersion thing 1, propylene glycol monomethyl ether, under 24 ℃ of temperature (± 2 ℃), mix, and stirred 10 minutes with the rotating speed of 150rpm, then, take by weighing binding agent-1, Hydroquinone monomethylether, DPHA liquid, polymerization starter A (2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl) amino-3 '-bromophenyl]-the s-triazine), tensio-active agent 1, under 25 ℃ of temperature (± 2 ℃), add successively, and the rotating speed with 150rpm stirred 30 minutes under 40 ℃ of temperature (± 2 ℃).

＜K colo(u)rant dispersion thing 1 〉

(デグ Star サ society makes carbon black, trade(brand)name: Special Black250)

13.1 mass parts

Above-mentioned pigment dispersing agent A 0.65 mass parts

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand) 6.72 mass parts

Propylene glycol monomethyl ether 79.53 mass parts

＜binding agent 1 〉

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=78/22 mol ratio, molecular weight 40,000) 27 mass parts

Propylene glycol monomethyl ether 73 mass parts

[formula 16]

＜DPHA liquid 〉

(contain stopper MEHQ 500ppm, Japanese chemical drug (strain) society makes dipentaerythritol acrylate, trade(brand)name: 76 mass parts KAYARAD DPHA)

Propylene glycol monomethyl ether 24 mass parts

(formation) with next door of opacifying property

For alkali-free glass substrate, on one side spray the glass cleaner 20 seconds that is adjusted to 25 ℃ with water-jet, clean with rotating brush on one side with nylon hair, after using the pure water spray Cleaning for High Capacity again, spray silane coupling solution (the 0.3 quality % aqueous solution of N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane with water-jet, trade(brand)name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) society makes) 20 seconds, and use the pure water spray Cleaning for High Capacity.This substrate was heated 2 minutes at 100 ℃ with the substrate preheating apparatus.

After the protective membrane of above-mentioned photosensitive resin transfer material K1 peeled off; with laminating machine (イ of Co., Ltd. Hitachi Application ダストリイズ system (LamicII type)), be set forth in 100 ℃ down on the substrate of heating after 2 minutes last in the condition laminated of 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transfer rate 2.2m/ minute.

After peeling off interim upholder, employing has the contiguous type exposure machine (manufacturing of the Ha イテ of Hitachi Network electronics エ Application ジニアリ Application グ Co., Ltd.) of extra-high-pressure mercury vapour lamp, make substrate keep the vertical state that stands up with mask (quartzy exposed mask) with picture pattern, with the distance setting of exposed mask face and this thermoplastic resin interlayer is 200 μ m, at 100mJ/cm ²Exposure under carry out pattern exposure.Mask shape is a reticulation, is being equivalent to the part of pixel with the boundary line in the next door with opacifying property, and the radius-of-curvature that makes the protrusion angle of next door one side with opacifying property is 0.6 μ m.

Then, (contain 2.5% trolamine, nonionic surface active agent, poly-propyl ester defoamer with trolamine class developing solution, trade(brand)name: T-PD1, Fuji description Off イ Le system Co., Ltd. makes) under 30 ℃, the condition of tack nozzle pressure 0.04MPa, spray and developed 50 seconds, remove thermoplastic resin and middle layer (oxygen barrier layers).

Then, (contain the sodium bicarbonate of 0.06 mol, the yellow soda ash of 0.06 mol, 1% sodium dibutyl naphthalene sulfonate, anion surfactant, defoamer, stablizer with yellow soda ash class developing solution, trade(brand)name T-CD1, the description Off イ of Fuji Le system Co., Ltd. system), under 29 ℃, the condition of conical nozzle pressure 0.15MPa, spray and developed 30 seconds, resin layer with opacifying property is developed, obtain pattern portrayal next door (partition pattern) with opacifying property.

Then (contain phosphoric acid salt, silicate, nonionic surface active agent, defoamer, stablizer with clean-out system, trade(brand)name " T-SD1 (the description Off イ of Fuji Le system Co., Ltd. system) "), under 33 ℃, the condition of conical nozzle pressure 0.02MPa, sprayed 20 seconds, and remove residue with rotary brush with nylon hair, obtain having the next door of opacifying property.Then, for this substrate, use extra-high-pressure mercury vapour lamp at 500mJ/cm from this resin layer side again ²Illumination under carry out post-exposure, then 240 ℃ of following thermal treatments 50 minutes.

[plasma body is refused water treatment]

Afterwards, carry out plasma body with following method and refuse water treatment.

For the aforesaid substrate that is formed with next door, use cathode coupling formula parallel plate-type plasma processing apparatus to carry out plasma body and refuse water treatment by following condition with opacifying property.

Using gas: CF ₄

Gas flow: 80sccm

Pressure: 40Pa

RF power: 50W

Treatment time: 30 seconds

[preparation of ink-jet ink for color filter]

With reference to the embodiment 1 of TOHKEMY 2002-201387 communique, by following formulation ink-jet ink for color filter.

[table 2-B]

Mixing about each composition among the above-mentioned table 2-B at first joins pigment and macromolecule dispersing agent in a part of solvent, mixes, and stirs with three roller mixing rolls and microballon shredder again, obtains dispersible pigment dispersion.On the other hand, other system component is joined in the remaining solvent, stir with dissolving and disperse, obtain binder solution.Then, Yi Bian dispersible pigment dispersion or pigment dispensing composition are added in the binder solution bit by bit, Yi Bian fully stir with dissolving machine, prepare ink-jet ink for color filter thus.

On glass substrate, making it is 2.0 μ m at the coated film thickness of 100 ℃ of dryings after 10 minutes, has made sample with above-mentioned R ink for ink-jet print 1～9 separate application that obtains.Adopt the method identical, the contrast gradient of the sample of mensuration made with embodiment 1.And, after disperseing 30 days, adopt method same as described above, be coated with above-mentioned R ink for ink-jet print 1～9 once more, and measure contrast gradient.According to this through the time contrast gradient and just completed after be coated with the contrast gradient of mensuration at once, calculate through the time contrast gradient velocity of variation (through the time contrast gradient velocity of variation)=(initial stage contrast gradient)/(through the time contrast gradient).In addition, above-mentioned R ink for ink-jet print 1～9 was kept 6 hours down at 80 ℃, thereafter,, utilize TEM, calculate the median size of water-insoluble coloured material with the same before the heating.And, calculate the change of size rate that heat causes according to following formula.It the results are shown among the table 2-C.

[table 2-C]

Compare with duplicate 6～8, R ink for ink-jet print 1～5 of the present invention demonstrated the contrast gradient height, it is low to change the lower and hot change of size rate that causes of contrast gradient velocity of variation in time.

(formation of pixel)

Use the piezoelectric type shower nozzle, R ink 1, G ink 1, the B ink 1 of above-mentioned acquisition at first is instilled into ink in the recess that is surrounded by the opacifying property next door in the following manner.Obtained colour filter of the present invention by following mode then.

Shower nozzle has the density of 150 nozzles to have 318 nozzles by every 25.4mm, and it is fixed in 1/2 the nozzle mode at interval that staggers on two nozzle rows directions, instils 300 at the every 25.4mm of the orientation of substrate upper edge nozzle thus.

Shower nozzle and ink are controlled, made and in shower nozzle, carry out the warm water circulation, thereby reach 50 ± 0.5 ℃ near making the ejection part.

From shower nozzle ejection ink is to control by the piezoelectric drive signal that is applied on the shower nozzle, can reach every ejection 6～42pl, in the present embodiment, on one side below shower nozzle the 1mm position carry glass substrate, instil from shower nozzle on one side.Transfer rate can be set at 50～200mm/s.In addition, Piezoelectric Driving frequency maximum can reach 4.6kHz, can control dropped amount by these settings.

Control transfer rate, driving frequency make the coated weight of R, G, each pigment of B be respectively 1.1g/m ², 1.8g/m ², 0.75g/m ², and to desired R, G, B corresponding concave part in instil R, G, B ink.

The ink that instils is transported to exposed portion, utilizes ultraviolet light-emitting diode (UV-LED) to expose.That UV-LED uses is day NCCU033 (trade(brand)name) of inferior chemical society manufacturing.This LED is that output wavelength is the UV-light of 365nm from the wafer, by the electric current of about 500mA, can send the light of about 100mW from wafer.With a plurality of LED of being spaced of 7mm, can obtain 0.3W/cm from the teeth outwards ²Power.Can change according to the transfer rate of medium and shower nozzle and the distance of LED on throughput direction to the time of exposing and time shutter from the back of instiling.Drip fall behind in 100 ℃ dry 10 minutes down, expose then.

Setting according to distance and transfer rate can be adjusted to 0.01～15J/cm with the exposure energy on the medium ²Regulate exposure energy according to transfer rate.

In the mensuration of these exposure powers, exposure energy, the spectroradiometer URS-40D (trade(brand)name) that uses ウシオ motor society to make adopts the integrated value between the wavelength 220nm to 400nm.

Glass substrate after instiling was toasted 30 minutes in 230 ℃ baking oven, thereby make opacifying property next door, each pixel completely solidified simultaneously.

[making of liquid crystal indicator]

Use the colour filter (being referred to as colour filter 1) of above-mentioned making, make liquid crystal indicator, and estimate display characteristic.

(formation of ITO electrode)

The glass substrate that will be formed with colour filter is packed in the sputter equipment, 100 ℃ of comprehensive vacuum evaporations down

Behind the thick ITO (indium tin oxide), annealing made the ITO crystallization in 90 minutes under 240 ℃, formed ito transparent electrode.

(formation of dottle pin)

Adopt and [embodiment 1] of the TOHKEMY 2004-240335 communique middle identical method of putting down in writing of dottle pin formation method, on the ito transparent electrode of above-mentioned making, form dottle pin.

(being used to control the formation of the projection of liquid crystal aligning)

Use following positive-working photosensitive resin layer coating liquid, on the above-mentioned ito transparent electrode that is formed with dottle pin, be formed for controlling the projection of liquid crystal aligning.

But exposure, development and roasting procedure adopt following method.

Contiguous type exposure machine (manufacturing of the Ha イテ of Hitachi Network electronics エ Application ジニアリ Application グ Co., Ltd.) is installed, and making the photomask of regulation and the distance of photoresist laminar surface is 100 μ m, utilizes extra-high-pressure mercury vapour lamp with 150mJ/cm ²Irradiation energy see through this photomask and carry out the close induction type exposure.Then, use 2.38% tetramethylammonium hydroxide aqueous solution, under 33 ℃, sprayed 30 seconds, develop simultaneously to substrate by the spray-type developing apparatus.Removed by development thus and do not needed part (exposed portion) on the photo-sensitive resin, thereby obtained base plate for liquid crystal display device, wherein the colour filter side at this substrate has formed the projection that is used to control liquid crystal aligning that is made of the photo-sensitive resin that forms desired pattern form.

Then, the base plate for liquid crystal display device that will be formed with this projection that is used to control liquid crystal aligning is 230 ℃ of bakings 30 minutes down, thereby forms the projection that solidified is used to control liquid crystal aligning on base plate for liquid crystal display device.

＜positive-working photosensitive resin layer is filled a prescription with coating liquid 〉

Eurymeric resist liquid (FH-2413F that the Off イ of Fuji Le system エレ Network トロニ Network スマテリア Le ズ (strain) society makes) 53.3 mass parts

Methylethylketone 46.7 mass parts

メガ Off ア Star Network F-780F (big Japanese ink chemical industry (strain) society makes)

0.04 mass parts

(making of liquid crystal indicator)

The alignment films that is made of polyimide further is set on the base plate for liquid crystal display device of above-mentioned acquisition.

Then, the position that is equivalent to the black matrix housing around being arranged at, printing epoxy encapsulant in the mode of surrounding the color filter pixel group, the MVA pattern that instils simultaneously liquid crystal, and paste with opposing substrates, then the substrate after pasting is heat-treated, make sealant cures.On the two sides of the liquid crystal cells that obtains by this way, paste the polarization plate HLC2-2518 that (strain) サ Application リ Star Star society makes.Then, backlight by three-wavelength cold-cathode tube light source (FWL18EX-N that Toshiba's ライテ Star Network (strain) society makes) structure, it is installed in the rear side of the liquid crystal cells that is provided with above-mentioned polarization plate, form liquid crystal indicator 1.

Adopt with making colour filter 1 and liquid crystal indicator 1 identical method and make colour filter 2～9 and liquid crystal indicator 2～9, and estimate equally, difference is that the R ink 1 that will be adopted in the time of will making liquid crystal indicator 1 by colour filter 1 changes to R ink 2～9 respectively.

The evaluation of＜ink and liquid crystal indicator 〉

1-3 compares with comparative example, and the colour filter and the liquid crystal indicator that adopt ink-jet ink for color filter of the present invention to make have high contrast gradient.And when showing black, light leak is few, black density height.The result demonstrates the high power of describing.In addition, the contrast gradient measurement result of Ci Shi colour filter is shown in following table.

[table 2-D]

2. the liquid crystal indicator that adopts coloring photosensitive combination making CF and used CF

Pigment dispensing composition 1 is mixed with other composition, and forming the composition of following table 3-A, and the preparation colour filter is with photosensitive composition 1.

[table 3-A]

＜binding agent 2 〉

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid/methyl methacrylate=38/25/37 mol ratio, molecular weight 40,000) 27 mass parts

Propylene glycol monomethyl ether 73 mass parts

＜tensio-active agent 2 〉

Following works 130 mass parts

Methylethylketone 70 mass parts

[formula 17]

Works 1

(n＝6，x＝55，y＝5，Mw＝33940，Mw/Mn＝2.55，

PO: propylene oxide, EO: oxyethane)

Adopt method same as described above, prepare colour filter photosensitive composition 2～9 respectively, difference is, uses pigment dispensing composition 2～9 to replace pigment dispensing composition 1 respectively.

Adopt spin coater, above-mentioned making colour filter is coated on the glass substrate with coloring photosensitive combination A～N, drying is 2 minutes under 100 ℃, forms the film of the about 2 μ m of thickness.Adopt the method identical, the contrast gradient of the sample of mensuration made with embodiment 1.And, after disperseing 30 days, adopt method same as described above once more, be coated with above-mentioned coloring photosensitive combination A～N, and measure contrast gradient.According to this through the time contrast gradient and just made the contrast gradient that the back horse back is coated with mensuration, calculate through the time contrast gradient velocity of variation (through the time contrast gradient velocity of variation)=(initial stage contrast gradient)/(through the time contrast gradient).The results are shown in following table 3-B.

[table 3-B]

As show shown in the 3-B, to compare with duplicate 6～8, it is low that colour filter of the present invention has demonstrated the change of size rate that high contrast gradient, low contrast gradient velocity of variation and heat causes with photosensitive composition 1～5.

[making of colour filter (adopting the slit-shaped nozzle to make)] by applying

(formation of black (K) image)

Behind UV washing unit cleaning alkali-free glass substrate, use hairbrush to clean with clean-out system again, adopt ultrasonic wave to clean with ultrapure water again.After carrying out thermal treatment in 3 minutes under 120 ℃, make condition of surface stable this substrate.

After this substrate is cooled to 23 ℃, use has glass substrate coating machine (manufacturing of エ Off エ one エスアジア society, the trade(brand)name: MH-1600) will be coated on this substrate by the photosensitive composition K2 that is constituted that forms that puts down in writing among the following table 3-C of slit-shaped nozzle.Then with VCD (Minton dryer; Tokyo ying chemical industry (strain) society makes) dry 30 seconds, partial solvent drying and coating layer are no longer flowed after, 120 ℃ of following prebakes 3 minutes, obtaining film thickness was the photo-sensitive resin K2 of 2.4 μ m.In addition, the preparation method of photosensitive composition K2 is identical with the method for above-mentioned resin combination K1.

[table 3-C]

Employing has the contiguous type exposure machine (the Ha イテ of Hitachi Network electronics エ Application ジニアリ Application グ Co., Ltd. system) of extra-high-pressure mercury vapour lamp, make substrate keep the vertical state that stands up with mask (quartzy exposed mask) with picture pattern, with the distance setting of exposed mask face and this photoresist interlayer is 200 μ m, at 300mJ/cm ²Exposure under carry out pattern exposure.

Next, with spray spout pure water is sprayed, make the surface of this photo-sensitive resin K1 evenly wetting, use KOH class developing solution (to contain KOH, nonionic surface active agent then, trade(brand)name: CDK-1, the Off イ of Fuji Le system エレ Network トロニ Network スマテア Le ズ company makes) be that spray developed 80 seconds under the 0.04MPa at 23 ℃, the pressure of tack nozzle, obtain having the image of pattern.Next, under the pressure of 9.8MPa, spray ultrapure water, remove residue, obtain black (K) image K with the ultra-high voltage washing nozzle.Then 220 ℃ of following thermal treatments 30 minutes.

＜K colo(u)rant dispersion thing 2 〉

Carbon black (trade(brand)name: Nipex 35, デグサジヤパ Application (strain) society makes)

13.1 mass parts

Dispersion agent (following compound 2J) 0.65 mass parts

Propylene glycol monomethyl ether 79.53 mass parts

[formula 18]

＜binding agent 3 〉

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=78/22 mol ratio, molecular weight 3.8 ten thousand) 27 mass parts

Propylene glycol monomethyl ether 73 mass parts

(formation of red (R) pixel)

On the substrate that is formed with above-mentioned image K, use by the photosensitive composition R1 that is constituted that forms that puts down in writing among the following table 3-D, adopt and the identical operation of formation above-mentioned black (K) image, heat-treat the back and form pixel R.The thickness of this photo-sensitive resin R1 and the coated weight of pigment are as follows.In addition, the preparation method of photosensitive composition is identical with the method for above-mentioned photosensitive composition K2.

Photoresist thickness (μ m) 1.60

Pigment coated weight (g/m ²) 1.00

Coated weight (the g/m of C.I.P.R.254 ²) 0.80

Coated weight (the g/m of C.I.P.R.177 ²) 0.20

[table 3-D]

＜R pigment dispensing composition 1 〉

Pigment dispensing composition 1 (C.I.P.R.254) 11 mass parts of embodiment 1

Propylene glycol monomethyl ether 68.2 mass parts

＜R colo(u)rant dispersion thing 2 〉

C.I.P.R.177 (trade(brand)name: Cromophtal Red A2B, チバスペシヤ Le テイケミカ Le ズ (strain) society make) 18 mass parts

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio, molecular weight 30,000) 12 mass parts

Propylene glycol monomethyl ether 70 mass parts

(formation of green (G) pixel)

On the substrate that is formed with above-mentioned image K and pixel R, adopt photosensitive composition G1 with composition of putting down in writing among the following table 3-E, according to the identical operation of operation that forms above-mentioned black (K) image, after thermal treatment is finished, form pixel G.The thickness of this photo-sensitive resin G1 and the coated weight of pigment are as follows.In addition, the preparation method of photosensitive composition is identical with the method for above-mentioned photosensitive composition K2.

Photoresist thickness (μ m) 1.60

Pigment coated weight (g/m ²) 1.92

Coated weight (the g/m of C.I.P.G.36 ²) 1.34

Coated weight (the g/m of C.I.P.Y.150 ²) 0.58

[table 3-E]

G colo(u)rant dispersion thing 1 uses is the product of the commodity GT-2 by name that makes of the Off イ of Fuji Le system エレ Network トロニ Network スマテリア Le ズ (strain) society, and Y colo(u)rant dispersion thing 1 uses is the product of driving commodity CF イエロ one EX3393 by name that state's pigment (strain) society makes.

(formation of blue (B) pixel)

On the above-mentioned substrate that is formed with image K, pixel R and pixel G, employing has the photosensitive composition B1 of the composition of putting down in writing among the following table 3-F, according to the identical operation of operation that forms above-mentioned black (K) image, after thermal treatment is finished, form pixel B, thereby obtain target colour filter A.The thickness of this photo-sensitive resin B1 and the coated weight of pigment are as follows.The thickness of this photo-sensitive resin R1 and the coated weight of pigment are as follows.In addition, the preparation method of photosensitive composition is identical with the method for above-mentioned photosensitive composition K2.

Photoresist thickness (μ m) 1.60

Pigment coated weight (g/m ²) 0.75

Coated weight (the g/m of C.I.P.B.15:6 ²) 0.705

Coated weight (the g/m of C.I.P.V.23 ²) 0.045

[table 3-F]

What B colo(u)rant dispersion thing 1 used is the product of driving commodity CF Block Le one EX3357 by name of state's pigment (strain) society manufacturing.What B colo(u)rant dispersion thing 2 used is the product of driving commodity CF Block Le one EX3383 by name of state's pigment (strain) society manufacturing.

＜binding agent 4 〉

Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid/methyl methacrylate=36/22/42 mol ratio, molecular weight 3.8 ten thousand) 27 mass parts

Propylene glycol monomethyl ether 73 mass parts

Use color compositions 2～9 to replace color compositions 1 used in the R colo(u)rant dispersion thing 1 respectively, thus preparation R colo(u)rant dispersion thing 2～9.And, adopt the identical method of making method with above-mentioned colour filter 1, making colour filter 2～9, difference is, uses R colo(u)rant dispersion thing 2～9 to replace R colo(u)rant dispersion thing 1 respectively.

[making of liquid crystal indicator and evaluation]

Use colour filter 1～9 to make liquid crystal indicator, and estimate display characteristic.

(formation of ITO electrode)

Colour filter 1 is packed in the sputter equipment, 100 ℃ of comprehensive vacuum evaporations down

(formation of dottle pin)

But exposure, development and roasting procedure adopt following method.

Contiguous type exposure machine (manufacturing of the Ha イテ of Hitachi Network electronics エ Application ジニアリ Application グ Co., Ltd.) is installed, and making the photomask of regulation and the distance of photoresist laminar surface is 100 μ m, utilizes extra-high-pressure mercury vapour lamp with 150mJ/cm ²Irradiation energy see through this photomask and carry out the close induction type exposure.

Then, use 2.38% tetramethylammonium hydroxide aqueous solution, under 33 ℃, sprayed 30 seconds, develop simultaneously to substrate by the spray-type developing apparatus.Removed by development thus and do not needed part (exposed portion) on the photo-sensitive resin, thereby obtained base plate for liquid crystal display device, wherein the colour filter side at this substrate has formed the projection that is used to control liquid crystal aligning that is made of the photo-sensitive resin that forms desired pattern form.

Then, the base plate for liquid crystal display device that will be formed with this projection that is used to control liquid crystal aligning is 230 ℃ of bakings 30 minutes down, thereby in the projection that is used to control liquid crystal aligning that forms on the base plate for liquid crystal display device after solidifying.

Methylethylketone 46.7 mass parts

0.04 mass parts

(making of liquid crystal indicator)

[making of liquid crystal indicator and evaluation]

Take out base plate for liquid crystal display device from liquid crystal indicator 1, and the identical method of employing and embodiment 1, the mensuration contrast gradient.

Adopt and above-mentioned identical method, make liquid crystal indicator 2～9, and estimate according to identical method, difference is, colour filter 1 is changed to colour filter 2～9 respectively.It the results are shown in table 3-G.In addition, the contrast gradient of employed colour filter is shown in following table at this moment.

[table 3-G]

Shown in above-mentioned result, to compare with duplicate 6～8, colour filter 1～5 of the present invention demonstrates high contrast gradient.Colour filter of the present invention is the contrast gradient height, does not cause CR to reduce phenomenon, excellent colour filter by baking.

In addition, 1-3 compares with comparative example, and liquid crystal indicator of the present invention has high contrast gradient.And when showing black, light leak is few, black density height.The result shows the high power of describing.

On the other hand, the colour filter of comparative example is the sample that does not meet the demands on aspect the practicality, as have the low comparative example of contrast gradient (3-4), comparative example (1-4), contrast gradient and the colourity that can see precipitate changes big comparative example (2-4) etc.

(embodiment 10)

Use pigment green 36, Pigment green 58, pigment Blue 15 respectively: 6, Pigment blue 79, Pigment Yellow 73 185 replace the Pigment red 254 among the embodiment 1, have prepared

pigment dispensing composition

10,11,12,13,14 thus.The same with embodiment 1, measure the particle diameter of the pigment particle in the dispersion liquid that is obtained, the result, volume average particle size Mv and single dispersity (Mv/Mn) are respectively: pigment dispensing composition 10 is 15.6nm, 1.31, pigment dispensing composition 11 is 22.1nm, 1.23, pigment dispensing composition 12 is 24.8nm, 1.28, and pigment dispensing composition 13 is 19.1nm, 1.22, and pigment dispensing composition 14 is 25.6nm, 1.38.

Adopt the method identical with embodiment 1, the dispersion agent of measuring

pigment dispensing composition

10,11,12,13,14 wrap into rate, degree of crystallinity, contrast gradient, through the time contrast gradient changes, heat causes change of size, the dispersion agent that all as a result pigment dispensing compositions all demonstrate more than 10% wraps into rate, the degree of crystallinity more than 65%, and demonstrate high contrast gradient and low through the time contrast gradient velocity of variation and change of size rate that heat causes is low.On the other hand, use used pigment type in

pigment dispensing composition

10,11,12,13,14, adopt the method identical with comparative example 1, prepared the relatively color compositions of usefulness, but, to compare with the sample of the foregoing description, the change of size rate that heat causes rises significantly.

(embodiment 11)

The preparation of＜pigment dispensing composition 15 〉

[preparation of dispersible pigment dispersion]

Adopt with embodiment 1 in the identical method of preparation of pigment solution 1, preparation dispersible pigment dispersion 15, difference is, use methylsulfonic acid to replace the N-Methyl pyrrolidone and Tetramethylammonium hydroxide 25% aqueous solution, and use C.I. pigment Violet 23 (Hostaperm VioletRL-NF, Network ラリア Application ト society makes) to come replaced C .I. Pigment red 254.The same with embodiment 1, measure the particle diameter of the pigment particle in the resulting dispersion liquid, the result, volume average particle size Mv is 17.9nm, single dispersity (Mv/Mn) is 1.17.

The same with embodiment 1, the dispersion agent of measuring above-mentioned pigment dispensing composition 15 wrap into rate, degree of crystallinity, contrast gradient, through the time contrast gradient changes, heat causes change of size, all as a result pigment dispensing compositions all demonstrate dispersion agent more than 10% wrap into rate, the degree of crystallinity more than 65%, high-contrast and low through the time contrast gradient velocity of variation, and the change of size that heat causes is also lower.On the other hand, use pigment type used in pigment dispensing composition 15, adopt the method identical with comparative example 1, prepare the relatively color compositions of usefulness, still, compare with the sample of the foregoing description, the change of size rate that heat causes rises significantly.

Claims

1. the particulate of a water-insoluble compound, it is characterized in that, this particulate is embedded with dispersion agent, and this particulate is by mixing with poor solvent and generate water-insoluble compound being dissolved in the solution that forms in the good solvent, described hybrid mode is: (i) add dispersion agent in described good solvent and/or poor solvent, then with resulting two kinds of liquid mixing; Perhaps (ii) prepare in addition dispersion agent is dissolved in the good solvent and the solution that forms, the solution and the described poor solvent of formation are mixed together with above-mentioned water-insoluble compound is dissolved in the good solvent this solution then; Wherein, at least 10 quality % of the described dispersion agent of dissolved are embedded in the described particulate, and the degree of crystallinity of described particulate in dispersion medium is more than 65%.

2. the described particulate of claim 1 is characterized in that, median size is below the 100nm.

3. claim 1 or 2 described particulates is characterized in that, the crystallization particle diameter of the crystallising part of described particulate is 2～50nm.

4. claim 1 or 2 described particulates is characterized in that, described dispersion agent is that the matter average molecular weight is the macromolecule dispersing agent more than 1000.

5. claim 1 or 2 described particulates is characterized in that, described dispersion agent is the macromolecule dispersing agent that intramolecularly contains a heterocycle alkyl at least.

6. claim 1 or 2 described particulates, it is characterized in that, described dispersion agent is the macromolecule dispersing agent that has by aromatic nucleus and nitrogenous cyclic hydrocarbon radical and/or the structure division that quaternary ammonium group constituted, and this structure division can interact with described water-insoluble compound.

7. claim 1 or 2 described particulates is characterized in that, described water-insoluble compound is a pigment dyestuff.

8. microparticulate thing, it is characterized in that, its main component for claim 1 or 2 described microparticulate in the material that is selected from the organic solvent that is selected from by (a) aqueous medium, (b) in ester cpds solvent, ketone compound solvent and the alkylol cpd and (c) obtains at least a solvent in the group that reactive diluent constituted.

9. the described microparticulate thing of claim 8 is characterized in that, this dispersion thing is used to prepare resist or the ink that forms on base material.

10. colour filter, it is made by using the described microparticulate thing of claim 8.

11. preparation method who is embedded with dispersion agent and crystallized particulate, it is characterized in that, this particulate is by mixing with poor solvent and generate water-insoluble compound being dissolved in the solution that forms in the good solvent, described hybrid mode is: (i) add dispersion agent in described good solvent and/or poor solvent, then with resulting two kinds of liquid mixing; Perhaps (ii) prepare in addition dispersion agent is dissolved in the good solvent and the solution that forms, the solution and the described poor solvent of formation are mixed together with above-mentioned water-insoluble compound is dissolved in the good solvent this solution then; Wherein, at least 10 quality % of the described dispersion agent of dissolved are embedded in this particulate,

12. the preparation method of a microparticulate thing is characterized in that, preparation method according to claim 11 obtains the particulate of crystallization, and with the microparticulate of this crystallization in medium.