CN101302354A

CN101302354A - Preparation of pigment particle agglutination dispersion, resin composition and color filter

Info

Publication number: CN101302354A
Application number: CNA2008100818344A
Authority: CN
Inventors: 大元诚
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2007-05-08
Filing date: 2008-05-08
Publication date: 2008-11-12
Also published as: JP2008280391A; KR20080099208A; TW200904907A

Abstract

The invention provides a method of producing easily filtered agglutinin; wherein, for the procedure of producing temporary aqueous paste adopting purging operation as the represent when the organic nanoparticle aqueous dispersant is phase changed to form organic nanoparticle non-aqueous dispersant (that is: the procedure of adopting filter to need waste a lot of time), the invention converts the nanoparticle in the organic nanoparticle aqueous dispersant into easily filtered agglutinin. The invention provides a method of producing organic nanometer dye particle agglutinin; wherein the organic nanometer dye particle dispersed in the aqueous medium acts with at least an organic low molecular compound with molecular weight less than 1000 and at least an organic high molecular compound with weight average molar mass more than 1000 to agglutinate the organic nanometer dye particle and then separate.

Description

Pigment particle agglutination body, the method for making of disperseing thing, resin combination, and colour filter

Technical field

The present invention relates to a kind of thereby organic nano granules of pigments aqueous dispersion be carried out the preparation method that phase transition obtains the non-aqueous dispersion thing of organic nano granules of pigments to the non-aqueous media.More particularly, the present invention relates to a kind of like this method: will be difficult to all the time that organic nano granules of pigments in the filtering organic nano granules of pigments aqueous dispersion is converted into can easy filtering agglomeration, and separate this agglomeration by filter operation, and in non-aqueous media, make its redispersion, thereby obtain the non-aqueous dispersion thing of organic nano granules of pigments.

Background technology

People are carrying out reducing the research of particle size in recent years.Particularly, the purpose of research is to make granular size to be reduced to nano-scale (for example, the scope of 10nm～100nm), this by methods such as comminuting method, the precipitator method be difficult to produced.In addition, the purpose of research not only is to make particle have nanometer scale, and people are attempting making it to become the high particle of monodispersity (" monodispersity " is meant the uniformity coefficient of particle diameter among the present invention).

The size of this nano_scale particle is different from bigger macrobead, also be different from less molecule and atom, its size is between between the two, and it belongs to the field of the size that does not up to the present still have appearance, and this nano particle is considered to show the characteristic of beyond thought novelty.And, if can improve these particulate monodispersities, their characteristic is stablized, so the possibility that these nano particles possessed all obtains paying close attention in different fields, and in such as extensive fields such as biological chemistry, type material, electronic component, illuminated display element, printing, medical treatment they has been carried out a large amount of research.

Particularly, the organic nanometer granule of being made by organic compound is because organic compound itself has diversity, so it has great potential as functional materials.For example, polyimide has thermotolerance, solvent resistance, mechanical characteristics etc., is the material of a kind of chemically stable and mechanically stable, because it has excellent electrical insulating property etc., so utilized in numerous areas.With medlin particulateization, and after making the characteristic and combination of shapes of polyimide, can be used for field widely.For example, the someone proposes micronized polyimide with (referring to the patent documentations 1) such as additives that act in the powder toner that image forms.

In addition, in organic nanometer granule,, can enumerate and for example be used for coating, printing with ink, electrophoto-graphic toner, ink for ink-jet print and colour filter etc. with regard to pigment dyestuff.At present, this pigment dyestuff is indispensable important compound in our daily life.Wherein those require the pigment that pigment dyestuff high performance, particularly important in practicality for example has pigment that ink for ink-jet print uses and colour filter to use.

All the time, dyestuff is as the pigment of ink for ink-jet print, but dyestuff have problems aspect water tolerance and photostabilization, and in order to improve water tolerance and photostabilization, employing pigment is as pigment.The image that uses paint ink to obtain has such advantage: their photostabilization and water tolerance are better than the image that obtains with the dye class ink.Yet, owing to be difficult to obtain being penetrated into intrapore nanometer size and the pigment particle that have high monodispersity on paper surface, so exist the problem of image to the poor adhesion of paper.

In addition, along with the raising of the number of pixels of digital camera, more and more expect the thickness attenuation of colour filter used in optical elements such as ccd sensor or the display element.Though pigment dyestuff has been used for colour filter, the thickness of colour filter depends on the particle diameter of pigment dyestuff to a great extent, and therefore, people expect to prepare nano-scale and also have the particulate of stability when monodisperse status.

Preparation method about organic granular, people have studied following method: vapor phase process (makes the sample distillation under inert gas atmosphere, in substrate, reclaim the particulate method then), liquid phase method (for example, the agitation condition and the temperature of control poor solvent, to be dissolved in that sample in the good solvent is injected in this poor solvent and the reprecipitation method that obtains particulate) and laser ablation method (shine with laser it is ablated being scattered in sample in the solution, thereby make the method for fine particlesization) etc.In addition, the decentralized manufacturing example of the list with desired size that adopts these methods to prepare is also reported to some extent.Wherein, liquid phase method is as a kind of simple and have the method for preparing organic granular of excellent productivity and receive publicity (referring to patent documentation 2,3 etc.).The organic granular for preparing for adopting liquid phase method is separated out condition (solvent species, injection speed, temperature etc.) by adjusting, can adjust the character of its crystal formation and particle surface.In patent documentation 3, put down in writing by regulating the kind of poor solvent the example that the crystal formation of quinoline a word used for translation ketone pigment is adjusted.

On the one hand, with regard to the improvement of particles dispersed, all the time, the various dispersion machines of industrial employing (roller mill, ball mill, second reduction machine etc.) carry out the dispersion of pigment dyestuff, yet, owing to make particle generation miniaturization, so viscosity can raise sometimes.And if viscosity raises, then can produce following situation: product is difficult to take out from dispersion machine, can not carry and in storage gelation takes place and can not continue to use by pipeline.In order to address these problems, often add to help the dispersive dispersion agent or add to make to disperse to be able to stable polymer, but can not reach effect of sufficient (referring to non-patent literature 1 etc.).

In addition, the pigment dyestuff dispersion liquid of using for colour filter is in order to improve its dispersiveness, when making colour filter, need to add and to give the alkali-developable of this colour filter necessity and the polymkeric substance or the pigment dispersing agent (for example, referring to patent documentation 4) of these two kinds of character of dispersion stabilization.But, in these methods, owing to disperse and will expend time in, and factor such as viscosity rising, so be difficult to fully reach requirement.

In addition, having had bibliographical information uses according to the prepared granules of pigments of above-mentioned liquid phase method, the example that dispersiveness is improved.In patent documentation 5, reported and adopted liquid phase method to prepare the example of granules of pigments aqueous dispersion.But this method finally provides aqueous dispersion, and does not mention any method that organic solvent dispersion can be provided.

Patent documentation 6 has been reported and has been used according to the prepared granules of pigments of liquid phase method, the example of organic solvent dispersion is provided.In patent documentation 6, reported such method: pigment dissolved in basic cpd and/or basic solution, is added liquid neutral compound and/or acidic cpd then, and perhaps neutral liquid and/or acidic liquid are so that pigment is separated out.But, adopt the primary granule particle diameter of the organic pigment particle that this method obtains big, can not fully satisfy micronized requirement.

In above-mentioned liquid phase method, when carrying out the preparation of nano particle,, need to use low-molecular-weight surfactant or neutral water-soluble nonionic type macromolecular compound in order to prevent nano particle generation aggegation.Therefore, there is such shortcoming: even can under the high density condition, make nano particle obtain disperseing, but must use a large amount of dispersing auxiliaries, so in the extremely low situation of the containing ratio of and macromolecular compound low in the viscosity such as ink for ink-jet print, above-mentioned these technology are difficult to direct application.In addition, known have such irrigation, this method is: can be with its phase transition such requirement to another solvent system in order to satisfy after making the nano particle of water-based, need make the water-based soup compound or the water-based mashed prod of the pigment that contains high density, then to wherein adding resin or resin solution, and mix and stir, thereby the moisture around the pigment is replaced by resin or resin solution.But, when adopting this method, there is such problem: because the water-based particle will be through the so together form of aggegation consumingly quickly, so the deterioration of efficiency that pigment is surrounded by resin in the method, and be difficult to redispersion (for example, referring to patent documentation 7～8 etc.).In addition, when adopting such method, in order to make the mashed prod of water-based, the nano dye particle of the water-based state with primary granule directly need be filtered with strainer or filters with strainer with the state after the aggegation, but there is such problem in this method: need expend a large amount of time during filtration, this industrial be very inefficent, and the operation very numerous and diverse.In addition, also can use low molecular anionic or cationic surfactant as dispersion agent, yet owing to be low molecule, so there is the inadequate problem of dispersion stabilization.Therefore, the someone attempts using such method: do not carry out the operation of water-based particle filtration, but adopt the cationic macromolecular compound, make granules of pigments phase transition (for example, referring to non-patent literature 2) to ionic liquid.But, the method that non-patent literature 2 is put down in writing is only limited to the inorganic particle of lower concentration, does not mention pigment dyestuff in non-patent literature 2, and, final dispersion medium is the ionic liquid of non-volatility, so the method for record in the non-patent literature 2 is unsuitable for the industry use.

[patent documentation 1] Japanese kokai publication hei 11-237760 communique

[patent documentation 2] Japanese kokai publication hei 6-79168 communique

[patent documentation 3] TOHKEMY 2004-91560 communique

[patent documentation 4] TOHKEMY 2000-239554 communique

[patent documentation 5] TOHKEMY 2004-43776 communique

[patent documentation 6] TOHKEMY 2004-123853 communique

[patent documentation 7] Japanese kokai publication hei 5-301037 communique

[patent documentation 8] Japanese kokai publication hei 6-161154 communique

[non-patent literature 1] colo(u)rant dispersion Ji Intraoperative-surface treatment と dispersion agent makes い side お I び Fen San Evaluation value-Ji Intraoperative Qing Reported Association meeting 1999

[non-patent literature 2] small, 2006, Vol.2, No.7, p.879-883

Summary of the invention

The problem that invention will solve

In view of above-mentioned problem, the manufacture method that the purpose of this invention is to provide the non-aqueous dispersion thing of a kind of organic nano granules of pigments, this manufacture method is: for make that organic nano granules of pigments aqueous dispersion carries out being adopted when phase transition forms the non-aqueous dispersion thing of organic nano dye particle with the irrigation be the such operation of the temporary water-based mashed prod of preparation of representative (, employing strainer filtration etc. need expend such complicated procedures of forming of plenty of time), the inventive method is converted into the nano dye particle in the organic nano granules of pigments aqueous dispersion can easy filtering agglomeration, isolate this agglomeration, and with its redispersion in non-aqueous media, thereby can obtain the non-aqueous dispersion thing of organic nano granules of pigments expeditiously.In addition, the present invention also aims to provide photosensitive composition that uses the formation of above-mentioned organic nano granules of pigments dispersion thing and the colour filter of making by this photosensitive composition.

The means of dealing with problems

The inventor has carried out deep research, found that: the solution that is dissolved with organic low molecular compounds and organic high molecular compound by adding, can make the organic nano pigment particle agglutination that is scattered in the aqueous medium is easy filtering agglomeration, isolate this agglomeration, and with its redispersion in non-aqueous media, thereby can obtain the non-aqueous dispersion thing of organic nano granules of pigments expeditiously.Finish the present invention based on above discovery.

Above-mentioned problem is reached by following means:

(1) a kind of manufacture method of organic nano pigment particle agglutination body, it is characterized in that, organic low molecular compounds by making the organic nano granules of pigments that is scattered in the aqueous medium and at least a molecular weight less than 1000 and at least a weight-average molecular weight are that the organic high molecular compound more than 1000 is had an effect, make described organic nano pigment particle agglutination, separate then.

(2) manufacture method of above-mentioned (1) described organic nano pigment particle agglutination body, it is characterized in that, with described organic low molecular compounds and organic high molecular compound with can with described aqueous medium blended dissolution with solvents mutually, join then in this aqueous medium, make the organic nano pigment particle agglutination that is scattered in the aqueous medium thus.

(3) manufacture method of above-mentioned (1) or (2) described organic nano pigment particle agglutination body is characterized in that described separation is undertaken by filtration.

(4) manufacture method of any described organic nano pigment particle agglutination body in above-mentioned (1) to (3) is characterized in that, this manufacture method comprises the operation of removing to the unnecessary described organic low molecular compounds of major general.

(5) manufacture method of any described organic nano pigment particle agglutination body in above-mentioned (1) to (4), it is characterized in that, the pigment dyestuff solution that pigment dyestuff is dissolved in the good solvent and obtains with can be miscible and for the medium of the poor solvent of described pigment dyestuff mixes mutually with this good solvent, thereby obtain the organic nano granules of pigments in the described aqueous medium of being scattered in the form generation of nanometer sized particles.

(6) manufacture method of any described organic nano pigment particle agglutination body in above-mentioned (1) to (5) is characterized in that the average primary particle diameter of described organic nano granules of pigments is below the 100nm.

(7) manufacture method of any described organic nano pigment particle agglutination body in above-mentioned (1) to (6) is characterized in that the median size of described agglomeration is more than the 10000nm.

(8) manufacture method of the non-aqueous dispersion thing of a kind of organic nano granules of pigments, it is characterized in that, after any described organic nano pigment particle agglutination body redispersion in above-mentioned (1) to (7) of separating is in non-aqueous media, obtain the non-aqueous dispersion thing of this organic nano granules of pigments.

(9) manufacture method of any non-aqueous dispersion thing of described organic nano granules of pigments in above-mentioned (1) to (8) is characterized in that, described organic high molecular compound such as following general formula (11) or general formula (14) are represented,

General formula (11)

In the above-mentioned general formula (11), A ¹Expression has the 1 valency organic group that the group, urea groups, urethano, the group of band coordination Sauerstoffatom, the carbon number that are selected from acidic-group, have basic nitrogen atom are the group in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl 4 or more, or represents to contain that substituent organic pigment structure or heterocyclic 1 valency organic group can be arranged.N A ¹Can be identical, also can be different.R ¹The linking group of expression (m+n) valency.M+n represents 3～10, and m represents 1～8 integer, and n represents 2～9 integer.R ²The linking group of expression singly-bound or divalent.P ¹Expression polymer residue.

General formula (14)

In the above-mentioned general formula (14), G ^-Expression-COO ^-,-SO ₃ ^-,-OSO ₃ ^-,-P (O) is O (OH) ^-, or-(OH) O of OP (O) ^-J represents the linking group or the singly-bound of divalent.Q represents the linking group of (m+1) valency.R represents the macromolecular compound residue.Z ⁺Expression organic or inorganic positively charged ion.M+1 represents 3～6.

(10) manufacture method of the non-aqueous dispersion thing of above-mentioned (9) described organic nano granules of pigments is characterized in that, described organic high molecular compound is directly as the dispersion agent in the described non-aqueous media.

(11) a kind of photosensitive composition, it contains the non-aqueous dispersion thing of above-mentioned (9) or (10) described organic nano granules of pigments (that is, adopting the non-aqueous dispersion thing of organic nano granules of pigments (perhaps agglomeration) of above-mentioned (9) or (10) described method preparation), binding agent, monomer or oligopolymer and Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system at least.

(12) a kind of colour filter is characterized in that, this colour filter is to use above-mentioned (11) described photosensitive composition to make.

The invention effect

Manufacturing method according to the invention can be made organic nano pigment particle agglutination body by organic nano granules of pigments aqueous dispersion effectively.In addition, by using this organic nano pigment particle agglutination body, can at an easy rate its phase transition be made its depolymerization (redispersion) to non-aqueous media, thereby can make the non-aqueous dispersion thing of organic nano granules of pigments efficiently with technical scale.Manufacturing method according to the invention can be applicable to that the organic nano granules of pigments of colour filter coating liquid or ink for ink-jet print disperses thing and dispersion liquid thereof with industrial-scale production.In addition, the non-aqueous dispersion thing of organic nano granules of pigments of the present invention has excellent dispersiveness, high contrast gradient, uses the colour filter of the non-aqueous dispersion thing preparation of this organic nano granules of pigments to have achieve the goal required purity of color and high contrast gradient.

Preferred forms of the present invention

Below the manufacture method of organic nano granules of pigments of the present invention is described.

[pigment dyestuff]

For employed pigment dyestuff in the manufacture method of organic nano granules of pigments of the present invention and without particular limitation, as long as it can form particle by liquid phase method, can be used alone, also can use multiple combination back.

For pigment dyestuff, there is not the restriction of tone.Can enumerate example as perylene, perylene ketone, quinoline a word used for translation ketone, quinoline a word used for translation ketone quinone, anthraquinone, three benzopyrene diketone, benzimidazolone, disazo condensation thing, tetrazo, azo, indanthrene, phthalocyanine, triaryl carbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrolecocrystals, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or their mixture etc.

More particularly, can enumerate for example C.I. Pigment red 190 (C.I. sequence number 71140), C.I. Pigment red 224 (C.I. sequence number 71127), C.I. pigment violet 29 (pigment such as compound such as perylene such as C.I. sequence number 71129) Deng, C.I. pigment orange 43 (C.I. sequence number 71105), or C.I. Pigment red 194 (C.I. sequence number 71100) perylene ketone compound pigment, C.I. pigment violet 19 (C.I. sequence number 73900), C.I. pigment violet 42, C.I. pigment red 122 (C.I. sequence number 73915), C.I. Pigment red 192, C.I. Pigment red 202 (C.I. sequence number 73907), C.I. Pigment Red 207 (C.I. sequence number 73900,73906), or C.I. Pigment red 209 quinoline a word used for translation ketone compound pigment such as (C.I. sequence numbers 73905), C.I. Pigment red 206 (C.I. sequence number 73900/73920), C.I. pigment orange 48 (C.I. sequence number 73900/73920), or C.I. pigment orange 49 quinoline a word used for translation ketone naphtoquinone compounds pigment such as (C.I. sequence numbers 73900/73920), C.I. pigment yellow 147 anthraquinone compounds pigment such as (C.I. sequence numbers 60645), C.I. Pigment red 168 three benzopyrene dione compounds pigment such as (C.I. sequence numbers 59300), C.I. pigment brown 25 (C.I. sequence number 12510), C.I. pigment violet 32 (C.I. sequence number 12517), C.I. Pigment Yellow 73 180 (C.I. sequence number 21290), C.I. Pigment Yellow 73 181 (C.I. sequence number 11777), C.I. pigment orange 62 (C.I. sequence number 11775), or C.I. Pigment red 185 benzimidazolone compound pigment such as (C.I. sequence numbers 12516), C.I. Pigment Yellow 73 93 (C.I. sequence number 20710), C.I. Pigment Yellow 73 94 (C.I. sequence number 20038), C.I. Pigment Yellow 73 95 (C.I. sequence number 20034), C.I. pigment Yellow 12 8 (C.I. sequence number 20037), C.I. Pigment Yellow 73 166 (C.I. sequence number 20035), C.I. pigment orange 34 (C.I. sequence number 21115), C.I. pigment Orange 13 (C.I. sequence number 21110), C.I. pigment orange 31 (C.I. sequence number 20050), C.I. Pigment red 144 (C.I. sequence number 20735), C.I. Pigment red 166 (C.I. sequence number 20730), C.I. Pigment red 220 (C.I. sequence number 20055), C.I. Pigment red 221 (C.I. sequence number 20065), C.I. Pigment red 242 (C.I. sequence number 20067), C.I. Pigment red 248, C.I. Pigment red 262, or C.I. pigment brown 23 disazo condensation compound pigment such as (C.I. sequence numbers 20060), C.I. pigment yellow 13 (C.I. sequence number 21100), C.I. pigment yellow 83 (C.I. sequence number 21108), or C.I. Pigment Yellow 73 188 tetrazo compound pigment such as (C.I. sequence numbers 21094), C.I. Pigment red 187 (C.I. sequence number 12486), C.I. Pigment red 170 (C.I. sequence number 12475), C.I. Pigment Yellow 73 74 (C.I. sequence number 11714), C.I. Pigment Yellow 73 150 (C.I. sequence number 48545), C.I. pigment red 48 (C.I. sequence number 15865), C.I. Pigment red 53 (C.I. sequence number 15585), C.I. pigment orange 64 (C.I. sequence number 12760), or C.I. Pigment red 247 azo-compound pigment such as (C.I. sequence numbers 15915), C.I. pigment blue 60 indanthrene compound pigment such as (C.I. sequence numbers 69800), C.I. pigment Green 7 (C.I. sequence number 74260), C.I. pigment green 36 (C.I. sequence number 74265), C.I. Pigment green 37 (C.I. sequence number 74255), C.I. pigment blue 16 (C.I. sequence number 74100), C.I. Pigment blue 75 (C.I. sequence number 74160:2), or 15 phthalocyanine compound pigment such as (C.I. sequence numbers 74160), C.I. Pigment blue 56 (C.I. sequence number 42800), or C.I. pigment Blue-61 triaryl carbonium compound pigment such as (C.I. sequence number 42765:1), C.I. pigment Violet 23 (C.I. sequence number 51319), or C.I. pigment violet 37 (C.I. sequence number 51345) dioxazine compound pigment, C.I. Pigment red 177 aminoanthraquinone compound pigment such as (C.I. sequence numbers 65300), C.I. Pigment red 254 (C.I. sequence number 56110), C.I. Pigment red 255 (C.I. sequence number 561050), C.I. Pigment red 264, C.I. Pigment red 272 (C.I. sequence number 561150), C.I. pigment orange 71, or diketopyrrolo-pyrrole compound pigment such as C.I. pigment orange 73, C.I. pigment Red 88 thioindigo compound pigment such as (C.I. sequence numbers 73312), C.I. pigment yellow 13 9 (C.I. sequence number 56298), C.I. pigment orange 66 isoindoline compounds pigment such as (C.I. sequence numbers 48210), C.I. Pigment Yellow 73 109 (C.I. sequence number 56284), or C.I. pigment orange 61 isoindoline ketone compound pigment such as (C.I. sequence numbers 11295), C.I. pigment orange 40 (C.I. sequence number 59700), or C.I. pigment red 21 6 pyranthrone compound pigment such as (C.I. sequence numbers 59710), or C.I. pigment violet 31 isoviolanthrone compound pigment such as (C.I. sequence numbers 60010).Wherein preferred quinoline a word used for translation ketone compound pigment, Diketopyrrolo-pyrrole compounds pigment, dioxazine compound pigment, phthalocyanine compound pigment or azo-compound pigment, more preferably Diketopyrrolo-pyrrole compounds pigment Huo dioxazine compound pigment.

With C.I.P.R.254,255,264 is the absorption region that the pyrrolopyrrole compound pigment of representative has the purity of color that is suitable for improving the red pixel that constitutes colour filter, can enlarge the color reproduction zone, is therefore attempted being used for colour filter.But pigment does not in the past satisfy the requirement of purity of color and contrast gradient etc.For example, adopt the ink for ink-jet print put down in writing in the TOHKEMY 2003-336001 communique, by microballon disperses or salt mill method obtains material etc., can not obtain good colour filter.

Manufacturing method according to the invention can be with the pyrrolopyrrole compound pigment particle of the sharp-pointed state acquisition nano-scale of size distribution.In addition, when this pigment particle is used for colour filter, can satisfy the purity of color that reaches expectation and the requirement of high-contrast simultaneously, and the photostabilization excellence, the generation of precipitate can also be suppressed in addition.

In the present invention, also can use solid solution or its combination of two or more pigment dyestuffs, pigment dyestuff.

[preparation of organic nano granules of pigments aqueous liquid dispersion]

Preparation method to organic nano granules of pigments aqueous liquid dispersion describes below.

In the present invention, the organic nano granules of pigments be by pigment dyestuff is dissolved in the pigment dyestuff solution that forms in the good solvent with have for above-mentioned good solvent compatibility, for pigment dyestuff be poor solvent solvent (below, sometimes also this solvent is called by " poor solvent of pigment dyestuff ", or abbreviate " poor solvent " as) mix and generate (below, sometimes also this method is called " reprecipitation method ", also the dispersion liquid that contains organic nanometer granule that obtains this moment is called " organic nano granules of pigments redeposition liquid " sometimes).

There is no particular limitation to the poor solvent of pigment dyestuff, if its can with the miscible or uniform mixing of good solvent of dissolving pigment dyestuff.As the poor solvent of this pigment dyestuff, preferred pigment dyestuff solubleness therein is below the 0.02 quality %, more preferably below the 0.01 quality %.Do not have special lower limit for the solubleness of pigment dyestuff in poor solvent, yet consider normally used pigment dyestuff, the lower limit of solubleness is actually more than the 0.000001 quality %.This solubleness also can be the solubleness when dissolving in the presence of acid or alkali are arranged.In addition, the compatibility of good solvent and poor solvent or uniform mixing are meant that the meltage of good solvent in poor solvent is preferably more than the 30 quality %, more preferably more than the 50 quality %.Do not have special ceiling restriction for the meltage of good solvent in poor solvent, in fact can mix with arbitrary proportion.

Have no particular limits for poor solvent, so long as aqueous medium gets final product.For example, (for example can enumerate aqueous solvent, water, or hydrochloric acid, aqueous sodium hydroxide solution), the alcohol compound solvent, the ketone compounds solvent, the ether compound solvent, aromatic compound solvent, the dithiocarbonic anhydride solvent, the fatty compounds solvent, the nitrile compounds solvent, the halogen contained compound solvent, the ester compound solvent, ionic liquid, their mixed solvent etc., be preferably aqueous solvent, the alcohol compound solvent, the ketone compounds solvent, the ether compound solvent, the ester compound solvent, or their mixture, more preferably aqueous solvent, alcohol compound solvent or ester compound solvent.

As the alcohol compound solvent, for example can enumerate methyl alcohol, ethanol, Virahol, n-propyl alcohol, 1-methoxyl group-2-propyl alcohol etc.As the ketone compounds solvent, for example can enumerate acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone.As the ether compound solvent, for example can enumerate dme, Anaesthetie Ether, tetrahydrofuran (THF) etc.As aromatic compound solvent, for example can enumerate benzene, toluene etc.As the fatty compounds solvent, for example can enumerate hexane etc.As the nitrile compounds solvent, for example can enumerate acetonitrile etc.As the halogen contained compound solvent, for example can enumerate methylene dichloride, trieline etc.As the ester compound solvent, for example can enumerate vinyl acetic monomer, ethyl lactate, 2-(1-methoxyl group) propyl group acetic ester etc.As ionic liquid, for example can enumerate 1-butyl-3-Methylimidazole and PF ₆ ^-Salt etc.

Below the good solvent that is dissolved with machine pigment is described.

Good solvent is had no particular limits, as long as can dissolve employed pigment dyestuff, and can be with above-mentioned poor solvent miscible or uniform mixing get final product.For the solvability of pigment dyestuff in good solvent, preferred pigment dyestuff solubleness therein is more than the 0.2 quality %, more preferably more than the 0.5 quality %.Do not have special ceiling restriction for the solubleness of pigment dyestuff in good solvent, yet consider normally used pigment dyestuff, in fact upper solubility limit is below the 50 quality %.This solubleness also can be the solubleness when dissolving in the presence of acid or alkali are arranged.The compatibility of poor solvent and good solvent or the preferable range of uniform mixing are as previously mentioned.

As good solvent, for example (for example can enumerate aqueous solvent, water, or hydrochloric acid, aqueous sodium hydroxide solution), the alcohol compound solvent, the amides solvent, the ketone compounds solvent, the ether compound solvent, aromatic compound solvent, the dithiocarbonic anhydride solvent, the fatty compounds solvent, the nitrile compounds solvent, the sulfoxide compound solvent, the halogen contained compound solvent, the ester compound solvent, ionic liquid, carboxylic acid cpd, sulfoacid compound, sulfuric acid, their mixed solvent etc., preferred aqueous solvent, the alcohol compound solvent, the ketone compounds solvent, the ether compound solvent, the sulfoxide compound solvent, the ester compound solvent, the amides solvent, carboxylic acid cpd, sulfoacid compound, sulfuric acid, or their mixture, more preferably aqueous solvent, the alcohol compound solvent, the ester compound solvent, the sulfoxide compound solvent, the amides solvent, carboxylic acid cpd, sulfoacid compound, sulfuric acid, preferred especially sulfoxide compound solvent, the amides solvent, carboxylic acid cpd, sulfoacid compound, sulfuric acid.

As the sulfoxide compound solvent, for example can enumerate dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexa-methylene sulfoxide, tetramethylene sulfone etc.As the amides solvent, for example can enumerate 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, hexamethyl phosphoric triamide etc.

A certain solvent is good solvent or poor solvent, depends on the kind as the pigment dyestuff of object.In the present invention, for a certain pigment dyestuff, good solvent and poor solvent can not be with a kind of compound.

In addition, as the concentration that pigment dyestuff is dissolved in the pigment dyestuff solution that forms in the good solvent, preferably its scope be under the condition in when dissolving pigment dyestuff for the saturation concentration of good solvent to about 1/100 of this saturation concentration.

Preparation condition to pigment dyestuff solution is not particularly limited, 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.

In the present invention, though pigment dyestuff must be dissolved in the good solvent equably, also preferably under acidity or alkaline condition, dissolve.Usually, adopt intramolecularly have can be at dissociative group under the alkaline condition pigment the time use alkaline condition, do not use acidic conditions when dissociative group under the alkaline condition and intramolecularly have a large amount of nitrogen-atoms that is easy to the addition proton and do not exist in.For example, quinoline a word used for translation ketone compounds pigment, diketopyrrolopyrroles compound pigment, disazo condensation thing compounds pigment dissolve under alkaline condition, and phthalocyanine-like compound pigment dissolves under acidic conditions.

The alkali that uses when dissolving under alkaline condition is mineral alkalis such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide or hydrated barta, or organic basess such as trialkylamine, diazabicyclo hendecene (DBU), metal alkoxide, but preferred mineral alkali.

The amount of the alkali that uses is the amount that can make the pigment uniform dissolution, this amount is had no particular limits, but under the situation of using mineral alkali, be 1.0～30 molar equivalents preferably with respect to organic materials, more preferably 1.0～25 molar equivalents, more preferably 1.0～20 molar equivalents.Using under the situation of organic bases, be 1.0～100 molar equivalents preferably with respect to organic materials, more preferably 5.0～100 molar equivalents, more preferably 20～100 molar equivalents.

The acid of using when dissolving under acidic conditions is mineral acids such as sulfuric acid, hydrochloric acid or phosphoric acid, perhaps organic acids such as acetic acid, trifluoracetic acid, oxalic acid, methylsulfonic acid or trifluoromethanesulfonic acid, but preferred mineral acid.Special preferably sulfuric acid.

To use the amount of acid be the amount that can make the pigment dyestuff uniform dissolution, this amount is had no particular limits, but compares often excessive use with alkali.No matter be to use mineral acid or organic acid, be 3～500 molar equivalents preferably with respect to organic materials, more preferably 10～500 molar equivalents, more preferably 30～200 molar equivalents.

When alkali or acid are mixed the back as the good solvent use of pigment dyestuff with organic solvent, dissolve fully, can in organic solvent, add some water or lower alcohol etc. alkali or sour solvent with high-dissolvability in order to make alkali or acid.The amount of preferably water or lower alcohol is below the 50 quality % with respect to the organic material solution total amount, more preferably below the 30 quality %.Specifically, can make water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols etc.

There is no particular limitation for the condition at the poor solvent of preparation during organic granular (, separate out, when forming organic granular), can select from normal pressure to scope subcritical, super critical condition.Temperature under the normal pressure is preferably-30～100 ℃, more preferably-10～60 ℃, is preferably 0～30 ℃ especially.

When pigment dyestuff solution mixes with poor solvent, can mix by any one of adding among both, mix but preferably pigment dyestuff solution is added in the poor solvent, this moment, preferred poor solvent kept whipped state.Stirring velocity is preferably 100rpm～10000rpm, and more preferably 150rpm～8000rpm is preferably 200rpm～6000rpm especially.Can use during interpolation, also can not use equipment such as pump.In addition, can in liquid, submergence add, also can outside liquid, add, but more preferably submergence interpolation in liquid.The ratio of mixture of pigment dyestuff solution and poor solvent (ratio of the good solvent/poor solvent in the organic nano granules of pigments redeposition liquid) is preferably 1/50～2/3 by volume, and more preferably 1/40～1/2, be preferably 1/20～3/8 especially.In the present invention, at first the organic nano granules of pigments is scattered in the aqueous medium, aqueous medium used herein is preferably the medium of the above-mentioned aqueous solvent that contains 80 quality % for containing the medium of the above-mentioned aqueous solvent of 60 quality % at least.

There is no particular limitation to the concentration of organic nano granules of pigments redeposition liquid, as long as can generate the organic nano granules of pigments, but preferably with respect to the 1000ml aqueous medium, organic pigment particle is 10～40000mg, more preferably 20～30000mg is preferably 50～25000mg especially.

In addition, the preparative-scale during to generation organic nano granules of pigments is not particularly limited, and the combined amount of preferred poor solvent is the preparative-scale of 10～1000L, more preferably the preparative-scale of 1～100L.

Particle diameter about the organic nano granules of pigments, quantize and the method for expression group mean sizes thereby have by 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 pigment dyestuff nano particle (primary granule) is a nano-scale, and preferred median size is 1nm～1 μ m, 1～200nm more preferably, and more preferably 2～100nm is preferably 5～80nm especially.Also have, in the present invention, formed particle can be a crystal grain, also can be the amorphous particle, or their mixture.

In addition, as the index of expression particle monodispersity, short of in the present invention specifying, the ratio (Mv/Mn) of use volume average particle size (Mv) and number average bead diameter (Mn).The monodispersity of contained particle (primary granule) in the organic nano granules of pigments dispersion liquid that in the concentration method of organic nano granules of pigments, uses, 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 nano granules of pigments, can enumerate microscopy, mass method, light scattering method, light and block method, electrical resistance method, acoustic method, dynamic light scattering method, preferred especially microscopy, dynamic light scattering method.As the microscope that uses in the microscopy, for example can enumerate scanning electronic microscope, transmission electron microscope etc.As the particle determinator that utilizes light scattering method, for example can enumerate ダイ Na ミ Star Network light-scattering photometer DLS-7000 series, the hole field of Na ノトラッ Network UPA-EX 150, Otsuka Electronics Co., Ltd. manufacturing of Nikkiso Company Limited's manufacturing and make (being trade(brand)name) such as LB-400 that Co., Ltd. of institute makes.

When preparation organic nano granules of pigments aqueous liquid dispersion, preferably make and wherein contain the dispersion agent dispersion agent of aqueous liquid dispersion (below be also referred to as).To the operation that described dispersion liquid contains dispersion agent is not particularly limited, preferably in both or a side of pigment dyestuff solution and poor solvent, adds dispersion agent and it is contained.In addition, also preferably when forming organic nano dye particle, utilize the system interpolation dispersant solution different with above-mentioned two kinds of liquid.Also preferred the use carried out the surface-treated granules of pigments with dispersion agent in advance, also can carry out promoting the surface treatment of dispersant adsorption to granules of pigments.Dispersion agent has following effect: (1) is adsorbed on the surface of pigments of separating out quickly, forms fine nano particle, and (2) prevent that these particles from aggegation taking place again.

As operable dispersion agent, for example can use the low molecule or the macromolecule dispersing agent of anionic, cationic, amphoteric ion type, non-ionic type or pigment derivative.In addition, with respect to the amount of institute's dissolved pigment, the addition of low molecule or macromolecule dispersing agent be preferably 10 quality % above, below the 1000 quality %, more preferably 50 quality % above, below the 200 quality %.If this addition is very few, sometimes suppress the growth and the agglutinative deleterious of granules of pigments, and if this addition is too much, problems such as viscosity rises, dissolving is bad sometimes take place.

Below macromolecule dispersing agent is described.

Preferred its number-average molecular weight of the molecular weight of macromolecule dispersing agent is more than 1,000, below 200,000, more preferably more than 3,000, below 40,000.If this molecular weight is too small, sometimes suppress the growth and the agglutinative deleterious of granules of pigments, and if this molecular weight is excessive, problems such as viscosity rises, dissolving is bad sometimes take place.In addition, the polymer among the present invention is meant that number-average molecular weight is the compound more than 1,000.

In the macromolecule dispersing agent, as the non-ionic type macromolecule dispersing agent, specifically can enumerate part butyralization thing, vinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide/propylene oxide segmented copolymer of part formalizing thing, the polyvinyl alcohol of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyoxyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol etc.Preferably polyethylene pyrrolidone wherein.

As the anionic macromolecule dispersing agent, can enumerate polyacrylate, polyvinyl vitriol, poly-(4-vinylpridine) salt, polymeric amide, PAH salt, polyphenyl sulfonate, condensation naphthalenesulfonate, derivatived cellulose, starch derivative etc.Wherein, more preferably polyphenyl sulfonate, condensation naphthalenesulfonate.

Though these anionic macromolecule dispersing agents can obtain by anionic monomer generation copolyreaction, whether but, also can obtain by anionic monomer and nonionic monomers generation copolyreaction only with by anionic monomer generation copolyreaction itself and obtain this anionic macromolecule dispersing agent.As the monomer of non-ionic type, specifically can enumerate vinyl pyrrolidone, vinylbenzene, naphthalene, styryl methyl chloride, vinyl imidazole, vinyl pyridine, acrylamide, vinylamide etc.

As the cationic high-molecular dispersion agent, the macromolecular compound that especially preferably has quaternary ammonium group can be enumerated poly-(methacryloxy alkylammonium salt), poly-(methacryloxy aryl ammonium salt), poly-(acryloxyalkyl ammonium salt), poly-(acryloxy aryl ammonium salt), poly-(diallyl ammonium salt) etc.As macromolecular compound, be preferably macromolecular compound with the represented cationic repeating unit of following general formula (I) with quaternary ammonium group.

General formula (1)

(in the formula, R ₁～R ₃Represent alkyl, aralkyl or aryl independently of one another.R ₁, R ₂, R ₃In any two can be interconnection, and can further form the heterocycle that contains Sauerstoffatom, nitrogen-atoms and/or sulphur atom.X represents halogen atom or organic or inorganic negatively charged ion.N represents 1～5 natural number.A represents hydrogen atom or alkyl.L represent singly-bound or divalent linking group or expression further with R ₁, R ₂, R ₃In any two 4 valency linking groups that are connected)

In general formula (1), R ₁～R ₃Represented alkyl is 1～12 alkyl for replacing or unsubstituted straight chain, side chain or cyclic alkyl, being preferably carbon number, and more preferably carbon number is 1～4 alkyl.R ₁～R ₃Represented aralkyl is 7～10 aralkyl for replacing or unsubstituted aralkyl, being preferably carbon number.R ₁～R ₃Represented aryl is 6～10 aryl for replacing or unsubstituted aryl, being preferably carbon number.Aralkyl or aryl can be respectively monocycles, also can be condensed ring.

As described alkyl, specifically, be preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl group, uncle's octyl group, 2-ethylhexyl, decyl, dodecyl.Be preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl especially.

As described aralkyl, specifically, be preferably benzyl, 4-benzyl chloride base, 4-methyl-benzyl, 4-butoxy benzyl, 4-methoxybenzyl p-methoxy-phenyl, 4-hydroxybenzyl.Be preferably benzyl, 4-benzyl chloride base, 4-methyl-benzyl, 4-butoxy benzyl especially.

As described aryl, specifically, be preferably phenyl, 4-chloro-phenyl-, 4-aminomethyl phenyl, 4-butoxy phenyl, 4-p-methoxy-phenyl, 4-hydroxy phenyl.Be preferably phenyl, 4-chloro-phenyl-, 4-aminomethyl phenyl, 4-butoxy phenyl especially.

At R ₁, R ₂, R ₃In any two interconnection and form and to have in the nitrogenous heterocyclic situation of quaternary ammonium group, this heterocycle is preferably 4～6 yuan of rings.In addition, this heterocycle can also further contain Sauerstoffatom, nitrogen-atoms and/or sulphur atom.As described heterocycle, can enumerate imidazoles, pyridine, oxazole, thiazole, tetrahydroglyoxaline, oxazoline, thiazoline etc.More preferably imidazoles, pyridine, oxazole, thiazole.

In general formula (1), X can be 1 valency group, also can be the multivalence group.The represented halogen atom of X is fluorine atom, chlorine atom, bromine atoms, iodine atom.The object lesson of the organic anion that X is represented has carboxylate anion, sulfonic acid anion, alkoxyl group negatively charged ion, Phenylsulfonic acid negatively charged ion, naphthene sulfonic acid negatively charged ion, naphthalene disulfonic acid negatively charged ion, anthracene sulfonic acid negatively charged ion etc.The object lesson of the inorganic anion that X is represented has tetrafluoride bromine anions, phosphorus hexafluoride negatively charged ion, hydroxide ion etc.Particularly preferably be, satisfy n and be the organic or inorganic negatively charged ion of 1～2 natural condition.

In general formula (1),, specifically, be preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl as the represented alkyl of A.Be preferably methyl, ethyl especially.

In general formula (1), L represents singly-bound or divalent linking group, perhaps the expression further with R ₁, R ₂, R ₃In any two 4 valency linking groups that are connected.The represented divalent linking group of L is the linking group that contains aryl or aralkyl.The aryl or aralkyl that contains in the represented divalent linking group of L can also can be condensed ring for monocycle.What L was represented goes back and R ₁, R ₂, R ₃In any two 4 valency linking groups of being connected form quaternary ammonium salt group and heterocyclic radical in the general formulas (1).

As the object lesson of the represented divalent linking group of L, wherein aryl can be enumerated phenylene, naphthylidene etc., and aralkyl can be enumerated phenylmethylene, naphthyl methylene radical etc.What L was represented goes back and R ₁, R ₂, R ₃In any two 4 valency linking groups of being connected form quaternary ammonium salt group and heterocyclic radical in the general formulas (1), the example can be enumerated imidazoles, pyridine, oxazole, thiazole, tetrahydroglyoxaline, oxazoline, thiazoline etc.More preferably imidazoles, pyridine, oxazole, thiazole.

What illustrate below is the example with macromolecular compound of the represented cationic repeating unit of above-mentioned general formula (1), wherein also comprises R ₁, R ₂, R ₃In the heterocyclic object lesson that contains Sauerstoffatom, nitrogen-atoms and/or sulphur atom of any two interconnection and further formation.For example, polyvinyl imidazol quinoline salt, polyvinyl benzimidazoline salt, the polyvinylpyridine salt, polystyrene methylene imidazole salt, polystyrene methylene imidazoline salt class, polystyrene methylene pyridinium salt class, polystyrene methylene oxazole salt, polystyrene-based Ya Jia oxazolin salt, polystyrene methylene thiazole salt class, polystyrene methylene thiazoline salt, polystyrene methylene ammonium salt class, poly-naphthyl methylene radical imidazole salt, poly-naphthyl methylene radical tetrahydroglyoxaline salt, poly-naphthyl methylene radical pyridine salt, poly-naphthalene methylene oxazole salt, poly-naphthyl Ya Jia oxazolin salt, poly-naphthyl methylene radical thiazole salt, poly-naphthyl methylene radical thiazoline salt, poly-naphthyl methylene radical ammonium salt class.

Wherein, as more preferred example, can enumerate polystyrene methylene imidazole salt, polystyrene methylene imidazoline salt class, polystyrene methylene pyridinium salt class, polystyrene methylene oxazole salt, polystyrene-based inferior first oxazolin salt, polystyrene methylene thiazole salt class, polystyrene methylene thiazoline salt, polystyrene methylene ammonium salt class.

The macromolecular compound that contains quaternary ammonium group that uses among the present invention more preferably has the macromolecular compound of the represented cationic repeating unit of following general formula (2).

General formula (2)

In general formula (2), R ₁～R ₃, X and n meaning respectively with general formula (1) in R ₁～R ₃, the same meaning represented of X and n, its preferable range is also identical.

In addition, the macromolecular compound that contains quaternary ammonium group that uses among the present invention also can be by represented cationic repeating unit of above-mentioned general formula (1) and other the random copolymers that repeating unit constituted.The polymerization ratio is, with respect to the above-mentioned macromolecular compound that contains quaternary ammonium group, preferably makes this other repeating unit copolymerization of 0.1～0.7 quality %, more preferably makes this other repeating unit copolymerization of 0.1～0.5 quality %.

As the copolymerization component, for example can enumerate vinyl imidazole quinoline salt, vinyl benzo imidazoline salt class, the vinyl pyridine salt, styryl methylene radical imidazole salt, styryl methylene radical tetrahydroglyoxaline salt, styryl methylene radical pyridine salt, vinylbenzene methylene oxazole salt, styryl Ya Jia oxazolin salt, styryl methylene radical thiazole salt, styryl methylene radical thiazoline salt, styryl methylene radical ammonium salt class, naphthyl methylene radical imidazole salt, naphthyl methylene radical tetrahydroglyoxaline salt, naphthyl methylene radical pyridine salt, naphthalene methylene oxazole salt, naphthyl Ya Jia oxazolin salt, naphthyl methylene radical thiazole salt, naphthyl methylene radical thiazoline salt, naphthyl methylene radical ammonium salt class, vinyl pyrrolidone, vinylbenzene, naphthalene, the styryl methyl chloride, vinyl imidazole, vinyl pyridine, acrylamide, vinylamide etc.Special optimization styrene methylene imidazole salt, styryl methylene radical tetrahydroglyoxaline salt, styryl methylene radical pyridine salt, styryl methylene radical ammonium salt class, vinyl pyrrolidone, vinylbenzene, naphthalene, styryl methyl chloride, vinyl imidazole, vinyl pyridine, acrylamide, vinylamide etc.

The employed object lesson that contains the macromolecular compound of quaternary ammonium group among the present invention is shown below, but the present invention is not limited to this.In the object lesson below, employed macromolecular compound is to obtain after the shown repeating unit polymerization among the present invention.

The above-mentioned macromolecular compound that contains quaternary ammonium group can be with reference to " small ", and 2006, Vol.2, No.7, p.879～883 the method in prepares.

In addition, also can use natural high moleculer eompounds such as alginate, gelatin, albumin, casein, Sudan Gum-arabic, tragacanth gum, sulfonated lignin.

These macromolecular compounds can be used alone, and also can be used in combination.These dispersion agents can use separately, also can share.The dispersion agent that uses during about colo(u)rant dispersion is documented in 29～46 pages of " colo(u)rant dispersion stabilization and process for treating surface evaluation " (chemical corps intelligence association, distribution in December calendar year 2001).

Below low dispersal agent molecule is described.

As the low dispersal agent molecule of anionic, can enumerate N-acyl-N-alkyltaurate, soap, alkyl sulfuric ester salt, alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl sulfosuccinates, alkyl phosphate salt, naphthalene sulfonic acidformaldehyde condensation product, polyxyethylated sulfuric acid etc.Wherein, preferred N-acyl-N-alkyltaurate.As the N-acyl-N-alkyltaurate, preferably be recorded in the Japanese kokai publication hei 3-273067 specification sheets those.These anionic dispersing agents can be used alone or in combination of two or more kinds.

As cationic low dispersal agent molecule, comprise quaternary ammonium salt, alkoxylate polyamines, fatty amine polyglycol ether, fatty amine, by fatty amine and fatty alcohol deutero-diamines and polyamines, by the tetrahydroglyoxaline of fatty acid derived and the salt of these cationic materials.These cationic dispersing agents can be used alone or in combination of two or more kinds.

The amphoteric ion type dispersion agent is that intramolecularly has the cation radical dispersion agent partly that contains in the anion-radicals part that contains in the above-mentioned anionic dispersing agent molecule and the cationic dispersing agent molecule simultaneously.

As non-ionic dispersing 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, preferred polyoxyethylene alkylaryl ether.These non-ionic dispersing agents can be used alone or in combination of two or more kinds.

Pigment derivative type dispersion agent is defined as by as the pigment dyestuff deutero-of parent material, carry out the pigment derivative type dispersion agent that chemically modified prepares by this precursor structure, or the pigment derivative type dispersion agent that is formed through the pigmenting reaction by the pigment precursors of chemically modified.For example have and contain sugared pigment derivative type dispersion agent, contain piperidyl pigment derivative type dispersion agent Nai Huo perylene deutero-pigment derivative type dispersion agent, has the pigment derivative type dispersion agent that is connected the structural functional group of pigment matrix by methylene radical, have the pigment matrix structure and the sulfonic pigment derivative type dispersion agent that have carried out chemically modified with polymkeric substance, pigment derivative type dispersion agent with sulfoamido, pigment derivative type dispersion agent with ether, or has a pigment derivative type dispersion agent of carboxylic acid group or carboxylic acid ester groups or carboxamide groups.

In the present invention, in good solvent, dissolve and when making pigment dyestuff solution, the preferred existence simultaneously contains amino pigment dispersing agent.Here, amino comprises primary amine groups, secondary amino group, uncle's amino, and amino number can be 1, also can be for a plurality of.Containing amino pigment dispersing agent as this, can be to import the pigment derivative compound that forms behind the substituting group that contains amino on the pigment skeleton, also can be by containing amino monomer as aggregating into the polymer compound that branch forms.As their example, for example can enumerate the compound put down in writing in TOHKEMY 2000-239554 communique, 2003-96329 communique, 2001-31885 communique, Japanese kokai publication hei 10-339949 communique, the special open 5-72943 communique of Japan etc., but be not limited to these compounds.

[organic low molecular compounds and organic high molecular compound]

In the present invention, thereby organic low molecular compounds by making the organic nano granules of pigments that is scattered in the aqueous medium and at least a molecular weight less than 1000 (below be also referred to as " low molecular compound ") and at least a weight-average molecular weight are the organic high molecular compound (below be also referred to as " macromolecular compound ") more than 1000 have an effect and make the organic nano pigment particle agglutination, isolate the organic nanometer granule agglomeration then.In the present invention, low molecular compound can make the organic nano granules of pigments condense.Macromolecular compound can make the concrement generation aggegation that generates by condensing, thereby forms filtering big agglomeration easily.In the present invention, use low molecular compound and macromolecular compound simultaneously,,, can not form big agglomeration,, then can pass filter paper if use filter paper filtering though the organic nano granules of pigments is condensed if only use low molecular compound; If filter with strainer, then can spend a large amount of time.In addition, if only use macromolecular compound,, thereby just can not filter owing to concrement itself can generate hardly.For the macromolecular compound among the present invention, because being dispersed with the aqueous solvent of organic nano granules of pigments is poor solvent, by this macromolecular compound is adsorbed on the above-mentioned concrement, make the polarity of concrement become and be insoluble in the above-mentioned aqueous solvent, thereby make this concrement be grown to big agglomeration.

As described agglomeration, preferably its median size is more than the 10000nm, and median size is big more preferred more.This median size does not have the special upper limit, but is actually below the 10000000nm.If the median size of agglomeration is too small, need the plenty of time when separating agglomeration so, and if when filtering out these agglomeratioies, sometimes agglomeration may pass filter paper or strainer, perhaps stops up filter paper or strainer.If the median size of agglomeration is excessive, need such problem of plenty of time when sometimes redispersion taking place.

In addition, because low molecular compound among the present invention and macromolecular compound are adsorbed on the organic nano granules of pigments after the aggegation, even so carried out filtration, washing described later, redispersion described later (dispergation) afterwards, since these low molecular compounds and macromolecular compound still can be directly as the dispersion agent in the non-aqueous media (below be also referred to as " dispersion agent of non-aqueous dispersion "), so needn't add new dispersion agent again.In order to regulate dispersiveness, though also can after above-mentioned operation, add new dispersion agent again, consider from the aspect of manufacturing cost, preferably do not add new dispersion agent.

In addition, owing to constitute the organic nano granules of pigments of agglomeration among the present invention is under by the state of low molecular compound and macromolecular compound coating aggegation to take place, so with the agglutinative situation takes place under the condition that does not have these low molecular compounds and macromolecular compound (for example, make organic nano granules of pigments generation aggegation by hydrochloric acid etc.) compare, follow-up redispersion is easier, and the organic nano granules of pigments separately forms primary granule easily, and contrast gradient improves.

Although this low molecular compound and macromolecular compound can directly add with the form of itself, consider from the viewpoint that obtains good filterableness, preferably low molecular compound and macromolecular compound are dissolved in interpolation more afterwards in the solvent.

Have no particular limits for above-mentioned solvent, as long as this solvent can be mixed with organic nano granules of pigments aqueous liquid dispersion, and can dissolve this low molecular compound and macromolecular compound, and after adding this low molecular compound and macromolecular compound itself are separated out to get final product.

In addition, this solvent is preferably such solvent: even this solvent itself is added in the organic nano granules of pigments aqueous liquid dispersion, can not make organic nano granules of pigments generation aggegation yet, even aggegation has perhaps taken place, generation also be can redispersion weak aggegation (not pulverizing or high shear forces such as stirring also can redispersion fast throw out) even do not apply.

As this solvent, for example (for example can enumerate aqueous solvent, water, or hydrochloric acid, aqueous sodium hydroxide solution), the alcohol compound solvent, the amides solvent, the ketone compounds solvent, the ether compound solvent, aromatic compound solvent, the dithiocarbonic anhydride solvent, the fatty compounds solvent, the nitrile compounds solvent, the sulfoxide compound solvent, the halogen contained compound solvent, the ester compound solvent, ionic liquid and their mixed solvent etc., preferred aqueous solvent, the alcohol compound solvent, the ketone compounds solvent, the ether compound solvent, the sulfoxide compound solvent, the ester compound solvent, the amides solvent, nitrile compounds solvent or their mixture, particularly, more preferably ketone compounds solvent, the ether compound solvent, nitrile compounds solvent or their mixture.

Usage quantity for this solvent has no particular limits, as long as this usage quantity can make low molecular compound and macromolecular compound dissolving, and can form and to get final product by easy filtering agglomeration, consider the fussy degree of manufacturing and material cost is further reduced, preferably this usage quantity will be lacked as much as possible.Represent that with mass ratio as 100 o'clock, the amount of the solvent that is added was preferably 1～100 with the amount of organic nano granules of pigments aqueous liquid dispersion, more preferably 10～70, be preferably 20～70 especially.When usage quantity was too much, the sedimentation of agglomeration sometimes needed the plenty of time, and usage quantity sometimes can not form agglomeration fully, and agglomeration is difficult to sedimentation when very few.

After adding this solvent,, preferably stir in order to make itself and organic nano granules of pigments aqueous liquid dispersion thorough mixing.Mix and to use usual method.Temperature when mixing behind this solvent adding has no particular limits, and is preferably 1～100 ℃, more preferably 5～60 ℃.For interpolation, the mixing of this solvent, just can use any device as long as can implement each operation satisfactorily, for example can use devices such as agitating vane, ラモ Application De agitator to carry out.

In addition, as mentioned above, among the present invention, during organic nano granules of pigments generation aggegation in making organic nano granules of pigments aqueous liquid dispersion, can make in the organic nano granules of pigments aqueous liquid dispersion by other approach and contain low molecular compound of the present invention and macromolecular compound.For the operation that contains low molecular compound of the present invention and macromolecular compound in the organic nano granules of pigments aqueous liquid dispersion is had no particular limits, can adopt following method: after adding in the organic nano granules of pigments aqueous liquid dispersion, again low molecular compound of the present invention and macromolecular compound are added together to above-mentioned solvent; After being dissolved in low molecular compound of the present invention and macromolecular compound in the above-mentioned solvent, again it is added in the organic nano granules of pigments aqueous liquid dispersion; Wherein more preferably, adopt be dissolved in low molecular compound of the present invention and macromolecular compound in the above-mentioned solvent after, add the method in the organic nano granules of pigments aqueous liquid dispersion again to.In addition, in this case, can add low molecular compound and macromolecular compound respectively, can adopt following method: earlier macromolecular compound is dissolved in the above-mentioned solvent, then it is added in the organic nano granules of pigments aqueous liquid dispersion, afterwards, directly add low molecular compound again; Earlier low molecular compound is added in the organic nano granules of pigments aqueous liquid dispersion, afterwards, add the solution that is dissolved with macromolecular compound again.

In addition, the addition of low molecular compound and macromolecular compound, the 10 quality % that are preferably pigment are above, below the 1000 quality %, more preferably 50 quality % above, below the 200 quality %.If addition is very few, the aggegation deleterious of nano particle sometimes, and if addition is too much, when the redispersion that aftermentioned is carried out, sometimes be easy to generate problems such as viscosity rising.Ratio to the addition of low molecular compound and macromolecular compound has no particular limits, and represents that with mass ratio if the addition of macromolecular compound was made as, the addition of low molecular compound is preferably 1～50 at 1 o'clock, and more preferably 10～30.

Below organic low molecular compounds is elaborated.

As organic low molecular compounds, for example can enumerate the low molecular compound of anionic, cationic or non-ionic type.As employed low molecular compound, can select according to the dispersion agent kind of employed aqueous liquid dispersion when the above-mentioned organic nano granules of pigments aqueous liquid dispersion of preparation.For example, the dispersion agent of aqueous liquid dispersion is non-ionic type (when particularly having alkalescence), and described low molecular compound is preferably non-ionic type (particularly having acidity); When the dispersion agent of aqueous liquid dispersion was anionic, described low molecular compound was preferably cationic; When the dispersion agent of aqueous liquid dispersion was cationic, described low molecular compound was preferably anionic.Wherein, preferably, the dispersion agent of aqueous liquid dispersion is non-ionic type (particularly having alkalescence), and described low molecular compound is non-ionic type (particularly having acidity), more preferably, the dispersion agent of aqueous liquid dispersion is cationic, and described low molecular compound is an anionic.

There is no particular limitation for the low molecular compound of non-ionic type, as long as its molecular weight less than 1000, the organic low molecular compounds of special preferred acidic, in this acidity organic low molecular compounds, preferred carboxylic acid, sulfonic acid, phosphate cpd more than 1 yuan, preferred especially 1～5 yuan carboxylic acid, sulfonic acid, phosphate cpd.

As described carboxylic acid, specifically, can enumerate formic acid, acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, isopropylformic acid, 2 Ethylbutanoic acid, pivalic, tertiary butyl acetic acid, the 2-Valproic acid, 2 ethyl hexanoic acid, propanedioic acid, butyl malonic acid, dimethyl malonic acid, diethyl malonic acid, Succinic Acid, pentanedioic acid, the third front three carboxylic acid, 1,2,3, the 4-BTCA, suitable-5,8,11,14, the 17-timnodonic acid, suitable-4,7,10,13,16, the 19-docosahexenoic acid, M-nitro benzoic acid, toluylic acid, 11-phenoxy group undeeanoic acid, phenylmalonic acid etc.

As sulfonic acid, specifically, can enumerate methylsulfonic acid, N-cyclohexyl-2-aminoethyl sulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid, Phenylsulfonic acid etc.

As phosphoric acid, specifically, can enumerate diformazan phosphonic acids, methylenediphosphonate (MDP) etc.

Low molecular compound for anionic has no particular limits, as long as its molecular weight less than 1000.The anionic compound that the preferred following general formula of described anionic compound (3) is represented.

General formula (3)

Y ^+-D-E

(in the formula, D represents-COO ^-,-SO ₃ ^-,-OSO ₃ ^-,-P (O) is O (OH) ^-Or-(OH) O of OP (O) ^-It is 10～100 alkyl, aralkyl, aryl or alkoxyl group that E represents to have substituent total carbon number.Y represents the positively charged ion of organic or inorganic)

In general formula (3), D represents-COO ^-,-SO ₃ ^-,-OSO ₃ ^-,-P (O) is O (OH) ^-, or-(OH) O of OP (O) ^-, be preferably-SO ₃ ^-,-P (O) is O (OH) ^-

In general formula (3), it is 10～100 alkyl, aralkyl, aryl or alkoxyl group that E represents to have substituent total carbon number, is preferably that can to have substituent total carbon number be 20～50 alkyl, aralkyl, aryl or alkoxyl group.Alkyl, alkoxyl group or substituting group can be respectively straight chains, also can be side chain; Aryl or aralkyl can be respectively monocycles, also can be condensed ring.

As described alkyl, specifically can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl group, uncle's octyl group, 2-ethylhexyl, decyl, dodecyl, octadecyl etc.Be preferably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, amyl group, cyclopentyl, hexyl, cyclohexyl, heptyl.

As described aralkyl, specifically can enumerate benzyl, naphthyl methylene radical.Be preferably benzyl especially.

As described aryl, specifically can enumerate phenyl, naphthyl.Be preferably phenyl especially.

As described alkoxyl group, specifically can enumerate methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, heptan oxygen base, octyloxy, uncle's octyloxy, 2-ethyl hexyl oxy, last of the ten Heavenly stems oxygen base, dodecyloxy, octadecane oxygen base.Be preferably methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy.

In general formula (3),, can enumerate imidazole salt, pyridine salt, thiazole salt, oxazole salt, tetrahydroglyoxaline salt, thiazoline salt, oxazoline salt etc. as the represented organic cation of Y.For the ease of follow-up desalination, preferably use inorganic cation, as described inorganic cation, can enumerate lithium ion, sodium ion, potassium ion etc.

Below, show the represented anionic compound object lesson of above-mentioned general formula (3), but be not limited thereto.

The molecular weight of these low molecular compounds needs only less than 1000 and just can.If molecular weight surpasses 1000, these low molecular compounds will show the character of macromolecular compound, thereby are difficult to make nano particle to condense.There is no particular limitation to the lower value of this molecular weight, is generally more than 40.

Below macromolecular compound is elaborated.

The same with low molecular compound, as embodiment preferred, the dispersion agent of organic nano granules of pigments aqueous liquid dispersion is a non-ionic type, particularly have alkalescence, and macromolecular compound is preferably non-ionic type, particularly has acidity; The dispersion agent of aqueous liquid dispersion is cationic, and macromolecular compound is preferably anionic.In the present invention, the weight-average molecular weight of macromolecular compound is preferably more than 1000.This weight-average molecular weight does not have special ceiling restriction, but is preferably below 3000000, more preferably below 300000.As the object lesson of the known macromolecular compound that uses among the present invention, can enumerate " the Disperbyk-110 (multipolymer that contains acidic-group); 130 (polymeric amide); 161; 162; 163; 164 that BYK Chemie society makes, 165,166,170 (high-molecular copolymers) "; " BYK-P104, P105 (high-molecular weight unsaturated polyester carboxylic acid) "; " EFKA4047 that EFKA society makes, 4050,4010,4165 (polyurethaness), EFKA4330,4340 (segmented copolymers), 4400,4402 (polyacrylic ester of modification), 5010 (polyesteramides), 5765 (high-molecular weight polycarboxylates), 6220 (fatty acid polyesters) "; " アジスパ-PB821 that monosodium glutamate Off ア Application テ Network ノ society makes, PB822 "; be total to " Off ロ one レ Application TG-710 (oligourethane) " that chemistry society of Sakae society makes; " Port リ Off ロ one No.50E, No.300 (acrylic copolymer) "; nanmu originally changes into " the デイスパロ Application KS-860 that society makes, 873SN, 874, #2150 (aliphatics polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725 "; " the デモ one Le RN that Hua Wangshe makes, N (naphthalene sulfonic acidformaldehyde condensation product), MS, C, SN-B (aromatic sulphonic acid formaldehyde condensation products) "; " ホモゲノ one Le L-18 (polymeric polycarboxylic acid) "; " エマ Le ゲ Application 920,930,935,985 (polyoxyethylene nonylplenyl ethers) "; " アセミ Application 86 (stearyl amine acetates) "; " ソ Le スパ one ス 55000 (graft type polymer) that Le one Block リゾ one Le society makes, 13240 (polyesteramines), 3000,17000,27000 (end has the polymer of funtion part), 24000,28000,32000,38500 (graft type polymers) "; " the ニ Star コ one Le T106 (polyoxyethylene sorbitan monoleate) that daylight ケミカ Le society makes, MYS-IEX (polyoxyl 40 stearate) " etc.As the macromolecular compound among the present invention, these known macromolecular compounds can be used alone, and also can be used in combination.In addition, these known macromolecular compounds also can share with the macromolecular compound described later more than a kind, in addition, also can use macromolecular compound described later separately.

Below the macromolecular compound of non-ionic type is illustrated in greater detail.

The macromolecular compound of non-ionic type is preferably the represented macromolecular compound of following general formula (11).

General formula (11)

In above-mentioned general formula (11), A ¹Expression has 1 valency organic group of the group of selecting from acidic-group, the group that has basic nitrogen atom, urea groups, urethano, the group of band coordination Sauerstoffatom, carbon number are alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and hydroxyl 4 or more, or represents to contain that substituent organic pigment structure or heterocyclic 1 valency organic group can be arranged.N A ¹Can be identical, also can be different.

Specifically, though to A ¹Have no particular limits, but as above-mentioned " 1 valency organic group " with acidic-group, can enumerate for example have the carboxylic acid group, the 1 valency organic group of sulfonic group, sulfate mono ester group, phosphate, phosplate base, boronate etc.In addition, as above-mentioned " 1 valency organic group ", can enumerate and for example have amino (NH with the group that has basic nitrogen atom ₂) 1 valency organic group, have substituted imine base (NHR ⁸,-NR ⁹R ¹⁰) 1 valency organic group (wherein, R ⁸, R ⁹And R ¹⁰Independent respectively expression carbon number is that 1～20 alkyl, carbon number are that the aryl below 20 6 or more, carbon number are the aralkyl below 30 more than 7), have the guanidine radicals that following general formula (a1) represents 1 valency organic group [in the general formula (a1), R ^A1, R ^A2Independent respectively expression carbon number is that 1～20 alkyl, carbon number are that the aryl below 20 6 or more, carbon number are the aralkyl below 30 more than 7], have the amidino groups that following general formula (a2) represents 1 valency organic group [in the general formula (a2), R ^A3, R ^A4Independence expression carbon number is that 1～20 alkyl, carbon number are that the aryl below 20 more than 6, carbon number are the aralkyl below 30 more than 7 respectively] etc.

As above-mentioned " 1 valency organic group ", for example can enumerate-NHCONHR with urea groups ¹⁵(wherein, R ¹⁵Expression hydrogen atom, carbon number are that 1～20 alkyl, carbon number are that the aryl below 20 more than 6, carbon number are the aralkyl below 30 more than 7) etc.

As above-mentioned " 1 valency organic group ", for example can enumerate-NHCOOR with urethano ¹⁶,-OCONHR ¹⁷(wherein, R ¹⁶And R ¹⁷Carbon number is that 1～20 alkyl, carbon number are that the aryl below 20 more than 6, carbon number are the aralkyl below 30 more than 7 independently respectively) etc.

As above-mentioned " 1 valency organic group ", for example can enumerate the group with acetylacetonate group, group etc. with crown ether with ' group of band coordination Sauerstoffatom '.

As above-mentioned " having the group that carbon number is the alkyl more than 4 ", can enumerate carbon number and be more than 4 alkyl (for example, octyl group, dodecyl etc.), carbon number is that aryl (for example, phenyl, naphthyl etc.), carbon number more than 6 is aralkyl (for example, benzyl etc.) more than 7 etc.The carbon number of this moment does not have the upper limit, but is preferably below 30.As above-mentioned " group ", for example can enumerate group with trimethoxysilyl, triethoxysilyl etc. with alkoxysilyl.

As above-mentioned " group ", for example can enumerate group with glycidyl etc. with epoxy group(ing).

As above-mentioned " group ", for example can enumerate 3-isocyanato-propyl group etc. with isocyanate group.

As above-mentioned " group ", for example can enumerate 3-hydroxypropyl etc. with hydroxyl.

In foregoing, as above-mentioned A ¹, preferably those have the 1 valency organic group that the group, urea groups and the carbon number that are selected from acidic-group, have basic nitrogen atom are the group in the alkyl more than 4.

In addition, above-mentioned organic pigment structure or heterocycle are not particularly limited, more particularly, as the organic pigment structure, can enumerate for example phthalocyanine compound, insoluble azo-compound, azo lake compound, anthraquinone compounds, quinoline a word used for translation ketone compound, dioxazine compound, Diketopyrrolo-pyrrole compounds, anthracene pyridine compounds, anthanthrone (anthanthrone) compound, indanthrene compound, yellow anthrone compound, perylene ketone compound, perylene compound, thioindigo compound etc.In addition, as heterocycle, for example can enumerate thiophene, furans, xanthene, 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, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, anthraquinone etc.

In addition, above-mentioned organic pigment structure or heterocycle can have substituting group, as this substituting group, can enumerate carbon number such as methyl, ethyl for example and be 1～20 alkyl, carbon number such as phenyl, naphthyl is 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, and carbon numbers such as methoxyl group, oxyethyl group are 1～6 alkoxyl group, halogen atom such as chlorine, bromine, carbon numbers such as methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl are 2～7 carbalkoxy, cyano group, carbonate groups such as the carbonic acid tert-butyl ester etc.

In addition, as above-mentioned A ¹, be preferably the 1 valency organic group that following general formula (4) is represented.

General formula (4)

In above-mentioned general formula (4), B ¹The group that expression is selected from acidic-group, the group that has basic nitrogen atom, urea groups, urethano, the group with coordination Sauerstoffatom, carbon number are alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and hydroxyl more than 4, or expression can have substituent organic pigment structure or heterocycle, R ¹⁸The organic or inorganic linking group of expression singly-bound or a1 valency.A1 represents 1～5, a1 B ¹Can be identical, also can be different.

B in the general formula (4) ¹With above-mentioned A ¹Synonym, preferred scheme is also identical, but as above-mentioned organic pigment structure or heterocycle, can enumerate for example phthalocyanine compound, insoluble azo-compound, the azo lake compound, anthraquinone compounds, quinoline a word used for translation ketone compound dioxazine compound, Diketopyrrolo-pyrrole compounds, the anthracene pyridine compounds, anthanthrone (anthanthrone) compound, the indanthrene compound, yellow anthrone compound perylene ketone compound perylene compound, organic pigment structures such as thioindigo compound, for example 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, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, heterocycles such as anthraquinone.

R ¹⁸The linking group of expression singly-bound or a1+1 valency.A1 represents 1～5.As linking group R ¹⁸, comprise by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 Sauerstoffatom, 1～200 hydrogen atom, and the group that constitutes of 0～20 sulphur atom can unsubstituteds, also can have substituting group.R ¹⁸Be preferably organic linking group.

As R ¹⁸Object lesson, the group that can enumerate following structural unit or combine by following structural unit.

Wherein, R ¹⁸When having substituting group,, can enumerate carbon number such as methyl, ethyl for example and be 1～20 alkyl as this substituting group, carbon number such as phenyl, naphthyl is 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, carbon number such as methoxyl group, oxyethyl group is 1～6 alkoxyl group, and halogen atoms such as chlorine, bromine, carbon numbers such as methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl are 2～7 carbalkoxy, cyano group, carbonate groups such as the carbonic acid tert-butyl ester etc.

In above-mentioned general formula (11), R ¹The linking group of expression (m+n) valency.M+n equals 3～10.

As above-mentioned R ¹The linking group of (m+n) valency of expression comprises by 1～100 carbon atom, 0～10 nitrogen-atoms, and 0～50 Sauerstoffatom, 1～200 hydrogen atom, and 0～20 group that sulphur atom constitutes can unsubstituteds, also can have substituting group.R ¹Be preferably organic linking group.

As R ¹Object lesson, can enumerate the structural unit of above-mentioned (t-1)～(t-34) or the group that combines by this structural unit (can also form ring texture).

When above-mentioned linking group has substituting group, as this substituting group, can enumerate carbon number such as methyl, ethyl for example and be 1～20 alkyl, carbon number such as phenyl, naphthyl is 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, carbon number such as methoxyl group, oxyethyl group is 1～6 alkoxyl group, and halogen atoms such as chlorine, bromine, carbon numbers such as methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl are 2～7 carbalkoxy, cyano group, carbonate groups such as the carbonic acid tert-butyl ester etc.

R ²Expression singly-bound or divalent linking group.As R ², comprise by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 Sauerstoffatom, 1～200 hydrogen atom, and the group that constitutes of 0～20 sulphur atom can unsubstituteds, also can have substituting group.R ²Be preferably organic linking group.

As R ²Object lesson, the group that can enumerate the structural unit shown in the above-mentioned t-3,4,7～18,22～26,32,34 or combine by this structural unit.

Wherein, R ²When having substituting group,, can enumerate carbon number such as methyl, ethyl for example and be 1～20 alkyl as this substituting group, carbon number such as phenyl, naphthyl is 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, carbon number such as methoxyl group, oxyethyl group is 1～6 alkoxyl group, and halogen atoms such as chlorine, bromine, carbon numbers such as methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl are 2～7 carbalkoxy, cyano group, carbonate groups such as the carbonic acid tert-butyl ester etc.

In above-mentioned general formula (11), m represents 1～8.M is preferably 1～5, and more preferably 1～3, be preferably 1～2 especially.

In addition, n represents 2～9.N is preferably 2～8, and more preferably 2～7, be preferably 3～6 especially.

In above-mentioned general formula (11), P ¹Expression polymer residue can be according to purpose selection from common polymkeric substance etc.

In polymkeric substance, in order to constitute macromolecular scaffold, be preferably selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer, acylamide polymer, epoxide polymer, silicone based polymkeric substance, and their modifier or multipolymer (for example comprise, polyethers/polyurethane copolymer, the multipolymer of polyethers/polymers of vinyl monomers etc. (can be a random copolymers, segmented copolymer, in the graft copolymer any one)) at least a in, more preferably be selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, at least a in polyurethane polymer and their modifier or the multipolymer, special preferred vinyl polymer of monomers or multipolymer.

And preferred above-mentioned polymkeric substance dissolves in the organic solvent.And if the affinity of organic solvent is low, when then for example using, a little less than the affinity of dispersion medium, can not guarantee the sufficient adsorption layer of stably dispersing sometimes as pigment dispersing agent.

In the macromolecular compound of above-mentioned general formula (11) expression, more preferably by the macromolecular compound of following general formula (12) expression.

General formula (12)

In above-mentioned general formula (12), A ²With the A in the above-mentioned general formula (11) ¹Synonym, its concrete preferred version is also identical, but object lesson as the organic pigment structure, more preferably phthalocyanine compound, azo lake compound, anthraquinone compounds, dioxazine compound, Diketopyrrolo-pyrrole compounds etc., as heterocycle, more preferably imidazoles, triazole, pyridine, piperidines, morpholine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, anthraquinone etc.

In addition, all right and A ¹Has same substituting group, about this substituting group, with A ¹Situation identical, preferred scheme is also identical.

And, as A ², be preferably the 1 valency organic group that above-mentioned general formula (4) is represented, about detailed and object lesson, the preferred version of this organic group, also same as described above.

In above-mentioned general formula (12), R ³The linking group of expression (x+y) valency.As above-mentioned R ³The linking group of (x+y) valency of expression comprises by 1～60 carbon atom, 0～10 nitrogen-atoms, and 0～50 Sauerstoffatom, 1～100 hydrogen atom, and 0～20 group that sulphur atom constitutes can unsubstituteds, also can have substituting group.

As above-mentioned R ³The linking group of (x+y) valency of expression is with above-mentioned R ¹In the linking group synonym of (m+n) valency, preferred version is also identical.In addition, as object lesson, the group that can enumerate structural unit same as described above or combine by this structural unit.

In these groups, R ³The linking group of expression is preferably organic linking group, and the preferred object lesson of this organic linking group (concrete example (r-1)～(r-17)) is as follows.But the present invention is not limited thereto.

Aspect acquired, the synthetic easiness of raw material, solvability all kinds of SOLVENTS, the group of preferably above-mentioned (r-1), (r-2), (r-10), (r-11), (r-16), (r-17) in above-mentioned group.

In addition, above-mentioned R ³When having substituting group,, can enumerate carbon number such as methyl, ethyl for example and be 1～20 alkyl as this substituting group, carbon number such as phenyl, naphthyl is 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, carbon number such as methoxyl group, oxyethyl group is 1～6 alkoxyl group, and halogen atoms such as chlorine, bromine, carbon numbers such as methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl are 2～7 carbalkoxy, cyano group, carbonate groups such as the carbonic acid tert-butyl ester etc.

In above-mentioned general formula (12), R ⁴And R ⁵The linking group of representing singly-bound or divalent independently of one another.

As above-mentioned R ⁴, R ⁵" linking group of divalent " of expression, can enumerate unsubstituted or have substituent, straight chain, side chain or cyclic alkylidene group, arylidene, inferior aralkyl and-O-,-S-,-C (=O)-,-N (R ¹⁹)-,-SO-,-SO ₂-,-CO ₂-,-N (R ²⁰) SO ₂-, or the divalent group that these two or more moiety combinations form is as preferred example (above-mentioned R ¹⁹And R ²⁰Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl).Wherein preferred organic linking group.

As above-mentioned R ⁴, more preferably the alkylidene group of straight or branched, inferior aralkyl and-O-,-C (=O)-,-N (R ¹⁹)-,-SO ₂-,-CO ₂-,-N (R ²⁰) SO ₂-(above-mentioned R ¹⁹And R ²⁰Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl), or the divalent group that forms of these two or more moiety combinations, be preferably especially the alkylidene group of straight or branched, inferior aralkyl and-O-,-C (=O)-,-N (R ¹⁹Above-mentioned R of)-( ¹⁹Expression hydrogen atom or carbon number are 1～4 alkyl) ,-CO ₂-, or the divalent group that forms of these two or more moiety combinations.

As above-mentioned R ⁵, more preferably the alkylidene group of singly-bound, straight or branched, inferior aralkyl ,-O-,-C (=O)-,-N (R ¹⁹)-,-SO ₂-,-CO ₂-,-N (R ²⁰) SO ₂-(above-mentioned R ¹⁹And R ²⁰Represent that independently of one another hydrogen atom or carbon number are 1～4 alkyl), or the divalent group that forms of these two or more moiety combinations, be preferably especially the alkylidene group of straight or branched, inferior aralkyl ,-O-,-C (=O)-,-N (R ¹⁹Above-mentioned R of)-( ¹⁹Expression hydrogen atom or carbon number are 1～4 alkyl) ,-CO ₂-, or the divalent group that forms of these two or more moiety combinations.

In addition, above-mentioned R ⁴, R ⁵When having substituting group,, can enumerate carbon number such as methyl, ethyl for example and be 1～20 alkyl as this substituting group, carbon number such as phenyl, naphthyl is 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, carbon number such as methoxyl group, oxyethyl group is 1～6 alkoxyl group, and halogen atoms such as chlorine, bromine, carbon numbers such as methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl are 2～7 carbalkoxy, cyano group, carbonate groups such as the carbonic acid tert-butyl ester etc.

In above-mentioned general formula (12), y represents 1～8, is preferably 1～5, more preferably 1～3, be preferably 1～2 especially.In addition, x represents 2～9, is preferably 2～8, more preferably 2～7, be preferably 3～6 especially.

In addition, the P in the above-mentioned general formula (12) ²Expression polymer residue can be according to purpose selection from common polymkeric substance etc.About the preferred version of polymkeric substance, with the P in the above-mentioned general formula (11) ¹Synonym, preferred version are also identical.

In the macromolecular compound of above-mentioned general formula (12) expression, preferred especially R ³For above-mentioned object lesson (r-1), (r-2), (r-10), (r-11), (r-16) or (r-17), R ⁴For the alkylidene group of singly-bound, straight or branched, inferior aralkyl ,-O-,-C (=O)-,-N (R ¹⁹Above-mentioned R of)-( ¹⁹Expression hydrogen atom or carbon number are 1～4 alkyl) ,-CO ₂-or the divalent group that forms of these two or more moiety combinations, R ⁵For singly-bound, ethylidene, propylidene or following general formula (s-a) or (s-b) expression linking group, P ²Be polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer or their modifier, y is 1～2, and x is 3～6 macromolecular compound.Also have, in the following radicals, R ²¹Expression hydrogen atom or methyl, l represents 1 or 2.

The weight-average molecular weight of the macromolecular compound that uses in the manufacture method of the present invention is more than 1000, and preferable weight-average molecular weight is 3000～100000, more preferably 5000～80000, be preferably 7000～60000 especially.If weight-average molecular weight is in the above-mentioned scope, then can give full play to the effect of a plurality of functional groups of polymer ends importing, in the excellent performance of performance aspect the adsorptivity of solid surface, micelle formation ability, surfactivity.When particularly macromolecular compound involved in the present invention being used as pigment dispersing agent, can obtain good dispersiveness and dispersion stabilization.

Macromolecular compound (compound that comprises general formula (12) expression) to above-mentioned general formula (11) expression has no particular limits, and can synthesize by following method etc.In following synthetic method, from synthetic easiness, synthetic methods such as more preferably following 2,3,4,5, synthetic methods such as preferred following 3,4,5 especially.

1, makes end import the polymkeric substance of the functional group that is selected from carboxyl, hydroxyl, amino etc., and have (the A in the above-mentioned general formula of a plurality of functional groups ¹Or A ²) carboxylic acid halides or have (the A in the above-mentioned general formula of a plurality of functional groups ¹Or A ²) haloalkane or have (the A in the above-mentioned general formula of a plurality of functional groups ¹Or A ²) isocyanic ester etc. carry out the method for high molecular weight reactive.

2, make end import the polymkeric substance of carbon-to-carbon double bond, and have (the A in the above-mentioned general formula of a plurality of functional groups ¹Or A ²) the mercaptan method of carrying out Michael reaction.

3, make end import the polymkeric substance of carbon-to-carbon double bond, and have (the A in the above-mentioned general formula of a plurality of functional groups ¹Or A ²) the mercaptan method of in the presence of radical initiator, reacting.

4, make end import the polymkeric substance of a plurality of thiol groups, with (the A in the above-mentioned general formula of the functional group that has imported carbon-to-carbon double bond ¹Or A ²) method of in the presence of radical initiator, reacting.

5, with having (the A in the above-mentioned general formula of a plurality of functional groups ¹Or A ²) mercaptan compound as chain-transfer agent, make vinyl monomer carry out the method for radical polymerization.

In foregoing, the macromolecular compound that uses in the manufacture method of the present invention (macromolecular compound of preferred formula (12) expression) can be synthetic by for example above-mentioned 2,3,4,5 any means, but it is, more preferably synthetic with above-mentioned 5 method from synthetic easiness.

More particularly, preferably use the compound of following general formula (13) expression to carry out radical polymerization as chain-transfer agent.

General formula (13)

In above-mentioned general formula (13), R ⁶, R ⁷, A ³, g and h respectively with above-mentioned general formula (12) in R ³, R ⁴, A ², x and y synonym, its preferred version is also identical.

There is no particular limitation to above-mentioned vinyl monomer, and preference is as the ester class of (methyl) esters of acrylic acid, crotonate class, vinyl ester, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol, styrenic, (methyl) vinyl cyanide etc.As its example, can be listed below described compound.

As the example of above-mentioned (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, 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 acetyl 2-ethoxyethyl acetate, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl 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 benzyl ester, (methyl) vinylformic acid diethylene glycol monomethyl ether ester, (methyl) vinylformic acid TC ester, (methyl) vinylformic acid triethylene glycol monomethyl ether-ether, (methyl) vinylformic acid triethylene glycol list ethyl ether-ether, (methyl) polyalkylene glycol acrylate monomethyl ether-ether, (methyl) polyalkylene glycol acrylate list ethyl ether-ether, (methyl) vinylformic acid beta-phenoxy ethoxy ethyl ester, (methyl) vinylformic acid Nonylphenoxy macrogol ester, (methyl) vinylformic acid two cyclopentenes esters, (methyl) vinylformic acid two cyclopentenes oxygen base ethyl esters, (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 tribromo-benzene 2-ethoxyethyl acetate etc.

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

As the example of above-mentioned vinyl ester, can enumerate vinyl acetate, propionate, vinyl butyrate, Methoxy acetic acid vinyl acetate, M-nitro benzoic acid vinyl acetate etc.

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

As the example of above-mentioned dimethyl ester class, can enumerate dimethyl fumarate, DEF, dibutyl fumarate etc.

As the example of above-mentioned methylene-succinic acid diester class, can enumerate dimethyl itaconate, diethyl itaconate, dibutyl itaconate etc.Example as above-mentioned (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-benzyl (methyl) acrylamide; (methyl) acryloyl morpholine; diacetone-acryloamide(DAA) etc.

As the example of above-mentioned 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, chlorostyrene, dichlorostyrene, bromostyrene, 1-chloro-4-methyl-benzene, with hydroxy styrenes, vinyl M-nitro benzoic acid methyl esters and the alpha-methyl styrene etc. that can protect by the de-protected group of acidic substance (for example t-Boc etc.).

As above-mentioned vinyl ethers, can enumerate methylvinylether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.

Except that above-claimed cpd, can also use (methyl) vinyl cyanide, hetero ring type group (for example, vinyl pyridine, vinyl pyrrolidone, vinylcarbazole etc.), N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactone etc. by vinyl substituted.

In addition, except that above-claimed cpd, can also use the vinyl monomer of functional groups such as for example having urethano, urea groups, sulfoamido, phenolic group, inferior amide group.As this monomer with urethano or urea groups, it is suitably synthetic for example can to utilize isocyanate group and hydroxyl or amino addition reaction to carry out.Specifically, monomer that can be by containing isocyanate group and contain the compound of 1 hydroxyl or contain the addition reaction of the compound of 1 primary amino or secondary amino group, or contain the monomer of hydroxyl or contain primary amino or the addition reaction of the monomer of secondary amino group and monoisocyanates is carried out suitably synthetic.

Above-mentioned vinyl monomer can be only a kind of polymerization of carrying out, and also can be to use simultaneously to carry out copolymerization more than 2 kinds, and this free radical polyalcohol can make each self-corresponding vinyl monomer carry out polymerization by ordinary method and obtain.

For example, can utilize following method to obtain, be about to these vinyl monomers and chain-transfer agent and be dissolved in the appropriate solvent, and add radical polymerization initiator therein, under about 50 ℃～about 220 ℃, in solution, carry out polymerization (solution polymerization process).

As the example of the appropriate solvent that uses in the solution polymerization process, can select arbitrarily according to the solvability of the multipolymer of employed monomer and generation.For example can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl group acetic ester, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methoxy-propyl acetic ester, ethyl lactate, vinyl acetic monomer, acetonitrile, tetrahydrofuran (THF), dimethyl formamide, chloroform, toluene.These solvents can be to mix more than two kinds to use.

In addition, as radical polymerization initiator, can use 2,2 '-Diisopropyl azodicarboxylate (AIBN), 2,2 '-azo-compound of azo two (2,4 '-methyl pentane nitrile) and so on, the superoxide of benzoyl peroxide and so on reaches the persulphate of Potassium Persulphate, ammonium persulphate and so on etc.

The compound of above-mentioned general formula (13) expression can wait by the following method and synthesize, but from synthetic easiness, more preferably following method 7.

6, will have (the A in the above-mentioned general formula of a plurality of functional groups ¹Or A ²) halogenide change into mercaptan compound method (can enumerate the method that makes itself and thiocarbamide reaction posthydrolysis, make itself and NaSH direct reaction method, make itself and CH ₃The method of COSNa reaction posthydrolysis etc.)

7, make the compound that has 3～10 sulfydryls in the per molecule the and have (A in the above-mentioned general formula of functional group ¹Or A ²) and have the method that can carry out addition reaction with the compound of the functional group of sulfydryl reaction

" can with the functional group of sulfydryl reaction " as in the aforesaid method 7 can preferably enumerate carboxylic acid halides, haloalkane, isocyanic ester, carbon-to-carbon double bond etc.

Preferred especially " can with the functional group of sulfydryl reaction " be carbon-to-carbon double bond, and addition reaction is the synthesis mode of free radical addition reaction.As carbon-to-carbon double bond, from the reactivity of sulfydryl on, more preferably 1 replaces or 2 vinyl that replace.

As the object lesson (concrete example (18)～(34)) of above-mentioned " compound that has 3～10 sulfydryls in the per molecule ", can enumerate following compound.

In above-claimed cpd, on acquired, the synthetic easiness of raw material, solvability to all kinds of SOLVENTS, preferred (u-18), (u-19), (u-27), (u-28), (u-33), (u-34).

Has (an A in the above-mentioned general formula of functional group to described ¹Or A ²) and have the compound of carbon-to-carbon double bond, have no particular limits, can be listed below compound.

For example, above-mentioned " compound that has 3～10 sulfydryls in the per molecule " " has the acidic-group of being selected from; the group of band basic nitrogen atom; urea groups; urethano; the group of band coordination Sauerstoffatom; carbon number is the alkyl more than 4 with above-mentioned, alkoxysilyl, epoxy group(ing), at least 1 functional group in isocyanate group and the hydroxyl, and compound with carbon-to-carbon double bond " the free radical addition resultant of reaction can obtain by the following method; for example; above-mentioned " compound that has 3～10 sulfydryls in the per molecule " reached " have the acidic-group of being selected from, the group of band basic nitrogen atom, urea groups, urethano, the group of band coordination Sauerstoffatom, carbon number is the alkyl more than 4, alkoxysilyl, epoxy group(ing), at least 1 functional group in isocyanate group and the hydroxyl, and compound with carbon-to-carbon double bond " be dissolved in the appropriate solvent; and, under about 50 ℃～about 100 ℃, carry out addition (thiol-ene reaction method) to wherein adding radical polymerization initiator.

As the preferred solvent of in aforesaid method, using, can according to employed " compound that has 3～10 sulfydryls in the per molecule ", " have the group, urea groups, urethano, the group of band coordination Sauerstoffatom, the carbon number that are selected from acidic-group, band basic nitrogen atom and be at least 1 functional group in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl 4 or more, and have can with the compound of functional group's (for example carbon-to-carbon double bond) of sulfydryl reaction ", and the solvability of the free radical addition resultant of reaction of generation select arbitrarily.For example, can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl group acetic ester, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methoxy-propyl acetic ester, ethyl lactate, vinyl acetic monomer, acetonitrile, tetrahydrofuran (THF), dimethyl formamide, chloroform, toluene.These solvents can mix use more than two kinds.

The object lesson of the compound of the general formula that can preferably use in the manufacture method of the present invention (11) expression is as follows.But the present invention is not limited thereto.

In addition, this macromolecular compound is preferably the macromolecular compound with acidic-group, the macromolecular compound that more preferably has carboxyl is preferably especially and contains (A) by at least a the reaching (B) by at least a copolymerization in the repeating unit of the compound deriving with carboxylic acid ester groups in the repeating unit of the compound deriving with carboxyl.

As (A) repeating unit by compound deriving with carboxyl, be preferably the repeating unit of following general formula (I) expression, more preferably by acrylic or methacrylic acid repeat units derived, as (B) repeating unit by compound deriving with carboxylic acid ester groups, be preferably the repeating unit of following general formula (II) expression, the repeating unit of more preferably following general formula (IV) expression is preferably especially by the vinylformic acid benzyl ester, the methacrylic acid benzyl ester, phenylethyl, the methacrylic acid phenethyl ester, vinylformic acid 3-phenyl propyl ester or methacrylic acid 3-phenyl propyl ester repeat units derived.

General formula (1)

(R ₁Expression hydrogen atom or carbonatoms are 1～5 alkyl)

General formula (II)

(R ₂Expression hydrogen atom or carbonatoms are 1～5 alkyl.R ₃Represent the group shown in the following general formula (III))

General formula (III)

(R ₄Expression hydrogen atom, carbonatoms are that 1～5 alkyl, hydroxyl, carbonatoms are that 1～5 hydroxyalkyl or carbonatoms are 6～20 aryl.R ₅And R ₆Represent that respectively hydrogen atom or carbonatoms are 1～5 alkyl.X1 represents 1～5 number)

General formula (IV)

(R ₇Expression hydrogen atom or carbonatoms are 1～5 alkyl.R ₈Represent the group shown in the following logical formula V.)

Logical formula V

(R ₉The expression carbonatoms is that 2～5 alkyl or carbonatoms are 6～20 aryl.R ₁₀And R ₁₁Represent that respectively hydrogen atom or carbonatoms are 1～5 alkyl.Y1 represents 1～5 number.)

In addition, with regard to (A) by the repeating unit of compound deriving with (B) with regard to the polymerization ratio of the repeating unit of compound deriving with carboxylic acid ester groups with carboxyl, repeating unit (A) is preferably 3～40 with respect to the quantity of whole number of repeat unit than %, and more preferably 5～35.

In addition, in the manufacture method of organic nano granules of pigments of the present invention, also preferred the use contained graft copolymer that possesses amino and ether and the macromolecular compound that also contains other composition of suitable selection in case of necessity.

Above-mentioned graft copolymer has amino and ether at least, also can contain other monomer etc. as copolymer unit.

The weight-average molecular weight of above-mentioned graft copolymer (Mw) is preferably 3000～100000, more preferably 5000～5O000.If (Mw) is too small for above-mentioned weight-average molecular weight, then can not prevent the aggegation of organic nanometer granule, viscosity rises sometimes, if above-mentioned weight-average molecular weight is excessive, the solvability deficiency in organic solvent then, viscosity rises sometimes.Also have, this weight-average molecular weight is by gel permeation chromatography (carrier: tetrahydrofuran (THF)) measure and through the weight-average molecular weight of polystyrene conversion.

Preferred this graft copolymer contains (i) end at least to have the polyreactive oligomers of ethylenical unsaturated double bonds, (ii) has a monomer of amino and ethylenical unsaturated double bonds and (iii) have the polymerizable monomer of ether, as copolymer unit, also can contain (iv) other monomer in case of necessity as copolymerization units.

As the content of these copolymer unit in above-mentioned graft copolymer, preferably (i) above-mentioned polyreactive oligomers is 15～98 quality %, 25～90 quality % more preferably, the preferred monomer that (ii) contains amino is 1～40 quality %, more preferably 5～30 quality %, preferred (iii) above-mentioned polymerizable monomer with ether is 1～70 quality %, preferred 5～60 quality %.

If the content of above-mentioned polyreactive oligomers is very few, can not obtain steric repulsion effect sometimes as dispersion agent, can not prevent the aggegation of organic nanometer granule, if too high levels, then the ratio of above-mentioned nitrogen containing monomer reduces, and to the adsorptive power reduction of organic granular, dispersed possibility is not enough.If the content of above-mentioned nitrogen containing monomer is very few, then the adsorptive power to organic granular is low, and dispersed possibility is not enough, if too high levels, then the ratio of above-mentioned polyreactive oligomers descends, and therefore can not obtain the steric repulsion effect as dispersion agent sometimes, can not fully prevent the aggegation of organic granular.If the content of above-mentioned polymerizable monomer with ether is very few, then development adaptability may be not enough when the manufacturing of colour filter etc., if too high levels, then the ability as dispersion agent may descend.

(i) polyreactive oligomers

Above-mentioned polyreactive oligomers (below, be sometimes referred to as " big monomer ".) be the oligopolymer that end has the group that contains ethylenical unsaturated double bonds.In the present invention, preferably in above-mentioned polyreactive oligomers, only there is a side to have the group that contains above-mentioned ethylenical unsaturated double bonds in these oligopolymer two ends.

As above-mentioned oligopolymer, usually for example can enumerate the homopolymer that forms by at least a monomer that is selected from (methyl) alkyl acrylate, (methyl) acrylic acid hydroxy alkyl ester, vinylbenzene, vinyl cyanide, vinyl acetate and the divinyl or multipolymer etc., wherein homopolymer or multipolymer, the polystyrene etc. of preferred (methyl) alkyl acrylate.In the present invention, these oligopolymer can be substituted base and replace, and are not particularly limited for this substituting group, for example can enumerate halogen atom etc.

As above-mentioned group, can for example suitably enumerate (methyl) acryl, vinyl etc., wherein preferred especially (methyl) acryl with ethylenical unsaturated double bonds.

In the present invention, be preferably the oligopolymer of following general formula (E6) expression in the above-mentioned polyreactive oligomers.

General formula (E6)

In above-mentioned general formula (E6), R ⁶¹And R ⁶³Expression hydrogen atom or methyl.R ⁶²The expression carbon number is 1～8 and the alkylidene group that can be replaced by alcoholic extract hydroxyl group, and preferred carbon number is 2～4 alkylidene group.Y ⁶The expression phenyl, have phenyl that carbon number is 1～4 alkyl or-COOR ⁶⁴(R herein, ⁶⁴The expression carbon number be 1～6 and alkyl, phenyl or the carbon number that can be replaced by alcoholic extract hydroxyl group, halogen be 7～10 aralkyl), preferred phenyl or-COOR ⁶⁴(R herein, ⁶⁴The expression carbon number be 1～4 and the alkyl that can be replaced by alcoholic extract hydroxyl group).Q represents 20～200.

As the object lesson of above-mentioned polyreactive oligomers, preferred poly-(methyl) vinylformic acid 2-hydroxyl ethyl ester, polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, poly-(methyl) isobutyl acrylate, as they multipolymer be combined with the polymkeric substance of (methyl) acryl a molecular end.

Above-mentioned polyreactive oligomers can be commercially available; or suitable synthetic; as the commercially available prod; for example can enumerate single terminal methyl group acryl polystyrene oligopolymer (Mn=6000; trade(brand)name: AS-6; East Asia synthetic chemical industry (strain) society system); single terminal methyl group acryl polymethyl methacrylate oligomer (Mn=6000; trade(brand)name: AA-6; East Asia synthetic chemical industry (strain) society system); the positive butyl ester oligopolymer of single terminal methyl group acryl polyacrylic acid (Mn=6000; trade(brand)name: AB-6; East Asia synthetic chemical industry (strain) society system); single terminal methyl group acryl polymethylmethacrylate/methacrylic acid 2-hydroxyl ethyl ester oligopolymer (Mn=7000; trade(brand)name: AA-714; East Asia synthetic chemical industry (strain) society system); single terminal methyl group acryl poly-n-butyl methacrylate/methacrylic acid 2-hydroxyl ethyl ester oligopolymer (Mn=7000; trade(brand)name: 707S; East Asia synthetic chemical industry (strain) society system); single terminal methyl group acryl polymethyl acrylic acid 2-ethylhexyl/methacrylic acid 2-hydroxyl ethyl ester oligopolymer (Mn=7000; trade(brand)name: AY-707S; AY-714S, East Asia synthetic chemical industry (strain) society system) etc.

In the present invention; preferred object lesson as above-mentioned polyreactive oligomers; can enumerate as at least a kind of oligopolymer in the multipolymer of the polymkeric substance, (methyl) alkyl acrylate and the polystyrene that are selected from (methyl) alkyl acrylate; and number-average molecular weight is 1000～20000, and end has the oligopolymer of (methyl) acryl.

(ii) contain amino monomer

Contain amino monomer as above-mentioned, can be fit to enumerate at least a in the compound that for example is selected from following general formula (E2) expression.

General formula (E2)

In above-mentioned general formula (E2), R ²¹Expression hydrogen atom or methyl.R ²²The expression carbon number is 1～8 alkylidene group, and wherein preferred carbon number is 1～6 alkylidene group, and preferred especially carbon number is 2～3 alkylidene group.X ²Expression-N (R ²³) (R ²⁴) ,-R ²⁵N (R ²⁶) (R ²⁷).Herein, R ²³And R ²⁴Expression hydrogen atom, carbon number are 1～6 alkyl or phenyl.R ²⁵The expression carbon number is 1～6 alkylidene group, R ²⁶And R ²⁷Expression hydrogen atom, carbon number are 1～6 alkyl or phenyl.

In foregoing ,-N (R ²³) (R ²⁴) in R ²³And R ²⁴Be preferably hydrogen atom or carbon number and be 1～4 alkyl or phenyl ,-R ²⁵-N (R ²⁶) (R ²⁷) in R ²⁵Be preferably carbon number and be 2～6 alkylidene group, R ²⁶And R ²⁷Be preferably carbon number and be 1～4 alkyl.M2 and n2 represent 1 or 0, preferred m2=1 and n2=1, or m2=1 and n2=0 (that is the monomer of representing corresponding to following general formula (E3), (E4)).

In the present invention, the monomer of above-mentioned general formula (E2) expression is preferably and is selected from following (E3) and (E4) at least a in the monomer represented of arbitrary formula.

General formula (E3)

In above-mentioned general formula (E3), R ³¹With the R in the general formula (E2) ²¹Synonym.R ³²With the R in the general formula (E2) ²²Synonym.X ³With the X in the general formula (E2) ²Synonym.

General formula (E4)

In above-mentioned general formula (E4), R ⁴¹With the R in the general formula (E2) ²¹Synonym.X ⁴With the X in the general formula (E2) ²Synonym is preferably-N (R ⁴³) (R ⁴⁴) (R herein, ⁴³And R ⁴⁴With the R in the general formula (E2) ²³And R ²⁴Synonym) or-R ⁴⁵-N (R ⁴⁶) (R ⁴⁷) (R herein, ⁴⁵, R ⁴⁶And R ⁴⁷Respectively with general formula (E2) in R ²⁵, R ²⁶And R ²⁷Synonym).

Monomeric object lesson as above-mentioned general formula (E2) expression, can enumerate dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide, di-isopropyl (methyl) acrylamide, di-n-butyl (methyl) acrylamide, diisobutyl (methyl) acrylamide, morpholino base (methyl) acrylamide, piperidino-(1-position only) (methyl) acrylamide, N-methyl-2-pyrrolidyl (methyl) acrylamide and N, N-aminomethyl phenyl (methyl) acrylamide (above is (methyl) acrylic amide); 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, 6-(N, N-dimethylamino) hexyl (methyl) acrylamide (above is aminoalkyl group (methyl) acrylic amide) etc. are as preferred monomers.

The polymerizable monomer that (iii) has ether

As above-mentioned polymerizable monomer, can suitably enumerate and for example be selected from the monomeric at least a of following general formula (E1) expression with ether.

General formula (E1)

In above-mentioned general formula (E1), R ¹¹Expression hydrogen atom or methyl.R ¹²The expression carbon number is 1～8 alkylidene group, and wherein preferred carbon number is 1～6 alkylidene group, and more preferably carbon number is 2～3 alkylidene group.X ¹Expression-OR ¹³Or-OCOR ¹⁴Herein, R ¹³Expression hydrogen atom, carbon number are 1～18 alkyl, phenyl or are the phenyl that 1～18 alkyl replaces by carbon number.R ¹⁴The expression carbon number is 1～18 alkyl.In addition, m3 represents 2～200, preferred 5～100, preferred especially 10～100.

To as above-mentioned polymerizable monomer with ether, there is no particular limitation, so long as have ether and get final product for the monomer of polymerizability, can from common monomer, select, for example can enumerate polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyoxyethylene glycol polypropylene glycol list (methyl) acrylate, polytetramethylene glycol monomethacrylates etc., these monomers can be commercially available or suitable synthetic.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 (more than, East Asia synthetic 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 (more than, Japan 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-370B, 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.

(iv) other monomer

Above-mentioned graft copolymer can also contain above-mentioned other monomer as copolymer unit, there is no particular limitation to this other monomer, can select according to purpose, for example (for example can enumerate aromatic ethenyl compound, vinylbenzene, alpha-methyl styrene and Vinyl toluene), (methyl) alkyl acrylate (for example, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate and (methyl) isobutyl acrylate), (methyl) acrylic acid alkyl aryl ester (for example, (methyl) vinylformic acid benzyl ester), (methyl) glycidyl acrylate, vinyl esters of carboxylic acids (for example, vinyl acetate and vinyl propionate base ester), vinyl nitrile (for example, (methyl) vinyl cyanide and α-Lv Daibingxijing), the aliphatics conjugated diolefine (for example, 1,3-butadiene and isoprene), (methyl) vinylformic acid etc.Wherein preferred unsaturated carboxylic acid, (methyl) alkyl acrylate, (methyl) acrylic acid alkyl aryl ester and vinyl esters of carboxylic acids.

As this other monomeric content in the above-mentioned graft copolymer, for example be preferably 5～70 quality %.If this other monomeric containing ratio is very few, then can not control the rerum natura of coated film sometimes, if containing ratio is too high, then can not give full play to ability sometimes as dispersion agent.

As the preferred object lesson of above-mentioned graft copolymer, can enumerate

(11) poly-(methyl) methyl acrylate copolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate,

(12) 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate polystyrene copolymer,

(13) 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/(methyl) methyl acrylate/terminal methyl group propylene acidylate polystyrene copolymer,

(14) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate (methyl) methyl acrylate and methacrylic acid 2-hydroxyl ethyl ester multipolymer,

(15) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate methyl methacrylate and methacrylic acid 2-hydroxyl ethyl ester multipolymer,

(16) multipolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyethyleneglycol (methyl) acrylate/terminal methyl group propylene acidylate methyl methacrylate and methacrylic acid 2-hydroxyl ethyl ester multipolymer,

(17) poly-(methyl) methyl acrylate copolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polypropylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(18) poly-(methyl) methyl acrylate copolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyoxyethylene glycol polypropylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(19) poly-(methyl) methyl acrylate copolymer of 3-(N, N-dimethylamino) propyl group acrylamide/polyoxyethylene glycol polytetramethylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate,

(20) 3-(N, N-dimethylamino) propyl group acrylamide/polypropylene glycol polytetramethylene glycol list (methyl) acrylate/terminal methyl group propylene acidylate is gathered (methyl) methyl acrylate copolymer etc.

Wherein, preferred (11), (14), (18), the compound of more preferably following formula (D4) expression.In the formula (D4), Me represents methyl.

Formula (D4)

A: b: c=15: 20: 65 (mass ratio)

Above-mentioned graft copolymer can obtain by making the composition that will form above-mentioned each copolymer unit for example carry out radical polymerization in solvent.This radical polymerization is fashionable carrying out, and can use radical polymerization initiator, in addition, can also use chain-transfer agent (for example, 2 mercapto ethanol and lauryl mercaptan).For the pigment dispersing agent that contains graft copolymer, can be with reference to the record of TOHKEMY 2001-31885 communique.

In order further to improve the uniformly dispersed and package stability of organic granular, with respect to the pigment of 100 mass parts, the content of graft copolymer is preferably 0.1～1000 mass parts, more preferably 1～500 mass parts, more preferably 5～20 mass parts.If content is very few, then may can't see the raising of organic nanometer granule dispersion stabilization.In addition, graft copolymer can use separately, also can multiplely be combined into to exercise to use.

If do not specify, the molecular weight polymeric among the preparation method of the present invention is meant weight-average molecular weight.As the measuring method of molecular weight polymeric, can enumerate chromatography, viscosimetry, light scattering method, sedimentation velocity method etc.In the present invention, if not otherwise specified, all be to use weight-average molecular weight by chromatography determination.

Below, the macromolecular compound of anionic is described.

In above-mentioned aggegation, can add macromolecular compound with at least one anionic group.The weight-average molecular weight of this macromolecular compound is more than 1000, and the represented macromolecular compound of preferred following general formula (14).

General formula (14)

(in the formula, G represents-COO ^-,-SO ₃ ^-,-OSO ₃ ^-,-P (O) is O (OH) ^-, or-(OH) O of OP (O) ^-J represents divalent linking group or singly-bound.Q represents (m+1) valency linking group.R represents the macromolecular compound residue.Z represents the organic or inorganic positively charged ion.M+1 represents 3～6)

In general formula (14), G represents-COO ^-,-SO ₃ ^-,-OSO ₃ ^-,-P (O) is O (OH) ^-, or-(OH) O of OP (O) ^-, be preferably-SO ₃ ^-,-OSO ₃ ^-,-P (O) is O (OH) ^-In having the situation of a plurality of G, G can be same anionic group, also can be different anionic groups.

In general formula (14), as the represented divalent linking group of J, be preferably the alkylidene group of straight or branched, inferior aralkyl and-O-,-C (=O)-,-SO ₂-,-CO ₂-or these groups in the two or more divalent groups that combine, more preferably, the position that is connected with Q in the general formula (14) in this divalent group is a sulphur atom.

In addition, have in the substituent situation at the represented divalent linking group of J, as this substituting group, can enumerate carbon numbers such as methyl, ethyl and be 1～20 alkyl, carbon number such as phenyl, naphthyl is 6～16 aryl, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido, carbon numbers such as acetoxyl group are 1～6 acyloxy, and carbon numbers such as methoxyl group, oxyethyl group are 1～6 alkoxyl group, halogen atom such as chlorine, bromine, carbon numbers such as methoxycarbonyl, ethoxycarbonyl, hexamethylene oxygen carbonyl are 2～7 carbalkoxy, cyano group, carbonate groups such as the carbonic acid tert-butyl ester etc.

In general formula (14),, can enumerate imidazole salt, pyridine salt, thiazole salt, oxazole salt, tetrahydroglyoxaline salt, thiazoline salt, oxazoline salt etc. as the represented organic cation of Z.As the represented inorganic cation of Z, can enumerate lithium ion, sodium ion, potassium ion etc.Z is preferably inorganic cation.

In above-mentioned general formula (14), Q represents (m+1) valency linking group.M+1 represents 3～6.

As represented (m+1) valency linking group of above-mentioned Q, comprise by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 Sauerstoffatom, and 1～200 group that hydrogen atom constitutes, can unsubstituted, also can further have substituting group.Q is preferably organic linking group, and (exemplary compounds (r-1)～(r-17)) is as follows for the preferred object lesson of this organic linking group.But the present invention is not limited thereto.

In above-mentioned general formula (14), m represents 1～5 integer, and m is preferably 2～5, more preferably 3～5.In addition, l represents 1～5 integer, and l is preferably 1～4, more preferably 1～3, be preferably 1～2 especially.

In above-mentioned general formula (14), R represents macromolecular compound residue (macromolecular scaffold), can select from common polymkeric substance etc. according to purpose.Herein, macromolecular scaffold is meant that number-average molecular weight is the macromolecular structure more than 1000.In polymkeric substance, in order to constitute macromolecular scaffold, be preferably selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer, acylamide polymer, epoxide polymer, silicone based polymkeric substance, and their modifier or multipolymer (for example comprise, polyethers/polyurethane copolymer, the multipolymer of polyethers/polymers of vinyl monomers etc. (can be a random copolymers, segmented copolymer, in the graft copolymer any one)) at least a in, more preferably be selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, at least a in polyurethane polymer and their modifier or the multipolymer, special preferred vinyl polymer of monomers or multipolymer.

And preferred above-mentioned polymkeric substance dissolves in the organic solvent.And if the affinity of organic solvent is low, when then (for example) uses as pigment dispersing agent, a little less than the affinity of dispersion medium, can not guarantee to form the sufficient adsorption layer of dispersion stabilization sometimes.

The weight-average molecular weight of the macromolecular compound that contains the anionic group of Shi Yonging is that weight-average molecular weight is preferably 3000～100000 more than 1000 in the present invention, more preferably 5000～80000, be preferably 7000～60000 especially.If weight-average molecular weight is in the above-mentioned scope, then can give full play to the effect of a plurality of functional groups of polymer ends importing, in the excellent performance of performance aspect the adsorptivity of solid surface, micelle formation ability, surfactivity.During the pigment dispersing agent of the macromolecular compound that particularly will have an above-mentioned anionic group when making organic nano pigment particle agglutination body redispersion, can obtain good dispersiveness and dispersion stabilization.

Have no particular limits for the represented macromolecular compound of above-mentioned general formula (14), can synthesize by following method etc.Employing have can roll into a ball (G in the above-mentioned general formula) in a plurality of palaces mercaptan compound as chain-transfer agent, make vinyl monomer carry out the method for radical polymerization.

More particularly, preferably use the compound of following general formula (15) expression to carry out radical polymerization as chain-transfer agent.

General formula (15)

In general formula (15), G, J, Q, Z and m+1 respectively with above-mentioned general formula (14) in G, J, Q, Z and m+1 synonym, its preferable range is also identical.

As the example of above-mentioned crotonate class, can enumerate butyl crotonate, the own ester of Ba Dousuan etc.As the example of above-mentioned vinyl ester, can enumerate vinyl acetate, propionate, vinyl butyrate, Methoxy acetic acid vinyl acetate, M-nitro benzoic acid vinyl acetate etc.As the example of above-mentioned maleic acid diester class, can enumerate dimethyl maleate, ethyl maleate, dibutyl maleinate etc.As the example of above-mentioned dimethyl ester class, can enumerate dimethyl fumarate, DEF, dibutyl fumarate etc.As the example of above-mentioned methylene-succinic acid diester class, can enumerate dimethyl itaconate, diethyl itaconate, dibutyl itaconate etc.Example as above-mentioned (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-benzyl (methyl) acrylamide; (methyl) acryloyl morpholine; diacetone-acryloamide(DAA) etc.

As the example of above-mentioned 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, chlorostyrene, dichlorostyrene, bromostyrene, 1-chloro-4-methyl-benzene, with hydroxy styrenes, vinyl M-nitro benzoic acid methyl esters and the alpha-methyl styrene etc. that can protect by the de-protected group of acidic substance (for example t-Boc etc.).As above-mentioned vinyl ethers, can enumerate methylvinylether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.

For example, can utilize following method to obtain, be about to these vinyl monomers and chain-transfer agent and be dissolved in the appropriate solvent, and add radical polymerization initiator therein, under about 50 ℃～about 220 ℃, in solution, carry out polymerization (solution polymerization process).As the example of the appropriate solvent that uses in the solution polymerization process, can select arbitrarily according to the solvability of the multipolymer of employed monomer and generation.For example can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl group acetic ester, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methoxy-propyl acetic ester, ethyl lactate, vinyl acetic monomer, acetonitrile, tetrahydrofuran (THF), dimethyl formamide, chloroform, toluene, dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP).These solvents can be to mix more than two kinds to use.

In addition, as radical polymerization initiator, can use 2,2 '-Diisopropyl azodicarboxylate (AIBN), 2,2 '-azo-compound of azo two (2,4 '-methyl pentane nitrile) and so on, the superoxide of benzoyl peroxide and so on, and the persulphate of Potassium Persulphate, ammonium persulphate and so on etc.

The object lesson of the macromolecular compound of above-mentioned general formula (14) expression below is shown, but the present invention is not limited thereto.

[separation]

Below, the separation method of the organic nanometer granule after the aggegation is described.

At first, before separating, preferably the liquid after the aggegation was left standstill 0.5～2 hour.Because agglomeration generation sedimentation, so or with the supernatant liquid sucking-off, remove supernatant liquor, the easier like this separation of carrying out agglomeration by supernatant liquid is toppled over gently.In addition, also can replace leaving standstill, make the settling velocity of agglomeration faster, shorten working hours by adopting centrifugation.

As separation method, can adopt various filter methods, for example can adopt ultrafiltration, centrifugation, filter with filter paper or strainer.

In the situation of carrying out ultrafiltration, for example can use the desalination/spissated method that is used for silver emulsion.Known have open (Research Disclosure) No.10 of research, and 208 (1972), No.13,122 (1975) and No.16,351 (1977).For pressure difference and flow as the important operation condition, can publish (1978) with reference to the big spring man of virtue and ability of arrow work " film utilizes technology Ha Application De Block Star Network " good fortune study, the rational curve of putting down in writing among the p275 is selected, but disperse the object space face at the processing target organic nanometer granule, in order to suppress the particulate aggegation, also need to find out optimum condition.In addition, with regard to replenishing, the constant volume formula of continuous interpolation solvent and the batch-type that gradation is intermittently added are arranged, but the preferred desalting treatment time is than the constant volume formula of weak point because of film sees through for the method for the solvent that lose.Solvent for replenishing thus can use the pure water that obtains by ion-exchange or distillation, but also can sneak into the poor solvent of dispersion agent, dispersion agent in pure water, also can directly add organic nanometer granule to and disperse in the thing.

When using strainer to filter, for example can use the device of pressure filtration and so on.As preferred strainer, can enumerate filter paper, nanofilter, ultra-fine filter etc.

As concentrating employed separating centrifuge in the organic nanometer granule,, can use any device as long as can make the organic nanometer granule sedimentation in the organic nanometer granule dispersion liquid (or organic nanometer granule concentrated extracting solution) by centrifugation.As separating centrifuge, for example, outside multipurpose plant, the separating centrifuge etc. that can 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.

For isolated agglomeration, the purpose of washing is for desalination, dewaters, removes unnecessary dispersion agent.Can carry out washing operation according to following manner: can after adopt ultrafiltration, centrifugation, filter paper or strainer filtration, directly add washings and wash; Also can temporarily agglomeration be taken out, and it is made in washings after the soup compound again, filter to separate by adopting ultrafiltration, centrifugation, filter paper or strainer; Also these methods can be used in combination and wash.

In addition, washing operation not only can carry out after above-mentioned lock out operation, also can carry out before lock out operation.Agglutinative nano dye particle dispersion is left standstill, remove supernatant liquor, add washings, it is made soup compound again.After making soup compound again, can leave standstill and remove supernatant liquor and filter again, also can direct filtration.If washed before lock out operation, agglomeration is normally moistening, thus not only can improve detersive efficiency, and also redispersion described later also becomes easier.

Have no particular limits for washings, so long as can realize desalination, the aqueous solvent that dewaters, remove unnecessary dispersion agent agglutinant gets final product.Specifically, (for example can enumerate aqueous solvent, water, or hydrochloric acid, aqueous sodium hydroxide solution), the alcohol compound solvent, the amides solvent, the ketone compounds solvent, the ether compound solvent, aromatic compound solvent, the dithiocarbonic anhydride solvent, the fatty compounds solvent, the nitrile compounds solvent, the sulfoxide compound solvent, the halogen contained compound solvent, the ester compound solvent, ionic liquid and their mixed solvent etc., be preferably aqueous solvent, the alcohol compound solvent, the ketone compounds solvent, the ether compound solvent, the nitrile compounds solvent, the sulfoxide compound solvent, the ester compound solvent, amides solvent or their mixture, more preferably aqueous solvent, the alcohol compound solvent, the ester compound solvent, the nitrile compounds solvent.

Agglomeration for after the washing can directly carry out redispersion described later; After also can soaking into, carry out redispersion again with redispersion solvent (will there be description the back); Can also be dried, obtain carrying out redispersion again after the powder of organic nanometer granule dispersion thing.

There is no particular limitation to cryodesiccated method, any method that can use those skilled in the art to adopt.For example, can enumerate refrigerant direct expansion method, repeated freezing method, heating agent circulation method, triple heat-exchanging method, indirect heating cold method, but preferably use refrigerant direct expansion method, indirect heating cold method, more preferably use the indirect heating cold method.All preferably after carrying out precooling, carry out lyophilize in any method.There is no particular limitation to the precooling condition, and to carry out cryodesiccated sample freezing equably but must make.

Device as the indirect heating cold method, can enumerate small frozen drying machine, FTS freeze drier, LYOVAC freeze drier, experiment freeze drier, research freeze drier, triple heat exchange vacuum freeze drier, single-cooling type freeze drier, HULL freeze drier, but preferably small frozen drying machine, experiment with freeze drier, research with freeze drier, single-cooling type freeze drier, preferred small frozen drying machine, single-cooling type freeze drier.

There is no particular limitation to cryodesiccated temperature, for example is-190～about-4 ℃ approximately, and preferred-120～about-20 ℃ approximately, more preferably from about-80～approximately-60 ℃.Also there is no particular limitation to cryodesiccated pressure, and those skilled in the art can suitably select, for example can be at about 0.1～about 35Pa, and preferred about 1～about 15Pa more preferably from about carries out under 5～about 10Pa.Sublimation drying is for example about 2～about 48 hours, preferred about 6～about 36 hours, and more preferably from about 16～about 26 hours.Importantly, these conditions can suitably be selected by those skilled in the art.About freeze-drying, can reference example such as pharmaceutical machine technology Ha Application De Block Star Network: pharmaceutical machine technical study meeting be compiled, book shop, people from ground, p.120～129 (in September, 2000); Vacuum Ha Application De Block Star Network: ULVAC Corp compiles, オ-system society, p.328～331 (1992); Freezing and drying study Hui Hui Chi: her rattan filial piety is controlled etc., No.15, p.82 (nineteen sixty-five) etc.

There is no particular limitation for the device that uses when concentrating organic nanometer granule by drying under reduced pressure, as long as can make the solvent evaporation of organic nanometer granule dispersion liquid (or organic nanometer granule concentrated extracting solution).Thereby for example can enumerate general vacuum drier and rotor pump and on one side stirred liq heat on one side drying under reduced pressure device, can make the pipe of liquid by the heating decompression carry out the device etc. of successive drying.

Heating drying under reduced pressure temperature is preferably 30～230 ℃, more preferably 35～200 ℃, is preferably 40～180 ℃ especially.Pressure during decompression is preferably 100～100000Pa, and more preferably 300～90000Pa is preferably 500～80000Pa especially.

[redispersion]

According to manufacture method of the present invention, as required, can be with the organic nano granules of pigments that is in state of aggregation fine decentralized (in the present invention, fine decentralized be to instigate the agglutinating particle in the dispersion liquid to scatter, improve dispersity).

At this moment, become possibility for rapid filter is filtered, and obtain good dispersion state once more, the organic nano granules of pigments of preferred above-mentioned aggegationization obtains as carrying out the agglutinative floss carrying out the degree of redispersion.

For this reason, adopt common decentralized method and the decentralized degree that reaches, its micronize degree is insufficient, so need the higher method of miniaturization efficient.

As the fine decentralized method of the agglomeration that makes this nano particle, 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, for example can enumerate ultrasonic homogenizer, Ultrasonic Cleaners etc.If the liquid temperature rises during ultrasonic irradiation, then can cause the thermal thermocoagulation (referring to non-patent literature 1) 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 and implement.

To being not particularly limited, for example can enumerate dispersion machines such as kneader, roll crusher, second reduction machine (アトライダ one), high-speed grinder, dissolving machine, homo-mixer, sand mill as applying the dispersion machine that uses when physical energy disperses nanometer organic granular after concentrating.In addition, also can adopt the dispersion machine that is suitable for the high pressure dispersion method or adopts the dispersing method that microballon carries out.

Preferable production process as organic nanometer granule, preferred adopt following method, promptly tinting material is carried out mixing dispersion treatment, make that the viscosity under 25 ℃ is 10 after the mixing dispersion treatment with resinous principle, more than the 000mPas, be preferably 100, the viscosity higher that 000mPas is above is added solvent then, carry out the diffusing processing of differential, viscosity after making differential loose handle is 1, below the 000mPas, be preferably 100mPas following than low viscosity.

The machinery that uses during redispersion is handled is two roller mixing rolls, three roller mixing rolls, ball mill, Tron mill (トロ Application ミ Le), dissolving machine, kneader, is total to kneader, homogenizer, blender, single screw rod or twin screw extruder etc., disperses while apply high shear force.Then, add solvent, main perpendicular type or horizontal type sand mill, needle mill, seam grinding machine (slitmill), ultrasonic dispersing machine, the high pressure dispersion machine etc. of using utilize the microballon that is made of the glass of 0.1～1mm particle diameter, zirconium white etc. to carry out differential and loose and handle.Can also use the following microballon of 0.1mm to carry out accurate dispersion treatment in addition.

In addition, also prime pigments and auxiliary pigment can be carried out dispersion treatment respectively after, mix two kinds of dispersion liquids, carry out dispersion treatment again, or prime pigments and auxiliary pigment carried out dispersion treatment together.

In addition,, be recorded in T.C.Patton work " Paint Flowand Pigment Dispersion " (1964, John Wiley and Sons company publication), also can use this method about the dispersive detailed content.

Disperse in order to improve the dispersiveness of organic nano granules of pigments, can add common pigments dispersion agent or tensio-active agent in the thing at the organic nano granules of pigments.As these dispersion agents, can use multiple compound, for example can enumerate phthalocyanine derivates (commercially available product EFKA-6745 (エ Off カ society system)), ソ Le スパ-ス 5000 (ゼネカ (strain) society system); Organosiloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) society system), (methyl) acrylic acid or the like (being total to) polymkeric substance Port リ Off ロ-No.75, No.90, No.95 (society of common prosperity society oil chemistry industry (strain) system), W001 cationic tensio-active agents such as (abundant company systems); Nonionic class tensio-active agents such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan-fatty acid ester; W004, W005, W017 anionic species tensio-active agents such as (abundant company systems); EFKA-46, EFKA-47, EFKA-47EA, EFKA Port リマ-100, EFKA Port リマ-400, EFKA Port リマ-401, EFKA Port リマ-450 (above is the gloomy system of industry (strain) down), デイスパ-スエイ De 6, デイスパ-スエイ De 8, デイスパ-スエイ De 15, デイスパ-スエイ De 9100 macromolecule dispersing agents such as (サ Application ノプコ society systems); Various ソ Le スパ-ス dispersion agents (ゼネカ (strain) society system) such as ソ Le スパ-ス 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000; アデカプ Le ロニ Star Network L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification (strain) society system) and イソネ Star ト S-20 (Sanyo changes into (strain) society system).In addition, the pigment dispersing agent of putting down in writing in the also suitable use 2000-239554 communique, and the compound of the synthesis example of putting down in writing in compound of putting down in writing in the special fair 5-72943 communique of Japan (C) and the TOHKEMY 2001-31885 communique 1 etc.

For the organic nanometer granule dispersive composition, can make the organic nanometer granule (primary granule) behind the redispersion form fine dispersed particles, particle diameter is preferably 1～200nm, and more preferably 2～100nm is preferably 5～50nm especially.In addition, particulate Mv/Mn is preferably 1.0～2.0 behind the redispersion, and more preferably 1.0～1.8, excellent especially is 1.0～1.5.

Manufacturing method according to the invention, for example for contained granules of pigments in organic nano granules of pigments dispersive composition or the photosensitive composition described later, although be that (for example 10～100nm) nominal particle size also can concentrate redispersion to so-called nano-scale.Therefore, when being used for colour filter, the excellent in uniformity on its optical concentration height, colour filter surface, contrast gradient height, and reduced picture noise.

And, can make organic nano granules of pigments contained in organic nano granules of pigments dispersive composition, the photosensitive composition carry out height or fine equably dispersion, therefore than also bringing into play the brilliant idea depth of shade under the minimal thickness, for example can make colour filter etc. realize thin layerization.

For organic nano granules of pigments dispersive composition, photosensitive composition, by it being contained demonstrate distinct tone and high-strength pigment, for example color is drawn a design or the Image forming material of colour filter etc. is excellent as being used to make for it.

And; exposure during for the formation rendered image, the alkaline-based developer that uses when developing; can use as the material in the alkaline aqueous solution of dissolving in of binding agent in organic nanometer granule dispersive composition, coloring photosensitive combination, this also meets the needs of environment protection.

In addition,, can use organic solvent with appropriate drying property as the solvent that uses in organic nano granules of pigments dispersive composition, the coloring photosensitive combination (dispersing of pigments medium), from the coating after drying, also can satisfy this requirement.

[photosensitive composition]

Photosensitive composition of the present invention contains (a) organic nano granules of pigments, (b) binding agent, (c) monomer or oligopolymer and (d) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system at least.Below, each composition of photosensitive composition of the present invention is described.

(a) organic nano granules of pigments

Making method about the organic nano granules of pigments is described in detail.The content of organic nano granules of pigments, with respect to the whole solid substances in the photosensitive composition (in the present invention, all solid substances are meant the total of the component except that 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 on the adaptability sometimes.If very few, tinting strength deficiency sometimes.As the organic nano granules of pigments with tinting material function, its particle diameter is preferably below the 0.1 μ m, and particularly preferable particle size is below the 0.08 μ m.In addition, also can be used in combination with the common pigments that is used to mix colours.Pigment can use above-described kind.In the present invention, organic nanometer granule is preferably as the non-aqueous dispersion thing of above-mentioned organic nano pigment.

(b) binding agent

As the binding agent in the photosensitive composition, can preferably use above-mentioned weight-average molecular weight is macromolecular compound more than 1000.The content of binding agent is generally 15～50 quality % with respect to whole solid substances of photosensitive composition, is preferably 20～45 quality %.If should measure too much, sometimes the viscosity of composition is too high, makes on the adaptability and can have problems.If very few, then having problems aspect the formation coated film.

(c) monomer or oligopolymer

Monomer or oligopolymer contained in the photosensitive composition of the present invention are preferably the ethylenical unsaturated double bonds that has more than 2, and can carry out the monomer or the oligopolymer of addition polymerization by illumination.As this monomer or oligopolymer, can enumerate and have at least one ethylenically 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 Dipentaerythritol six (methyl) acrylate, 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 (acryloyl-oxy propyl group) ether, three (acrylyl oxy-ethyl) isocyanuric acid ester, three (acrylyl oxy-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 material 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 those compounds that form through (methyl) acroleic acid esterification again of record in (2) as suitable material behind addition of ethylene oxide on the polyfunctional alcohol or propylene oxide.

In addition, also can enumerate Japanese Patent Publication 48-41708 communique, special public clear 50-6034 communique and the special urethane acrylate class of putting down in writing in the clear 51-37193 communique of opening; The spy opens the polyester acrylate class of putting down in writing in clear 48-64183 communique, special public clear 49-43191 communique and the special public clear 52-30490 communique; Polyfunctional acrylic ester or methacrylic esters such as epoxy acrylate class as Resins, epoxy and (methyl) acrylic acid resultant of reaction.

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

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

These monomers or oligopolymer are (as monomer or oligopolymer, preferred its molecular weight is 200～1000) can use separately, or mix more than 2 kinds and use, this monomer or oligopolymer are generally 5～50 quality % with respect to the content of whole solid substances of photosensitive composition, are 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 sometimes exposing.

(d) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system

As the Photoepolymerizationinitiater initiater that in photosensitive composition of the present invention, contains 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 disclosed ortho position idol acyl ketone compound (vicinalpolyketaldonyl) 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; 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 benzene salt etc. are as preferred material.

These Photoepolymerizationinitiater initiaters or Photoepolymerizationinitiater initiater system can be used separately, also can mix more than 2 kinds and use, and especially preferably use more than 2 kinds.If use at least 2 kinds of Photoepolymerizationinitiater initiaters, then can reduce the demonstration non-uniform phenomenon in the display characteristic especially.

With respect to photosensitive 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, sometimes susceptibility is too high, is difficult to control.If very few, sometimes exposure sensitivity is low excessively.The radioactive rays that adopt during as exposure, ultraviolet rays such as preferred especially g line, i line.Irradiation dose is preferably 5～1500mJ/cm ², 10～1000mJ/cm more preferably ², most preferably be 10～500mJ/cm ²

(other additive)

[solvent]

In photosensitive composition of the present invention, except that mentioned component, in addition can also be with an organic solvent.To being not particularly limited as representative examples of organic, can enumerate the ester class, for example vinyl acetic monomer, n-butyl acetate, isobutyl acetate, the formic acid pentyl ester, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, the hydroxacetic acid methyl esters, the hydroxacetic acid ethyl ester, the hydroxacetic acid butyl ester, Methoxy Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid butyl ester, the oxyethyl group ritalin, the oxyethyl group vinyl acetic monomer, the 3-hydroxy methyl propionate, 3-hydroxy-propionic acid alkyl esters such as 3-hydroxy-propionic acid ethyl ester; 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 2-methoxyl group-2 Methylpropionic acid methyl esters, 2-oxyethyl group-2 Methylpropionic acid ethyl ester, Pyruvic Acid Methyl ester, Pyruvic Acid Ethyl ester, Propyl pyruvate, methyl acetoacetate, ethyl 3-oxobutanoate, the 2-beta-hydroxymethyl butyrate, 2-3-hydroxyethyl butyrate etc.; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran (THF), glycol monomethyl methyl ether, ethylene glycol monomethyl ether, acetic acid methylcyclohexane, acetic acid ethyl cellosolve, diethylene glycol monomethyl ether, propylene glycol methyl ether acetate etc.; Ketone, for example methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone, hexalin, 2-heptanone, 3-heptanone etc.; Arene, for example toluene, dimethylbenzene etc.In these solvents, preferably use 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, acetic acid ethyl cellosolve, ethyl lactate, N-BUTYL ACETATE, 3-methoxypropionic acid methyl esters, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, diethylene glycol monobutyl ether acetic ester, propylene glycol methyl ether acetate etc. as the solvent among the present invention.These solvents can use separately or organize more than 2 kinds and close use.

In addition, can use boiling point in case of necessity is 180 ℃～250 ℃ solvent.As these high boiling solvents, can the following material of illustration.Diethylene Glycol single-butyl ether, TC acetic ester, TC, 3,5,5-trimethylammonium-2-tetrahydrobenzene-1-ketone, n-Butyl lactate, DPGME acetic ester, propylene glycol monomethyl ether acetate, PGDA, propylene glycol n-propyl ether acetic ester, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxyl group-3-methyl butyl acetic ester, gamma-butyrolactone, tripropylene glycol methylethyl acetic ester, dipropylene glycol n-butyl acetate, propylene glycol phenyl ether acetate, 1,3 butylene glycol diacetate.

The content of solvent is preferably 10～95 quality % with respect to the resin combination total amount.

[tensio-active agent]

The colour filter of Shi Yonging in order to realize high color purity, need make each color of pixel enriching in the past, and people recognize and do the following problem that exists like this that promptly the membrane thickness unevenness of pixel causes color inhomogeneous.Therefore, when forming the photo-sensitive resin that (coating) have a direct impact the pixel film thickness, need the change of improvement thickness.

For colour filter of the present invention or use the transfer materials of coloring phototonus resin of the present invention, from controlling uniform thickness, effectively preventing from the viewpoint of crawling even (color that Thickness Variation causes is inhomogeneous) from preferably to make and containing suitable tensio-active agent in this photosensitive composition.

As above-mentioned 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 resin combination total amount, the content of tensio-active agent is preferably below the 5 quality %.

[thermopolymerization prevents agent]

In photosensitive composition of the present invention, preferably contain thermopolymerization 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 '-sulphur two (3 methy 6 tert butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole, thiodiphenylamine etc.With respect to the resin combination total amount, thermopolymerization prevents that the content of agent is preferably below the 1 quality %.

[auxiliary dyestuff, the pigment that uses]

In case of necessity, in photosensitive composition of the present invention, except that above-mentioned tinting material (pigment), can also add tinting material (dyestuff, pigment).When using the pigment in the tinting material, preferably make it in photosensitive composition, reach homodisperse, so its particle diameter is preferably below the 0.1 μ m, below 0.08 μ m.

As dyestuff or pigment, specifically, as above-mentioned pigment, be fit to use the coloured material of putting down in writing in [0038]～[0040] of TOHKEMY 2005-17716 communique, the spy opens the pigment of record in 2005-361447 communique [0068]～[0072], and the special tinting material of putting down in writing in [0080]～[0088] of 2005-17521 communique of opening.With respect to the resin combination total amount, the auxiliary dyestuff that uses or the content of pigment are preferably below the 5 quality %.

[UV light absorber]

In case of necessity, can contain UV light absorber in the photosensitive composition of the present invention.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.

Specifically, can enumerate the Whitfield's ointment phenylester, 4-tert-butyl-phenyl salicylate, 2,4-di-tert-butyl-phenyl-3 ', 5 '-di-t-butyl-4 '-hydroxybenzoate, 4-tert-butyl-phenyl salicylate, 2, the 4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, Octabenzone, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-cyano group-3, the 3-diphenyl-ethyl acrylate, 2,2 '-hydroxyl-4-methoxy benzophenone, nickel dibutyl dithiocarbamate, two (2,2,6,6-tetramethyl--4-pyridine)-sebacate, 4-tert-butyl-phenyl salicylate, the Whitfield's ointment phenylester, 4-hydroxyl-2,2,6,6-tetramethyl piperidine condenses, succsinic acid-two (2,2,6,6-tetramethyl--4-piperidyl)-ester, 2-[2-hydroxyl-3, two (α, the α-Er Jiajibianji) phenyl of 5-]-the 2H-benzotriazole, 7-{[4-chloro-6-(diethylin)-5-triazine-2-yl] amino }-3-phenyl tonka bean camphor etc.With respect to the resin combination 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 photosensitive composition of the present invention.

[coated film of photosensitive composition]

The composition that is contained in the coated film with photosensitive composition formation of the present invention is identical with the composition of having put down in writing in [photosensitive composition] item.In addition, the thickness of the coated film that forms with photosensitive composition of the present invention 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.For the coated film that forms with photosensitive composition of the present invention, make wherein contained (c) monomer or oligopolymer carry out the polymeric membrane that polymerization forms photosensitive composition, can make the colour filter (, hereinafter stating) that contains this film about the making of colour filter.The polymerization of polymerizable monomer or polyreactive oligomers can be undertaken by (d) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system are worked.

[colour filter and manufacture method thereof]

Below colour filter of the present invention and manufacture method thereof are described.

Colour filter of the present invention is characterised in that to have by the formed colored pattern of Photocurable composition of the present invention (photosensitive composition) on supporting mass.

Under regard to colour filter of the present invention, be elaborated by its manufacture method (manufacturing method of color filter of the present invention).

Manufacturing method of color filter of the present invention is characterised in that, this manufacture method comprises following operation: Photocurable composition of the present invention directly or by other layer is attached on the substrate, to form the operation (following suitably abbreviate as " photosensitive film formation operation ") of photosensitive film; Carry out the operation (following suitably abbreviate as " exposure process ") of pattern exposure (exposing) by mask; Photosensitive film after the exposure is developed, to form the operation (following suitably abbreviate as " developing procedure ") of colored pattern.

Below, each operation in the color filter manufacturing method of the present invention is described.

(photosensitive film formation operation)

In photosensitive film forms operation, Photocurable composition of the present invention directly is coated with (add) on the substrate or be coated on the substrate with other layer, with the formation photosensitive film.

As the substrate that in this operation, uses, for example, can enumerate the soda glass that is used for liquid crystal display device etc., パイレ Star Network ス (registered trademark) glass, silica glass and at these substrates that are attached with nesa coating and form on glass, the photo-electric conversion element substrate (for example, silicon substrate etc.) that is used for imaging apparatus etc., complementary burning film semiconductor (CMOS) etc.On these substrates, sometimes can form the black streaking of isolating each pixel.

In addition, in case of necessity, for the adherence of improving substrate and top layer or prevent the diffusion of material or make the flattening surface of substrate, coating (other layer) down can be set on these substrates also.

Method as Photocurable composition of the present invention being coated on the substrate can suitably adopt various coating processes such as slot coated method, spraying method, method of spin coating, curtain coating coating method, rolling method, silk screen print method.

As the coating film thickness of Photocurable composition, be preferably 0.1～10 μ m, more preferably 0.2～5 μ m, more preferably 0.2～3 μ m.

For the drying that is coated on the photosensitive film on the substrate (prebake), can be to heat 10～300 seconds under 50 ℃～140 ℃ the condition in temperature with hot-plate or baking oven etc.

(exposure process)

In exposure process, will in above-mentioned photosensitive film formation operation, expose by mask by formed photosensitive film with predetermined mask pattern, that is, carry out pattern exposure.

In this operation, the photosensitive film as coated film is exposed by the predetermined mask pattern, just be cured thereby only make by light-struck that part of coated film.

Operable radioactive rays during as exposure especially preferably use ultraviolet rays such as g line, i line.Irradiation dose is preferably 5～1500mJ/cm ², 10～1000mJ/cm more preferably ², most preferably be 10～500mJ/cm ²

When colour filter of the present invention was used for liquid crystal display device, irradiation dose was preferably 5～200mJ/cm in the above range ², 10～150mJ/cm more preferably ², most preferably be 10～100mJ/cm ²In addition, when colour filter of the present invention was used for solid-state imager, irradiation dose was preferably 30～1500mJ/cm in the above range ², 50～1000mJ/cm more preferably ², most preferably be 80～500mJ/cm ²

(developing procedure)

Next, by being partly dissolved in the developing solution of carrying out development treatment, make in exposure process, not being exposed, only remaining by the part of photocuring.As developing solution, can use any material, as long as it can be with that part of film dissolving that is not cured in the Photocurable composition, and do not dissolve the part that has been cured and get final product.Specifically, can use the combination of various organic solvents or the aqueous solution of alkalescence.

Development temperature is generally 20 ℃～30 ℃, and development time is 20～90 seconds.

As described organic solvent, the solvent that those preambles that use in the time of can being set forth in preparation pigment dispensing composition of the present invention or Photocurable composition have been described.

The aqueous solution as above-mentioned alkalescence, preferably following basic cpd to be diluted to concentration with pure water be 0.001～10 quality %, be preferably the alkaline aqueous solution that 0.01～1 quality % obtains, wherein said basic cpd for example is sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, water glass, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-the 7-hendecene etc.

In addition, when using the developing solution that is made of these alkaline aqueous solutions, in general, (flushing) washed with pure water in the back of developing.

Behind developing procedure, after remaining developing solution and drying are removed in washing, carry out heat treated (back oven dry).

The back oven dry is the heat treated of carrying out behind developing procedure in order to make the substrate completely solidified, carries out thermofixation usually and handle under 100 ℃～240 ℃.When if substrate is glass substrate or silicon substrate, in the said temperature scope preferred 200 ℃～240 ℃.

Employing can reach the hot-plate or the heater meanses such as convection oven (heated air circulation type drying machine), high frequency heating machine of above-mentioned condition, the coated film after developing is carried out the back oven dry continuously or in batch handle.

As mentioned above, form operation, exposure process and developing procedure (if desired, also having heat treated), can produce the colour filter that constitutes by desired color by the photosensitive film that repeats corresponding desired number of colors purpose number of times.

Photocurable composition of the present invention is attached on the substrate when forming film, and the dried thickness of film is generally 0.3～5.0 μ m, is preferably 0.5～3.5 μ m, and expectation is 1.0～2.5 μ m.

As substrate, for example, can enumerate the non-alkali glass that is used for liquid crystal display device etc., soda glass, パイレ Star Network ス (registered trademark) glass, silica glass and in these substrates that are attached with nesa coating and form on glass, the photo-electric conversion element substrate (for example, silicon substrate etc.) that is used for solid-state imager and plastic etc.On these substrates, can form usually in order to isolate the black streaking of each pixel.

For plastic, barrier layer for gases and/or anti-solvent layer are arranged in its surface preferably.

As the purposes of Photocurable composition of the present invention, its purposes as the pixel of colour filter has mainly been described in this article, also be suitable for being arranged on the black matrix between the pixel of colour filter certainly.Can use a kind of like this black matrix, this black matrix is to form by add black colorants such as carbon black, titanium as tinting material be black in Photocurable composition of the present invention after, in addition, adopt the method identical with the making method of above-mentioned pixel, this black matrix is carried out pattern exposure, alkaline development, and then back curing of drying, thereby form this black matrix with the promotion film.

Embodiment

(embodiment 1)

[preparation of organic nano granules of pigments aqueous liquid dispersion]

C.I. Pigment red 254 (45 mass parts) and polyvinylpyrrolidone (K-25, Wako Pure Chemical Industries, Ltd.'s system, 90 mass parts) are joined in the dimethyl sulfoxide (DMSO) (DMSO) (953 mass parts), and stir.The methanol solution (30 parts by volume) that adds the sodium methylate of 28 quality % in this solution is prepared into pigment solution A.In addition, prepare the insoluble solvent B of water (4000 mass parts) as pigment.

The rotating speed stirring of the GK-0222-10 type ラモ Application De agitator (trade(brand)name) of rattan pool pharmaceutical industry Co., Ltd. manufacturing with 500rpm used with the insoluble solvent B of above-mentioned pigment in the limit under 30 ℃, the limit is injected into above-mentioned pigment solution A among the insoluble solvent B of this pigment with the flow velocity of 100ml/min with the NP-KX-500 type large vol pulseless pump (trade(brand)name) that Japanese exact science society makes, injection length is 4 minutes 4 seconds, the crystallization of pigment dyestuff nano particle is separated out, thereby obtain the organic nanometer granule aqueous liquid dispersion.

Adopt the hole field to make the LB-400 (trade(brand)name) that Co., Ltd. of institute makes, it is estimated according to dynamic light scattering method.With median diameter as median size and as the dispersiveness evaluation index.In addition, because dynamic light scattering method also can be observed secondary agglutinative particle, so adopt transmission electron microscope that primary granule is estimated.

[aggegation]

To be dissolved in the acetone (200 mass parts) as the acetic acid (45 mass parts) of non-ionic type low molecular compound with as the C-1 (3 mass parts) of non-ionic macromolecule compound, then it is joined in the above-mentioned organic nanometer granule aqueous liquid dispersion (300 mass parts), stirred 0.5 hour.After leaving standstill 0.5 hour, the agglomeration with observation by light microscope generates makes the agglomeration sedimentation then, supernatant liquor is decanted remove.

[separating, washing drying]

Adopt filter paper (manufacturing of ADVANTEC society, No.2) to filter out above-mentioned agglomeration, measure this moment and filter the needed time.With solid water (300 mass parts) and methyl alcohol (200 parts by volume) washing that filters out.The solid that obtains was made soup compound again with acetonitrile (100 parts by volume) in 0.5 hour, left standstill then 0.5 hour, supernatant liquor is decanted remove.The solid vacuum-drying at room temperature that obtains is spent the night.

[redispersion]

Following non-aqueous solvent acetic acid 1-methoxyl group-2-propyl ester (4 mass parts) is joined in this pigment dyestuff solid (1 mass parts), adopt that Japan is accurate to make the ultrasonic irradiation that ultrasonic homogenizer US series (trade(brand)name) that Co., Ltd. of institute makes was carried out 3 hours, obtain thus with following non-aqueous solvent as the organic nanometer granule non-aqueous dispersion of dispersion agent (below be also referred to as pigment dispensing composition A).

Non-aqueous solvent

(evaluation test)

Resulting dispersive composition is carried out following evaluation, and the result is as shown in table 1.

(1) median size of organic nanometer granule aqueous liquid dispersion

Adopt the hole field to make the LB-500 (trade(brand)name) that Co., Ltd. of institute makes, it is estimated according to dynamic light scattering method.As median size, measure the median size of organic nanometer granule aqueous liquid dispersion with median diameter.

(2) diameter of agglomeration

Use the observation by light microscope agglomeration, and with the observed benchmark of other method as reference, the diameter of agglomeration is measured.About the diameter of said agglomeration herein, measure from the length of the end to end of agglomeration, and the longest length in this length is defined as diameter.Said herein agglomeration is meant the second particle that forms by growing up behind the nanoparticle aggregate as primary granule that originally is invisible to the naked eye.

(3) filtration time

Use Nutsche filter and the filter paper (Off イ Le one ペ one パ, one No.2 (trade(brand)name) that ア De バ Application テ Star Network society makes) of diameter 9cm, and adopt vacuum fan to carry out filtration under diminished pressure, measure the required filtration time of every filtration 1g pigment.

(4) mensuration of viscosity

For resulting dispersive composition, adopt E type viscometer after disperseing, to measure the viscosities il of pigment dispensing composition immediately ¹And in the viscosities il of disperseing (at room temperature) week back mensuration pigment dispensing composition ², estimate the degree that viscosity increases.Herein, low expression dispersiveness of viscosity and dispersion stabilization are good.

(5) evaluation of contrast gradient

The pigment dispensing composition A separate application that obtains is made thickness on glass substrate be 2 μ m, to make 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 FWL18EX-N), between two polaroids (the polaroid HLC2-2518 that (strain) サ Application リ Star society makes), place 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 , plant wood, Xiao Guan, good fortune forever, in the mountain " etc.).For the mensuration of colourity, use color briliancy instrument (BM-5 that (strain) トプコ Application society makes).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 briliancy was 1280cd/m when two polaroids were arranged at parallel Nicol ²

(embodiment 2)

Carry out operation similarly to Example 1, difference is the non-ionic type low molecular compound among the embodiment 1 is replaced with the valeric acid 2-propyl ester of non-ionic type.With the organic nanometer granule non-aqueous dispersion that obtains as pigment dispensing composition B.Pigment dispensing composition B is carried out similarly to Example 1 evaluation test, and the result is as shown in table 1.

(embodiment 3)

Carry out operation similarly to Example 1, difference is the non-ionic macromolecule compound among the embodiment 1 is replaced with the C-10 of non-ionic type.With the organic nanometer granule non-aqueous dispersion that obtains as pigment dispensing composition C.Pigment dispensing composition C is carried out similarly to Example 1 evaluation test, and the result is as shown in table 1.

(embodiment 4)

Carry out operation similarly to Example 1, difference is that the polyvinylpyrrolidone among the embodiment 1 is replaced with cationic high-molecular disperses drug C-5, the non-ionic type low molecular compound is replaced with anionic low molecular compound E-3, the anionic macromolecular compound is replaced with anionic macromolecular compound F-2.With the organic nanometer granule non-aqueous dispersion that obtains as pigment dispensing composition D.Pigment dispensing composition D is carried out similarly to Example 1 evaluation test, and the result is as shown in table 1.

(embodiment 5)

Carry out operation similarly to Example 1, difference is for the organic nanometer granule aqueous liquid dispersion among the embodiment 1, non-ionic macromolecule compound is wherein replaced with the methacrylic acid/methacrylic acid benzyl ester multipolymer of non-ionic type.With the organic nanometer granule non-aqueous dispersion that obtains as pigment dispensing composition E.Pigment dispensing composition E is carried out similarly to Example 1 evaluation test, and the result is as shown in table 1.

(embodiment 6)

Carry out operation similarly to Example 1, difference is for the organic nanometer granule aqueous liquid dispersion among the embodiment 1, after the acetic acid that wherein adds as the non-ionic type low molecular compound, the C-1 as non-ionic macromolecule compound is dissolved in the acetone and with it adds in the organic nanometer granule aqueous liquid dispersion.With the organic nanometer granule non-aqueous dispersion that obtains as pigment dispensing composition F.Pigment dispensing composition F is carried out similarly to Example 1 evaluation test, and the result is as shown in table 1.

(embodiment 7)

Carry out operation similarly to Example 1, difference is for the organic nanometer granule aqueous liquid dispersion among the embodiment 1, C-1 as non-ionic macromolecule compound is dissolved in the acetone and with it adds in the organic nanometer granule aqueous liquid dispersion, and then add acetic acid as the non-ionic type low molecular compound.With the organic nanometer granule non-aqueous dispersion that obtains as pigment dispensing composition G.Pigment dispensing composition G is carried out similarly to Example 1 evaluation test, and the result is as shown in table 1.

(embodiment 8)

Make resulting agglomeration sedimentation among the embodiment 1, and supernatant liquid decanted remove, add entry (200 mass parts) then, in 0.5 hour, make soup compound again, leave standstill again to make in 0.5 hour and disperse the thing sedimentation, and supernatant liquid decanted remove.In addition, go into methyl alcohol (100 mass parts), in 0.5 hour, make soup compound again, leave standstill again to make in 0.5 hour and disperse the thing sedimentation, and supernatant liquid decanted remove to machine wherein.Add acetonitrile (100 mass parts) again, in 0.5 hour, make soup compound again, leave standstill again to make in 0.5 hour and disperse the thing sedimentation, supernatant liquid is decanted remove.Then, carry out similarly to Example 1 operation.With the organic nano granules of pigments non-aqueous dispersion that obtains as pigment dispensing composition H.Pigment dispensing composition H is carried out similarly to Example 1 evaluation test, and the result is as shown in table 1.

(comparative example 1)

Add hydrochloric acid (64 mass parts) in the organic nanometer granule aqueous liquid dispersion for preparing to adopting operation similarly to Example 1, make the nano particle aggegation, use strainer (H010A047A, trade(brand)name that ア De バ Application テ Star Network society makes) to filter, measure the needed time.Adopt for the solid that filters out that similarly to Example 1 method is washed, drying, in resulting solid (1 mass parts), add methacrylic acid/methacrylic acid benzyl ester multipolymer (1 mass parts) and acetic acid 1-methoxyl group-2-propyl ester (8 mass parts), the ultrasonic irradiation that adopts the accurate ultrasonic homogenizer US series (trade(brand)name) of making the manufacturing of Co., Ltd. of institute of Japan to carry out 3 hours obtains thus with the organic nanometer granule non-aqueous dispersion of following non-aqueous solvent as dispersion agent.With the organic nanometer granule non-aqueous dispersion that obtains as pigment dispensing composition I.According to estimating with the same mode of the evaluation test of embodiment 1.Pigment dispensing composition I is carried out similarly to Example 1 evaluation test, and the result is as shown in table 1.

(test example 1)

Adding is dissolved with the acetone (200 mass parts) of acetic acid (45 mass parts) in adopting the organic nanometer granule aqueous liquid dispersion (300 mass parts) for preparing with the same operation of embodiment 1～8 and comparative example 1, with this agglomeration of observation by light microscope, use strainer (H010A047A, trade(brand)name that ア De バ Application テ Star Network society makes) to filter then, measure the needed time.

Evaluation result is as follows.

(reference example 1)

Add the acetone (200 mass parts) that is dissolved with acetic acid (45 mass parts) in the organic nanometer granule aqueous liquid dispersion (300 mass parts) for preparing to adopting operation similarly to Example 1, with this agglomeration of observation by light microscope, use strainer (H010A047A, trade(brand)name that ア De バ Application テ Star Network society makes) to filter then, measure the needed time.

Evaluation result is as follows.

[table 1]

By The above results as can be seen, the invention provides non-aqueous dispersion thing of a kind of organic nanometer granule and manufacture method thereof, wherein, adopted when forming the non-aqueous dispersion thing of organic nanometer granule in that the organic nanometer granule aqueous dispersion is carried out phase transition such as with the flushing operation be the manufacturing water-based mashed prod of representative operation (, needs such as strainer filtration etc. expend numerous and diverse operation of plenty of time), the present invention is can easy filtering agglomeration with the nanoparticle conversion in the organic nanometer granule aqueous dispersion, isolate this agglomeration, and with its redispersion in non-aqueous solvent, thereby can obtain the non-aqueous dispersion thing of described organic nanometer granule expeditiously.In addition, the present invention also provides a kind of excellent dispersion and has the non-aqueous dispersion thing of organic nanometer granule and the manufacture method thereof of high-contrast.

[preparation of photosensitive composition]

In embodiment 1～8, comparative example 1, among resulting pigment dispensing composition A～I, add the composition of following composition, mix, make photosensitive composition of the present invention (colored liquid against corrosion).

Form

Dipentaerythritol acrylate 80 mass parts

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

Methacrylic acid benzyl ester/methacrylic acid (=70/30[mol ratio]) multipolymer (weight-average molecular weight: propylene glycol monomethyl ether acetate solution (solid substance accounts for 40%) 10,000)

200 mass parts

Acetic acid 1-methoxyl group-2-propyl ester 490 mass parts

Resulting Photocurable composition (colored liquid against corrosion) is coated on the glass substrate (1737, コ one ニ Application グ society makes) of 100mm * 100mm, feasible x value as the depth of shade index is 0.650, dry (prebake) in 60 seconds in 90 ℃ baking oven.Then, at 200mJ/cm ²(illumination is 20mW/cm ²) condition under carry out blanket exposure to filming, with filming after the exposure, placed for 60 seconds with 1% aqueous solution coating of alkaline-based developer CDK-1 (the Off イ of Fuji Le system エレ Network トロニ Network スマテリア Le ズ (strain) manufacturings).After the placement, with pure water drip washing to wash away developing solution.Then, will carry out above-mentioned exposure and develop after the heat treated 1 hour (back oven dry) in 220 ℃ baking oven of filming, thereby on glass substrate, form the pigmentary resin overlay film that colour filter is used, make painted filter substrate (colour filter).

Adopt the contrast gradient of the R composition of resulting each film of method mensuration similarly to Example 1, the result is as shown in the table.

[table 2]

By The above results as can be seen, compare the photosensitive composition that forms by the resulting organic nanometer granule non-aqueous dispersion of the present invention organic granular and the colour filter that makes demonstrates very excellent contrast gradient with comparative example.

Claims

1. the manufacture method of an organic nano pigment particle agglutination body, it is characterized in that, organic low molecular compounds by making the organic nano granules of pigments that is scattered in the aqueous medium and at least a molecular weight less than 1000 and at least a weight-average molecular weight are that the organic high molecular compound more than 1000 is had an effect, make described organic nano pigment particle agglutination, separate then.

2. the manufacture method of the described organic nano pigment particle agglutination of claim 1 body, it is characterized in that, with described organic low molecular compounds and organic high molecular compound with can with described aqueous medium blended dissolution with solvents mutually, join then in this aqueous medium, make the organic nano pigment particle agglutination that is scattered in the aqueous medium thus.

3. the manufacture method of claim 1 or 2 described organic nano pigment particle agglutination bodies is characterized in that described separation is undertaken by filtration.

4. the manufacture method of any described organic nano pigment particle agglutination body in the claim 1～3 is characterized in that, this manufacture method comprises the operation of removing to the unnecessary described organic low molecular compounds of major general.

5. the manufacture method of any described organic nano pigment particle agglutination body in the claim 1～4, it is characterized in that, the pigment dyestuff solution that pigment dyestuff is dissolved in the good solvent and obtains with can be miscible and for the medium of the poor solvent of described pigment dyestuff mixes mutually with this good solvent, thereby obtain the organic nano granules of pigments in the described aqueous medium of being scattered in the form generation of nanometer sized particles.

6. the manufacture method of any described organic nano pigment particle agglutination body in the claim 1～5 is characterized in that, the average primary particle diameter of described organic nano granules of pigments is below the 100nm.

7. the manufacture method of any described organic nano pigment particle agglutination body in the claim 1～6 is characterized in that, the median size of described agglomeration is more than the 10000nm.

8. the manufacture method of the non-aqueous dispersion thing of organic nano granules of pigments, it is characterized in that, with any described organic nano pigment particle agglutination body redispersion in the claim of separating 1～7 in non-aqueous media and obtain the non-aqueous dispersion thing of described organic nano granules of pigments.

9. the manufacture method of the non-aqueous dispersion thing of the described organic nano granules of pigments of claim 8 is characterized in that, described macromolecular compound such as following general formula (11) or general formula (14) are represented,

General formula (11)

In the above-mentioned general formula (11), A ¹It is 1 valency organic group of the group in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl more than 4 that expression has the group, urea groups, urethano, the group of band coordination Sauerstoffatom, the carbon number that are selected from acidic-group, band basic nitrogen atom, or represent to contain to have substituent organic pigment structure or heterocyclic 1 valency organic group, n A ¹Can be identical, also can be different; R ¹The linking group of expression (m+n) valency, m+n represents 3～10; M represents 1～8 integer, and n represents 2～9 integer; R ²The linking group of expression singly-bound or divalent; P ¹Expression polymer residue;

General formula (14)

In the above-mentioned general formula (14), G ^-Expression-COO ^-,-SO ₃ ^-,-OSO ₃ ^-,-P (O) is O (OH) ^-, or-(OH) O of OP (O) ^-J represents the linking group or the singly-bound of divalent; Q represents the linking group of (m+1) valency; R represents the macromolecular compound residue; Z ⁺Expression organic or inorganic positively charged ion; M+1 represents 3～6.

10. the manufacture method of the non-aqueous dispersion thing of the described organic nano granules of pigments of claim 9 is characterized in that, described organic high molecular compound is directly as the dispersion agent in the described non-aqueous media.

11. a photosensitive composition, it contains claim 9 or the non-aqueous dispersion thing of 10 described organic nano granules of pigments, binding agent, monomer or oligopolymer and Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system at least.

12. a colour filter is characterized in that, this colour filter is to use the described photosensitive composition of claim 11 to make.