CN101400742A - Process for producing organic nanoparticle, organic nanoparticle obtained by the same, ink-jet ink for color filter containing the same, colored photosensitive resin composition, photosensitive resin - Google Patents

Process for producing organic nanoparticle, organic nanoparticle obtained by the same, ink-jet ink for color filter containing the same, colored photosensitive resin composition, photosensitive resin Download PDF

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CN101400742A
CN101400742A CNA2006800539472A CN200680053947A CN101400742A CN 101400742 A CN101400742 A CN 101400742A CN A2006800539472 A CNA2006800539472 A CN A2006800539472A CN 200680053947 A CN200680053947 A CN 200680053947A CN 101400742 A CN101400742 A CN 101400742A
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pigment
compound
group
solvent
organic
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松本圭右
草野隆之
宫下阳介
伊藤惟成
儿玉知启
伊藤英明
柴田直也
高桥秀知
吉野晴彦
鸭崎彻
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Fujifilm Corp
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Abstract

A process for producing organic nanoparticles which comprises mixing a solution of an organic material in a good solvent therefor with a solvent which is compatible with the good solvent and is a poor solvent for the organic material to precipitate the organic material and thereby prepare a dispersion of fine organic particles of a nanometer size, wherein a polymer having a mass-average molecular weight of 1,000 or higher represented by the following general formula (1) is incorporated in the dispersion. General formula (1) [In the formula, R<1> represents a connecting group having a valence of (m+n); R<2> represents a single bond or divalent connecting group; A<1> represents a specific monovalent organic group, provided the n A<1>'s may be the same or different; m is a number of 1-8 and n is a number of 2-9, provided that m+n is 3-10; and P<1> represents a residue of a polymer.

Description

The manufacture method of organic nano particle, the organic nano particle that obtains by this method, the ink-jet ink for color filter that contains this particle, photosensitive composition, and photosensitive resin transfer material and the colour filter, liquid crystal indicator and the CCD device that use them
Technical field
The colour filter, liquid crystal indicator and the CCD device that the present invention relates to the manufacture method of organic nano particle and the organic nano particle that obtains by this method, the ink-jet ink for color filter that contains this organic nano particle, photosensitive composition and photosensitive resin transfer material and use them.
Background technology
People study the size that reduces particle in recent years.Particularly, the purpose of research is to make size of particles to be reduced to nano-scale (for example, the scope of 10nm～100nm), this by methods such as comminuting method be difficult to produced.In addition, people are attempting not only making size of particles be reduced to nanometer scale, but also will make it become monodispersed particle.
The particulate of this nano-scale but is in position between common macroparticle and molecule or atom not in size range in the past, the someone points out that this nanoparticle shows the characteristic of beyond thought novelty.And, if can improve the monodispersity of these nanoparticles, their characteristic is stablized.So the nanoparticle that possesses this possibility all obtains paying close attention in different fields, and in such as a plurality of 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 nano particle of being made by organic compound is because organic compound itself has diversity, so it has great potential as functional materials.For example, polyimide is the material of a kind of chemically stable and mechanically stable, and has outstanding electrical insulation characteristics owing to have thermotolerance, solvent resistance, mechanical characteristics etc., therefore is used to different fields.With medlin particulateization, and characteristic and the shape that polyimide has made up, can further be widely used in every field.For example, the someone has proposed such motion: with the polyimide after the micronize as (referring to the patent documentations 1) such as additives that form in the powder toner that image uses.
In addition, in organic nano particle, pigment dyestuff is used to such as coating, printing with in the application such as ink, electrophoto-graphic toner, ink for ink-jet print and colour filter.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 used as the pigment of ink for ink-jet print, but dyestuff has problems aspect water tolerance and photostabilization, in order to address this problem, adopts pigment 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 lip-deep intrapore nanometer size and the pigment particle that have high monodispersity of paper, there is its problem to the poor adhesion of paper in the such image of result.
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.Pigment dyestuff is used in the colour filter, and the thickness of colour filter depends on the particle diameter of pigment dyestuff to a great extent, and therefore, the particulate of nano-scale is made in expectation, and it has stability when monodisperse status.
Preparation method about organic filler, people have studied following method: vapor phase process (makes the sample distillation under inert gas atmosphere, in substrate, reclaim the method for particle then), liquid phase method (for example, the agitation condition and the temperature of control poor solvent will 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 (thereby by to be scattered in sample in the solution shine with laser make its ablation make the method for particle miniaturization) 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 large-duty method for preparing organic filler, especially noticeable (referring to patent documentation 2,3 etc.).Adopt liquid phase method to prepare organic filler,, can adjust the character of crystal formation and particle surface by solvent species, injection speed, temperature etc. are separated out condition adjustment.In patent documentation 3, put down in writing by the kind of adjusting poor solvent and come 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 particle dispersiveness, all the time, the various dispersion machines of industrial employing (roller mill, ball mill, runner milling etc.) disperse pigment dyestuff, yet when adopting these methods to carry out the miniaturization of particle, sometimes viscosity can rise.And if viscosity rises, will cause product to be difficult to from dispersion machine, take out, perhaps can not carry by pipeline, perhaps what is more, gelation takes place and can not use in meeting in storage.In order to address these problems, can help the dispersive dispersion agent, can make the method for disperseing to obtain stable polymer though adopt to add, can not get effect of sufficient (referring to non-patent literature 1 etc.).
And the pigment dyestuff dispersion liquid of using for colour filter, in order to improve its dispersiveness, in the manufacturing processed of colour filter, need to add and to give the polymkeric substance and the pigment dispersing agent (for example, referring to patent documentation 4) of its necessary alkali-developable and these two kinds of character of dispersion stabilization.But in these methods, dispersion will expend time in, and viscosity can rise etc., thereby can not reach requirement fully.
In addition, bibliographical information has been arranged adopted the pigment particles for preparing according to above-mentioned liquid phase method, made dispersed improved example.In patent documentation 5, put down in writing the example for preparing the pigment particles aqueous dispersion according to liquid phase method.But this method is that a kind of providing finally is the method for aqueous dispersion, and does not mention any about the method for organic solvent dispersion is provided.
In patent documentation 6, put down in writing pigment dissolved in basic cpd and/or basic solution, in liquid, add neutral compound and/or acidic cpd then, or neutral liquid and/or acidic liquid, so that the method that pigment is separated out.But, the organic pigment particles that adopts this method to obtain, its primary particle diameter is very big, can not fully satisfy micronized requirement.
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
Non-patent literature 1: face material Fen San Ji Intraoperative-surface treatment と dispersion agent makes い side お I び Fen San Evaluation value — Ji Intraoperative Qing Reported Association meeting 1999
Summary of the invention
The manufacture method that the purpose of this invention is to provide a kind of organic nano particle.In addition, the purpose of this invention is to provide a kind of method that agglutinative, organic nano particle that dispersion stabilization is high do not take place of can be in dispersion liquid making expeditiously.In addition, the purpose of this invention is to provide a kind of nanometer size and size distribution peak is the organic nano particle and the manufacture method thereof of sharp-pointed type.Further, the purpose of this invention is to provide the ink-jet ink for color filter, photosensitive composition and the photosensitive resin transfer material that have used above-mentioned organic nano particle, further, the purpose of this invention is to provide used above-mentioned ink-jet ink for color filter, photosensitive composition and photosensitive resin transfer material, have high-contrast and can bring into play colour filter, liquid crystal indicator and the CCD device of excellent display characteristic.
The invention provides following means:
(1) a kind of manufacture method of organic nano particle, it is characterized in that, the solution that will be dissolved in organic materials in the good solvent and form, with can be miscible and be that the solvent phase of poor solvent mixes to above-mentioned organic materials with above-mentioned good solvent, make described organic materials separate out the organic fine particles that generates nano-scale, thereby make the dispersion liquid of the organic fine particles of nano-scale, wherein, in this dispersion liquid, contain the represented matter average molecular weight of following general formula (1) and be the macromolecular compound more than 1000.
General formula (1)
(in the formula, R 1The connection base of expression (m+n) valency, R 2Expression singly-bound or divalent connect base; A 1Expression has 1 valency organic group of the group of selecting from acidic-group, the basic group that contains nitrogen-atoms, urea groups, urethano, the group that contains the coordination Sauerstoffatom, carbonatoms are alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and hydroxyl 4 or more, or represents to contain to have substituent organic pigment structure or heterocyclic 1 valency organic group; Wherein, n A 1Mutually can be identical, also can be different; M represents 1～8 number, and n represents 2～9 number, and m+n equals 3～10; P 1Expression macromolecular compound residue.〕
(2) manufacture method of the organic nano particle described in above-mentioned (1) is characterized in that, above-mentioned macromolecular compound is represented with following general formula (2).
Figure A200680053947D00132
General formula (2)
(in the formula, R 3The connection base of expression (x+y) valency, R 4And R 5Represent singly-bound or divalent linking group independently of one another; A 2Expression has 1 valency organic group of the group of selecting from acidic-group, the basic group that contains nitrogen-atoms, urea groups, urethano, the group that contains the coordination Sauerstoffatom, carbonatoms are alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and hydroxyl 4 or more, or represents to contain to have substituent organic pigment structure or heterocyclic 1 valency organic group; Wherein, x A 2Mutually can be identical, also can be different; Y represents 1～8 number, and x represents 2～9 number, and x+y equals 3～10; P 2Expression macromolecular compound residue.〕
(3) manufacture method of above-mentioned (1) or (2) described organic nano particle is characterized in that above-mentioned A 1Perhaps above-mentioned A 2For having the 1 valency organic group that the basic group, urea groups and the carbonatoms that are selected from acidic-group, contain nitrogen-atoms are the group in the alkyl more than 4.
(4) manufacture method of any described organic nano particle in above-mentioned (1)～(3) is characterized in that above-mentioned P 1Perhaps above-mentioned P 2Represented macromolecular compound residue is served as reasons and is selected from down at least a deutero-macromolecular compound residue in the group, and described group is made of polymer of vinyl monomer or multipolymer, ester cpds polymkeric substance, ether compound polymkeric substance, urethanes polymkeric substance, amide compound polymkeric substance, synthesis of epoxy compounds thing, polymerizable organosilicon compound thing and their modifier and multipolymer.
(5) a kind of manufacture method of organic nano particle, it is characterized in that, will be in good solvent and the pigment solution that forms pyrrolopyrrole compound pigment dissolved, with can be miscible with above-mentioned good solvent and solvent phase that be poor solvent to above-mentioned pyrrolopyrrole compound pigment mix, make described pigment dyestuff separate out the organic fine particles that generates nano-scale, thereby make the dispersion liquid of the organic fine particles of nano-scale, wherein, containing the matter average molecular weight in this dispersion liquid is macromolecular compound more than 1000.
(6) manufacture method of any described organic nano particle in above-mentioned (1)～(4) is characterized in that, described organic nano particle is a pyrrolopyrrole compound pigment.
(7) manufacture method of above-mentioned (5) or (6) described organic nano particle is characterized in that, above-mentioned pyrrolopyrrole compound pigment is the following represented pigment of formula V.
Figure A200680053947D00151
(8) manufacture method of above-mentioned (5) or (6) described organic nano particle is characterized in that, above-mentioned pyrrolopyrrole compound pigment is the represented pigment of following formula (Z).
Formula (Z)
(9) manufacture method of any described organic nano particle in above-mentioned (5) or (6) is characterized in that, above-mentioned pyrrolopyrrole compound pigment is the represented pigment of following formula (W).
Formula (W)
Figure A200680053947D00153
(10) a kind of manufacture method of organic nano particle, it is characterized in that, with Ba the dioxazine compound pigment dissolved in good solvent and the pigment dyestuff solution that forms, with can be miscible with above-mentioned good solvent and solvent phase that be poor solvent to above-mentioned dioxazine compound pigment mix, make described pigment dyestuff separate out the organic fine particles that generates nano-scale, thereby make the dispersion liquid of the organic fine particles of nano-scale, wherein, containing the matter average molecular weight in this dispersion liquid is macromolecular compound more than 1000.
(11) manufacture method of any described organic nano particle in above-mentioned (1)～(4) is characterized in that, described organic nano particle Wei dioxazine compound pigment.
(12) manufacture method of above-mentioned (10) or (11) described organic nano particle is characterized in that, above-mentioned dioxazine compound pigment is C.I. pigment violet 37.
(13) manufacture method of above-mentioned (10) or (11) described organic nano particle is characterized in that, above-mentioned dioxazine compound pigment is the C.I. pigment Violet 23.
(14) a kind of manufacture method of organic nano particle, it is characterized in that, will be in good solvent and the pigment dyestuff solution that forms the phthalocyanine compound pigment dissolved, with can be miscible with above-mentioned good solvent and solvent phase that be poor solvent to above-mentioned phthalocyanine compound pigment mix, make described pigment dyestuff separate out the organic fine particles that generates nano-scale, thereby make the dispersion liquid of the organic fine particles of nano-scale, wherein, in this dispersion liquid, contain the matter average molecular weight and be the macromolecular compound more than 1000.
(15) manufacture method of any described organic nano particle in above-mentioned (1)～(4) is characterized in that described organic nano particle is a phthalocyanine compound pigment.
(16) manufacture method of above-mentioned (14) or (15) described organic nano particle is characterized in that, above-mentioned phthalocyanine compound pigment is the C.I. pigment Green 7.
(17) manufacture method of above-mentioned (14) or (15) described organic nano particle is characterized in that, above-mentioned phthalocyanine compound pigment is the C.I. pigment green 36.
(18) manufacture method of above-mentioned (14) or (15) described organic nano particle is characterized in that, above-mentioned phthalocyanine compound pigment is C.I. Pigment green 15:6.
(19) manufacture method of any described organic nano particle in above-mentioned (1)～(18) is characterized in that, above-mentioned dispersion liquid is concentrated.
(20) manufacture method of any described organic nano particle in above-mentioned (1)～(19) is characterized in that described macromolecular compound is the macromolecular compound with acidic-group.
(21) manufacture method of any described organic nano particle in above-mentioned (1)～(20) is characterized in that the acidic-group of above-mentioned macromolecular compound is a carboxyl.
(22) manufacture method of any described organic nano particle in above-mentioned (1)～(21) is characterized in that the matter average molecular weight of above-mentioned macromolecular compound is 3000～100000.
(23) manufacture method of any described organic nano particle in above-mentioned (1)～(22) is characterized in that, in dispersion liquid during the above-mentioned organic nano particle of preparation, all has in any one operation and has amino pigment dispersing agent.
(24) manufacture method of any described organic nano particle in above-mentioned (1)～(23), it is characterized in that, in dispersion liquid during the above-mentioned organic nano particle of preparation, this dispersion liquid contains in a kind of general formula (D1), (D3) and the formula (D4) the represented compound of the same form arbitrarily at least.
General formula (D1)
A—N＝N—X—Y
(in general formula (D1), the common expression of A and X-Y can form the composition of azopigment.X represents singly-bound or is selected from following formula (i)～(divalent linker shown in the structural formula v).Y represents the group shown in the following general formula (D2).)
(ii) formula is (iii) for formula (i) formula
Figure A200680053947D00172
(iv) formula is (v) for formula
General formula (D2)
Figure A200680053947D00173
(in general formula (D2), Z represents low-grade alkylidene.-NR 21Expression low-grade alkyl amino or contain 5～6 yuan of saturated heterocyclyls of nitrogen-atoms.A represents 1 or 2.)
General formula (D3)
Figure A200680053947D00174
(in general formula (D3), Q represents to be selected from the organic pigment residue in anthraquinone compounds pigment, azo-compound pigment, phthalocyanine compound pigment, quinoline a word used for translation ketone compound pigment, dioxazine compound pigment, anthracene pyrimidine compound pigment, anthanthrone compound pigment, indanthrone compound pigment, yellow anthrone compound pigment, pyranthrone compound pigment, perylene ketone compound pigment, perylene compound pigment and the thioindigo compound pigment.X 1Expression-CONH-Y 2-,-SO 2NH-Y 2-or-CH 2NHCOCH 2NH-Y 2-.Y 2Expression can have substituent alkylidene group or arylidene.R 11And R 12Expression independently of one another replaces or unsubstituted alkyl, or R 11And R 12Lump together formation and contain the heterocyclic radical of nitrogen-atoms at least.Y 1Expression-NH-or-O-.Z 1Group shown in expression hydroxyl or the general formula (D3a) is 1 o'clock Z at n1 still 1Can be-NH-X 1-Q.M1 represents 1～6 integer, and n1 represents 1～4 integer.)
General formula (D3a)
Figure A200680053947D00181
(in general formula (D3a), Y 3Expression-NH-or-O-, m1, R 11And R 12Identical with its implication in general formula (D3).)
Formula (D4)
Figure A200680053947D00182
A:b:c=15:20:65 (weight ratio)
(in formula (D4), Me represents methyl.)
(25) manufacture method of any described organic nano particle in above-mentioned (1)～(24), it is characterized in that the poor solvent of above-mentioned organic materials is aqueous solvent, alkylol cpd solvent, ketone compound solvent, ether compound solvent, ester cpds solvent or their mixture.
(26) manufacture method of any described organic nano particle in above-mentioned (1)～(25), it is characterized in that the good solvent of above-mentioned organic materials is aqueous solvent, alkylol cpd solvent, ketone compound solvent, ether compound solvent, sulfoxide compound solvent, ester cpds solvent, amide compound solvent or their mixture.
(27) manufacture method of any described organic nano particle in above-mentioned (1)～(26), it is characterized in that, in dispersion liquid during the above-mentioned organic fine particles of preparation, above-mentioned organic material solution is mixed mutually with poor solvent, this organic fine particles is separated out, and after it is concentrated, add above-mentioned macromolecular compound, thereby obtain the concentrated dispersion liquid of organic fine particles.
(28) manufacture method of any described organic nano particle in above-mentioned (1)～(27), it is characterized in that, when above-mentioned organic material solution and poor solvent being mixed mutually, in the above-mentioned poor solvent of the above scale of 10L, generate this particulate with the generation organic fine particles.
(29) organic nano particle of any described method manufacturing in employing above-mentioned (1)～(28).
(30) a kind of ink-jet ink for color filter is characterized in that, is in the medium that contains polymerizable monomer and/or polyreactive oligomers, contain above-mentioned (29) described organic nano particle and and form.
(31) a kind of photosensitive composition is characterized in that, contains above-mentioned (29) described organic nano particle, binding agent, monomer or oligopolymer, Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system at least.
(32) a kind of photosensitive resin transfer material is characterized in that, is provided with the photo-sensitive resin that contains above-mentioned (31) described photosensitive composition at least on interim upholder.
(33) a kind of colour filter is characterized in that, is to use above-mentioned (30) described ink for ink-jet print, above-mentioned (31) described photosensitive composition and/or above-mentioned (32) described photosensitive resin transfer material to make.
(34) a kind of liquid crystal indicator is characterized in that, has above-mentioned (33) described colour filter.
(35) above-mentioned (34) described liquid crystal indicator is characterized in that, described display unit is the VA standard.
(36) a kind of CCD device is characterized in that, has above-mentioned (33) described colour filter.
By following description also suitably with reference to the accompanying drawings, above-mentioned and other feature and advantage of the present invention will show fully.
Brief description of drawings
[Fig. 1-1] summary shows the sectional drawing of a preferred embodiment of employed manufacturing installation in the manufacture method of the present invention.
[Fig. 1-2] summary shows the sectional drawing of another preferred embodiment of employed manufacturing installation in the manufacture method of the present invention.
[Fig. 1-3] at the mixing section as an embodiment of the manufacturing installation of Fig. 1-2, carries out the sectional drawing of the amplifier section that summary shows according to a part of section.
[Fig. 1-4] at the mixing section as another embodiment of the manufacturing installation of Fig. 1-2, carries out the sectional drawing of the amplifier section that summary shows according to a part of section.
[Fig. 2] summary shows the sectional drawing of the another preferred embodiment of the manufacturing installation that uses in the manufacture method of the present invention.
[Fig. 3] summary shows the sectional drawing of another preferred embodiment of the manufacturing installation that uses in the manufacture method of the present invention.
[Fig. 4-1] is the front view that summary shows an example of the dissolving machine agitating vane that uses in the manufacture method of the present invention.
[Fig. 4-2] is that replacement shows the photo that the drawing of the dissolving machine agitating vane shown in Fig. 4-1 is used.
[Fig. 5] be summary show use in the manufacture method of the present invention by rotatable turbine portion and be positioned at around it and the sectional drawing of an example of the mixing part that the fixed stator department constitutes with minim gap.
[Fig. 6] shows an explanatory view that constitutes example of the ultra-filtration equipment that uses among the preparation method of the present invention.
Embodiment
Below, the manufacture method of organic nano particle of the present invention is described.
Employed organic materials in the manufacture method of organic nano particle of the present invention for example can be enumerated polymer organic materialss such as pigment dyestuff, organic pigment, soccerballene, polydiacetylene or polyimide, be waited the particle of formation by aromatic hydrocarbon or aliphatic hydrocarbon (as having the aromatic hydrocarbon or the aliphatic hydrocarbon of orientation characteristic or aromatic hydrocarbon or the aliphatic hydrocarbon with distillation characteristic).Wherein, preferred pigment dyestuff, organic pigment or macromolecule organic material, preferred especially pigment dyestuff.In addition, organic filler can be used alone, and also can use multiplely, also can be used in combination.
Pigment dyestuff is not limited by 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, indanthrone, 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 compounds 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 compounds 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 compounds 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 quinones pigment such as (C.I. sequence numbers 73900/73920), C.I. pigment yellow 147 anthraquinone analog compound pigment such as (C.I. sequence numbers 60645), C.I. Pigment red 168 three benzopyrene cyclohexadione 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 benzoglyoxaline ketone compounds 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 compounds 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 compounds 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 indanthrone compounds 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), C.I. pigment Blue 15: 6 (C.I. sequence numbers 74160), or C.I. pigment Blue 15: 3 phthalocyanine-like 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 compounds 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) dioxazines compound pigment, C.I. Pigment red 177 aminoanthraquinone compounds 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 compounds pigment such as C.I. pigment orange 73, C.I. pigment Red 88 thioindigo compounds 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), C.I. Pigment Yellow 73 185 (C.I. sequence number 56290), or C.I. pigment orange 61 isoindoline ketone compounds 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 pigment such as (C.I. sequence numbers 59710), isoviolanthrone compounds pigment such as C.I. pigment yellow 13 8 pigment such as ketone such as phthalein such as a word used for translation such as quinoline such as grade, or C.I. pigment violet 31 (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, dioxazine compound pigment, phthalocyanine compound pigment.
Manufacturing method according to the invention, can with size distribution be the state of sharp-pointed type and obtain nano-scale Diketopyrrolo-pyrrole compounds pigment (below, also abbreviate " pyrrolopyrrole compound pigment " as.) particulate.In addition, when this pigment particle is used for colour filter, desirable colour purity and high-contrast can be taken into account simultaneously, and the photostabilization excellence, and the generation of precipitate can be suppressed.And, possessing the liquid crystal indicator of this colour filter, its black density and redness are described the power excellence, and can suppress to show inhomogeneous.
In above-mentioned Diketopyrrolo-pyrrole compounds pigment, preferred C.I.P.R.254 (compound of following formula (Z) expression), 255 (compounds of following formula (W) expression), 264 (compounds that following formula V is represented), from absorption spectrum, more preferably C.I.P.R.254.Also have,, can use all commercially available products such as Irgaphor Red B-CF, Cromophtal DPP Red BO, Irgazin DPP Red BO, Microlen DPP RED BP as C.I.P.R.254.As C.I.P.R.255, can use Cromophtal Coral Red C, Irgazin DPP Red 5G etc.As C.I.P.R.264, can use Hostapeperm Rubin D3B LP2615, Irgazin DPP Rubin TR etc.
Formula (Z)
Figure A200680053947D00231
Formula (W)
Figure A200680053947D00232
Formula V
Figure A200680053947D00233
As the tinting material of the blue pixel of colour filter, use C.I.P.B.15:6 (phthalocyanine compound pigment) mostly in recent years, improved the purity of color of colour filter thus.But the light source that often uses in the liquid crystal indicator is light sources such as cold-cathode tube, and its long wave side at the blue-light-emitting peak also has luminous on a small quantity, and therefore colourity can variation in NTSC.
This problem can be that representative De dioxazine compound pigment (for example about 5%) improves by adding with C.I.P.V.23,37.So just improve the contrast gradient of the high colour filter of this purity of color, further improved display characteristic; But be to use in the past microballon dispersion method or salt mill method, can not obtain satisfied result.
To this, manufacturing method according to the invention can obtain the nano-sized pigments of dioxazine compound pigment as the size distribution unanimity.Can make the dispersion liquid that contains this dioxazine compound pigment particle have excellent aging stability like this.Therefore, the colour filter that uses this material to form can have high purity of color and high contrast gradient simultaneously, and the photostabilization excellence.In addition, it is all excellent to possess the black density of the liquid crystal indicator of this colour filter, blue illustrative, reproducibility, and can suppress to show inhomogeneous.Also have,, can use commercially available products such as Cromofine Violet RE, FastgenSuper Violet BBL, Helio Fast Violet EB, Microlith Violet RL-WA, Sanyo Fast Violet BLD as C.I.P.V.23.As C.I.P.V.37, can use commercially available products such as Cromophtal Violet B, Microlith Violet B-A.
About employed phthalocyanine compound pigment among the present invention, except above-described, the pigment of using as colour filter, the pigment of record can enumerating in " face material topical reference book " (Japan-Korean storehouse bookstore distribution in September in 2000 25) from the 300th page to the 314th page, wherein, consider the blue 15:6 of preferred pigments, pigment Green 7, pigment green 36 from the aspect of absorption spectrum.
Phthalocyanine compound pigment structurally has chemical stability, and thermotolerance, photostabilization excellence.Furthermore, can be used as have high-strength, the B pixel of colour filter, the basic pigment that the G pixel is used.If with these pigment particleizations, can improve contrast gradient, and its display characteristic is expected to be further enhanced.But, adopt conventional microballon dispersion method and salt mill method, can not obtain gratifying result.To this, manufacturing method according to the invention can access the pigment of phthalocyanine compound pigment as the nano-scale of size distribution unanimity, and can be used as the pixel material that good colour filter is used.
In manufacture method of the present invention, also the solid solution of two or more pigment dyestuffs or pigment dyestuff can be used in combination, and, can also use with known dye combinations.
Have no particular limits for the dyestuff that uses among the present invention, can use the known dyestuff that in the past was used for colour filter.For example, can use Japanese kokai publication sho 64-90403 communique, the spy opens clear 64-91102 communique, Te Kaiping 1-94301 communique, Te Kaiping 6-11614 communique, the spy steps on No. 2592207, United States Patent (USP) the 4th, 808, No. 501 specification sheetss, United States Patent (USP) the 5th, 667, No. 920 specification sheetss, United States Patent (USP) the 5th, 059, No. 500 specification sheets, Te Kaiping 5-333207 communique, Te Kaiping 6-35183 communique, Te Kaiping 6-51115 communique, Te Kaiping 6-194828 communique, Te Kaiping 8-211599 communique, Te Kaiping 4-249549 communique, Te Kaiping 10-123316 communique, Te Kaiping 11-302283 communique, Te Kaiping 7-286107 communique, the spy opens the 2001-4823 communique, Te Kaiping 8-15522 communique, Te Kaiping 8-29771 communique, Te Kaiping 8-146215 communique, Te Kaiping 11-343437 communique, Te Kaiping 8-62416 communique, the spy opens the 2002-14220 communique, the spy opens the 2002-14221 communique, the spy opens the 2002-14222 communique, the spy opens the 2002-14223 communique, Te Kaiping 8-302224 communique, Te Kaiping 8-73758 communique, Te Kaiping 8-179120 communique, disclosed pigment in the Te Kaiping 8-151531 communique etc.
With regard to chemical structure, can use dyestuffs such as pyrazoles azo class, aniline azo class, triphenylmethane, anthraquinone class, anthrapyridones, Ben Yajiaji class, oxygen alcohols, pyrazolone and triazole azo class, pyridone azo class, cyanine class, phenothiazines, pyrrolo-pyrazoles azomethine class, xanthene class, phthalocyanines, benzo pyran, indigo class.
In addition, in the situation of resist (it can carry out water or alkali develops) class, do not considered by the angle of the binding agent of rayed part and/or dyestuff, be fit to use matching stain and/or its derivative from removing fully by developing.
In addition, can also use substantive dyestuff, basic dyestuff, mordanting dye, chrome dye, glacial dye, dispersed dye, oil-soluble dyes, food dye and/or their derivative etc.
Have no particular limits for above-mentioned matching stain, as long as have acidic-groups such as sulfonic acid or carboxylic acid, take all factors into consideration this matching stain to necessary performance such as the photostabilization of the interaction between other composition, this matching stain in the absorbancy that becomes salt, this matching stain, this matching stain and the composition of the solvability of organic solvent or developing solution, this matching stain and basic cpd, thermotolerances to select.
Below enumerated the object lesson of above-mentioned matching stain, still, this matching stain is not limited thereto.For example can enumerate alizarin violet N (acid alizarin violet N); Erie black (acidblack) 1,2,24,48; Acid blue (acid blue) 1,7,9,15,18,23,25,27,29,40,45,62,70,74,80,83,86,87,90,92,103,112,113,120,129,138,147,158,171,182,192,243,324:1; The purple K (acid chrome violet K) of acidic intermedium; C.I. 42685 (acid Fuchsin); Acid green (acid green) 1,3,5,9,16,25,27,50; Von Muller's indicator (acid orange) 6,7,8,10,12,50,51,52,56,63,74,95; Xylene Red (acid red) 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274; Acid violet (acidviolet) 6B, 7,9,17,19; Turmeric yellow (acid yellow) 1,3,7,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116,184,243; Food Huang (Food Yellow) 3, and the derivative of these dyestuffs.
In addition, except that above-mentioned matching stain, also preferred azo is, xanthene is, the matching stain of phthalocyanine system, also preferably uses C.I. solvent blue 44,38; C.I. the solvent orange 45; The derivative of rhodamine B (Rhodamine B), rhodamine 110 matching stains such as (Rhodamine 110) and these dyestuffs.
As organic pigment, can enumerate for example azopigment, cyanine class pigment, merocyanine class pigment, coumarins pigment etc.As macromolecule organic material, for example can enumerate polydiacetylene, polyimide etc.
[organic fine particles separate out generation]
Below, separating out of organic nano particle generated describe.
In manufacture method of the present invention, organic nano particle (in the present invention, " nanoparticle " is meant the particle of nano-scale, sometimes be also referred to as " particulate ") be to generate like this: will be dissolved in organic materials in the good solvent and the organic material solution that forms, with have for above-mentioned good solvent compatibility and for organic materials be poor solvent solvent (below, sometimes also this solvent is called by " poor solvent of organic materials ", or abbreviate " poor solvent " etc. as) mix mutually and generate (below, sometimes also this method is called " particulate liberation method ", and also will contain sometimes this moment resulting organic nano particle dispersion liquid be called " organic fine particles lye ", " organic nano particle dispersion liquid " etc.).In addition, though above-mentioned poor solvent and good solvent must be the combinations that has sufficient poor solubility for organic materials, and must select to be suitable for the preferably combination of material, can select to make up arbitrarily, as long as can implement this operation.
There is no particular limitation to the poor solvent of organic materials, if can with the miscible or uniform mixing of good solvent of dissolving organic materials.As the poor solvent of organic materials, the solubleness of preferred organic materials is following, following those of 0.01 quality % more preferably of 0.02 quality %.The solubleness of organic materials in poor solvent does not have specific lower limit, if but consider normally used organic materials, then be 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, about the compatibility or the uniform mixing of good solvent and poor solvent, the preferred meltage of good solvent in poor solvent is more than the 30 quality %, more preferably more than the 50 quality %.The meltage of good solvent in poor solvent do not have specific upper limit, in fact can mix with arbitrary proportion.
As poor solvent, for example (for example can enumerate the water kind solvent, water, or hydrochloric acid, aqueous sodium hydroxide solution), the alcohol compound solvent, the ketone compounds solvent, the ether compound solvent, aromatic series compounds solvent, the dithiocarbonic anhydride solvent, aliphatic category compound solvent, the nitrile compounds solvent, halogen-containing compounds solvent, the ester compound solvent, ionic liquid, perhaps their mixed solvent etc., the preferably water kind solvent, the alcohol compound solvent, the ketone compounds solvent, the ether compound solvent, the ester compound solvent, or their mixture, more preferably water kind 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, butanone, methyl iso-butyl ketone (MIBK), pimelinketone.As the ether compound solvent, for example can enumerate dimethyl ether, Anaesthetie Ether, tetrahydrofuran (THF) etc.As aromatic series compounds solvent, for example can enumerate benzene, toluene etc.As aliphatic category compound solvent, for example can enumerate hexane etc.As the nitrile compounds solvent, for example can enumerate acetonitrile etc.As halogen-containing compounds solvent, for example can enumerate methylene dichloride, trieline etc.As the ester compound solvent, for example can enumerate ethyl acetate, ethyl lactate, acetate 2-(1-methoxyl group) propyl ester etc.As ionic liquid, for example can enumerate 1-butyl-3-Methylimidazole and PF 6 -Salt etc.
Below, the good solvent that dissolves organic materials is described.
Good solvent is had no particular limits, as long as it can dissolve employed organic materials, and can be with above-mentioned poor solvent miscible or uniform mixing get final product.For the solvability of organic materials in good solvent, the solubleness of preferred organic materials is more than the 0.2 quality %, more preferably more than the 0.5 quality %.Do not have the special upper limit for the solubleness of organic materials in good solvent, consider the organic materials of common employing, this solubleness is actually below the 50 quality %.This solubleness also can be the solubleness when dissolving under acidity or alkaline condition.The compatibility of good solvent and poor solvent or the preferable range of uniform mixing are as previously mentioned.
As good solvent, for example (for example can enumerate the water kind 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 series compounds solvent, the dithiocarbonic anhydride solvent, aliphatic category compound solvent, the nitrile compounds solvent, the sulfoxide compound solvent, halogen-containing compounds solvent, the ester compound solvent, ionic liquid, perhaps their mixed solvent etc., the preferably water kind solvent, the alcohol compound solvent, the ketone compounds solvent, the ether compound solvent, the sulfoxide compound solvent, the ester compound solvent, amides solvent or their mixed solvent etc., more preferably water kind solvent, the alcohol compound solvent, the ester compound solvent, sulfoxide compound solvent or amides solvent, further preferably water kind solvent, sulfoxide compound solvent or amides solvent, preferred especially sulfoxide compound solvent or amides solvent.
As the sulfoxide compound solvent, for example can enumerate dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexamethylene sulfone, 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, HMPA etc.
In addition, as organic materials being dissolved in the good solvent and the concentration of the organic material solution that forms, preferably its scope be under the condition when dissolving the saturation concentration of organic materials in good solvent to about 1/100 of this saturation concentration.
There is no particular limitation for the preparation condition of organic material solution, can select from normal pressure to scope subcritical, super critical condition.When in normal pressure following time, temperature is preferably-10 ℃～150 ℃, more preferably-5 ℃～130 ℃, be preferably 0 ℃～100 ℃ especially.
Here, as the object lesson of good solvent and the solvent of enumerating with as the object lesson of poor solvent and though the solvent of enumerating has identical, as long as but satisfy following condition, described condition is not for making up identical solvent as good solvent and poor solvent, and fastening with the pass of employed various organic materialss, the solubleness of this organic materials in good solvent is fully greater than the solubleness of this organic materials in poor solvent, for example the difference of their solubleness is preferably more than the 0.2 quality %, more preferably more than the 0.5 quality %.Be not particularly limited for the upper limit of organic materials, but consider normally used organic materials, be actually below the 50 quality % in the difference of good solvent and the solubleness in poor solvent.
In the present invention, organic materials must be dissolved in the good solvent equably, but also preferably dissolves under acidity or alkaline condition.Usually, adopt intramolecularly have can be at dissociative group under the alkaline condition pigment the time use alkaline condition, and intramolecularly does not exist in and uses acidic conditions when dissociative group under the alkaline condition and intramolecularly have a plurality of nitrogen-atoms that is easy to the addition proton.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.
There is no particular limitation for the amount of employed alkali, so long as the amount of pigment uniform dissolution is got final product, 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 acetate, trifluoroacetic acid, oxalic acid, methylsulfonic acid or trifluoromethanesulfonic acid, but preferred mineral acid.Special preferably sulfuric acid.
There is no particular limitation for the amount of employed acid, so long as the amount of organic materials uniform dissolution is got final product, but compare 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.
Alkali or acid with after organic solvent mixes, during as the good solvent use of organic materials, are dissolved in order to make alkali or acid fully, can in organic solvent, add some water or lower alcohol etc. alkali or sour solvent with high-dissolvability.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 of the poor solvent when generating organic filler to separating out, and 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.The viscosity of organic fine particles lye is preferably 0.5～80.0mPas, more preferably 1.0～50.0mPas.
For organic material solution and poor solvent blended method are had no particular limits, preferably organic material solution is joined in the poor solvent and mix, this moment, preferred poor solvent was in the state that is stirred.Stirring velocity is preferably 100～10000rpm, and more preferably 150～8000rpm is preferably 200～6000rpm especially.Can use equipment such as also can not using pump during interpolation.In addition, can in liquid, submergence add, also can outside liquid, add, but more preferably submergence interpolation in liquid.The preferred pump that uses is supplied with in liquid continuously by supply-pipe among the present invention.Preferred 0.1～the 200mm of the internal diameter of supply-pipe, more preferably 0.2～100mm.Preferred 1～the 10000mL/min of speed that to liquid, supplies with from supply-pipe, more preferably 5～5000mL/min.
The ratio of mixture of organic material solution and poor solvent (ratio of the good solvent/poor solvent in the organic fine particles lye) is preferably 1/50～2/3 by volume, and more preferably 1/40～1/2, be preferably 1/20～3/8 especially.
There is no particular limitation to the concentration of organic fine particles lye, as long as can generate organic filler, but preferably with respect to the 1000mL dispersion solvent, organic filler is the scope of 10～40000mg, the scope of 20～30000mg more preferably is preferably the scope of 50～25000mg especially.
In addition, the preparative-scale during to the generation organic nano particle is not particularly limited, and the combined amount of preferred poor solvent is the preparative-scale of 10～2000L, more preferably the preparative-scale of 50～1000L.
Particle diameter about organic filler, 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 organic nano particle (primary particle) 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 having, can be crystal particles by the formed particle of manufacture method of the present invention, also can be non-crystal grain, can also be 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 organic nano particle (primary particle), 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 filler, can enumerate microscopy, weighting method, light scattering method, light and block method, electrical resistance method, sound equipment method, dynamic light scattering method, preferred especially microscopy, dynamic light scattering method.As the microscope that uses in the microscopy, for example can enumerate scanning electronic microscope, transmission electron microscope etc.As the particle assay device that utilizes dynamic light scattering method, for example can enumerate day ダ イ Na ミ Star Network light-scattering photometer DLS-7000 series of the Na ノ ト ラ Star Network UPA-EX150 ， Da mound electronics society manufacturing that machine dress society makes etc.
[dispersion agent]
In the manufacture method of organic nano particle of the present invention, when preparation organic nano particle dispersion liquid, preferably make and wherein contain dispersion agent.To the operation that described dispersion liquid contains dispersion agent is not particularly limited, preferably organic material solution and poor solvent both or one in add dispersion agent and it contained.In addition, also preferably when forming organic nano particle, utilize the system different to add dispersant solution with above-mentioned two kinds of liquid.Also preferred the use carried out the surface-treated pigment particles with dispersion agent in advance, also can apply the surface treatment that can promote dispersant adsorption to pigment particles.Dispersion agent has following effect: (1) is adsorbed on the surface of pigments of separating out quickly, forms fine nanoparticle, 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.Also have, the molecular weight of macromolecule dispersing agent is not particularly limited, as long as can allow this macromolecule dispersing agent to be dissolved in the solution equably, but preferred molecular weight is 1,000～2,000,000, more preferably 5,000～1,000,000, more preferably 10,000～500,000, be preferably 10 especially, 000～100,000.As macromolecule dispersing agent, specifically can enumerate polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyoxyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, the part formalizing thing of polyvinyl alcohol, the part butyralization thing of polyvinyl alcohol, vinylpyrrolidone/vinyl acetate copolymer, the polyethylene oxide/propylene oxide segmented copolymer, polyacrylate, polyvinyl vitriol, poly-(4-vinylpridine) salt, polymeric amide, PAH salt, the condensation naphthalenesulfonate, derivatived cellulose, starch derivative etc.In addition, can also use natural polymer subclasses such as alginate, gelatin, albumin, casein, gum arabic, tragacanth gum, sulfonated lignin.Wherein, preferably polyethylene base pyrrolidone.These polymers can use a kind separately, also can be used in combination more than two kinds.These dispersion agents can use separately or share.About the dispersion agent that uses in the colo(u)rant dispersion, write up is in 29～46 pages of " evaluation of colo(u)rant dispersion stabilization と process for treating surface " (chemical corps intelligence association, distribution in December calendar year 2001).
As anionic dispersing agent (aniorfic surfactant), 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 may be used singly or in combination of two or more kinds.
Cationic dispersing agent (cationic surfactant) comprises 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 may be used singly 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 (nonionic surface active agent), can enumerate Voranol EP 2001, polyoxyethylene alkylaryl ether, polyoxyethylene fatty acid ester, sorbitan fatty(acid)ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl amine, glycerol fatty acid ester etc.Wherein, preferred polyoxyethylene alkylaryl ether.These non-ionic dispersing agents may be used singly 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 manufacture method of the present invention, in good solvent, dissolve and when making organic material 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 compound of putting down in writing in TOHKEMY 2000-239554 communique, 2003-96329 communique, 2001-31885 communique, Japanese kokai publication hei 10-339949 communique, the special fair 5-72943 communique etc., but be not limited to these compounds.
As the dispersion agent that in manufacture method of the present invention, uses, preferred use at least a in the compound that is selected from following general formula (D1), (D3) and formula (D4) expression.
＜1, the compound of general formula (D1) expression 〉
General formula (D1)
A—N＝N—X—Y
In general formula (D1), the common expression of A and X-Y can form the composition of azopigment.Above-mentioned A can select arbitrarily, and the compound that forms azopigment so long as can carry out coupling with diazonium compound gets final product.The object lesson of above-mentioned A is as follows, but the present invention never is confined to these structures.
Figure A200680053947D00341
Formula 1-1 formula 1-2
Formula 1-3 formulas 1-4
Figure A200680053947D00343
Formula 1-5 formulas 1-6 formulas 1-7
Formula 1-8 formulas 1-9
Figure A200680053947D00345
Formula 1-10 formulas 1-11 formulas 1-12
In general formula (D1), X represents singly-bound or is selected from following formula (i)～(divalent linker shown in the structural formula v).
Figure A200680053947D00351
(ii) formula is (iii) for formula (i) formula
Figure A200680053947D00352
(iv) formula is (v) for formula
In general formula (D1), Y represents the group shown in the following general formula (D2).
General formula (D2)
Figure A200680053947D00353
In general formula (D2), Z represents low-grade alkylidene.Z represents-(CH 2) b-, b represents 1～5 integer, is preferably 2 or 3.In general formula (D2) ,-NR 21Expression low-grade alkyl amino or contain 5～6 yuan of saturated heterocyclyls of nitrogen-atoms.This-NR 21During the expression low-grade alkyl amino, its expression-N (C rH 2r+1) 2, r represents 1～4 integer, preferably represents 1 or 2.-NR 21When expression contains 5～6 yuan of saturated heterocyclyls of nitrogen-atoms, be preferably any one heterocyclic radical that following structural formula is represented.
Figure A200680053947D00354
Pyridine ring piperidine ring morpholine ring
In above-mentioned general formula (D2), Z reaches-NR 21Can have low alkyl group, alkoxyl group respectively as substituting group.In above-mentioned general formula (D2), a represents 1 or 2, preferably represents 2.
Below, list the object lesson of the compound of above-mentioned general formula (D1) expression, but the present invention never is confined to these object lessons.
Figure A200680053947D00361
Figure A200680053947D00371
Figure A200680053947D00381
Figure A200680053947D00391
The compound of general formula (D1) expression can synthesize by the method for putting down in writing in the TOHKEMY 2000-239554 communique for example.
＜2, the compound of general formula (D3) expression 〉
General formula (D3)
In general formula (D3),
Q represents to be selected from the organic pigment residue of anthraquinone compounds pigment, azo-compound pigment, phthalocyanine compound pigment, quinoline a word used for translation ketone compound pigment, dioxazine compound pigment, anthracene pyrimidine compound pigment, anthanthrone compound pigment, indanthrone compound pigment, yellow anthrone compound pigment, pyranthrone compound pigment, perylene ketone compound pigment, perylene compound pigment and thioindigo compound pigment, wherein preferred azo-compound pigment Huo dioxazine compound pigment, more preferably azo-compound pigment.
X 1Expression-CO-,-CONH-Y 2-,-SO 2NH-Y 2-or-CH 2NHCOCH 2NH-Y 2-, preferred-CO-,-CONH-Y 2-.
Y 2Expression can have substituent alkylidene group or arylidene, wherein preferred phenylene, methylene phenyl or hexylidene, more preferably phenylene.
R 11And R 12Can represent independently of one another to replace or unsubstituted alkyl, or R 11And R 12Lump together and to form the heterocyclic radical that contains nitrogen-atoms at least.Wherein, preferable methyl, ethyl, propyl group or contain the pyridyl of nitrogen-atoms, more preferably ethyl.
Y 1Expression-NH-or-O-.
Z 1Group shown in expression hydroxyl or the general formula (D3a) is 1 o'clock Z at n1 still 1Can be-NH-X 1-Q.M1 represents 1～6 integer, preferred 2～3.N1 represents 1～4 integer, preferred 1～2.
General formula (D3a)
In general formula (D3a), Y 3Expression-NH-or-O-, m1, R 11And R 12Identical with its implication in general formula (D3).
As the compound of general formula (D3) expression, more specifically use-case such as following general formula are represented.
Figure A200680053947D00411
General formula (D3-1)
Figure A200680053947D00412
General formula (D3-2)
Figure A200680053947D00413
General formula (D3-3)
Figure A200680053947D00414
General formula (D3-4)
Figure A200680053947D00415
General formula (D3-5)
Figure A200680053947D00416
General formula (D3-6)
In general formula (D3-1)～(D3-6), Q, m1, n1, R 11, R 12Identical with its implication in general formula (D3).Below enumerate the object lesson of compound shown in the general formula (D3), but the present invention never is confined to this.Also have, the Cu-Pc in the formula represents copper phthalocyanine.
Figure A200680053947D00421
Figure A200680053947D00431
The compound of general formula (D3) expression for example can have R by making 11And R 12Amine compound and have a R 11And R 12Alkylol cpd and halogenation triaizine compounds react, the intermediate that obtains and dye compound reacted and form.In addition, can also be with reference to the record in the special fair 5-72943 specification sheets of Japan.
＜3, the pigment dispersing agent that contains graft copolymer 〉
In organic nano particle manufacture method of the present invention, also preferred the use contained the graft copolymer with amino and ether and contained other the dispersion agent of suitably selecting in case of necessity of composition.
Above-mentioned graft copolymer has amino and ether at least, and the monomer etc. that also can contain other is as copolymer unit.
The matter average molecular weight of above-mentioned graft copolymer is preferably 3000～100000, and more preferably 5000～50000.If above-mentioned matter average molecular weight less than 3000 then can not prevent the aggegation of organic nano particle, viscosity can rise sometimes, if surpass 100000, and the solvability deficiency in organic solvent then, viscosity can rise sometimes.
Preferred above-mentioned 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, the monomer that also can contain (iv) other in case of necessity is 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 %, more preferably 5～60 quality %.
If above-mentioned polyreactive oligomers contain quantity not sufficient 15 quality %, sometimes can not obtain steric repulsion effect as dispersion agent, can not prevent the aggegation of organic nano particle, if surpass 98 quality %, then the ratio of above-mentioned nitrogen containing monomer reduces, adsorptive power to organic filler reduces, and dispersed possibility is not enough.If above-mentioned nitrogen containing monomer contain quantity not sufficient 1 quality %, then the adsorptive power to organic filler is low, dispersed possibility is not enough, if surpass 40 quality %, then the ratio of above-mentioned polyreactive oligomers descends, therefore steric repulsion effect can not be obtained sometimes, the aggegation of organic filler can not be fully prevented as dispersion agent.If above-mentioned polymerizable monomer with ether contain quantity not sufficient 1 quality %, then development adaptability may be not enough when the manufacturing of colour filter etc., if surpass 70 quality %, then the ability as dispersion agent may descend.
(i) polyreactive oligomers
Above-mentioned polyreactive oligomers (below, be sometimes referred to as " macromonomer ") 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 aforementioned 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-acetic ester 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 carbonatoms is 1～8 and the alkylidene group that can be replaced by alcoholic extract hydroxyl group, and preferred carbonatoms is 2～4 alkylidene group.Y 6The expression phenyl, have phenyl that carbonatoms is 1～4 alkyl or-COOR 64(R herein, 64The expression carbonatoms be 1～6 and alkyl, phenyl or the carbonatoms that can be replaced by alcoholic extract hydroxyl group, halogen be 7～10 aralkyl), preferred phenyl or-COOR 64(R herein, 64The expression carbonatoms 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 makes); single terminal methyl group acryl polymethyl methacrylate oligomer (Mn=6000; trade(brand)name: AA-6; East Asia synthetic chemical industry (strain) society makes); the positive butyl ester oligopolymer of single terminal methyl group acryl polypropylene (Mn=6000; trade(brand)name: AB-6; East Asia synthetic chemical industry (strain) society makes); 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 makes); 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 makes); 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 makes) 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.
Figure A200680053947D00461
General formula (E2)
In above-mentioned general formula (E2), R 21Expression hydrogen atom or methyl.R 22The expression carbonatoms is 1～8 alkylidene group, and wherein preferred carbonatoms is 1～6 alkylidene group, and preferred especially carbonatoms 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, carbonatoms are 1～6 alkyl or phenyl.R 25The expression carbonatoms is 1～6 alkylidene group, R 26And R 27Expression hydrogen atom, carbonatoms are 1～6 alkyl or phenyl.
In above-mentioned substance ,-N (R 23) (R 24) in R 23And R 24Be preferably hydrogen atom or carbonatoms and be 1～4 alkyl or phenyl ,-R 25-N (R 26) (R 27) in R 25Be preferably carbonatoms and be 2～6 alkylidene group, R 26And R 27Be preferably carbonatoms 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.
Figure A200680053947D00462
General formula (E3)
In above-mentioned general formula (E3), R 31And R 21Synonym.R 32And R 22Synonym.X 3With X 2Synonym.
Figure A200680053947D00463
General formula (E4)
In above-mentioned general formula (E4), R 41And R 21Synonym.X 4With X 2Synonym is preferably-N (R 43) (R 44) (R herein, 43And R 44With R 23And R 24Synonym) or-R 45-N (R 46) (R 47) (R herein, 45, R 46And R 47Respectively with 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-diethylamino) 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.
Figure A200680053947D00471
General formula (E1)
In above-mentioned general formula (E1), R 11Expression hydrogen atom or methyl.R 12The expression carbonatoms is 1～8 alkylidene group, and wherein preferred carbonatoms is 1～6 alkylidene group, and more preferably carbonatoms is 2～3 alkylidene group.X 1Expression-OR 13Or-OCOR 14Herein, R 13Expression hydrogen atom, carbonatoms are 1～18 alkyl, phenyl or are the phenyl that 1～18 alkyl replaces by carbonatoms.R 14The expression carbonatoms 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 the monomer that has ether and have a polymerizability gets final product, 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 makes); 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 makes)), polyethylene glycol monomethacrylate (trade(brand)name: Block レ Application マ one PE-90, PE-200, PE-350, Japan grease (strain) society makes), polypropylene glycol monomethacrylate (trade(brand)name: Block レ Application マ one PP-500, PP-800, PP-1000, Japan grease (strain) society makes), polyoxyethylene glycol polypropylene glycol monomethacrylate (trade(brand)name: Block レ Application マ one 70PEP-370B, Japan grease (strain) society makes), polyoxyethylene glycol polytetramethylene glycol monomethacrylates (trade(brand)name: Block レ Application マ one 55PET-800, Japan grease (strain) society makes), polypropylene glycol polytetramethylene glycol monomethacrylates (trade(brand)name: Block レ Application マ one NHK-5050, Japanese grease (strain) society makes) etc.
(iv) other monomer
Above-mentioned graft copolymer can also contain above-mentioned other monomer as copolymer unit, there is no particular limitation to these 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-acetic ester 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 these other monomeric content in the above-mentioned graft copolymer, for example be preferably 5～70 weight %.If these other the monomeric quantity not sufficient 5 weight % that contain then can not control the physical properties of coat film sometimes,, then can not give full play to ability sometimes as dispersion agent if surpass 70 weight %.
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 more preferably compound of following formula (D4) expression.In the formula (D4), Me represents methyl.
Formula (D4)
Figure A200680053947D00491
A:b:c=15:20:65 (weight ratio)
Above-mentioned graft copolymer can obtain by making the composition (for example) that will form above-mentioned each copolymer unit 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 nano particle, as the content of dispersion agent, preferably the pigment with respect to 100 mass parts is 0.1～1000 mass parts, more preferably 1～500 mass parts, more preferably 5～20 mass parts.If less than 0.1 mass parts then may be can't see the raising of organic nano particle dispersion stabilization.In addition, dispersion agent can use separately, also can make up several and use.
In order further to improve the uniformly dispersed and package stability of organic filler, as the content of dispersion agent, preferably the organic filler with respect to 100 mass parts is 0.1～1000 mass parts, more preferably 1～500 mass parts, more preferably 5～20 mass parts.If less than 0.1 mass parts then may be can't see the raising of organic nano particle dispersion stabilization.
[manufacturing installation]
Below the preferred embodiment that is used to form the manufacturing installation of organic nano particle in manufacture method of the present invention is described, but this is not that the present invention is carried out limited explanation.
(manufacturing installation example 1)
Fig. 1-the 1st in the manufacture method of the present invention, is used as a kind of sketch chart of manufacturing installation of embodiment.In Fig. 1-1, in container 11, provide organic material solution continuously by supply-pipe 14.Wherein, in container 11, accommodate poor solvent 11a, make poor solvent integral body keep convection current always by stirring action.
Fig. 1-2 is the sketch chart as the manufacturing installation of another more preferred use of the present invention.This device is mixing section (stirring area) 13 backs to be set form in the container 11 of Fig. 1-1 manufacturing installation.Mixing section 13 is arranged under the liquid level of poor solvent, and its inside is full of poor solvent.In addition, under the stirring action in this mixing section 13, the mode that (along the direction of arrow among the figure) runs through these mixing section 13 inside with from the bottom to top of the poor solvent integral body in the reaction vessel 11 keeps convection current always.
Fig. 1-the 3rd, after the mixing section 13 as an embodiment of manufacturing installation shown in Fig. 1-2 amplified, the sectional drawing of the amplifier section of Xian Shiing roughly.By supply-pipe 14 organic material solution is provided in the mixing section 13.This mixing section 13 is formed by shell 17, shell 17 is that the cube tube by constant cross section constitutes, the upper end of shell 17 forms open end (open portion), the lower end is provided with circular hole 18, make poor solvent and stirring area in the mixing tank 13 (press the structure among the figure outward, in poor solvent 11a, the zone beyond the mixing section 13 is equivalent to outside the stirring area, is also referred to as to stir exterior domain) poor solvent integral body interconnect.Herein, organic material solution supply pipe 14 is set in the wall that constitutes shell 17 lower ends, forms opening towards above-mentioned circular hole.In addition, be provided with agitating vane 12 in the above-mentioned mixing tank 13, agitating vane is installed on the axle 15, utilizes electric motor 16 to be rotated.By the rotation of this agitating vane 12, poor solvent by circular hole 18 in mixing tank 13 from below constantly carry out cyclic motion upward.
The agitating vane 12 that is arranged in the above-mentioned mixing section 13 must form desirable mixture strength in mixing section.By inference, be important operating parameters for the size of this mixture strength drop (droplet) when sneaking into pigment dyestuff solution.
In addition, preferred agitating vane 12 is selected from the blade with following ability, promptly can not produce because the organic nano particle that generates in mixing space rests in the mixing section 13 and to combine with other organic nano particle and form bigger particle or be subjected to supplying to the influence of the organic material solution in the mixing section 13 and form macroparticle, thereby generate the situation of huge particle, and the organic nano particle that generates can be extracted out rapidly, promptly be discharged into mixing section 13 outsides.
As agitating vane 12, as long as can achieve the above object, can have any form, for example can use Scroll-type, fan Scroll-type etc.
In addition, preferred shell 17 is by being made of the cube tube as mentioned above.Thus, the liquid stream that is caused by agitating vane 12 reaches chaotic in the bight of shell 17, do not need the annex of interceptor and so on just can further improve mixed effect.
Fig. 1-the 4th will be set at the sectional drawing of amplifier section of the mixing tank of two (mixing with agitating vane 19a, discharging agitating vane 19b) as the agitating vane in the mixing section of another embodiment of manufacturing installation shown in Fig. 1-2.By two agitating vanes are set like this, make that can and organic pigment particles be discharged into the outer ability of mixing tank to the ability of control mixture strength select independently, mixture strength, internal circulating load can be set at desirable value independently and operate.
(manufacturing installation example 2)
Fig. 2 is the sectional drawing that roughly shows another embodiment of the manufacturing installation that uses in the manufacture method of the present invention.In Fig. 2, by supply- pipe 24a, 24b organic material solution and poor solvent are supplied with among the stirred pot 21a continuously respectively.Can not produce the organic materials particle that generates among the stirred pot 21a because rest in the stirred pot 21a, combine with other organic pigment particles and form bigger particle or the influence of the organic material solution that is subjected to supplying with and form macroparticle by supply- pipe 24a, 24b, thereby form the situation of huge particle, the organic materials particle dispersion that generates is extracted out rapidly by delivery pipe 23.
Fig. 3 is the sectional drawing that roughly shows the another embodiment of the manufacturing installation that uses in the manufacture method of the present invention.In the manufacturing installation of Fig. 3, whipping appts 50 possesses cylindric stirred pot 38 and as a pair of agitating vane 41,42 of whipping device, described stirred pot 38 has two liquid supply ports 32,33 that make organic material solution and poor solvent inflow respectively and the leakage fluid dram 36 that discharges the mixing liquid after stir process is finished, and above-mentioned agitating vane 41,42 is by being driven in rotation the whipped state of controlling liquid in this stirred pot 38 in this stirred pot 38.
Stirred pot 38 is that the sealing plate 40 of the tank skin of the cylindric can body 39 of above-below direction and the being formed for upper and lower opening end that stops up this can body 39 constitutes by central shaft.In addition, stirred pot 38 and can body 39 are formed by the nonmagnetic substance of magnetic permeability excellence.Two liquid supply ports 32,33 are set at the position of end on the lower side of can body 39, and leakage fluid dram 36 is set at the position of end on the upper side of can body 39.
And, a pair of agitating vane 41, the 42 separated stirred pot 38 interior relative upper and lower ends that are assemblied in, and oppositely driven rotation mutually.Each agitating vane 41,42 and the external magnet 46 that is equipped on contiguous tank skin (sealing plate 40) outside of each agitating vane 41,42 constitute magnetic coupling C.That is, each agitating vane 41,42 links to each other with external magnet 46 respectively by magnetic force, by the rotation of independent electric motors 48,49 each external magnet 46 of driving, carries out reverse rotating operation mutually.
Shown in dotted arrow among Fig. 3 (X) and solid arrow (Y), jar 38 interior a pair of agitating vanes 41,42 of equipment have relatively formed the different stirring stream of direction respectively in jar 38.And, because the flow direction difference of the stirring stream that each agitating vane 41,42 forms, therefore collide mutually, thereby in jar 38, generated the high speed turbulent flow that promotes stirring in the jar 38, prevented that jar 38 interior liquid streams from forming stable state, under the situation that makes agitating vane 41,42 high speed rotating, stop agitating vane 41,42 turning axles to form the cavity on every side, also stoped simultaneously along the formation of inner peripheral surface mobile stable state liquid stream in jar 38 of the jar 38 that is not subjected to abundant stirring action.Therefore,, can easily improve processing speed, and stop this moment, can prevent to handle the decline of quality because of liquid stream formation stable state in the jar 38 causes discharge to mix inadequate liquid by the high speed rotating of agitating vane 41,42.
In addition, each agitating vane the 41, the 42nd in the stirred pot 38, the electric motor 48,49 outer with being configured in stirred pot 38 by magnetic coupling C links to each other, therefore do not need to make turning axle insert the tank skin of stirred pot 38, can make stirred pot 38 form the encloses container structure that does not have the turning axle insertion section, thereby can prevent the leakage of liquid outside jar that mix, also can prevent simultaneously turning axle with lubricator (sealing liquid) etc. sneak into the processing downgrade that is caused in the liquid in jars 38 as impurity.
In manufacture method of the present invention, use manufacturing installation with these structures, not only can pass through intermittent mode, also can make organic nano particle by continuous mode, can adapt to production in enormous quantities.In addition, by the organic nano particle dispersion liquid that promptly discharge to generate, can make the organic material solution that is provided in the stirred pot and the ratio of poor solvent reach constant all the time.Therefore, make and finish up to making that the solubleness of organic materials reaches constant in the dispersion liquid, can stably make monodispersed organic nano particle from making beginning.
And, cause discharge to mix inadequate organic nano particle dispersion liquid by stoping because of liquid stream in the jar forms stable state, and in the liquid in preventing turning axle with lubricator (sealing liquid) etc. sneaking into jar as impurity, can stably make monodispersed organic nano particle thus.
(manufacturing installation example 3)
This example is to another embodiment as the device that uses in the manufacture method of the present invention, that is, use is had the manufacture method that the blade of shearing force stirs describe.
Said shearing force is meant that agitating vane sneaks into the shearing force that the drop (droplet) that generates behind the poor solvent applies to organic material solution among the present invention.
There is no particular limitation to the shape of the mixing part that can use in the present invention, get final product so long as can apply the form of high shear force, usually can enumerate blade, turbine blade, ribbon blade, the pull-up blade of Fa Ede etc., dissolver blade preferably further preferably has by rotatable turbine portion and is being positioned at around it with minim gap and stirring, emulsification, the dispersion machine of the mixing part that the fixed stator department constitutes.
The dissolver blade is the special agitating vane with the function that can form high shear force, has roughly shown its example among Fig. 4-1 with front view, and Fig. 4-2 has shown the photo that substitutes this accompanying drawing.
In addition, also preferably use having by rotatable turbine portion and be positioned at around it with minim gap and the device of the mixing part that the fixed stator department constitutes as shown in Figure 5, as this stirring, emulsification, dispersion machine, for example can enumerate the T.K homo-mixer (homomixer) that ヒ ス コ ト ロ Application that マ イ Network ロ テ Star Network ニ チ オ Application society makes, special machine chemical industry society make, the ULTRA-TURRAX that IKA society makes.
Stirring velocity is got different values according to the kind and the addition of the viscosity of poor solvent, temperature, tensio-active agent, but is preferably 100～10000rpm, and more preferably 150～8000rpm is preferably 200～6000rpm especially.If revolution is low excessively, then can not give full play to mixing effect, if instead too high, then easily be involved in bubble in the poor solvent, be not preferred.
[concentrating]
In the manufacture method of organic nano particle of the present invention,, can be suitable for the concentrated solution of colour filter coating liquid and ink for inkjet with industrial-scale production by the organic nano particle dispersion liquid is carried out desalination and concentration.
Below, concentration method is described.
Concentration method is had no particular limits, as long as can concentrate organic nano particle liquid, for example preferably in the organic nano particle dispersion liquid, add and extract solvent and mixing, the organic nano particle concentration extraction is extracted in the solvent phase to this, and formed the method that concentrates nanoparticle liquid with this concentrated extracting solution of filtrations such as strainer; Utilize centrifugation to make the organic nano particle sedimentation and carry out spissated method; Utilize ultrafiltration to carry out the method for desalination and concentration; Make the solvent distillation carry out spissated method by vacuum lyophilization; Make solvent seasoning carry out spissated method etc. by heating or decompression.Or very preferably use the combination of these methods.
Concentration about the organic nano particle after concentrating is preferably 1～100 quality %, and more preferably 5～100 quality % are preferably 10～100 quality % especially.
Below, the concentration extraction method is described.
There is no particular limitation to the extraction solvent that uses in this concentration extraction, but basically with the dispersion solvent of organic nano particle dispersion liquid (for example, the water kind solvent) do not mix (in the present invention, basically do not take place to mix and be meant that mutual solubility is low, meltage is preferably below the 50 quality %, more preferably below the 30 quality %.This meltage does not have special lower limit, if but consider the solvability of usual solvents, then the lower limit of this meltage is actually more than the 1 quality %) and the solvent that forms the interface when after mixing, leaving standstill be preferred.In addition, preferred this extraction solvent is to make the organic nano particle redispersion also produce the solvent of weak aggegation (even not applying the throw out that high shear force also can carry out redispersion by grind or high-speed stirring etc.) in extracting solvent.If reach this state, then can not form the strong aggegation that size of particles is changed, available extraction wet with solvent purpose organic nano particle can easily remove the diffusing solvent of the five equilibrium that anhydrates by filtering to wait on the other hand, from these aspects, described solvent is preferred.As extracting solvent, preferred ester compound solvent, alcohol compound solvent, aromatic series compounds solvent, aliphatic category compound solvent, more preferably ester compound solvent, aromatic series compounds solvent or aliphatic category compound solvent, preferred especially ester compound solvent.
As the ester compound solvent, for example can enumerate 2-(1-methoxyl group) propyl-acetic acid ester, ethyl acetate, ethyl lactate etc.As the alcohol compound solvent, for example can enumerate propyl carbinol, isopropylcarbinol etc.As aromatic series compounds solvent, for example can enumerate benzene,toluene,xylene etc.As aliphatic category compound solvent, for example can enumerate normal hexane, hexanaphthene etc.In addition, the extraction solvent can be the simple solvent in the above-mentioned preferred solvent, also can be the mixed solvent that is formed by multiple solvent.
The amount of extracting solvent is not particularly limited, as long as can extract above-mentioned organic nano particle, considers concentration extraction, preferably its amount ratio organic nano particle dispersion liquid still less.If represent with volume ratio, then the organic nano particle dispersion liquid was made as 100 o'clock, the extraction solvent that is added is preferably 1～100, and more preferably 10～90, be preferably 20～80 especially.If too much, then concentrating needs a large amount of time, if very few, then extract insufficient, residual nanoparticle in the dispersion solvent.
After adding the extraction solvent,, preferably mix in order fully to contact with dispersion liquid.Mix and to use usual method.There is no particular limitation to adding the temperature of extracting solvent and mixing when, but be preferably 1～100 ℃, more preferably 5～60 ℃.For interpolation, the mixing of extracting solvent, just can use any device as long as can implement each operation satisfactorily, for example can use separating funnel type device to carry out.
Under the situation that adopts ultrafiltration, for example can use the desalination/spissated method that is used for silver emulsion.Known have research to disclose (Research Disclosure) No.10208 (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 nano particle, in order to suppress the aggegation of particle, also need to find out top 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 nano particle to and disperse in the thing.
Fig. 6 has shown that one of the device that is used to carry out ultrafiltration constitutes example.As shown in Figure 6, this device possesses the jar 81 that holds lipid acid silver and disperse thing, makes dispersion thing in this jar 81 carry out the round-robin circulation with pump 82 and the ultra-filtration module 83 that will remove as permeate water with the by-product inorganic salts in the dispersion thing of pump 82 importings by circulation.The dispersion thing of isolated permeate water is turned back in the jar 81 once more, carries out same operation repeatedly, until reaching the predetermined purpose of removing by-product inorganic salts.In addition, also be provided with additional pure water metering in this device, be used for measuring, and be provided with the permeate water metering under meter 85 that is used for determining the pure water magnitude of recruitment replenish used a certain amount of water because of the solvent that runs off by permeate water with under meter 84.In addition, also can be provided for importing the reverse flushing pump 86 of the dilution water of permeate water.
As ultra-filtration membrane, ultra-filtration membrane such as plate, the spiral type of packing into, round tube type, macaroni yarn type, hollow fiber type as module, there are society of Asahi Chemical Industry's (strain), ダ イ セ Le chemistry (strain) society, (strain) DongレShe, (strain) day Dong Diangongshe etc. to sell, but on total membrane area and cleaning, preferred spiral type or macaroni yarn type ultra-filtration membrane.In addition,, must determine, be preferably more than 5,000 below 50,000, more preferably more than 5,000 below 15,000 according to the molecular weight of employed dispersion agent as the molecular weight cut-off of the threshold value index of membrane-permeable composition.
For the dispersion solvent with the organic nano particle dispersion liquid separates with concentrated extracting solution, preferably carry out strainer and filter.As the filtration unit that strainer uses, for example can use the device of pressure filtration and so on.As preferred strainer, can enumerate nanofilter, ultra-fine filter etc.Preferably filter, remove residual dispersion solvent, the organic nano particle in the concentrated extracting solution is concentrated and forms concentrated nanoparticle liquid by strainer.
There is no particular limitation to freeze-drying 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.Certainly, 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: she controls him at the rattan filial piety, No.15, p.82 (nineteen sixty-five) etc.
Below centrifugation is described.
As concentrating the separating centrifuge that uses in the organic nano particle,, can use any device as long as can make the organic nano particle sedimentation in the organic nano particle dispersion liquid (or organic nano particle concentrated extracting solution) by centrifugation.As separating centrifuge, for example, outside multipurpose plant, the continuous 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.
Below drying is described.
There is no particular limitation for the device that uses when concentrating organic nano particle by drying under reduced pressure, as long as can make the solvent evaporation of organic nano particle dispersion liquid (or organic nano particle 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.
According to above-mentioned concentration method, can concentrate out organic nano particle from the organic nano particle dispersion liquid effectively.About concentration rate,, then can be concentrated into the concentration that concentrates in the organic nano particle paste and be preferably about 100～3000 times, more preferably about 500～2000 times if for example will be made as 1 as the nanoparticle concentration in the organic nano particle dispersion liquid of raw material.
[fine dispersion]
Manufacturing method according to the invention in case of necessity can be by for example concentrating, and the organic filler that will be in state of aggregation carries out fine dispersion (in the present invention, fine dispersion is to instigate the particles aggregate in the dispersion liquid to be scattered, and improves dispersity).
Concentrate organic filler contained in the organic filler liquid that forms by said extracted solvent, centrifugation, drying etc. and can aggegation take place because of concentrating usually.At this moment, become possibility for rapid filter is filtered, obtain good dispersion state once more, preferred organic filler obtains as carrying out the agglutinative floss according to the degree that can carry out redispersion.
Therefore, utilize common dispersing method to carry out the dispersive degree, can not reach sufficient micronize, thereby need the high method of miniaturization efficient.For such agglutinative organic filler (in the present invention, " agglutinative organic filler " is meant that organic filler passes through the effect of secondary force and the accumulative particle (as, agglomeration etc.), primary particle is also referred to as the agglutinative nanoparticle during for nano-scale), by contain the matter average molecular weight in agglutinative organic filler liquid is macromolecular compound more than 1000, organic filler suitably can be carried out fine dispersion (in the present invention, " agglutinative organic filler liquid " is meant the liquid that wherein contains the agglutinative organic filler, it can be dispersion liquid, concentrated solution, mashed prod, soup compounies etc. are as long as contain the agglutinative organic filler).
Below, employed macromolecular compound is elaborated in the manufacture method to organic nano particle of the present invention.
Employed macromolecular compound is preferably the represented macromolecular compound of following general formula (1) in the manufacture method of organic nano particle of the present invention.
Figure A200680053947D00591
General formula (1)
In above-mentioned general formula (1), A 1Expression has 1 valency organic group of the group of selecting from acidic-group, the basic group that contains nitrogen-atoms, urea groups, urethano, the group of band coordination Sauerstoffatom, carbonatoms 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 basic group that contains nitrogen-atoms 2) 1 valency organic group, have substituted imine base (NHR 8,-NR 9R 10) 1 valency organic group (wherein, R 8, R 9And R 10Represent that independently of one another carbonatoms is that the alkyl below 20 more than 1, carbonatoms are that the aryl below 20 or carbonatoms are the aralkyl below 30 more than 7 more than 6), have the guanidine radicals of following general formula (a1) expression 1 valency organic group [in the general formula (a1), R A1, R A2Represent that independently of one another carbonatoms is that the alkyl below 20 more than 1, carbonatoms are that the aryl below 20 or carbonatoms are the aralkyl below 30 more than 7 more than 6], have the amidino groups of following general formula (a2) expression 1 valency organic group [in the general formula (a2), R A3, R A4Represent that independently of one another carbonatoms is that the alkyl below 20 more than 1, carbonatoms are that the aryl below 20 or carbonatoms are the aralkyl below 30 more than 7 more than 6] etc.
Figure A200680053947D00592
As above-mentioned " 1 valency organic group ", for example can enumerate-NHCONHR with urea groups 15(wherein, R 15Expression hydrogen atom, carbonatoms are that the alkyl below 20 more than 1, carbonatoms are that the aryl below 20 or carbonatoms are the aralkyl below 30 more than 7 more than 6) etc.
As above-mentioned " 1 valency organic group ", for example can enumerate-NHCOOR with urethano 16,-OCONHR 17(wherein, R 16And R 17Represent that independently of one another carbonatoms is that the alkyl below 20 more than 1, carbonatoms are that the aryl below 20 or carbonatoms are the aralkyl below 30 more than 7 more than 6) 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 carbonatoms is 1 valency organic group of the alkyl more than 4 ", can enumerate carbonatoms and be more than 4 alkyl (for example, octyl group, dodecyl etc.), carbonatoms be more than 6 aryl (for example, phenyl, naphthyl etc.), carbonatoms is aralkyl (for example, benzyl etc.) more than 7 etc.The carbonatoms of this moment does not have the upper limit, but is preferably below 30.As above-mentioned " 1 valency organic group ", for example can enumerate group with trimethoxysilyl, triethoxysilyl etc. with alkoxysilyl.
As above-mentioned " 1 valency organic group ", for example can enumerate group with glycidyl etc. with epoxy group(ing).
As above-mentioned " 1 valency organic group ", for example can enumerate 3-isocyanato-propyl group etc. with isocyanate group.
As above-mentioned " 1 valency organic group ", for example can enumerate 3-hydroxypropyl etc. with hydroxyl.
As above-mentioned A 1, preferably those have acidic-group, the basic group, urea groups or the carbonatoms that contain nitrogen-atoms be 1 valency organic group of 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, indanthrone 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 T, as this substituting group T, can enumerate for example methyl, carbonatomss such as ethyl are 1～20 alkyl, phenyl, carbonatomss such as naphthyl are 6～16 aryl, carbonatomss such as acetoxyl group are 1～6 acyloxy, methoxyl group, carbonatomss such as oxyethyl group are 1～6 alkoxyl group, chlorine, halogen atoms such as bromine, methoxycarbonyl, ethoxycarbonyl, carbonatomss such as hexamethylene oxygen carbonyl are 2～7 carbalkoxy, cyano group, carbonate groups such as the carbonic acid tert-butyl ester, hydroxyl, amino, carboxyl, sulfoamido, N-sulfoamido etc.
In addition, above-mentioned A 1Can represent with following general formula (4).
Figure A200680053947D00611
General formula (4)
In above-mentioned general formula (4), B 1The group that expression is selected from acidic-group, the basic group that contains nitrogen-atoms, urea groups, urethano, the group that contains the coordination Sauerstoffatom, carbonatoms 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.The preferred embodiment and the above-mentioned A of the group of general formula (4) expression 1Synonym.
R 18The linking group of expression singly-bound or a1+1 valency.A1 represents 1～5.As connecting basic R 18, comprise by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 Sauerstoffatom, 1～200 hydrogen atom, and 0～20 group that sulphur atom constitutes can not have replacement, can have substituting group yet.R 18Be preferably organic linking group.
As R 18Object lesson, the group that can enumerate following structural unit or combine by following structural unit.In addition, this links radicals R 18Also can have above-mentioned substituting group T.
Figure A200680053947D00621
In above-mentioned general formula (1), R 1The connection base of expression (m+n) valency.M+n equals 3～10.
As above-mentioned R 1The connection base 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 not have replacement, can have substituting group yet.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).Above-mentioned linking group R 1When having substituting group,, can enumerate above-mentioned substituting group T as this substituting group.
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 0～20 group that sulphur atom constitutes can not have replacement, can have substituting group yet.As R 2Object lesson, the group that can enumerate the group shown in above-mentioned t-3～5,7～18,22～26,32,34 or form by a plurality of these moiety combinations.R 2Preferably with R 1The coupling position place have sulphur atom.Above-mentioned R 2When having substituting group,, can enumerate above-mentioned substituting group T as this substituting group.
In above-mentioned general formula (1), 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 (1), P 1Expression macromolecular compound residue (macromolecular scaffold) 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, ester compound polymkeric substance, ether compound polymkeric substance, polyurethanes compound polymer, amides polymkeric substance, epoxy compounds polymkeric substance, organosilicon compound polymkeric substance, and their modifier or multipolymer [for example comprise that the multipolymer of polyethers/polyurethane copolymer, polyethers/polymers of vinyl monomers etc. (can be in random copolymers, segmented copolymer, the graft copolymer any.)] at least a, more preferably be selected from least a in polymer of vinyl monomer or multipolymer, ester compound polymkeric substance, ether compound polymkeric substance, polyurethanes compound 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.If low, when then (for example) uses as pigment dispersing agent, a little less than the affinity of dispersion medium, can not guarantee the sufficient adsorption layer of stably dispersing sometimes with the affinity of organic solvent.
In addition, preferred P 1With R 1The coupling position place sulphur atom is arranged.
In the macromolecular compound of above-mentioned general formula (1) expression, more preferably by the macromolecular compound of following general formula (2) expression.
Figure A200680053947D00631
General formula (2)
In above-mentioned general formula (2), A 2With the A in the above-mentioned general formula (1) 1Synonym, its concrete preferred version is also identical.In addition, A 2Can also have substituting group, can enumerate above-mentioned substituting group T.
In above-mentioned general formula (2), R 3The linking group of expression (x+y) valency.R 3With R 1Synonym, its preferable range is also identical.At this moment, R 3Be the linking group of x+y valency, the value of its x and preferable range thereof are identical with n in the general formula (1), and the value of y and preferable range thereof are identical with m, and the value of x+y and preferable range thereof are identical with m+n.
R 3The linking group of expression is preferably organic linking group, and the preferred object lesson of this organic linking group is as follows.But, in that the present invention is not limited thereto.
Figure A200680053947D00641
Figure A200680053947D00651
Wherein, 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 substituting group T as this substituting group.
In above-mentioned general formula (2), 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 do not have to replace or have substituent straight chain, side chain or cyclic alkylidene group, arylidene or inferior aralkyl ,-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 carbonatoms are 1～4 alkyl).Wherein preferred organic linking group.
As above-mentioned R 4, more preferably the alkylidene group of straight or branched or inferior aralkyl ,-O-,-C (=O)-,-N (R 19)-,-SO 2-,-CO 2-,-N (R 20) SO 2-, or the divalent group that forms of these two or more moiety combinations, be preferably especially the alkylidene group of straight or branched or inferior aralkyl ,-O-,-C (=O)-,-N (R 19)-,-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-, 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 19)-,-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 above-mentioned substituting group T as this substituting group.
In addition, the P in the general formula (2) 2The expression macromolecular scaffold 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 (1) 1Synonym, its preferred version is also identical.
In the macromolecular compound of above-mentioned general formula (2) 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 or inferior aralkyl ,-O-,-C (=O)-,-N (R 19)-,-CO 2-or the divalent organic 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, ester compound polymkeric substance, ether compound polymkeric substance, 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, 1 expression 1 or 2.
Figure A200680053947D00671
The matter average molecular weight of the macromolecular compound that is adopted in manufacture method of the present invention is preferably more than 1000, matter average molecular weight more preferably 3000～100000, and more preferably 5000～80000, be preferably 7000～60000 especially.If the matter 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, and can obtain good dispersiveness and dispersion stabilization.
Macromolecular compound (compound that comprises general formula (2) expression) to above-mentioned general formula (1) 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 (2) 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 (3) expression to carry out radical polymerization as chain-transfer agent.
Figure A200680053947D00681
General formula (3)
In above-mentioned general formula (3), R 6, R 7, A 3, g and h respectively with above-mentioned general formula (2) 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-acetic ester, propionate, vinyl butyrate, methoxyacetic 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, heterocyclic 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 two kinds, and this free radical polyalcohol can make corresponding respectively vinyl monomer carry out polymerization by ordinary method and obtain.
For example, can utilize following method to obtain, that is, these vinyl monomers and chain-transfer agent are 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-acetic acid ester, acetone, butanone, methyl iso-butyl ketone (MIBK), methoxy propyl yl acetate, ethyl lactate, ethyl acetate, 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, the azo-compound of 2 '-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 (3) 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 suitably enumerate carboxylic acid halides, haloalkane, isocyanic ester, carbon-to-carbon double bond etc.
Particularly preferably be, " 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 of above-mentioned " compound that has 3～10 sulfydryls in the per molecule ", can enumerate following compound.
Figure A200680053947D00721
Figure A200680053947D00731
In above-claimed cpd, on acquired, the synthetic easiness of raw material, solvability to all kinds of SOLVENTS, preferred (u-1), (u-2), (u-10), (u-11), (u-16), (u-17).
To having (the A in the above-mentioned general formula of functional group 1Or A 2) and the compound with carbon-to-carbon double bond have no particular limits, can be listed below compound.
Figure A200680053947D00741
Figure A200680053947D00751
Figure A200680053947D00771
For example, above-mentioned " compound that has 3～10 sulfydryls in the per molecule " and above-mentionedly " have the acidic-group of being selected from; have the basic group of nitrogen-atoms; urea groups; urethano; the group of band coordination Sauerstoffatom; carbonatoms is the alkyl more than 4, alkoxysilyl, epoxy group(ing), at least 1 group in isocyanate group and the hydroxyl, and compound with carbon-to-carbon double bond " the free radical addition reaction product 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, basic group with nitrogen-atoms, urea groups, urethano, the group of band coordination Sauerstoffatom, carbonatoms is the alkyl more than 4, alkoxysilyl, epoxy group(ing), at least 1 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 basic group, urea groups, urethano, the group of band coordination Sauerstoffatom, the carbonatoms that are selected from acidic-group, have nitrogen-atoms and be at least 1 group in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl more than 4, 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 that generates select arbitrarily.For example, can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl-acetic acid ester, acetone, butanone, methyl iso-butyl ketone (MIBK), methoxy propyl yl acetate, ethyl lactate, ethyl acetate, 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, the azo-compound of 2 '-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 object lesson of the compound of the general formula that can preferably use in the manufacture method of the present invention (1) expression is as follows.But the present invention never is confined to these object lessons.
Figure A200680053947D00791
Figure A200680053947D00801
Figure A200680053947D00811
Figure A200680053947D00821
Figure A200680053947D00831
Figure A200680053947D00851
Figure A200680053947D00871
In addition, as molecular weight is macromolecular compound more than 1000, also can use macromolecular compound with following acidic-group (below, this compound is called " macromolecular compound that contains acidic-group "), this macromolecular compound is preferably the macromolecular compound with carboxyl, is preferably especially to contain (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 above-mentioned (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 above-mentioned (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, benzyl methacrylate, phenylethyl, the methacrylic acid phenethyl ester, vinylformic acid 3-phenyl propyl ester or methacrylic acid 3-phenyl propyl ester repeat units derived.
General formula (I)
Figure A200680053947D00872
(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)
Figure A200680053947D00882
(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 separately hydrogen atom or carbonatoms are 1～5 alkyl.I represents 1～5 number.)
General formula (IV)
Figure A200680053947D00883
(R 7Expression hydrogen atom or carbonatoms are 1～5 alkyl.R 8Represent the group shown in the following logical formula V.)
Logical formula V
Figure A200680053947D00884
(R 9The expression carbonatoms is that 2～5 alkyl or carbonatoms are 6～20 aryl.R 10And R 11Represent that separately hydrogen atom or carbonatoms are 1～5 alkyl.J 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.
If do not specify, the molecular weight in the manufacture method of the present invention is meant the matter average molecular weight.As the measuring method of molecular weight, can enumerate chromatography, viscosimetry, light scattering method, sedimentation velocity method etc.In the present invention, if not otherwise specified, all be to use by gel permeation chromatography (carrier: tetrahydrofuran (THF)) measure and through the matter average molecular weight of polystyrene conversion.
Macromolecular compound can be any in water-soluble, the oil soluble, also can be water-soluble and oil-soluble.
The addition manner of macromolecular compound can be that macromolecular compound is dissolved in the solution that forms in water kind solvent or the organic solvent, also can be solid state, in addition, also can be their combination.Be dissolved in the method that the solution that forms in the solvent adds as employing, for example can enumerate be dissolved in the solvent phase of agglutinative organic filler liquid with solvent in, add method in the agglutinative organic filler liquid to this state; Be dissolved in the solvent miscible but different, add method in the agglutinative organic filler liquid to this state with the solvent of agglutinative organic filler liquid.Employing is dissolved in the solution that forms in the solvent when adding, and the concentration of macromolecular compound is not particularly limited, but is preferably 1～70 quality %, and more preferably 2～65 quality % are preferably 3～60 quality % especially.
The interpolation of macromolecular compound can be following random time: separate out (or before and after it) when generating organic nano particle, after (or before and after it), these operations finish when (or before and after it) when concentrating, the aggegation organic filler after disperseing to concentrate, also can divide in addition for several times and add.In manufacture method of the present invention, also can make the matter average molecular weight is that macromolecular compound more than 1000 is included in the composition as following binding agent, for example preferably after the organic fine particles lye concentrates, when being carried out fine dispersion, adds the agglutinative organic filler.
When organic nano particle was made as 100 mass parts, the addition of macromolecular compound was preferably 0.1～1000 mass parts, and more preferably 5～500 mass parts are preferably 10～300 mass parts especially.
As molecular weight is macromolecular compound more than 1000, except above-claimed cpd, for example can enumerate part butyralization thing, vinylpyrrolidone/vinyl acetate copolymer, polyethylene oxide/propylene oxide segmented copolymer, polymeric amide, derivatived cellulose, starch derivative of part formalizing thing, the polyvinyl alcohol of Polyvinylpyrolidone (PVP), polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyoxyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol etc.In addition, can also use natural high moleculer eompounds such as alginate, gelatin, albumin, casein, gum arabic, tragacanth gum, sulfonated lignin.In addition, as macromolecular compound, can enumerate poly-sulfuric acid vinyl ester, condensation naphthene sulfonic acid etc. with acidic-group.
As macromolecular compound, for example can enumerate polyacrylic acid, polymethyl acrylic acid, side chain and have derivatived cellulose of carboxyl etc. with carboxyl.As containing (A), can enumerate communique such as Japanese kokai publication sho 59-44615 by at least a the reaching in the repeating unit of compound deriving (B) by at least a copolymerization in the repeating unit of compound deriving with carboxylic acid ester groups with carboxyl, special public clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, the spy opens clear 59-53836 communique and the special Sipacril 2739OF of putting down in writing in the clear 59-71048 communique of opening, acrylic copolymer, itaconic acid copolymer, the Ba Dousuan multipolymer, maleic acid, the maleic acid of partial esterification etc.In addition, as more preferred example, can enumerate acrylic acid and acrylic ester copolymers, methacrylic acid-acrylate copolymer, acrylic acid-methacrylate copolymer, methacrylic acid-alkylmethacrylate polymer, acrylic or methacrylic acid and the acrylate put down in writing in No. 4139391 specification sheets of United States Patent (USP) or the multiple copolymer of methacrylic ester and other vinyl compound.
As the example of vinyl compound, can enumerate vinyl naphthalene, acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile of vinylbenzene (for example Vinyl toluene, vinyl ethylbenzene), vinyl naphthalene or the replacement of vinylbenzene or replacement etc.Optimization styrene.
These molecular weight are that the macromolecular compound more than 1000 can only use a kind, also can be used in combination more than two kinds, also can also use with the compound of molecular weight less than 1000.
In the manufacture method of organic nano particle of the present invention, contain the above organic solvent of 60 quality % in the dispersion liquid of preferred organic nano particle, more preferably more than the 65 quality %.There is no particular limitation to this organic solvent, can suitably select from common solvent.For example preferred ester compound solvent, alcohol compound solvent, aromatic series compounds solvent, aliphatic category compound solvent, ketone compounds solvent, preferred especially ester compound solvent, ketone compounds solvent.These solvents can use a kind separately, also can share more than two kinds.
As the ester compound solvent, for example can enumerate 2-(1-methoxyl group) propyl-acetic acid ester, ethyl acetate, ethyl lactate etc.As the alcohol compound solvent, for example can enumerate propyl carbinol, isopropylcarbinol etc.As aromatic series compounds solvent, for example can enumerate benzene,toluene,xylene etc.As aliphatic category compound solvent, for example can enumerate normal hexane, hexanaphthene etc.As the ketone compounds solvent, for example can enumerate butanone, acetone, pimelinketone etc.
[organic nano particle dispersive composition]
Below, the embodiment that forms composition when organic nano particle being used for (for example) colour filter or ink for ink-jet print etc. is elaborated.Organic nano particle can be scattered in the state in the carrier and uses with (for example).Above-mentioned carrier is meant the medium part that makes colo(u)rant dispersion when coating is in liquid state, comprises aqueous the combination with above-mentioned pigment and part (binding agent) that set is filmed and it is carried out the composition (organic solvent) of dissolved dilution.In addition, in the present invention, the binding agent that the binding agent that is adopted when forming nanoparticle is adopted during with redispersion can be identical, also can be different, also they are divided into the binding agent that binding agent that the formation nanoparticle uses and redispersion are used sometimes.
Can come suitably to determine the concentration of the organic nano particle in the organic nano particle dispersive composition behind the redispersion according to purpose, but preferred organic nano particle is 2～30 quality % with respect to the total amount of dispersive composition, more preferably 4～20 quality % are preferably 5～15 quality % especially.Utilizing carrier to carry out under the dispersive situation as mentioned above, the amount of binding agent and dissolved dilution composition can suitably be selected according to organic materials kind etc., with respect to the dispersive composition total amount, binding agent is preferably 1～30 quality %, more preferably 3～20 quality % are preferably 5～15 quality % especially.The dissolved dilution composition is preferably 5～80 quality %, more preferably 10～70 quality %.
For the nanoparticle liquid after the above-mentioned concentration extraction, as previously mentioned, become possibility in order to make strainer filtration fast, preferably make the organic nano particle aggegation by concentrating, preferably concentrate and make its aggegation by centrifugation or drying.
As this aggegation nanoparticle is carried out fine dispersive method, 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 nanoparticle thermal thermocoagulation (referring to " and colo(u)rant dispersion technology-surface treatment と disperses drug to make い side and び Fen San Evaluation value-technical intelligence association; 1999), 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 as applying the dispersion machine that uses when physical energy disperses organic nano particle after concentrating, be not particularly limited, for example can enumerate dispersion machines such as kneader, roll crusher, second reduction machine (ア ト ラ イ ダ-), high-speed grinder, dissolving machine, homo-mixer, sand mill.In addition, can also enumerate the high pressure dispersion method, and by using microballon to carry out the dispersive method as preferred method.
＜1〉dispersive mode
As the preferable production process of organic nano particle dispersive composition, preferably adopt following method, promptly, with resinous principle tinting material is carried out mixing dispersion treatment, make that the viscosity under 25 ℃ is 10 after the mixing dispersion treatment, more than the 000mPas, be preferably 100, the viscosity higher that 000mPas is above, add solvent then, carry out the diffusing processing of differential, the viscosity that makes differential loose after handling is 1, below the 000mPas, be preferably 100mPas following than low viscosity.
The machinery that uses in the mixing dispersion treatment 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 can save mixing dispersion treatment.In this case, by microballon pigment and dispersion agent or surface treatment agent are dispersed in acrylic copolymer of the present invention and the solvent.
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 " PaintFlow and Pigment Dispersion " (1964, John Wiley and Sons company publication) of T.C.Patton work, also can use this method about mixing, dispersive detailed content.
＜2〉example of dispersion agent
In the organic nano particle dispersive composition,, can add pigment dispersing agent commonly used or tensio-active agent in order to improve the dispersiveness of organic nano particle.As these dispersion agents, can use multiple compound, for example can enumerate phthalocyanine derivates (commercially available product EFKA-6745 (manufacturing of エ Off カ society)), ソ Le ス パ-ス 5000 (manufacturing of ゼ ネ カ (strain) society); Organosiloxane polymer KP341 (manufacturing of SHIN-ETSU HANTOTAI's chemical industry (strain) society), (methyl) acrylic acid or the like (being total to) polymkeric substance Port リ Off ロ-No.75, No.90, No.95 (manufacturing of society of common prosperity society oil chemistry industry (strain)), W001 cationic surfactants such as (abundant company make); Nonionic surface active agent 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 aniorfic surfactant such as (abundant company make); 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 that gloomy industry (strain) is down made), 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 (manufacturings of サ Application ノ プ コ society); Various ソ Le ス パ-ス dispersion agents (manufacturing of ゼ ネ カ (strain) society) 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 (manufacturing of rising sun electrification (strain) society) and イ ソ ネ Star ト S-20 (Sanyo changes into (strain) society and makes).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.
The dispersion agent that uses when forming nanoparticle during as redispersion preferably reuses the compound shown in [dispersion agent] item.
For the organic nano particle dispersive composition, can make the organic nano particle (primary particle) behind the redispersion form fine divided particles, particle diameter is preferably 1～200nm, and more preferably 2～100nm is preferably 5～50nm especially.In addition, the Mv/Mn of particle 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 pigment particles in organic nano particle dispersive composition or the photosensitive composition described later, although be that (for example 10～100nm) such nominal particle size still 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, organic nano particle contained in organic nano particle dispersive composition, the photosensitive composition is carried out to heavens and fine equably dispersion, therefore than also bringing into play high depth of shade under the minimal thickness, can make (for example) colour filter etc. realize thin layerization.
For organic nano particle dispersive composition, photosensitive composition, by it being contained demonstrate distinct tone and high-strength pigment, it is excellent as the Image forming material that is used to make color correction device for example or colour filter.
And; exposure during for the formation rendered image, the alkaline-based developer that uses when developing; can use the material that dissolves in the alkaline aqueous solution as binding agent (binder) in organic nano particle dispersive composition, photosensitive composition, 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 particle dispersive composition, the coloring photosensitive combination (dispersing of pigments medium), the drying after apply, this requirement also is satisfiable.
[ink-jet ink for color filter]
Ink-jet ink for color filter of the present invention contains: (a) organic nano particle and (b) polymerizable monomer and/or polyreactive oligomers.At this moment, ink-jet ink for color filter or photosensitive composition are contained: (a) organic nano particle, (b) polymerizable monomer and/or polyreactive oligomers, (c) binding agent and (d) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.Below, the composition of above-mentioned (a)～(d) is described.
(a) organic nano particle
About organic nanometer particle preparing process, be described in detail.The content of organic nano particle, with respect to the whole solid substances in the ink-jet ink for color filter (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 then.As the particulate with tinting material function, particle diameter is preferably below the 0.1 μ m, and special preferable particle size is below the 0.08 μ m.In addition, also can use in order to mix colours with pigment combinations commonly used.
(b) polymerizable monomer and/or polyreactive oligomers
As polymerizable monomer contained in the ink-jet ink for color filter of the present invention and/or polyreactive oligomers, be 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 polymerizable monomer and/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 (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 reaction product.
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.
The molecular weight of these polymerizable monomers and/or polyreactive oligomers is preferably 200～1000, can use separately, or mix more than two kinds and to use, be generally 5～50 quality % with respect to the content of whole solid substances of ink-jet ink for color filter, be preferably 10～40 quality %.If should measure too much, then be difficult to control development, can on manufacturing adaptability, have problems.If very few, the curing power deficiency when then exposing.
(c) binding agent
As binding agent, the binding agent that preferably has acidic-group, can when preparation ink-jet ink for color filter or photosensitive composition, add this binding agent, also preferably when making above-mentioned organic nano particle dispersive composition or when forming organic nano particle, add.Binding agent can be added to pigment dyestuff solution and poor solvent (in this poor solvent, adding organic pigment solution) to generate organic nano particle both or one in.Perhaps also preferably when forming organic nano particle, add binder solution by other system.As binding agent, preferably on side chain, has the alkali-soluble polymer of carboxylic acid group or carboxylic acid ester groups ion isopolarity group.As its example, can be set forth in the maleic acid etc. that Japanese kokai publication sho 59-44615 communique, special public clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, spy are opened the Sipacril 2739OF put down in writing in clear 59-53836 communique and the clear 59-71048 communique of Te Kai, acrylic copolymer, itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, partial esterification.In addition, can also be set forth in the derivatived cellulose that has carboxylic acid group or carboxylic acid ester groups etc. on the side chain, in addition, also preferred the use having the material that forms behind the addition cyclic acid anhydride on the polymkeric substance of hydroxyl.And, as more preferred example, can be set forth in United States Patent (USP) the 4th, 139, (methyl) vinylformic acid benzyl ester of putting down in writing in No. 391 the specification sheets and (methyl) acrylic acid multipolymer, and the multiple copolymer of (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid and the formation of other monomer.These have the binder polymer of polar group, can use separately, and the state that also can form composition also to use with the film-forming properties polymkeric substance of routine uses.With respect to the organic nano particle of 100 mass parts, addition is generally 10～200 mass parts, preferred 25～100 mass parts.
In addition,, the compound that on side chain, has polymerizable group can be used, also UV-cured resin and thermosetting resin etc. can be adopted in order to improve cross-linking efficiency.Though below show the example of the polymkeric substance that contains these polymerizable groups, be not limited to following these examples, as long as this polymkeric substance contains caustic solubility group and carbon-carbon unsaturated link(age)s such as COOH base, OH base, ammonium.Can use following compound etc.; this compound obtains like this: make by the compound with OH base (for example) vinylformic acid 2-hydroxy methacrylate with compound (for example) methacrylic acid that contains the COOH base and can take place containing the acryloyl base class or containing the multipolymer that monomer such as vinylic chemical compound forms of copolymerization with them, react with the compound (for example compound of epihydric alcohol acrylic ester and so on) with oxirane ring (this oxirane ring and OH base have reactivity) and carbon-carbon unsaturated link(age) group and obtain.Aspect the OH reaction, except using oxirane ring, also can use acid anhydrides, have isocyanate group compound, have the compound of acryl.Can use such reaction product in addition, this reaction product obtains like this: make disclosedly in Japanese kokai publication hei 6-102669 number, Japanese kokai publication hei 6-1938 number to have the compound of oxirane ring with unsaturated carboxylic acid reaction such as vinylformic acid and obtain compound, this compound and saturated or undersaturated multi-anhydride are reacted and obtain described reaction product.Compound as the caustic solubility group that has COOH and so on simultaneously and carbon-carbon unsaturated group, for example can enumerate ダ イ ヤ Na one Le NR series (production of レ イ ヨ Application Co., Ltd. of Mitsubishi), Photomer 6173 (urethane acrylate oligomer that contains COOH, Diamond Shamrock Co., Ltd. produces), PVC ス コ one ト R-264, KS resist 106 (producing) by Osaka Organic Chemical Industry Co., Ltd., サ イ Network ロ マ one P series, プ ラ Network セ Le CF200 series (producing) by ダ イ セ Le chemical industry Co., Ltd., Ebecryl3800 (production of ダ イ セ Le ユ one シ one PVC one Co., Ltd.) etc.
In addition, as resin glue, can adopt the organic high molecular polymer that on the part of side chain, has water-soluble atomic group.Above-mentioned resin glue is the wire organic high molecular polymer that has intermiscibility with monomer, and it is soluble in organic solvent and alkali (preferably, can develop with weak alkaline aqueous solution).As above-mentioned alkali soluble resins, can be set forth in the polymkeric substance that has carboxylic acid on the side chain, for example open maleic acid that clear 59-53836 number, spy open the Sipacril 2739OF put down in writing in the clear 59-71048 communique, acrylic copolymer, itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, partial esterification etc., also have the acid cellulose derivative that on side chain, has carboxylic acid equally Japanese kokai publication sho 59-44615 number, special public clear 54-34327 number, special public clear 58-12577 number, special public clear 54-25957 number, spy.In addition, as above-mentioned alkali soluble resins, the material that forms etc. also are useful having after addition has acid anhydrides on the polymkeric substance of hydroxyl.Wherein, specifically, preferred especially (methyl) vinylformic acid benzyl ester/(methyl) acrylic copolymer or (methyl) vinylformic acid benzyl ester/(methyl) vinylformic acid/and the multiple copolymer that forms of other monomers.As above-mentioned alkali soluble resins, can use at least by (i) and be selected from least a acidic component monomer and (ii) alkyl polyoxyethylene (methyl) acrylate and (iii) (methyl) multipolymer that benzyl acrylate constituted (below be sometimes referred to as " copolymer A ") in maleic anhydride (MAA), vinylformic acid (AA), methacrylic acid (MA) and the fumaric acid (FA).
As the composition of above-mentioned copolymer A, (i) acidic component monomer, (ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) n:CH 3(OC 2H 4) nOCOC (R)=CH 2), and (iii) the composition mass ratio of (methyl) vinylformic acid benzyl ester (Bz (M) A) be preferably 10～25/5～25/50～85, more preferably 15～20/5～20/60～80.In addition, above-mentioned multipolymer is measured by GPC and through the matter average molecular weight (Mw) after the polystyrene conversion, is preferably 3,000～50,000, and more preferably 5,000～30,000.
(i) the monomeric composition mass ratio of acidic component is in above-mentioned scope, and caustic solubility and the solvability in solvent can not reduce.In addition, (ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) n:CH 3(OC 2H 4) nOCOC (R)=CH 2) the composition mass ratio in above-mentioned scope, composition liquid launches on substrate easily, and the dispersiveness of tinting material can not reduce, so can reach effect of the present invention effectively.When the composition mass ratio of (iii) (methyl) benzyl acrylate (Bz (M) A) was in above-mentioned scope, the alkali development adaptability of the dispersion stabilization of tinting material and solvability in composition and coated film can not reduce.
Also has above-mentioned (ii) alkyl polyoxyethylene (methyl) acrylate (Acr (EO) n:CH 3(OC 2H 4) nOCOC (R)=CH 2) middle polyoxyethylene (EO) nMultiplicity n preferred 2～15, more preferably 2～10, preferred especially 4～10.In the time of in above-mentioned multiplicity n is in above-mentioned scope, with not producing the development residue after the alkaline developer development, flowability in the time of can preventing composition as coating fluid reduces, and can prevent to produce the even phenomenon of crawling, can also prevent that the homogeneity of coated film thickness from descending and province's fluidity reduction.
These have the binder polymer of polar group, can use separately, and the state that also can form composition also to use with the film-forming properties polymkeric substance of routine uses.With respect to the organic nano particle of 100 mass parts, addition is generally 10～200 mass parts, is preferably 25～100 mass parts.
At binding agent is under the situation of macromolecular compound, quantity for the acidic-group in this macromolecular compound has no particular limits, when the number of the repeating unit that is contained in 1 molecule was 100, the repeating unit with acidic-group was preferably 5～100, and more preferably 10～100.In addition, as (1) by the compound institute repeat units derived with carboxyl and (2) polymerization ratio by compound institute repeat units derived with carboxylic acid ester groups, the mole % of repeating unit (1) is preferably 5～40, the mole % of repeating unit (2) is preferably 40～90, and the mole % of other repeating unit except repeating unit (1) or (2) is preferably below 25.In addition, the molecular weight with caustic solubility binding agent macromolecular compound of acidic-group is preferably 3000～1000000, and more preferably 4000～200000, be preferably 5000～80000 especially.
In addition, the above-mentioned matter average molecular weight of also preferred use is the macromolecular compound more than 1000, and its content is generally 15～50 quality % with respect to whole solid substances of ink-jet ink for color filter or photosensitive composition, is preferably 20～45 quality %.If should measure too much, then the viscosity of composition is too high, makes on the adaptability and can have problems.If very few, then having problems aspect the formation coat film.
(d) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system
As the Photoepolymerizationinitiater initiater that in ink-jet ink for color filter 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 the even acyl ketone of disclosed neighbour (vicinal polyketaldonyl) compound in No. 2367660 specification sheets of United States Patent (USP), the acyloin ether compound of putting down in writing in No. 2448828 specification sheets of United States Patent (USP), the aromatic series acyloin compound 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 acyl-oxygen, phosphofluoric acid-trialkyl Ben phosphonium 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 performance especially.
With respect to whole solid substances of ink-jet ink for color filter, the content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system is generally 0.5～20 quality %, is preferably 1～15 quality %.If should measure too much, then susceptibility is too high, is difficult to control.If very few, then exposure sensitivity is low excessively.
(other additive)
[solvent]
In ink-jet ink for color filter 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 ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, Isoamyl Acetate FCC, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, the oxyacetic acid butyl ester, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 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, methyl aceto acetate, 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 methyl cellosolve, acetate ethyl cellosolve, diethylene glycol monomethyl ether, methyl proxitol acetate etc.; Ketone, for example butanone, 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, acetate ethyl cellosolve, ethyl lactate, butylacetate, 3-methoxypropionic acid methyl esters, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, acetate of butyl carbitol, methyl proxitol acetate etc. as the solvent among the present invention.These solvents can be used alone or in combination of two or more kinds.
In addition, can use boiling point in case of necessity is 180 ℃～250 ℃ solvent.As these high boiling solvents, following material can be shown.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, propylene-glycol diacetate, propylene glycol n-propyl ether acetic ester, diethylene glycol diethyl ether, 2-ethylhexyl acetic ester, 3-methoxyl group-3-methyl butyl acetic ester, gamma-butyrolactone, tripropylene glycol ethyl methyl acetic acid ester, dipropylene glycol normal-butyl acetic ester, propylene glycol phenyl ether acetic acid ester, 1,3 butylene glycol diacetate esters.
The content of solvent is preferably 10～95 quality % with respect to the ink-jet ink for color filter total amount.
[tensio-active agent]
In the colour filter of Shi Yonging, in order to realize high color purity, need make each color of pixel enriching, people recognize and do the following problem that exists like this that promptly the membrane thickness unevenness of pixel causes color inhomogeneous in the past.Therefore, because the film thickness of pixel is had a direct impact, so need the change of thickness be improved.
For colour filter of the present invention, from controlling uniform thickness, effectively preventing from the uneven viewpoint of color that Thickness Variation causes from preferably to make and containing suitable tensio-active agent in the ink-jet ink for color filter.
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 hold back agent]
Preferably contain the thermopolymerization hold back agent in the ink-jet ink for color filter of the present invention.Example as this thermopolymerization hold back agent, 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 ink-jet ink for color filter total amount, the content of thermopolymerization hold back agent is preferably below the 1 quality %.
[auxiliary dyestuff, the pigment that uses]
In case of necessity, in ink-jet ink for color filter 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 ink-jet ink for color filter, reach homodisperse, so its particle diameter is preferably below the 0.1 μ m, below 0.08 μ m.
As dyestuff or pigment, specifically, be fit to use the coloured material of putting down in writing in [0038]～[0040] section of TOHKEMY 2005-17716 communique as above-mentioned pigment, the spy opens the pigment of record in the section of 2005-361447 communique [0068]～[0072], and the special tinting material of putting down in writing in [0080]～[0088] section of 2005-17521 communique of opening.With respect to the ink-jet ink for color filter 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 ink-jet ink for color filter 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 ink-jet ink for color filter 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 ink-jet ink for color filter of the present invention.
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 ink-jet ink for color filter of the present invention.
In ink-jet ink for color filter of the present invention, preferably control ink temperature and make the amplitude of fluctuation of viscosity in ± 5%.Viscosity during injection is preferably at 5～25mPas, more preferably at 8～22mPas, particularly preferably in 10～20mPas (in the present invention, if not otherwise specified, viscosity is meant the value in the time of 25 ℃).Except that above-mentioned injection temperature is set, also can regulate viscosity by kind and the addition of regulating the composition that contains in the ink.Above-mentioned viscosity can be measured by common devices such as for example cone-plate type rotational viscosimeter or E type viscometers.
In addition, consider that from the angle of the flatness that improves pixel the surface tension of ink is preferably 15～40mN/m (in the present invention during injection, if not otherwise specified, surface tension is meant the value in the time of 23 ℃), more preferably 20～35mN/m most preferably is 25～30mN/m.Can come the reconciliation statement surface tension by interpolation tensio-active agent, change solvent types.(consonance interface science Co., Ltd. makes, CBVP-Z), full automatic balance type electron surface tonometer ESB-V known survey meters such as (consonance science Co., Ltd. make) measures above-mentioned surface tension according to platinum plate method for example can to use surface tension apparatus.
[injection of ink-jet ink for color filter]
Injection method as ink-jet ink for color filter of the present invention, the method that can adopt continuity ground to spray charged ink and utilize electric field to control, the method of utilizing piezoelectric element intermittently to spray ink, and the whole bag of tricks such as method that ink is heated and utilizes the bubble that produces that ink is intermittently sprayed.
In addition, the ink jet method of using when forming each pixel can adopt the method that makes the ink thermofixation, makes the method for ink photocuring, forms the usual methods such as method that instil after the transparent image receiving layer in advance on substrate.
Inkjet head (following also abbreviate as " shower nozzle ") can be suitable for common shower nozzle, can use ink gun commonly used, can use continuous injection type, need based jet type (dot on demand).In the need based jet type, aspect temperature-sensitive shower nozzle (thermal head), for the ink that spues, preferably as the sort of temperature-sensitive shower nozzle described in the Japanese kokai publication hei 9-323420 communique with operating valve.Aspect piezo jets, the shower nozzle described in for example can use European patent A 277, No. 703,278, No. 590 grades of European patent A.The shower nozzle that preferably has temp regulating function is so that can control the temperature of ink.Set injection temperature so that the viscosity when spraying is 5～25mPas, preferably ink temperature is controlled so that spread of viscosity in ± 5%.In addition, preferably carry out work with the driving frequency of 1～500kHz.
After each pixel forms, the heating process of heat treated (so-called oven dry processing) can be set.That is, will have the substrate that photopolymerisable layer is taken place by rayed is placed on and heats in electric furnace, the moisture eliminator etc. or shine with infrared lamp.The temperature and time of heating depends on the composition of photosensitivity heavy colour composition and the thickness of formed layer, generally consider, preferably heated about 10 minutes～about 120 minutes down at about 120 ℃～about 250 ℃ from the aspect that can obtain sufficient solvent resistance, alkali resistance and ultraviolet radiation absorption degree.
Pattern form to formed colour filter does not thus limit especially, its can for the bar shaped of general black matrix (black matrix) shape, also can be for grid, can also be the shape of rounded projections arranged.
In the present invention, preferably, before forming the operation of pixel, make the next door in advance, sprayed the such making method of ink by the part that this next door surrounded with previously described ink-jet ink for color filter.Though described next door can be any material, when making colour filter, preferably, has the next door (following also abbreviate as " next door ") of the opacifying property of black matrix function.Can adopt with colour filter commonly used and make this next door with black matrix identical materials, method.For example in the TOHKEMY 2005-3861 communique in [0021]～[0074] section, TOHKEMY 2004-240039 communique in the black matrix described in [0012]～[0021] section or the TOHKEMY 2006-17980 communique in [0015]～[0020] section, TOHKEMY 2006-10875 communique the ink for ink-jet print described in [0009]～[0044] section with black matrix etc.
[coat film of photosensitive composition]
Can form coat film with photosensitive composition of the present invention, its thickness can suitably determine, but is preferably 0.5～5.0 μ m, more preferably 1.0～3.0 μ m.For the coat 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.
(slit-shaped nozzle)
In addition, though above-mentioned coat film can be by forming with common coating method coating and dry photosensitive composition, for purposes of the invention, the slit-shaped nozzle that preferably adopts hydrojet portion to have slit-shaped apertures applies.Specifically, preferably using TOHKEMY 2004-89851 communique, spy to open 2004-17043 communique, spy opens 2003-170098 communique, spy and opens 2003-164787 communique, spy and open 2003-10767 communique, spy and drive slit-shaped nozzle and the slot coated device that 2002-79163 communique, spy are opened record in the 2001-310147 communique etc.
As the method that photosensitive composition is coated on the substrate, from can all even aspect that applies the film of 1～3 μ m accurately, it be excellent that rotation applies, and this method has obtained extensive widespread usage in colour filter is made.But, be accompanied by the maximization and the batch process of liquid crystal indicator in recent years, to make efficient and save manufacturing cost in order further to improve, in the making of colour filter, adopting than rotating to apply to be more suitable in carrying out the slot coated that the wide cut large-area substrates applies.In addition, from saving the viewpoint of liquid, slot coated also applies excellent than rotation, can be filmed uniformly with coating liquid measure still less.
Slot coated is a kind of like this coating method, promptly, making front end have width is that the gap of tens of microns slit (gap) and length application head corresponding with the coating width of rectangular substrate and substrate remains tens of～hundreds of microns, make substrate and application head keep the constant speed of relative movement simultaneously, will be coated on the substrate by the coating liquid that slit provides by predetermined coated weight.This slot coated have (1) and rotation apply compare the liquid loss less, (2) no coating liquid disperses, therefore reduced the liquid that can not that disperses in clean, (3) and sneaked into the time that coat film, (4) rotates beginning and stop again, therefore shortened and produce interval, (5) easily to advantages such as large substrate apply.Owing to have these advantages, slot coated is suitable for the making of the liquid crystal indicator of large-scale picture with colour filter, also is expected to become favourable coating method with regard to the minimizing of coated weight.
Because slot coated can form area and apply big coat film more than rotation, therefore when the slit from broadness exports the ejection coating liquid, must make the speed of relative movement that keeps between applicator and the coated article to a certain degree.Therefore, the coating liquid that uses in the slot coated mode requires to have good flowability.In addition, in slot coated, the various conditions that especially require to be provided to the coating liquid on the substrate from the slit of application head keep constant at whole coating width.If liquid rerum natura deficiencies such as the flowability of coating liquid and viscoelastic property then can produce following problem, it is inhomogeneous that coating promptly takes place easily, is difficult to keep the constant coating thickness in the coating width direction, can not form uniform coat film.
Because above situation in order there not to be the even coat film of non-uniform phenomenon, has been carried out flowability and viscoelastic property that a large amount of trials improve coating liquid.But, as mentioned above, though proposed to reduce the molecular weight of polymkeric substance, or selection is to the polymkeric substance of the solvability excellence of solvent, or select all kinds of SOLVENTS in order to control velocity of evaporation, or use means such as tensio-active agent, but do not have a kind of means can fully improve above-mentioned variety of issue.
[photosensitive resin transfer material]
Below, photosensitive resin transfer material of the present invention is described.
Preferably with the photosensitive resin transfer material of putting down in writing in the Japanese kokai publication hei 5-72724 communique, promptly the film of monolithic devices forms photosensitive resin transfer material of the present invention.The example that constitutes of this monolithic devices film as an illustration; can enumerate and carry out laminated successively interim upholder/thermoplastic resin/middle layer/photo-sensitive resin/protective membrane and structure that obtain, photosensitive resin transfer material of the present invention is to be arranged to photoresist by the photosensitive composition that uses the invention described above form.
(interim upholder)
In photosensitive resin transfer material of the present invention,, has flexible also can not produce remarkable distortion, contraction or elongation under pressurization or heating and pressurizing material even must be as interim upholder.As the example of this interim upholder, can enumerate polyethylene terephthalate film, tri cellulose acetate membrane, Polystyrene Film, polycarbonate membrane etc., wherein preferred especially biaxial stretch-formed polyethylene terephthalate film.
(thermoplastic resin)
As the composition that uses in the thermoplastic resin, the organic polymer material of putting down in writing in the preferred Japanese kokai publication hei 5-72724 communique, be to select in about organic polymer material below 80 ℃ especially preferably from the softening temperature that records by Wei Ka-Vicat method (specifically, being the method for measuring the polymkeric substance softening temperature according to U.S. material test method(s) ASTMD1235).Specifically, can enumerate polyethylene, polyolefine such as polypropylene, the ethylene copolymer that ethene and vinyl-acetic ester or its are saponified etc., ethene and acrylate or its are saponified, polyvinyl chloride, vinylchlorid and vinyl-acetic ester and saponified etc. vinyl chloride copolymer thereof, polyvinylidene chloride, polyvinylidene chloride copolymer, polystyrene, the styrol copolymer that vinylbenzene and (methyl) acrylate or its are saponified etc., polyvinyl toluene, the vinyl toluene copolymer that Vinyl toluene and (methyl) acrylate or its are saponified etc., poly-(methyl) acrylate, (methyl) acrylate copolymer that (methyl) butyl acrylate and vinyl-acetic ester etc. form, vinyl acetate copolymerization nylon, copolymer nylon, N-alkoxy methyl nylon, the organic polymers such as polyamide resin of N-dimethylamino nylon and so on.
(middle layer)
For photosensitive resin transfer material of the present invention, when after coating, preserving, prevent the mixing of composition in order when applying a plurality of coat, to reach, the middle layer preferably is set.As this middle layer, the preferred oxygen barrier film that uses conduct " separating layer " in the Japanese kokai publication hei 5-72724 communique and put down in writing with the function that stops oxygen, in this case, the susceptibility during exposure rises, reduce the time load of exposure machine, improved productivity.
As the oxygen barrier film, the lower oxygen perviousness of preferred demonstration can be dispersed or dissolved in the material in water or the alkali aqueous solution, can suitably select from common material.Wherein, the combination of the special pure and mild polyvinylpyrrolidone of preferably polyethylene.
(protective membrane)
The thin protective membrane of pollution when preferably on photo-sensitive resin, being provided for protecting it to avoid storing and damage.Protective membrane can be to be made of or materials similar identical with interim upholder, but must separate with photo-sensitive resin easily.As the material of protective membrane, for example organosilicon paper, polyolefine or polytetrafluoroethylsheet sheet suit.
(making method of photosensitive resin transfer material)
Photosensitive resin transfer material of the present invention can be made in the following manner, promptly, on interim upholder, apply the additive dissolving that makes thermoplastic resin and the coating liquid (thermoplastic resin coating liquid) that forms, dry then, thermoplastic resin is set thus, on thermoplastic resin, apply the intermediate layer material solution that constitutes by the solvent of solution heat plastic resin layer not then, and carry out drying, adopt the solvent that does not dissolve the middle layer to apply and drying then, thereby photo-sensitive resin is set.
In addition, also can make in the following manner, that is, prepare the sheet material that above-mentioned interim upholder is provided with thermoplastic resin and middle layer, and protective membrane is provided with the sheet material of photo-sensitive resin, carries out bonding mutually according to the mode that the middle layer is contacted with photo-sensitive resin; Also have, prepares the sheet material that above-mentioned interim upholder is provided with thermoplastic resin, and protective membrane is provided with the sheet material in photo-sensitive resin and middle layer, carry out bonding mutually according to the mode that makes thermoplastic resin and middle layer joint.
In photosensitive resin transfer material of the present invention, the thickness of photo-sensitive resin is preferably 1.0～5.0 μ m, and more preferably 1.0～4.0 μ m are preferably 1.0～3.0 μ m especially.In addition, though be not particularly limited, as other the preferred thickness of each layer, preferred usually interim upholder is 15～100 μ m, and thermoplastic resin is 2～30 μ m, and the middle layer is 0.5～3.0 μ m, and protective membrane is 4～40 μ m.
In addition, coating in the above-mentioned making method can utilize common coating unit etc. to carry out, but for the present invention, preferred employing coating unit (slot coated device) that described in " coat film of photosensitive composition " item, use slit-shaped nozzle applies.The preferred object lessons of slot coated device etc. are same as described above.
[colour filter]
Colour filter of the present invention is characterised in that the contrast gradient excellence.In the present invention, contrast gradient is illustrated between two polaroids, the ratio of the light transmission capacity the when light transmission capacity when polarizing axis is parallel is vertical with polarizing axis (referring to " nineteen ninety the 7th the color reversion glory learn コ Application Off ァ 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.).
Light and shade difference when the contrast gradient height of colour filter is meant and makes up with liquid crystal can become big, and in order to replace CRT with liquid-crystal display, this is very important performance.The contrast gradient of colour filter of the present invention is preferably more than 3000 when monochrome, more preferably more than 5000, is preferably more than 7000 especially.For containing the colour filter that R pixel, G pixel, B pixel also also are provided with black matrix as required, contrast gradient is preferably more than 3000, more preferably more than 5000, is preferably more than 6000 especially.The invention is characterized in and to realize such high-contrast.
When colour filter of the present invention is used with colour filter as TV, preferably under the F10 light source, all the monochromatic colourities of red (R), green (G) and blue (B) and following table record value (below, be called " standard chroma " in the present invention) poor (Δ E) in 5, more preferably in 3, in 2.
x y Y
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R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
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Colourity among the present invention is to utilize microscope spectrophotometer (オ リ Application パ ス optics society make, OSP100 or 200) to measure, and calculates as the results in the 2 degree visuals field under the F10 light source, represents with the xyY value of xyz color specification system.In addition, with the difference of target colourity with La *b *The aberration of color specification system is represented.
(photo-sensitive resin)
Number of times that can be by repeating to be equivalent to number of color, on substrate, form the methods such as method that photo-sensitive resin, exposure back develop and make colour filter of the present invention.In addition, as required, also can form the structure of distinguishing the border with black matrix.
In above-mentioned manufacture method, as the method that on substrate, forms above-mentioned photo-sensitive resin, can enumerate (a) and adopt method that applying device commonly used etc. will above-mentioned each photosensitive composition applies and (b) utilize above-mentioned photosensitive resin transfer material, the method for pasting by lamination etc.
(a) adopt coating unit to apply
When making colour filter of the present invention, can adopt coating unit commonly used to carry out the coating of photosensitive composition, wherein preferred especially the use in [coat film of a photosensitive composition] described slot coated.The preferred object lesson of slot coated also as previously mentioned in addition.When forming photo-sensitive resin by applying, its film thickness is preferably 1.0～3.0 μ m, and more preferably 1.0～2.5 μ m are preferably 1.5～2.5 μ m especially.
(b) paste by lamination
Using photosensitive resin transfer material of the present invention to form membranaceous and photo-sensitive resin that obtain, use through the roller of heating and/or pressurization or dull and stereotyped pressing or heating to be pressed together on the substrate described later, thereby paste.Specifically, can enumerate Japanese kokai publication hei 7-110575 communique, spy and open that flat 11-77942 communique, spy are opened the 2000-334836 communique, the spy opens laminating machine and the laminating method of putting down in writing in the 2002-148794 communique, but from the few viewpoint of impurity, the special method of putting down in writing in the flat 7-110575 communique of opening of preferred employing.In addition, when the photosensitive resin transfer material that utilizes the invention described above formed photo-sensitive resin, its preferred thickness was identical with the preferred thickness of record in [photosensitive resin transfer material] item.
(substrate)
In the present invention, the substrate as forming colour filter for example can use transparency carrier, can enumerate known sheet glass such as soda glass plate that the surface has silicon oxide film, low expansion glass, non-alkali glass, quartz glass plate or plastic film etc.
In addition, by in advance aforesaid substrate being carried out coupling processing, itself and photosensitive composition or photosensitive resin transfer material are close to well.As this coupling processing, preferably use the method for putting down in writing in the TOHKEMY 2000-39033 communique.In addition, though do not do special qualification, the thickness of substrate is preferably 700～1200 μ m usually, is preferably 500～1100 μ m especially.
(oxygen barrier film)
When by applying photosensitive composition when forming photosensitive resin film in the colour filter of the present invention, can the oxygen barrier film be set further on this photo-sensitive resin, can improve exposure sensitivity thus.As this oxygen barrier film, can enumerate with at the identical film of film described in (middle layer) of [photosensitive resin transfer material].In addition, though do not do special qualification, the thickness of oxygen barrier film is preferably 0.5～3.0 μ m usually.
(exposure and development)
Above the photo-sensitive resin that forms on the aforesaid substrate, be provided with predetermined mask, see through this mask, thermoplastic resin and middle layer then, top exposure from mask, then develop with developing solution, such operation of the number of times by repeating to be equivalent to number of color just can obtain colour filter of the present invention.
Herein,, can suitably select to use, get final product so long as can penetrate the light (for example 365nm, 405nm etc.) that makes photo-sensitive resin solidified wavelength region as the light source of described exposure.Particularly, extra-high-pressure mercury vapour lamp, high pressure mercury vapour lamp, metal halide lamp etc. are for example arranged.Exposure is generally 5～200mJ/cm 2About, be preferably 10～100mJ/cm 2About.
In addition, have no particular limits, can use as developing solutions commonly used such as the described developing solutions of Japanese kokai publication hei 5-72724 communique for above-mentioned developing solution.In addition, the preferred use carried out the developing solution that lysotype is developed to photo-sensitive resin, and the compound and its concentration that for example preferably contain pKa=7～13 are the developing solution of 0.05～5mol/L, can also add a small amount of and the miscible organic solvent of water in this developing solution.
As the organic solvent miscible, can enumerate for example methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, Pyranton, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzylalcohol, acetone, butanone, pimelinketone, 6-caprolactone, gamma-butyrolactone, dimethyl formamide, N,N-DIMETHYLACETAMIDE, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-Ji Neixianan, N-Methyl pyrrolidone etc. with water.The concentration of this organic solvent is preferably 0.1 quality %～30 quality %.
In addition, in above-mentioned developing solution, can also add tensio-active agent commonly used.Surfactant concentrations is preferably 0.01 quality %～10 quality %.
About the mode of developing, can use to stir and develop, spray development, spray and methods such as rotation development, immersion development.
Above-mentioned spray is developed herein and describe.On the photo-sensitive resin after the exposure,, can remove uncured part by the mode spray developing liquid of spray.In addition, preferably, before development, spray the alkaline liquid low, to remove thermoplastic resin, middle layer etc. to the solvability of photo-sensitive resin in modes such as sprays.In addition also preferably, after development,,, remove the development residue with wipings such as brushes with the mode jet cleaning agent etc. of spray.
The temperature of developing solution is preferably 20 ℃～40 ℃, and the pH of developing solution is preferably 8～13.
In addition, when making colour filter of the present invention, as described in Japanese kokai publication hei 11-248921 communique, No. 3255107 communiques of Japanese Patent, the stacked matrix that forms of photosensitive composition of colour filter will be formed, on this matrix, form transparency electrode, the protuberance layer that division alignment is used is laminated on the established dottle pin again, considers that from the aspect that reduces cost this is preferred.
Photosensitive composition is applied the back when stacked in order, because the levelling (leveling) of coating liquid, along with stacked, the thickness attenuation of film.Therefore, preferably,, again that division alignment is stacked with projection earlier with K (deceiving), R, G, these 4 kinds of colour superimpositions of B.On the other hand, use when having the transfer materials of thermoplastic resin, keep certain in order to make thickness, the eclipsed color is preferably 3 looks or 2 looks.
In addition, photo-sensitive resin deforms during lamination after preventing stacked transfer materials, and keeps the aspect of certain thickness to consider, the size of above-mentioned matrix is preferably 25 μ m * more than the 25 μ m, is preferably 30 μ m * more than the 30 μ m especially.
[liquid crystal indicator]
Liquid crystal indicator of the present invention uses the colour filter of contrast gradient excellence of the present invention, and the black density of this display unit etc. is described the power excellence.Also be suitable as notebook computer with the liquid crystal indicator of big picture such as indicating meter and TV monitor etc.
[CCD device]
CCD device of the present invention possesses the organic nano particle that use obtains by manufacture method of the present invention and the colour filter of making.Below, employed various materials when making CCD device of the present invention are elaborated.
As the alkali soluble resins that uses in the CCD device, preferably as the wire organic high molecular polymer, dissolve in organic solvent and can develop with weak base aqueous solution those.As such wire organic high molecular polymer, there is side chain to have the polymkeric substance of carboxylic acid, for example open maleic acid that clear 59-53836 number, spy open the Sipacril 2739OF put down in writing in the clear 59-71048 specification sheets, acrylic copolymer, itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, partial esterification etc., also have the acid cellulose derivative that on side chain, has carboxylic acid equally in addition such as Japanese kokai publication sho 59-44615 number, special public clear 54-34327 number, special public clear 58-12577 number, special public clear 54-25957 number, spy.In addition, it also is useful having the material that forms behind the addition acid anhydrides on the polymkeric substance of hydroxyl.(methyl) vinylformic acid benzyl ester/(methyl) acrylic copolymer in preferred especially these materials, and (methyl) vinylformic acid benzyl ester/(methyl) vinylformic acid/and other monomeric multiple copolymer.As other water-soluble polymers, can also use methacrylic acid 2-hydroxyl ethyl ester, Polyvinylpyrolidone (PVP) or polyethylene oxide, polyvinyl alcohol etc.
In addition, can also enumerate in Japanese kokai publication hei 7-140654 number the big monomer of (methyl) vinylformic acid 2-hydroxypropyl acrylate/polystyrene/methacrylic acid benzyl ester/Sipacril 2739OF, the big monomer of 2-hydroxyl-3-phenoxy propyl acrylate/polymethylmethacrylate/methacrylic acid benzyl ester/Sipacril 2739OF, the big monomer/methyl methacrylate of methacrylic acid 2-hydroxyl ethyl ester/polystyrene/Sipacril 2739OF, the big monomer of methacrylic acid 2-hydroxyl ethyl ester/polystyrene/methacrylic acid benzyl ester/Sipacril 2739OF etc. of record.As the addition of above-mentioned alkali soluble resins in solidification compound, be 5～90 quality % preferably with respect to the composition total mass, 10～60 quality % more preferably.
As polymerizable monomer, preferably has the compound that at least one can carry out the vinyl of addition polymerization, has the boiling point more than 100 ℃ under normal pressure with ethylenically unsaturated group.
As having at least one ethylenically unsaturated group that can carry out addition polymerization, boiling point, can enumerate monofunctional acrylate or methacrylic esters such as polyethyleneglycol (methyl) acrylate, polypropylene glycol list (methyl) acrylate, (methyl) phenoxyethyl acrylate under the normal pressure being compound more than 100 ℃; Polyoxyethylene glycol two (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, neopentyl glycol two (methyl) vinylformic acid, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, hexylene glycol (methyl) acrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, three (acrylyl oxy-ethyl) isocyanuric acid ester, polyfunctional alcohol such as glycerine or trimethylolethane goes up the material that forms through (methyl) acroleic acid esterification again behind addition of ethylene oxide or the propylene oxide, special public clear 48-41708 number, special public clear 50-6034 number, the spy opens the sort of urethane acrylate class of putting down in writing in clear 51-37193 number each communique, the spy opens clear 48-64183 number, special public clear 49-43191 number, the polyester acrylate class of putting down in writing in special public clear 52-30490 number each communique, polyfunctional acrylic ester or methacrylic esters such as epoxy acrylate class as Resins, epoxy and (methyl) acrylic acid reaction product.In addition, can also use then Xie Hui Chi Vol.20 of Japan, No.7, the material of introducing as light solidified monomer and oligopolymer in 300～308 pages.
In addition, can also use following general formula (B-1) or (B-2) shown in compound.
General formula (B-1)
Figure A200680053947D01131
General formula (B-2)
Figure A200680053947D01132
{ among general formula (B-1), (B-2), B represents-(CH independently of one another 2CH 2O)-and-(CH 2CH (CH 3) O)-in arbitrary group; X represents the arbitrary group in acryl, methacryloyl and the hydrogen atom independently of one another, and acryl in the formula (B-1) and methacryloyl add up to 5 or 6, and it is 3 or 4 in formula (B-2); N represents 0～6 integer independently of one another, and each n adds up to 3～24; M represents 0～6 integer independently of one another, and each m adds up to 2～16}.
As these polymerizable monomers, have filming of cementability if can form when being subjected to radiation exposure, then can use with arbitrary proportion.With respect to whole solid substances of composition, this monomeric usage quantity is generally 5～90 quality %, is preferably 10～50 quality %.
As tinting material, can use a kind of in known in the past dyestuff, mineral dye or the pigment dyestuff or be mixed with two or more.
There is no particular limitation to dyestuff, can use the known dyestuff that in the past was used for colour filter.For example, can use Japanese kokai publication sho 64-90403 communique, Japanese kokai publication sho 64-91102 communique, Japanese kokai publication hei 1-94301 communique, Japanese kokai publication hei 6-11614 communique, Japanese spy to step on disclosed pigment in No. 2592207, No. 4808501 specification sheetss of United States Patent (USP), No. 5667920 specification sheetss of United States Patent (USP), No. 505950 specification sheetss of United States Patent (USP), No. 5667920 specification sheetss of United States Patent (USP), Japanese kokai publication hei 5-333207 communique, Japanese kokai publication hei 6-35183 communique, Japanese kokai publication hei 6-51115 communique, Japanese kokai publication hei 6-194828 communique etc.As chemical structure, can use dyestuffs such as pyrazoles azo class, aniline azo class, triphenylmethane, anthraquinone class, Ben Yajiaji class, oxygen alcohols, pyrazolone and triazole azo class, pyridone azo class, cyanine class, phenothiazines, pyrrolo-pyrazoles azomethine class.Especially, because solidification compound can solidify at a lower temperature,, also can make to be exposed to the problems such as decomposition that back baking high temperature following time of being used to give the cured film weather resistance occurs and to be alleviated even therefore thermotolerance is than the dyestuff of pigment difference.
Mineral dye is represented metallic compounds such as metal oxide, metallic complex salt, specifically, can enumerate the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc., and the composite oxides of above-mentioned metal.
As pigment dyestuff, can enumerate C.I. Pigment Yellow 73 11,24,31,53,83,85,99,108,109,110,138,139,150,151,154,167,185, C.I. pigment orange 36,38,43,71, C.I. Pigment red 105,122,149,150,155,171,175,176,177,209,224,242,254, C.I. pigment violet 19,23,32,39, C.I. pigment blue 1,2,15,16,22,60,66,15:3,15:6, C.I. pigment Green 7,36,37, C.I. pigment brown 25,28, C.I. Pigment black 1,7, carbon black etc.
These pigment dyestuffs can use separately, or carry out various being used in combination in order to improve purity of color.Concrete example is as follows.As red, can use anthraquinone class pigment, perylene class pigment separately, or use mixing of at least a and tetrazo class yellow ultramarine in them or isoindoline class yellow ultramarine.For example, as anthraquinone class pigment, can enumerate C.I. Pigment red 177, Zuo Wei perylene class pigment can be enumerated C.I. Pigment red 155, and from the angle of colorrendering quality, it is good mixing with C.I. pigment yellow 83 or C.I. pigment yellow 13 9.The mass ratio of red pigment and yellow ultramarine is that 100:5 to 100:50 is good.When being in this scope, can suppress the light transmission rate of 400nm～500nm, improve purity of color, be preferred therefore.
As veridian, can use halogenated phthalocyanines class pigment separately, or mix use with tetrazo class yellow ultramarine, quinophthalone class yellow ultramarine or isoindoline class yellow ultramarine, for example preferred C.I. pigment Green 7,36,37 and C.I. pigment yellow 83,138,139 mixing.The mass ratio of veridian and yellow ultramarine is preferably 100:5 to 100:100.When being in this scope, can suppress the light transmission rate of 400nm～450nm, obtain good purity of color.
As blue pigments, can use phthalocyanine pigment separately, or mix use, for example preferred C.I. pigment Blue 15: 6 and the mixing of C.I. pigment Violet 23 Yu the dioxazines violet pigment.The mass ratio of blue pigments and violet pigment is preferably 100:0 to 100:50.When being in this scope, can suppress the light transmission rate of 400nm～420nm, improve purity of color.
In addition, by using, can obtain to contain the photosensitive resin of all good pigment of dispersiveness and dispersion stabilization with the fine Powdered processed pigment that forms in acrylic resin, toxilic acid resinoid, vinylchlorid-vinyl acetate polymer and the ethyl cellulose resin etc. that is scattered in of above-mentioned pigment.
In addition, as the pigment that uses in the black matrix, can use separately or mix and use carbon, titanium oxide, ferric oxide, the situation of carbon and titanium oxide be used in preferred mixing.The mixing quality ratio is preferably 100:5 to 100:40.When being in this scope, long wavelength's light transmission rate is low, also has good dispersion stabilization in addition.
As solvent, can enumerate the ester class, for example 3-hydroxy-propionic acid alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, Isoamyl Acetate FCC, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, oxyacetic acid butyl ester, methoxy menthyl acetate, methoxyacetic acid ethyl ester, methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, 3-hydroxy methyl propionate, 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, methyl aceto acetate, 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 methyl cellosolve, acetate ethyl cellosolve, diethylene glycol monomethyl ether, TC, Diethylene Glycol single-butyl ether, methyl proxitol acetate, propylene glycol ethyl ether acetic ester, propylene glycol propyl ether acetic ester etc.; Ketone, for example butanone, pimelinketone, 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, acetate ethyl cellosolve, ethyl lactate, diethylene glycol dimethyl ether, butylacetate, 3-methoxypropionic acid methyl esters, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, acetate of butyl carbitol, methyl proxitol acetate etc.In composition, the addition of solvent is generally 60～90 quality %, is preferably 70～90 quality %.
These solvents can use separately or be used in combination more than 2 kinds.
Can also and use sensitizer.As its object lesson, can enumerate 9-Fluorenone, 2-chloro-9-Fluorenone, 2-methyl-9-Fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, the 2-tertiary butyl-9,10-anthraquinone, 2,6-two chloro-9,10-anthraquinone, benzil, dibenzalacetone, right-(dimethylamino) styryl phenyl base ketone, right-(dimethylamino) phenyl-p-methylstyrene base ketone, benzanthrone etc., and the benzothiazole compound of putting down in writing in the Japanese Patent Publication 51-48516 communique.
Can use various mixing machines, dispersion machine other additive of above-mentioned main component and use in case of necessity to be carried out blending dispersion, thereby be prepared.
The general manufacture method of the colour filter that uses in the CCD device is as follows.Carry out following operation successively: be coated on composition of the present invention (colored resist liquid) on the substrate and carry out the exsiccant operation, with i line stepping exposure machine etc. the drying coated film that obtains carried out carrying out after the operation, exposure of pattern exposure operation that alkali develops, carry out the operation of heat treated then, repeat above-mentioned operation successively for shades of colour (3 looks or 4 looks), make cured film, thereby obtain colour filter.
More particularly, utilize spinner etc. on suitable substrate, to apply above-mentioned solidification compound, make dried thickness be generally 0.1～5 μ m, be preferably 0.2～2 μ m, in 85 ℃ baking oven, placed 2 minutes, smoothly filmed.
There is no particular limitation to substrate, can enumerate sheet glass, plastic plate, aluminium sheet, imaging apparatus base material, and transparent resin plate, resin molding, the sensitive surface that is formed with Braun tube display surface, pick up tube, CCD, BBD, the wafer of solid-state imagers such as CID, BASIS, the closing-type image sensor that has used thin film semiconductor, liquid-crystal display face, color electronography are with the substrate of the display unit of photoreceptor, エ ト Network ト ロ Network ロ ミ イ-(EC) etc. with electronic units such as silicon chips.In addition, in order to improve the cementability of substrate and color-filter layer, preferably substrate is implemented high driving fit and handle.Specifically, on substrate, carry out thin layer with silane coupling agent etc. in advance and apply, form the pattern of solidification compound then, or in solidification compound, contain silane coupling agent in advance.
In addition, when on substrate, having difference of altitude, can on substrate, apply planarization film is set,, apply solidification compound of the present invention then to eliminate difference of altitude, to make coated side level and smooth.For example, image sensors such as CCD are by producing the photoelectric conversion part (photorectifier) of electronics according to light income and on the organosilicon substrate and being used to export the read out gate portion formation of its electronics that produces, if but read out gate is subjected to light, then can cause noise, output data correctly, therefore the shading rete to be set on the top of read out gate portion, itself and do not have between the photorectifier portion of shading rete and produce difference of altitude sometimes.If on this difference of altitude, apply colored resist, directly form colour filter, then optical path length becomes big, so image deepening and light harvesting variation.In order to improve this problem, preferably between CCD and colour filter, form transparent planarization film, purpose is the landfill difference of altitude.As the material of this planarization film, can enumerate thermosetting resins such as light solidified resist liquid, acrylic acid or the like, epoxies etc.
After applying Photocurable composition,, to carry out preliminary drying usually for evaporating solvent obtains the exsiccant coat film.As the method for preliminary drying, drying under reduced pressure is arranged, utilize high temperature air etc. to carry out the indirect heating drying, utilize electric furnace etc. to carry out direct drying (about 80～about 140 ℃, 50～200 seconds) etc.In addition, fully solidify, obtain the high permanent film of physical strength, need carry out the back baking in order to make the pattern that obtains after the development.For example, when making 3 look colour filters, after this initial pattern that forms can be subjected to coating, exposure, the development of other color resist liquid once more.At this moment, for fear of owing to the pattern defect that causes with coated resist liquid colour mixture, exposure, development, carry out the back baking.The baking of this back can be used the method identical with preliminary drying, but will carry out under the temperature higher than prebake conditions, longer time.For example, utilizing baking oven to carry out under the situation of indirect heating, under about 180～250 ℃, carrying out about 0.5～2 hour, when utilizing electric furnace to carry out direct heating, under about 180～250 ℃, carrying out about 2 minutes～10 minutes.
There is no particular limitation to the light source that is used to expose, but as for forming pattern the light source of unusual effect being arranged, can enumerate the i line of mercuryvapour lamp.Consider that from the suitable aspect of technology when using i line as one of mercuryvapour lamp spectral line to come the construction drawing image-position sensor use colour filter, feature of the present invention is remarkable especially, and is certain, also can be used for LCD.
The developing solution that uses during to the development of solidification compound is not particularly limited, and can use known in the past developing solution.Wherein, the tetramethyl ammonium hydroxide organic bases developing solutions of quaternary ammonium salt such as (TMAH) is preferred.
As polymerization starter, can use common Photoepolymerizationinitiater initiater.Specifically, can enumerate United States Patent (USP) the 2nd, 367, the vicinal polyketaldonyl compound of putting down in writing in No. 660 specification sheetss, United States Patent (USP) the 2nd, 367, No. 661 and the 2nd, 367, the alpha-carbonyl compound of putting down in writing in No. 670 specification sheetss, the acyloin ether compound of putting down in writing in the United States Patent (USP) the 2nd, 448, No. 828 specification sheetss, United States Patent (USP) the 2nd, 722, the aromatic series acyloin compound that the α that puts down in writing in No. 512 specification sheetss-hydrocarbon replaces, United States Patent (USP) the 3rd, 046, No. 127 specification sheetss and the 2nd, 951, the polynucleation quinone compound of putting down in writing in No. 758 specification sheetss, the combination of triarylimidazoles dipolymer/p-aminophenyl ketone of putting down in writing in the United States Patent (USP) the 3rd, 549, No. 367 specification sheetss, benzothiazole compound/trihalogenmethyl of putting down in writing in the Japanese Patent Publication 51-48516 communique-s-compound in triazine class etc.
Solid substance (quality) with respect to free radical polymerization monomer, the content of Photoepolymerizationinitiater initiater (comprising above-mentioned common Photoepolymerizationinitiater initiater) in containing the minus solidification compound of dyestuff is preferably 0.01～50 quality %, more preferably 1～30 quality % is preferably 1～20 quality % especially.If this content is in the above-mentioned scope, then can carry out polymerizing curable fully, polymerization can not occur and be difficult to carry out, or percent polymerization raises and the molecular weight reduction situation that film toughness weakens.
In addition, above-mentioned Photoepolymerizationinitiater initiater can and be used with sensitizer or photostabilizer.
As its object lesson, can enumerate bitter almond oil camphor, benzoin methyl ether, the 9-Fluorenone, 2-chloro-9-Fluorenone, 2-methyl-9-Fluorenone, the 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9, the 10-anthraquinone, 2-ethyl-9, the 10-anthraquinone, the 2-tertiary butyl-9, the 10-anthraquinone, 2,6-two chloro-9, the 10-anthraquinone, xanthene, 2-methyl xanthene, 2-methoxyl group xanthene, 2-oxyethyl group xanthene, thioxanthone, 2, the 4-diethyl thioxanthone, dihydroketoacridine, 10-butyl-2-chloro-acridine ketone, benzil, dibenzalacetone, right-(dimethylamino) styryl phenyl base ketone, right-(dimethylamino) phenyl-p-methylstyrene base ketone, benzophenone, right-(dimethylamino) benzophenone (or michaelis ketone), right-(diethylamino) benzophenone, benzanthrone etc., and the benzothiazole compound of Japanese Patent Publication 51-48516 communique record etc., チ ヌ PVC Application 1130,400 etc.
Manufacturing method according to the invention can obtain the organic nano particle of miniaturization to the nanometer size expeditiously, further can access the nanometer size and can obtain the high organic nano particle of monodispersity by control.In addition, manufacturing method according to the invention when preparation organic filler dispersion liquid, concentrates as required and can obtain nanoparticle, even the agglutination particle in the concentrated solution also can obtain dispersible organic nano particle expeditiously.Also have, manufacturing method according to the invention can be applicable to the organic nano particle and the dispersion liquid thereof of colour filter coating liquid and ink for inkjet with industrial-scale production.In addition, used the colour filter of organic nano particle of the present invention, it has the colour purity of target and high contrast gradient, and has excellent weather resistance.The liquid crystal indicator that possesses this colour filter has the effect that black density and color reprodubility are all good, show excellences such as non-uniform phenomenon is improved.
The present invention will be described in more detail based on embodiment below, but the present invention is not limited to these examples.
[embodiment]
(embodiment 1) has been used pyrrolopyrrole compound pigment and has been contained the embodiment of the macromolecular compound of acidic-group
(embodiment 1-1)
With pigment (Pigment red 254) be dissolved in aqueous sodium hydroxide solution by 1-Methyl-2-Pyrrolidone and 1mol/L according to the mixed of 6:1 (mass ratio) after and in the solution that forms, be prepared into the pigment solution of 15mmol/L.In addition, other prepares water as poor solvent.
At this moment, temperature is controlled to be 1 ℃, in poor solvent-water 1000mL of the GK-0222-10 type ラ モ Application De ス -ラ that utilizes Fujisawa Pharmaceutical Co., Ltd to make-stir with the rotating speed of 500rpm, the NP-KX-500 type large vol pulseless pump made from Japanese precision chemical society press the flow velocity injection 100mL pigment solution of 50mL/min, makes the organic pigment particles dispersion liquid thus.
Use day Na ノ ト ラ Star Network UPA-EX150 of machine dress society manufacturing to measure resulting organic filler dispersion liquid, its particle diameter, single dispersity are estimated, the number average bead diameter that the result records is 31nm, and single dispersity is 1.40.
2-(1-methoxyl group) the propyl-acetic acid ester that in the organic pigment particles dispersion liquid (the about 0.05 quality % of pigment particles concentration) of preparation, adds 500mL, left standstill 1 day after 10 minutes in the rotating speed stirring with 500rpm under 25 ℃, with pigment particles extract 2-(1-methoxyl group) propyl-acetic acid ester mutually in, make concentrated extracting solution.
Utilize Sumitomo Electric Industries' Off, the FP-010 type filter that イ Application Port リ マ Co., Ltd. produces has the concentrated extracting solution of pigment particles to filter to wherein extracting, and obtains the concentrated pigment liquid [I] (pigment particles concentration 30 quality %) of pasty state.
Use the concentrated pigment liquid [I] of above-mentioned pasty state, preparation has the organic filler dispersion liquid of the present invention [I] of following composition.
Concentrated pigment liquid [I] 21.3g of pasty state
Pigment dispersing agent A (example compound (7.) of the compound that general formula (D1) is represented) 0.6g
Methacrylic acid/benzyl methacrylate multipolymer * 15.8g
1-methoxyl group-2-propyl-acetic acid ester 42.3g
* the copolymerization mol ratio is 28/72, the matter average molecular weight: the 1-methoxyl group of 30,000,40 quality %-2-propyl-acetic acid ester solution
Utilize electronic mill M-50 (manufacturing of ア イ ガ one ジ ヤ パ Application society) and use the zirconium white microballon of diameter, under the condition of circumferential speed 9m/s, stir organic filler dispersion liquid [I] with above-mentioned composition as 0.65mm.With churning time is that 1 hour, 3 hours, 5 hours, 9 hours, 15 hours liquid is respectively as sample pigment liquid (1)～(5).
In order to estimate the performance of sample pigment liquid, prepared the film sample.The rotation coating machine 1H-D7 that adopts ミ カ サ society to make will be coated in the glass substrate of 75mm * 75mm by sample pigment liquid (1)～(5) that aforesaid method obtains, and descend dry 2 minutes at 100 ℃ by electric furnace, make film sample (1)～(5) thus.
(embodiment 1-2)
Pigment (Pigment red 254) is dissolved in the solution that forms after the mixed of potassium hydroxide aqueous solution according to 6:1 by dimethyl sulfoxide (DMSO) and 8mol/L, is prepared into the pigment solution of 150mmol/L.In addition, other prepares water as poor solvent.
At this moment, temperature is controlled to be 1 ℃, in poor solvent-water 1000mL of the GK-0222-10 type ラ モ Application De ス -ラ that utilizes rattan pool medicine Co., Ltd. to make-stir with the rotating speed of 500rpm, the NP-KX-500 type large vol pulseless pump made from Japanese precision chemical society press the flow velocity injection 100mL pigment solution of 50mL/min, makes the organic pigment particles dispersion liquid thus.
Use day Na ノ ト ラ Star Network UPA-EX150 of machine dress society manufacturing to measure prepared organic pigment particles dispersion liquid, and particle diameter, single dispersity are estimated, the number average bead diameter that the result records is 32nm, and single dispersity is 1.41.
2-(1-methoxyl group) the propyl-acetic acid ester that in the organic pigment particles dispersion liquid (the about 0.5 quality % of pigment particles concentration) of preparation, adds 500mL, left standstill 1 after 10 minutes in the rotating speed stirring with 500rpm under 25 ℃, with pigment particles extract 2-(1-methoxyl group) propyl-acetic acid ester mutually in, make concentrated extracting solution.
Utilize Sumitomo Electric Industries' Off, the FP-010 type filter that イ Application Port リ マ Co., Ltd. produces has the concentrated extracting solution of pigment particles to filter to wherein extracting, and obtains the concentrated pigment liquid [II] (pigment particles concentration 35 quality %) of pasty state.
Concentrated pigment liquid [II] 18.3g of above-mentioned pasty state
Pigment dispersing agent A 0.6g
Methacrylic acid/benzyl methacrylate multipolymer * 15.8g
1-methoxyl group-2-propyl-acetic acid ester 45.3g
* the copolymerization mol ratio is 28/72, the matter average molecular weight: the 1-methoxyl group of 30,000,40 quality %-2-propyl-acetic acid ester solution
According to the method identical, make sample pigment liquid (6)～(10) by having the above-mentioned organic filler dispersion liquid of forming of the present invention [II] with embodiment 1-1.According to the method identical, make film sample (6)～(10) by sample pigment liquid (6)～(10) that make with embodiment 1-1.
(embodiment 1-3)
Adopt the method identical to make sample pigment liquid (11)～(15) with embodiment 1-1, difference is, use 15.8g methacrylic acid/benzyl methacrylate/styrol copolymer (mol ratio 27:60:13, matter average molecular weight: the methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 20,000 8 thousand, 40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (11)～(15) by sample pigment liquid (11)～(15) that obtain with embodiment 1-1.
(embodiment 1-4)
Adopt the method identical to make sample pigment liquid (16)～(20) with embodiment 1-1, difference is, use 15.8g methacrylic acid/propyl methacrylate/styrol copolymer (mol ratio 26:62:12, matter average molecular weight: the methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 20,000 9 thousand, 40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (16)～(20) by sample pigment liquid (16)～(20) that obtain with embodiment 1-1.
(embodiment 1-5)
Adopt the method identical to make sample pigment liquid (21)～(25) with embodiment 1-1, difference is, use 15.8g methacrylic acid/methyl methacrylate/styrol copolymer (mol ratio 25:62:13, matter average molecular weight: the methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 30,000,40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (21)～(25) by sample pigment liquid (21)～(25) that obtain with embodiment 1-1.
(embodiment 1-6)
Adopt the method identical to make sample pigment liquid (26)～(30) with embodiment 1-1, difference is, use 15.8g polyacrylic acid (matter average molecular weight: the methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 30,000 3 thousand, 40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (26)～(30) by sample pigment liquid (26)～(30) that obtain with embodiment 1-1.
(embodiment 1-7)
Adopt the method identical to make sample pigment liquid (31)～(35) with embodiment 1-1, difference is, use 15.8g polyvinyl sulfuric acid (matter average molecular weight: the methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 30,000 2 thousand, 40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (31)～(35) by sample pigment liquid (31)～(35) that obtain with embodiment 1-1.
(embodiment 1-8)
Adopt the method identical to make sample pigment liquid (36)～(40) with embodiment 1-1, difference is, use 15.8g polyvinyl alcohol (matter average molecular weight: the above-mentioned methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 30,000 1 thousand, 40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (36)～(40) by sample pigment liquid (36)～(40) that obtain with embodiment 1-1.
(embodiment 1-9)
Adopt the method identical with embodiment 1-1 to make sample pigment liquid (41)～(45), difference is, does not add the pigment dispersing agent A among the embodiment 1-1.
Adopt the method identical, make film sample (41)～(45) by sample pigment liquid (41)～(45) that obtain with embodiment 1-1.
(embodiment 1-10)
Adopt the method identical to make sample pigment liquid (46)～(50) with embodiment 1-1, difference is, use methacrylic acid/benzyl methacrylate multipolymer (copolymerization mol ratio 28/72, matter average molecular weight: the above-mentioned methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 10,000,40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (46)～(50) by sample pigment liquid (46)～(50) that obtain with embodiment 1-1.
(embodiment 1-11)
Adopt the method identical to make sample pigment liquid (51)～(55) with embodiment 1-1, difference is, use methacrylic acid/benzyl methacrylate multipolymer (copolymerization mol ratio 28/72, matter average molecular weight: the above-mentioned methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 4,000,40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (51)～(55) by sample pigment liquid (51)～(55) that obtain with embodiment 1-1.
(comparative example 1)
(comparative example 1-1)
Adopt the method identical to make sample pigment liquid (56)～(60) with embodiment 1-1, difference is, use the concentrated pigment liquid [I] of the pasty state among 6.4g Pigment red 254 (powdered samples) the replacement embodiment 1-1, and the quantitative change of 1-methoxyl group-2-propyl-acetic acid ester is 57.2g.Adopt the method identical, make film sample (56)～(60) by sample pigment liquid (56)～(60) that obtain with embodiment 1-1.
(comparative example 1-2)
Adopt the method identical with embodiment 1-1 to make sample pigment liquid (61)～(65), difference is, does not add the methacrylic acid/benzyl methacrylate multipolymer among the embodiment 1-1.Adopt the method identical, attempt making film sample (61)～(65), but do not form film, thereby can not get sample by sample pigment liquid (61)～(65) that obtain with embodiment 1-1.
(comparative example 1-3)
Adopt the method identical to make sample pigment liquid (66)～(70) with embodiment 1-1, difference is, use methacrylic acid/benzyl methacrylate multipolymer (copolymerization mol ratio 28/72, matter average molecular weight: the above-mentioned methacrylic acid/benzyl methacrylate multipolymer among the replacement embodiment 1-1 1-methoxyl group of 800,40 quality %-2-propyl-acetic acid ester solution).
Adopt the method identical, make film sample (66)～(70) by sample pigment liquid (66)～(70) that obtain with embodiment 1-1.
Use E type viscometer (VISCONIC-ELD, eastern machine industry society makes) to measure the viscosity of sample pigment liquid (1)～(70).The result is shown in table 1-1,1-2.
[table 1-1]
Specimen coding Jitter time (hour) Viscosity (mPas)
Sample pigment liquid (1) sample pigment liquid (2) sample pigment liquid (3) sample pigment liquid (4) Embodiment (1-1) 1 3 5 9 28 28 28 28
Sample pigment liquid (5) 15 28
Sample pigment liquid (6) sample pigment liquid (7) sample pigment liquid (8) sample pigment liquid (9) sample pigment liquid (10) Embodiment (1-2) 1 3 5 9 15 29 29 29 29 29
Sample pigment liquid (11) sample pigment liquid (12) sample pigment liquid (13) sample pigment liquid (14) sample pigment liquid (15) Embodiment (1-3) 1 3 5 9 15 30 30 30 30 30
Sample pigment liquid (16) sample pigment liquid (17) sample pigment liquid (18) sample pigment liquid (19) sample pigment liquid (20) Embodiment (1-4) 1 3 5 9 15 26 26 26 26 26
Sample pigment liquid (21) sample pigment liquid (22) sample pigment liquid (23) sample pigment liquid (24) sample pigment liquid (25) Embodiment (1-5) 1 3 5 9 15 27 27 27 27 27
Sample pigment liquid (26) sample pigment liquid (27) sample pigment liquid (28) sample pigment liquid (29) sample pigment liquid (30) Embodiment (1-6) 1 3 5 9 15 31 31 31 31 31
Sample pigment liquid (31) sample pigment liquid (32) sample pigment liquid (33) sample pigment liquid (34) sample pigment liquid (35) Embodiment (1-7) 1 3 5 9 15 35 35 35 35 35
[table 1-2]
Specimen coding Jitter time (hour) Viscosity (mPas)
Sample pigment liquid (36) sample pigment liquid (37) sample pigment liquid (38) sample pigment liquid (39) sample pigment liquid (40) Embodiment (1-8) 1 3 5 9 15 26 26 26 26 26
Sample pigment liquid (41) sample pigment liquid (42) sample pigment liquid (43) sample pigment liquid (44) Embodiment (1-9) 1 3 5 9 32 32 32 32
Sample pigment liquid (45) 15 32
Sample pigment liquid (46) sample pigment liquid (47) sample pigment liquid (48) sample pigment liquid (49) sample pigment liquid (50) Embodiment (1-10) 0.1 0.2 0.3 0.5 1 26 26 26 26 26
Sample pigment liquid (51) sample pigment liquid (52) sample pigment liquid (53) sample pigment liquid (54) sample pigment liquid (55) Embodiment (1-11) 1 3 5 9 15 30 30 30 30 30
Sample pigment liquid (56) sample pigment liquid (57) sample pigment liquid (58) sample pigment liquid (59) sample pigment liquid (60) Comparative example (1-1) 1 3 5 9 15 26 26 26 26 26
Sample pigment liquid (61) sample pigment liquid (62) sample pigment liquid (63) sample pigment liquid (64) sample pigment liquid (65) Comparative example (1-2) 1 3 5 9 15 30 30 30 30 100
Sample pigment liquid (66) sample pigment liquid (67) sample pigment liquid (68) sample pigment liquid (69) sample pigment liquid (70) Comparative example (1-3) 1 3 5 9 15 26 26 26 26 26
Observe film sample (1)～(70) with opticmicroscope (500 times), choose the part of 175 μ m * 130 μ m sizes, this image is divided into 1,220,000 pixels, estimate the deviation of concentration according to variation coefficient (mean value of the standard deviation/concentration of=concentration).In addition, adopt the scattering of 8453 type spectrophotometric determination film samples of ア ジ レ Application ト (Agilent) company manufacturing to measure absorbancy, estimate its absorbancy under 700nm.Absorbancy is zero, 0.02～0.05 the △ that is designated as of being designated as below 0.02, being designated as more than 0.05 *.The result is shown in table 1-3,1-4.
[table 1-3]
Figure A200680053947D01261
Figure A200680053947D01271
[table 1-4]
Figure A200680053947D01272
Figure A200680053947D01281
By above result as can be known, by the manufacture method of organic nano particle of the present invention, can access the nanoparticle and the dispersion liquid thereof that can form the uniform film of concentration.
As the dispersing method of traditional pigment dyestuff, the resulting pigment particles of dispersion method that adopts various dispersion machines (roll crusher, ball mill, attritor etc.) to carry out does not reach the purpose of carrying out miniaturization in dispersion liquid.Therefore, viscosity rises, and is difficult to take out from dispersion machine, maybe can not utilize pipeline to carry, and in storage process gelation takes place what is more and can not use.That is,, be difficult to provide the dispersible pigment dispersion that can form the uniform film of concentration according to method in the past.
To this, adopt the manufacture method of organic nano particle of the present invention, organic filler can be realized miniaturization state and mobile excellent state simultaneously, and viscosity can not rise, so the nanoparticle and the dispersion liquid thereof that can form the uniform film of concentration can be provided.In addition, in can be below half of the required time in the past very short time, obtain the uniform film of concentration.Hence one can see that, adopts this method significantly to enhance productivity.In addition, by using the macromolecular compound of predetermined molecular weight, can further improve the preparation efficiency of particle as can be known.
In addition, the details of the reagent that uses in the foregoing description, comparative example is as follows.
(embodiment 2)
(embodiment 2-1～2-4) uses pyrrolopyrrole compound pigment and contains the embodiment of the macromolecular compound of acidic-group
(embodiment 2-1)
In the 1000mL dimethyl sulfoxide (DMSO), add 28% methanol solution of sodium methylate, 50g pigment C.I. Pigment red 254 (the trade(brand)name Irgaphor Red BT-CF of 33.3mL, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) society makes), the 100.0g Polyvinylpyrolidone (PVP), be mixed with pigment solution A.The water 1000mL of 1mol/L hydrochloric acid for preparing to contain 16mL in addition is as poor solvent.
At this moment, temperature is controlled to be 18 ℃, in poor solvent-water 1000mL of the GK-0222-10 type ラ モ Application De ス -ラ that utilizes rattan pool pharmaceutical industries society to make-stir with the rotating speed of 500rpm, the NP-KX-500 type large vol pulseless pump made from Japanese precision chemical society press the flow velocity injection 100mL pigment solution A of 100mL/min, thereby the formation organic pigment particles is made dispersible pigment dispersion A.Use day Na ノ ト ラ Star Network UPA-EX150 of machine dress society manufacturing to measure the particle diameter of this dispersible pigment dispersion, single dispersity, the number average bead diameter that the result records is 29nm, and Mv/Mn is 1.29.
For pigment nanoparticle dispersion liquid with method for preparing, high speed centrifugation cooler HIMAC SCR20B with the manufacturing of the worker of Hitachi machine (strain) society, centrifugation is 1 hour under 3500rpm (2000g), removes supernatant liquid, and the pigment nanoparticle after the recovery sedimentation concentrates to be stuck with paste.Pigment content in the 8453 type spectrophotometric determination mashed prod that use ア ジ レ Application ト (Agilent) society makes, the result is 12.5 quality %.
In sticking with paste, the above-mentioned pigment nanoparticle preparation of 16.0g adds the 50.0cc ethyl lactate, stirred 60 minutes under the rotating speed of 1500rpm with dissolving machine, the FP-010 type filter made from the Off ァ イ of Sumitomo Electric Industries Application Port リ マ society filters then, thereby obtains the concentrated pigment liquid A (nano dye concentration 33 quality %) of pasty state.
[preparation of pigment dispensing composition]
Use above-mentioned mashed prod, preparation has the pigment dispensing composition A of following composition.
The concentrated pigment liquid A 19.5g of above-mentioned pasty state
Pigment dispersing agent A 0.6g
Methacrylic acid/benzyl methacrylate multipolymer * 6.4g
1-methoxyl group-2-propyl-acetic acid ester 45.3g
Pigment dispersing agent A is synthetic according to the method for TOHKEMY 2000-239554 communique.
* mol ratio is 28/72, the matter average molecular weight: 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution
Utilize electronic mill M-50 (manufacturing of ア イ ガ one ジ ヤ パ Application society) and use the zirconium white microballon of diameter as 0.65mm, under the condition of circumferential speed 9m/s, the pigment dispensing composition that will have above-mentioned composition disperseed 1 hour.
(embodiment 2-2)
Adopt the method identical to make the concentrated pigment liquid B and the pigment dispensing composition B of pigment solution B, dispersible pigment dispersion B, pasty state with embodiment 2-1, difference is, in the pigment dispensing composition A of embodiment 2-1, use pigment dispersing agent B (example compound (c) in the represented compound of above-mentioned general formula (D3)) to replace employed pigment dispersing agent A when forming the nano dye particle.Adopt the method identical with embodiment 2-1 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 33nm, and Mv/Mn is 1.34.In addition, pigment dispersing agent B is synthetic according to the special fair 5-72943 communique of Japan.
(embodiment 2-3)
Adopt the method identical to make concentrated pigment liquid C, the pigment dispensing composition C of pigment solution C, dispersible pigment dispersion C, pasty state with embodiment 2-1, difference is, in the pigment dispensing composition A of embodiment 2-1, use pigment dispersing agent C (the represented compound of above-mentioned general formula (D4)) to replace employed pigment dispersing agent A when forming the nano dye particle.Adopt the method identical with embodiment 2-1 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 32nm, and Mv/Mn is 1.33.In addition, pigment dispersing agent C synthesizes according to the synthesis example 1 of TOHKEMY 2001-31885 communique.
(embodiment 2-4)
Adopt the method identical to make concentrated pigment liquid D, the pigment dispensing composition D of pigment solution D, dispersible pigment dispersion D, pasty state with embodiment 2-1, difference is, in the pigment dispensing composition A of embodiment 2-1, do not use employed pigment dispersing agent when forming the nano dye particle.Adopt the method identical with embodiment 2-1 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 31nm, and Mv/Mn is 1.33.
(embodiment 2-5～2-8) uses the embodiment of the represented macromolecular compound of general formula (1)
(embodiment 2-5)
Adopt the method identical to make concentrated pigment liquid E, the pigment dispensing composition E of pigment solution E, dispersible pigment dispersion E, pasty state with embodiment 2-1, difference is, in the pigment dispensing composition A of embodiment 2-1, use 3.2g macromolecular compound (C-16) to replace 6.4g methacrylic acid/benzyl methacrylate multipolymer.Adopt the method identical with embodiment 2-1 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 33nm, and Mv/Mn is 1.31.
(embodiment 2-6)
Adopt the method identical to make concentrated pigment liquid F, the pigment dispensing composition F of pigment solution F, dispersible pigment dispersion F, pasty state with embodiment 2-2, difference is, in the pigment dispensing composition B of embodiment 2-2, use 3.2g macromolecular compound (C-16) to replace 6.4g methacrylic acid/benzyl methacrylate multipolymer.Adopt the method identical with embodiment 2-2 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 30nm, and Mv/Mn is 1.29.
(embodiment 2-7)
Adopt the method identical to make concentrated pigment liquid G, the pigment dispensing composition G of pigment solution G, dispersible pigment dispersion G, pasty state with embodiment 2-3, difference is, in the pigment dispensing composition C of embodiment 2-3, use 3.2g macromolecular compound (C-16) to replace 6.4g methacrylic acid/benzyl methacrylate multipolymer.Adopt the method identical with embodiment 2-3 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 32nm, and Mv/Mn is 1.33.
(embodiment 2-8)
Adopt the method identical to make concentrated pigment liquid H, the pigment dispensing composition H of pigment solution H, dispersible pigment dispersion H, pasty state with embodiment 2-4, difference is, in the pigment dispensing composition D of embodiment 2-4, use 3.2g macromolecular compound (C-16) to replace 6.4g methacrylic acid/benzyl methacrylate multipolymer.Adopt the method identical with embodiment 2-4 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 30nm, and Mv/Mn is 1.28.
(comparative example 2)
(comparative example 2-1)
In the following manner, the pigment dispensing composition I that uses the microballon dispersal mechanism to get everything ready and form by following.
Pigment (Pigment red 254) 6.4g
Pigment dispersing agent A 0.6g
Polyvinylpyrrolidone (with the pure medicine of light (strain) society system, K30, molecular weight 40,000) 6g
Methacrylic acid/benzyl methacrylate multipolymer * 6.4g
1-methoxyl group-2-propyl-acetic acid ester 45.3g
* mol ratio is 28/72, the matter average molecular weight: 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution
In 1-methoxyl group-2-propyl-acetic acid ester solution, add pigment (Pigment red 254) powder, 6g polyvinylpyrrolidone, methacrylic acid/benzyl methacrylate multipolymer, stir, obtain mixed solution.Then, utilize electronic mill M-50 (manufacturing of ア イ ガ one ジ ヤ パ Application society) and use the zirconium white microballon of diameter, under the condition of circumferential speed 9m/s, above-mentioned mixed solution was disperseed 9 hours as 0.65mm.Adopt the method identical with embodiment 2-1 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 82nm, and Mv/Mn is 1.56.
(comparative example 2-2)
Preparation has the pigment dispensing composition J of following composition in the following manner.
Pigment (Pigment red 254) 6.4g
Sodium-chlor 64.0g
Methacrylic acid/benzyl methacrylate multipolymer * 6.4g
* mol ratio is 28/72, the matter average molecular weight: 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution
In 1-methoxyl group-2-propyl-acetic acid ester solution, add sodium-chlor, the powder of pigment (Pigment red 254), methacrylic acid/benzyl methacrylate multipolymer, it is sent in the twin screw kneader, descended mixing 10 hours at 80 ℃.After mixing, put in 80 ℃ 1% aqueous hydrochloric acid of 500 weight parts, stirred 1 hour, filter then, hot water wash, drying, pulverizing, add ratio interpolation 1-methoxyl group-2-propyl-acetic acid ester of 2.4g1-methoxyl group-2-propyl-acetic acid ester then according to every 1g crushed material, and mix.Utilize electronic mill M-50 (manufacturing of ア イ ガ ジ ヤ パ Application society) and use the zirconium white microballon of diameter, under the condition of circumferential speed 9m/s, above-mentioned color compositions was disperseed 1 hour as 0.65mm.Obtain pigment dispensing composition J.Adopt the method identical with embodiment 2-1 to handle, measure its particle diameter, single dispersity, the number average bead diameter that records is 63nm, and Mv/Mn is 1.88.
In addition, when preparation above-mentioned pigment dispensing composition A～J, use following reagent.
Figure A200680053947D01331
With the pigment dispensing composition A～J that obtains, being coated on respectively and making thickness on the glass substrate is 2 μ m, makes 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 ァ 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
In addition, as sunproof index, employing uses high pressure mercury vapour lamp with 90mW/cm on this sample 2Intensity irradiation 24 hours, measure the aberration behind the pre-irradiation.Also have, in the present invention, colourity adopts microscope spectrophotometer (オ リ Application パ ス optics society makes, OSP100 or 200) to measure, and calculates the result under the F10 light source 2 degree visuals field, represents with the xyY value of xyz coloring system.In addition, the difference La of colourity *b *The aberration of coloring system is represented.This aberration is the smaller the better.
The contrast gradient of the sample that is obtained by pigment dispensing composition A～J and sunproof measurement result are shown in table 2-A.
[table 2-A]
As show the result shown in the 2-A as can be known, and compare with sample I, the J of comparative example, adopt manufacture method of the present invention, organic filler is disperseed to be generated as the particle of nano-scale and the dispersion thing that obtains demonstrates very high contrast gradient, photostabilization.In addition, use the sample E～H of the represented macromolecular compound of general formula (1), in each embodiment, all had high-contrast and high-light-fastness, demonstrated more excellent result.
(embodiment 2-9)
Other listed among pigment dispensing composition A and following tabulation 2-1 moietys are mixed preparation colour filter photosensitive composition A mutually.
[table 2-1]
Moiety Content (mass parts)
Pigment dispensing composition A 44.5
Propylene glycol monomethyl ether 7.6
Butanone 37
Binding agent 1 0.7
DPHA liquid 3.8
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.12
2, amino-the 3 '-bromophenyl of two (trichloromethyl)-6-[4 '-(N, the N-di ethoxy carbonyl methyl) of 4-]-the s-triazine 0.05
Thiodiphenylamine 0.01
Tensio-active agent 1 0.06
＜binding agent 1 〉
Polymkeric substance (benzyl methacrylate/methacrylic acid/methyl methacrylate=
The random copolymers of 38/25/37 mol ratio, molecular weight 40,000) 27 mass parts
Propylene glycol monomethyl ether 73 mass parts
＜DPHA liquid 〉
(contain stopper MEHQ500ppm, Japanese chemical drug (strain) society makes dipentaerythritol acrylate, trade(brand)name: 76 mass parts KAYARAD DPHA)
Propylene glycol monomethyl ether 24 mass parts
＜tensio-active agent 1 〉
Following compound 1 30 mass parts
Butanone 70 mass parts
Compound 1
Figure A200680053947D01351
(n=6, x=55, y=5, Mw=33940, Mw/Mn=2.55, PO: propylene oxide, EO: oxyethane)
Adopt method same as described above to make colour filter photosensitive composition B～J respectively, difference is, uses pigment dispensing composition B～J to replace pigment dispensing composition A respectively.
The coloring photosensitive combination that adopts the rotation coating machine that above-mentioned preparation colour filter is used is coated on the glass substrate, and drying is 2 minutes under 100 ℃, forms the thick film of about 2 μ m.Then, under nitrogen gas stream, after the extra-high-pressure mercury vapour lamp exposure, use 1% aqueous sodium carbonate to develop.Adopt the contrast gradient and the photostabilization of the R composition of each film that the method mensuration identical with embodiment 2 obtains thus, the result is shown in following table 2-B.
[table 2-B]
Figure A200680053947D01361
As show the result shown in the 2-B as can be known, compare with sample I, the J of comparative example, used the photosensitive composition of the dispersion thing that adopts manufacture method of the present invention that the organic filler dispersion is generated as the particle of nano-scale and obtain to demonstrate very high contrast gradient, photostabilization.In addition, use the sample E～H of the represented macromolecular compound of general formula (1), in each embodiment, all demonstrated more excellent result aspect contrast gradient and the photostabilization two.
(embodiment 2-10)
[making of colour filter (adopting the slit-shaped nozzle to make)] by applying
(formation of black (K) image)
Behind UV washing unit cleaning alkali-free glass substrate, use hairbrush to clean with clean-out system again, adopt ultrasonic wave to clean with ultrapure water again.After carrying out thermal treatment in 3 minutes under 120 ℃, make condition of surface stable this substrate.
After this substrate is cooled to 23 ℃, use has the coating machine that is used for glass substrate (manufacturing of エ Off エ one エ ス ア ジ ア society, the trade(brand)name: MH-1600) will be coated on this substrate by the photosensitive composition K1 that is constituted that forms that puts down in writing among the following table 2-2 of slit-shaped ozzle.Then with VCD (Minton dryer; Tokyo ying chemical industry (strain) society makes) dry 30 seconds, partial solvent drying and coating layer are no longer flowed after, 120 ℃ of following prebakes 3 minutes, obtaining film thickness was the photo-sensitive resin K1 of 2.4 μ m.
[table 2-2]
Moiety Content (mass parts)
K colo(u)rant dispersion thing 1 (carbon black) 25
Propylene glycol monomethyl ether 8.0
Butanone 53
Binding agent 2 9.1
Hydroquinone monomethylether 0.002
DPHA liquid 4.2
2, amino-the 3 '-bromophenyl of two (trichloromethyl)-6-[4 '-(N, the N-di ethoxy carbonyl methyl) of 4-]-the s-triazine 0.16
Tensio-active agent 1 0.044
Employing has the contiguous type exposure machine (the Ha イ テ of Hitachi Network electronics エ Application ジ ニ ア リ Application グ Co., Ltd. system) of extra-high-pressure mercury vapour lamp, make substrate keep the vertical state that stands up with mask (quartzy exposed mask) with picture pattern, with the distance setting of exposed mask face and this photoresist interlayer is 200 μ m, at 300mJ/cm 2Exposure under carry out pattern exposure.
Next, pure water is sprayed, make the surface of this photo-sensitive resin K1 evenly wetting with spray spout.Use KOH class developing solution (to contain KOH, nonionic surface active agent then, trade(brand)name: CDK-1, the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テ ア Le ズ company makes, liquid after diluting 100 times) be that spray developed 80 seconds under the 0.04MPa at 23 ℃, the pressure of tack nozzle, obtain having the image of pattern.Next, under the pressure of 9.8MPa, spray ultrapure water, remove residue, deceived the image K of (K) with the ultra-high voltage washing nozzle.Then 220 ℃ of following thermal treatments 30 minutes.
(formation of red (R) pixel)
On the substrate that is formed with above-mentioned image K, use by the photosensitive composition R1 that is constituted that forms that puts down in writing among the following table 2-3, adopt and the identical operation of formation above-mentioned black (K) image, heat-treat the back and form pixel R.
The coated weight of the thickness of this photo-sensitive resin R1 and pigment (C.I.P.R.254 and C.I.P.R.177) is as follows.
Photoresist thickness (μ m) 1.60
Pigment coated weight (g/m 2) 1.00
Coated weight (the g/m of C.I.P.R.254 2) 0.80
Coated weight (the g/m of C.I.P.R.177 2) 0.20
[table 2-3]
Moiety Content (mass parts)
R colo(u)rant dispersion thing A 40
R colo(u)rant dispersion thing 2 (C.I.P.R.177) 4.5
Propylene glycol monomethyl ether 7.6
Butanone 37
Binding agent 1 0.7
DPHA liquid 3.8
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.12
2, amino-the 3 '-bromophenyl of two (trichloromethyl)-6-[4 '-(N, the N-di ethoxy carbonyl methyl) of 4-]-the s-triazine 0.05
Thiodiphenylamine 0.01
Tensio-active agent 1 0.06
(formation of green (G) pixel)
On the substrate that is formed with above-mentioned image K and pixel R, adopt photosensitive composition G1 with composition of putting down in writing among the following table 2-4, according to the identical operation of operation that forms above-mentioned black (K) image, after thermal treatment is finished, form pixel G.The coated weight of the thickness of this photo-sensitive resin G1 and pigment (C.I.P.G.36 and C.I.P.Y.150) is as follows.
Photoresist thickness (μ m) 1.60
Pigment coated weight (g/m 2) 1.92
Coated weight (the g/m of C.I.P.G.36 2) 1.34
Coated weight (the g/m of C.I.P.Y.150 2) 0.58
[table 2-4]
Moiety Content (mass parts)
G colo(u)rant dispersion thing 1 (C.I.P.G.36) 28
Y colo(u)rant dispersion thing 1 (C.I.P.Y.150) 15
Propylene glycol monomethyl ether 29
Butanone 26
Pimelinketone 1.3
Binding agent 2 2.5
DPHA liquid 3.5
2-trichloromethyl-5-is to styryl styryl-1,3, the 4-oxadiazole 0.12
2, amino-the 3 '-bromophenyl of two (trichloromethyl)-6-[4 '-(N, the N-di ethoxy carbonyl methyl) of 4-]-the s-triazine 0.05
Thiodiphenylamine 0.01
Tensio-active agent 1 0.07
(formation of blue (B) pixel)
On the substrate that is formed with above-mentioned image K, pixel R and pixel G, employing has the photosensitive composition B1 of the composition of putting down in writing among the following table 2-5, according to the identical operation of operation that forms above-mentioned black (K) image, after thermal treatment is finished, form pixel B, thereby obtain target colour filter A.
The coated weight of the thickness of this photo-sensitive resin B1 and pigment (C.I.P.B.15:6 and C.I.P.V.23) is as follows.
Photoresist thickness (μ m) 1.60
Pigment coated weight (g/m 2) 0.75
Coated weight (the g/m of C.I.P.B.15:6 2) 0.705
Coated weight (the g/m of C.I.P.V.23 2) 0.045
[table 2-5]
Moiety Content (mass parts)
B colo(u)rant dispersion thing 1 (C.I.P.B.15:6) 8.6
B colo(u)rant dispersion thing 2 (C.I.P.B.15:6+C.I.P.V.23) 15
Propylene glycol monomethyl ether 28
Butanone 26
Binding agent 3 17
DPHA liquid 4.0
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.17
Thiodiphenylamine 0.02
Tensio-active agent 1 0.06
Here, photosensitive composition K1, the R1 that puts down in writing among above-mentioned table 2-2～2-5, the preparation of G1, B1 are illustrated in greater detail.
Photosensitive composition K1 obtains in the following manner,, at first takes by weighing K colo(u)rant dispersion thing 1, the propylene glycol monomethyl ether of record amount among the table 2-2 that is, mixes under 24 ℃ of temperature (± 2 ℃), and stirs 10 minutes with the rotating speed of 150rpm.Then, take by weighing butanone, binding agent 2, Hydroquinone monomethylether, the DPHA liquid, 2 of record amount among the table 2-2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl) amino-3 '-bromophenyl]-s-triazine, tensio-active agent 1, under 25 ℃ of temperature (± 2 ℃), add successively, and the rotating speed with 150rpm stirred 30 minutes under 40 ℃ of temperature (± 2 ℃).
In addition, in the composition of table 2-2 record, about following compositions, shown in it is composed as follows.
＜K colo(u)rant dispersion thing 1 〉
Carbon black (trade(brand)name: Nipex 35, デ グ サ ジ ヤ パ Application (strain) society make)
13.1 mass parts
Dispersion agent (following compound 2J) 0.65 mass parts
Polymkeric substance (random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand) 6.72 mass parts
Propylene glycol monomethyl ether 79.53 mass parts
Figure A200680053947D01401
Compound 2J
＜binding agent 2 〉
Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=78/22 mol ratio, molecular weight 3.8 ten thousand) 27 mass parts
Propylene glycol monomethyl ether 73 mass parts
Photosensitive composition R1 obtains in the following manner, promptly, at first take by weighing R colo(u)rant dispersion thing A, R colo(u)rant dispersion thing 2, the propylene glycol monomethyl ether of record amount among the table 2-3, under 24 ℃ of temperature (± 2 ℃), mix, and stirred 10 minutes with the rotating speed of 150rpm.Then, take by weighing butanone, binding agent-1, DPHA liquid, the 2-trichloromethyl-5-(to the styryl styryl)-1 of record amount among the table 2-3,3,4-oxadiazole, 2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl) amino-3 '-bromophenyl]-s-triazine, thiodiphenylamine, under 24 ℃ of temperature (± 2 ℃), add successively, and stirred 30 minutes with the rotating speed of 150rpm.Then, take by weighing the tensio-active agent 1 of record amount among the table 2-3, add down, and stirred 5 minutes, filter with nylon mesh #200 then with the rotating speed of 30rpm in 24 ℃ of temperature (± 2 ℃).
In addition, in the composition of table 2-3 record, R colo(u)rant dispersion thing A adopts the method identical with the pigment dispensing composition A of embodiment 2-1 to obtain, and its composition has mass parts as follows.
＜R colo(u)rant dispersion thing A 〉
Concentrated pigment liquid A (C.I.P.R.254) 23 mass parts of the pasty state of embodiment 2-1
Dispersion agent (above-claimed cpd 2J) 0.8 mass parts
Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio, molecular weight 30,000) 8 mass parts
Propylene glycol monomethyl ether 68.2 mass parts
＜R colo(u)rant dispersion thing 2 〉
C.I.P.R.177 (trade(brand)name: Cromophtal Red A2B, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) society make) 18 mass parts
Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio, molecular weight 30,000) 12 mass parts
Propylene glycol monomethyl ether 70 mass parts
Photosensitive composition G1 obtains in the following manner, promptly, at first take by weighing G colo(u)rant dispersion thing 1, Y colo(u)rant dispersion thing 1, the propylene glycol monomethyl ether of record amount among the table 2-4, under 24 ℃ of temperature (± 2 ℃), mix, and stirred 10 minutes with the rotating speed of 150rpm.Then, take by weighing butanone, pimelinketone, binding agent-2, DPHA liquid, the 2-trichloromethyl-5-(to the styryl styryl)-1 of record amount among the table 2-4,3,4-oxadiazole, 2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl) amino-3 '-bromophenyl]-s-triazine, thiodiphenylamine, under 24 ℃ of temperature (± 2 ℃), add successively, and stirred 30 minutes with the rotating speed of 150rpm.Then, take by weighing the tensio-active agent 1 of record amount among the table 2-4, add down, and stirred 5 minutes, use nylon mesh #200 to filter then with the rotating speed of 30rpm in 24 ℃ of temperature (± 2 ℃).
In addition, in the composition of table 2-4 record, G colo(u)rant dispersion thing 1 uses is the product of the commodity GT-2 by name that makes of the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ (strain) society, and Y colo(u)rant dispersion thing 1 uses is the product of driving commodity CF イ エ ロ one EX3393 by name that state's pigment (strain) society makes.
Photosensitive composition B1 obtains in the following manner, promptly, at first take by weighing the B colo(u)rant dispersion thing 1 of table 2-5 record amount, B colo(u)rant dispersion thing 2, propylene glycol monomethyl ether, under 24 ℃ of temperature (± 2 ℃), mix, and stirred 10 minutes with the rotating speed of 150rpm, then, take by weighing the butanone of table 2-5 record amount, binding agent-3, DPHA liquid, 2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole, 2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl) amino-3 '-bromophenyl]-the s-triazine, thiodiphenylamine, under 25 ℃ of temperature (± 2 ℃), add successively, and the rotating speed with 150rpm stirred 30 minutes under 40 ℃ of temperature (± 2 ℃).Then, take by weighing the tensio-active agent 1 of table 2-5 record amount, add down in 24 ℃ of temperature (± 2 ℃), and stirred 5 minutes, use nylon mesh #200 to filter then with the rotating speed of 30rpm.
In addition, in the composition of table 2-5 record, B colo(u)rant dispersion thing 1 uses the product of commodity CF Block Le one EX3357 by name that drives the manufacturing of state's pigment (strain) society.B colo(u)rant dispersion thing 2 uses the product of commodity CF Block Le one EX3383 by name that drives the manufacturing of state's pigment (strain) society.
Shown in binding agent 3 composed as follows.
＜binding agent 3 〉
Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid/methyl methacrylate=36/22/42 mol ratio, molecular weight 3.8 ten thousand)
27 mass parts
Propylene glycol monomethyl ether 73 mass parts
Replace employed concentrated pigment liquid A among the R colo(u)rant dispersion thing A with concentrating pigment liquid B～H respectively, make R colo(u)rant dispersion thing B～H respectively.Then, adopt the preparation method identical with above-mentioned colour filter A, make colour filter B～H respectively, difference is, replaces R colo(u)rant dispersion thing A with R colo(u)rant dispersion thing B～H respectively.
(comparative example 2-3)
Adopt the preparation method identical with above-mentioned colour filter A, produce colour filter I, J respectively, difference is, replaces the concentrated pigment liquid A of employed pasty state among the R colo(u)rant dispersion thing A respectively with pigment dispensing composition I, J.
Adopt the method identical with embodiment 2, measure the contrast gradient and the photostabilization of each colour filter, the result is as showing shown in the 2-C.In addition, for the R pixel portion of colour filter A～F, adopt opticmicroscope (manufacturing of オ リ Application パ ス Co., Ltd., MX-50), observation has or not precipitate under 500 times enlargement ratio.Observations is divided into: in pixel and pixel end when not observing foreign matter, dirt settling, thinking does not have precipitate, is uniform; In pixel or pixel end when observing foreign matter, dirt settling, think unevenly, precipitate is arranged.Its result is shown in table 2-C.
[table 2-C]
Figure A200680053947D01431
By above-mentioned result as can be known, compare with comparison test thing I, J, colour filter of the present invention demonstrates very high contrast gradient and photostabilization.If aberration more than 2, is the degree that can distinguish for the beholder.When long-term like this (for example, more than 1 year) used, this difference further enlarged, and becomes marked difference in the display frame.Any one colour filter of the present invention is the good colour filter of contrast gradient height, no precipitate.On the other hand, the colour filter of comparative example, its contrast gradient is low, can see precipitate, can not reach to satisfy the practical level that requires.In addition, used the trier E～H of the represented macromolecular compound of general formula (1), in each embodiment, all demonstrated higher contrast gradient, and do not have precipitate, photostabilization is also excellent.
(embodiment 2-11)
[preparation of liquid crystal indicator and evaluation]
Use colour filter A～H to prepare liquid crystal indicator, and estimate their display characteristic.
(formation of ITO electrode)
The glass substrate that will be formed with colour filter is packed in the sputter equipment, behind 100 ℃ of ITO (indium tin oxide) that comprehensive vacuum evaporation 1300 dusts are thick down, 240 ℃ down annealing made the ITO crystallization in 90 minutes, form ito transparent electrode.
(formation of dottle pin)
Adopt and [embodiment 1] of the TOHKEMY 2004-240335 communique middle identical method of putting down in writing of dottle pin formation method, on the ito transparent electrode of above-mentioned making, form dottle pin.
(being used to control the formation of the projection of liquid crystal aligning)
Use following positive-working photosensitive resin layer coating liquid, on the above-mentioned ito transparent electrode that is formed with dottle pin, be formed for controlling the projection of liquid crystal aligning.
But exposure, development and roasting procedure adopt following method.
Contiguous type exposure machine (manufacturing of the Ha イ テ of Hitachi Network electronics エ Application ジ ニ ア リ Application グ Co., Ltd.) is installed, and making the photomask of regulation and the distance of photoresist laminar surface is 100 μ m, utilizes extra-high-pressure mercury vapour lamp with 150mJ/cm 2Irradiation energy see through this photomask and carry out the close induction type exposure.
Then, use 2.38% the tetramethyl ammonium hydroxide aqueous solution, under 33 ℃, sprayed 30 seconds, develop simultaneously to substrate by the spray-type developing apparatus.Removed by development thus and do not needed part (exposed portion) on the photo-sensitive resin, thereby obtained base plate for liquid crystal display device, wherein the colour filter side at this substrate has formed the projection that is used to control liquid crystal aligning that is made of the photo-sensitive resin that forms desired pattern form.
Then, the base plate for liquid crystal display device that will be formed with this projection that is used to control liquid crystal aligning is 230 ℃ of bakings 30 minutes down, thereby forms the projection that solidified is used to control liquid crystal aligning on base plate for liquid crystal display device.
＜positive-working photosensitive resin layer is filled a prescription with coating liquid 〉
Eurymeric resist liquid (FH-2413F that the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ (strain) society makes) 53.3 mass parts
Butanone 46.7 mass parts
メ ガ Off ァ Star Network F-780F (big Japanese ink chemical industry (strain) society makes)
0.04 mass parts
(making of liquid crystal indicator)
The alignment films that is made of polyimide further is set on the base plate for liquid crystal display device of above-mentioned acquisition.
Then, be equivalent to the position of housing on the next door around being arranged at, the printing epoxy encapsulant with opacifying property in the mode of surrounding the color filter pixel group.Further instillation MVA pattern liquid crystal, and paste with opposing substrates, then the substrate of stickup is heat-treated, make sealant cures.On the two sides of the liquid crystal cells that obtains by this way, paste the Polarizer HLC2-2518 that (strain) サ Application リ Star Star society makes.Then, backlight by three-wavelength cold-cathode tube light source (FWL18EX-N that Toshiba's ラ イ テ Star Network (strain) society makes) structure, it is installed in the rear side of the liquid crystal cells that is provided with above-mentioned Polarizer, form liquid crystal indicator.
(comparative example 2-4)
[preparation of liquid crystal indicator and evaluation]
Adopt the method identical, use colour filter I, J to prepare liquid crystal indicator, and estimate their display characteristic with embodiment 2-11.
With respect to the liquid crystal indicator of the colour filter that has used comparative example, use the liquid crystal indicator of colour filter of the present invention to demonstrate excellent black density and redness and described power, do not show non-uniform phenomenon, have good display performance.
(embodiment 2-12)
[making of colour filter (by the laminates of photosensitive resin transfer material)]
(making of photosensitive resin transfer material)
At thickness is on the interim upholder of polyethylene terephthalate of 75 μ m, applies the thermoplastic resin coating liquid that is made of following prescription H1 with the slit-shaped nozzle, and carries out drying.Then, apply the middle layer coating liquid that constitutes by following prescription P1, and carry out drying.Apply above-mentioned photosensitive composition K1 again; and carry out drying; thereby the thermoplastic resin that dry film thickness is 14.6 μ m is set on this interim upholder, middle layer, the dry film thickness that dry film thickness is 1.6 μ m is the photo-sensitive resin of 2.4 μ m, and pressing protective membrane (thickness is the polypropylene screen of 12 μ m).
Make the photosensitive resin transfer material K1 that forms one by the photo-sensitive resin of interim upholder, thermoplastic resin, middle layer (oxygen barrier layers) and black (K) thus.
＜thermoplastic resin coating liquid: prescription H1 〉
Methyl alcohol 11.1 mass parts
Propylene glycol monomethyl ether 6.36 mass parts
Butanone 52.4 mass parts
Methyl methacrylate/2-EHA/benzyl methacrylate/Sipacril 2739OF (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight: 90,000, Tg: about 70 ℃) 5.83 mass parts
Styrene/acrylic acid co-polymer (copolymerization ratio of components (mol ratio)=63/37, molecular weight: 10,000, Tg: about 100 ℃) 13.6 mass parts
Compound behind dihydroxyphenyl propane and the pentanediol monomethacrylates 2 equivalent dehydrating condensations (Xin Zhong village chemical industry (strain) is made, trade(brand)name: 2, and two [4-(methacryloxy polyethoxye) phenyl] propane of 2-) 9.1 mass parts
Above-mentioned tensio-active agent 1 0.54 mass parts
＜middle layer coating liquid: prescription P1 〉
PVA205 (polyvinyl alcohol, (strain) Network ラ レ society makes, saponification degree=88%, the polymerization degree 550) 32.2 mass parts
(ア イ エ ス ピ-ジ ヤ パ Application Co., Ltd. makes polyvinylpyrrolidone, K-30)
14.9 mass parts
Distilled water 524 mass parts
Methyl alcohol 429 mass parts
Then, adopt the method identical to prepare photosensitive resin transfer material R101, G101 and B101 with aforesaid method, difference is, will replace with following photosensitive composition R101, G101 and the B101 with composition of putting down in writing among following table 2-6～2-8 respectively by employed photosensitive composition K1 when making above-mentioned photosensitive resin transfer material K1.In addition, the preparation method of photosensitive composition R101, G101 and B101 carries out according to the preparation method of above-mentioned photosensitive composition R1, G1 and B1 respectively.
[table 2-6] R101
Moiety Content (mass parts)
R colo(u)rant dispersion thing A 40
R colo(u)rant dispersion thing 2 (C.I.P.R.177) 4.5
Propylene glycol monomethyl ether 7.6
Butanone 37
Binding agent 1 0.8
DPHA liquid 4.4
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.14
2, two (trichloromethyl)-6-[4 '-(N, the N-diethoxy carbonyl methyl) amino-3 of 4-'-bromophenyl]-the s-triazine 0.06
Thiodiphenylamine 0.01
Additive 1 0.52
Tensio-active agent 1 0.06
[table 2-7] G101
Moiety Content (mass parts)
G colo(u)rant dispersion thing 1 (C.I.P.G.36) 28
Y colo(u)rant dispersion thing 1 (C.I.P.Y.150) 15
Propylene glycol monomethyl ether 29
Butanone 26
Pimelinketone 1.3
Binding agent 2 3.0
DPHA liquid 4.3
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.15
2, two (trichloromethyl)-6-[4 '-(N, the N-diethoxy carbonyl methyl) amino-3 of 4-'-bromophenyl]-the s-triazine 0.06
Thiodiphenylamine 0.01
Tensio-active agent 1 0.07
[table 2-8] B101
Moiety Content (mass parts)
B colo(u)rant dispersion thing 1 (C.I.P.B.15:6) 8.6
B colo(u)rant dispersion thing 2 (C.I.P.B.15:6+C.I.P.V.23) 15
Propylene glycol monomethyl ether 28
Butanone 26
Binding agent 3 18.5
DPHA liquid 4.3
2-trichloromethyl-5-(to the styryl styryl)-1,3, the 4-oxadiazole 0.17
Thiodiphenylamine 0.02
Tensio-active agent 1 0.06
Also have, in the constituent of putting down in writing among the table 2-6, what additive 1 used is that phosphoric acid ester is that (nanmu originally changes into (strain) society and makes, trade(brand)name: HIPLAAD ED152) in the sp act agent.
(formation of black (K) image)
For alkali-free glass substrate, on one side spray the glass cleaner 20 seconds that is adjusted to 25 ℃ with water-jet, clean with rotating brush on one side with nylon hair, after using the pure water spray Cleaning for High Capacity again, spray silane coupling agent (the 0.3 quality % aqueous solution of N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane with water-jet, trade(brand)name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) society makes) 20 seconds, and use the pure water spray Cleaning for High Capacity.This substrate was heated 2 minutes under 100 ℃ with the substrate preheating apparatus, send into laminating machine then.
After the protective membrane of above-mentioned photosensitive resin transfer material K1 peeled off; with laminating machine (イ of Co., Ltd. Hitachi Application ダ ス ト リ イ ズ system (LamicII type)), be set forth on 100 ℃ of substrates that heat down last in the condition laminated that 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transfer rate 2.2m/ divide.
With thermoplastic resin form at the interface interim upholder is peeled off after, employing has the contiguous type exposure machine (manufacturing of the Ha イ テ Network electronics エ Application ジ ニ ア リ Application グ of Hitachi (strain) society) of extra-high-pressure mercury vapour lamp, make substrate keep the vertical state that stands up with mask (quartzy exposed mask) with picture pattern, with the distance setting of exposed mask face and this thermoplastic resin interlayer is 200 μ m, at 70mJ/cm 2Exposure under carry out pattern exposure.
Then, (contain 30% trolamine with trolamine class developing solution, trade(brand)name: T-PD2, the description Off イ of Fuji Le system Co., Ltd. makes, with the liquid after the pure water dilution 12 times (mixing with the ratio of 11 parts pure water) according to 1 part T-PD2) under 30 ℃, the condition of tack nozzle pressure 0.04MPa, spray development 50 seconds, remove thermoplastic resin and middle layer.
Then, (contain the sodium bicarbonate of 0.38 mol, the yellow soda ash of 0.47 mol, 5% sodium dibutyl naphthalene sulfonate, anion surfactant, defoamer, stablizer with yellow soda ash class developing solution, trade(brand)name T-CD1, the description Off イ of Fuji Le system Co., Ltd. system, with the liquid after 5 times of the pure water dilutions), under 29 ℃, the condition of conical nozzle pressure 0.15MPa, spray and developed 30 seconds, photo-sensitive resin is developed, obtain having the image of pattern.
Then with clean-out system (trade(brand)name " T-SD3 (the description Off イ of Fuji Le system Co., Ltd. system) ", with the liquid after 10 times of the pure water dilutions), under 33 ℃, the condition of conical nozzle pressure 0.02MPa, sprayed 20 seconds, and remove residue with rotary brush with nylon hair, obtain the image of black (K).Then, for this substrate, use extra-high-pressure mercury vapour lamp at 500mJ/cm from this resin layer side again 2Illumination under carry out post-exposure, then 220 ℃ of following thermal treatments 15 minutes.
To be formed with the substrate of this image K, and once more as mentioned above, after the use brush cleans, use the pure water spray Cleaning for High Capacity again, and under the condition of not using silane coupling agent, it is delivered in the substrate preheating apparatus.
(formation of red (R) pixel)
Adopt and the identical operation of above-mentioned photosensitive resin transfer material K1, use above-mentioned photosensitive resin transfer material R101, after thermal treatment is finished, obtain redness (R) pixel R.But exposure is 40mJ/cm 2, and the condition when adopting yellow soda ash class image-developing liquor to carry out video picture be 35 ℃ following 35 seconds.The coated weight of the thickness of this photo-sensitive resin R101 and pigment (C.I.P.R.254 and C.I.P.R.177) is as follows.
Photoresist thickness (μ m) 2.00
Pigment coated weight (g/m 2) 1.00
Coated weight (the g/m of C.I.P.R.254 2) 0.80
Coated weight (the g/m of C.I.P.R.177 2) 0.20
To be formed with the substrate of this image K and pixel R, and once more as mentioned above, after the use brush cleans, use the pure water spray Cleaning for High Capacity again, and under the condition of not using silane coupling agent, it is delivered in the substrate preheating apparatus.
(formation of green (G) pixel)
Adopt and the identical operation of above-mentioned photosensitive resin transfer material R101, use above-mentioned photosensitive resin transfer material G101, after thermal treatment is finished, obtain green (G) pixel G.But exposure is 40mJ/cm 2, and the condition when adopting yellow soda ash class image-developing liquor to carry out video picture be 34 ℃ following 45 seconds.The coated weight of the thickness of this photo-sensitive resin G101 and pigment (C.I.P.G.36 and C.I.P.Y.150) is as follows.
Photoresist thickness (μ m) 2.00
Pigment coated weight (g/m 2) 1.92
Coated weight (the g/m of C.I.P.G.36 2) 1.34
Coated weight (the g/m of C.I.P.Y.150 2) 0.58
To be formed with the substrate of this image K, pixel R and pixel G, and once more as mentioned above, after the use brush cleans, use the pure water spray Cleaning for High Capacity again, and under the condition of not using silane coupling agent, it is delivered in the substrate preheating apparatus.
(formation of blue (B) pixel)
Adopt and the identical operation of above-mentioned photosensitive resin transfer material R101, use above-mentioned photosensitive resin transfer material B101, after thermal treatment is finished, obtain blueness (B) pixel B.But exposure is 30mJ/cm 2, and the condition when adopting yellow soda ash class image-developing liquor to carry out video picture be 36 ℃ following 40 seconds.The coated weight of the thickness of this photo-sensitive resin B101 and pigment (C.I.P.B.15:6 and C.I.P.V.23) is as follows.
Photoresist thickness (μ m) 2.00
Pigment coated weight (g/m 2) 0.75
Coated weight (the g/m of C.I.P.B.15:6 2) 0.705
Coated weight (the g/m of C.I.P.V.23 2) 0.045
The substrate that will be formed with pixel R, pixel G, pixel B and image K was dried 50 minutes down at 240 ℃, obtained colour filter A1.
Adopt the making method of above-mentioned colour filter A1 to make colour filter B1～H1, difference is, replaces R colo(u)rant dispersion thing A with R colo(u)rant dispersion thing B～H respectively.
(comparative example 2-5)
Adopt the making method of above-mentioned colour filter A1 to make colour filter I1, J1, difference is, replaces R colo(u)rant dispersion thing A with pigment dispensing composition I, J respectively.
Adopt the method identical with embodiment 2-10 to measure contrast gradient, the aberration of resulting colour filter A1～J1, have or not precipitate, the result is shown in table 2-D.
[table 2-D]
Figure A200680053947D01501
By the result of above-mentioned table 2-D as can be known, use disperses to be generated as the dispersion thing that the particle of nano-scale obtains by manufacture method of the present invention with organic filler, can access colour filter A1～H1 that contrast gradient is very high, photostabilization is excellent and the generation of precipitate is suppressed, the R pixel portion does not have non-uniform phenomenon.In addition, use the colour filter E1～H1 of the represented macromolecular compound of general formula (1), in each embodiment, all demonstrated higher contrast gradient, and do not have precipitate, demonstrated good photostabilization.
(embodiment 2-13)
[preparation of liquid crystal indicator and evaluation]
Adopt the method identical, use colour filter A1～H1 to prepare liquid crystal indicator, and estimate their display characteristic with embodiment 2-11.
(comparative example 2-6)
[preparation of liquid crystal indicator and evaluation]
Adopt the method identical, use colour filter I1, J1 to prepare liquid crystal indicator, and estimate their display characteristic with embodiment 2-11.
With respect to the liquid crystal indicator of the colour filter that has used comparative example, can confirm to have used the black density and the redness of the liquid crystal indicator of colour filter of the present invention to describe the power excellence, do not show non-uniform phenomenon, demonstrate good display performance.
(embodiment 3) use the embodiment of triazine dioxin pigment
(embodiment 3-1)
Adopt the method identical to make concentrated pigment liquid VA～VH, the pigment liquid dispersive composition VA～VH of dispersible pigment dispersion VA～VH, pasty state respectively with embodiment 2-1～2-8, difference is that use C.I. pigment Violet 23 (manufacturing of Hostaperm Violet RL-NF Network ラ リ ア Application ト society) replaces the pigment C.I. Pigment red 254 (Irgaphor Red BT-CF) in the preparation of the pigment dispensing composition of embodiment 2-1～2-8.
Adopt the method identical with 2-2 with comparative example 2-1 respectively, make pigment dispensing composition VI～VJ, difference is that use C.I. pigment Violet 23 replaces the pigment C.I. Pigment red 254 in the preparation of the pigment dispensing composition of comparative example 2-1 and 2-2.
Adopt the number average bead diameter and the Mv/Mn of the pigment particles in above-mentioned each dispersive composition of method mensuration identical with embodiment 2.The result is as described below.
[table 3-A]
Figure A200680053947D01511
Figure A200680053947D01521
Adopt the method identical with embodiment 2 to measure the contrast gradient of above-mentioned pigment dispensing composition VA～VJ, the result is as described below.
[table 3-B]
Figure A200680053947D01522
By above-mentioned result as can be known, compare, adopt manufacture method of the present invention that organic filler is disperseed to be generated as the particle of nano-scale and the dispersion thing that obtains demonstrates very excellent contrast gradient and photostabilization with duplicate VI, VJ.
(embodiment 3-2)
Adopt the method identical to make colour filter photosensitive composition VA～VJ respectively with embodiment 2-9, difference is, uses above-mentioned pigment dispensing composition VA～VJ to replace pigment dispensing composition A in the prepared coloring photosensitive combination A of embodiment 2-9.Adopt the method identical to measure the contrast gradient of resulting photosensitive composition respectively with embodiment 2-9.The result is as described below.
[table 3-C]
Figure A200680053947D01523
Figure A200680053947D01531
By above-mentioned result as can be seen, compare with sample VI, VJ (it has utilized the pigment that adopts normally used ア イ ガ one pulverizer and prepare or has adopted pigment after salt mill method is carried out miniaturization), used photosensitive composition to have very excellent contrast gradient according to the nanoparticle of manufacture method manufacturing of the present invention.
(embodiment 3-3)
[preparation of colour filter (adopting the slit-shaped nozzle to be prepared)] by coating
Adopt the method identical to make colour filter VA with embodiment 2-10, difference is, in the prepared colour filter A of embodiment 2-10, replace R colo(u)rant dispersion thing A with following R colo(u)rant dispersion thing 1, and with following B colo(u)rant dispersion thing VA replacement B colo(u)rant dispersion thing 2.
＜R colo(u)rant dispersion thing 1 〉
C.I.P.R.254 (trade(brand)name: Irgaphor Red B-CF, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) society makes) 8 mass parts
Dispersion agent (above-claimed cpd 1J) 0.8 mass parts
Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio, matter average molecular weight 3.7 ten thousand) 8 mass parts
Propylene glycol monomethyl ether 83.2 mass parts
＜B colo(u)rant dispersion thing VA 〉
Concentrated pigment liquid VA 3.64 mass parts of pasty state
C.I.P.B.15:6 11.1 mass parts
Dispersion agent (above-claimed cpd 1J) 0.8 mass parts
Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=72/28 mol ratio, molecular weight 30,000) 4.9 mass parts
Propylene glycol monomethyl ether 80 mass parts
Use respectively to concentrate employed concentrated pigment liquid VA among pigment liquid VB～VH replacement B colo(u)rant dispersion thing VA, prepared B colo(u)rant dispersion thing VB～VH.Then, prepared colour filter VB～VH according to the method identical with above-mentioned colour filter VA, difference is, uses B colo(u)rant dispersion thing VB～VH to replace B colo(u)rant dispersion thing VA respectively.
Adopt the preparation method of above-mentioned colour filter VA, the pasty state that uses pigment dispensing composition VI, VJ to replace using among the B colo(u)rant dispersion thing VA respectively concentrates pigment liquid VA, has prepared colour filter VI, VJ.Adopt the method identical to measure the contrast gradient of each colour filter with embodiment 2.The result is shown in following table 3-D.
[table 3-D]
By table 3-D as can be seen, the pigment that has prepared with having used normally used ア イ ガ one pulverizer or adopt salt mill method and the colour filter of the pigment that obtains is compared has used the colour filter according to the nanoparticle of manufacture method manufacturing of the present invention to have very excellent contrast gradient.
(embodiment 3-4)
[preparation of liquid crystal indicator and evaluation]
Use colour filter VA～VJ to prepare liquid crystal indicator, and the employing method identical with embodiment 2-11 estimated their display characteristic.The result can confirm, with respect to the liquid crystal indicator of the colour filter that has used comparative example, used the liquid crystal indicator of colour filter of the present invention all to demonstrate excellent black density and blueness and described power, and demonstrated good display performance.
(embodiment 3-5)
[preparation of colour filter (lamination by photosensitive resin transfer material is prepared)]
Adopt the method identical to make colour filter VA1 with embodiment 2-12, difference is, use above-mentioned R colo(u)rant dispersion thing 1 to replace R colo(u)rant dispersion thing A in the prepared colour filter A1 of embodiment 2-12, and replace B colo(u)rant dispersion thing 2 with above-mentioned B colo(u)rant dispersion thing VA.
In addition, adopt the method identical with above-mentioned colour filter VA1 to make colour filter VB1～VH1, difference is, uses B colo(u)rant dispersion thing VB～VH to replace B colo(u)rant dispersion thing VA respectively.
In addition, adopt the making method of above-mentioned colour filter VA1, use pigment dispensing composition VI, VJ to replace B colo(u)rant dispersion thing VA respectively, make colour filter VI1, VJ1.
Adopt the method identical to measure the contrast gradient of each colour filter with embodiment 2.The result is shown in following table 3-E.
[table 3-E]
Figure A200680053947D01551
By table 3-E as can be seen, compare with the comparative example colour filter of the pigment that has used the pigment that adopts normally used ア イ ガ one pulverizer and prepare or obtained by salt mill method, used colour filter to have very excellent contrast gradient according to the nanoparticle of manufacture method manufacturing of the present invention.
(embodiment 3-6)
[preparation of liquid crystal indicator and evaluation]
Use above-mentioned colour filter VA1～VJ1, and the employing method identical with embodiment 3-4 prepare liquid crystal indicator, estimated their display characteristic.Can confirm,, use the liquid crystal indicator of colour filter of the present invention to demonstrate excellent black density and blueness and described power, demonstrate good display performance with respect to the liquid crystal indicator of the colour filter that has used comparative example.
(embodiment 4)
Adopt the method identical to prepare pasty state and concentrate pigment liquid A-10, A-100 with the concentrated pigment liquid A of the pasty state of embodiment 2-1, difference is, pigment solution being mixed in the process of poor solvent, is 10 times, 100 times with the quantitative change of employed pigment, solvent.Further use pasty state to concentrate pigment liquid A-10, A-100, adopt the method identical, prepared colour filter A1-10, A1-100 with embodiment 2-12.
In addition, adopt the method identical to prepare pasty state and concentrate pigment liquid H-10, H-100 with the concentrated pigment liquid H of the pasty state of embodiment 2-8, difference is, pigment solution is being mixed in the process of poor solvent, and be 10 times, 100 times with the pigment that uses, the quantitative change of solvent.Further use pasty state to concentrate pigment liquid H-10, H-100, adopt the method identical, prepared colour filter H1-10, H1-100 with embodiment 2-12.
The evaluation result of the contrast gradient of prepared colour filter is shown in following table 4-A.
[table 4-A]
Figure A200680053947D01561
By the result who shows 4-A as can be known, by the organic nano particle that uses manufacturing method according to the invention to obtain, can access the colour filter of high-contrast, in the process of making nanoparticle, enlarging the preparative scale while, also can keep and further improve its excellent characteristic.Hence one can see that, and manufacturing method according to the invention when making colour filter, can realize high-quality and high productivity simultaneously.
(embodiment 5) use the embodiment of pyrrolopyrrole compound pigment
(embodiment 5-1)
Adopt the method identical to prepare colour filter respectively with the preparation section of the manufacturing process of each colour filter in the manufacturing of colour filter A～J, colour filter A1～J1 and material thereof, difference is, use イ Le ガ Off オ ア レ Star De BT-C (manufacturing of チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society) to replace employed Pigment red 254 in the making of above-mentioned colour filter (trade(brand)name イ Le ガ Off オ ア レ Star De BT-CF, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society makes).Use resulting colour filter to prepare liquid crystal indicator, with respect to the liquid crystal indicator of the colour filter that has used comparative example, liquid crystal indicator of the present invention demonstrates good performance.
(embodiment 5-2)
Adopt the method identical to prepare colour filter respectively with the preparation section of the manufacturing process of each colour filter in the manufacturing of colour filter A～J, colour filter A1～J1 and material thereof, difference is, uses Irgaphor Red B-CF, Irgazin DPP Red BO, Pigment red 255 (Irgazin DPP Red 5G) or Pigment red 264 (Irgazin DPP Rubine TR) to replace employed Pigment red 254 in the making of above-mentioned colour filter (Irgaphor Red BT-CF) (being チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society makes).Use resulting colour filter to prepare liquid crystal indicator, with respect to the liquid crystal indicator of the colour filter that has used comparative example, liquid crystal indicator of the present invention demonstrates good performance.
(embodiment 5-3)
Adopt respectively with at colour filter VA～VJ, the method that the preparation section of the manufacturing process of each colour filter and material thereof is identical in the manufacturing of colour filter VA1～VJ1 has prepared colour filter, difference is, use Fastgen Super Violet BBL (big Japanese イ Application キ chemical industry society make), バ イ オ レ Star ト RE 388-180NO (Dainichiseika Color Chem's manufacturing), perhaps pigment violet 37 (Cromophtal Violet B, チ バ ガ イ ギ one society makes) replaces employed pigment Violet 23 in the making of above-mentioned colour filter (Hostaperm VioletRL-NF).Use resulting colour filter to prepare liquid crystal indicator, with respect to the liquid crystal indicator of the colour filter that has used comparative example, liquid crystal indicator of the present invention demonstrates good performance.
(embodiment 6) use the embodiment of the represented macromolecular compound of general formula (1)
(embodiment 6-1)
The preparation of＜pigment dispensing composition L 〉
[preparation of dispersible pigment dispersion]
In 1500mL dimethyl sulfoxide (DMSO) (making), add 28% methanol solution of sodium methylate, 70g pigment C.I. Pigment red 254 (the trade(brand)name Irgaphor RedBT-CF of 55.0mL with the pure medicine of light society, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) manufacturing), reach 125.0g polyvinylpyrrolidone (trade(brand)name K-30, make with the pure medicine of light society), be mixed with pigment solution L.Use viscometer VM-10A-L (trade(brand)name, CBC マ テ リ ア Le ズ society makes) to measure the viscosity of this pigment solution L, the result shows that the viscosity when the liquid temperature of pigment solution L is 20.0 ℃ is 16.8mPas.In addition, prepare to contain the water 1800mL of the 1mol/L hydrochloric acid (making) of 20mL, as poor solvent with the pure medicine of light society.
At this moment, temperature is controlled to be 20 ℃, to utilizing GK-0222-10 type ラ モ Application De ス -ラ-(trade(brand)name, Fujisawa Pharmaceutical Co., Ltd makes) among poor solvent-water 1800mL of stirring with the rotating speed of 500rpm, with NP-KX-500 type large vol pulseless pump (trade(brand)name, the manufacturing of Japan precision chemical society) flow velocity by 100mL/min is the pigment solution L of the liquid-transport pipe-line injection 100mL of 0.8mm by the fluid passage diameter, form organic pigment particles thus, thereby make dispersible pigment dispersion L.Use Na ノ ト ラ Star Network UPA-EX150 (trade(brand)name, day machine dress society makes) to measure number average bead diameter Mn and single dispersity (Mv/Mn) of this dispersible pigment dispersion, the result is shown in following table 6-A.
The H-112 type centrifugal filter that utilizes the manufacturing of (strain) コ Network サ Application society is Ji the P89C type filter cloth that Fu Island カ Application バ ス (strain) society makes, pigment nanoparticle dispersion liquid that will be by method for preparing concentrates 90 minutes with the rotating speed of 4500rpm, resulting pigment nanoparticle is concentrated to stick with paste reclaim.
Utilize the pigment content of 8453 these mashed prod of type spectrophotometric determination of ア ジ レ Application ト (Agilent) company manufacturing, the result is 15.5 weight %.
In the 50.0cc ethyl lactate, add method synthetic pigment dispersing agent A, the 2.3g macromolecular compound C-1 of 0.1g according to TOHKEMY 2000-239554 communique, obtain solution, this solution is joined in the above-mentioned pigment nanoparticle preparation paste of 16.0g, after stirring 60 minutes with dissolving machine with the speed of 1500rpm, the FP-010 type filter that utilizes the Off ァ イ of Sumitomo Electric Industries Application Port リ マ Co., Ltd. to produce filters, and obtains the concentrated pigment liquid L (concentration of nano dye is 31.5 quality %) of pasty state thus.
[preparation of pigment dispensing composition L]
Use above-mentioned mashed prod, preparation has the pigment dispensing composition L of following composition.
The concentrated pigment liquid L 20.4g of above-mentioned pasty state
1,3 butylene glycol diacetate esters 43.9g
Utilize electronic mill M-50 (manufacturing of ア イ ガ one ジ ヤ パ Application society) and use the zirconium white microballon of diameter as 0.65mm, under the condition of circumferential speed 9m/s, the pigment dispensing composition that will have above-mentioned composition disperseed 1 hour.
(embodiment 6-2)
The preparation of＜pigment dispensing composition M 〉
Adopt the method identical to prepare pigment dispensing composition M with embodiment 6-1, difference is, the fluid passage diameter of employed liquid-transport pipe-line changes to 0.25mm during with the described pigment solution L of the injection among the embodiment 6-1, and will inject flow velocity and change to 8mL/min.Adopt the method identical to measure number average bead diameter and the single dispersity of the dispersible pigment dispersion M for preparing with embodiment 6-1.
(embodiment 6-3)
The preparation of＜pigment dispensing composition N 〉
Adopt the method identical to prepare pigment dispensing composition N with embodiment 6-1, difference is, the fluid passage diameter of employed liquid-transport pipe-line changes to 2.20mm during with the described pigment solution L of the injection among the embodiment 6-1, and will inject flow velocity and change to 400mL/min.Adopt the method identical to measure number average bead diameter and the single dispersity of the dispersible pigment dispersion N for preparing with embodiment 6-1.The result is shown in following table 6-A.
(embodiment 6-4)
The preparation of＜pigment dispensing composition O 〉
Adopt the method identical to prepare pigment dispensing composition O with embodiment 6-1, difference is, employed macromolecular compound C-1 among the embodiment 6-1 is changed to methacrylic acid/benzyl methacrylate multipolymer (mol ratio 28/72 of 5.75g, matter average molecular weight 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution), addition with the 1,3 butylene glycol diacetate esters changes to 40.45g in addition.
(comparative example 6-1)
The preparation of＜pigment dispensing composition P 〉
In the following manner, use microballon to grind the pigment dispensing composition P that dispersal mechanism is got everything ready and is made up of following.
Pigment (Pigment red 254) 6.43g
Pigment dispersing agent A 0.26g
Polyvinylpyrrolidone 7.10g
Methacrylic acid/benzyl methacrylate multipolymer * 14.9g
(the * mol ratio is 28/72, the matter average molecular weight: 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution)
1,3 butylene glycol diacetate esters 35.80g
(comparative example 6-2)
The preparation of＜pigment dispensing composition Q 〉
In the following manner, preparation has the pigment dispensing composition Q of following composition.
Pigment (Pigment red 254) 6.43g
Sodium-chlor 64.0g
Methacrylic acid/benzyl methacrylate multipolymer * 14.9g
* mol ratio is 28/72, the matter average molecular weight: 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution
In 1,3 butylene glycol diacetate esters liquid, add sodium-chlor, pigment (Pigment red 254) powder, methacrylic acid/benzyl methacrylate multipolymer, then it is joined in the twin screw kneader, descended mixing 10 hours at 80 ℃.After mixing, said mixture is joined in 80 ℃ 1% aqueous hydrochloric acid of 500 weight parts, stir after 1 hour, filter, use hot wash, dry, pulverize, the ratio of adding the 1,3 butylene glycol diacetate esters of 2.4g according to every 1g crushed material adds 1 then, 3-butyleneglycol diacetate esters mixes then.Adopt electronic mill M-50 (manufacturing of ア イ ガ one ジ ヤ パ Application society) and use the zirconium white microballon of diameter, under the condition of circumferential speed 9m/s, above-mentioned color compositions was disperseed 1 hour, obtain pigment dispensing composition Q as 0.65mm.
Particle diameter, single dispersity to resulting pigment dispensing composition among embodiment 6-1～6-4 and comparative example 6-1, the 6-2 are measured, and the result is shown in following table 6-A.
[table 6-A]
Number average bead diameter (Mn) Single dispersity (Mv/Mn)
Embodiment 6-1 29.5 1.30
Embodiment 6-2 48.7 1.68
Embodiment 6-3 26.6 1.38
Embodiment 6-4 37.5 1.57
Comparative example 6-1 88.4 1.62
Comparative example 6-2 65.6 2.55
(embodiment 6-5)
The making of＜liquid crystal indicator 〉
(making of photosensitive transfer printing material)
At thickness is on the interim upholder of polyethylene terephthalate of 75 μ m, applies the thermoplastic resin coating liquid that is made of following prescription H2 with the slit-shaped nozzle, and carries out drying.Then, apply the middle layer coating liquid that constitutes by following prescription P2, and carry out drying.Apply again and have resin combination K2 composition, that have opacifying property that puts down in writing among the following table 6-B; and carry out drying; thereby the thermoplastic resin that dry film thickness is 15 μ m is set on this interim upholder, middle layer, the dry film thickness that dry film thickness is 1.6 μ m is the resin layer with opacifying property of 2.4 μ m, and pressing protective membrane (thickness is the polypropylene screen of 12 μ m).
Make the photosensitive resin transfer material that forms one by interim upholder, thermoplastic resin, middle layer (oxygen barrier layers) and resin layer with opacifying property thus, the sample name is decided to be photosensitive resin transfer material K2.
* thermoplastic resin coating liquid: prescription H2
Methyl alcohol 11.1 mass parts
Propylene glycol monomethyl ether 6.4 mass parts
Butanone 52.4 mass parts
Methyl methacrylate/2-EHA/benzyl methacrylate/Sipacril 2739OF (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight=100,000,70 ℃ of Tg ≈) 5.83 mass parts
Styrene/acrylic acid co-polymer (copolymerization ratio of components (mol ratio)=63/37, molecular weight=10,000,100 ℃ of Tg ≈) 3.6 mass parts
2, two [4-(methacryloxy polyethoxye) phenyl] propane (Xin Zhong village chemical industry (strain) manufacturing) 9.1 mass parts of 2-
Tensio-active agent 1A 0.54 mass parts
Consisting of tensio-active agent 1A (メ ガ Off ァ Star Network F-780-F (big Japanese ink chemical industry (strain) society make) *):
C 6F 13CH 2CH 2OCOCH=CH 2: 40 mass parts
H (OCH (CH 3) CH 2) 7OCOCH=CH 2: 55 mass parts and
H (OCH 2CH 2) 7OCOCH=CH 2: 5 mass parts
Multipolymer (molecular weight 30,000) 30 mass parts that form
Butanone 70 mass parts
* middle layer (oxygen barrier layers) fills a prescription with coating liquid: P2
Polyvinyl alcohol 32.2 mass parts
(PVA205 (saponification degree=88%), (strain) Network ラ レ society makes)
Polyvinylpyrrolidone 14.9 mass parts
(PVP, K-30; ア イ エ ス ピ-ジ ヤ パ Application Co., Ltd. makes)
Methyl alcohol 429 mass parts
Distilled water 524 mass parts
[table 6-B]
Moiety Content (mass parts)
K colo(u)rant dispersion thing 2 (carbon black) 25
Propylene glycol monomethyl ether 8.0
Butanone 53
Binding agent 4 9.1
Hydroquinone monomethylether 0.002
DPHA liquid 4.2
2, amino-the 3 '-bromophenyl of two (trichloromethyl)-6-[4 '-(N, the N-di ethoxy carbonyl methyl) of 4-]-the s-triazine 0.16
Tensio-active agent 1A 0.044
At this, the preparation of the resin combination K2 with opacifying property that puts down in writing among the above-mentioned table 6-B is described.
Resin combination K2 with opacifying property obtains in the following manner, promptly, at first take by weighing the K colo(u)rant dispersion thing 2 of record amount among the table 6-B, propylene glycol monomethyl ether, under 24 ℃ of temperature (± 2 ℃), mix, and stirred 10 minutes with the rotating speed of 150rpm, then, take by weighing the binding agent 4 of record amount among the table 6-B, Hydroquinone monomethylether, DPHA liquid, 2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-di ethoxy carbonyl methyl) amino-3 '-bromophenyl]-the s-triazine, tensio-active agent 1A, under 25 ℃ of temperature (± 2 ℃), add successively, and the rotating speed with 150rpm stirred 30 minutes under 40 ℃ of temperature (± 2 ℃).
In addition, in the composition of table 6-B record,
* shown in K colo(u)rant dispersion thing 2 composed as follows:
(デ グ Star サ society makes carbon black, trade(brand)name: Special Black250)
13.1 mass parts
Above-mentioned pigment dispersing agent A 0.65 mass parts
Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=7,2/2 8 mol ratio, molecular weight 3.7 ten thousand) 6.72 mass parts
Propylene glycol monomethyl ether 79.53 mass parts
* consisting of of binding agent 4:
Polymkeric substance (random copolymers of methacrylic acid benzyl ester/methacrylic acid=78/22 mol ratio, molecular weight 40,000) 27 mass parts
Propylene glycol monomethyl ether 73 mass parts
* consisting of of DPHA liquid:
(contain stopper MEHQ 500ppm, Japanese chemical drug (strain) society makes dipentaerythritol acrylate, trade(brand)name: 76 mass parts KAYARAD DPHA)
Propylene glycol monomethyl ether 24 mass parts
In addition, tensio-active agent 1A is identical with tensio-active agent 1A used among the coating liquid H2 with above-mentioned thermoplastic resin.
(formation) with next door of opacifying property
For alkali-free glass substrate, on one side spray the glass cleaner 20 seconds that is adjusted to 25 ℃ with water-jet, clean with rotating brush on one side with nylon hair, after using the pure water spray Cleaning for High Capacity again, spray silane coupling solution (the 0.3 quality % aqueous solution of N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane with water-jet, trade(brand)name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) society makes) 20 seconds, and use the pure water spray Cleaning for High Capacity.This substrate was heated 2 minutes at 100 ℃ with the substrate preheating apparatus.
After the protective membrane of above-mentioned photosensitive resin transfer material K2 peeled off; with laminating machine (イ of Co., Ltd. Hitachi Application ダ ス ト リ イ ズ system (LamicII type)), be set forth in 100 ℃ down on 2 minutes the substrate of heating last in the condition laminated of 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transfer rate 2.2m/ minute.
After peeling off interim upholder, employing has the contiguous type exposure machine (manufacturing of the Ha イ テ of Hitachi Network electronics エ Application ジ ニ ア リ Application グ Co., Ltd.) of extra-high-pressure mercury vapour lamp, make substrate keep the vertical state that stands up with mask (quartzy exposed mask) with picture pattern, with the distance setting of exposed mask face and this thermoplastic resin interlayer is 200 μ m, at 100mJ/cm 2Exposure under carry out pattern exposure.Mask shape is a reticulation, is being equivalent to the part of pixel with the boundary line in the next door with opacifying property, and the radius-of-curvature that makes the protrusion angle of next door one side with opacifying property is 0.6 μ m.
Then, (contain 30% trolamine with trolamine class developing solution, trade(brand)name: T-PD2, the description Off イ of Fuji Le system Co., Ltd. makes, with the liquid after the pure water dilution 12 times (mixing with the ratio of 11 parts pure water) according to 1 part T-PD2) under 30 ℃, the condition of tack nozzle pressure 0.04MPa, spray development 50 seconds, remove thermoplastic resin and middle layer (oxygen barrier layers).
Then, (contain the sodium bicarbonate of 0.38 mol, the yellow soda ash of 0.47 mol, 5% sodium dibutyl naphthalene sulfonate, aniorfic surfactant, defoamer, stablizer with yellow soda ash class developing solution, trade(brand)name T-CD1, the description Off イ of Fuji Le system Co., Ltd. system, with the liquid after 5 times of the pure water dilutions), under 29 ℃, the condition of conical nozzle pressure 0.15MPa, spray and developed 30 seconds, resin layer with opacifying property is developed, obtain pattern portrayal next door (partition pattern) with opacifying property.
Then with clean-out system (trade(brand)name " T-SD3 (the description Off イ of Fuji Le system Co., Ltd. system) ", with the liquid after 10 times of the pure water dilutions), under 33 ℃, the condition of conical nozzle pressure 0.02MPa, sprayed 20 seconds, and remove residue with rotary brush with nylon hair, obtain having the next door of opacifying property.Then, for this substrate, use extra-high-pressure mercury vapour lamp at 500mJ/cm from this resin layer side again 2Illumination under carry out post-exposure, then 240 ℃ of following thermal treatments 50 minutes.
[plasma body is refused water treatment]
Afterwards, carry out plasma body with following method and refuse water treatment.
For the aforesaid substrate that is formed with next door, use cathode coupling formula parallel plate-type plasma processing apparatus to carry out plasma body and refuse water treatment by following condition with opacifying property.
Using gas: CF 4
Gas flow: 80sccm
Pressure: 40Pa
RF power: 50W
Treatment time: 30 seconds
[preparation of ink-jet ink for color filter]
With reference to the embodiment 1 of TOHKEMY 2002-201387 communique, by following formulation ink.
[table 6-C]
Moiety content (mass parts) R ink 1 R ink 2 R ink 3 R ink 4 R ink 5 R ink 6 G ink 1 B ink 1
Pigment dispensing composition L 49
Pigment dispensing composition M 49
Pigment dispensing composition N 49
Pigment dispensing composition O 49
Pigment dispensing composition P 49
Pigment dispensing composition Q 49
G pigment (C.I.P.G.36) 5.0
B pigment (C.I.P.B.15:6) 5.0
Macromolecule dispersing agent (ソ Le パ-ス 24000, AVECIA company makes) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Binding agent (methacrylic acid benzyl ester-Sipacril 2739OF) 4.6 4.6
Dipentaerythritol five acrylate 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Tripropylene glycol diacrylate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl propane)-1-ketone 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Diethylene Glycol single-butyl ether acetic ester, 29.9dyn/cm 39 39 39 39 39 39 81 81
Mixing about each composition among the above-mentioned table 6-C at first joins pigment and macromolecule dispersing agent in a part of solvent, mixes, and stirs with 3 roller mixing rolls and microballon shredder again, obtains dispersible pigment dispersion.On the other hand, other system component is joined in the remaining solvent, carry out stirring and dissolving and disperse, obtain binder solution.Then, Yi Bian dispersible pigment dispersion or pigment dispensing composition are added in the binder solution bit by bit, Yi Bian fully stir with dissolving machine, prepare ink-jet ink for color filter thus.
(formation of pixel)
Use the piezoelectric type shower nozzle, R ink 1, G ink 1, the B ink 1 of above-mentioned acquisition is instilled in the recess that is surrounded by the opacifying property next door at first in the following manner.The result has just obtained colour filter of the present invention by following mode.
Shower nozzle has the density of 150 nozzles to have 318 nozzles by every 25.4mm, and it is fixed in 1/2 the nozzle mode at interval that staggers on two nozzle rows directions, instils 300 at the every 25.4mm of the orientation of substrate upper edge nozzle thus.
Shower nozzle and ink are controlled, made and in shower nozzle, carry out the warm water circulation, thereby reach 50 ± 0.5 ℃ near making the ejection part.
From shower nozzle ejection ink is to control by the piezoelectric drive signal that is applied to shower nozzle, can reach every ejection 6～42pl, in the present embodiment, on one side below shower nozzle 1mm place carry glass substrate, instil with shower nozzle in one side.Transfer rate can be set at 50～200mm/s.In addition, Piezoelectric Driving frequency maximum can reach 4.6KHz, can control dropped amount by these settings.
Control transfer rate, driving frequency make that the coated weight of R, G, each pigment of B is respectively 1.1,1.8,0.75g/m 2, and to desired R, G, B corresponding concave part in instil R, G, B ink.
The ink that instils is transported to exposed portion, utilizes ultraviolet light-emitting diode (UV-LED) to expose.That UV-LED uses is day NCCU033 of inferior chemical society manufacturing.This LED is that output wavelength is the UV-light of 365nm from the wafer, utilizes the electric current of about 500mA, can send the light of about 100mW from wafer.With a plurality of LED of being spaced of 7mm, can obtain 0.3W/cm from the teeth outwards 2Power.From the back of instiling to the time of exposing, and the time shutter can change in the distance of throughput direction according to the transfer rate of medium and shower nozzle and LED.Drip fall behind in 100 ℃ dry 10 minutes down, expose then.
Setting according to distance and transfer rate can be adjusted to 0.01～15J/cm with the exposure energy on the medium 2Regulate exposure energy according to transfer rate.
In the mensuration of these exposure powers, exposure energy, the spectroradiometer URS-40D that uses ウ シ オ motor to make adopts the integrated value between the wavelength 220nm to 400nm.
Glass substrate after instiling was toasted 30 minutes in 230 ℃ baking oven, thereby make opacifying property next door, each pixel completely solidified simultaneously.
Adopt the colour filter of above-mentioned making, make liquid crystal indicator L according to the method identical with embodiment 2-11.
Adopt with making the identical method of liquid crystal indicator L and make liquid crystal indicator M～Q, difference is, the R ink 1 that is adopted when making is used for the colour filter of liquid crystal indicator L changes to R ink 2～6 respectively.
(embodiment 6-5)
The evaluation of＜ink and liquid crystal indicator 〉
(mensuration of contrast gradient)
Adopt the contrast gradient of pigment dispensing composition L～Q prepared among the method mensuration embodiment 6-1～6-4 identical and comparative example 6-1, the 6-2 with embodiment 2.
[the long-time demonstration test of liquid crystal indicator]
Make the liquid crystal indicator of making show 1000 hours continuously, in the darkroom, at distance liquid crystal indicator picture 400mm place luxmeter UV-M10-S[(strain is set) オ-Network makes manufacturing] measure the illumination (illumination that shows the light when red) of ruddiness, wherein will measure the angle and be set at 2 °.The data of the contrast gradient of the relative value before and after the test of each embodiment, comparative example (illumination before the illumination/test after the test), pigment dispensing composition are shown among the table 6-D.
As can be seen, the colour filter that adopts ink-jet ink for color filter of the present invention to make demonstrates high contrast gradient, as the colour filter of liquid crystal indicator, has and can satisfy the practical long-time demonstration tolerance that requires.
[table 6-D]
Pigment dispensing composition Ink for ink-jet print Liquid crystal indicator The contrast gradient of ink for ink-jet print Liquid crystal shows test (%) for a long time
Embodiment 6-1 L R ink 1 L 7700 100
Embodiment 6-2 M R ink 2 M 7200 101
Embodiment 6-3 N R ink 3 N 7600 100
Embodiment 6-4 O R ink 4 O 5100 102
Comparative example 6-1 P R ink 5 P 3100 109
Comparative example 6-2 Q R ink 6 Q 3800 114
(embodiment 7)
Use pigment green 36, pigment Blue 15 respectively: 6 replace employed Pigment red 254 when the preparation of the pigment dispensing composition L of embodiment 6-1, prepare pigment dispensing composition R, S thus.
Use pigment dispensing composition R, S to replace in the preparation of the liquid crystal indicator of embodiment 6-5 when preparation G ink 1, B ink 1 employed pigment PG36 and PB15:6 respectively and under the condition that does not change pigment concentration, reduce the amount of Diethylene Glycol single-butyl ether acetic ester, make G ink 2, B ink 2.Replace G ink 1, replace B ink 1 with G ink 2, make colour filter with B ink 2.Used the colour filter of G ink 2 or B ink 2 all to demonstrate good performance.
(embodiment 8)
(comparative example 8-1)
(the CCD preparation of dispersible pigment dispersion)
According to following prescription, use resulting pigment dispensing composition P among the comparative example 6-1, preparation dispersible pigment dispersion (1) ... green G, dispersible pigment dispersion (2) ... blue B, dispersible pigment dispersion (3) ... red R.
Dispersible pigment dispersion (1)
C.I.P.G.36 95 mass parts
C.I.P.G.7 30 mass parts
C.I.P.Y.139 45 mass parts
PLAAD ED151 20 mass parts
(nanmu originally changes into (strain) society and makes)
Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Propylene glycol monomethyl ether 625 mass parts
Dispersible pigment dispersion (2)
C.I.P.B.15:6 125 mass parts
C.I.P.V.23 20 mass parts
PLAAD ED151 40 mass parts
(nanmu originally changes into (strain) and makes)
Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Propylene glycol monomethyl ether 790 mass parts
Dispersible pigment dispersion (3)
Pigment dispensing composition P 600 mass parts
Macromolecular compound C-14 40 mass parts
Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Propylene glycol monomethyl ether 345 mass parts
(preparation of colored resin composition)
For each 200 mass parts of dispersible pigment dispersion of each color of above-mentioned acquisition, use stirrer and following composition uniform mixing respectively, prepare the colour filter colored resin composition that is used for each color.
＜form
Methacrylic acid benzyl ester/Sipacril 2739OF 35 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Dipentaerythritol five acrylate 38 mass parts
Propylene glycol monomethyl ether 120 mass parts
3-ethoxyl ethyl propionate 40 mass parts
Monochloromethyl triazines initiator 4 mass parts
(body ど り chemistry (strain) is made for Photoepolymerizationinitiater initiater, ProductName: TAZ107)
(making of colour filter and CCD device)
Mix following composition with stirrer, preparation planarization film resist liquid.
(composition)
Methacrylic acid benzyl ester/Sipacril 2739OF 165 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Dipentaerythritol five acrylate 65 mass parts
Propylene glycol monomethyl ether 138 mass parts
3-ethoxyl ethyl propionate 123 mass parts
Monochloromethyl triazines initiator 3 mass parts
(body ど り chemistry (strain) is made for Photoepolymerizationinitiater initiater, ProductName: TAZ107)
The planarization that obtains evenly is coated on the 6-inch silicon chip that is formed with photorectifier with the rotation coating machine with resist liquid.In addition, regulate the revolution of rotation coating machine, making and applying the thickness of back after heat-treating with electric furnace under 100 ℃ * 120 seconds conditions of coat film surface temperature is about 1.5 μ m.
Then, in 220 ℃ baking oven, placed 1 hour, coat film is solidified, form planarization film according to the mode that the photodiode surface that forms on the silicon chip is covered equally.
Then, for shades of colour, order according to G, R, B, applying with respect to above-mentioned planarization film on above-mentioned planarization film is the above-mentioned colour filter colored resin composition of 100 mass parts with resist liquid preparation prescription, and carry out that drying (prebake conditions), pattern exposure, alkali are developed, flushing, solidify dry (back baking), form the pigmentary resin tunicle, thereby made colour filter having on the silicon chip of photorectifier.
In addition, pattern exposure is the mask pattern by 2 μ m, uses i line stepping exposure machine (trade(brand)name: FPA-3000i5+, キ ヤ ノ Application (strain) is made) at 500mJ/cm 2Condition under carry out.
In addition, alkali develops and is to use organic basic developing solution (trade(brand)name: CD-2000, the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ (strain) manufacturing) the 40 quality % aqueous solution, the stirring of at room temperature carrying out 60 seconds is developed, utilize revolving distributor to carry out 20 seconds pure water rinsing then, clean with pure water again.Afterwards, blow down water droplet with high temperature air, make the substrate seasoning, obtain pattern, the back baking of implementing 5 minutes with the condition of 200 ℃ of surface temperatures on electric furnace is handled then.
On digital camera, install by the CCD device that obtains with upper type, under same light source, the colour chart that has KODAK system gray scale photographed, on watch-dog during observable image, observe image rock and red inhomogeneous.
(embodiment 8-1)
According to making the CCD device with the identical mode of comparative example 8-1, difference is, replace the pigment dispensing composition P that uses among the comparative example 8-1 with pigment dispensing composition L, this CCD device is installed on the digital camera, carry out same evaluation, the result has obtained rocking less and having the image of uniform smooth color.In addition, when promptly using the pigment dispensing composition P that pigment dispensing composition M～O replaces using among the comparative example 8-1, also can confirm to have obtained equally to rock few image.
The embodiment of the macromolecular compound that (embodiment 9) use phthalocyanine compound pigment and general formula (1) are represented
(embodiment 9-1)
The preparation of＜pigment dispensing composition GL 〉
[preparation of dispersible pigment dispersion]
In 800mL dimethyl sulfoxide (DMSO) (making), add with the pure medicine of light society 20.0mL 28% methanol solution of sodium methylate, 30g pigment C.I. pigment green 36 (イ Application キ Co., Ltd. in trade(brand)name Lionol Green 6YK East ocean makes), reach 70.0g polyvinylpyrrolidone (trade(brand)name K-30, make with the pure medicine of light society), be mixed with pigment solution GL.Use viscometer VM-10A-L (trade(brand)name, CBC マ テ リ ア Le ズ society makes) to measure the viscosity of this pigment solution GL, the result shows that the viscosity when the liquid temperature of pigment solution GL is 22.0 ℃ is 15.0mPas.In addition, prepare to contain the water 800mL of the 1mol/L hydrochloric acid (making) of 12mL, as poor solvent with the pure medicine of light society.
At this moment, temperature is controlled to be 22 ℃, to utilizing GK-0222-10 type ラ モ Application De ス -ラ-(trade(brand)name, Fujisawa Pharmaceutical Co., Ltd makes) among poor solvent-water 800mL of stirring with the rotating speed of 500rpm, with NP-KX-500 type large vol pulseless pump (trade(brand)name, the manufacturing of Japan precision chemical society) flow velocity by 100mL/min is the pigment solution GL of the liquid-transport pipe-line injection 100ml of 0.8mm by the fluid passage diameter, form organic pigment particles thus, thereby prepare dispersible pigment dispersion GL.Use Na ノ ト ラ Star Network UPA-EX150 (trade(brand)name, day machine dress society makes) to measure number average bead diameter Mn and single dispersity (Mv/Mn) of this dispersible pigment dispersion, the result is shown in following table 9-A.
The H-110A type centrifugal filter that utilizes the manufacturing of (strain) コ Network サ Application society is Ji the P89C type filter cloth that Fu Island カ Application バ ス (strain) society makes, to concentrate 160 minutes with the rotating speed of 3000rpm by the prepared pigment nanoparticle dispersion liquid of aforesaid method, and resulting pigment nanoparticle be concentrated to stick with paste reclaim.
Utilize the pigment content of 8453 these mashed prod of type spectrophotometric determination of ア ジ レ Application ト (Agilent) company manufacturing, the result is 14.0 weight %.
In the 50.0cc ethyl lactate, add method synthetic pigment dispersing agent A, the 2.3g macromolecular compound C-1 of 0.2g according to TOHKEMY 2000-239554 communique, obtain solution, this solution is joined in the above-mentioned pigment nanoparticle preparation of the 16.0g paste, after adopting dissolving machine to stir 60 minutes with the speed of 1500rpm, the FP-010 type filter that utilizes the Off ァ イ of Sumitomo Electric Industries Application Port リ マ Co., Ltd. to produce filters, and obtains the concentrated pigment liquid GL (concentration of nano dye is 33.5 quality %) of pasty state thus.
[preparation of pigment dispensing composition GL]
Use above-mentioned mashed prod, preparation has the pigment dispensing composition GL of following composition.
The concentrated pigment liquid GL 19.2g of above-mentioned pasty state
1,3 butylene glycol diacetate esters 45.1g
Utilize electronic mill M-50 (manufacturing of ア イ ガ one ジ ヤ パ Application society) and use the zirconium white microballon of diameter as 0.65mm, under the condition of circumferential speed 9m/s, the color compositions that will have above-mentioned composition disperseed 1 hour.
(embodiment 9-2)
The preparation of＜pigment dispensing composition GM 〉
Adopt the method identical to prepare pigment dispensing composition GM with embodiment 9-1, difference is, the fluid passage diameter of employed liquid-transport pipe-line changes to 0.25mm when injecting described pigment solution GL among the embodiment 9-1, and will inject flow velocity and change to 8mL/min.Adopt the method identical to measure number average bead diameter and the single dispersity of the dispersible pigment dispersion GM for preparing with embodiment 9-1.
(embodiment 9-3)
The preparation of＜pigment dispensing composition GN 〉
Adopt the method identical to prepare pigment dispensing composition GN with embodiment 9-1, difference is, the fluid passage diameter of employed liquid-transport pipe-line changes to 2.20mm when injecting described pigment solution GL among the embodiment 9-1, and will inject flow velocity and change to 400mL/min.Adopt the method identical to measure number average bead diameter and the single dispersity of the dispersible pigment dispersion GN for preparing with embodiment 9-1.
(embodiment 9-4)
The preparation of＜pigment dispensing composition GO 〉
Adopt the method identical to prepare pigment dispensing composition GO with embodiment 9-1, difference is, employed macromolecular compound C-1 changes to methacrylic acid/benzyl methacrylate multipolymer (mol ratio 28/72 of 5.75g in the time of will preparing the colo(u)rant dispersion thing in embodiment 9-1, matter average molecular weight 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution), addition with the 1,3 butylene glycol diacetate esters changes to 40.45g in addition.
(comparative example 9-1)
The preparation of＜pigment dispensing composition GP 〉
In the following manner, use microballon to grind the pigment dispensing composition GP that dispersal mechanism is got everything ready and is made up of following.
Pigment (pigment green 36) 6.43g
Pigment dispersing agent A 0.26g
Polyvinylpyrrolidone 7.10g
Methacrylic acid/benzyl methacrylate multipolymer * 14.9g
(the * mol ratio is 28/72, the matter average molecular weight: 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution)
1,3 butylene glycol diacetate esters 35.80g
(comparative example 9-2)
The preparation of＜pigment dispensing composition GQ 〉
In the following manner, preparation has the pigment dispensing composition GQ of following composition.
Pigment (pigment green 36) 6.43g
Sodium-chlor 64.0g
Methacrylic acid/benzyl methacrylate multipolymer * 14.9g
* mol ratio is 28/72, the matter average molecular weight: 30,000,40% 1-methoxyl group-2-propyl-acetic acid ester solution
In 1,3 butylene glycol diacetate esters liquid, add sodium-chlor, pigment (pigment green 36) powder, methacrylic acid/benzyl methacrylate multipolymer, then it is joined in the twin screw kneader, descended mixing 10 hours at 80 ℃.After mixing, said mixture is joined in 80 ℃ 1% aqueous hydrochloric acid of 500 weight parts, stir after 1 hour, filter, use hot wash, drying is pulverized, add the ratio interpolation 1,3 butylene glycol diacetate esters and the mixing of the 1,3 butylene glycol diacetate esters of 2.4g then according to every 1g crushed material.Adopt electronic mill M-50 (manufacturing of ア イ ガ one ジ ヤ パ Application society) and use the zirconium white microballon of diameter, under the condition of circumferential speed 9m/s, above-mentioned color compositions was disperseed 1 hour, obtain pigment dispensing composition GQ as 0.65mm.
Particle diameter, single dispersity to resulting pigment dispensing composition among embodiment 9-1～9-4 and comparative example 9-1, the 9-2 are measured, and the result is shown in following table 9-A.
[table 9-A]
Number average bead diameter (Mn) Single dispersity (Mv/Mn)
Embodiment 9-1 30.3 1.29
Embodiment 9-2 46.2 1.54
Embodiment 9-3 27.5 1.33
Embodiment 9-4 39.5 1.46
Comparative example 9-1 96.4 1.75
Comparative example 9-2 72.2 2.83
(embodiment 9-5)
The making of＜liquid crystal indicator 〉
(embodiment 9-5)
The evaluation of＜ink and liquid crystal indicator 〉
Adopt the method identical to prepare colour filter with embodiment 6, and further prepare liquid crystal indicator, difference is, use pigment dispensing composition GL～GQ to come pigment dispensing composition L～Q among the substitution list 6-C, and use common C.I.P.R254 to prepare the R ink with preparation G ink 11～16.But, use G1220DUN (trade(brand)name, day eastern electrician (strain) society makes) to replace employed polaroid HLC2-2518 among the embodiment 2.
[liquid-crystal display performance test]
For the display performance of the liquid crystal indicator of made,, estimate according to 10 people groups from black density and the green angle of describing power.Estimate according to following 5 levels, the mean value of 10 people's evaluation result is shown in table 9-D.As can be seen, with respect to comparative example GP, GQ, liquid crystal watch showing device GL～GO of the present invention demonstrates the excellent display performance of absolute predominance.
5: black density and green are described power all excellent (very good)
4: black density and green are described power all no problem (good)
3: black has grey color sensation a little, and perhaps green is described power inadequate slightly (generally)
2: can obviously find black and the green level (poor slightly) that all is in than cathode-ray tube TV difference
1: black and green color reprodubility all very poor (non-constant)
[table 9-D]
Pigment dispensing composition Ink for ink-jet print Liquid crystal indicator The contrast gradient of ink for ink-jet print The liquid-crystal display performance
Embodiment 9-1 GL G ink 11 GL 8200 5.0
Embodiment 9-2 GM G ink 12 GM 7100 4.7
Embodiment 9-3 GN G ink 13 GN 7500 4.8
Embodiment 9-4 GO G ink 14 GO 4600 4.5
Comparative example 9-1 GP G ink 15 GP 3300 3.1
Comparative example 9-2 GQ G ink 16 GQ 3000 2.2
(embodiment 10)
(comparative example 10-1)
(the CCD preparation of dispersible pigment dispersion)
According to following prescription, use the pigment dispensing composition GP that obtains among the comparative example 9-1, preparation dispersible pigment dispersion (4) ... green G, dispersible pigment dispersion (5) ... blue B, dispersible pigment dispersion (6) ... red R.
Dispersible pigment dispersion (4)
Pigment dispensing composition GP 800 mass parts
C.I.P.G.7 30 mass parts
C.I.P.Y.139 45 mass parts
PLAAD ED151 20 mass parts
(nanmu originally changes into (strain) society and makes)
Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Propylene glycol monomethyl ether 125 mass parts
Dispersible pigment dispersion (5)
C.I.P.B.15:6 125 mass parts
C.I.P.V.23 20 mass parts
PLAAD ED151 40 mass parts
(nanmu originally changes into (strain) and makes)
Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Propylene glycol monomethyl ether 790 mass parts
Dispersible pigment dispersion (6)
C.I.P.R.254 80 mass parts
C.I.P.Y.139 20 mass parts
PLAAD ED472 45 mass parts
Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Propylene glycol monomethyl ether 820 mass parts
(preparation of colored resin composition)
For each 200 mass parts of dispersible pigment dispersion of each color of above-mentioned acquisition, use stirrer and following composition uniform mixing respectively, prepare the colour filter colored resin composition that is used for each color.
＜form
Methacrylic acid benzyl ester/Sipacril 2739OF 35 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Dipentaerythritol five acrylate 38 mass parts
Propylene glycol monomethyl ether 120 mass parts
3-ethoxyl ethyl propionate 40 mass parts
Monochloromethyl triazines initiator 4 mass parts
(body ど り chemistry (strain) is made for Photoepolymerizationinitiater initiater, ProductName: TAZ107)
(making of colour filter and CCD device)
Mix following composition with stirrer, preparation planarization film resist liquid.
＜form
Methacrylic acid benzyl ester/Sipacril 2739OF 165 mass parts
(copolymerization mol ratio 70:30, matter average molecular weight 30,000)
Dipentaerythritol five acrylate 65 mass parts
Propylene glycol monomethyl ether 138 mass parts
3-ethoxyl ethyl propionate 123 mass parts
Monochloromethyl triazines initiator 3 mass parts
(body ど り chemistry (strain) is made for Photoepolymerizationinitiater initiater, ProductName: TAZ107)
The planarization that obtains evenly is coated on the 6-inch silicon chip that is formed with photorectifier with the rotation coating machine with resist liquid.In addition, regulate the revolution of rotation coating machine, making and applying the thickness of back after heat-treating with electric furnace under 100 ℃ * 120 seconds conditions of coat film surface temperature is about 1.5 μ m.
Then, in 220 ℃ baking oven, placed 1 hour, coat film is solidified, form planarization film according to the mode that the photodiode surface that forms on the silicon chip is covered equally.
Then, for each color, order according to G, R, B, applying with respect to above-mentioned planarization film on above-mentioned planarization film is the above-mentioned colour filter colored resin composition of 100 mass parts with resist liquid preparation prescription, and carry out that drying (prebake conditions), pattern exposure, alkali are developed, flushing, solidify dry (back baking), form the pigmentary resin tunicle, thereby made colour filter having on the silicon chip of photorectifier.
In addition, pattern exposure is the mask pattern by 2 μ m, uses i line stepping exposure machine (trade(brand)name: FPA-3000i5+, キ ヤ ノ Application (strain) is made) at 500mJ/cm 2Condition under carry out.
In addition, when developing, uses in alkali organic basic developing solution (trade(brand)name: CD-2000, the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ (strain) manufacturing) the 40 quality % aqueous solution, the stirring of at room temperature carrying out 60 seconds is developed, utilize revolving distributor to carry out 20 seconds pure water rinsing then, clean with pure water again.Afterwards, blow down water droplet, make the substrate seasoning, obtain pattern, on electric furnace, implement the back baking then and handle with 200 ℃ of conditions of 5 minutes of surface temperature with high temperature air.
To be installed on the digital camera according to the CCD device that obtains with upper type, under same light source, the colour chart that has KODAK system gray scale be photographed, on watch-dog during observable image, observe image rock and red inhomogeneous.
(embodiment 10-1)
According to making the CCD device with the identical mode of comparative example 10-1, difference is, replace the pigment dispensing composition GP that in comparative example 10-1, uses with pigment dispensing composition GL, this CCD device is installed on the digital camera, carry out and above-mentioned same evaluation, the result has obtained rocking less and having the image of uniform smooth color.In addition, promptly use pigment dispensing composition GM～GO to replace the pigment dispensing composition GP that in comparative example 10-1, uses, also can confirm to have obtained equally to rock few image.
Industrial usability
The organic fine particles that adopts manufacture method of the present invention to obtain is nano-scale and is monodispersity, can bring into play excellent optical when being used for colour filter, is applicable to liquid crystal indicator and CCD device.
Though describe the present invention by embodiment, but, short of specifying, we are not on any one details that will limit the invention in this specification sheets, only otherwise violate the represented spirit and scope of scope of the claims of enclosing, can explain widely the present invention.
The application requires the Japanese patent application 2006-055274 that submits in the Japanese patent application 2006-014399 that submitted on January 23rd, 2006, the Japanese patent application 2006-024630 of submission on February 1st, 2006, on March 1st, 2006, the right of priority that reaches these applications of Japanese patent application 2006-129714 of submitting on May 8th, 2006, they all in this application as a reference, and its content is incorporated this paper into way of reference.

Claims (36)

1. the manufacture method of an organic nano particle, it is characterized in that, the solution that will be dissolved in organic materials in the good solvent and form, with can be with described good solvent miscible and be that the solvent phase of poor solvent mixes to described organic materials, make described organic materials separate out generation, thereby make the dispersion liquid of the organic fine particles of nano-scale, wherein, in this dispersion liquid, contain the represented matter average molecular weight of following general formula (1) and be the macromolecular compound more than 1000
Figure A200680053947C00021
General formula (1)
In the formula, R 1The connection base of expression (m+n) valency; R 2The connection base of expression singly-bound or divalent; A 1Expression has 1 valency organic group of the group of selecting from acidic-group, the basic group that contains nitrogen-atoms, urea groups, urethano, the group that contains the coordination Sauerstoffatom, carbonatoms are alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and hydroxyl 4 or more, or represents to contain to have substituent organic pigment structure or heterocyclic 1 valency organic group; Wherein, n A 1Mutually can be identical, also can be different; M represents 1～8 number, and n represents 2～9 number, and m+n equals 3～10; P 1Expression macromolecular compound residue.
2. the manufacture method of the described organic nano particle of claim 1 is characterized in that, described macromolecular compound is with following general formula (2) expression,
General formula (2)
In the formula, R 3The connection base of expression (x+y) valency; R 4And R 5The linking group of representing singly-bound or divalent independently of one another; A 2Expression has 1 valency organic group of the group of selecting from acidic-group, the basic group that contains nitrogen-atoms, urea groups, urethano, the group that contains the coordination Sauerstoffatom, carbonatoms are alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and hydroxyl 4 or more, or represents to contain to have substituent organic pigment structure or heterocyclic 1 valency organic group; Wherein, x A 2Mutually can be identical, also can be different; Y represents 1～8 number, and x represents 2～9 number, and x+y equals 3～10; P 2Expression macromolecular compound residue.
3. the manufacture method of claim 1 or 2 described organic nano particles is characterized in that, described A 1Perhaps described A 2For having 1 valency organic group of the group in basic group, urea groups and the alkyl of carbonatoms more than 4 that is selected from acidic-group, contains nitrogen-atoms.
4. the manufacture method of any described organic nano particle in the claim 1～3 is characterized in that, described P 1Perhaps described P 2Represented macromolecular compound residue is served as reasons and is selected from down at least a macromolecular compound deutero-residue in the group, and described group is made of polymer of vinyl monomer or multipolymer, ester cpds polymkeric substance, ether compound polymkeric substance, urethanes polymkeric substance, amide compound polymkeric substance, synthesis of epoxy compounds thing, polymerizable organosilicon compound thing and their modifier and multipolymer.
5. the manufacture method of an organic nano particle, it is characterized in that, will be in good solvent and the pigment dyestuff solution that forms pyrrolopyrrole compound pigment dissolved, with can be with described good solvent miscible and solvent phase that be poor solvent to described pyrrolopyrrole compound pigment mix, make described pigment dyestuff separate out the organic fine particles that generates nano-scale, thereby make the dispersion liquid of the organic fine particles of nano-scale, wherein, containing the matter average molecular weight in this dispersion liquid is macromolecular compound more than 1000.
6. the manufacture method of any described organic nano particle in the claim 1～4 is characterized in that, described organic nano particle is a pyrrolopyrrole compound pigment.
7. the manufacture method of claim 5 or 6 described organic nano particles is characterized in that, described pyrrolopyrrole compound pigment is the following represented pigment of formula V,
Figure A200680053947C00031
8. the manufacture method of claim 5 or 6 described organic nano particles is characterized in that, described pyrrolopyrrole compound pigment is the represented pigment of following formula (Z),
Figure A200680053947C00041
9. the manufacture method of any described organic nano particle in the claim 5 or 6 is characterized in that, described pyrrolopyrrole compound pigment is the represented pigment of following formula (W),
10. the manufacture method of an organic nano particle, it is characterized in that, with Ba the dioxazine compound pigment dissolved in good solvent and the pigment dyestuff solution that forms, with can be with described good solvent miscible and solvent phase that be poor solvent to described dioxazine compound pigment mix, make described pigment dyestuff separate out generation, thereby make the dispersion liquid of the organic fine particles of nano-scale, wherein, in this dispersion liquid, contain the matter average molecular weight and be the macromolecular compound more than 1000.
11. the manufacture method of any described organic nano particle is characterized in that in the claim 1～4, described organic nano particle Wei dioxazine compound pigment.
12. the manufacture method of claim 10 or 11 described organic nano particles is characterized in that, described dioxazine compound pigment is C.I. pigment violet 37.
13. the manufacture method of claim 10 or 11 described organic nano particles is characterized in that, described dioxazine compound pigment is the C.I. pigment Violet 23.
14. the manufacture method of an organic nano particle, it is characterized in that, will be in good solvent and the pigment dyestuff solution that forms the phthalocyanine compound pigment dissolved, with can be with described good solvent miscible and solvent phase that be poor solvent to described phthalocyanine compound pigment mix, make described pigment dyestuff separate out the organic fine particles that generates nano-scale, thereby make the dispersion liquid of the organic fine particles of nano-scale, wherein, in this dispersion liquid, contain the matter average molecular weight and be the macromolecular compound more than 1000.
15. the manufacture method of any described organic nano particle is characterized in that in the claim 1～4, described organic nano particle is a phthalocyanine compound pigment.
16. the manufacture method of claim 14 or 15 described organic nano particles is characterized in that, described phthalocyanine compound pigment is the C.I. pigment Green 7.
17. the manufacture method of claim 14 or 15 described organic nano particles is characterized in that, described phthalocyanine compound pigment is the C.I. pigment green 36.
18. the manufacture method of claim 14 or 15 described organic nano particles is characterized in that, described phthalocyanine compound pigment is C.I. Pigment green 15: 6.
19. the manufacture method of any described organic nano particle is characterized in that in the claim 1～18, and described dispersion liquid is concentrated.
20. the manufacture method of any described organic nano particle is characterized in that in the claim 1～19, described macromolecular compound is the macromolecular compound with acidic-group.
21. the manufacture method of any described organic nano particle is characterized in that in the claim 1～20, the acidic-group of described macromolecular compound is a carboxyl.
22. the manufacture method of any described organic nano particle is characterized in that in the claim 1～21, the matter average molecular weight of described macromolecular compound is 3000～100000.
23. the manufacture method of any described organic nano particle is characterized in that in the claim 1～22, in dispersion liquid during the described organic nano particle of preparation, all has in any one operation and has amino pigment dispersing agent.
24. the manufacture method of any described organic nano particle in the claim 1～23, it is characterized in that, in dispersion liquid during the described organic nano particle of preparation, described dispersion liquid contains in a kind of general formula (D1), (D3) and the formula (D4) the represented compound of the same form arbitrarily at least
General formula (D1)
A—N＝N—X—Y
In general formula (D1), the common expression of A and X-Y can form the composition of azopigment, X represent singly-bound or be selected from following formula (i)～(divalent linker shown in the structural formula v), Y are represented the group shown in the following general formula (D2),
Figure A200680053947C00061
(ii) formula is (iii) for formula (i) formula
Figure A200680053947C00062
(iv) formula is (v) for formula
General formula (D2)
Figure A200680053947C00063
In general formula (D2), Z represents low-grade alkylidene ,-NR 21Expression low-grade alkyl amino or contain 5～6 yuan of saturated heterocyclyls of nitrogen-atoms, a represents 1 or 2,
General formula (D3)
Figure A200680053947C00064
In general formula (D3), Q represents to be selected from the organic pigment residue in anthraquinone compounds pigment, azo-compound pigment, phthalocyanine compound pigment, quinoline a word used for translation ketone compound pigment, dioxazine compound pigment, anthracene pyrimidine compound pigment, anthanthrone compound pigment, indanthrone compound pigment, yellow anthrone compound pigment, pyranthrone compound pigment, perylene ketone compound pigment, perylene compound pigment and the thioindigo compound pigment; X 1Expression-CONH-Y 2-,-SO 2NH-Y 2-or-CH 2NHCOCH 2NH-Y 2-; Y 2Expression can have substituent alkylidene group or arylidene; R 11And R 12Expression independently of one another replaces or unsubstituted alkyl, or R 11And R 12Lump together and to form the heterocyclic radical that contains nitrogen-atoms at least; Y 1Expression-NH-or-O-; Z 1Group shown in expression hydroxyl or the general formula (D3a) is 1 o'clock Z at n1 still 1Can be-NH-X 1-Q; M1 represents 1～6 integer, and n1 represents 1～4 integer,
General formula (D3a)
Figure A200680053947C00071
In general formula (D3a), Y 3Expression-NH-or-O-, m1, R 11And R 12It is identical with its implication in general formula (D3),
Formula (D4)
A:b:c=15:20:65 (weight ratio)
In formula (D4), Me represents methyl.
25. the manufacture method of any described organic nano particle in the claim 1～24, it is characterized in that the poor solvent of described organic materials is aqueous solvent, alkylol cpd solvent, ketone compound solvent, ether compound solvent, ester cpds solvent or their mixture.
26. the manufacture method of any described organic nano particle in the claim 1～25, it is characterized in that the good solvent of described organic materials is aqueous solvent, alkylol cpd solvent, ketone compound solvent, ether compound solvent, sulfoxide compound solvent, ester cpds solvent, amide compound solvent or their mixture.
27. the manufacture method of any described organic nano particle in the claim 1～26, it is characterized in that, in dispersion liquid during the described organic fine particles of preparation, described organic material solution is mixed mutually with poor solvent, organic fine particles is separated out, after it is concentrated, add described macromolecular compound, thereby obtain the concentrated dispersion liquid of organic fine particles.
28. the manufacture method of any described organic nano particle in the claim 1～27, it is characterized in that, when described organic material solution and poor solvent being mixed mutually, in the described poor solvent of the above scale of 10L, generate described particulate with the generation organic fine particles.
29. adopt any organic nano particle that described method is made in the claim 1～28.
30. an ink-jet ink for color filter is characterized in that, is in the medium that contains polymerizable monomer and/or polyreactive oligomers, contains the described organic nano particle of claim 29 and forms.
31. a photosensitive composition is characterized in that, contains the described organic nano particle of claim 29, binding agent, monomer or oligopolymer, Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system at least.
32. a photosensitive resin transfer material is characterized in that, is provided with the photo-sensitive resin that contains the described photosensitive composition of claim 31 at least on interim upholder.
33. a colour filter is characterized in that, is to use the described photosensitive resin transfer material of the described ink for ink-jet print of claim 30, the described photosensitive composition of claim 31 and/or claim 32 to make.
34. a liquid crystal indicator is characterized in that, possesses the described colour filter of claim 33.
35. the described liquid crystal indicator of claim 34 is characterized in that, described display unit is the VA standard.
36. a CCD device is characterized in that, possesses the described colour filter of claim 33.
CNA2006800539472A 2006-01-23 2006-11-08 Process for producing organic nanoparticle, organic nanoparticle obtained by the same, ink-jet ink for color filter containing the same, colored photosensitive resin composition, photosensitive resin Pending CN101400742A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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CN102472964A (en) * 2009-09-29 2012-05-23 东丽株式会社 Positive photosensitive resin composition, cured film obtained using same, and optical device
CN102676159A (en) * 2012-05-25 2012-09-19 南京邮电大学 White-light nano particle preparation method
CN105722895A (en) * 2014-06-13 2016-06-29 Lg化学株式会社 Polymer particle, method for manufacturing same, and battery separator film comprising same
CN110658581A (en) * 2019-08-20 2020-01-07 深圳市融光纳米科技有限公司 Color filter, nano color filter crystal and coating

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102472964A (en) * 2009-09-29 2012-05-23 东丽株式会社 Positive photosensitive resin composition, cured film obtained using same, and optical device
CN102472964B (en) * 2009-09-29 2013-08-07 东丽株式会社 Positive photosensitive resin composition, cured film obtained using same, and optical device
CN102676159A (en) * 2012-05-25 2012-09-19 南京邮电大学 White-light nano particle preparation method
CN105722895A (en) * 2014-06-13 2016-06-29 Lg化学株式会社 Polymer particle, method for manufacturing same, and battery separator film comprising same
CN105722895B (en) * 2014-06-13 2018-08-28 Lg化学株式会社 Polymer particle, preparation method, and the battery diaphragm comprising the polymer particle
US10287404B2 (en) 2014-06-13 2019-05-14 Lg Chem, Ltd. Polymer particle, manufacturing method thereof, and separator for battery comprising the same
CN110658581A (en) * 2019-08-20 2020-01-07 深圳市融光纳米科技有限公司 Color filter, nano color filter crystal and coating
CN110658581B (en) * 2019-08-20 2022-04-15 宁波融光纳米科技有限公司 Color filter, nano color filter crystal and coating

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