CN101081941A - Organic nano particle and dispersive combination, photo-sensitive resin combination, trans-printing material, filter, liquid display device and CCD device - Google Patents

Abstract

The invention provides organic nanometer particles with nanometer dimension and sharp size distribution peak and with stability and organic nm particle dispersion combination with good stability, dispersibility and fluidity and color filter formed by the said particles with high contrast and excellent display character, and liquid crystal display device and CCD device, and color light-sensitive resin combination and light-sensitive resin transferal material. The said organic nanometer particles are constituted of organic material, with number-average grainsize of below 50nm and (volume-average grainsize)/(number-average grainsize) of 1.0~2.0.

Description

Organic nano particle and dispersive composition thereof, photosensitive polymer combination, transfer materials, colour filter, liquid crystal indicator and CCD device

Technical field

The present invention relates to organic nano particle and dispersive composition thereof by reprecipitation method formation; In addition, the invention still further relates to the photosensitive composition and the photosensitive resin transfer material that contain them, and colour filter, liquid crystal indicator and the CCD device with distinct tone, high tinting strength and high-contrast that form with their.

Background technology

Pigment has distinct tone, high tinting strength, photostabilization etc., has obtained in a lot of fields using widely.In these pigment, important in practicality is minuteness particle usually mostly.This is to attempt to obtain the distinct high tinting strength of color harmony by preventing that the miniaturization of pigment agglutinative from handling.But if by the physical method of for example salt mill and so on pigment is carried out the miniaturization processing, then dispersible pigment dispersion often demonstrates high viscosity.Therefore, when preparing this dispersible pigment dispersion, just be difficult to from dispersion machine, take out this dispersible pigment dispersion, maybe can not utilize pipeline to carry, and in storing gelation can take place with technical scale.

Obtain the dispersible pigment dispersion or the coloring photosensitive combination of flowability, excellent dispersion in order to improve these problems, be known that pigment dyestuff (is for example carried out surface treatment, referring to patent documentation 1 and 2), or use various dispersion agents (for example, referring to patent documentation 3 and 4).In addition, thus also addressed in patent documentation 5 and 6 and to have adopted the sample that will be dissolved in good solvent to inject the method that poor solvent obtains the reprecipitation method of particle.

These pigment are being used to form when for example using the rendered image that coloring photosensitive combination obtains, the layer that is formed by coloring photosensitive combination requires as thin as a wafer usually, and requires than showing the brilliant idea depth of shade under the minimal thickness.Therefore, just pigment dyestuff for example need be dispersed in the organic solvent with the state of height miniaturization or evenly miniaturization.But, the colo(u)rant dispersion thing and the composition thereof with performances such as excellent dispersiveness, flowabilities that can satisfy these requirements also are not provided at present.

On the other hand, with C.I.P.R.254 the absorption region that the pyrrolopyrrole class pigment of representative has the purity of color that is suitable for improving the red pixel that constitutes colour filter, can enlarge the color reproduction zone.Therefore, this pigment is attempted being used for colour filter.But pigment does not in the past satisfy the requirement of purity of color and contrast gradient etc.In addition, situation about confirming according to the inventor with regard to the ink for ink-jet print of record in the patent documentation 6, with regard to microballon disperses or salt mill method obtains material etc., can not obtain good colour filter.

[patent documentation 1] Japanese kokai publication hei 11-269401 communique

[patent documentation 2] Japanese kokai publication hei 11-302553 communique

[patent documentation 3] Japanese kokai publication hei 8-48890 communique

[patent documentation 4] TOHKEMY 2000-239554 communique

[patent documentation 5] TOHKEMY 2004-123853 communique

[patent documentation 6] TOHKEMY 2003-336001 communique

Summary of the invention

Invent problem to be solved

The purpose of this invention is to provide and have the sharp-pointed organic nano particle of nano-scale and size distribution peak, have stability and good dispersiveness, mobile organic nano particle dispersive composition, and the photosensitive composition and the photosensitive resin transfer material that contain them.And the present invention also aims to provide can be by its colour filter of making that has high-contrast and given play to excellent display characteristic, and with the liquid crystal indicator and the CCD device of its formation.

The means of dealing with problems

Address the above problem by following means.

(1) organic nano particle is characterized in that being made of organic materials, and number average bead diameter is below the 50nm, and (volume average particle size)/(number average bead diameter) is 1.0～2.0.

(2) above the organic nano particle described in (1) is characterized in that described organic materials is a pigment dyestuff.

(3) above the organic nano particle described in (2) is characterized in that described pigment dyestuff is selected from azo class pigment, phthalocyanine pigment, quinoline a word used for translation ketone pigment, indoline-like pigment, cyanine class pigment, merocyanine class pigment, fullerene pigment, Ppolynuclear aromatic class pigment and poly-diacetylene class pigment.

(4) above the organic nano particle described in (2) or (3) is characterized in that described pigment dyestuff is redness or purple pigment dyestuff.

(5) above the organic nano particle described in (4) is characterized in that described pigment dyestuff is a pyrrolopyrrole class pigment.

(6) above the organic nano particle described in (5) is characterized in that described pyrrolopyrrole class pigment is the diketopyrrolo-pyrrole pigment with following formula (Z) expression.

Formula (Z)

(7) above the organic nano particle described in (5) is characterized in that described pyrrolopyrrole class pigment is the diketopyrrolo-pyrrole pigment with following formula (W) expression.

Formula (W)

(8) above the organic nano particle described in (5) is characterized in that described pyrrolopyrrole class pigment is the diketopyrrolo-pyrrole pigment of representing with following formula V.

Formula V

(9) above the organic nano particle described in (4) is characterized in that described pigment dyestuff Shi dioxazines pigment.

(10) above the organic nano particle described in (9) is characterized in that described dioxazines pigment is C.I. pigment violet 37.

(11) above the organic nano particle described in (9) is characterized in that described dioxazines pigment is the C.I. pigment Violet 23.

(12) above each described organic nano particle in (1)～(11), it is characterized in that it being solution by will being dissolved in the described organic materials in the good solvent and miscible with described good solvent and be that the solvent of poor solvent mixes and prepares for described organic materials.

(13) above the organic nano particle described in (12) is characterized in that the poor solvent of described organic materials is selected from water kind solvent, alcoholic solvent, ketones solvent, ether solvent, sulfoxide kind solvent, esters solvent, and their mixture.

(14) above the organic nano particle described in (12) or (13), the good solvent that it is characterized in that described organic materials is selected from water kind solvent, alcoholic solvent, ketones solvent, ether solvent, sulfoxide kind solvent, esters solvent, amide solvent, and their mixture.

(15) organic nano particle dispersive composition, it is characterized in that containing above (1)～(11) in each described organic nano particle and quality molecular-weight average be macromolecular compound more than 1000.

(16) above the organic nano particle dispersive composition described in (15) is characterized in that described macromolecular compound with following general formula (1) expression,

(A ¹-R ² _nR ¹ P ¹) _mGeneral 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 ¹It is 1 valency organic group of the group selected alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl 4 or more that expression has from group, urea groups, urethano, the group of band coordination Sauerstoffatom, the carbon number of acidic-group, band basic nitrogen atom, 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; P ¹Expression macromolecular compound residue; M represents 1～8 number, and n represents 2～9 number, and m+n equals 3～10.

(17) above the organic nano particle dispersive composition described in (15) or (16) is characterized in that described organic nano particle dispersive composition is an ink for ink-jet print.

(18) a kind of photosensitive composition, it contains above in (1) to (14) each described organic nano particle dispersive composition, binding agent and monomer or oligopolymer in each described organic nano particle or (15) to (17) at least, and Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.

(19) a kind of photosensitive resin transfer material is characterized in that, interim upholder is provided with the photo-sensitive resin that contains above the photosensitive composition described in (18).

(20) colour filter is characterized in that this colour filter is to use above the photosensitive resin transfer material described in the photosensitive composition described in (18) or (19) to make.

(21) liquid crystal indicator is characterized in that this liquid crystal indicator possesses above the colour filter described in (20).

(22) above the liquid crystal indicator described in (21) is characterized in that described display unit is the VA mode.

(23) CCD device is characterized in that this CCD device possesses above the colour filter described in (22).

The invention effect

Organic nano particle of the present invention has reached and has had nano-scale and the sharp-pointed excellent effect of size distribution.In addition, organic nano particle dispersive composition of the present invention and use the ink for ink-jet print of said composition to reach to have stability and good dispersiveness, the excellent effect of flowability.Organic nano particle of the present invention and dispersive composition thereof and use the ink for ink-jet print of this dispersive composition thermal thermocoagulation can not occur being subjected to can be controlled the particle diameter of nanoparticle under the situation that does not make the monodispersity variation.Photosensitive composition of the present invention and photosensitive resin transfer material and use the ink for ink-jet print of dispersive composition of the present invention to have high-contrast.In addition, by using these photosensitive compositions and photosensitive resin transfer material or ink for ink-jet print, can provide the colour filter of having given play to excellent display characteristic.In addition, by using them, can provide the liquid crystal indicator and the CCD device that have high-contrast and given play to excellent display characteristic.

Description of drawings

[Fig. 1] is the sectional drawing that summary shows the preferred embodiment of the manufacturing installation that uses in the organic nano particle manufacturing of the present invention.

[Fig. 2] is the sectional drawing that summary shows another preferred embodiment of the manufacturing installation that uses in the organic nano particle manufacturing of the present invention.

[Fig. 3] is the mixing section at an embodiment of manufacturing installation shown in Figure 2, carries out the sectional drawing of the amplifier section of summary demonstration according to a part of section.

[Fig. 4] is the mixing section at another embodiment of manufacturing installation shown in Figure 2, carries out the sectional drawing of the amplifier section of summary demonstration according to a part of section.

[Fig. 5] is the sectional drawing that summary shows the another preferred implementation of the manufacturing installation that uses in the organic nano particle manufacturing of the present invention.

[Fig. 6] is the sectional drawing that summary shows another preferred implementation of the manufacturing installation that uses in the organic nano particle manufacturing of the present invention.

[Fig. 7] is the sectional drawing that summary shows an example of the dissolving machine agitating vane that uses in the organic nano particle manufacturing of the present invention.

[Fig. 8] is that replacement shows the photo that the drawing of dissolving machine agitating vane shown in Figure 7 is used.

[Fig. 9] be summary show use in the organic nano particle manufacturing of the present invention by rotatable turbine part and be positioned at around it and the sectional drawing of an example of the mixing part that the fixed stationary part constitutes with minim gap.

[Figure 10] is an explanatory view that constitutes example that shows the ultra-filtration equipment that uses in the organic nano particle manufacturing of the present invention.

[nomenclature]

11 containers

11a liquid tank (solvent)

The 11b liquid level

12 agitating vanes

13 mixing sections

14 supply-pipes

14a supply-pipe peristome

15

16 electric motor

17 shells (mixing locular wall)

18 holes (circular hole)

19a, 19b agitating vane

21 containers (stirred pot outer wall)

The 21a stirred pot

22 agitating vanes

23 delivery pipes

24a, 24b supply-pipe

25

50 whipping apptss

32,33 supplying openings

36 discharge outlets

40 sealing plates

41,42 agitating vanes

46 external magnets

48,49 electric motor

61 round plates

62 blades

63

74 rotatable turbine portion

75 fixed stator departments

81 hold the container that disperses thing

82 circulation pumps

83 ultra-filtration modules

84 replenish pure water metering under meter

85 permeate water metering under meter

86 reverse flushing pumps

Embodiment

Below, the present invention is described in detail.

To the organic materials that in organic nano particle of the present invention, uses, be not particularly limited, as long as can form particle by reprecipitation method, for example can enumerate polymer organic materialss such as pigment dyestuff, organic pigment, soccerballene (Fullerene), poly-diacetylene, polyimide, aromatic hydrocarbon or aliphatic hydrocarbon are (for example, the aromatic hydrocarbon or the aliphatic hydrocarbon that have the aromatic hydrocarbon or the aliphatic hydrocarbon of orientation or have sublimability) etc., preferred pigment dyestuff, organic pigment or macromolecule organic material, preferred especially pigment dyestuff.In addition, organic filler can use separately, also can multiplely use together, also they 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, indanthrene, phthalocyanine, triaryl carbonium, dioxazine, aminoanthraquinone, diketopyrrolo-pyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone compound pigment, or their mixture.

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

Below, diketopyrrolo-pyrrole compound pigment Huo dioxazine compound pigment is illustrated in greater detail.

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

According to the present invention, can obtain the pyrrolopyrrole compound pigment particle of nano-scale with the sharp-pointed state of size distribution.In addition, when this pigment particle is used for colour filter, can reach the purity of color and the high-contrast of expectation simultaneously, and the photostabilization excellence, the generation of precipitate can also be suppressed in addition.Therefore black density, the redness that possesses the liquid crystal indicator of this colour filter described the power excellence, can suppress to show inhomogeneous.

In described diketopyrrolo-pyrrole compound pigment, preferred C.I. Pigment red 254 (compound of following formula (Z) expression), 255 (compounds of following formula (W) expression), 264 (compounds that following formula V is represented) are from more preferably C.I. Pigment red 254 of absorption spectrum.

Also have, as C.I. Pigment red 254, can use Irgaphor Red B-CF (CibaSpecialty Chemicals (チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ strain) manufacturing), Cromophtal DPP Red BO, Irgazin DPP Red BO, Microlen DPP RED BP etc., as C.I. Pigment red 255, can use Cromophtal Coral Red C, IrgazinDPP Red 5G etc., as C.I. Pigment red 264, can use Hostapeperm RubinD3B LP2615, (the above-mentioned substance title are trade(brand)name) such as Irgazin DPP Rubin TR.

Formula (Z)

Formula (W)

Formula V

Then Dui dioxazine compound pigment describes.As the blue pixel tinting material of in recent years colour filter, use the C.I. pigment Blue 15 mostly: 6, 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 wherein the long wave side at blue-light-emitting peak also has luminously 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. pigment Violet 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 De dioxazine compound pigment as the size distribution unanimity.Can make the dispersion liquid that contains this dioxazine compound pigment particle have excellent ageing stability like this.Therefore, the colour filter that uses this material to form can possess high color purity and high-contrast simultaneously, and the photostabilization excellence.In addition, possess the black density of the liquid crystal indicator of this colour filter, blue illustrative, reproducibility excellence, can suppress to show inhomogeneous.

Also have,, can use Cromofine Violet RE, FastgenSuper Violet BBL, Helio Fast Violet EB, Microlith VioletRL-WA, Sanyo Fast Violet BLD etc. as the C.I. pigment Violet 23.As C.I. pigment violet 37, can use Cromophtal Violet B, Microlith Violet B-A etc. the title of material (shown in be trade(brand)name).

In the manufacturing of organic nano particle of the present invention, also can be used in combination the pigment dyestuff more than 2 kinds or the sosoloid of pigment dyestuff.

As organic pigment, for example can enumerate azopigment, anthocyanidin, merocyanine pigment, tonka bean camphor pigment etc.As macromolecule organic material, for example can enumerate poly-diacetylene, polyimide etc.

In the present invention, organic nano particle be by will in good solvent, dissolve organic material solution that organic materials forms and for described good solvent have compatibility, for organic materials be poor solvent solvent (below, sometimes also this solvent is called by " poor solvent of organic materials ", or abbreviates " poor solvent " as.) mix and generate (below, also this method is called " reprecipitation method " sometimes, also the dispersion liquid that contains organic nano particle that obtains this moment is called " organic filler redeposition liquid " sometimes.)。Here, " good solvent " is meant the big solvent of solubleness for pigment dyestuff, and " poor solvent " is meant the little solvent of solubleness for pigment dyestuff.As good solvent that uses among the present invention and poor solvent, in order to generate organic pigment nano particle, must have sufficient pigment dyestuff poor solubility, the solvent that satisfies this requirement can be combined into mutually to exercise and use.

There is no particular limitation to the poor solvent of pigment dyestuff, 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 below the 0.02 quality %, more preferably below the 0.01 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 of carrying out in the presence of acid or the alkali under the dissolving situation having.In addition, as the compatibility or the uniform mixing of good solvent and poor solvent, preferred good solvent is more than the 30 quality % to the meltage of poor solvent, more preferably more than the 50 quality %.Good solvent does not have specific upper limit to the meltage of poor solvent, is actually with arbitrary proportion and mixes.

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

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

Below, the good solvent that dissolves organic materials is described.

There is no particular limitation to good solvent, as long as can dissolve employed organic materials, and can be with described 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 %.The solubleness of organic materials in good solvent does not have specific upper limit, if consider that from normally used organic materials then the upper limit of this solubleness is actually below the 50 quality %.This solubleness also can be the solubleness of carrying out in the presence of acid or the alkali under the dissolving situation having.The compatibility of good solvent and poor solvent or the preferable range of uniform mixing are for as mentioned above.

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

As the sulfoxide compound solvent, for example can enumerate dimethyl sulfoxide (DMSO), diethyl sulfoxide, hexa-methylene sulfoxide, tetramethylene sulfone etc.As the amide compound solvent, for example can enumerate N, dinethylformamide, 1-Methyl-2-Pyrrolidone, 2-Pyrrolidone, 1,3-dimethyl-2-imidazolidone, 2-Pyrrolidone, 2-Pyrrolidone, ε-Ji Neixianan, methane amide, N-methylformamide, ethanamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl propanamide, hexamethyl phosphoric triamide etc.

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

Preparation condition to organic material solution is not particularly limited, and can select in the scope smaller or equal to subcritical, the super critical condition of the temperature～solvent of solvent boiling point under the normal pressure.Temperature under the normal pressure is preferably-10～150 ℃, more preferably-5～130 ℃, is preferably 0～100 ℃ especially.

In the present invention, organic materials must be dissolved in the good solvent equably, but 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, do not use acidic conditions when dissociative group under the alkaline condition and intramolecularly have a large amount of nitrogen-atoms that is easy to the addition proton and do not exist in.For example, quinoline a word used for translation ketone compound pigment, diketopyrrolo-pyrrole compound pigment, disazo condensation compounds pigment dissolve under alkaline condition, and phthalocyanine compound pigment dissolves under acidic conditions.

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

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

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

To use the amount of acid be the amount that can make the organic materials uniform dissolution, there is no particular limitation to this amount, 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 pigment dyestuff, more preferably 10～500 molar equivalents, more preferably 30～200 molar equivalents.

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

When making organic nano particle, promptly separate out, there is no particular limitation for the poor solvent condition when forming organic nano particle, can select from normal pressure to scope subcritical, super critical condition.Temperature under the normal pressure is preferably-30～100 ℃, more preferably-10～60 ℃, is preferably 0～30 ℃ especially.

When organic material solution and poor solvent mix, can mix by adding among both any, mix but preferably organic material solution is added in the poor solvent, this moment, preferred poor solvent kept whipped state.Stirring velocity is preferably 100～10000rpm, and more preferably 150～8000rpm is preferably 200～6000rpm especially.Can use during interpolation, also can not use equipment such as pump.In addition, can in liquid, submergence add, also can outside liquid, add, but more preferably submergence interpolation in liquid.

The ratio of mixture of organic material solution and poor solvent (ratio of the good solvent/poor solvent in the organic filler redeposition liquid) 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 filler redeposition liquid, as long as can generate organic filler, but preferably with respect to the 1000ml dispersion solvent, organic filler is 10～40000mg, and more preferably 20～30000mg is preferably 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, weight average, 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 filler of the present invention (progenitor) is 50nm following (for example, the crystal of this size or aggregate), is preferably below the 40nm, more preferably below the 30nm.Also have, organic filler of the present invention can be a crystal particles, 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 of the present invention (progenitor) (in the present invention, monodispersity is meant the degree of particle diameter unanimity), promptly Mv/Mn is 1.0～2.0, is preferably 1.0～1.8, more preferably 1.0～1.5.

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 light scattering method, for example can enumerate day ダ イ Na ミ Star Network light-scattering photometer DLS-7000 series (title of described equipment is trade(brand)name) of the Na ノ ト ラ Star Network UPA-EX150 ， Da mound electronics society manufacturing that machine dress society makes etc.

It is macromolecular compound more than 1000 that organic nano particle dispersive composition of the present invention contains described organic nano particle and quality molecular-weight average.(, hereinafter state about this macromolecular compound.)

Organic nano particle dispersive composition of the present invention (contains the organic nano particle dispersion liquid as liquid composition.) preferably contain dispersion agent.There is no particular limitation to making the operation that contains dispersion agent in the organic filler dispersive composition, preferably adds dispersion agent in organic material solution and poor solvent both or a side and it is contained.In addition, also preferably utilize the system interpolation dispersant solution different during particle forming organic receiving with described 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 Polyvinylpyrolidone (PVP), polyvinyl alcohol, polyvinyl methyl ether, polyoxyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, the part formolation thing of polyvinyl alcohol, the part butyral thing of polyvinyl alcohol, vinyl pyrrolidone-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 (ト Application ガ Application ト go system), sulfonated lignin.Wherein, preferably polyethylene base pyrrolidone.These polymers can be used singly or in combination of two or more.These dispersion agents can use separately or use simultaneously.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 communique those.These anionic dispersing agents can be used alone or in combination of two or more kinds.

Cationic dispersing agent (cationic exchange tensio-active agent) 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 can be used alone or in combination of two or more kinds.

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

As non-ionic dispersing agent (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 can be used alone or in combination of two or more kinds.

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

When making pigment dispensing composition of the present invention, in good solvent, dissolve and when making organic material solution, the preferred existence simultaneously contains amino pigment dispersing agent.Here, described amino comprises primary amine groups, secondary amino group, uncle's amino, and amino number can be 1, also can be for a plurality of.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 those compounds 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 of Japan etc., but be not limited to these compounds.

As the amino dispersion agent that has that uses among the present invention, can use at least a in the compound that is selected from following general formula (D1), (D3) and formula (D4) expression, but be not limited thereto.

＜1, the compound of general formula (D1) expression 〉

General formula (D1)

A-N＝N-X-Y

In general formula (D1), A and X-Y represent to form the composition of azopigment simultaneously.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 as shown below, but the present invention never is confined to these structures.

Formula 1-1 formula 1-2

Formula 1-3 formula 1-4

Formula 1-5 formula 1-6 formula 1-7

Formula 1-8 formula 1-9 formula 1-10

Formula 1-11 formula 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).

(ii) formula is (iii) for formula (i) formula

(iv) formula is (v) for formula

In general formula (D1), Y represents the group shown in the following general formula (D2).

General formula (D2)

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 heterocyclic radical that following structural formula is represented.

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.

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 (anthrapyrimidine) compound pigment, anthanthrone (anthanthrone) compound pigment, indanthrene 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 be replacement or unsubstituted alkyl or R independently of one another 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 ₁Expression hydroxyl or the group shown in the general formula (D3a) hereinafter, or be 1 o'clock Z at n1 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.

General formula (D3-1)

General formula (D3-2)

General formula (D3-3)

General formula (D3-4)

General formula (D3-5)

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.

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 communique of Japan.

＜3, the pigment dispersing agent that contains graft copolymer 〉

Under the situation of making pigment dispensing composition of the present invention, also preferred the use contained the graft copolymer that possesses amino and ether, the dispersion agent that contains other composition of suitably selecting in case of necessity.

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

The weight-average molecular weight of above-mentioned graft copolymer (Mw) is preferably 3000～100000, and more preferably 5000～50000.If above-mentioned weight-average molecular weight (Mw) less than 3000 then can not prevent the aggegation of organic nano particle, viscosity rises sometimes, if surpass 100000, and the solvability deficiency in organic solvent then, viscosity rises sometimes.Also have, this weight-average molecular weight is by gel permeation chromatography (carrier: tetrahydrofuran (THF)) measure and through the weight-average molecular weight of polystyrene conversion.

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

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

If 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 pigment particles 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 pigment particles 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, the aggegation of organic pigment particles can not be 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 " big monomer ".) be the oligopolymer that end has the group that contains ethylenical unsaturated double bonds.In the present invention, preferably in above-mentioned polyreactive oligomers, only there is a side to have the group that contains 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 acetate and the divinyl or multipolymer etc., wherein homopolymer or multipolymer, the polystyrene etc. of preferred (methyl) alkyl acrylate.In the present invention, these oligopolymer can be substituted base and replace, and are not particularly limited for this substituting group, for example can enumerate halogen atom etc.

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

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

General formula (E6)

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

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

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

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

(ii) contain amino monomer

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

General formula (E2)

In above-mentioned general formula (E2), R ²¹Expression hydrogen atom or methyl.R ²²The expression carbon number is 1～8 alkylidene group, and wherein preferred carbon number is 1～6 alkylidene group, and preferred especially carbon number is 2～3 alkylidene group.

X ²Expression-N (R ²³) (R ²⁴) ,-R ²⁵N (R ²⁶) (R ²⁷).Herein, R ²³And R ²⁴Expression hydrogen atom, carbon number are 1～6 alkyl or phenyl.R ²⁵The expression carbon number is 1～6 alkylidene group, R ²⁶And R ²⁷Expression hydrogen atom, carbon number are 1～6 alkyl or phenyl.

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

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

General formula (E3)

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

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-dimethylamino) hexyl (methyl) acrylamide (above is aminoalkyl group (methyl) acrylic amide) etc. are as preferred monomers.

The polymerizable monomer that (iii) has ether

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

General formula (E1)

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

To as above-mentioned polymerizable monomer with ether, there is no particular limitation, so long as 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 (NK エ ス テ Le M-40G, M-90G, M-230G (East Asia synthetic chemical industry (strain) society system); Block レ Application マ-PME-100, PME-200, PME-400, PME-1000, PME-2000, PME-4000 (Japanese grease (strain) society system)), polyethylene glycol monomethacrylate (Block レ Application マ-PE-90, PE-200, PE-350 (Japanese grease (strain) society system)), polypropylene glycol monomethacrylate (Block レ Application マ-PP-500, PP-800, PP-1000 (Japanese grease (strain) society system)), polyoxyethylene glycol polypropylene glycol monomethacrylate (Block レ Application マ-70PEP-370B (Japanese grease (strain) society system)), polyoxyethylene glycol polytetramethylene glycol monomethacrylates (Block レ Application マ-55PET-800 (Japanese grease (strain) society system)), polypropylene glycol polytetramethylene glycol monomethacrylates (title of described material are trade(brand)name) such as (Block レ Application マ-NHK-5050 (Japanese grease (strain) society systems)).

(iv) other monomer

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Formula (D4)

A: d: c=15: 20: 65 (weight ratio)

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

In order further to improve the uniformly dispersed and package stability of organic pigment particles, 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.

[manufacturing installation]

Preferred embodiment to the manufacturing installation that uses in the manufacturing of pigment dispensing composition of the present invention describes, but this is not that the present invention is carried out limited explanation.

(manufacturing installation example 1)

Fig. 1 is the preferred embodiment of the manufacturing installation that uses in the manufacturing of organic nano particle of the present invention.In Fig. 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. 2 is the sketch chart of another preferred embodiment that is used to make the manufacturing installation of organic nano particle of the present invention.This device is mixing section (stirring area) 13 backs to be set form in the container 11 of manufacturing installation shown in Figure 1.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 top to bottom of the poor solvent integral body in the reaction vessel 11 keeps convection current always.

Fig. 3 is after the mixing section 13 with an embodiment of manufacturing installation shown in Figure 2 amplifies, roughly the sectional drawing of the amplifier section of Xian Shiing.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 the stirring 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.Be important operating parameters for the size of this mixture strength drop (droplet) when sneaking into pigment dyestuff solution by inference.

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. 4 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 Figure 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. 5 is the sectional drawing that roughly shows another embodiment of the manufacturing installation that uses in the manufacturing of organic nano particle of the present invention.In Fig. 5, by supply- pipe 24a, 24b organic material solution and poor solvent are supplied 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 that generates is extracted out rapidly by delivery pipe 23.

Fig. 6 is the sectional drawing that roughly shows the another embodiment of the device that uses in the manufacturing of organic nano particle of the present invention.In manufacturing installation shown in Figure 6, 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 the stirred pot 38 in 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.

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, drive the rotation of each external magnet by independent electric motors 48,49, carry out reverse rotating operation mutually.

Shown in dotted arrow among Fig. 6 (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 the manufacturing of organic nano particle of the present invention, use manufacturing installation with these structures, not only can pass through intermittent mode, also can make organic nano particle by the continuous flow 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)

Below to another embodiment of the device that uses in the manufacturing as organic nano particle of the present invention, that is, utilization is had the manufacturing installation that the blade of shearing force stirs describe.

Said shearing force is meant that agitating vane is to sneaking into organic material solution the shearing force that the drop (droplet) that generates behind the poor solvent applies 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 dissolving machine blade is the special agitating vane with the function that can form high shear force, has roughly shown its example among Fig. 7 with front view, and Fig. 8 has shown the photo that substitutes 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 9, 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 (title of described instrument is trade(brand)name) 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 worthless.

For organic nano particle dispersive composition of the present invention, can concentrate, forming with respect to said composition is 10～1000 times organic nano particle concentration, thereby can be suitable for the concentrated solution of colour filter coating fluid and ink for inkjet with industrial-scale production.

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 in fact with the dispersion solvent of organic nano particle dispersion liquid (for example, aqueous solvent) do not mix (in the present invention, do not take place in fact 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 the solvability of consideration usual solvents, then the lower limit of this meltage is actually more than the 1 quality %.After mixing, form the interface when leaving standstill) solvent 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 cpds solvent, alkylol cpd solvent, aromatic compound solvent, fatty compounds solvent, more preferably ester cpds solvent, aromatic compound solvent or fatty compounds solvent, especially preferably ester cpds solvent.

As the ester cpds solvent, for example can enumerate 2-(1-methoxyl group) propyl group acetic ester, vinyl acetic monomer, ethyl lactate etc.The operation alkylol cpd for example can be enumerated propyl carbinol, isopropylcarbinol etc.As aromatics, for example can enumerate benzene,toluene,xylene etc.As fatty compounds, for example can enumerate normal hexane, hexanaphthene etc.In addition, the extraction solvent can be the single 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 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 nanoparticle,, 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 halide.Be known that research open (Research Disclosure) No.10208 (1972), No.13122 (1975) and No.16351 (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 optimum condition.In addition, replenishing, the constant volume formula of continuous interpolation solvent and the batch-type that gradation is intermittently added are being arranged because of film sees through in the method for the solvent that loses, but short constant volume formula of preferred desalting treatment time.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.

One that has shown the device that is used to carry out ultrafiltration among Figure 10 constitutes example.As shown in figure 10, 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 inorganic salt of by-product 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 the by-product inorganic salt.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 as " pharmaceutical machine technology Ha Application De Block Star Network ", pharmaceutical machine technical study meeting is 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 separating centrifuge etc. that can enumerate the whizzer of the skin function of taking (suction supernatant layer in rotation, and be discharged into system outer function with it) and discharge solid substance continuously.

As the condition of centrifugation, centrifugal force (be expressed as need times over the value of the centrifugal acceleration of universal gravity constant) is preferably 50～10000, and more preferably 100～8000, be preferably 150～6000 especially.Temperature during centrifugation depends on the solvent species of dispersion liquid, but is preferably-10～80 ℃, more preferably-5～70 ℃, is preferably 0～60 ℃ especially.

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 concentrates extract).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～about 3000 times, more preferably about 500～about 2000 times if for example will be made as 1 as the nanoparticle concentration in the organic nano particle dispersion liquid of raw material.

For organic nano particle dispersive composition of the present invention, can pass through in case of necessity for example to concentrate etc., the organic nano particle 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 nano particle dispersion 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 nano particle obtains as carrying out the agglutinative floss by the degree that can carry out redispersion.

Therefore, with regard to using the degree that common dispersing method disperses to be reached, the micronize deficiency needs the higher method of miniaturization efficient.(in the present invention, the agglutinative organic filler is meant organic filler agglomeration etc., is that organic filler is by secondary power accumulative particle, when progenitor is also referred to as the aggegation nanoparticle during for nano-scale for this agglutinative organic filler.), manufacture method according to organic nano particle dispersion liquid of the present invention, to contain the quality molecular-weight average in the agglutinative organic filler liquid be macromolecular compound more than 1000 by making, can make organic filler reach fine dispersion (in the present invention, agglutinative organic filler liquid is meant the material that contains the agglutinative organic filler in the liquid, can be dispersion liquid, concentrated solution, paste, slurry etc., as long as contain the agglutinative organic filler.)。

Then, to the above-mentioned macromolecular compound that in pigment dispensing composition of the present invention, uses (in the present invention, " macromolecular compound " is meant that the quality molecular-weight average is the organic compound more than 1000, though there is not the special upper limit, the quality molecular-weight average is to be actual below 500,000, be preferably 100, below 000, more preferably below 50,000.) be elaborated.

It is more than 1000 that the macromolecular compound that uses in the organic nano particle dispersive composition of the present invention is preferably the quality molecular-weight average, with the macromolecular compound of following general formula (1) expression.

(A ¹-R ² _nR ¹ P ¹) _mGeneral formula (1)

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

Specifically, though to A ¹Have no particular limits, but as above-mentioned " 1 valency organic group " with acidic-group, can enumerate for example have the carboxylic acid group, the 1 valency organic group of sulfonic group, sulfate mono ester group, phosphate, phosplate base, boronate etc.In addition, as above-mentioned " 1 valency organic group ", can enumerate and for example have amino (NH with the group that has basic nitrogen atom ₂) 1 valency organic group, have substituted imine base (NHR ⁸,-NR ⁹R ¹⁰) 1 valency organic group (wherein, R ⁸, R ⁹And R ¹⁰Independence expression carbon number is that 1～20 alkyl, carbon number are that the aryl below 20 more than 6, carbon number are the aralkyl below 30 more than 7 respectively.), have the guanidine radicals of following general formula (a1) expression 1 valency organic group [in the general formula (a1), R ^A1, R ^A2Independence expression carbon number is that 1～20 alkyl, carbon number are that the aryl below 20 more than 6, carbon number are the aralkyl below 30 more than 7 respectively.], have the amidino groups of following general formula (a2) expression 1 valency organic group [in the general formula (a2), R ^A3, R ^A4Independence expression carbon number is that 1～20 alkyl, carbon number are that the aryl below 20 more than 6, carbon number are the aralkyl below 30 more than 7 respectively.] etc.

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

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

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

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

As above-mentioned " group ", for example can enumerate group with trimethoxysilyl, triethoxysilyl etc. with alkoxysilyl.

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

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

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

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

In addition, above-mentioned organic pigment structure or heterocycle are not particularly limited, more particularly, as the organic pigment structure, can enumerate for example phthalocyanine compound, insoluble azo-compound, azo lake compound, anthraquinone compounds, quinoline a word used for translation ketone compound, dioxazine compound, diketopyrrolo-pyrrole compound, anthracene pyridine compounds, anthanthrone (anthanthrone) compound, indanthrene compound, yellow anthrone compound, perylene ketone compound, perylene compound, thioindigo compound etc.In addition, as heterocycle, for example can enumerate thiophene, furans, xanthene, pyrroles, pyrroline, tetramethyleneimine, dioxolane, pyrazoles, pyrazoline, pyrazolidine, imidazoles, oxazole, thiazole, oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines, diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithian, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, anthraquinone etc.

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

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

(B ¹ _A1R ¹⁸-general formula (4)

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

B in the general formula (4) ¹With above-mentioned A ¹Synonym, preferred scheme is also identical, but as above-mentioned organic pigment structure or heterocycle, can enumerate for example phthalocyanine compound, insoluble azo-compound, the azo lake compound, anthraquinone compounds, quinoline a word used for translation ketone compound dioxazine compound, the diketopyrrolo-pyrrole compound, the anthracene pyridine compounds, anthanthrone (anthanthrone) compound, the indanthrene compound, yellow anthrone compound perylene ketone compound perylene compound, organic pigment structures such as thioindigo compound, for example thiophene, furans, xanthene, the pyrroles, pyrroline, tetramethyleneimine, dioxolane, pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithian, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, heterocycles such as anthraquinone.

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

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.

-O- -S-

(t-1)(t-2)(t-3)(t-4)(t-5)(t-6)(t-7)(t-8)(t-9)(t-10)(t-11)(t-12)

-C＝N-

-C≡C-

(t-20)(t-21)(t-22)(t-23)(t-24)(t-25)(t-26)

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

In above-mentioned general formula (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 structure).

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

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.R ²Be preferably organic linking group.

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

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

In above-mentioned general formula (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 (below, be also referred to as macromolecular scaffold.), can from common polymkeric substance etc., select according to purpose.

In polymkeric substance, in order to constitute macromolecular scaffold, be preferably selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, polyurethane polymer, acylamide polymer, epoxide polymer, silicone based polymkeric substance, and their modifier or multipolymer [for example comprise 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, esters polymer, ether polymer, polyurethane polymer and their modifier or the multipolymer, special preferred vinyl polymer of monomers or multipolymer.

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

In the macromolecular compound of above-mentioned general formula (1) expression, more preferably by the macromolecular compound of following general formula (2) expression.

(A ²-R ⁴-S  _xR ³ S-R ⁵-P ²) _yGeneral 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, but object lesson as the organic pigment structure, more preferably phthalocyanine compound, azo lake compound, anthraquinone compounds, dioxazine compound, diketopyrrolo-pyrrole compound etc., as heterocycle, more preferably imidazoles, triazole, pyridine, piperidines, morpholine, triazine, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, anthraquinone etc.

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

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

In above-mentioned general formula (2), R ³The linking group of expression (x+y) valency.As above-mentioned R ³The linking group of expression (x+y) valency comprises by 1～60 carbon atom, 0～10 nitrogen-atoms, and 0～50 Sauerstoffatom, 1～100 hydrogen atom, and 0～20 group that sulphur atom constitutes can not have replacement, can have substituting group yet.

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

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

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

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

In above-mentioned general formula (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, 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 carbon number are 1～4 alkyl.)。Wherein preferred organic linking group.

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

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

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

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

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

The quality molecular-weight average of macromolecular compound is more than 1000, but the preferred mass molecular-weight average is 1000～500,000, more preferably 3000～100000, more preferably 5000～80000, be preferably 7000～60000 especially.If the quality molecular-weight average is in the above-mentioned scope, then can give full play to the effect of a plurality of functional groups of polymer ends importing, in the excellent performance of performance aspect the adsorptivity of solid surface, micelle formation ability, surfactivity.When particularly this macromolecular compound being used as pigment dispersing agent, 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 and imported (the A in the above-mentioned general formula of functional group of 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, macromolecular compound (macromolecular compound of preferred formula (2) expression) contained in the organic nano particle dispersive composition of the present invention 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.

(A ³-R ⁷-S  _gR ⁶ SH) _hGeneral 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 acetate, propionate, vinyl butyrate, Methoxy acetic acid vinyl acetate, M-nitro benzoic acid vinyl acetate etc.

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

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

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

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

As the example of above-mentioned styrenic, can enumerate vinylbenzene, vinyl toluene, dimethyl styrene, Three methyl Benzene ethene, ethyl styrene, isopropyl benzene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorostyrene, bromostyrene, 1-chloro-4-methyl-benzene, with hydroxy styrenes, vinyl M-nitro benzoic acid methyl esters and the alpha-methyl styrene etc. that can protect by the de-protected group of acidic substance (for example t-Boc etc.).

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

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

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

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

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

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

In addition, as radical polymerization initiator, can use 2,2 '-Diisopropyl azodicarboxylate (AIBN), 2, 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 preferably enumerate carboxylic acid halides, haloalkane, isocyanic ester, carbon-to-carbon double bond etc.

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

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

In above-claimed cpd, on acquired, the synthetic easiness of raw material, solvability to all kinds of SOLVENTS, preferred (u-1), (u-2), (u-10), (u-11), (u-16), (u-17).

Conduct had the (A in the above-mentioned general formula of functional group ¹Or A ²) and have can with the compound of the functional group of sulfydryl reaction, have no particular limits, can be listed below compound.

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

As the preferred solvent of in aforesaid method, using, can according to employed " compound that has 3～10 sulfydryls in the per molecule ", " have the group, urea groups, urethano, the group of band coordination Sauerstoffatom, the carbon number that are selected from acidic-group, band basic nitrogen atom and be at least 1 group in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl 4 or more, and have can with the compound of functional group's (for example carbon-to-carbon double bond) of sulfydryl reaction " and the solvability of the free radical addition resultant of reaction of generation select arbitrarily.For example, can enumerate methyl alcohol, ethanol, propyl alcohol, Virahol, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl group acetic ester, acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methoxy-propyl acetic ester, ethyl lactate, vinyl acetic monomer, acetonitrile, tetrahydrofuran (THF), dimethyl formamide, chloroform, toluene.These solvents can 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 preferred general formula (1) expression of using is as follows in the organic nano particle dispersive composition of the present invention.But the present invention never is confined to these object lessons.

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

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

General formula (I)

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

General formula (II)

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

General formula (III)

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

General formula (IV)

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

Logical formula V

(R ₉The expression carbonatoms is that 2～5 alkyl or carbonatoms are 6～20 aryl.R ₁₀And R ₁₁Represent that respectively hydrogen atom or carbonatoms are 1～5 alkyl.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 high molecular molecular weight among the present invention is meant the quality molecular-weight average.As the measuring method of high molecular 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 quality molecular-weight average by chromatography determination.

Macromolecular compound can be any in water-soluble, the oil soluble, also can be water-soluble and oil-soluble.

The addition means of macromolecular compound can be to be dissolved in the solution that forms in aqueous 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, be dissolved in the solvent miscible but different with this state, add method in the agglutinative organic nano particle 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: (or before and after it) when forming organic nano particle by reprecipitation method, extraction or (or before and after it) when concentrated, after (or before and after it), these operations finish when concentrating the back and disperseing the agglutinative organic filler, also can be their combination in addition.In the present invention, can make also that to contain the quality molecular-weight average in the following composition as binding agent be macromolecular compound more than 1000, for example preferably after organic filler redeposition liquid concentrates, when making agglutinative organic filler fine dispersion, add.

When organic filler contained in the agglutinative organic filler 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, for example can enumerate part butyral thing, vinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide/propylene oxide segmented copolymer, polymeric amide, derivatived cellulose, starch derivative of part formolation 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 (ト Application ガ Application ト go system), sulfonated lignin.

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, the spy opens 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 macromolecular compounds can only be used singly, or in combination of two or more kinds, and also can also use with the compound of molecular weight less than 1000.

In the present invention, contain the above organic solvent of 60 quality % in the dispersion thing of preferred organic nano particle, more preferably more than the 65 quality %.There is no particular limitation to organic solvent, can suitably select from common solvent.For example preferred ester cpds solvent, alkylol cpd solvent, aromatic compound solvent, fatty compounds solvent, ketone compound solvent, preferred especially ester cpds solvent, ketone compound solvent.These solvents can use a kind separately, also can use simultaneously more than 2 kinds.

As the ester cpds solvent, for example can enumerate 2-(1-methoxyl group) propyl group acetic ester, vinyl acetic monomer, ethyl lactate etc.As the alkylol cpd solvent, for example can enumerate propyl carbinol, isopropylcarbinol etc.As aromatic compound solvent, for example can enumerate benzene,toluene,xylene etc.As the fatty compounds solvent, for example can enumerate normal hexane, hexanaphthene etc.As the ketone compound solvent, for example can enumerate methylethylketone, acetone, pimelinketone etc.

Below, the scheme of colour filter and ink for ink-jet print etc. is elaborated for being used for organic nano particle dispersive composition of the present invention for example.Except ink-jet ink for color filter, can also use printing with common ink for ink-jet prints such as ink for ink-jet prints.Organic nano particle can use with the state that for example is scattered in the carrier.As above-mentioned carrier, coating is meant the medium part that makes colo(u)rant dispersion when being in liquid state, comprise 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.Also have, in the present invention, the binding agent that uses in binding agent that uses when forming nanoparticle and the redispersion can be identical or different, is that the binding agent when forming the binding agent of nanoparticle and redispersion is distinguished sometimes.

Can come suitably to determine the organic nano particle concentration 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 pigment dyestuff 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 making this aggegation nanoparticle carry 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 (for example referring to, " using method of colo(u)rant dispersion technology-surface treatment and dispersion agent and dispersed the evaluation-" 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〉dispersing mode

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

The machinery that uses 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 T.C.Patton work " PaintFlow and Pigment Dispersion " (1964, John Wiley and Sons company publication), also can use this method about mixing, dispersive detailed content.

＜2〉example of dispersion agent

In the organic nano particle dispersive composition,, can add common pigments dispersion agent 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 (エ Off カ society system)), ソ Le ス パ-ス 5000 (ゼ ネ カ (strain) society system); Organosiloxane polymer KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) society system), (methyl) acrylic acid or the like (being total to) polymkeric substance Port リ Off ロ-No.75, No.90, No.95 (society of common prosperity society oil chemistry industry (strain) system), W001 cationic tensio-active agents such as (abundant company systems); Nonionic class tensio-active agents such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan-fatty acid ester; W004, W005, W017 anionic species tensio-active agents such as (abundant company systems); EFKA-46, EFKA-47, EFKA-47EA, EFKA Port リ マ-100, EFKA Port リ マ-400, EFKA Port リ マ-401, EFKA Port リ マ-450 (above is the gloomy system of industry (strain) down), デ イ ス パ-ス エ イ De 6, デ イ ス パ-ス エ イ De 8, デ イ ス パ-ス エ イ De 15, デ イ ス パ-ス エ イ De 9100 macromolecule dispersing agents such as (サ Application プ コ society systems); Various ソ Le ス パ-ス dispersion agents (ゼ ネ カ (strain) society system) such as ソ Le ス パ-ス 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000; ア デ カ プ Le ロ ニ Star Network L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification (strain) society system) and イ ソ ネ Star ト S-20 (Sanyo changes into (strain) society system).In addition, the pigment dispersing agent of putting down in writing in the also suitable use 2000-239554 communique, and the compound of the synthesis example of putting down in writing in compound of putting down in writing in the special fair 5-72943 communique of Japan (C) and the TOHKEMY 2001-31885 communique 1 etc.

The dispersion agent that uses when forming nanoparticle as redispersion preferably reuses the compound shown in [dispersion agent] item.

For the organic nano particle dispersive composition, can make the organic nano particle (progenitor) 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.

According to the present 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) nominal particle size also can concentrate redispersion to so-called nano-scale.Therefore, when being used for colour filter, the excellent in uniformity on optical concentration height, colour filter surface, contrast gradient height, and reduced picture noise.

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

For organic nano particle dispersive composition, coloring photosensitive combination, by it being contained demonstrate distinct tone and high-strength pigment, it is excellent as being used to make the Image forming material that colour filter for example or color draw a design.

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, coloring photosensitive combination, this also meets the needs of environment protection.

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

[photosensitive composition]

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

(a) organic nano particle

Making method about organic nano particle is described in detail.The content of organic nano particle, with respect to the whole solid substances in the photosensitive composition (in the present invention, all solid substances are meant the component total 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 concentration of dispersion liquid rises, and causes making the problem on the adaptability sometimes.If very few, tinting strength deficiency then.As the organic nano particle with tinting material function (pigment particles), 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 be used in combination with the common pigments that is used to mix colours.Pigment can use above-described kind.

(b) binding agent

As the binding agent in the photosensitive composition, can preferably use above-mentioned quality molecular-weight average is macromolecular compound more than 1000.The content of binding agent is generally 15～50 quality % with respect to whole solid substances of photosensitive composition, is preferably 20～45 quality %.If should measure too much, 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 coated film.

(c) monomer or oligopolymer

Monomer or oligopolymer contained in the photosensitive composition of the present invention are preferably the ethylenical unsaturated double bonds that has more than 2, and can carry out the monomer or the oligopolymer of addition polymerization by illumination.As this monomer or oligopolymer, can enumerate and have at least one ethylenically unsaturated group that can carry out addition polymerization, the boiling point under the normal pressure in the molecule at the compound more than 100 ℃.As its example, can enumerate monofunctional acrylate or simple function methacrylic esters such as Dipentaerythritol six (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate and phenoxy group ethyl (methyl) acrylate; Polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, the trimethylolethane trimethacrylate acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane diacrylate, neopentyl glycol two (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, hexylene glycol two (methyl) acrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, three (acrylyl oxy-ethyl) isocyanuric acid ester, three (acrylyl oxy-ethyl) cyanurate, glycerine three (methyl) acrylate; Polyfunctional alcohol such as TriMethylolPropane(TMP) or glycerine goes up polyfunctional acrylic ester or the multifunctional methacrylic esters such as material that forms through (methyl) acroleic acid esterification again behind addition of ethylene oxide or the propylene oxide.In addition, the general formula (1) that can also enumerate as Japanese kokai publication hei 10-62986 communique reaches those compounds that form through (methyl) acroleic acid esterification again of record in (2) as suitable material behind addition of ethylene oxide on the polyfunctional alcohol or propylene oxide.

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

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

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

(as monomer or oligopolymer, preferred molecular weight is 200～1000 for these monomers or oligopolymer.) can use separately, or mix more than 2 kinds and use, this monomer or oligopolymer are generally 5～50 quality % with respect to the content of whole solid substances of photosensitive composition, are preferably 10～40 quality %.If should measure too much, then be difficult to control development, can on manufacturing adaptability, have problems.If very few, the curing power deficiency when then exposing.

(d) Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system

(in the present invention, the Photoepolymerizationinitiater initiater system is meant to be combined by multiple compound and realizes that photopolymerization causes the mixture of function as the Photoepolymerizationinitiater initiater that contains in photosensitive composition of the present invention or Photoepolymerizationinitiater initiater system.), can enumerate disclosed vicinal polyketaldonyl compound in No. 2367660 specification sheets of United States Patent (USP), the acyloin ether compound of putting down in writing in No. 2448828 specification sheets of United States Patent (USP), the aromatic series acyloin compound 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 11-133660 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 characteristic especially.

With respect to photosensitive composition, the content of Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system is generally 0.5～20 quality %, is preferably 1～15 quality %.If should measure too much, then susceptibility is too high, is difficult to control.If very few, then exposure sensitivity is low excessively.

(other additive)

[solvent]

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

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

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

[tensio-active agent]

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

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

As above-mentioned tensio-active agent, can enumerate TOHKEMY 2003-337424 communique, spy and open in the flat 11-133600 communique disclosed tensio-active agent as the tensio-active agent that is fit to.With respect to the resin combination total amount, the content of tensio-active agent is preferably below the 5 quality %.

[thermopolymerization prevents agent]

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

[auxiliary dyestuff, the pigment that uses]

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

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

[UV light absorber]

In case of necessity, can contain UV light absorber in the photosensitive composition of the present invention.As UV light absorber, the compound of in Japanese kokai publication hei 5-72724 communique, putting down in writing, also can enumerate salicylate class, benzophenone, benzotriazole category, cyanoacrylate, nickel chelate class, hindered amines etc.

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

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

[coated film of photosensitive composition]

The composition that is contained in the coated film with photosensitive composition formation of the present invention is identical with the composition of having put down in writing in [photosensitive composition] item.In addition, the thickness of the coated film that forms with photosensitive composition of the present invention can carry out suitably determining according to purposes, but is preferably 0.5～5.0 μ m, more preferably 1.0～3.0 μ m.For the coated film that forms with photosensitive composition of the present invention, make wherein contained (c) monomer or oligopolymer carry out the polymeric membrane that polymerization forms photosensitive composition, can make the colour filter that contains this film (about the making of colour filter, hereinafter states.)。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 coated film can be by forming with common coating process coating and dry photosensitive composition, for purposes of the invention, the slit-shaped nozzle that preferably adopts hydrojet portion to have slit-shaped apertures is coated with.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 for photosensitive composition being coated on the substrate, from can all even aspect that is coated with the film of 1～3 μ m accurately, rotary coating be excellent, 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 cost in order further to improve, in the making of colour filter, adopting than the rotation coating to be more suitable in the slot coated of carrying out the coating of wide cut big area substrate.In addition, from saving the viewpoint of liquid, slot coated is also excellent than the rotation coating, can be filmed uniformly with coating liquid measure still less.

Slot coated is a kind of like this coating process, promptly, making front end have width is that the gap of tens of microns slit (gap) and length dispense tip corresponding with the coating width of rectangular substrate and substrate remains tens of～hundreds of microns, make substrate and dispense tip keep the constant speed of relative movement simultaneously, will be coated on the substrate by the coating fluid that slit provides by predetermined glue spread.This slot coated have (1) compare with rotary coating liquid loss less, (2) no coating fluid disperses, therefore reduced the liquid that can not that disperses in clean, (3) and sneaked into the time that coated film, (4) rotates beginning and stop again, therefore shortened and produce interval, (5) easily to advantages such as large-sized substrate are coated with.Owing to have these advantages, slot coated is suitable for the making of the liquid crystal indicator of large-scale picture with colour filter, also is expected to become favourable coating process with regard to the minimizing of glue spread.

Because slot coated can form area more than the big coated film of rotary coating, therefore when the slit outlet from broadness sprays coating fluid, must make the speed of relative movement that keeps between spreader and the coated article to a certain degree.Therefore, the coating fluid 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 fluid on the substrate from the slit of dispense tip keep constant at whole coating width.If liquid rerum natura deficiencies such as the flowability of coating fluid and viscoelastic property then can produce following problem, it is even that crawling promptly takes place easily, is difficult to keep the constant coating thickness in the coating width direction, can not form uniform coated film.

Because above situation in order there not to be uneven even coated film, has been carried out flowability and viscoelastic property that a large amount of trials improve coating fluid.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 monolithic devices film 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 in this order 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, three 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 acetate or its are saponified etc., ethene and acrylate or its are saponified, polyvinyl chloride, vinylchlorid and vinyl acetate 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 acetate etc. form, vinyl acetate copolymerized 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 being coated with a plurality of coating layer, 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, coating is dissolved and the coating fluid (thermoplastic resin coating fluid) of formation the additive of thermoplastic resin on interim upholder, dry then, thermoplastic resin is set thus, the intermediate layer material solution that coating is made of the solvent of solution heat plastic resin layer not on thermoplastic resin then, and carry out drying, adopt the solvent that does not dissolve the middle layer to be coated with and drying then, thereby photo-sensitive resin is set.

In addition, also can make in the following manner, that is, prepare on above-mentioned interim upholder, to be provided with the sheet material in thermoplastic resin and middle layer, and the sheet material that on protective membrane, is provided with photo-sensitive resin, carry out bonding mutually according to the mode that the middle layer is contacted with photo-sensitive resin; Also have, prepare on above-mentioned interim upholder, to be provided with the sheet material of thermoplastic resin, and the sheet material that on protective membrane, is provided with photo-sensitive resin and middle layer, carry out bonding mutually according to the mode that thermoplastic resin and middle layer are engaged.

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, preferred thickness of each layer as other, 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 apparatus for coating etc. to carry out, but for the present invention, preferably adopt the apparatus for coating (slot coated device) of the use slit-shaped nozzle that in " photosensitive composition " item, has described to be coated with.The preferred object lessons of slot coated device etc. are same as described above.

[colour filter]

The goods that colour filter of the present invention can be used as the contrast gradient excellence use.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 ア レ Application ス; 512 colour specifications 10.4 " サ イ 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.

When colour filter of the present invention is used 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
				R G B	0.656 0.293 0.146	0.336 0.634 0.088	21.4 52.1 6.90

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 result of F10 light source downward view 2 degree, 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)

Colour filter of the present invention can be by forming photo-sensitive resin on substrate, and make according to the modes such as method that the kind number of color carries out exposure imaging repeatedly.In addition, can also form the structure of distinguishing its border with black matrix in case of necessity.

In above-mentioned manufacture method, as the method that on substrate, forms photo-sensitive resin, can enumerate (a) method with above-mentioned each photosensitive compositions of coating such as common apparatus for coating, reach and (b) use above-mentioned photosensitive resin transfer material, carry out adherent method etc. by laminating.

(a) utilize apparatus for coating to be coated with

When making colour filter of the present invention, for the coating of photosensitive composition, can adopt common apparatus for coating, but the wherein preferred especially slit coater of explanation in [coated film of photosensitive composition] item that uses.In addition, the preferred object lesson of slit coater is same as described above.Forming under the situation of photo-sensitive resin by coating, as its thickness, be preferably 1.0～3.0 μ m, more preferably 1.0～2.5 μ m are preferably 1.5～2.5 μ m especially.

(b) undertaken bonding 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 utilizing photosensitive resin transfer material of the present invention to form photo-sensitive resin, its preferred thickness is 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 transparent substrate, 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 above-mentioned 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)

For colour filter of the present invention, forming under the situation of photo-sensitive resin, can the oxygen barrier film be set further on this photo-sensitive resin by the coating photosensitive composition, 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 above-mentioned substrate, predetermined mask is set, seeing through this mask, thermoplastic resin and middle layer from this mask top then exposes, then use developing liquid developing, kind number according to color repeats above-mentioned steps, thereby obtains colour filter of the present invention.

Herein, as above-mentioned exposure light source, as long as from the light source that can shine the light (for example, 365nm, 405nm etc.) that can make photo-sensitive resin solidified wavelength region may, suitably select to get final product.Specifically, can enumerate extra-high-pressure mercury vapour lamp, high pressure mercury vapour lamp, metal halide lamp etc.Exposure is generally 5～200mJ/cm ²About, be preferably 10～100mJ/cm ²About.

In addition, there is no particular limitation to above-mentioned developing solution, can use the developing solutions of putting down in writing in the Japanese kokai publication hei 5-72724 communique commonly used such as material.In addition, preferred developing solution is to make photo-sensitive resin have the developing solution of lysotype development behavior, for example preferably contains the compound of pKa=7～13 of 0.05～5mol/L concentration, but also can add on a small quantity with glassware for drinking water blended organic solvent is arranged.

Have blended organic solvent as having, can enumerate methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, Pyranton, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl n-butyl ether, benzylalcohol, acetone, methylethylketone, 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, can also in above-mentioned developing solution, add tensio-active agent commonly used.This surfactant concentrations is preferably 0.01 quality %～10 quality %.

As visualization way, can use to stir and develop, spray and develop, spray Lin ﹠amp; Methods such as rotation development, immersion development.

Herein, above-mentioned spray development is described.Can remove uncured portion by spray developing liquid on the photo-sensitive resin after the exposure.In addition, preferably before development,, remove thermoplastic resin, middle layer etc. by injection alkaline liquids low such as water-jets to the solvability of photo-sensitive resin.In addition, also preferably after development, on one side with water-jet jet cleaner etc., carry out wiping with brush etc., the development residue is removed on one side.

The temperature of developing solution is preferably 20 ℃～40 ℃, and in addition, the pH value of developing solution is preferably 8～13.

In addition, when making colour filter of the present invention, as putting down in writing in Japanese kokai publication hei 11-248921 communique, No. 3255107 communiques of special permission, with the photosensitive composition that the forms colour filter formation pedestal that is superimposed together, form transparency electrode thereon, the projection that superimposed again control liquid crystal aligning is used and form spacer, this is preferred in view of reducing cost.

Undertaken when superimposed by being coated with photosensitive composition successively, because the levelling of coating fluid, each superimposed thickness all can attenuation.Therefore, preferred four looks of superimposed K (deceiving) RGB earlier, superimposed again control orientation projection.On the other hand, use when having the transfer materials of thermoplastic resin, in order to keep the constant of thickness, preferred superimposed color is 3 looks or 2 looks.

In addition, from preventing the angle of photo-sensitive resin distortion when stacking with the lamination transfer materials, said base is preferably dimensioned to be more than the 25 μ m, is preferably especially more than the 30 μ m.

[liquid crystal indicator]

Liquid crystal indicator of the present invention uses the colour filter of contrast gradient excellence of the present invention, and the closely knit grade of the black of liquid crystal indicator of the present invention is described the power excellence.Wherein, preferred colour filter of the present invention is the VA mode.Liquid crystal indicator of the present invention also is 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 colour filter that use is made by pigment dispensing composition of the present invention.Below, CCD device of the present invention is elaborated.

(alkali soluble resins)

As the alkali soluble resins that uses in the CCD device, preferably as the material wire organic high molecular polymer, that dissolve in organic solvent and can develop with weak base aqueous solution.As this 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 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 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 the big monomer of (methyl) vinylformic acid 2-hydroxypropyl acrylate/polystyrene/methacrylic acid benzyl ester/Sipacril 2739OF of putting down in writing in the Japanese kokai publication hei 7-140654 communique, 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.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.

Polymerizable monomer

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 vinyl 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 resultant of reaction.In addition, can also use " Japan then Xie Hui Chi ", Vol.20, 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)

General formula (B-2)

{ among general formula (B-1), (B-2), B represents-(CH independently of one another ₂CH ₂O)-and-(CH ₂CH (CH ₃) O)-in any group; X represents any 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, it is 3 or 4 in formula (B-2); N represents 0～6 integer independently of one another, and each n add up to 3～24; M represents 0～6 integer independently of one another, and each m add 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 %.

(tinting material)

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 disclosed pigment in 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, No. 2592207, patent registration, 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, the Japanese kokai publication hei 6-194828 communique etc.As chemical structure, can use dyestuffs such as pyrazoles azo class, anilino azo class, triphenylmethane, anthraquinone class, benzal class, Oxonol class, pyrazoles triazole azo class, pyridinone, cyanine class, phenothiazines, pyrrolo-pyrazoles azomethine class.Especially, because solidification compound can solidify at a lower temperature,, also can alleviate the problems such as decomposition that back baking high temperature following time of being used to give the cured film weather resistance occurs that are exposed to even therefore thermotolerance is than the dyestuff of pigment difference.

As mineral dye is the metallic compound of representing with metal oxide, metallic complex salt etc., specifically, can enumerate the metal oxide of 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 at least a and tetrazo class yellow ultramarine in them or the mixing of 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 100: 5～100: 50th, and 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, Kui phthalein ketone 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～and 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～and 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 polymer combination of the good pigment of dispersiveness and dispersion stabilization with the fine Powdered processed pigment that forms in acrylic resin, toxilic acid resinoid, vinyl chloride-vinyl acetate copolymer 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～and 100: 40.When being in this scope, long wavelength's light transmission rate is low, also has good dispersion stabilization in addition.

(solvent)

As solvent, can enumerate the ester class, for example 3-hydroxy-propionic acid alkyl esters such as vinyl acetic monomer, n-butyl acetate, isobutyl acetate, formic acid pentyl ester, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxacetic acid methyl esters, hydroxacetic acid ethyl ester, hydroxacetic acid butyl ester, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, oxyethyl group ritalin, oxyethyl group vinyl acetic monomer, 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, ethyl 3-oxobutanoate, the 2-beta-hydroxymethyl butyrate, 2-3-hydroxyethyl butyrate etc.; Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran (THF), glycol monomethyl methyl ether, ethylene glycol monomethyl ether, acetic acid methylcyclohexane, acetic acid ethyl cellosolve, diethylene glycol monomethyl ether, TC, Diethylene Glycol single-butyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetic ester, propylene glycol propyl ether acetic ester etc.; Ketone, for example methylethylketone, 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, acetic acid ethyl cellosolve, ethyl lactate, diethylene glycol dimethyl ether, N-BUTYL ACETATE, 3-methoxypropionic acid methyl esters, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, diethylene glycol monobutyl ether acetic ester, propylene glycol methyl ether acetate etc.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 coating composition of the present invention (colored resist liquid) on the substrate successively and carry out the exsiccant operation, carry out the operation of pattern exposure, the operation developed with alkali in exposure back, carry out the operation of heat treated then with i line stepping exposure machine, above-mentioned operation is carried out in reaction for shades of colour (3 looks or 4 looks), make cured film, thereby obtain colour filter.

More particularly, utilize turner to be coated with above-mentioned solidification compound on suitable substrate, the thickness when making drying is generally 0.1～5 μ m, is preferably 0.2～2 μ m, places 2 minutes in 85 ℃ baking oven, is smoothly filmed.

There is no particular limitation to substrate, can enumerate sheet glass, plastic plate, aluminium sheet, imaging apparatus with substrate for electronic component such as silicon chips, 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.In addition, preferably substrate is implemented to be used to improve itself and the high driving fit processing of the cementability of color-filter layer.Specifically, on substrate, carry out the thin layer coating with coupling agent etc. in advance, form solidification compound then, or make in advance and contain coupling agent in the solidification compound.

In addition, when on substrate, having difference of altitude, can on substrate, be coated with and be provided for eliminating difference of altitude, make the level and smooth planarization film of coated face, be coated with solidification compound of the present invention then.For example, image sensors such as CCD are made of the read out gate portion that produces the photoelectric conversion part (photorectifier) of electronics according to light income and be used to export its electronics that produces on the organosilicon substrate, 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 coating chromatic resist on this difference of altitude directly forms colour filter, then optical path length becomes big, so image deepening or light harvesting variation.In order to improve this problem, preferably between CCD and colour filter, form the transparent planarization film that purpose is the landfill difference of altitude.As the material of this planarization film, can enumerate thermosetting resins such as the sort of light solidified resist liquid among the present invention, acrylic acid or the like, epoxies etc.

Behind the coating Photocurable composition,, to carry out preliminary drying usually for evaporating solvent obtains the exsiccant coated 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 stand coating, exposure, the development of other color resist liquid once more.At this moment, for fear of the pattern defect that colour mixture, exposure, development with the resist liquid that is coated with cause, 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～about 250 ℃, carrying out about 0.5～about 2 hours, when utilizing electric furnace to carry out direct heating, under about 180～about 250 ℃, carrying out about 2～about 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 aspect that technology is suitable when use was used colour filter as the i line construction drawing image-position sensor of one of mercuryvapour lamp spectral line, feature of the present invention was remarkable especially, certainly, also can use for CCD.

The developing solution that uses in the solidification compound is not particularly limited, can uses known in the past developing solution.Wherein, organic bases developing solution of tetramethyl ammonium hydroxide quaternary ammonium salts such as (TMAH) can reach purpose of the present invention, is preferred therefore.

(polymerization starter)

As polymerization starter, can use common Photoepolymerizationinitiater initiater.Specifically, can enumerate the vicinal polyketaldonyl compound of putting down in writing in No. 2367660 specification sheets of United States Patent (USP), the alpha-carbonyl compound of putting down in writing in No. the 2367661st, United States Patent (USP) and No. 2367670 specification sheets, 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, the combination of triarylimidazoles dipolymer/p-aminophenyl ketone of putting down in writing in No. 3549367 specification sheets of United States Patent (USP), 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 negativity 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, xanthone, 2-methyl xanthone, 2-methoxyl group xanthone, 2-oxyethyl group xanthone, 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 benzotriazole compound of Japanese Patent Publication 51-48516 communique record etc., チ ヌ PVC Application 1130,400 etc.

Embodiment

Below the present invention will be described in more detail based on embodiment, but the present invention is not limited to these embodiment.

Embodiment

Embodiment 1

The preparation of＜dispersible pigment dispersion A 〉

In 1000ml dimethyl sulfoxide (DMSO) (with the pure medicine of light society system), add methanol solution, 50g pigment C.I. Pigment red 254 (the Irgaphor Red BT-CF of the sodium methylate 28% of 33.3ml, trade(brand)name, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) makes) and 100.0g Polyvinylpyrolidone (PVP) (K-30, trade(brand)name, with the pure medicine of light society system), the pigment preparation solution A.Prepare the water 1000ml that contains 1mol/l hydrochloric acid (with the pure medicine of light society system) 16ml in addition as poor solvent.

At this moment, temperature is controlled to be 18 ℃, utilizing GK-0222-10 type ラ モ Application De ス -ラ-(trade(brand)name, rattan pool pharmaceutical industries society makes) poor solvent that stirs with the rotating speed of 500rpm---among the water 1000ml, with NP-KX-500 type large vol pulseless pump (trade(brand)name, Japan precision chemical society makes) press the flow velocity injection 100ml pigment solution A of 100ml/min, thus form organic pigment particles, make dispersible pigment dispersion A.Use Na ノ ト ラ Star Network UPA-EX150 (trade(brand)name, a day machine dress society makes) to measure the number average bead diameter Mn of this dispersible pigment dispersion, single dispersity (Mv/Mn).The results are shown in the following table 1.

Embodiment 2

The preparation of＜dispersible pigment dispersion B 〉

Change the temperature of the above-mentioned poor solvent among the embodiment 1 into 40 ℃, change the injection flow velocity of above-mentioned pigment solution A into 130ml/min, in addition, prepare dispersible pigment dispersion B by the mode identical with embodiment 1.Measure number average bead diameter and the single dispersity of prepared dispersible pigment dispersion B by the mode identical with embodiment 1.The results are shown in the following table 1.

Embodiment 3

The preparation of＜dispersible pigment dispersion C 〉

Change the injection flow velocity of the above-mentioned pigment solution A among the embodiment 1 into 75ml/min, in addition, prepare dispersible pigment dispersion C by the mode identical with embodiment 1.Measure number average bead diameter and the single dispersity of prepared dispersible pigment dispersion C by the mode identical with embodiment 1.The results are shown in the following table 1.

Embodiment 4

The preparation of＜dispersible pigment dispersion D 〉

Change the temperature of the above-mentioned poor solvent among the embodiment 1 into 35 ℃, in addition, prepare dispersible pigment dispersion D by the mode identical with embodiment 1.Measure number average bead diameter and the single dispersity of prepared dispersible pigment dispersion D by the mode identical with embodiment 1.The results are shown in the following table 1.

Embodiment 5

The preparation of＜dispersible pigment dispersion E 〉

Change the injection flow velocity of the above-mentioned pigment solution A among the embodiment 1 into 130ml/min, in addition, prepare dispersible pigment dispersion E by the mode identical with embodiment 1.Measure number average bead diameter and the single dispersity of prepared dispersible pigment dispersion E by the mode identical with embodiment 1.The results are shown in the following table 1.

Comparative example 1

The preparation of＜dispersible pigment dispersion F 〉

1-methoxyl group-2-propyl group the acetic ester, 6.4g pigment C.I. Pigment red 254 (the Irgaphor Red BT-CF that add 45.3g, trade(brand)name, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (strain) system), the 12.8g Polyvinylpyrolidone (PVP), stir, obtain mixed solution.Then utilize electronic mill M-50 (trade(brand)name, ア イ ガ ジ ヤ パ Application society system) and use the zirconium white microballon of diameter, under the condition of circumferential speed 9m/s, this mixed solution carried out 9 hours dispersion treatment, obtain dispersible pigment dispersion F as 0.65mm.Measure number average bead diameter and the single dispersity of prepared dispersible pigment dispersion F by the mode identical with embodiment 1.The results are shown in the following table 1.

Comparative example 2

The preparation of＜dispersible pigment dispersion G 〉

Changed the dispersion treatment time in the comparative example 1 into 8 hours by 9 hours, in addition, prepare dispersible pigment dispersion G by the mode identical with comparative example 1.Measure number average bead diameter and the single dispersity of prepared dispersible pigment dispersion G by the mode identical with embodiment 1.The results are shown in the following table 1.

Comparative example 3

The preparation of＜dispersible pigment dispersion H 〉

Change the injection flow velocity of the above-mentioned pigment solution A among the embodiment 1 into 30ml/min, in addition, prepare dispersible pigment dispersion H by the mode identical with embodiment 1.Measure number average bead diameter and the single dispersity of prepared dispersible pigment dispersion H by the mode identical with embodiment 1.The results are shown in the following table 1.

Comparative example 4

The preparation of＜dispersible pigment dispersion I 〉

Changed the dispersion treatment time in the comparative example 1 into 4 hours by 9 hours, in addition, prepare dispersible pigment dispersion I by the mode identical with comparative example 1.Measure number average bead diameter and the single dispersity of prepared dispersible pigment dispersion I by the mode identical with embodiment 1.The results are shown in the following table 1.

Table 1

		Number average bead diameter Mn (nm)	Single dispersity (Mv/Mn)
				Embodiment 1	Dispersible pigment dispersion A	33	1.32
Embodiment 2	Dispersible pigment dispersion B	32	1.79
				Embodiment 3	Dispersible pigment dispersion C	50	1.31
Embodiment 4	Dispersible pigment dispersion D	47	1.92
				Embodiment 5	Dispersible pigment dispersion E	29	1.31
Comparative example 1	Dispersible pigment dispersion F	32	2.45
				Comparative example 2	Dispersible pigment dispersion G	45	2.10
Comparative example 3	Dispersible pigment dispersion H	108	1.35
				Comparative example 4	Dispersible pigment dispersion I	95	3.27

Embodiment 6～10, comparative example 5～8

The preparation of＜pigment dispensing composition A～I 〉

[preparation of pigment dispensing composition A]

In the dispersible pigment dispersion A (the about 0.05 quality % of pigment particles concentration) of preparation, add 2-(1-methoxyl group) propyl group acetic ester 500ml, under 25 ℃ and 500rpm, stir 10 minutes after, left standstill 1 day, with pigment particles extract 2-(1-methoxyl group) propyl group acetic ester mutually in, form concentrated extracting solution.

To extract the concentrated extracting solution of formation to above-mentioned pigment particles, and use FP-010 type filter (trade(brand)name, the Off ア イ of Sumitomo Electric Industries Application Port リ マ society makes) to filter, thereby obtain the concentrated pigment liquid A (pigment particles concentration is 30 quality %) of pasty state.

Use the concentrated pigment liquid A of above-mentioned pasty state to prepare pigment dispensing composition A with following composition.About following pigment dispersing agent A, synthesize according to TOHKEMY 2000-239554 communique.

The concentrated pigment liquid A 21.3g of above-mentioned pasty state

Pigment dispersing agent A 0.6g

(exemplary compounds 7 in the compound of above-mentioned general formula (D1) expression)

Methacrylic acid/methacrylic acid benzyl ester copolymer 1 5.8g

(copolymerization mol ratio 28/72, weight-average molecular weight 30,000,

40%1-methoxyl group-2-propyl group acetic ester solution)

1-methoxyl group-2-propyl group acetic ester (with the pure medicine of light society system) 42.3g

Change dispersible pigment dispersion A into dispersible pigment dispersion B～I respectively, in addition, press and concentrated dispersible pigment dispersion A and the identical mode of pigment dispensing composition A, preparation concentrates dispersible pigment dispersion B～I and pigment dispensing composition B～I respectively.

[preparation of film Sample A～I]

To having the pigment dispensing composition A～I of above-mentioned composition, utilize electronic mill M-50 (trade(brand)name respectively, ア イ ガ ジ ヤ パ Application society system) and use the zirconium white microballon of diameter, under the condition of circumferential speed 9m/s, stirred 1 hour, form sample pigment liquid A-I as 0.65mm.

In order to estimate the performance of sample pigment liquid, make the film sample.With rotary coating machine 1H-D7 (trade(brand)name, ミ カ サ society system) the sample pigment liquid A～I of above-mentioned acquisition is coated on the glass substrate of 75mm * 75mm, the usefulness electric furnace descended dry 2 minutes at 100 ℃, thereby made film Sample A～I.

[mensuration of contrast gradient]

For the film sample of making, use is at the three-wavelength cold-cathode tube light source (FWL18EX-N as backlight assembly, trade(brand)name, the manufacturing of the ラ イ of Toshiba Star Network (strain) society) device that on diffuser plate is set and forms, at two polaroid (HLC2-2518, trade(brand)name, the manufacturing of (strain) サ Application リ Star society) places sample between, measure polarizing axis light transmission capacity when vertical when parallel, with its liken to into contrast gradient (referring to, plant wood, Xiao Guan, good fortune forever, work in the mountain, " 512 colour specification 10.4 " サ イ ズ TFT-LCD カ ラ-Off イ Le ", the 7th color reversion glory is learned コ Application Off ア レ Application ス (nineteen ninety) 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 film 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 the film sample is not set briliancy was 1280cd/m when two polaroids were arranged at parallel Nicol ²

The measurement result of the contrast gradient of film Sample A～I is shown in the following table 2 and (has also listed number average bead diameter listed in the table 1 of corresponding sample and single dispersity simultaneously).

Table 2

		Number average bead diameter Mn (nm)	Single dispersity (Mv/Mn)	Contrast gradient
					Embodiment 6	The film Sample A	33	1.32	17000
Embodiment 7	The film sample B	32	1.79	12000
					Embodiment 8	Film sample C	50	1.31	12000
Embodiment 9	Film sample D	47	1.92	11000
					Embodiment 10	Film sample E	29	1.31	19000
Comparative example 5	Film sample F	32	2.45	8000
					Comparative example 6	Film sample G	45	2.10	8500
Comparative example 7	Film sample H	108	1.35	4000
					Comparative example 8	Film sample I	95	3.27	1000

From result shown in the table 2, film Sample A～E of embodiment 6～10 has demonstrated the high contrast gradient of film sample F～I than comparative example 5～8 as can be known, has shown good display characteristic.

In addition, under 220 ℃, respectively above-mentioned film Sample A～I was heated 30 minutes, make film sample J～R, observing on each film sample face whether precipitate is being arranged under 500 times the multiplying power with opticmicroscope (オ リ Application パ ス Co., Ltd. makes for MX-50, trade(brand)name).The results are shown in the following table 3 (also having listed number average bead diameter and the single dispersity shown in the table 1 of corresponding sample simultaneously).

Table 3

	Number average bead diameter Mn (nm)	Single dispersity (Mv/Mn)	Having or not of precipitate
					Film sample J	33	1.32	Do not have and to separate out, evenly	Example of the present invention
Film sample K	32	1.79	Do not have and to separate out, evenly	Example of the present invention
					Film sample L	50	1.31	Do not have and to separate out, evenly	Example of the present invention
Film sample M	47	1.92	Do not have and to separate out, evenly	Example of the present invention
					Film sample N	29	1.31	Do not have and to separate out, evenly	Example of the present invention
Film sample O	32	2.45	Separate out	Comparative example
					Film sample P	45	2.10	Separate out	Comparative example

Film sample Q	108	1.35	Do not have and to separate out, evenly	Comparative example
					Film sample R	95	3.27	Separate out	Comparative example

From result shown in the table 3, single dispersity of pigment particles surpasses on the face of 2.0 sample O, P and R and has observed precipitate in the film sample O～R of comparative example as can be known, and in contrast, film sample J～N of the present invention has all formed the homogeneous surface state of no precipitate.

Embodiment 11

The Pigment red 254 that uses when making dispersible pigment dispersion A～I and film Sample A～R in embodiment 1～10 and the comparative example 1～8 is changed into pigment Violet 23, in addition, makes the film sample according to the mode identical with embodiment 1～10 and comparative example 1～8 respectively.

Measure, observe contrast gradient and have or not precipitate with the film sample that obtains, film sample of the present invention has demonstrated than comparative example better properties.

Embodiment 12

The making of＜colour filter 〉

[making of photosensitive resin transfer material K1]

At thickness is on the interim upholder of polyethylene terephthalate of 75 μ m, is coated with the thermoplastic resin coating fluid that is made of following prescription H1 with the slit-shaped nozzle, and carries out drying.Then, the middle layer coating fluid that coating is made of following prescription P1, and carry out drying.Be coated with the resin combination K1 that constitutes by the component of putting down in writing in the following table 4 again with opacifying property; and carry out drying; the thermoplastic resin that dry film thickness is 15 μ m is set on this interim upholder, middle layer, the dry film thickness that dry film thickness is 1.6 μ m is the resin layer with opacifying property of 2.4 μ m, and pressing protective membrane (thickness is the polypropylene screen of 12 μ m).

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

(thermoplastic resin coating fluid: prescription H1)

Methyl alcohol 11.1 mass parts

Propylene glycol monomethyl ether acetate 6.4 mass parts

Methylethylketone 52.4 mass parts

Methyl methacrylate/2-EHA/methacrylic acid benzyl ester/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-(methacryloxypropyl polyethoxye) phenyl] propane of 2-(chemical industry (strain) system in new) 9.1 mass parts

Tensio-active agent 1 0.54 mass parts

^*Consisting of of tensio-active agent 1 (メ ガ Off ア Star Network F-780-F (big Japanese ink chemical industry (strain) system)):

C ₆F ₁₃CH ₂OCOCH=CH ₂: 40 mass parts and H (OCH (CH ₃) CH ₂) ₇OCOCH=CH ₂: 55 mass parts and H (OCH ₂CH ₂) ₇OCOCH=CH ₂: 5 parts multipolymer (molecular weight 30,000), 30 mass parts

Methylethylketone 70 mass parts

^*Fill a prescription with coating fluid in middle layer (oxygen barrier layers): P1

Polyvinyl alcohol 32.2 mass parts

((strain) Network レ ラ society system, trade(brand)name: PVA205, saponification degree=88%, the polymerization degree 550)

Polyvinylpyrolidone (PVP) 14.9 mass parts

(trade(brand)name: PVP, K-30, ア イ エ ス ピ ピ-ジ ヤ パ Application Co., Ltd. system)

Methyl alcohol 429 mass parts

Distilled water 524 mass parts

Table 4

Moiety K	Content (mass parts)
		K colo(u)rant dispersion thing 1 (carbon black)	25
Propylene glycol monomethyl ether acetate	8.0
		Methylethylketone	53
Binding agent 1	9.1
		Hydroquinone monomethylether	0.002
DPHA liquid	4.2
		2, two (the trichloromethyl)-6-[4 ' of 4--(N, N-diethoxy carbonyl	0.16

Ylmethyl) amino-3 '-bromophenyl]-the s-triazine
		Tensio-active agent 1	0.044

Herein, the preparation to the resin combination K1 with opacifying property of record in the above-mentioned table 4 describes.

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

In addition, in the composition of table 4 record, K colo(u)rant dispersion thing 1, binding agent-1 and DPHA liquid composed as follows.In addition, tensio-active agent 1 is identical with the tensio-active agent 1 that uses among the coating fluid H1 with above-mentioned thermoplastic resin.

(K colo(u)rant dispersion thing 1)

Carbon black (デ グ Star サ society system, trade(brand)name Special Black 250) 13.1 mass parts

Above-mentioned pigment dispersing agent A 0.65 mass parts

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

Propylene glycol monomethyl ether acetate 79.53 mass parts

(binding agent-1)

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

Propylene glycol monomethyl ether acetate 73 mass parts

(DPHA liquid)

Dipentaerythritol acrylate (containing stopper MEHQ 500ppm, Japanese chemical drug (strain) society system, trade(brand)name KAYARAD DPHA) 76 mass parts

Propylene glycol monomethyl ether acetate 24 mass parts

[formation] with next door of opacifying property

For the non-alkali 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-(aminoethyl)-γ-An Bingjisanjiayangjiguiwan with water-jet, trade(brand)name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) society system) 20 seconds, and use the pure water spray Cleaning for High Capacity.This substrate was heated 2 minutes at 100 ℃ with the substrate preheating apparatus.

After the protective membrane of above-mentioned photosensitive resin transfer material K1 peeled off; with Lamic II type laminating machine ((strain) イ of Hitachi Application ダ ス ト リ イ ズ society system; trade(brand)name), be set forth on 2 minutes the substrate of 100 ℃ of following heating last in the condition laminated that 130 ℃ of rubber rollers temperature, line pressure 100N/cm, transfer rate 2.2m/ divide.

After peeling off interim upholder, 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 thermoplastic resin interlayer is 200 μ m, at 100mJ/cm ²Exposure under carry out pattern exposure.Mask shape is a reticulation, is being equivalent to the part of pixel with the boundary line in the next door with opacifying property, and the radius-of-curvature that makes the protrusion angle of next door one side with opacifying property is 0.6 μ m.

Then, (contain 2.5% trolamine, nonionogenic tenside, polypropylene-base defoamer with trolamine class developing solution, trade(brand)name: T-PD1, Fuji description Off イ Le system Co., Ltd. makes) spray development by 30 ℃ of following 30 seconds, the condition of tack nozzle pressure 0.04MPa, remove thermoplastic resin and middle layer (oxygen barrier layers).

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

Then (contain phosphoric acid salt, silicate, nonionogenic tenside, defoamer, stablizer with clean-out system, trade(brand)name " T-SD1 (the description Off イ of Fuji Le system Co., Ltd. system) "), spray by 33 ℃ of following 20 seconds, the condition of conical nozzle pressure 0.02MPa, and remove residue with 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 one 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 above-mentioned 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 ₄Gas flow: 80sccm

Pressure: 40Pa

RF power: 50W

Treatment time: 30sec

[preparation of ink-jet ink for color filter]

With reference to the special embodiment 1 that opens the 2002-201387 communique, by formulation ink shown in the following table 5.

Table 5

Moiety content (mass parts)	R ink 1	G ink 1	B ink 1
				Concentrate pigment liquid A (C.I.P.R. 254)	14	-	-
G pigment (C.I.P.G.36)	-	5.0	-
				B pigment (C.I.P.B.15:6)	-	-	5.0
Macromolecule dispersing agent (the ソ Le パ-ス 24000 of AVECIA corporate system)	2.0	2.0	2.0
				Binding agent (methacrylic acid benzyl ester-Sipacril 2739OF)	3.0	3.0	3.0
Dipentaerythritol five acrylate	2.0	2.0	2.0
				Tripropylene glycol diacrylate	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
				Diethylene Glycol single-butyl ether acetic ester, 29.9dyn/cm	72	81	81
Ink viscosity during ejection (mPas)	15	10	10
				Ink surface tension during ejection (mN/m)	26	21	21

＜viscosity 〉

The viscosity of ink is to use E type viscometer (RE80L, trade(brand)name, eastern machine industry (strain) system), 25 ℃, to use 1 ° of 34 ' * R24 of rotor, minute be to measure under 2 minutes the condition.

＜surface tension 〉

The surface tension of ink is to utilize surface tension instrument (FACE SUFACETENSIOMETER CBVB-A3, trade(brand)name, consonance science society system), measures under 23 ℃ mensuration temperature.

About the mixing of each composition in the above-mentioned table 5, at first pigment and macromolecule dispersing agent are put in a part of solvent, mix, stir with 3 roller mixing rolls and ball mill again, obtain dispersible pigment dispersion.On the other hand, other gradation composition is put in the remaining solvent, carried out stirring and dissolving, obtain binder solution.On one side dispersible pigment dispersion is added in the binder solution bit by bit, with dissolving machine fully stir preparation ink-jet ink for color filter on one side.

In addition, the concentrated pigment liquid A that uses in the making with above-mentioned R ink 1 changes into and concentrates pigment B～I, in addition, prepares R ink 2～9 by the mode identical with R ink 1.

[pixel formation]

Use the piezoelectric type shower nozzle, R ink 1, G ink 1, the B ink 1 of above-mentioned acquisition is instilled into the recess that is surrounded by the opacifying property next door at first in the following manner.The result has just obtained colour filter 1 of the present invention by following mode.In addition, change the R ink 1 in the making of colour filter 1 into R ink 2～9, in addition, prepare colour filter 2～9 by the mode identical with colour filter 1.

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, and its mode is to carry out the warm water circulation in shower nozzle, thereby reaches 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 transport substrates, 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.

In the present embodiment, control transfer rate, driving frequency, the amount of spreading that makes R, G, each pigment of B be 1.1,1.8,0.75g/m ², to R, G, the B corresponding recess of expection in instil R, G, B ink.

The ink that instils is transported to exposed portion, utilizes ultraviolet light-emitting diode (UV-LED) to expose.In the present embodiment, UV-LED uses day NCCU033 (trade(brand)name) of inferior chemical society manufacturing.This LED is that output wavelength is the UV-light of 365nm from the wafer, 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.In the present embodiment, 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 ²In the present embodiment, regulate exposure energy according to transfer rate.

In the mensuration of these exposure powers, exposure energy, the spectroradiometer URS-40D (trade(brand)name) that uses ウ シ オ motor company 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, make colour filter.

Embodiment 13

(making of liquid crystal display device)

Use colour filter 1～9 respectively, make liquid crystal indicator in the following manner.

(formation of ITO electrode)

The substrate that has formed colour filter is packed in the sputter equipment, behind the thick ITO (indium tin oxide) of 100 ℃ of comprehensive vacuum evaporation 1300 dusts, 240 ℃ down annealing made the ITO crystallization in 90 minutes, form ito transparent electrode.

(formation of spacer)

By with [embodiment 1] of TOHKEMY 2004-240335 communique in the identical method of spacer formation method of record, on the ito transparent electrode of above-mentioned making, form spacer.

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

Use following positivity photo-sensitive resin coating fluid, on the above-mentioned ito transparent electrode that forms spacer, be formed for controlling the projection of liquid crystal aligning.

But exposure, development and roasting procedure adopt following method.

Proximity exposure machine (the Ha イ テ of Hitachi Network electronics エ Application ジ ニ ア リ Application グ Co., Ltd. system) 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 proximity exposure.

Then, use 2.38% the tetramethyl ammonium hydroxide aqueous solution, sprayed 30 seconds down at 33 ℃, develop simultaneously by the spray-type developing apparatus.Removed by development thus and do not needed part (exposed portion) on the photo-sensitive resin, thereby obtained the liquid crystal indicator substrate, 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, with the liquid crystal indicator that formed this projection that is used to control liquid crystal aligning with substrate 230 ℃ of bakings 30 minutes down, thereby form the projection that solidified is used to control liquid crystal aligning at liquid crystal indicator on substrate.

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

(the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ リ ア Le ズ (strain) society makes positive corrosion-resisting agent liquid, trade(brand)name: FH-2413F) 53.3 mass parts

Methylethylketone 46.7 mass parts

·メガフアツクF-780F

(trade(brand)name, big Japanese ink chemical industry (strain) society system) 0.04 mass parts

(making of liquid crystal indicator)

The alignment films that is made of polyimide is set at the liquid crystal indicator of above-mentioned acquisition on substrate again.

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, the MVA pattern that instils simultaneously liquid crystal, and paste with relative substrate, then the substrate of pasting is heat-treated, make sealant cures.On the two sides of the liquid crystal cells that obtains by this way, paste polaroid (trade(brand)name: HLC2-2518, (strain) サ Application リ Star society makes).Then, backlight by three-wavelength cold-cathode tube light source (FWL18EX-N that the イ of Toshiba Star Network (strain) society makes) structure, it is installed in the rear side of the liquid crystal cells that is provided with above-mentioned polaroid, form liquid crystal indicator.

As can be known, compare with the display unit of the colour filter 6～9 that has used comparative example, it is excellent having used the liquid crystal indicator of colour filter 1～5 of the present invention to describe aspect the power in black density, redness.

Embodiment 14

[making of PVA pattern, IPS mode liquid crystal display element]

[making of liquid crystal indicator of PVA pattern]

On R pixel, G pixel, B pixel and the black matrix of the colour filter substrate of above-mentioned acquisition, form ITO (Indium Tin Oxide) transparency electrode by sputter again.Then, according to the embodiment 1 of TOHKEMY 2006-64921 communique, the position that is equivalent to black matrix top on the ITO of above-mentioned formation film forms spacer.

Prepare glass substrate in addition, applying the patterning that is used for the PVA pattern respectively on the transparency electrode of colour filter substrate and on the relative substrate, and the alignment films that is made of polyimide is being set thereon again as relative substrate.

Then, the position that is equivalent to housing on the black matrix around being arranged in the mode of surrounding the color filter pixel group, utilize and divide leakage device mode to be coated with the ultraviolet curable resin sealing agent, and instillation PVA pattern liquid crystal, paste with relative substrate, the substrate of pasting with the UV irradiation is heat-treated then then, makes sealant cures.On the two sides of the liquid crystal cells that obtains by this way, paste polaroid (trade(brand)name: HLC2-2518, (strain) サ Application リ Star society makes).Then, use red (R) chip type LED (FR1112H, trade(brand)name, レ-(strain) of ス Application made), green (G) chip type LED (DG1112H, trade(brand)name, ス Application レ-(strain) manufacturing), blue (B) chip type LED (DB1112H, trade(brand)name, レ-(strain) of ス Application made), construct the backlight of sidelight mode, it is installed in the rear side of the liquid crystal cells that is provided with above-mentioned polaroid, forms liquid crystal indicator.

[making of liquid crystal indicator of IPS pattern]

On R pixel, G pixel, B pixel and the black matrix of the colour filter substrate of above-mentioned acquisition, form ITO (Indium Tin Oxide) transparency electrode by sputter again.Then, according to the embodiment 1 of TOHKEMY 2006-64921 communique, the position that is equivalent to black matrix top on the ITO of above-mentioned formation film forms spacer.

In adhering to of above-mentioned acquisition be coated with polyimide on the colour filter substrate of spacer, and carry out friction treatment, form alignment films.

In addition,, driving side substrate and liquid crystal material are made up, thereby make liquid crystal display device at the aforementioned colour filter substrate that obtains.Promptly, as the driving side substrate, preparation is arranged the IPS TFT substrate that forms by TFT and comb shape pixel electrode (conductive layer), make on the colour filter substrate of the surface that is provided with sides such as pixel electrode on this TFT substrate and aforementioned acquisition and formed the surperficial relative of colored pixels layer one side, assemble in this way, cause having at the spacer of aforementioned formation under the state in gap and fixing.Encapsulated liquid crystals material in this gap is provided with the liquid crystal layer of bearing pictorial display.On the two sides of the liquid crystal cells that obtains by this way, paste polaroid (trade(brand)name: HLC2-2518, (strain) サ Application リ Star society makes).Then, the structure cold-cathode tube is backlight, and it is installed in the rear side of the liquid crystal cells that is provided with above-mentioned polaroid, forms liquid crystal indicator.

As can be known, the liquid crystal indicator that forms with colour filter of the present invention all has excellent black density, redness and describes power under any pattern of PVA and IPS, and it is excellent that the redness under the PVA pattern is described Z-TEK.

Embodiment 15

[making of CCD device]

(the CCD making of dispersible pigment dispersion)

According to following prescription, make green (G) dispersible pigment dispersion (1), (B) dispersible pigment dispersion (2), red (R) dispersible pigment dispersion (3).

Dispersible pigment dispersion (1)

C.I.P.G.36 90 mass parts

C.I.P.G.7 25 mass parts

C.I.P.Y.139 40 mass parts

PLAAD ED151 (trade(brand)name, nanmu originally change into (strain) system) 20 mass parts

Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts

(copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 625 mass parts

Dispersible pigment dispersion (2)

C.I.P.B.15:6 125 mass parts

C.I.P.V.23 25 mass parts

PLAAD ED151 (trade(brand)name, nanmu originally change into (strain) system) 40 mass parts

Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts

(copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 785 mass parts

Dispersible pigment dispersion (3)

Pigment dispensing composition A 650 mass parts

Dispersion agent (exemplary compounds C-16) 40 mass parts

Methacrylic acid benzyl ester/Sipacril 2739OF 25 mass parts

(copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Propylene glycol monomethyl ether acetate 335 mass parts

[the CCD making of photosensitive composition]

Each 200 mass parts of versicolor dispersible pigment dispersion for above-mentioned acquisition mix with stirrer and following composition respectively, and preparation is used for versicolor CCD colored resin composition.

＜form

Methacrylic acid benzyl ester/Sipacril 2739OF 35 mass parts

(copolymerization mol ratio 70: 30, weight-average molecular weight 30,000)

Dipentaerythritol five acrylate 38 mass parts

Propylene glycol monomethyl ether acetate 120 mass parts

3-ethoxyl ethyl propionate 40 mass parts

Monochloromethyl triazines initiator (Photoepolymerizationinitiater initiater) 4 mass parts

(trade(brand)name: TAZ107, body ど り chemistry (strain) system)

(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, weight-average molecular weight 30,000)

Dipentaerythritol five acrylate 65 mass parts

Propylene glycol monomethyl ether acetate 138 mass parts

3-ethoxyl ethyl propionate 123 mass parts

Monochloromethyl triazines initiator (Photoepolymerizationinitiater initiater) 3 mass parts

(trade(brand)name: TAZ107, body ど り chemistry (strain) system)

Utilize the rotary coating machine that the planarization that obtains is uniformly coated on the 6-inch silicon chip that has formed photorectifier with resist liquid.In addition, regulate the revolution of rotary coating machine, making the thickness of coating back after heat-treating with electric furnace under 100 ℃ * 120 seconds conditions of coated film surface temperature is about 1.5 μ m.

Then, be positioned over 220 ℃ baking oven 1 hour, coated 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, coating is the above-mentioned CCD photosensitive composition of 100 mass parts with respect to above-mentioned planarization film with resist liquid preparation prescription on above-mentioned planarization film, 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) system) 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) system) the 40 quality % aqueous solution, the stirring of at room temperature carrying out 6 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.

The making of＜CCD device 2～9 〉

Change the pigment dispensing composition A in the making of CCD device 1 into pigment dispensing composition B～I, in addition, press the same manner and make CCD device 2～9.

＜estimate

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 is photographed, observable image on watch-dog finds that CCD device 1～5 of the present invention has obtained the reproduced image distincter than CCD device 6～9.

Claims (23)

1. an organic nano particle is characterized in that being made of organic materials, and number average bead diameter is below the 50nm, and volume average particle size/number average bead diameter is 1.0～2.0.

2. the described organic nano particle of claim 1 is characterized in that described organic materials is a pigment dyestuff.

3. the described organic nano particle of claim 2 is characterized in that described pigment dyestuff is selected from azo class pigment, phthalocyanine pigment, quinoline a word used for translation ketone pigment, indoline-like pigment, cyanine class pigment, merocyanine class pigment, fullerene pigment, Ppolynuclear aromatic class pigment and poly-diacetylene class pigment.

4. claim 2 or 3 described organic nano particles is characterized in that described pigment dyestuff is redness or purple pigment dyestuff.

5. the described organic nano particle of claim 4 is characterized in that described pigment dyestuff is a pyrrolopyrrole class pigment.

6. the described organic nano particle of claim 5 is characterized in that described pyrrolopyrrole class pigment is the diketopyrrolo-pyrrole pigment with following formula (Z) expression.

Formula (Z)

7. the described organic nano particle of claim 5 is characterized in that described pyrrolopyrrole class pigment is the diketopyrrolo-pyrrole pigment with following formula (W) expression.

Formula (W)

8. the described organic nano particle of claim 5 is characterized in that described pyrrolopyrrole class pigment is the diketopyrrolo-pyrrole pigment of representing with following formula V.

Formula V

9. the described organic nano particle of claim 4 is characterized in that described pigment dyestuff Shi dioxazines pigment.

10. the described organic nano particle of claim 9 is characterized in that described dioxazines pigment is C.I. pigment violet 37.

11. the described organic nano particle of claim 9 is characterized in that described dioxazines pigment is the C.I. pigment Violet 23.

12. each described organic nano particle in the claim 1～3, it is characterized in that it being solution by will being dissolved in the described organic materials in the good solvent and miscible with described good solvent and be that the solvent of poor solvent mixes and prepares for described organic materials.

13. the described organic nano particle of claim 12 is characterized in that the poor solvent of described organic materials is selected from water kind solvent, alcoholic solvent, ketones solvent, ether solvent, sulfoxide kind solvent, esters solvent, and their mixture.

14. the described organic nano particle of claim 12 is characterized in that the good solvent of described organic materials is selected from water kind solvent, alcoholic solvent, ketones solvent, ether solvent, sulfoxide kind solvent, esters solvent, amide solvent, and their mixture.

15. the organic nano particle dispersive composition is characterized in that containing described organic nano particle of claim 1 and quality molecular-weight average and is the macromolecular compound more than 1000.

16. the described organic nano particle dispersive composition of claim 15 is characterized in that described macromolecular compound with following general formula (1) expression,

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 ¹It is 1 valency organic group of the group selected alkyl, alkoxysilyl, epoxy group(ing), isocyanate group and the hydroxyl 4 or more that expression has from group, urea groups, urethano, the group of band coordination Sauerstoffatom, the carbon number of acidic-group, band basic nitrogen atom, 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; P ¹Expression macromolecular compound residue; M represents 1～8 number, and n represents 2～9 number, and m+n equals 3～10.

17. photosensitive composition, wherein contain described organic nano particle of claim 1 or claim 15 or 16 described organic nano particle dispersive compositions, binding agent and monomer or oligopolymer at least, and Photoepolymerizationinitiater initiater or Photoepolymerizationinitiater initiater system.

18. claim 15 or 16 described organic nano particle dispersive compositions is characterized in that described organic nano particle dispersive composition is an ink for ink-jet print.

19. a photosensitive resin transfer material is characterized in that, interim upholder is provided with the photo-sensitive resin that contains the described photosensitive composition of claim 17.

20. a colour filter is characterized in that this colour filter is to use described photosensitive composition of claim 17 or the described photosensitive resin transfer material of claim 19 to make.

21. a liquid crystal indicator is characterized in that this liquid crystal indicator possesses the described colour filter of claim 20.

22. the described liquid crystal indicator of claim 21 is characterized in that this liquid crystal indicator is the VA mode.

23. a CCD device is characterized in that this CCD device possesses the described colour filter of claim 22.

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