CN101555362A - Pigment dispersing composition and manufacturing method thereof, coloured polymerized composition, colour filter and manufacturing method thereof - Google Patents

Abstract

The invention provides a pigment dispersing composition and a manufacturing method thereof, coloured polymerized composition, colour filter and manufacturing method thereof. The pigment dispersing composition contains pyrrolo-pyrrole-dione series pigments, 1 to 30 mass parts of phthaloyl imidoalkylated pyrrolo-pyrrole-dione in terms of 100 mass parts of pyrrolo-pyrrole-dione series pigments; 0.1 to 20 mass parts of phthaloyl imidoalkylated quinacridone in terms of 100 mass parts of pyrrolo-pyrrole-dione series pigments and at least an organic solvent.

Description

Pigment dispensing composition and its manufacture method, coloured polymerized composition, colour filter and its manufacture method

Technical field

The present invention relates to pigment dispensing composition, this pigment dispensing composition manufacture method, comprise this pigment dispensing composition coloured polymerized composition, use this coloured polymerized composition and the colour filter and this manufacturing method of color filter that form.

Background technology

Colour filter is to contain polyfunctional monomer, Photoepolymerizationinitiater initiater, alkali soluble resins and other composition and form coloured polymerized composition in the pigment dispensing composition that is dispersed with pigment dyestuff or mineral dye, and uses this coloured polymerized composition to make by formation colored patterns such as photoetch methoies.

In recent years, colour filter has the trend that not only purposes enlarges in watch-dog but also in televisor (TV) in liquid crystal display device (LCD) purposes, along with the trend that this purposes enlarges, also begins the colour characteristics of requirement height in colourity, contrast gradient etc.In addition, in image sensor (solid-state imager) purposes, also require the high colour filter of colour characteristics gradually equally.

For above-mentioned requirements, use primary particle size by miniaturization pigment be effective.As method with the primary particle size miniaturization of pigment, following method is for example arranged: solid and water-insoluble synthetic resins will be under pigment and the room temperature, water-soluble inorganic salts such as salt, and the water-miscible organic solvent one that dissolves at least a portion of above-mentioned synthetic resins reinstate kneader (kneader) etc. carry out mechanically mixing (below, will be to comprising pigment, mixing that the mixture of water-soluble inorganic salt and water-miscible organic solvent carries out is called " salt grinds (salt-milling) "), by washing, remove water-soluble inorganic salt and water-miscible organic solvent (for example with reference to Japanese kokai publication hei 7-13016 communique) then.In the method, because the pulverizing and the crystal growth of the primary particle of pigment are carried out simultaneously, therefore be fit to obtain the final size narrowly distributing, median size is little but pigment that surface-area is little, be fit to obtain as colour filter needs with the pigment high density of fine particle size the method for the pigment in the dispersive purposes.

But the pigment of Zhi Zuoing is the bad situation of dispersiveness and dispersion stabilization owing to cause fierce cohesion in the drying process after desalination mostly like this.Use such pigment, be difficult to obtain dispersiveness, the good colo(u)rant dispersion thing of dispersion stabilization.Under the inadequate situation of dispersing of pigments, striped (fringe has appearred on the colored pattern that forms by the Polymerizable composition that comprises the colo(u)rant dispersion thing, edge section unevenly) or concave-convex surface, have the colourity or the problems such as dimensional precision decline, the remarkable deterioration of contrast gradient of the colour filter that manufactures.

In addition, under the situation of dispersing of pigments poor stability, be accompanied by the passage of time, the constituent of coloured polymerized composition causes cohesion, and viscosity rises, and has the problem that becomes extremely short working life (potlife).In addition, using such coloured polymerized composition to make under the situation of colour filter, the film uniformity in the painting process descends, and causes problems such as sensitivity change, the caustic solubility in developing procedure in exposure process changes, inhomogeneous thus easily.Particularly when on glass substrate, forming coloring film with coloured polymerized composition in order to form large-area colour filter, carry out under the situation of slot coated (slit coating) (perhaps being also referred to as " mouthful mould coating (die coating) "), have the following problems point: coated face is easy to generate defectives such as bar muscle, the surface texture of coating reduces, and this becomes the picture element flaw of colour filter.

Therefore, as the method that improves dispersing of pigments and dispersion stabilization, proposing has the method (for example with reference to Japanese kokai publication hei 8-179111 communique) of adding rosin or rosin derivative or synthetic macromolecular compound when salt grinds.

In addition, for the diketopyrrolo-pyrrole series pigments, proposition has interpolation pigment derivative when salt grinds and promotes micronize, the method (for example with reference to TOHKEMY 2001-220520 communique and Te Kai 2007-31539 communique) that contrast gradient is improved.

But, according to above-mentioned technology in the past, when the contrast gradient of miniaturization that only is conceived to pigment particles and image, though can get the effect of improving to a certain degree, but in miniaturization the diketopyrrolo-pyrrole series pigments in, be used to make the operation of colour filter, particularly developing repeatedly, under the situation that back baking, UV are cleaned, having the withered such problem points in surface.

Summary of the invention

Therefore, the present invention puts in view of the above problems and finishes, to reach following purpose as problem.

That is, the 1st purpose of the present invention is to provide the pigment dispensing composition and the manufacture method thereof of the coloring film that can form high pigment-dispersing and excellent in stability thereof, excellent contrast.

In addition, the 2nd purpose of the present invention is to provide epithelium that can form excellent contrast and then the coloured polymerized composition that can form the colour filter of surface smoothing.

The 3rd purpose of the present invention is to provide the colour filter with high-contrast, surface smoothing, and this manufacturing method of color filter.

The means that are used to solve above-mentioned problem are as follows.

Promptly, pigment dispensing composition of the present invention is characterised in that, contains: diketopyrrolo-pyrrole series pigments, with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts, with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts be 0.1～20 mass parts O-phthalic imide alkylation quinoline a word used for translation ketone and at least a organic solvent.

The average primary particle diameter of preferred above-mentioned diketopyrrolo-pyrrole series pigments is 10nm～30nm.

Can be used for that the diketopyrrolo-pyrrole series pigments of pigment dispensing composition of the present invention preferably obtains by the method with following operation, described operation is: the operation of diketopyrrolo-pyrrole series pigments, water-soluble inorganic salt and the water-miscible organic solvent that do not dissolve this water-soluble inorganic salt in fact being carried out mechanically mixing; Remove the operation of this water-soluble inorganic salt and described water-miscible organic solvent; This diketopyrrolo-pyrrole series pigments is carried out the exsiccant operation; And the operation that described diketopyrrolo-pyrrole series pigments is contacted with resin.

Wherein, the resin that is added preferably acid number be the macromolecular compound of 50～300mgKOH/g.

The manufacture method of pigment dispensing composition of the present invention has following operation: to average primary particle diameter be to add the O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts in the diketopyrrolo-pyrrole series pigments of 10nm～30nm and the O-phthalic imide alkylation quinoline a word used for translation ketone that is 0.1～20 mass parts with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts in the operation of at least a portion; With with the diketopyrrolo-pyrrole series pigments, with respect to this diketopyrrolo-pyrrole series pigments of per 100 mass parts O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts and with respect to this diketopyrrolo-pyrrole series pigments of per 100 mass parts O-phthalic imide alkylation quinoline a word used for translation ketone that is 0.1～20 mass parts with organic solvent dispersive operation.

Coloured polymerized composition of the present invention contains pigment dispensing composition, optical polymerism compound and the Photoepolymerizationinitiater initiater of the invention described above, preferably further contains alkali soluble resins.

Colour filter of the present invention preferably uses the coloured polymerized composition of the invention described above to form, and is preferably the form that possesses the painted areas that forms by coloured polymerized composition of the present invention especially.

In addition, manufacturing method of color filter is characterised in that, utilizes the coloured polymerized composition of the invention described above preferably by coating method it to be formed film on substrate, with the exposure of formed film, then uncured film is developed and removes.

Pigment dispensing composition of the present invention is the O-phthalic imide alkylation diketopyrrolo-pyrrole of specified quantitative and O-phthalic imide alkylation quinoline a word used for translation ketone are disperseed in organic solvent and to form with respect to the diketopyrrolo-pyrrole series pigments.

In the present invention, by also with O-phthalic imide alkylation diketopyrrolo-pyrrole and O-phthalic imide alkylation quinoline a word used for translation ketone, accessing the pigment dispensing composition of dispersion stabilization and excellent contrast with respect to the diketopyrrolo-pyrrole series pigments; Viscosity stability is good, can form the coloured polymerized composition of the good colour filter of contrast gradient height and then surface smoothing; The colour filter that contrast gradient height and surface smoothing are good.

By also using O-phthalic imide alkylation diketopyrrolo-pyrrole and O-phthalic imide alkylation quinoline a word used for translation ketone, can bring into play the bigger synergy of the stability of improving the diketopyrrolo-pyrrole series pigments, therefore by containing the composition that this pigment constitutes, can form excellent contrast, coloring film that surface smoothing is high.Its mechanism of action is still uncertain; but can think: 2 kinds of O-phthalic imide alkylation pigment derivative with different parent nucleus have strong interaction with the different respectively position on the surface of diketopyrrolo-pyrrole pigment; thus; unsettled diketopyrrolo-pyrrole surface is protected; compare with situation about using separately separately; by their synergy; can obtain unforeseeable advantages of excellent stability; by containing the coloured polymerized composition of this pigment, can form pigment and evenly and stably disperse; the contrast gradient height; the coloring film that surface smoothing is good.

According to the present invention, can provide the pigment dispensing composition and the manufacture method thereof of the coloring film that can form high pigment-dispersing and excellent in stability thereof, excellent contrast.

In addition, according to the present invention, can provide the coloured polymerized composition that viscosity stability is good, can form the good epithelium of excellent contrast and surface smoothing, this coloured polymerized composition is suitable for making colour filter.

And then, according to the present invention, can provide colour filter with high-contrast, surface smoothing, and this manufacturing method of color filter.

Embodiment

Manufacture method, coloured polymerized composition, colour filter and manufacture method thereof to pigment dispensing composition of the present invention, pigment dispensing composition described in detail below.

＜pigment dispensing composition 〉

Pigment dispensing composition of the present invention is characterised in that, contain (A) diketopyrrolo-pyrrole series pigments, with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts (B) O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts, with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts (C) O-phthalic imide alkylation quinoline a word used for translation ketone that is 0.1～20 mass parts and (D) at least a organic solvent, as required, also can contain other composition.

((A) diketopyrrolo-pyrrole series pigments)

Diketopyrrolo-pyrrole series pigments among the present invention (following be also referred to as sometimes " DPP series pigments ") is the red～orange pigment of the structure of following general formula (A) expression, has good photostabilization, thermotolerance.

General formula (A)

In the above-mentioned general formula (A), X, Y represent hydrogen atom, alkyl, cyano group, aryl, halogen group independently of one another.

Wherein, alkyl is saturated or undersaturated alkyl.Alkyl, aryl also can further have substituting group.As the substituting group that can import alkyl, for example can list halogen atom, alkenyl, aryl, hydroxyl, alkoxyl group etc., as the substituting group that can import aryl, for example can list halogen atom, alkyl, alkoxyl group etc.

The concrete example of the DPP series pigments of above-mentioned general formula (A) expression with color index (color indexnumber) expression, can be listed C.I. Pigment red 254,255,264 and C.I. pigment orange 71.Wherein, can especially preferably use C.I. Pigment red 254 in the present invention.

In order to obtain the colour filter of high-contrast, the particle diameter of used DPP series pigments is preferably small size and narrowly distributing among the present invention, and preferred average primary particle diameter is 10nm～30nm.By using the particle of this scope, can obtain the good dispersion liquid of dispersion stabilization, by using this dispersion liquid, can form the color solidification film of high-contrast.

Wherein, the particle diameter of DPP series pigments can be measured by for example pigment being taken the image that obtains with transmission electron microscope with 100,000 times of multiplying powers.In addition,, for example can measure the major diameter of particle and the mean value of minor axis, 500 particles are carried out this mensuration for median size, with its mean value as median size.Average primary particle diameter among the present invention is measured by this method and is obtained.

Diketopyrrolo-pyrrole series pigments with such average primary particle diameter can pass through dry type comminuting method, case of wet attrition method, recrystallization method, acid cream paste (acid paste, also be acid wash, acid pasting) known method such as method obtains, but, preferably grind in the present invention and carry out miniaturization by salt in order to obtain the minuteness particle of narrow diameter distribution.Below, to grind by salt obtain miniaturization the situation of diketopyrrolo-pyrrole series pigments be elaborated.

Among the present invention, miniaturization the diketopyrrolo-pyrrole series pigments preferably obtain by following method, described method has:

After diketopyrrolo-pyrrole series pigments, water-soluble inorganic salt and the water-miscible organic solvent that do not dissolve this water-soluble inorganic salt in fact carried out mechanically mixing (salt grinding), remove above-mentioned water-soluble inorganic salt and above-mentioned water-miscible organic solvent, and then make its exsiccant operation;

With the operation that above-mentioned diketopyrrolo-pyrrole series pigments is contacted with resin.

In addition, herein, the resin that is added before salt grinds back and drying process preferably acid number is the macromolecular compound of 50～300mgKOH/g.

When carrying out the salt milled processed, under the prerequisite of not damaging effect of the present invention, except above-mentioned resin, can also and use additives such as pigment dispersion aids, softening agent, tensio-active agent according to purpose.

Below they are described in detail respectively.

(DPP series pigments)

The kind of used diketopyrrolo-pyrrole series pigments as mentioned above in grinding as salt.After grinding, obtain above-mentioned preferred particle diameter at salt, the particle diameter of the diketopyrrolo-pyrrole series pigments before grinding as salt, preferred average primary particle diameter is 20nm～300nm, more preferably 25nm～200nm is suitably for 30nm～150nm most.

In the present invention, used DPP series pigments can be synthetic with known method in grinding for salt, also can use commercially available commodity.As concrete trade(brand)name, can list (being Ciba Specialty Chemicals corporate system) such as IRGAPHOR RED BT-CF, IRGAPHOR RED B-CF, IRGAZIN RED 2030, IRGAZIN DPP RED80, IRGAZIN DPP RED BTR, IRGAZIN DPP RED BL, CROMOPHTAL RED2030, CROMOPHTAL DPP RED BP.

In the present invention, preferably the DPP series pigments is carried out salt separately and grind, but also DPP series pigments and other pigment dyestuffs combination carrying out salt can be ground.

Pigment dyestuff as being used in combination with the DPP series pigments for example can list following pigment dyestuff.

Promptly, the C.I. Pigment red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,270,272,279,

C.I. Pigment Yellow 73 1,2, and 3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214;

C.I. pigment orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,

C.I. pigment Green 7,10,36,37,

C.I. pigment blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79, the Cl substituting group of C.I. Pigment blue 79 changed to OH and pigment, C.I. Pigment blue 80,

C.I. pigment violet 1,19,23,27,32,37,42,

C.I. pigment brown 25,28,

C.I. Pigment black 1,7, etc.

In addition, in the present invention, as the pigment dyestuff that can be used in combination with the DPP series pigments, more preferably following pigment.

Promptly, C.I. Pigment Yellow 73 11,24,108,109,110,138,139,150,151,154,167,180,185,

C.I. pigment orange 36

C.I. pigment red 122,150,171,175,177,209,224,242.

In the present invention, under situation about DPP series pigments and other pigment dyestuffs being used in combination according to hope, the ratio of DPP series pigments can change arbitrarily according to desired form and aspect, but in general, with respect to whole pigment dyestuffs, be that 0.1 quality % is above and be lower than 100 quality %.

(water-soluble inorganic salt)

Employed water-soluble inorganic salt during salt grinds can use sodium-chlor, bariumchloride, Repone K, sodium sulfate etc. so long as be dissolved in the inorganic salt of water and just do not limit especially, but from the viewpoint of price, preferably uses sodium-chlor or sodium sulfate.

The particle diameter of water-soluble inorganic salt is more little can to obtain high micronize effect more, but because undersized inorganic salt price height is preferably 0.1 μ m～100 μ m, more preferably 1 μ m～50 μ m.

The amount of the water-soluble inorganic salt that uses in the salt grinding step is from processing efficiency and this two aspect of production efficiency, and 1～30 quality that is preferably the whole pigment dyestuffs that comprise the DPP series pigments is preferably 5～25 amounts doubly doubly, especially.With respect to pigment dyestuff, the amount of inorganic salt is bigger than more, and miniaturization efficient is high more, but because 1 time pigment treatment capacity tails off, is preferably set to above-mentioned scope.

(water-miscible organic solvent)

Water-miscible organic solvent is to play the material that pigment dyestuff, inorganic salt are carried out wetting action, so long as dissolving (mix) and do not dissolve the solvent of employed water-soluble inorganic salt in fact, just qualification especially in water.

But temperature rose when salt ground, and solvent becomes the state of easy evaporation, and therefore from the viewpoint of security, preferably using boiling point is high boiling solvent more than 120 ℃.

As water-miscible organic solvent, for example can use 2-methyl cellosolve, butoxy ethanol, 2-(isopentyl oxygen base) ethanol, 2-(hexyl oxygen base) ethanol, ethylene glycol, glycol ether, carbiphene, diethylene glycol monoethyl ether acetate, diglycol monotertiary butyl ether, triglycol, triglycol monomethyl ether, aqueous polyoxyethylene glycol, 1-methoxyl group-2-propyl alcohol, 1-oxyethyl group-2-propyl alcohol, dipropyl glycol, dipropyl glycol monomethyl ether, dipropyl glycol list ethyl ether, aqueous polypropylene glycol etc.

In addition, water-miscible organic solvent may be used alone, two or more kinds can also be used.

As the addition of water-miscible organic solvent, be 5 quality %～80 quality % preferably with respect to above-mentioned water-soluble inorganic salt.Be 10 quality %～60 quality % with respect to water-soluble inorganic salt more preferably, optimal is to be 15 quality %～50 quality % with respect to water-soluble inorganic salt.

Addition can mix in the above range equably, and particle diameter becomes evenly easily, and the pliability of the composition that mixes can be maintained the scope that is suitable for handling, and can give the shearing force of appropriateness when mixing, and therefore can obtain desirable micronized effect.

As the interpolation opportunity of water-miscible organic solvent in the salt grinding step, can all add at the initial stage of operation, also can add in batches.

(resin)

In the manufacturing of miniaturization diketopyrrolo-pyrrole series pigments in the present invention, for prevent miniaturization the strong cohesion of diketopyrrolo-pyrrole series pigments when the drying, it can easily be disperseed, pigment and water-soluble inorganic salt etc. is mixed, after removing water-soluble inorganic salt and water-miscible organic solvent, preferably before supplying with drying process, the diketopyrrolo-pyrrole series pigments is contacted with resin.

Here, the DPP series pigments is contacted be meant resin to stick to the meaning at least one of surface of DPP series pigments with resin.

The processing that this DPP series pigments is contacted with resin, can carry out in the arbitrary operation before dry, for example in initial stage of salt grinding step (mixing) or way, behind the salt grinding step, in the dispersion step of salt after grinding, behind the washing step etc., undertaken by adding solid resin or resin solution.

As the resin that contacts with the DPP series pigments, be preferably the macromolecular compound that acid number is 50～300mgKOH/g.By making DPP series pigments and acid number is that the macromolecular compound of 50～300mgKOH/g contacts, and can access the softish powder pigment, can access the high miniaturization DPP series pigments of dispersiveness and dispersion stabilization.

The acid number that uses among the present invention is the macromolecular compound of 50～300mgKOH/g, is preferably water-insoluble macromolecular compound, can use natural resin, modified natural resin, synthetic resins, by the natural resin modification synthetic resins etc.

As natural resin, representational is rosin, as modified natural resin, can use rosin derivative, derivatived cellulose, rubber derivative, protein derivatives and their oligopolymer.

In addition, as synthetic resins, can list Resins, epoxy, acrylic resin, maleic acid resin, butyral resin, vibrin, melamine resin, resol, urethane resin, polyamide resin etc.

As acid number be 50～300mgKOH/g macromolecular compound molecular memory acidic group, have no particular limits, can list sulfonic group, phosphate, carboxylic acid group, phenylol, sulfoamido etc., as particularly preferred acidic group, be the carboxylic acid group.

As acid number, be preferably 50～300mgKOH/g, 50～250mgKOH/g more preferably, optimal is 70～250mgKOH/g.

By acid number being adjusted in this scope, can reach the good caustic solubility of miniaturization DPP series pigments, agglomeration preventing effect, storage stability, dispersiveness when dry.

Acid number is that the molecular weight of the macromolecular compound of 50～300mgKOH/g is preferably counted more than 1000 with weight-average molecular weight and below 50000, more preferably more than 3000 and below 30000, optimal is more than 4000 and below 25000.By molecular weight being adjusted in this scope, can reach the good caustic solubility of miniaturization DPP series pigments, agglomeration preventing effect, dispersiveness when dry.

(macromolecular compound that contains the pigment adsorption base)

In addition, be the macromolecular compound of 50～300mgKOH/g as acid number, also be preferably macromolecular compound with pigment adsorption base.

As macromolecular compound with pigment adsorption base, be preferably particularly and contain from the polymkeric substance that is selected from a kind of monomeric polymerized unit among the group of forming by monomer, maleimide and maleimide derivatives shown in the following general formula (1) (below, be called " particular polymers ").Wherein, as particular polymers, be preferably the polymkeric substance that contains from the monomeric polymerized unit shown in the following general formula (1) especially.

General formula (1)

In the above-mentioned general formula (1), R ¹Expression hydrogen atom or alkyl.R ²The concatenating group of expression singly-bound or divalent.Y represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.Z represents to have the group of nitrogen heterocycle.

As R ¹The alkyl of expression is preferably carbonatoms and is 1～12 alkyl, and more preferably carbonatoms is 1～8 alkyl, is preferably carbonatoms especially and is 1～4 alkyl.

At R ¹The alkyl of expression has under the substituent situation, as this substituting group, for example can list alkoxyl groups such as hydroxyl or methoxyl group, oxyethyl group, cyclohexyloxy.As this alkoxyl group, be preferably carbonatoms and be 1～5 alkoxyl group, more preferably carbonatoms is 1～3 alkoxyl group.

As R ¹The preferred alkyl of expression can list methyl, ethyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl particularly.

Wherein, as R ¹, most preferably be hydrogen atom or methyl.

As the R in the general formula (1) ²The concatenating group of divalent of expression is preferably alkylidene group or contains the divalent group of alkylidene group.As this alkylidene group, be preferably carbonatoms and be 1～12 alkylidene group, more preferably carbonatoms is 1～10 alkylidene group, more preferably carbonatoms is 1～8 alkylidene group, is preferably carbonatoms especially and is 1～4 alkylidene group.

In addition, have under the substituent situation,, for example can list hydroxyl etc. as this substituting group at this alkylidene group.

As R ²The preferred alkylidene group of expression can list methylene radical, ethylidene, propylidene, trimethylene, tetramethylene particularly.

As R ²The divalent group that comprises alkylidene group of expression can be the divalent group that the above-mentioned alkylidene group more than 2 is situated between and is formed by connecting by heteroatoms (for example Sauerstoffatom, nitrogen-atoms or sulphur atom).

In addition, as R ²The divalent group that comprises alkylidene group of expression, can be in above-mentioned alkylidene group, be combined with Z bonded end be selected from-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-and-heteroatoms among the NHCO-or contain the group of heteroatomic part-structure.

The nitrogen heterocyclic ring structure of the nitrogen heterocycle of representing as the Z that constitutes in the general formula (1) can list particularly and has for example nitrogen heterocyclic ring structure of pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure and cyclic imide structure.

These nitrogen heterocyclic ring structures also can have substituting group, as this substituting group, can list for example alkyl, alkoxyl group, halogen atom, aliphatics ester group, aromatic series ester group, alkoxy carbonyl etc.

In the nitrogen heterocyclic ring group that Z represents, more preferably having carbonatoms is the group of the nitrogen heterocyclic ring structure more than 6, is preferably especially to have the group that carbonatoms is 6～12 nitrogen heterocyclic ring structure.

As carbonatoms is nitrogen heterocyclic ring structure more than 6, be preferably thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring, benzimidazole structure, benzotriazole structure, benzothiazole structure, cyclic amide structure, ring-type urea structure and cyclic imide structure particularly, be preferably the structure shown in following general formula (2), (3) or (4) especially.

General formula (2) general formula (3) general formula (4)

In the general formula (2), X represent to be selected from singly-bound, alkylidene group (for example methylene radical, ethylidene, propylidene, trimethylene, tetramethylene etc.) ,-O-,-S-,-NR ^A-and-C (=O)-in any.R wherein ^AExpression hydrogen atom or alkyl.R ^AAlkyl under the expression alkyl situation is preferably that carbonatoms is 1～18 alkyl, more preferably carbonatoms is 1～6 alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, Octadecane base etc.

In above-mentioned, as the X in the general formula (2), be preferably singly-bound, methylene radical ,-O-or-C (=O)-, be preferably especially-C (=O)-.

In the general formula (4), Y and Z represent independently of one another-N=,-NH-,-N (R ^B)-,-S-or-O-.R ^BThe expression alkyl, this alkyl is preferably that carbonatoms is 1～18 alkyl, more preferably carbonatoms is 1～6 alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, Octadecane base etc.

In above-mentioned, Y and Z as in the general formula (4), be preferably especially-N=,-NH-and-N (R ^B)-.As the combination of Y and Z, can list that the either party is among Y and the Z-N=, the opposing party is-combination (imidazolyl) of NH-is preferred combination.

In general formula (2), (3) and (4), ring A, ring B, ring C and ring D represent aromatic nucleus independently of one another.As this aromatic nucleus, can list for example phenyl ring, naphthalene nucleus, indenes ring, azulene, fluorenes ring, anthracene nucleus, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, thiodiphenylamine (phenothiazine) ring, phenoxazine (phenoxazine) ring, dihydroketoacridine ring, anthraquinone ring etc., wherein be preferably phenyl ring, naphthalene nucleus, anthracene nucleus, pyridine ring, phenoxazine ring, acridine ring, thiodiphenylamine ring, phenoxazine ring, dihydroketoacridine ring, anthraquinone ring, be preferably phenyl ring, naphthalene nucleus, pyridine ring especially.

Specifically, as ring A in the general formula (2) and ring B, can list for example phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.

As the ring C in the general formula (3), can list for example phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.

As the ring D in the general formula (4), can list for example phenyl ring, naphthalene nucleus, pyridine ring, pyrazine ring etc.

In the structure of general formula (2), (3) or (4) expression, from the viewpoint of the ageing stability of dispersed, dispersion liquid, ring A, ring B, ring C and ring D be phenyl ring, naphthalene nucleus more preferably, in general formula (2) or (4), phenyl ring more preferably, in general formula (3), naphthalene nucleus more preferably.

In addition, the maleimide derivatives among the present invention is meant the maleimide that the N position has been replaced by substituting groups such as alkyl or aryls.

Below, list the preferred concrete example (monomer M-1～M-30), but the present invention is not limited to these of monomer, maleimide and the maleimide derivatives of general formula (1) expression.

Particular polymers among the present invention can only contain a kind from a kind of monomeric polymerized unit in the monomer, maleimide and the maleimide derivatives that are selected from general formula (1) expression, also can contain more than 2 kinds.

Among monomer, maleimide and the maleimide derivatives of general formula (1) expression, because the monomer of general formula (1) expression is to the adsorptivity height of pigment, so preferred.

In the particular polymers of the present invention, content from a kind of monomeric polymerized unit in the monomer, maleimide and the maleimide derivatives that are selected from general formula (1) expression, when contained entire infrastructure unit is set at 100 quality % in polymkeric substance, preferably contain more than the 5 quality %, further preferably contain 10～50 quality %.

That is to say, for the aggregate of 1 particle suppressing pigment effectively promptly 2 aggregates generation or weaken the cohesive force of 2 aggregates effectively, be preferably more than the 5 quality % from the content of a kind of monomeric polymerized unit in the monomer, maleimide and the maleimide derivatives that are selected from general formula (1) expression.In addition, the viewpoint of the development when making colour filter by the optical polymerism composition that contains pigment dispensing composition is preferably below the 50 quality % from the content of a kind of monomeric polymerized unit in the monomer, maleimide and the maleimide derivatives that are selected from general formula (1) expression.

Particular polymers among the present invention preferably comprises from the monomeric polymerized unit with acidic group.By particular polymers is comprised from the monomeric polymerized unit with acidic group, pigment dispensing composition is being applicable under the situation of optical polymerism composition that the removing property of development of unexposed portion is good.

As monomer, can exemplify out unsaturated monocarboxylic classes such as vinylformic acid, methacrylic acid, Ba Dousuan, α-Lv Daibingxisuan, styracin with acidic group; Unsaturated dicarboxylic acid or its anhydrides such as toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride, methylfumaric acid; Unsaturated polycarboxylic acid more than 3 yuan or its anhydrides; List ((methyl) acryloxyalkyl) the ester class of mono succinate (2-acryloxy ethyl ester), mono succinate (2-methacryloxy ethyl ester), edicarboxylic acid list (2-acryloxy ethyl ester), the edicarboxylic acid list polycarboxylic acids more than 2 yuan such as (2-methacryloxy ethyl esters); List (methyl) esters of acrylic acid of two terminal carboxyl(group) polymkeric substance such as ω-carboxyl-polycaprolactone single-acrylate, ω-carboxyl-polycaprolactone monomethacrylates etc.

Particular polymers of the present invention can only comprise a kind from the monomeric polymerized unit with acidic group, also can comprise more than 2 kinds.

In particular polymers, be to make the acid number of particular polymers be preferably the amount that is preferably 50～300mgKOH/g more than the 50mgKOH/g, especially from the content of monomeric polymerized unit with acidic group.That is, the viewpoint of the generation of the precipitate from suppress developing solution makes preferably that from the content of the monomeric polymerized unit with acidic group the acid number of particular polymers is the amount more than the 50mgKOH/g.For the aggregate of 1 particle suppressing pigment effectively promptly 2 aggregates generation or weaken the cohesive force of 2 aggregates effectively, make preferably that from the content of monomeric polymerized unit the acid number of particular polymers is the amount of 50～300mgKOH/g with acidic group.

In addition, particular polymers in the present invention has under the situation of acid number of 50～300mgKOH/g, can be that the macromolecular compound of 50～300mgKOH/g uses as above-mentioned acid number with this particular polymers.

In addition, the particular polymers among the present invention also can further contain the polymerized unit from vinyl monomer in the scope of not damaging its effect.

Here, as operable vinyl monomer, have no particular limits, for example be preferably ester class, styrenic, (methyl) vinyl cyanide 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 etc.As the concrete example of such vinyl monomer, for example can list following compound.In addition, under any or boths' of expression " propenyl, methylpropenyl " situation, be recited as " (methyl) propenyl " sometimes in this specification sheets.

As the example of (methyl) esters of acrylic acid, can list (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 acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) vinylformic acid 3-phenoxy group-2-hydroxy propyl ester, (methyl) benzyl acrylate, (methyl) vinylformic acid diglycol monotertiary methyl ether, (methyl) vinylformic acid carbiphene, (methyl) vinylformic acid triglycol monomethyl ether, (methyl) vinylformic acid triglycol list ethyl ether, (methyl) polyalkylene glycol acrylate monomethyl ether, (methyl) polyalkylene glycol acrylate list ethyl ether, (methyl) vinylformic acid beta-phenoxy ethoxy ethyl ester, (methyl) vinylformic acid Nonylphenoxy polyoxyethylene glycol, (methyl) vinylformic acid dicyclopentenyl ester, (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 tribromophenoxy ethyl ester etc.

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

As the example of vinyl ester, can list vinyl-acetic ester, vinyl propionate base ester, butyric acid vinyl ester, methoxyacetic acid vinyl ester and phenylformic acid vinyl ester etc.

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

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

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

As (methyl) acrylic amide; can list (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 acrylamide etc.

As the example of vinyl ethers, can list methylvinylether, butyl vinyl ether, hexyl vinyl ether and methoxy ethyl vinyl ether etc.

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

The preferred molecular weight of the particular polymers among the present invention is preferably counted 1000～50000 scope with weight-average molecular weight (Mw), and (Mn) counts 400～30000 scope with number-average molecular weight.More preferably count 3000～30000 scope with weight-average molecular weight (Mw), (Mn) counts 1000～20000 scope with number-average molecular weight.

Particularly, most preferably count 4000～20000 scope with weight-average molecular weight (Mw), (Mn) counts 1500～15000 scope with number-average molecular weight.

That is to say, from for the aggregate of 1 particle suppressing pigment effectively promptly 2 aggregates generation or weaken the viewpoint of the cohesive force of 2 aggregates effectively, the weight-average molecular weight of particular polymers (Mw) is preferably more than 1000.In addition, from the viewpoint of the development when containing the optical polymerism composition of handling pigment and make colour filter, the weight-average molecular weight of particular polymers (Mw) is preferably below 50000.

Particular polymers can utilize the monomer of for example general formula (1) expression and make by common radical polymerization as other free-radical polymerised compounds of copolymer composition.Usually can adopt suspension polymerization or solution polymerization process etc.

The solvent that is adopted during as synthetic such particular polymers, for example can list ethylene dichloride, pimelinketone, methyl ethyl ketone, acetone, methyl alcohol, ethanol, propyl alcohol, butanols, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, 2-methyl cellosolve acetic ester, 1-methoxyl group-2-propyl alcohol, 1-methoxyl group-2-propyl alcohol acetic ester, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, vinyl acetic monomer, methyl lactate, ethyl lactate etc.These solvents can use separately or mix more than 2 kinds.

In addition, fashionable at radical polymerization, can use radical polymerization initiator.In addition, can also further use chain-transfer agent (for example 2 mercapto ethanol and lauryl mercaptan).

The resin that contacts with the DPP series pigments in these operations in the manufacturing process of miniaturization DPP series pigments, that drying is preceding preferably adds 1 quality %～80 quality % with respect to the total amount of the pigment dyestuff that comprises the DPP series pigments.Preferred addition is that the total amount with respect to the pigment dyestuff that comprises the DPP series pigments is 5 quality %～60 quality %, and optimal addition is that the total amount with respect to the pigment dyestuff that comprises the DPP series pigments is 7 quality %～35 quality %.

When addition is in the scope of 1 quality %～80 quality %, prevents flocculating result fully in the time of can obtaining drying, and can obtain the colour filter of preferred form and aspect.

(pigment derivative)

Among the present invention,, also can when grinding, add salt pigment derivative in order to promote the miniaturization of diketopyrrolo-pyrrole series pigments.

As the preferred skeleton that pigment derivative had, can list skeletons such as quinacridine ketone pigment, phthalocyanine pigment, azo class pigment, quinophthalone class pigment, isoindoline class pigment, isoindoline ketone pigment, diketopyrrolo-pyrrole pigment, Benzimidazolinone pigment.In addition, also comprise flaxen aromatic series polynuclear compounds such as naphthalene system, anthraquinone system, triazine system, quinoline system in the preferred skeleton.In these skeletons, the viewpoint from form and aspect and promotion micronized effect particularly preferably is quinacridone pigment, diketopyrrolo-pyrrole series pigments and azo pigment.

In addition, as the example of the pigment derivative that can add, can use Japanese kokai publication hei 11-49974 communique, spy to open flat 11-189732 communique, spy and open flat 10-245501 communique, spy and open 2006-265528 communique, spy and open flat 8-295810 communique, spy and open flat 11-199796 communique, spy and open 2005-234478 communique, spy and open 2003-240938 communique, spy and open 2001-356210 communique, spy and open the pigment derivative that 2001-220520 communique, spy are opened record in the 2007-186681 communique etc.

Add when salt grinds among the present invention under the situation of pigment derivative, with respect to DPP series pigments 100 mass parts, pigment derivative is preferably used with the ratio of 0.1～20 mass parts, further preferably uses in the scope of 0.5～10 mass parts.Content can obtain good micronized effect in the scope that with respect to DPP series pigments 100 mass parts is 0.1～20 mass parts the time.

When salt grinds, add among the present invention under the situation of pigment derivative, general mixing before with DPP series pigments and pigment derivative with the form cooperation of powder and use, but also can in the way of mixing, add pigment derivative.In addition, pigment derivative can once add whole amounts, also can be divided into several times and adding.

Add when salt grinds under the situation of pigment derivative among the present invention, an example of the compound that can use is expressed as follows.

(salt grinding step with and subsequent operation)

Salt grinding step among the present invention is with diketopyrrolo-pyrrole series pigments, water-soluble inorganic salt and does not dissolve the water-miscible organic solvent of this water-soluble inorganic salt in fact and resin as required (preferred acid number is the macromolecular compound of 50～300mgKOH/g) carries out the operation of mechanically mixing.

In this operation; the any device such as micro-granulating device of enough kneaders of energy or planetary-type mixer (planetary mixer), continous way are carried out; temperature during micronize is preferably 10 ℃～150 ℃, more preferably 20 ℃～120 ℃, the most suitable preferably 30 ℃～90 ℃.If carry out micronize being higher than under 150 ℃ the condition, then the speed of growth of particle is faster than micronize speed sometimes, the micronize difficulty that becomes.In addition,, then, make stability and produce fluctuation because the heating during micronize becomes difficult to temperature controlling if carry out micronize being lower than under 10 ℃ the temperature, therefore not preferred.The salt milled processed can carry out obtaining the random time of purpose particle diameter, but be generally 2 hours～24 hours, if the productivity of considering then is preferably 2 hours～15 hours.

Behind above-mentioned such salt grinding step, by removing water-soluble inorganic salt and the water-miscible organic solvent in the thing that mixes, can obtain miniaturization processed pigment.

At first, behind the salt grinding step, generally the thing that mixes that obtains is carried out desalting treatment.

Desalting treatment can use the device of any known to carry out, but general method is that mix thing and hot water are dropped into dispersion slot, stirs with high-speed mixer etc.

Pigment after the dispersion generally filters and cleans.Filter and clean and to use known device arbitrarily to carry out, generally use pressure filter (filter press), also preferably use pressure filter among the present invention.

Generally make desalting treatment and filter after the pigment drying.For drying, use baking oven usually mostly, but also can use spraying drying (spray dry) method or boulton process.Particularly in spray-drying process, the known drying that can obtain is condensed weak, the easy pigment powder of dispersion.

Using under the situation of oven drying, temperature is generally 30 ℃～150 ℃, is preferably 30 ℃～120 ℃, and optimal is 40 ℃～90 ℃.If carry out drying being higher than under 150 ℃ the temperature, then cause fierce drying cohesion, disperse sometimes to become difficult.In addition, be lower than drying under 30 ℃ the temperature need long-time, not preferred from productive viewpoint.

Amount of moisture in the dried processing pigment is generally 0.01 weight %～10 weight %, is preferably 0.05 weight %～5 weight %, and optimal is 0.05 weight %～3 weight %.

Pigment dispensing composition of the present invention contains the DPP series pigments, but preferably uses at least a formation of above-mentioned miniaturization DPP series pigments.

Pigment dispensing composition of the present invention can use with other pigment, dye combinations as required.The concrete example of combination is as follows.

For example, as the pigment of redness, can use at least a (the comprising above-mentioned miniaturization DPP series pigments) of diketopyrrolo-pyrrole series pigments is that yellow ultramarine, isoindoline are that yellow ultramarine, Kui phthalein ketone are that yellow ultramarine Huo perylene is mixing of red pigment etc. with tetrazo.In addition, in order to obtain preferred form and aspect, also preferably diketopyrrolo-pyrrole series pigments and anthraquione pigmentss are used in combination.As the diketopyrrolo-pyrrole series pigments, preferred pigment can list C.I. Pigment red 254, C.I. Pigment red 255, C.I. Pigment red 264 etc., but, be preferably C.I. Pigment red 254 from the viewpoint of form and aspect, dichroism.As anthraquione pigmentss, preferably can list C.I. pigment Red 89, C.I. Pigment red 177 etc., but, preferably use C.I. Pigment red 177 from the viewpoint of form and aspect, dichroism.

Preferred content with respect to the anthraquione pigmentss of diketopyrrolo-pyrrole series pigments 100 mass parts is 0～200 mass parts, and optimal is 0～120 mass parts.

In addition, from the viewpoint of form and aspect, dichroism, contrast gradient, preferably with C.I. Pigment red 254 and C.I. Pigment red 177 and C.I. Pigment Yellow 73 150 or yellow ultramarines such as C.I. pigment yellow 13 9, C.I. pigment yellow 13 8 and usefulness.Wherein, the combination of C.I. Pigment red 254 and C.I. Pigment red 177 and C.I. Pigment Yellow 73 150 and usefulness is from the viewpoint of contrast gradient, and is preferred especially.

As can with the pigment of pigment dispensing composition of the present invention and usefulness, have no particular limits, can use a series of known pigment of having stated in the project of above-mentioned diketopyrrolo-pyrrole series pigments, also as mentioned above as preferably combination.From the viewpoint of contrast gradient, also the pigment optimization of usefulness is extremely reached equal extent with miniaturization DPP series pigments with miniaturization.

As can with the dyestuff of pigment dispensing composition of the present invention and usefulness, have no particular limits, can use the known dyestuff that uses as former colour filter purposes.It for example is Japanese kokai publication sho 64-90403 communique, the spy opens clear 64-91102 communique, Te Kaiping 1-94301 communique, Te Kaiping 6-11614 communique, the spy steps on No. 2592207, United States Patent (USP) the 4th, 808, No. 501 specification sheetss, United States Patent (USP) the 5th, 667, No. 920 specification sheetss, United States Patent (USP) the 5th, 059, No. 500 specification sheets, Japanese kokai publication hei 5-333207 communique, Te Kaiping 6-35183 communique, Te Kaiping 6-51115 communique, Te Kaiping 6-194828 communique, Te Kaiping 8-211599 communique, Te Kaiping 4-249549 communique, Te Kaiping 10-123316 communique, Te Kaiping 11-302283 communique, Te Kaiping 7-286107 communique, the spy opens the 2001-4823 communique, Te Kaiping 8-15522 communique, Te Kaiping 8-29771 communique, Te Kaiping 8-146215 communique, Te Kaiping 11-343437 communique, Te Kaiping 8-62416 communique, the spy opens the 2002-14220 communique, the spy opens the 2002-14221 communique, the spy opens the 2002-14222 communique, the spy opens the 2002-14223 communique, Te Kaiping 8-302224 communique, Te Kaiping 8-73758 communique, Te Kaiping 8-179120 communique, the pigment of record in the Te Kaiping 8-151531 communique etc.

As chemical structure, can use dyestuffs such as pyrazoles azo system, aniline azo system, triphenyl methane system, anthraquinone system, anthrapyridone system, benzal base system, oxonols system, pyrazoles triazole azo system, pyridone azo system, cyanine system, thiodiphenylamine system, pyrroles's pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system.

In pigment dispensing composition of the present invention, can only use a kind of DPP series pigments, also can will also use more than 2 kinds.

As in the pigment dispensing composition comprise the DPP series pigments and according to hope and and the total content of the pigment of other pigment of usefulness, as the ratio of pigment with respect to the total solids composition (quality) of this pigment dispensing composition, be preferably 40～90 quality %, more preferably 50～80 quality %.If the content of pigment is in above-mentioned scope, then color depth fully and can guarantee good colour characteristics effectively.

In addition, with respect to the whole pigment in the pigment dispensing composition of the present invention, the DPP series pigments preferably comprises more than the 50 quality %, further preferably comprises more than the 70 quality %.Pigment whole can be the DPP series pigments more than a kind or 2 kinds.

((B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) O-phthalic imide alkylation quinacridone)

In the pigment dispensing composition of the present invention, with respect to above-mentioned (A) diketopyrrolo-pyrrole series pigments 100 mass parts, contain (B) O-phthalic imide alkylation diketopyrrolo-pyrrole of 0.1～30 mass parts and, contain (C) O-phthalic imide alkylation quinacridone of 0.1～20 mass parts with respect to above-mentioned (A) diketopyrrolo-pyrrole series pigments 100 mass parts.

(B) O-phthalic imide alkylation diketopyrrolo-pyrrole is that at least one O-phthalic imide alkyl is combined in the diketopyrrolo-pyrrole that forms on the diketopyrrolo-pyrrole.In addition, the representational phthalimidomethyl as O-phthalic imide alkyl has structure as follows.

The phthalimidomethyl diketopyrrolo-pyrrole is the diketopyrrolo-pyrrole series pigments derivative of the structure of following general formula (B) expression.

General formula (B)

In the above-mentioned general formula (B), X and Y represent hydrogen atom, alkyl, cyano group, aryl or halogen group independently of one another.N represents the replacement number of phthalimidomethyl, the integer of expression 1～3.X in the above-mentioned general formula (B) and Y are identical with X and Y implication in the above-mentioned general formula (A), and preferred form is also identical.

(B) O-phthalic imide alkylation diketopyrrolo-pyrrole can be with known manufacturing process, for example by being that red pigment is easily made with Paraformaldehyde 96 and adjacent phthalic imidine or the reaction of hydroxymethyl phthalic imidine etc. in sulfuric acid with diketopyrrolo-pyrrole.For this synthetic method, at length be recorded in the spy and open in clear 62-149759 communique etc., can be with reference to the document.As the diketopyrrolo-pyrrole that uses in this is synthetic is red pigment, for example can list C.I. Pigment red 254,255,264 and C.I. pigment orange 71,73 etc., from the viewpoint of synthetic easness and form and aspect, especially preferably use C.I. Pigment red 255.

As (B) O-phthalic imide alkylation diketopyrrolo-pyrrole, the replacement number that can use phthalimidomethyl is 1～3 phthalimidomethyl diketopyrrolo-pyrrole and is not the mixture of red pigment by the diketopyrrolo-pyrrole of O-phthalic imideization.Diketopyrrolo-pyrrole as this moment is a red pigment, for example can list the such diketopyrrolo-pyrrole pigment of C.I. Pigment red 254,255,264 and C.I. pigment orange 71,73 etc.

(C) O-phthalic imide alkylation quinacridone is that at least one O-phthalic imide alkyl has replaced quinacridone ring hydrogen atom and the quinacridone that is combined into.In addition, the representational phthalimidomethyl as O-phthalic imide alkyl has structure as follows.

The phthalimidomethyl quinacridone is the quinacridone pigment derivative of the structure of following general formula (C) expression.

General formula (C)

In the above-mentioned general formula (C), X and Y represent hydrogen atom, methyl or chlorine atom independently of one another.N represents the replacement number of phthalimidomethyl, the integer of expression 1～3.

As the said structure representative can be used for (C) of the present invention O-phthalic imide alkylation quinacridone, for example can list phthalimidomethylization does not have and replaces quinacridone, phthalimidomethyl dimethylquinacridone, phthalimidomethyl dichloro quinacridone etc.

(C) O-phthalic imide alkylation quinacridone contained in the pigment dispensing composition of the present invention can only use a kind, also can be the mixture more than 2 kinds.

(C) O-phthalic imide alkylation quinacridone can be by for example easily making the quinacridone red pigment with Paraformaldehyde 96 and phthalic imidine or the reaction of hydroxymethyl phthalic imidine etc. in sulfuric acid.For this method, be recorded in the spy and open in clear 55-108466 communique etc., can be with reference to the document.

As (C) O-phthalic imide alkylation quinacridone, the replacement number that can use phthalimidomethyl be 1～3 phthalimidomethyl quinacridone with not by the change of O-phthalic imide the mixture of quinacridone red pigment.As the quinacridone red pigment of this moment, for example can list the such nothings of C.I. pigment violet 19 and replace the such dichloro quinacridone pigment of the such dimethylquinacridone pigment of quinacridone pigment, C.I. pigment red 122, C.I. Pigment red 202, C.I. Pigment red 209 etc.

In the pigment dispensing composition of the present invention, (B) O-phthalic imide alkylation diketopyrrolo-pyrrole that contains 0.1～30 mass parts with respect to above-mentioned (A) diketopyrrolo-pyrrole series pigments 100 mass parts, (C) O-phthalic imide alkylation quinacridone that contains 0.1～20 mass parts with respect to (A) diketopyrrolo-pyrrole series pigments 100 mass parts is needs, particularly preferred content as (B) O-phthalic imide alkylation diketopyrrolo-pyrrole, with respect to diketopyrrolo-pyrrole series pigments 100 mass parts is 0.1 mass parts～25 mass parts, and optimal is 0.5 mass parts～20 mass parts.In addition, as the particularly preferred content of (C) O-phthalic imide alkylation quinacridone, be 0.1 mass parts～15 mass parts with respect to diketopyrrolo-pyrrole series pigments 100 mass parts, optimal is 0.5 mass parts～15 mass parts.

As both ratios of addition, respectively in above-mentioned content range separately and (B) addition of O-phthalic imide alkylation diketopyrrolo-pyrrole compare with (C) O-phthalic imide alkylation quinacridone equivalent or more be preferred.By O-phthalic imide alkylation diketopyrrolo-pyrrole and the O-phthalic imide alkylation quinacridone that contains this scope, can obtain the good surface smoothing of high pigment-dispersing, high-contrast and colour filter.

In the present invention, (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) O-phthalic imide alkylation quinacridone can use a kind separately respectively, also can will be more than 2 kinds and use.

In the modulation of pigment dispensing composition of the present invention, (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) O-phthalic imide alkylation quinacridone can add in (A) diketopyrrolo-pyrrole pigment on any opportunity, but preferred at least a portion is carried out back (preferably after average primary particle diameter becomes 10nm～30nm) in the miniaturization of diketopyrrolo-pyrrole and is added.Specifically, for example can list in the thing that mixes after salt grind to finish add, add in the interpolation when desalination disperses, the pigment powder after drying and crushing, add in the pigment dispensing composition to disperseing before, the interpolation of colo(u)rant dispersion on the way etc.Add after the miniaturization of diketopyrrolo-pyrrole by O-phthalic imide alkylation diketopyrrolo-pyrrole and O-phthalic imide alkylation quinacridone, can obtain the good surface smoothing of high pigment-dispersing, high-contrast and colour filter at least a portion.

In pigment dispensing composition of the present invention, in order to improve dispersion stabilization, obtain high-contrast, also preferred and use except above-mentioned (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) pigment derivative the O-phthalic imide alkylation quinacridone.

As can and the preferred pigments derivative of usefulness, can list and have the pigment derivative that possesses the position of affinity with dispersion agent and can be adsorbed on DPP series pigments surface.Have the position of the adsorption site that can become dispersion agent and can be adsorbed on the pigment derivative on DPP series pigments surface by use, dispersion agent becomes and is adsorbed in the DPP surface of pigments easily, the form of DPP series pigments with minuteness particle can be dispersed in the pigment dispensing composition, in addition, can also prevent that it from condensing again.

Can and the preferred pigments derivative of usefulness be specifically be precursor skeleton with the pigment dyestuff, imported acidic groups or basic group, aromatic series base as substituent compound at side chain.As the pigment dyestuff of precursor skeleton, specifically, can list phthualocyanine pigment, azo pigment, Kui phthalein ketone series pigments, isoindoline series pigments, isoindolinone pigment, Benzimidazolinone series pigments etc.In addition, can will have the skeleton of diketopyrrolo-pyrrole series pigments but be not included in the pigment derivative in above-mentioned (B) composition or have the skeleton of quinacridone pigment but be not included in derivative in above-mentioned (C) composition etc. also as pigment derivative and and use.

In addition, as precursor skeleton, also comprise flaxen aromatic series polynuclear compounds such as the naphthalene system that generally is not called pigment, anthraquinone system, triazine system, quinoline system.

Wherein, as preferred precursor skeleton, also can list azo pigment or have the precursor skeleton of quinacridone pigment, diketopyrrolo-pyrrole series pigments but pigment derivative with structure different with the neccessary composition of the invention described above as preferred example.

As can be preferably among the present invention and the pigment derivative of usefulness, can list for example Japanese kokai publication hei 3-153780 communique, spy and open flat 11-49974 communique, spy and open flat 11-189732 communique, spy and open flat 10-245501 communique, spy and open 2006-265528 communique, spy and open flat 8-295810 communique, spy and open flat 11-199796 communique, spy and open 2005-234478 communique, spy and open 2003-240938 communique, spy and open the pigment derivative that 2001-356210 communique, spy are opened record in the 2007-186681 communique etc.

In the present invention, and use except (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) under the situation of the pigment derivative the O-phthalic imide alkylation quinacridone, and the addition of other pigment derivative of usefulness in mass conversion, be preferably 0.1 part～30 parts with respect to 100 parts of pigment contained in the pigment dispensing composition (comprising the diketopyrrolo-pyrrole series pigments), more preferably 0.5 part～30 parts, optimal is 1 part～25 parts.In this scope, can obtain good dispersiveness and high-contrast.The total amount of other pigment derivative under the situation of using other pigment derivative except (B) composition, (C) composition with respect to (B) composition and (C) total amount of composition, is preferably set to 10 times below the amount.

((D) organic solvent)

Pigment dispensing composition of the present invention contains at least a kind of organic solvent.

Used (D) organic solvent in the modulation as pigment dispensing composition of the present invention can list 1-methoxyl group-2-propyl alcohol acetic ester, 1-methoxyl group-2-propyl alcohol, glycol monomethyl methyl ether, diglycol monotertiary methyl ether, vinyl acetic monomer, N-BUTYL ACETATE, ethyl lactate, acetone, methyl ethyl ketone, mibk, pimelinketone, n-propyl alcohol, 2-propyl alcohol, propyl carbinol, hexalin, ethylene glycol, glycol ether, toluene, dimethylbenzene etc.

Organic solvent can be selected according to the purposes of pigment dispensing composition, can only use a kind in composition, and also two or more kinds may be used.

In addition, the addition of organic solvent can be according to the selections that suit such as purposes of pigment dispensing composition, but under the situation of the modulation that is used for coloured polymerized composition described later, from the viewpoint of operability, can become the mode of 5～50 quality % and add so that comprise the solid component concentration of pigment etc.

(other compositions)

-dispersion agent-

In pigment dispensing composition of the present invention,, preferably add dispersion agent from improving the viewpoint of the dispersing of pigments that is contained.

As dispersion agent used among the present invention, can list macromolecule dispersing agent (for example, daiamid and salt thereof, poly carboxylic acid and salt thereof, high molecular unsaturated acid ester, modified polyurethane, modified poly ester, poly-(methyl) acrylate of modification, (methyl) acrylic copolymer, naphthalene sulfonic acidformaldehyde condensation product), polyxyethylated phosphoric acid ester, polyoxyethylene alkyl amine, alkanolamine etc.

Macromolecule dispersing agent can further be categorized into straight chain shape macromolecular compound, terminal-modified type macromolecular compound, graft type macromolecular compound and block type polymer compound from its structure.

Macromolecule dispersing agent is adsorbed on the surface of pigment, has played to prevent to condense such effect again.Therefore, as preferred construction, can list terminal-modified type macromolecular compound, graft type macromolecular compound, the block type polymer compound at position with anchoring on surface of pigments.

Below, be that block type polymer compound, graft type macromolecular compound and terminal-modified type macromolecular compound are illustrated respectively to being fit to macromolecule dispersing agent of the present invention.

(block type polymer compound)

As having no particular limits, can list the block type polymer compound that comprises the pigment adsorption block and be not adsorbed on the block on the pigment as the block type polymer compound of macromolecule dispersing agent.

Monomer as constituting the pigment adsorption block has no particular limits, and for example can list the monomer with functional group that can adsorption pigment.Specifically, can list monomer, monomer with organic pigment structure or heterocycle structure with acidic groups, have the monomer of basic nitrogen atom etc.

Below, for be suitable as constitute the pigment adsorption block monomeric have organic pigment structure or heterocycle structure monomer, have the monomer of acidic groups and have the monomer of basic nitrogen atom and describe.

As monomer with organic pigment structure or heterocycle structure, for example can list the monomer with following pigment structure or heterocycle structure, described pigment structure is a phthalocyanines for example, insoluble azo class, the azo lake class, the anthraquinone class, quinacridone dioxazines, the diketopyrrolo-pyrrole class, anthra pyridine (anthrapyridine) class, two and anthrone (anthanthrone) class, the indanthrone class, flavanthrones, purple perilla ketone; perylene class, thioindigo (thioindigoid) class pigment structure: described heterocycle structure is a thiophene for example, furans, xanthene, the pyrroles, pyrroline, tetramethyleneimine, dioxolane, pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithian, isoindoline, isoindolinone, Benzimidazolinone, benzothiazole, succinimide, phthalic imidine, naphthalimide, glycolylurea, indoles, quinoline, carbazole, acridine, dihydroketoacridine, heterocycle structures such as anthraquinone.

More specifically, have no particular limits, can list the monomer of following structure.

As monomeric example, can list vinyl monomer, have sulfonic vinyl monomer, have the vinyl monomer of phosphate with carboxyl with acidic groups.

As vinyl monomer, can list (methyl) vinylformic acid, vinyl M-nitro benzoic acid, toxilic acid, maleic acid mono alkyl ester, fumaric acid, methylene-succinic acid, Ba Dousuan, styracin, acrylic acid dimer etc. with carboxyl.

In addition, also can utilize (methyl) vinylformic acid 2-hydroxy methacrylate etc. to have addition reaction, ω-carboxyl-polycaprolactone list (methyl) acrylate of the such cyclic acid anhydride of the monomer of hydroxyl and maleic anhydride or phthalate anhydride, cyclohexane dicarboxylic acid acid anhydride etc.

And then, as the precursor of carboxyl, also can utilize the monomer of acid anhydrides such as containing maleic anhydride, itaconic anhydride, citraconic anhydride.

In addition, in these monomers,, be preferably (methyl) vinylformic acid especially from viewpoints such as copolymerization or cost, solvabilities.

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

As monomer,, can list vinyl pyridine, vinyl imidazole, vinyl triazole etc. as having the heterocyclic monomer with basic nitrogen atom; As (methyl) acrylate, can list (methyl) vinylformic acid N, the N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid 1-(N, the N-dimethylamino)-1,1-dimethyl methyl esters, (methyl) vinylformic acid N, the own ester of N-dimethylamino, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N, N-diisopropylaminoethyl ethyl ester, (methyl) vinylformic acid N, N-di-n-butyl amino ethyl ester, (methyl) vinylformic acid N, N-Di-Isobutyl amino ethyl ester, (methyl) vinylformic acid morpholinyl ethyl ester, (methyl) vinylformic acid piperidyl ethyl ester, (methyl) vinylformic acid 1-pyrrolidyl ethyl ester, (methyl) vinylformic acid N, N-methyl-2-pyrrolidyl amino ethyl ester and (methyl) vinylformic acid N, N-aminomethyl phenyl amino ethyl ester etc.; As (methyl) acrylic amide, can list N-(N ', N '-dimethyl aminoethyl) acrylamide, N-(N ', N '-dimethyl aminoethyl) Methacrylamide, N-(N ', N '-diethylamino ethyl) acrylamide, N-(N ', N '-diethylamino ethyl) Methacrylamide, N-(N ', N '-dimethylaminopropyl) acrylamide, N-(N ', N '-dimethylaminopropyl) Methacrylamide, N-(N ', N '-diethylamino propyl group) acrylamide, N-(N ', N '-diethylamino propyl group) Methacrylamide, 2-(N, the N-dimethylamino) ethyl (methyl) acrylamide, 2-(N, the N-diethylamino) ethyl (methyl) acrylamide, 3-(N, the N-diethylamino) propyl group (methyl) acrylamide, 3-(N, the N-dimethylamino) propyl group (methyl) acrylamide, 1-(N, the N-dimethylamino)-1,1-dimethyl methyl (methyl) acrylamide and 6-(N, N-diethylamino) hexyl (methyl) acrylamide, morpholinyl (methyl) acrylamide, piperidyl (methyl) acrylamide, N-methyl-2-pyrrolidyl (methyl) acrylamide etc.; As styrenic, can list N, N-dimethylamino vinylbenzene, N, N-dimethylaminomethyl vinylbenzene etc.

In addition, can also use the carbonatoms that has urea groups, carbamate groups, has a coordination Sauerstoffatom is alkyl, alkoxysilyl, epoxy group(ing), the isocyanate group more than 4, the monomer of hydroxyl.

Specifically, for example can list the monomer of following structure.

And then can utilize the monomer that contains ionic functional group.

Example as ionic vinyl monomer (anionic property vinyl monomer, cationic vinyl monomer), as the anionic property vinyl monomer, can list above-mentioned vinyl monomer with acidic groups an alkali metal salt or with salt of organic amine (for example, 3 grades of amine such as triethylamine, dimethylaminoethanol) etc.As the cationic vinyl monomer, can list above-mentioned nitrogenous vinyl monomer haloalkyl (alkyl: C1～18, halogen atom: chlorine atom, bromine atoms or iodine atom); Benzyl halides such as zephiran chloride, bromination benzyl; Alkyl sulfonic esters such as methanesulfonic (alkyl: C1～18); Aryl sulfonic acid such as Phenylsulfonic acid, toluenesulphonic acids alkyl ester (alkyl: C1～18); Sulfuric acid dialkyl (alkyl: C1～4) etc. carries out the 4 grades of cationic vinyl monomers changing and obtain and dialkyldiallyl ammonium salt etc.

Above-mentioned such have the monomer that can be adsorbed on the functional group on the pigment can be according to wanting the dispersive pigment type suit to select, they can use separately, also can be more than 2 kinds usefulness also.

As constituting the monomer that is not adsorbed on the block on the pigment, have no particular limits, for example can list (methyl) esters of acrylic acid, crotonate class, vinyl ester, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, styrenic, vinyl ethers, vinyl ketones, olefines, maleimide, (methyl) vinyl cyanide etc. and not have the monomer of pigment adsorption base.

Constitute these monomers that are not adsorbed on the block on the pigment, can use separately, also can will also use more than 2 kinds.

In addition, under the situation that is applicable to the pigment dispensing composition that needs the alkaline development processing, above-mentioned formation is not adsorbed on the monomer of the block on the pigment and can and uses with the vinyl monomer with acidic groups yet.

As the example of (methyl) esters of acrylic acid, can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid tertiary butyl cyclohexyl, (methyl) 2-EHA, (methyl) vinylformic acid uncle monooctyl ester, (methyl) dodecylacrylate, (methyl) vinylformic acid stearyl, (methyl) vinylformic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-(2-methoxyethoxy) ethyl ester, (methyl) vinylformic acid-2-chloroethene ester, (methyl) vinylformic acid vinyl ester, (methyl) vinylformic acid 2-phenyl vinyl ester, (methyl) vinylformic acid 1-propenyl ester, (methyl) vinylformic acid allyl ester, (methyl) vinylformic acid 2-allyloxy ethyl ester, (methyl) vinylformic acid propargyl ester, (methyl) vinylformic acid benzyl ester, (methyl) vinylformic acid diethylene glycol monomethyl ether ester, (methyl) vinylformic acid diethylene glycol monoethyl ether ester, (methyl) vinylformic acid triethylene glycol monomethyl ether ester, (methyl) vinylformic acid triglycol monoethyl ether ester, (methyl) polyalkylene glycol acrylate monomethyl ether ester, (methyl) polyalkylene glycol acrylate monoethyl ether ester, (methyl) propenoic acid beta-benzene oxygen ethoxy ethyl ester, (methyl) vinylformic acid Nonylphenoxy macrogol ester, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid octafluoro pentyl ester, (methyl) vinylformic acid perfluoro capryl ethyl ester, (methyl) vinylformic acid two pentamethylene base esters, (methyl) vinylformic acid tribromophenyl, (methyl) vinylformic acid tribromophenoxy ethyl ester, (methyl) vinylformic acid gamma-butyrolactone etc.

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

As the example of vinyl ester, can list vinyl-acetic ester, Mono Chloro Acetic Acid vinyl ester, vinyl propionate base ester, butyric acid vinyl ester, methoxyacetic acid vinyl ester and phenylformic acid vinyl ester etc.

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

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

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

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

As the example of styrenic, can list 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, by can be by hydroxy styrenes, vinyl benzoic acid methyl esters and the alpha-methyl styrene etc. of the group of acidic substance deprotection (for example t-Boc etc.) protection.

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

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

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

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

As the example of (methyl) vinyl cyanide, can list methacrylonitrile, vinyl cyanide etc.

As above-mentioned example, can list vinyl monomer, have sulfonic vinyl monomer or have the vinyl monomer of phosphate with carboxyl with vinyl monomer of acidic groups.

As vinyl monomer, can list (methyl) vinylformic acid, vinyl benzoic acid, toxilic acid, maleic acid mono alkyl ester, fumaric acid, methylene-succinic acid, Ba Dousuan, styracin, acrylic acid dimer etc. with carboxyl.

In addition, can also use (methyl) vinylformic acid 2-hydroxy methacrylate etc. to have the addition reaction of the such cyclic acid anhydride of the monomer of hydroxyl and maleic anhydride or phthalate anhydride, cyclohexyl dicarboxylic acid acid anhydride, ω-carboxyl-polycaprolactone list (methyl) acrylate etc.

In addition, can also use the monomer that contains acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride as carboxyl precursor.

In addition, from viewpoints such as copolymerization or cost, solvabilities, wherein preferred especially (methyl) vinylformic acid.

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

And then, as vinyl monomer, can also use the vinyl monomer that contains the phenol hydroxyl or have vinyl monomer of sulfoamido etc. with acidic groups.

As the method that obtains the block type polymer compound among the present invention, known method obtains before can utilizing.

For example known have living polymerization method (living polymerization method), a living radical polymerization (iniferter polymerization method) etc.And then as additive method; also known have a following method: radical polymerization is fashionable in that monomer with pigment adsorption base or the monomer that do not have the pigment adsorption base are carried out; will with the thiol carboxylic acid; or 2-ethanoyl sulfenyl ethyl ether; 10-ethanoyl sulfenyl decane mercaptan etc. contain the compound coexistence of thioesters and thiol group and polymkeric substance that polymerization obtains is handled with alkali such as sodium hydroxide or ammonia at intramolecularly; make the polymkeric substance that has thiol group on single end; in the presence of the polymkeric substance that has thiol group on resulting single end, make the method for the monomer component generation radical polymerization of another block.In these methods, the living polymerization method is preferred.

Weight-average molecular weight to the block type polymer compound has no particular limits, and is preferably 3,000～100,000 scope, more preferably 5,000～50,000 scope.If weight-average molecular weight more than 3,000, then can more effectively obtain stabilization effect, in addition,, weight-average molecular weight brings into play good dispersiveness if below 100,000, then can more effectively adsorbing.

As the block type polymer compound, also can utilize commercially available product.As concrete example, can list BYK Chemie corporate system " Disperbyk-2000,2001 ", EFKA corporate system " EFKA4330,4340 " etc.

(graft type macromolecular compound)

For the graft type macromolecular compound that uses as macromolecule dispersing agent, have no particular limits, can preferably exemplify out the spy and open clear 54-37082 communique, the spy opens record polyalkyleneimine and petchem are reacted in the clear 61-174939 communique etc. and the compound that obtains, the amino of putting down in writing in the Te Kaiping 9-169821 communique with the side chain of PAH is modified with polyester and the compound that obtains, the spy opens the polyester polyol of putting down in writing in the clear 60-166318 communique and adds generating polyurethane etc., and then can also preferably exemplify out the spy and open flat 9-171253 communique, " chemistry of macromonomer and industry " (IPC publishing department, 1989) etc. in like that, with the graft type macromolecular compound of polyreactive oligomers (hereinafter referred to as macromonomer) as copolymer composition.

The branch portion of graft type macromolecular compound can preferably list polystyrene, polyethylene oxide, poly(propylene oxide), poly-(methyl) acrylate, polycaprolactone etc.Wherein, the graft type macromolecular compound that more preferably has the structural unit of following general formula (5) expression in branch portion.

General formula (5)

In the general formula (5), R ⁷⁴Expression hydrogen atom or carbonatoms are 1～8 alkyl, Q represent cyano group, carbonatoms be 6～30 aryl or-COOR ⁷⁵(wherein, R ⁷⁵Expression hydrogen atom, carbonatoms are that 1～22 alkyl or carbonatoms are 6～30 aryl).

In the general formula (5), R ⁷⁴The alkyl of expression also can have substituting group, is preferably carbonatoms and is 1～6 alkyl, is preferably methyl especially.As the substituting group that can import this alkyl, can list halogen atom, carboxyl, alkoxy carbonyl, alkoxyl group etc.

As the concrete example of such alkyl, can list methyl, ethyl, hexyl, octyl group, trifluoromethyl, carboxyl methyl, methoxycarbonyl methyl etc.

As R ⁷⁴, be preferably hydrogen atom, methyl especially.

In the general formula (5), the aryl that Q represents also can have substituting group, is preferably carbonatoms and is 6～20 aryl, is preferably carbonatoms especially and is 6～12 aryl.As the substituting group that can import this aryl, can list halogen atom, alkyl, alkoxyl group, alkoxy carbonyl etc.

As the object lesson of such aryl, can list phenyl, naphthyl, tolyl, xylyl, propyl group phenyl, butyl phenyl, octyl phenyl, dodecylphenyl, p-methoxy-phenyl, ethoxyl phenenyl, butoxy phenyl, last of the ten Heavenly stems oxygen base phenyl, chloro-phenyl-, dichlorophenyl, bromophenyl, methoxycarbonyl phenyl, ethoxy carbonyl phenyl, butoxy carbonyl phenyl etc.

In these aryl, be preferably no substituted aryl or by the aryl that halogen atom, alkyl or alkoxyl group have replaced, be preferably no substituted aryl especially or by alkyl substituted aryl.

Q at general formula (5) is-COOR ⁷⁵Situation under, R ⁷⁵The alkyl of expression also can have substituting group, is preferably carbonatoms and is 1～12 alkyl, is preferably carbonatoms especially and is 1～8 alkyl.As the substituting group that can import this alkyl, can list halogen atom, alkenyl, aryl, hydroxyl, alkoxyl group, alkoxy carbonyl, amino, amido, formamyl etc.

Object lesson as such alkyl; can list methyl; ethyl; propyl group; butyl; heptyl; hexyl; octyl group; decyl; dodecyl; tridecyl; tetradecyl; hexadecyl; octadecyl; the 2-chloroethyl; the 2-bromotrifluoromethane; 2-methoxycarbonyl ethyl; the 2-methoxy ethyl; the 2-bromopropyl; crotyl; pentenyl; 3-methyl-pentenyl; the 2-hexenyl; 4-methyl-2-hexenyl; benzyl; styroyl; the 3-phenyl propyl; menaphthyl; 2-naphthalene ethyl; the benzyl chloride base; bromobenzyl; methyl-benzyl; Ethylbenzyl; methoxy-benzyl; dimethyl benzyl; dimethoxy-benzyl; cyclohexyl; 2-cyclohexyl ethyl; 2-cyclopentyl ethyl; dicyclo (3.2.1) suffering-2-base; the 1-adamantyl; dimethylaminopropyl; the acetylamino ethyl; N, N-dibutylamino carbamyl ylmethyl etc.

In such alkyl, be preferably no substituted alkyl or, be preferably no substituted alkyl especially by the alkyl that halogen atom, aryl or hydroxyl have replaced.

Q at general formula (5) is-COOR ⁷⁵Situation under, R ⁷⁵The aryl of expression also can have substituting group, is preferably carbonatoms and is 6～20 aryl, is preferably carbonatoms especially and is 6～12 aryl.

As the substituting group that can import this aryl, can list halogen atom, alkyl, alkenyl, alkoxyl group, alkoxy carbonyl, amido etc.

As the object lesson of such aryl, can list phenyl, naphthyl, tolyl, xylyl, propyl group phenyl, butyl phenyl, octyl phenyl, dodecylphenyl, p-methoxy-phenyl, ethoxyl phenenyl, butoxy phenyl, last of the ten Heavenly stems oxygen base phenyl, chloro-phenyl-, dichlorophenyl, bromophenyl, methoxycarbonyl phenyl, ethoxy carbonyl phenyl, butoxy carbonyl phenyl, acetamido phenyl, propionamido-phenyl, dodecanoyl amido phenyl etc.

In such aryl, be preferably no substituted aryl or, be preferably especially by alkyl substituted aryl by the aryl that halogen atom, alkyl or alkoxyl group have replaced.

At such R ⁷⁵In, be preferably hydrogen atom, carbonatoms and be 1～22 alkyl, be preferably hydrogen atom, carbonatoms especially and be 1～12 alkyl.

As the object lesson of the branch portion of the graft type macromolecular compound of such structural unit that has general formula (5) expression in branch portion, can list poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, poly-(methyl) isobutyl acrylate, poly-((methyl) methyl acrylate-copolymerization-(methyl) benzyl acrylate), poly-((methyl) methyl acrylate-copolymerization-vinylbenzene), poly-((methyl) methyl acrylate-copolymerization-(methyl) vinylformic acid), gather ((methyl) methyl acrylate-copolymerization-vinyl cyanide) etc.

Graft type macromolecular compound synthetic that has the structural unit of general formula (5) expression in branch portion also can utilize known any method.

Specifically, the macromonomer that can list structural unit with general formula (5) expression with can with the copolymerization of the ethylenically unsaturated monomers of this macromonomer copolymerization.

In the macromonomer of structural unit with general formula (5) expression, the macromonomer of preferably following general formula (6) expression.

General formula (6)

In the general formula (6), R ⁷⁶Expression hydrogen atom or carbonatoms are 1～8 alkyl; W represents singly-bound or concatenating group as follows or the concatenating group that is made of the arbitrary combination of divalent group as follows; A represents to have the group of the structural unit of above-mentioned general formula (5) expression.

-CH＝CH-，

-O-，-S-， -COO-，-SO ₂-

-NHCOO-，-NHCONH-

In above-mentioned concatenating group, Z ¹And Z ²Represent that independently of one another hydrogen atom, halogen atom, carbonatoms are 1～6 alkyl, cyano group or hydroxyl; Z ³Expression hydrogen atom, carbonatoms are that 1～18 alkyl or carbonatoms are 6～20 aryl.

Object lesson as the macromonomer of such general formula (6) expression can list macromonomer as follows.

A in the concrete structure of above-mentioned macromonomer is identical with A implication in the above-mentioned general formula (6).

As can be used as the macromonomer that commercially available product obtains; can list single terminal methyl group propylene acidylate polymethyl methacrylate oligomer (Mn=6; the inferior synthetic chemical industry of trade(brand)name: AA-6, East Co., Ltd. system) and the positive butyl ester oligopolymer of single terminal methyl group propylene acidylate polyacrylic acid (Mn=6 000; 000, the inferior synthetic chemical industry of trade(brand)name: AB-6, East Co., Ltd. system), single terminal methyl group propylene acidylate polystyrene oligopolymer (Mn=6,000, the inferior synthetic chemical industry of trade(brand)name: AS-6, East Co., Ltd. system).

As the molecular weight of above-mentioned macromonomer, be preferably 1,000～20,000 with the number-average molecular weight (Mn) of polystyrene conversion, more preferably 2,000～15,000.If above-mentioned number-average molecular weight in above-mentioned scope, then can more effectively obtain the steric repulsion effect as dispersion agent.

As can with the ethylenically unsaturated monomers of the macromonomer copolymerization of above-mentioned record, in order to improve dispersing of pigments, dispersion stabilization, preferably use above-mentioned " constituting the monomer of pigment adsorption block ".In addition, as other copolymer compositions, also can make above-mentioned " constituting the monomer that is not adsorbed on the block on the pigment " copolymerization.

Weight-average molecular weight to above-mentioned graft type macromolecular compound has no particular limits, and is preferably set to 3,000～100,000 scope, more preferably 5,000～50,000 scope.If weight-average molecular weight more than 3,000, then can more effectively obtain stabilization effect, in addition,, weight-average molecular weight brings into play good dispersiveness if below 100,000, then can more effectively adsorbing.

As the commercially available product of above-mentioned graft type macromolecular compound, can list Lubrizol company " SOLSPERSE 24000,28000,32000,38500,39000,55000 ", BYK Chemie corporate system " Disperbyk-161,171,174 " etc.

(terminal-modified type macromolecular compound)

As the terminal-modified type macromolecular compound of macromolecule dispersing agent, for example can list the spy and open flat 9-77994 communique, spy and open the macromolecular compound that the end at polymkeric substance of record in the 2002-273191 communique etc. has functional group.

Have no particular limits synthesizing the method that end at polymkeric substance has a macromolecular compound of functional group, for example can list following method or method that they are combined etc.

1. contain the polymerization (for example radical polymerization, anionoid polymerization, cationoid polymerisation etc.) of the polymerization starter of functional group and the synthetic method by use

2. contain the radical polymerization of chain-transfer agent of functional group and the synthetic method by use

Here, as the functional group that imports, the carbonatoms that can list and be selected from organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, carbamate groups, have the coordination Sauerstoffatom is the position in alkyl, alkoxysilyl, epoxy group(ing), isocyanate group, hydroxyl and the ionic functional group more than 4 etc.In addition, also can be the functional group that can be derivatized to these adsorption sites.

As the polymerization starter (polymerization starter that contains functional group) that can import functional group that in above-mentioned 1. synthetic method, adopts in polymer ends, for example can list 2,2 '-azo two (2-cyano group propyl alcohol), 2,2 '-azo two (2-cyano group amylalcohol), 4,4 '-azo two (4-cyanopentanoic acid), 4,4 '-azo two (4-cyano group valeryl chloride), 2,2 '-azo two (2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane), 2,2 '-azo two (2-(2-tetrahydroglyoxaline-2-yl) propane), 2,2 '-azo is two, and (2-(3,4,5,6-tetrahydropyrimidine-2-yl) propane), 2,2 '-azo two { 2-(1-(2-hydroxyethyl)-2-tetrahydroglyoxaline-2-yl) propane }, 2,2 '-azo two (2-methyl-N-(2-hydroxyethyl)-propionic acid amide) etc., and their derivative etc.

As the chain-transfer agent (chain-transfer agent that contains functional group) that can import functional group that in above-mentioned 2. synthetic method, adopts in polymer ends; for example can list sulfhydryl compound (Thiovanic acid for example; mercaptosuccinic acid; thiosalicylic acid; 2 mercaptopropionic acid; the 3-thiohydracrylic acid; 3-sulfydryl butyric acid; N-(2-mercapto radical propionyl group) glycine; 2-sulfydryl nicotinic acid; 3-(N-(2-mercaptoethyl) formamyl) propionic acid; 3-(N-(2-mercaptoethyl) amino) propionic acid; N-(3-mercapto radical propionyl group) L-Ala; mistabrom; 3-sulfydryl propanesulfonic acid; 4-sulfydryl fourth sulfonic acid; 2 mercapto ethanol; 3-sulfydryl-1, the 2-propane diol; 1-sulfydryl-2-propyl alcohol; 3-sulfydryl-2-butanols; mercapto-phenol; 2-mercaptoethyl amine; the 2-mercaptoimidazole; 2-sulfydryl-3-pyridone; benzenethiol; toluenethiol; the sulfydryl methyl phenyl ketone; naphthyl mercaptan; naphthalene methyl mercaptan etc.); the oxide compound of these sulfhydryl compounds is a disulphide; and halogenide (2-iodo ethyl sulfonic acid for example; 3-iodo propanesulfonic acid etc.).

The monomer that uses when carrying out polymerization as the macromolecular compound that has functional group at the end with polymkeric substance for example as free radical polymerization monomer, can use above-mentioned " constituting the monomer that is not adsorbed on the block on the pigment ".

As the molecular weight of terminal-modified type macromolecular compound, preferable weight-average molecular weight is 1,000～50,000.If above-mentioned weight-average molecular weight more than 1,000, then can more effectively obtain the steric repulsion effect as dispersion agent, if below 50,000, then can more effectively suppress stereoeffect, further shorten time to pigment adsorption.

As the commercially available product of terminal-modified type macromolecular compound, can list Lubrizol company " SOLSPERSE 3000,17000,27000 " etc.

In the present invention, as dispersion agent, be preferably graft type macromolecular compound, terminal-modified type macromolecular compound, wherein, the terminal-modified type macromolecular compound that contain graft type macromolecular compound from the monomeric copolymerization units with organic pigment structure or heterocycle structure, has organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups or a carbamate groups as terminal group is particularly preferred.

In addition, among the present invention, can use dispersion resin as required.By using dispersion resin, can improve and handle dispersing of pigments stability, keeping quality.

As the object lesson that can be used for dispersion resin of the present invention, be preferably have carboxyl, the resin of sulfonic group, phosphate, amino etc.

For example having the spy to open clear 59-44615 communique, special public clear 54-34327 communique, special public clear 58-12577 communique, special public clear 54-25957 communique, spy as the polymkeric substance that has carboxylic acid at side chain opens clear 59-53836 communique, spy and opens 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 maleic acid etc., similarly have the acid cellulose derivative of carboxylic acid in addition in addition at side chain.

The polymkeric substance that has carboxylic acid at side chain for example can list (methyl) vinylformic acid; toxilic acid (acid anhydride); Ba Dousuan; methylene-succinic acid; fumaric acid etc. have the monomer and the vinylbenzene of carboxyl; alpha-methyl styrene; (methyl) methyl acrylate; (methyl) ethyl propenoate; (methyl) propyl acrylate; (methyl) isopropyl acrylate; (methyl) butyl acrylate; (methyl) isobutyl acrylate; vinyl acetate between to for plastic base ester; vinyl cyanide; (methyl) acrylamide; glycidyl (methyl) acrylate; allyl glycidyl ether; the ethylacrylic acid glycidyl esters; the Ba Dousuan glycidyl ether; (methyl) acrylate chloride; (methyl) benzyl acrylate; (methyl) phenyl acrylate; (methyl) Hydroxyethyl Acrylate; N hydroxymethyl acrylamide; N; the N DMAA; N-methacryloyl morpholine; N; N-dimethyl aminoethyl (methyl) acrylate; N, N-dimethyl aminoethyl acrylamide; maleimide; the copolymer composition copolymerization more than a kind in the N-phenylmaleimide etc. and the polymkeric substance that obtains.Wherein preferably comprise (methyl) vinylformic acid or (methyl) alkyl acrylate (methyl) acrylic resin at least, also preferably comprise (methyl) vinylformic acid and cinnamic (methyl) acrylic resin as structural unit.These acrylic acid copolymer compositions are not limited to above-mentioned composition.

In addition, for these dispersion resins, also can be on side chain the two keys of addition ethylenic.By on side chain, giving two keys, can improve light solidified, further improve resolution, adaptation.

As the synthesizing mean that imports the two keys of ethylenic, for example can list the method for record in special public clear 50-34443 communique, the special public clear 50-34444 communique etc. etc.Specifically, can list carboxyl or hydroxyl and have the compound of glycidyl, epoxycyclohexyl and (methyl) acryl or the method for reaction such as acrylate chloride.For example use (methyl) glycidyl acrylate, allyl glycidyl ether, α-Yi Jibingxisuan glycidyl ester, crotonyl glycidyl ether, (different) Ba Dousuan glycidyl ether, (3; the 4-epoxycyclohexyl) compounds such as (methyl) methyl acrylate, (methyl) acrylate chloride, (methyl) acryloyl chloride; by with the resin reaction with carboxyl or hydroxyl, thereby can access the resin that has polymer-based group at side chain.

The resin that particularly preferably makes the reaction of (3, the 4-epoxycyclohexyl) (methyl) methyl acrylate and obtain.As these concrete compounds, for example can list DIANAL NR series (Mitsubishi Rayon Co., Ltd. system), Photomer 6173 (the Polyurethane acrylic oligopolymer, the Diamond Shamrock Co.Ltd. system that contain COOH), BISCOAT R-264, KS resist 106 (being Osaka Organic Chemical Industry Co., Ltd.'s system), CYCLOMERP series, PLACCEL CF200 series (being DAICEL chemical industry Co., Ltd. system), Ebecryl3800 (DAICELUCB Co., Ltd. system) etc.

In addition, the polymkeric substance that also can use monomer of representing by following at least general formula (7) and the copolyreaction that has the monomer (can list above-mentioned copolymer composition) of acidic groups at least to obtain.

H ₂C=CRC (=O) OCR ⁴R ⁵C (=R ³)=CR ²R ¹General formula (7)

In the above-mentioned general formula (7), R represents hydrogen atom or methyl, R ¹～R ⁵Expression independently of one another is selected from the group of hydrogen atom, halogen atom, cyano group, alkyl and aryl.

As the object lesson of above-mentioned halogen atom, can list Cl, Br, I etc.

Abovementioned alkyl can be straight chain, side chain or ring-type, for example can list methyl, n-propyl, sec.-propyl, the tertiary butyl etc., is preferably carbonatoms and is 1～7 alkyl.

As above-mentioned aryl, for example can list phenyl, furyl, naphthyl etc.

In above-mentioned, as dispersion resin, can select various monomers, control solubleness and acid number, therefore be preferably the multipolymer of (methyl) vinylformic acid and (methyl) acrylate.These dispersion resins are 1,000～80,000 by the preferable range of the weight-average molecular weight that gel permeation chromatography (GPC) is measured, more preferably 3,000～50,000, most preferably be 3,000～20,000.By weight-average molecular weight is controlled at below 80,000, can obtains good dispersiveness and liquid fluidity, and can obtain good development.

These dispersion resins not only can be when the modulation of pigment dispensing composition dispersing of pigments the time use, also can when the modulation of coloured polymerized composition described later, add and use.

The addition of dispersion agent adds in the mode that becomes 0.5～100 quality % with respect to pigment optimization, and more preferably 3～100 quality % are preferably 5～80 quality % especially.

If the addition of dispersion agent in this scope, then can obtain sufficient colo(u)rant dispersion effect.But the optimum addition of dispersion agent can pass through the adjustment that suit such as combination such as employed pigment, solvent.

In addition, more specifically,,, with respect to pigment, be preferably the scope of 5 quality %～100 quality %, more preferably the scope of 10 quality %～80 quality % as its usage quantity if use the situation of macromolecule dispersing agent.

In addition, in the pigment dispensing composition of the present invention, except above-mentioned dispersion agent,, can also use tensio-active agent etc. in order to improve dispersiveness.

By utilizing pigment dispensing composition of the present invention to modulate coloured polymerized composition, and it is applicable in the manufacturing of colour filter, can accesses contrast gradient height, the good colour filter of surface smoothing.

(modulation of pigment dispensing composition)

Pigment dispensing composition among the present invention can be modulated through the blending dispersion operation of carrying out blending dispersion by using various mixing machines, dispersion machine.

In addition, the blending dispersion operation preferably includes to mix disperses and looses at the differential that carries out continuously thereafter to handle, but also can omit the dispersion of mixing.

In the manufacture method of pigment dispensing composition of the present invention, the following operation of preferred enforcement: at first implement with the miniaturization of (A) diketopyrrolo-pyrrole series pigments, when its average primary particle diameter reaches the scope of 10nm～30nm, add at least a portion in the predetermined addition, be preferably whole (B) O-phthalic imide alkylation diketopyrrolo-pyrroles and (C) operation of O-phthalic imide alkylation quinacridone; Implement then with (A) diketopyrrolo-pyrrole series pigments, (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) O-phthalic imide alkylation quinacridone with organic solvent dispersive operation.Also can add (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) part of O-phthalic imide alkylation quinacridone before the scope of 10nm～30nm though reach, more preferably after the average primary particle diameter of (A) diketopyrrolo-pyrrole series pigments reaches the scope of 10nm～30nm and finishes miniaturization, add the whole of predetermined addition at the average primary particle diameter of (A) diketopyrrolo-pyrrole series pigments.

In addition, when beginning to disperse, preferred add whole (B) O-phthalic imide alkylation diketopyrrolo-pyrrole of predetermined addition and (C) O-phthalic imide alkylation quinacridone, but the part that also can when beginning to disperse, add the addition of being scheduled to.In this case, for example can in disperseing the way, remainder be added.

If manufacture method of the present invention is carried out specific description, then be for example with (A) diketopyrrolo-pyrrole pigment and (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) at least a portion in the predetermined addition of O-phthalic imide alkylation quinacridone so that with here as required and and the dispersion agent of usefulness be pre-mixed.Further will disperse in advance this mixture with homogenizer etc., having used the medium stirring-type dispersion machine (for example デ イ ス パ one マ Star ト of GETZMANN corporate system) etc. of zirconium oxide bead etc. to carry out differential with organic solvent utilization in dispersed this mixture in advance looses, can modulate pigment dispensing composition of the present invention thus.

In the present invention, utilizing medium stirring-type dispersion machine to carry out not carrying out gentle dispersion in order not give at short notice under the diffusing situation about handling of differential, preferably use median size to be the medium more than the 0.01mm and below the 0.2mm by dispersion with causing damage.Here, the median size among the present invention is meant the diameter of equivalent circle of medium, is to try to achieve according to the major diameter of 100 media and the mean value of minor axis.Specifically, medium is carried out bust shot with stereomicroscope, can obtain particle diameter from its image.

In the present invention, before the medium more than with 0.01mm and below the 0.2mm disperses, preferably carry out pre-dispersed so that oversize particle is carried out precrushing.In pre-dispersed,, preferably use larger sized medium, preferably use median size to be the medium more than the 0.3mm and below the 1.0mm, more preferably the medium that 0.4mm is above and 1.0mm is following for the purpose that oversize particle is pulverized.

As jitter time, can wait according to the amount of employed device, pigment dispensing composition and set Best Times, but be generally about 1～24 hour.

In addition, about mix, the dispersive detailed content, on the books in T.C.Patton work " Paint Flow andPigment Dispersion " (John Wiley and Sons society published in 1964), TOHKEMY 2007-16206 communique etc.

Resulting pigment dispensing composition is because the dispersiveness and the dispersion stabilization of diketopyrrolo-pyrrole pigment is good, is suitable for containing diketopyrrolo-pyrrole pigment as in the coloured polymerized composition of the various uses of tinting material, for example following explanation etc.

＜coloured polymerized composition 〉

Coloured polymerized composition of the present invention comprises above-mentioned pigment dispensing composition of the present invention, optical polymerism compound and Photoepolymerizationinitiater initiater, further preferably comprises alkali soluble resins, as required, also can comprise other compositions.

Below, each contained in the coloured polymerized composition of the present invention composition is described in detail.

(pigment dispensing composition)

Coloured polymerized composition of the present invention is to use at least a of above-mentioned pigment dispensing composition of the present invention and constitutes.For the detailed content of the pigment dispensing composition of the present invention that constitutes coloured polymerized composition, as mentioned above.

Content as the pigment dispensing composition in the coloured polymerized composition of the present invention, total solids composition (quality) with respect to coloured polymerized composition, the content that is preferably pigment becomes the amount of the scope of 5～70 quality %, more preferably becomes the amount of the scope of 15～60 quality %.If the content of pigment dispensing composition is in this scope, then color depth fully and can guarantee good colour characteristics effectively.

(optical polymerism compound)

Coloured polymerized composition of the present invention contains at least a kind optical polymerism compound.

The optical polymerism compound that can use in the present invention is the addition polymerization compound with at least one ethylenic unsaturated double-bond, be selected from have at least 1, the compound of preferred terminal olefinic link formula unsaturated link(age) more than 2.Such compound group is widely known by the people in this industrial field, and the present invention can not have particular determination ground to use these compounds.The optical polymerism compound for example can be, and monomer, prepolymer are 2 polymers, 3 polymers and oligopolymer or their mixture and their chemical forms such as multipolymer.

As the example of monomer and multipolymer thereof, can list unsaturated carboxylic acid (for example vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, iso-crotonic acid, toxilic acid etc.) or its ester class, amides.The preferred amides that uses ester, unsaturated carboxylic acid and the aliphatic polyamine compound formation of unsaturated carboxylic acid and aliphatic polyol compound formation.In addition, the also preferred addition reaction that uses the substituent esters of unsaturated carboxylic acids of nucleophilicity such as having hydroxyl, amino, sulfydryl or amides and simple function or polyfunctional isocyanates or epoxies, and with the dehydration condensation thing of simple function or polyfunctional carboxylic acid etc.In addition, also be preferably the addition reaction of substituent esters of unsaturated carboxylic acids of Electron Affinities such as having isocyanate group, epoxy group(ing) or amides and simple function or polyfunctional alcohols, amine, thio-alcohol, and then also be preferably the substituted reactant of the esters of unsaturated carboxylic acids of the substituents of leaving away such as having halogen radical, tosyloxy or amides and simple function or polyfunctional alcohols, amine, thio-alcohol.In addition, as other example, can also use by the compound group of replacements such as unsaturated phosphonic acids, vinylbenzene, vinyl ether to replace above-mentioned unsaturated carboxylic acid.

The monomeric object lesson of the ester that forms as aliphatic polyol compound and unsaturated carboxylic acid, as acrylate, glycol diacrylate is arranged, triethylene glycol diacrylate, 1, the 3-butylene glycol diacrylate, the tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, Viscoat 295, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, Viscoat 335HP, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the Dipentaerythritol diacrylate, dipentaerythritol acrylate, the Sorbitol Powder triacrylate, the Sorbitol Powder tetraacrylate, Sorbitol Powder five acrylate, Sorbitol Powder six acrylate, three (acryloxy ethyl) isocyanuric acid ester, the polyester acrylic ester oligomer, cyamelide EO modification triacrylate etc.

As methacrylic ester, have 1,4-butyleneglycol two (methacrylic acid) ester, triglycol two (methacrylic acid) ester, neopentyl glycol two (methacrylic acid) ester, trimethylolpropane tris (methacrylic acid) ester, trimethylolethane trimethacrylate (methacrylic acid) ester, ethylene glycol bisthioglycolate (methacrylic acid) ester, 1,3 butylene glycol two (methacrylic acid) ester, hexylene glycol two (methacrylic acid) ester, tetramethylolmethane two (methacrylic acid) ester, tetramethylolmethane three (methacrylic acid) ester, tetramethylolmethane four (methacrylic acid) ester, Dipentaerythritol two (methacrylic acid) ester, Dipentaerythritol six (methacrylic acid) ester, Sorbitol Powder three (methacrylic acid) ester, Sorbitol Powder four (methacrylic acid) ester, two [right-(3-methacryloxy-2-hydroxyl propoxy-) phenyl] dimethylmethane, two-[right-(methacryloxy oxyethyl group) phenyl] dimethylmethanes etc.

As itaconic ester, ethylene glycol bisthioglycolate itaconic ester, propylene glycol diitaconate, 1 are arranged, 3-butyleneglycol diitaconate, 1,4-butyleneglycol diitaconate, tetramethylene glycol diitaconate, tetramethylolmethane diitaconate, Sorbitol Powder four itaconic esters etc.

As crotonate, ethylene glycol bisthioglycolate crotonate, tetramethylene glycol two crotonates, tetramethylolmethane two crotonates, Sorbitol Powder four crotonates etc. are arranged.As the iso-crotonic acid ester, ethylene glycol bisthioglycolate iso-crotonic acid ester, tetramethylolmethane two iso-crotonic acid esters, Sorbitol Powder four iso-crotonic acid esters etc. are arranged.As maleic acid ester, ethylene glycol bisthioglycolate maleic acid ester, triglycol dimaleate, tetramethylolmethane dimaleate, Sorbitol Powder four maleic acid esters etc. are arranged.

Example as other ester, can suitably use and for example open the fatty alcohol of putting down in writing among the clear 57-196231 the public clear 51-47334 of spy, spy is the ester class, or open the spy that clear 59-5240, spy open clear 59-5241, the spy opens the ester of putting down in writing among the flat 2-226149 with aromatic series pastern bone frame, the spy open put down in writing among the flat 1-165613 contain amino ester etc.And then above-mentioned ester monomer can also use as mixture.

In addition, the monomeric object lesson of the acid amides that forms as aliphatic polyamine compound and unsaturated carboxylic acid, methylene diacrylamine, methylene radical two (Methacrylamide), 1 are arranged, 6-hexa-methylene diacrylamine, 1,6-hexa-methylene two (Methacrylamide), Diethylenetriamine three acrylamides, benzene two methylene diacrylamines, benzene two methylenes two (Methacrylamide) etc.As other the monomeric example of preferred amide class, can list the acid amides of putting down in writing among the special public clear 54-21726 with cyclohexylidene structure.

In addition, the amino formate addition polymerization compound that utilizes the addition reaction of isocyanic ester and hydroxyl and prepare also is suitable, as such concrete example, can list the polyisocyanate compounds that in 1 molecule, has the isocyanate group more than 2 for example in the public clear 48-41708 communique of spy, put down in writing and the vinyl monomer addition that contains hydroxyl shown in the following general formula (a) and vinyl carbamate compound that in 1 molecule, contains the polymerizability vinyl more than 2 of forming etc.

CH ₂=C (R) COOCH ₂CH (R ') OH general formula (a)

(wherein, R and R ' represent H or CH respectively ₃)

In addition, open the such urethane acrylate class of record in clear 51-37193 number, special fair 2-32293 number, special fair 2-16765 number the spy, the carbamate compounds class with ethylene oxide skeleton of record also is preferred in the public clear 58-49860 of spy number, special public clear 56-17654 number, special public clear 62-39417 number, special public clear 62-39418 number.And then, open clear 63-277653 number, spy the spy and open the addition polymerization compounds that intramolecularly that clear 63-260909 number, spy open record in flat 1-105238 number has amino structure or sulfide based structural by using, also can obtain the very good optical polymerism composition of film speed.

As other example, can list and open the spy that such polyester acrylate class, the Resins, epoxy of record reacts polyfunctional acrylate or the methacrylic esters such as epoxy acrylate class that forms with (methyl) vinylformic acid in each communique of clear 48-64183 number, special public clear 49-43191 number, special public clear 52-30490 number.In addition, can also list the specific unsaturated compound of record in the public clear 46-43946 of spy number, special fair 1-40337 number, special fair 1-40336 number, open the vinyl phosphonic acid compounds etc. of record in flat 2-25493 number the spy.In addition, in some cases, can suitably use the structure that contains perfluoroalkyl of opening record in clear 61-22048 number the spy.And then, can also use in Japan and follow in the will Vol.20 of association, No.7, the 300th～308 page (1984) as light solidified monomer and oligopolymer and the compound of introducing.

About the structure of these addition polymerization compounds, use still separately and, can set arbitrarily according to the functional design of final coloured polymerized composition with detailed using method such as, additions.

For example, can select according to following such viewpoint.Aspect sensitivity, the many structures of unsaturated group content in preferred per 1 molecule at most cases, are preferably more than 2 official's energy.In addition, in order to improve the curing film strength, it also can be the above compound of 3 officials energy, and then, by and with (for example having different functional number, different polymerizable group, acrylate, methacrylic ester, styrene compound, vinyl ethers compound) the addition polymerization compound, also be effectively to regulate the two method of sensitivity and intensity.

In addition, for with coloured polymerized composition in other composition (for example, consistency, the dispersiveness of binder polymers such as alkali soluble resins, Photoepolymerizationinitiater initiater, tinting material (pigment), the selection of addition polymerization compound, using method also are important factors, for example, sometimes by use the low-purity compound or and with 2 kinds with on improve consistency.

In addition, also can be and select specific structure in order to improve with the adaptation of substrate etc.The addition polymerization compound is with respect to the non-volatility composition in the coloured polymerized composition, preferably at 5～70 quality %, more preferably use in the scope of 10～60 quality %.In addition, they can use separately or also use more than 2 kinds.In addition, for the using method of addition polymerization compound, can be from viewpoints such as the size of the encumbering property of polymerization of oxygen, exploring degree, photographic fog (fogging), variations in refractive index, surface adhesive be gone out to send to select suitable structure, cooperation, addition.

(Photoepolymerizationinitiater initiater)

As Photoepolymerizationinitiater initiater, can list the Lu that puts down in writing in the Japanese kokai publication sho 60-3626 communique for example for the Jia oxadiazole; The spy opens clear 59-1281 communique, the spy opens the halogenated methyl-s-triazine isoreactivity halogen compounds of middle records such as clear 53-133428 communique; No. the 4318791st, United States Patent (USP), european patent application disclose the aromatic carbonyls of putting down in writing in each specification sheets such as the 88050th such as ketal, acetal or benzoin alkylether class; The aromatic ketone compounds of putting down in writing in No. 4199420 specification sheets of United States Patent (USP) such as benzophenone; French Patent is invented (sulfo-) xanthene ketone or the acridine compound of putting down in writing in No. 2456741 specification sheets; The coumarins of putting down in writing in the Japanese kokai publication hei 10-62986 communique or 2,4, compounds such as 5-triphenyl imidazole dimer class; The organic boron complex of sulfonium of Te Kaiping 8-015521 communique etc. etc.

As the Photoepolymerizationinitiater initiater among the present invention, be preferably methyl phenyl ketone system, ketal system, benzophenone series, bitter almond oil camphor system, benzoyl system, xanthone system, active halogen compound (triazine Xi, oxadiazole system, coumarin series), acridine system, bisglyoxaline system, oxime ester system etc.

As above-mentioned methyl phenyl ketone is Photoepolymerizationinitiater initiater, for example can preferably list 2,2-diethoxy acetophenone, to dimethylamino methyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, to dimethylamino methyl phenyl ketone, 4 '-sec.-propyl-2-hydroxy-2-methyl-propionyl benzene, 1-hydroxyl-cyclohexyl-phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone, 2-tolyl-2-dimethylamino-1-(4-morpholino phenyl)-Ding-1-ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino third-1-ketone etc.

As above-mentioned ketal is Photoepolymerizationinitiater initiater, can preferably list for example benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetal etc.

As above-mentioned benzophenone series Photoepolymerizationinitiater initiater, can preferably list for example benzophenone, 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4,4 '-dichloro benzophenone.

As above-mentioned bitter almond oil camphor system or benzoyl is Photoepolymerizationinitiater initiater, can preferably list for example bitter almond oil camphor isopropyl ether, bitter almond oil camphor isobutyl ether, benzoin methyl ether, methyl o-benzoyl yl benzoic acid ester etc.

As above-mentioned xanthone is Photoepolymerizationinitiater initiater, can preferably list for example diethyl thioxanthone, di-isopropyl thioxanthone, single isopropyl thioxanthone, clopenthixal ketone etc.

(triazine is oxadiazole system as above-mentioned active halogen compound, coumarin series), for example can preferably list 2, two (the trichloromethyl)-6-p-methoxyphenyls of 4--s-triazine, 2, two (the trichloromethyl)-6-of 4-are to methoxyl-styrene-s-triazine, 2, two (the trichloromethyl)-6-(1-is to dimethylaminophenyl)-1 of 4-, 3-butadienyl-s-triazine, 2, two (the trichloromethyl)-6-xenyls of 4--s-triazine, 2, two (the trichloromethyl)-6-(to methyl biphenyl) of 4--s-triazine, to hydroxyl-oxethyl styryl-2,6-two (trichloromethyl)-s-triazine, methoxyl-styrene-2,6-two (trichloromethyl-s-triazine, 3,4-dimethoxy-styryl-2,6-two (trichloromethyl)-s-triazine, 4-benzo tetrahydrofuran-2,6-two (trichloromethyl)-s-triazine, 4-(o-bromo-p-N, N-two (ethoxy carbonyl amino)-phenyl)-2,6-two (chloromethyl)-s-triazine, 4-(p-N, N-two (ethoxy carbonyl amino)-phenyl)-2,6-two (chloromethyl)-s-triazine, 2-trichloromethyl-5-styryl-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(cyano-styrene base)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3, the 4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3, the 4-oxadiazole, 3-methyl-5-amino-((s-triazine-2-yl) amino)-3-phenyl tonka bean camphor, 3-chloro-5-diethylamino-((s-triazine-2-yl) amino)-3-phenyl tonka bean camphor, 3-butyl-5-dimethylamino-((s-triazine-2-yl) amino)-3-phenyl tonka bean camphor etc.

As above-mentioned acridine is Photoepolymerizationinitiater initiater, can preferably list for example 9-phenylacridine, 1, two (9-acridyl) heptane of 7-etc.

As above-mentioned bisglyoxaline is Photoepolymerizationinitiater initiater, can preferably list for example 2-(o-chloro-phenyl-)-4,5-diphenyl-imidazole dimer, 2-(o-p-methoxy-phenyl)-4,5-diphenyl-imidazole dimer, 2-(2, the 4-Dimethoxyphenyl)-4,5-diphenyl-imidazole dimer etc.

Except above-mentioned; can also list 1-phenyl-1; 2-propanedione-2-(o-ethoxy carbonyl) oxime, O-benzoyl-4 '-(benzo sulfydryl) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl carbonyl-diphenylphosphine acyl-oxygen, hexafluoro idol phosphorus-trialkyl Ben Ji phosphonium salt etc.

Among the present invention, be not limited to above Photoepolymerizationinitiater initiater, also can use other known material.For example, can list poly-ketol aldose (vicinal polyketoaldonyl) compound of the vicinal 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 of putting down in writing in No. 2448828 specification sheets of United States Patent (USP), the aromatic series acyloin compound of putting down in writing in No. 2722512 specification sheets of United States Patent (USP) that is replaced by α-alkyl, the multinuclear naphtoquinone compounds of putting down in writing in No. the 3046127th, United States Patent (USP) and No. 2951758 specification sheets, the combination of triallyl imidazole dimer/p-aminophenyl ketone of putting down in writing in No. 3549367 specification sheets of United States Patent (USP), benzothiazole based compound/trihalomethyl group-s-triazine based compound of putting down in writing in the special public clear 51-48516 communique, J.C.S.PerkinII (1979) 1653-1660, J.C.S.PerkinII (1979) 156-162, Journal of Photopolymer Science andTechnology (1995) 202-232, the spy opens the oxime ester compound of 2000-66385 communique record etc.

In addition, these Photoepolymerizationinitiater initiaters also can and be used.

As the content of Photoepolymerizationinitiater initiater in coloured polymerized composition, with respect to the total solids composition of said composition, be preferably 0.1～10.0 quality %, more preferably 0.5～5.0 quality %.When the content of Photoepolymerizationinitiater initiater is in the above-mentioned scope time, can carry out polyreaction well and form the good film of intensity.

(alkali soluble resins)

Preferably contain alkali soluble resins in the coloured polymerized composition of the present invention.By in coloured polymerized composition, containing alkali soluble resins, when the pattern that this coloured polymerized composition is applicable to photoetch method forms, can further improve pattern formation property.

As alkali soluble resins, can be the wire organic high molecular polymer, can in molecule (being the molecule of main chain preferably), have at least one alkali soluble resins that promotes alkali-soluble group (for example carboxyl, phosphate, sulfonic group etc.) and suitably be selected with acrylic copolymer, styrene based copolymer.Wherein, the more preferably solvable and resin that can develop with weak alkaline aqueous solution in organic solvent.

For the manufacturing of alkali soluble resins, can suitably use the method for for example using known radical polymerization.The kind and the polymerizing conditions such as amount, solvent types thereof of the temperature during with radical polymerization manufactured alkali soluble resins, pressure, radical initiator can be that those skilled in the art are easy to set, and also can impose a condition by experiment.

As above-mentioned wire organic high molecular polymer, preferably has the polymkeric substance of carboxylic acid at side chain.For example; can list as the spy and open clear 59-44615 number; special public clear 54-34327 number; special public clear 58-12577 number; special public clear 54-25957 number; the spy opens clear 59-53836 number; the spy opens the Sipacril 2739OF of putting down in writing in clear 59-71048 number each communique; acrylic copolymer; itaconic acid copolymer; the Ba Dousuan multipolymer; maleic acid; partial esterification maleic acid etc.; and the acid cellulose derivative that has carboxylic acid at side chain; have the polymkeric substance of hydroxyl and material that the acid anhydrides addition obtains etc.; in addition; as preferred compound, also can list the high molecular polymer that has (methyl) acryl at side chain.

Wherein particularly preferably be by (methyl) benzyl acrylate/(methyl) acrylic copolymer or the multiple copolymer that constitutes by (methyl) benzyl acrylate/(methyl) vinylformic acid/other monomer.

In addition, as useful compound, also can enumerate material of sening as an envoy to the ethyl ester copolymerization of methacrylic acid 2-hydroxyl and obtaining etc.

Except that above-mentioned, also can list the spy and open methacrylic acid 2-hydroxypropyl acrylate/polystyrene macromolecular monomer/benzyl methacrylate/Sipacril 2739OF of putting down in writing in the flat 7-140654 communique, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester/polymethylmethacrylate macromonomer/benzyl methacrylate/Sipacril 2739OF, methacrylic acid 2-hydroxyl ethyl ester/polystyrene macromolecular monomer/methyl methacrylate/Sipacril 2739OF, methacrylic acid 2-hydroxyl ethyl ester/polystyrene macromolecular monomer/benzyl methacrylate/Sipacril 2739OF etc.

As the preferred resin of the alkali soluble resins among the present invention, can list especially (methyl) vinylformic acid with can with other monomeric multipolymers of its copolymerization.Here, (methyl) vinylformic acid is with vinylformic acid and methacrylic acid general name altogether, below similarly, (methyl) acrylate is the general name of acrylate and methacrylic ester.

As above-mentioned can with other monomer of (methyl) acrylic acid copolymer, can list (methyl) alkyl acrylate, (methyl) vinylformic acid aryl ester, vinyl compound etc.Wherein, the hydrogen atom of alkyl and aryl also can be substituted the base replacement.

Object lesson as above-mentioned (methyl) alkyl acrylate and (methyl) vinylformic acid aryl ester can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) Octyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) CA, (methyl) vinylformic acid naphthalene ester, (methyl) cyclohexyl acrylate etc.

In addition, as above-mentioned vinyl compound, can list for example vinylbenzene, alpha-methyl styrene, Vinyl toluene, glycidyl methacrylate, vinyl cyanide, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromolecular monomer, polymethylmethacrylate macromonomer, CH ₂=CR ¹R ², CH ₂=C (R ¹) (COOR ³) (wherein, R ¹Expression hydrogen atom or carbonatoms are 1～5 alkyl, R ²The expression carbonatoms is 6～10 aromatic hydrocarbons ring, R ³The expression carbonatoms is that 1～8 alkyl or carbonatoms are 6～12 aralkyl) etc.

These can copolymerization other monomer can be used alone or make up more than two kinds and use.

Other monomer that preferably can copolymerization is to be selected from CH ₂=CR ¹R ², CH ₂=C (R ¹) (COOR ³), at least a in (methyl) phenyl acrylate, (methyl) benzyl acrylate and the vinylbenzene, especially preferably CH ₂=CR ¹R ²And/or CH ₂=C (R ¹) (COOR ³).

As the content of alkali soluble resins in coloured polymerized composition, with respect to the total solids composition of said composition, be preferably 1～30 quality %, more preferably 1～20 quality % is preferably 2～15 quality % especially.

(solvent)

Coloured polymerized composition of the present invention generally can be by using each above-mentioned composition with solvent, thus modulation aptly.

As operable solvent, can list: ester class, for example pentyl formate; Acetic acid alkyl esters such as vinyl acetic monomer, n-butyl acetate, isobutyl acetate, isoamyl acetate, isobutyl acetate; Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, oxyacetic acid butyl ester, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, oxyethyl group ritalin, oxyethyl group vinyl acetic monomer; 3-hydroxy-propionic acid alkyl esters such as 3-hydroxy methyl propionate and 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, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester etc.; Ethers, for example diglyme, tetrahydrofuran (THF), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl glycol acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethyl carbitol acetic ester, acetate of butyl carbitol, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetic ester, propylene glycol propyl ether acetic ester etc.; Ketone, for example methylethylketone, pimelinketone, 2-heptanone, 3-heptanone etc.; Aromatic hydrocarbon based, for example toluene, dimethylbenzene etc.

In these solvents, preferably 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diglyme, n-butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, diethylene glycol monobutyl ether acetic ester, 1-Methoxy-2-propyl acetate etc.

Solvent can also make up more than two kinds and use except can using separately.

(other composition)

In coloured polymerized composition of the present invention, can contain sensitizing coloring matter, Resins, epoxy, fluorine class organic compound, thermal polymerization, thermopolymerization composition, thermopolymerization as required and prevent various additives such as macromolecular compound, tensio-active agent, driving fit promotor, antioxidant, UV light absorber, anti-flocculation agent beyond agent, weighting agent, the above-mentioned alkali soluble resins.

(sensitizing coloring matter)

In coloured polymerized composition of the present invention, can add sensitizing coloring matter as required.The wavelength exposure of sensitizing coloring matter through being absorbed by this sensitizing coloring matter can promote the radical initiation reaction etc. of above-mentioned Photoepolymerizationinitiater initiater and the polyreaction of the above-mentioned optical polymerism compound that causes thus.

As such sensitizing coloring matter, can list after known beam split sensitizing coloring matter or dyestuff or the absorb light and interactional dyestuff of Photoepolymerizationinitiater initiater or pigment.

(beam split sensitizing coloring matter or dyestuff)

As the sensitizing coloring matter that uses among the present invention and preferred beam split sensitizing coloring matter or dyestuff, (for example can list the polynuclear aromatic same clan, pyrene perylene, benzophenanthrene), the xanthene class (for example, fluorescein, eosin, tetraiodofluorescein, rhodamine B, rose-red), the cyanine class (for example, thia-carbonyl cyanine (thiacarbocyanine), oxa-carbocyanine (oxacarbocyanine)), the merocyanine class (for example, merocyanine, carbonyl merocyanine (carbomerocyanine)), thiazides (for example, thionine, methylenum coeruleum, toluidine blue), acridine (for example, acridine orange, chloroflavin, acriflavine), phthalocyanines (for example, phthalocyanine, metal phthalocyanine), the porphyrin class (for example, tetraphenylporphyrin, central metal metathetical porphyrin), the chlorophyll class (for example, chlorophyll, CHLOROPHYLLINE, central metal metathetical chlorophyll), metal complex (for example following compound), anthraquinone class (for example anthraquinone), squaric acid inner salt (squaryliums) class (for example, squaric acid inner salt) etc.

Following example shows the example of preferred beam split sensitizing coloring matter or dyestuff.

Can list the spy and open the cationic dyestuff of putting down in writing in the clear 62-143044 communique; The quinoxaline salt of in the public clear 59-24147 communique of spy, putting down in writing, open the new methylene blue compound of putting down in writing in the clear 64-33104 communique the spy; Open the anthraquinone class of putting down in writing in the clear 64-56767 communique the spy; Open the benzoxanthene dye of putting down in writing in the flat 2-1714 communique the spy; Open the acridine of putting down in writing in flat 2-226148 communique and the flat 2-226149 communique of Te Kai the spy; The pyrans salt of in the public clear 40-28499 communique of spy, putting down in writing; The cyanine class of in the public clear 46-42363 communique of spy, putting down in writing; Open the cumarone pigment of putting down in writing in the flat 2-63053 communique the spy; Open the conjugation ketone pigment that flat 2-85858 communique, spy are opened flat 2-216154 communique the spy; Open the pigment of putting down in writing in the clear 57-10605 communique the spy; The azo cinnamylidene derivative of in the fair 2-30321 communique of spy, putting down in writing; Open the cyanine class pigment of putting down in writing in the flat 1-287105 communique the spy; Open the spy that clear 62-31844 communique, spy are opened clear 62-31848 communique, the spy opens the xanthene class pigment of putting down in writing in the clear 62-143043 communique; The amino-benzene vinyl ketone of in the public clear 59-28325 communique of spy, putting down in writing; Open the pigment of putting down in writing in the flat 2-179643 communique the spy; Open the merocyanine pigment of putting down in writing in the flat 2-244050 communique the spy; The merocyanine pigment of in the public clear 59-28326 communique of spy, putting down in writing; Open the merocyanine pigment of putting down in writing in the clear 59-89303 communique the spy; Open the merocyanine pigment of putting down in writing in the flat 8-129257 communique the spy; Open the benzo pyran pigment of putting down in writing in the flat 8-334897 communique the spy.

(pigment that has maximum absorption wavelength at 350～450nm)

As other preferred configuration of sensitizing coloring matter, can list the compound group and the pigment have maximum absorption wavelength at 350～450nm that belongs to following.

For example can list salt (for example squaric acid inner salt) in the polynuclear aromatic same clan (for example pyrene, perylene, benzophenanthrene), xanthene class (for example fluorescein, eosin, tetraiodofluorescein, rhodamine B, rose-red), cyanine class (for example thia-carbonyl cyanine, oxa-carbocyanine), merocyanine class (for example merocyanine, carbonyl merocyanine), thiazides (for example thionine, methylenum coeruleum, toluidine blue), acridine (for example acridine orange, chloroflavin (chloroflavine), acriflavine), anthraquinone class (for example anthraquinone), the squaric acid.

As the example of preferred sensitizing coloring matter, can list the compound of following general formula (XIV)～(XVIII) expression.

General formula (XIV)

(in the general formula (XIV), A ¹The expression sulphur atom or-NR ⁶⁰-, R ⁶⁰The expression alkyl or aryl, L ⁰¹The A of expression and adjacency ¹Form the nonmetallic atom group of the alkalescence nuclear of pigment, R together with carbon atom ⁶¹, R ⁶²Represent hydrogen atom or monovalence nonmetallic atom group independently of one another, R ⁶¹And R ⁶²Also can be bonded to each other and form the acid core of pigment.W represents Sauerstoffatom or sulphur atom.)

Below, show the preferred concrete example ((A-1)～(A-5)) of the compound of general formula (XIV) expression.

General formula (XV)

(in general formula (XV), Ae ¹And Ar ²Represent aryl independently of one another, be situated between by-L ⁰²-key and link.Here ,-L ⁰²-expression-O-or-S-.In addition, W is identical with the implication shown in the general formula (XIV).)

Preference as the compound of general formula (XV) expression can list following ((A-6)～(A-8)).

General formula (XVI)

(in general formula (XVI), A ²The expression sulphur atom or-NR ⁶⁹-, L ⁰³The A of expression and adjacency ²Form the nonmetallic atom group of the alkalescence nuclear of pigment, R together with carbon atom ⁶³, R ⁶⁴, R ⁶⁵, R ⁶⁶, R ⁶⁷And R ⁶⁸Represent the univalent nonmetallic atom group independently of one another, R ⁶⁹The expression alkyl or aryl.)

Preference as the compound of general formula (XVI) expression can list following compound ((A-9)～(A-11)).

General formula (XVII)

(in general formula (XVII), A ³, A ⁴Independently of one another expression-S-or-NR ⁷³-, R ⁷³Expression replaces or the alkyl of non-replacement or the aryl of replacement or non-replacement, L ⁰⁴, L ⁰⁵Represent A independently of one another with adjacency ³, A ⁴Form the nonmetallic atom group of the alkalescence nuclear of pigment, R together with carbon atom ⁷¹, R ⁷²Represent the monovalence nonmetallic atom group independently of one another, also can interosculate forms the ring of aliphatics or aromatic series.)

Preference as the compound of general formula (XVII) expression can list following compound ((A-12)～(A-15)).

In addition, in addition to these,, can also list the compound shown in the following formula (XVIII) as the preferred sensitizing coloring matter that uses among the present invention.

General formula (XVIII)

(in the general formula (XVIII), A ⁵Expression can have substituent aromatic ring or heterocycle, X represent Sauerstoffatom or sulphur atom or-N (R ⁷⁴)-, Y represent Sauerstoffatom, sulphur atom or=N (R ⁷⁴).R ⁷⁴, R ⁷⁵, R ⁷⁶Represent hydrogen atom or monovalence nonmetallic atom group independently of one another, A ⁵With R ⁷⁴, R ⁷⁵, R ⁷⁶Can interosculate and form the ring of aliphatics or aromatic series.)

Here, work as R ⁷⁴, R ⁷⁵, R ⁷⁶During expression monovalence nonmetallic atom group, R ⁷⁴, R ⁷⁵, R ⁷⁶Preferred expression replaces or does not have the alkyl or aryl of replacement.

Below, to R ⁷⁴, R ⁷⁵, R ⁷⁶Preference specifically narrate.Example as preferred alkyl, can list carbonatoms and be 1～20 straight chain shape, chain and cyclic alkyl, as its concrete example, can list methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, petrosilane base, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, isopentyl, neo-pentyl, 1-methyl butyl, isohexyl, 2-ethylhexyl, 2-methyl hexyl, cyclohexyl, cyclopentyl, 2-norcamphyl.Wherein, more preferably carbonatoms is that 1～12 straight chain shape, carbonatoms are that 3～12 chain and carbonatoms are 5～10 cyclic alkyl.

Substituting group as substituted alkyl; can use the group of 1 valency nonmetallic atom group except hydrogen; as preference; can list; halogen atom (F;-Br; Cl; I); hydroxyl; alkoxyl group; aryloxy; sulfydryl; alkylthio; arylthio; the alkyl disulfide group; the aryl disulfide group; amino; the N-alkylamino; N; the N-dialkyl amido; the N-arylamino; N; the N-ammonia diaryl base; N-alkyl-N-arylamino; acyloxy; carbamoyloxy; N-alkyl carbamoyloxy base; N-arylamino methanoyl; N; N-dialkyl amido methanoyl; N; N-ammonia diaryl base methanoyl; N-alkyl-N-arylamino methanoyl; the alkyl sulfinyl; the aryl sulfinyl; the acyl sulfenyl; amido; the N-alkyl amido; N-aryl amido; the uride base; N-alkyl uride base; N; N-dialkyl group uride base; N-aryl uride base; N; N-diaryl uride base; N-alkyl-N-aryl uride base; N-alkyl-N-alkyl uride base; N; N-dialkyl group-N-alkyl uride base; N; N-dialkyl group-N-aryl uride base; N-aryl-N-alkyl uride base; N-aryl-N-aryl uride base; N; N-diaryl-N-alkyl uride base; N; N-diaryl-N-aryl uride base; N-alkyl-N-aryl-N-alkyl uride base; N-alkyl-N-aryl-N-aryl uride base; alkoxycarbonyl amino; aryloxycarbonyl amino; N-alkyl-N-alkoxycarbonyl amino; N-alkyl-N-aryloxycarbonyl amino; N-aryl-N-alkoxycarbonyl amino; N-aryl-N-aryloxycarbonyl amino; formyl radical; ethanoyl; carboxyl; alkoxy carbonyl; aryloxycarbonyl; formamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formyl radical; the N-aryl-amino-carbonyl; N, N-ammonia diaryl base formyl radical; N-alkyl-N-aryl-amino-carbonyl; alkyl sulphinyl; aryl sulfonyl kia; alkyl sulphonyl; aryl sulfonyl; sulfo group (SO ₃H) and its conjugation base (hereinafter be called " sulphonate-base), alkoxyl group alkylsulfonyl, aryloxy sulfonyl, sulfinamoyl, N-alkyl sulfinamoyl, N; N-dialkyl amino sulfinyl, N-aryl sulfinamoyl, N; N-ammonia diaryl sulfinyl, N-alkyl-N-aryl sulfinamoyl, sulfamyl, N-alkylsulfamoyl group, N; N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N, N-ammonia diaryl alkylsulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphono (PO ₃H ₂) and its conjugation base (hereinafter be called " phosphonate (ホ ス ホ Na ト) base), dialkyl phosphine acyl group (PO ₃(alkyl) ₂), diaryl phosphono (PO ₃(aryl) ₂), alkylaryl phosphono (PO ₃(alkyl) (aryl)), monoalkyl phosphono (PO ₃H (alkyl)) and its conjugation base (hereinafter be called " alkyl phosphonic acid alkali), single aryl phosphine acyl group (PO ₃H (aryl)) and its conjugation base (hereinafter be called " arylphosphonic acid alkali), phosphonato (OPO ₃H ₂) and its conjugation base (hereinafter be called " phosphonate oxygen base), dialkyl phosphine acyloxy (OPO ₃(alkyl) ₂), diaryl phosphonato (OPO ₃(aryl) ₂), alkylaryl phosphonato (OPO ₃(alkyl) (aryl)), monoalkyl phosphonato (OPO ₃H (alkyl)) and its conjugation base (hereinafter be called " alkyl phosphonate oxygen base), single aryl phosphine acyloxy (OPO ₃H (aryl)) and its conjugation base (hereinafter be called " aryl phosphine hydrochlorate oxygen base), cyano group, nitro, aryl, heteroaryl, alkenyl, alkynyl, silyl.

As the concrete example of the alkyl in these substituting groups, can list abovementioned alkyl, they can also further have substituting group.

In addition; concrete example as the aryl in the substituting group of above-mentioned substituted alkyl; can list phenyl; xenyl; naphthyl; tolyl; xylyl; the sym-trimethylbenzene base; isopropyl phenyl; chloro-phenyl-; bromophenyl; chloromethyl phenyl; hydroxy phenyl; p-methoxy-phenyl; ethoxyl phenenyl; Phenoxyphenyl; the acetoxyl group phenyl; the benzoyloxy phenyl; the methylthio group phenyl; the thiophenyl phenyl; the methylamino-phenyl; dimethylamino phenyl; acetylamino phenyl; carboxyl phenyl; the methoxycarbonyl phenyl; the ethoxyl phenenyl carbonyl; the phenyloxycarbonyl phenyl; N-phenyl amino formyl radical phenyl; phenyl; cyano-phenyl; the sulfo group phenyl; the sulphonate-base phenyl; the phosphono phenyl; phosphonic acids alkali phenyl etc.

As the heteroaryl in the substituting group of above-mentioned substituted alkyl, can use from containing nitrogen, oxygen, the monocycle of at least one in the sulphur atom, or the group that derives of Ppolynuclear aromatic ring, example as the hetero-aromatic ring in the particularly preferred heteroaryl, for example can list, thiophene, thianthrene, furans, pyrans, isobenzofuran, chromene (chromene), xanthene phenoxazine, the pyrroles, pyrazoles, isothiazole isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, different indolizine, indoles, indazole, purine, quinolizine, isoquinoline 99.9,2, the 3-naphthyridine, naphthyridines, quinazoline, quinoline, pteridine, carbazole, carboline, luxuriant and rich with fragrance, acridine, perimidine (Perimidine), phenanthroline, 2, the 3-naphthyridine, phenarsazine, furazan etc., they can also be fused benzo rings, can also have substituting group.

In addition,, can list vinyl, 1-propenyl, 1-butylene base, cinnamyl, 2-chloro-1-vinyl etc. as the example of the alkenyl in the substituting group of above-mentioned substituted alkyl.In addition, as the example of the alkynyl in the substituting group of above-mentioned substituted alkyl, can list ethynyl, 1-proyl, ethyl acetylene base, trimethyl silyl ethynyl etc.As acyl group (G ¹CO-) G in ¹, can list hydrogen and above-mentioned alkyl, aryl.In these substituting groups; as preferred; can list halogen atom (F;-Br;-Cl;-I); alkoxyl group; aryloxy; alkylthio; arylthio; the N-alkylamino; N; the N-dialkyl amido; acyloxy; N-alkyl carbamoyloxy base; N-arylamino methanoyl; amido; formyl radical; acyl group; carboxyl; alkoxy carbonyl; aryloxycarbonyl; formamyl; the N-alkyl-carbamoyl; N; N-dialkyl amido formyl radical; the N-aryl-amino-carbonyl; N-alkyl-N-aryl-amino-carbonyl; sulfo group; sulphonate-base; sulfamyl; the N-alkylsulfamoyl group; N, the N-dialkyl sulfamine; the N-ammonia aryl sulfonyl; N-alkyl-N-ammonia aryl sulfonyl; phosphono; the phosphonic acids alkali; the dialkyl phosphine acyl group; the diaryl phosphono; the monoalkyl phosphono; the alkyl phosphonic acid alkali; single aryl phosphine acyl group; the arylphosphonic acid alkali; phosphonato; phosphonate oxygen base; aryl; alkenyl.

As R by the combination of above-mentioned substituting group and alkylidene group is obtained ⁷⁴, R ⁷⁵Or R ⁷⁶The concrete example of preferred substituted alkyl; can list chloromethyl; brooethyl; the 2-chloroethyl; trifluoromethyl; methoxymethyl; methoxyethoxyethyl; allyl group oxygen ylmethyl; phenoxymethyl; methylthiomethyl; toluene sulfenyl methyl; the ethylamino ethyl; the diethylin propyl group; morpholinyl propyl; acetoxy-methyl; benzoyl oxygen ylmethyl; N-cyclohexyl carboxyamide base oxygen base ethyl; N-phenyl amino formyl radical oxygen base ethyl; the kharophen ethyl; N-methyl benzoyl aminopropyl; the 2-oxoethyl; the 2-oxopropyl; the carboxyl propyl group; the methoxycarbonyl ethyl; allyl group oxygen base carbonyl butyl; chlorophenoxy carbonyl methyl; the carbamyl ylmethyl; N-methylamino formyl radical ethyl; N; N-dipropyl carbamyl ylmethyl; N-(p-methoxy-phenyl) formamyl ethyl; N-methyl-N-(sulfo group phenyl) carbamyl ylmethyl; the sulfo group butyl; the sulphonate-base propyl group; the sulphonate-base butyl; the amino-sulfonyl butyl; N-ethylamino alkylsulfonyl methyl; N, N-dipropyl amino-sulfonyl propyl group; N-tolyl amino-sulfonyl propyl group; N-methyl-N-(phosphono phenyl) amino-sulfonyl octyl group; the phosphono butyl; phosphonic acids alkali hexyl; the diethyl phosphonyl butyl; diphenylphosphine acyl group propyl group; methylphosphine acyl group butyl; methyl-phosphorous acid alkali butyl; tolylphosphine acyl group hexyl; tolylphosphine hydrochlorate base hexyl; the phosphonato propyl group; phosphonic acids alkali oxygen Ji Dingji; benzyl; styroyl; α-Jia Jibianji; 1-methyl isophthalic acid-phenylethyl; to methyl-benzyl; cinnamyl; allyl group; 1-propenyl methyl; crotyl; the 2-methacrylic; 2-methacrylic ylmethyl; 2-propynyl; the 2-butyne base; 3-butynyl etc.

As R ⁷⁴, R ⁷⁵Or R ⁷⁶And the concrete example of preferred aryl groups, can list the group that 1～3 phenyl ring has formed condensed ring, phenyl ring and five yuan of unsaturated rings have formed the group of condensed ring, as concrete example, can list phenyl, naphthyl, anthryl, phenanthryl, indenyl, acenaphthenyl, fluorenyl, wherein more preferably phenyl, naphthyl.

As R ⁷⁴, R ⁷⁵Or R ⁷⁶And the concrete example of preferred substituted aryl, the group that can use on the one-tenth ring carbon atom of above-mentioned aryl and have (except that hydrogen atom) 1 valency nonmetallic atom group is as substituent substituted aryl.As the example of preferred substituted, can list the group that above-mentioned alkyl, substituted alkyl and front illustrate as the substituting group on the substituted alkyl.Preferred concrete example as this type of substituted aryl; can list; xenyl; tolyl; xylyl; the sym-trimethylbenzene base; isopropyl phenyl; chloro-phenyl-; bromophenyl; fluorophenyl; chloromethyl phenyl; trifluoromethyl; hydroxy phenyl; p-methoxy-phenyl; the methoxy ethoxy phenyl; allyl group oxygen base phenyl; Phenoxyphenyl; the methylthio group phenyl; tolyl sulfenyl phenyl; the ethylamino phenyl; the diethylin phenyl; the morpholinyl phenyl; the acetoxyl group phenyl; the benzoyloxy phenyl; N-cyclohexyl carboxyamide base oxygen base phenyl; N-phenyl amino formyl radical oxygen base phenyl; the acetylamino phenyl; N-methyl benzoyl aminophenyl; carboxyl phenyl; the methoxycarbonyl phenyl; allyl group oxygen base carbonyl phenyl; the chlorophenoxy carbonyl phenyl; the formamyl phenyl; N-methylamino formyl radical phenyl; N; N-dipropyl formamyl phenyl; N-(p-methoxy-phenyl) formamyl phenyl; N-methyl-N-(sulfo group phenyl) formamyl phenyl; the sulfo group phenyl; the sulphonate-base phenyl; the amino-sulfonyl phenyl; N-ethylamino alkylsulfonyl phenyl; N, N-dipropyl amino-sulfonyl phenyl; N-tolyl amino-sulfonyl phenyl; N-methyl-N-(phosphono phenyl) amino-sulfonyl phenyl; the phosphono phenyl; phosphonic acids alkali phenyl; the diethyl phosphonyl phenyl; diphenylphosphine acyl group phenyl; methylphosphine acyl group phenyl; methyl-phosphorous acid alkali phenyl; tolylphosphine acyl group phenyl; tolylphosphine hydrochlorate base phenyl; allyl phenyl; 1-propenyl aminomethyl phenyl; the crotyl phenyl; 2-methacrylic phenyl; 2-methylpropenyl phenyl; the 2-propynyl phenyl; 2-butyne base phenyl; 3-butynyl phenyl etc.

In addition, as R ⁷⁵And R ⁷⁶More preferably example, can list the alkyl that replaces or do not have replacement.In addition, as R ⁷⁴More preferably example, can list the aryl that replaces or do not have replacement.Its reason is not determined as yet, but infer be because, by having such substituting group, because of electron excitation state that photoabsorption produced and the interaction of initiator compounds become big especially, thereby improved the cause that initiator compounds produces the efficient of free radical, acid or alkali.

Below, the A in the mutual-through type (XVIII) ⁵Illustrated.A ⁵Expression can have substituent aromatic nucleus or heterocycle, as having substituent aromatic nucleus or heterocyclic concrete example, can list the R at mutual-through type (XVIII) ⁷⁴, R ⁷⁵Or R ⁷⁶Above-mentioned explanation in the listed same example of enumerating.

Wherein, as preferred A ⁵, can list have alkoxyl group, sulfane base, amino aryl, as particularly preferred A ⁵, can list aryl with amino.

Then, the Y in the mutual-through type (XVIII) describes.Y is situated between directly to be combined in non-metallic atom or nonmetallic atom group on the nitrogen heterocyclic ring in the general formula (XVIII) by two keys, more specifically, expression Sauerstoffatom, Sulfur atom or=N (R ⁷⁴).Here, R ⁷⁴Expression hydrogen atom or 1 valency nonmetallic atom group.

In addition, the X in the general formula (XVIII) represent Sauerstoffatom, Sulfur atom or-N (R ⁷⁴)-.R ⁷⁴Identical with the implication among the Y.

Below, be that the compound shown in the general formula (XVIII-1) is illustrated to the preferred configuration of compound shown in the general formula (XVIII) that uses among the present invention.

In above-mentioned general formula (XVIII-1), A ⁵Expression can have substituent aromatic nucleus or heterocycle, X represent Sauerstoffatom or sulphur atom or-N (R ⁷⁴)-.R ⁷⁴, R ⁷⁷, R ⁷⁸Represent hydrogen atom or monovalence nonmetallic atom group independently of one another, A ⁵Can be respectively and R ⁷⁴, R ⁷⁷, R ⁷⁸Interosculate to form the ring of aliphatics or aromatic series.Ar represents to have substituent aromatic nucleus or heterocycle.Wherein, the summation of the substituent Hammett value on the Ar skeleton (Hammett ' substituent constant) needs bigger than 0.Here, " summation of Hammett value is bigger than 0 " is meant to have a substituting group, and this substituent Hammett value is bigger than 0, also can have a plurality of substituting groups, and the summation of these substituent Hammett values is bigger than 0.

In general formula (XVIII-1), A ⁵And R ⁷⁴Identical with the implication in the general formula (XVIII), R ⁷⁷With the R in the general formula (XVIII) ⁷⁵Implication is identical, R ⁷⁸With the R in the general formula (XVIII) ⁷⁶Implication is identical.In addition, Ar represents to have substituent aromatic ring or heterocycle, with the A in the general formula (XVIII) ⁵Implication is identical.

As the substituting group on the Ar that can import to general formula (XVIII-1), the summation of Hammett value is required to be more than 0, as this type of substituent example, can list trifluoromethyl, carbonyl, ester group, halogen atom, nitro, cyano group, sulfoxide group, amide group, carboxyl etc.Show these substituent Hammett values below.Can list: trifluoromethyl (CF ₃, m:0.43, p:0.54), carboxyl (for example-COH, m:0.36, p:0.43), ester group (COOCH ₃, m:0.37, p:0.45), halogen atom (for example Cl, m:0.37, p:0.23), cyano group (CN, m:0.56, p:0.66), sulfoxide group (for example-SOCH ₃, m:0.52, p:0.45), amide group (for example-NHCOCH ₃, m:0.21, p:0.00), carboxyl (COOH, m:0.37, p:0.45) etc.Expression is that this substituting group imports to position and its Hammett value on the aryl skeleton in the bracket, (m:0.50) represent this substituting group import between Hammett value during position (meta position) be 0.50.Wherein,, can list and have substituent phenyl,, can list ester group, cyano group as the preferred substituents on the Ar skeleton as the preference of Ar.Position as replacing is preferably placed at the ortho position (ortho position) on the Ar skeleton especially.

Show the preferred concrete example (exemplary compounds (F1)～exemplary compounds (F56), but the present invention is not limited to these of the sensitizing coloring matter shown in the general formula of the present invention (XVIII) below.

In applicable to above-mentioned sensitizing coloring matter of the present invention, be cured to the viewpoint in deep from making film, be preferably the compound that above-mentioned general formula (XVIII) is represented.

About above-mentioned sensitizing coloring matter,, can carry out following such various chemically modifieds in order to improve the characteristic of coloured polymerized composition of the present invention.For example; (for example make sensitizing coloring matter and addition polymerization compound structure by methods such as covalent linkage, ionic linkage, hydrogen bonds; acryl, methacryloyl) combination, can obtain the high strength of crosslinking curing film thus, improve the unnecessary inhibition effect separated out of pigment from the crosslinking curing film.

The content of sensitizing coloring matter is preferably 0.01～20 quality % with respect to the total solids composition of coloured polymerized composition, 0.01～10 quality % more preferably, and then be preferably 0.1～5 quality %.

Content by making sensitizing coloring matter is high sensitivity with respect to the exposure wavelength of ultrahigh pressure mercury lamp in this scope, therefore makes film be cured to the deep, and from then on viewpoint forms the good viewpoint of property from Development margin (margin), pattern simultaneously, is preferred.

(Resins, epoxy)

In the coloured polymerized composition of the present invention,, can use Resins, epoxy as the thermopolymerization composition in order to improve formed intensity of filming.

As Resins, epoxy, be bisphenol A-type, cresols phenolic varnish type, biphenyl type, alicyclic epoxy compound etc. have 2 above oxirane rings in molecule compound.

For example, as bisphenol A-type, can list EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (above be Dongdu system of changing into), DENACOLE EX-1101, EX-1102, EX-1103 etc. (above be the Nagase system of changing into), PLACCEL GL-61, GL-62, G101, G102 (above be DAICEL chemistry system) etc.In addition, can also list and they similar Bisphenol F type and bisphenol S type.In addition, can also use the epoxy acrylate of Ebecryl 3700,3701,600 (above be DAICEL UCB system) etc.

As the cresols phenolic varnish type, can list EPOTOHTO YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704 etc. (above be Dongdu system of changing into), DENACOLEEM-125 etc. (above be the Nagase system of changing into).As biphenyl type, can list 3,5,3 ', 5 '-tetramethyl--4,4 '-diglycidyl biphenyl etc., as the alicyclic epoxy compound, can list CELLOXIDE 2021,2081,2083,2085, EPOLEAD GT-301, GT-302, GT-401, GT-403, EHPE-3150 (above is DAICEL chemistry system), SANTOHTO ST-3000, ST-4000, ST-5080, ST-5100 etc. (above be Dongdu system of changing into), Epiclon 430, Epiclon 673, Epiclon 695, Epiclon 850S, Epiclon 4032 (above is big Japanese ink system) etc.

In addition, can also use 1,1,2,2-four (to glycidyl oxygen base phenyl) ethane, three (to glycidyl oxygen base phenyl) methane, triglycidyl group three (hydroxyethyl) isocyanuric acid ester, o-phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester and as the skeleton of EPOTOHTO YH-434, the YH-434L of amine type Resins, epoxy, bisphenol A type epoxy resin by the glycidyl ester that imports dimeracid etc. and be modified etc.

Wherein, preferably " number of molecular weight/oxirane ring " be more than 100,130～500 resin more preferably." number of molecular weight/oxirane ring " is little, the solidified nature height, and the contraction during curing is big; In addition, when " number of molecular weight/oxirane ring " is excessive, can produce solidified nature insufficient, lack the worry of reliability, flatness variation etc.

As concrete preferred compound, can list EPOTOHTO YD-115,118T, 127, YDF-170, YDPN-638, YDPN-701, PLACCEL GL-61, GL-62,3,5,3 ', 5 '-tetramethyl--4,4 '-diglycidyl biphenyl, CELLOXIDE 2021,2081, EPOLEADGT-302, GT-403, EHPE-3150 etc.

(fluorine class organic compound)

Coloured polymerized composition of the present invention can improve the characteristics of liquids (particularly mobile) when making coating fluid by containing fluorine class organic compound, and can improve homogeneity, province's fluidity of coating thickness.

That is to say, the coloured polymerized composition that contains fluorine class organic compound can reduce the surface tension between applied and the coating fluid, improvement is to applied wettability (wettability), raising is to applied coating, therefore, even under the situation of the film that forms several μ m left and right thicknesses with a spot of liquid measure, also can effectively form the film of the less uniform thickness of uneven thickness.

Fluorine containing ratio in the fluorine class organic compound is preferably 3～40 quality %, more preferably 5～30 quality %, preferred especially 7～25 quality %.The fluorine containing ratio is in above-mentioned scope the time, the coating thickness homogeneity and economize fluidity aspect be that effectively the solvability in composition is also good.

As fluorine class organic compound, can list for example Megafac F171, Megafac F 172, Megafac F 173, Megafac F 177, Megafac F 141, Megafac F 142, Megafac F143, Megafac F 144, Megafac R30, Megafac F437 (above is Dainippon Ink. ﹠ Chemicals Inc's system), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above is Sumitomo ス リ one エ system Co., Ltd. system), Surflon S-382, Surflon SC-101, SurflonSC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above is Asahi Glass Co., Ltd's system) etc.

Particularly when using coloured polymerized composition of the present invention to form thin filming, fluorine class organic compound can effectively prevent crawling or uneven thickness.In addition, even in the slot coated that occurs the liquid cutout easily, when being suitable for coloured polymerized composition of the present invention, also be effective.

The addition of fluorine class organic compound is preferably 0.001～2.0 quality % with respect to the all-mass of coloured polymerized composition, more preferably 0.005～1.0 quality %.

(thermal polymerization)

It also is effective containing thermal polymerization in the coloured polymerized composition of the present invention.

As thermal polymerization, can list for example various azo compounds, superoxide compounds.

As above-mentioned azo compound; can list the tetrazo compounds; as above-mentioned superoxide compounds, can list ketone peroxide, ketal peroxide, hydroperoxide, dialkyl, peroxidation diacyl, peroxyester, peroxy dicarbonate etc.

(tensio-active agent)

In the coloured polymerized composition of the present invention,, also can add various tensio-active agents from the viewpoint of improvement coating.As tensio-active agent, except above-mentioned fluorine class tensio-active agent, can also use the various tensio-active agents of nonionic system, positively charged ion system, negatively charged ion system.

Wherein, being preferably above-mentioned nonionic is that fluorine class tensio-active agent or the negatively charged ion that has perfluoroalkyl in the tensio-active agent is tensio-active agent.

As the concrete example of fluorine class tensio-active agent, can list Megafac (registered trademark) series of Dainippon Ink. ﹠ Chemicals Inc's system, Fluorad (registered trademark) series of 3M corporate system etc.

In addition, as positively charged ion is tensio-active agent, specifically, can list phthalocyanine derivates (commercially available product EFKA-745 (gloomy industry corporate system down)), organosiloxane polymer KP341 (chemical industrial company of SHIN-ETSU HANTOTAI system), (methyl) acrylic acid series (being total to) polymkeric substance Port リ Off ロ one No.75, No.90, No.95 (chemical industrial company of Sakae company system altogether), W001 (abundant merchant's corporate system) etc.

As nonionic is tensio-active agent, specifically, can list PLURONIC L10, L31, L61, L62,10R5,17R2,25R2, TETRONIC 304,701,704,901,904, the 150R1 etc. of 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, BASF AG's system.

And then, be tensio-active agent as negatively charged ion, specifically, can list W004, W005, W017 (abundant merchant's corporate system) etc.

(other additives)

Except above-mentioned, can add various additives in the coloured polymerized composition of the present invention.

As the concrete example of additive, can list weighting agents such as glass, aluminum oxide; The soluble resin of alkali such as phenoxy resin that the polymkeric substance of the maleic acid of itaconic acid copolymer, Ba Dousuan multipolymer, maleic acid, partial esterification, acid cellulose derivative, the polymkeric substance with hydroxyl and acid anhydrides addition, alcohol soluble nylon, dihydroxyphenyl propane and Epicholorohydrin form; EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 macromolecule dispersing agents such as (above are gloomy industry corporate system down); SOLSPERSE3000,5000,9000,12000,13240,13940,17000,24000,26000, various SOLSPERSE dispersion agents (Lubrizol company) such as 28000; ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification corporate system) and IONET S-20 (Sanyo Chemical Industries, Ltd.'s system); UV light absorber such as 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; And anti-flocculation agent such as sodium polyacrylate.

In addition, promote the caustic solubility of uncured portion, further improve under the situation of development of coloured polymerized composition in desire, can in coloured polymerized composition of the present invention, add organic carboxyl acid, preferably add molecular weight and be the lower molecular weight organic carboxyl acid below 1000.

Specifically, for example can list formic acid, acetate, propionic acid, butyric acid, valeric acid, PIVALIC ACID CRUDE (25), caproic acid, diethylacetic acid, enanthic acid, aliphatic monocarboxylic acid such as sad; Aliphatic dicarboxylic acids such as oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane dicarboxylic acid, Methylpropanedioic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl-succsinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, equisetic acid, camphoronic acid; Phenylformic acid, tolyl acid, isopropyl acid, 2,3, aromatic monocarboxylates such as 5-mesitylenic acid; Aromatic series polycarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, phenylpropionic acid, phenylpropionic acid, amygdalic acid, phenyl succsinic acid, atropic acid, styracin, methyl cinnamate, cinnamein, Chinese cassia tree fork guanidine-acetic acid, coumaric acid, umbellic acid.

In coloured polymerized composition of the present invention, can also further add thermopolymerization and prevent agent.

Prevent agent as thermopolymerization, for example Resorcinol, p methoxy phenol, ditertbutylparacresol, pyrogallol, the tertiary butyl connect dihydroxy-benzene, benzoquinones, 4,4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole etc. are useful.

Coloured polymerized composition of the present invention can be by adding optical polymerism compound and Photoepolymerizationinitiater initiater and then as required with respect to above-mentioned pigment dispensing composition of the present invention, add alkali soluble resins or additives such as solvent, tensio-active agent, thereby modulate.

Because coloured polymerized composition of the present invention comprises pigment dispensing composition of the present invention, so the dispersing of pigments excellent in stability that contains as tinting material.In addition, use coloured polymerized composition of the present invention and the painted epithelium made, because the look material evenly and is stably disperseed, so the contrast gradient height, surface smoothing is good.

Therefore, coloured polymerized composition of the present invention is preferred for forming the painted areas of colour filter.

＜colour filter and manufacture method thereof 〉

Colour filter of the present invention is characterised in that to have the coloured polymerized composition that uses the invention described above and the colored pattern that forms on substrate.Below, for colour filter of the present invention, describe in detail by its manufacture method (manufacturing method of color filter of the present invention).

Manufacturing method of color filter of the present invention is characterised in that, forms the film of coloured polymerized composition of the present invention on substrate through coating, preferably with prebake conditions, secondly be that the exposure and the order of developing are carried out.

By such method, can technology on difficulty less, high-quality and make at low cost and be used for the colour filter that liquid crystal is represented element or solid-state imager.

Below, each operation is elaborated.

(coating)

Among the present invention, when making colour filter, form the film of coloured polymerized composition by coating.As coating process, can utilize known methods such as spin coating, slit-spin coating, slot coated, but, preferably utilize slot coated from productive viewpoint.

As the employed substrate of colour filter of the present invention, can list non-alkali glass, the soda glass that for example is used for liquid crystal display device etc., the glass of sending lachs (PYREX) (registered trademark) glass, silica glass and on them, having attached nesa coating, the photo-electric conversion element substrate that in solid-state imager etc., uses, for example silicone substrate etc., and plastic base.

On these substrates, can be formed with the black matrix" of isolating each pixel or be used to promote the transparent resin layer of driving fit etc.

In addition, on plastic base, preferably have barrier layer for gases (Gas BarrierLayer) or solvent resistance layer in its surface.

In addition, the driving of disposing thin film transistor (TFT) that also can use thin film transistor (TFT) formula color liquid crystal display arrangement is with substrate (hereinafter being called " TFT formula liquid crystal drive substrate "), also form to use coloured polymerized composition of the present invention on substrate and the colored pattern that forms in this driving, make colour filter.

With the substrate in the substrate, can list glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc. as TFT formula liquid crystal drive.These substrates, as required, suitable pre-treatment such as the chemical reagent processing that can carry out in advance being undertaken, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation by silane coupling agent etc.Can use substrate that for example on the surface of TFT formula liquid crystal drive, has formed passivation such as silicon nitride film (passivation) film etc. with substrate.

In the present invention, as the method that coloured polymerized composition of the present invention is coated on the substrate, preferably use slot coated.Condition as this slot coated, size condition difference because of coated substrates, for example to the 5th from generation to generation glass substrate (under the situation of 1100mm * 1250mm) be coated with, the amount of the coloured polymerized composition that penetrates from gap nozzle was preferably for 500～3000 microlitre/seconds usually, 800～2000 microlitre/seconds more preferably, in addition, surface covered is generally 50～300mm/ second, is preferably 100～250mm/ second.

In addition, the solids component as the coloured polymerized composition that uses in this slot coated operation is generally 10～23%, is preferably 13～20%.

Forming on substrate by coloured polymerized composition of the present invention when filming,, be generally 0.3～5.0 μ m, be preferably 0.5～4.0 μ m, most preferably be 0.5～3.0 μ m as this thickness of filming (prebake conditions is handled the back).

In addition, under the situation of the colour filter that solid-state imager is used, the thickness of filming (prebake conditions handle back) is preferably in the scope of 0.5 μ m～5.0 μ m.

(prebake conditions)

As described above on the substrate preferred form the film of coloured polymerized composition of the present invention by coating method after, preferably carry out prebake conditions.

In addition, as required, also can before prebake conditions, carry out vacuum-treat.

Vacuum drying condition is, vacuum tightness be generally 0.1～1.0torr (13～133Pa), be preferably 0.2～0.5torr (about 27～67Pa).

In addition, when carrying out prebake conditions according to hope when handling, can use hot plate, baking oven etc. 50～140 ℃ temperature range, be preferably and carried out under the condition about 70～110 ℃ 10～300 seconds.In addition, prebake conditions is handled also and can and be used with high frequency processing etc.Also can use high frequency to handle separately.

(exposure)

After the film drying of above-mentioned formation or according to hope, be situated between after by prebake conditions, to coated film and expose by the mask of stipulating.

As the radioactive rays that when exposing, use, ultraviolet rays such as preferred especially g line, h line, i line, j line.

In addition, when making the colour filter that liquid crystal indicator uses, preferably mainly used the exposure of h line, i line by proximity (proximity) exposure machine, mirror image projection exposure machine.

In addition, when the colour filter that the manufacturing solid-state imager is used, preferably use step-by-step exposure machine, mainly use the i line.

In addition, when using TFT mode liquid crystal drive to make colour filter with substrate, the photomask that uses can use following mask, described mask also is provided with the pattern that is used to form communicating pores or orthogonal depression (rectangular-shapeddepression) except being provided with the pattern that is used to form pixel (colored pattern).

(development)

After above-mentioned exposure, develop.Develop by this, the uncured portion of filming after the exposure is dissolved in the developing solution, cured portion is remained on the substrate.

As development temperature, be generally 20～30 ℃, as development time, be 20～90 seconds.

As developing solution, if in coloured polymerized composition of the present invention exposure, make exposure portion polymerizing curable after, can make the dissolving but do not dissolve solidified portion of filming of coloured polymerized composition in uncured, just can use any developing solution.

Specifically, can use developing solution or the alkaline aqueous solution that forms by the combination of various organic solvents.

As the organic solvent that uses in the developing solution, can list the aforementioned solvents of when modulation coloured polymerized composition of the present invention, using.

In addition, as alkaline aqueous solution, for example can list, sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, water glass, Starso, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicyclo-[5,4,0]-basic cpds such as 7-hendecene are 0.001～10 quality %, are preferably the alkaline aqueous solution that 0.01～1 quality % dissolving forms with concentration.

In alkaline aqueous solution, also can add an amount of water-miscible organic solvent such as for example methyl alcohol, ethanol etc. or tensio-active agent etc.

Visualization way can be any in impregnated, drip washing formula, the spraying type etc., also can with they with wave combinations such as (swing) formula, rotary, ultrasonic wave mode.With before developing solution contacts, can first water wait that wetting to be developed face uneven to prevent to develop.In addition, can make substrate tilt to develop.

In addition, under the situation of the colour filter that the manufacturing solid-state imager is used, can also use oar formula (paddle) to develop.

After the development treatment, handle through remaining developing solution being cleaned the drip washing of removing, and carry out drying,, implement heat treated (back baking) according to hope then for completion of cure.

Drip washing is handled and to be carried out with pure water usually, but in order to economize liquid, can use pure water in final cleaning, and uses used pure water when cleaning beginning, or makes substrate tilt to clean, or and use the method for ultrasonic irradiation.

After drip washing is handled, moisture removed and drying after, carry out 100～250 ℃ heat treated usually.Back baking like this is the heating after the development of carrying out in order to make completion of cure, preferably heats (hard baking, hard bake) under 200～250 ℃.

This heat treated (back baking) can use hot-plate or heater meanses such as convection oven (heated air circulation type drying machine), high frequency heating machine to carry out with continous way or intermittent type filming after developing under these conditions.

Preferably carrying out UV before the coating of baking back, back, next color cleans.UV cleans and can be undertaken by (for example LC4000, the electronics エ of Hitachi Application ジ ニ ア リ Application グ Co., Ltd. systems) such as glass substrate scrubbers, as the UV irradiation dose, and 100mJ/cm normally ²～1000mJ/cm ²About.Clean by carrying out UV, can remove the development residue, improve pattern formation property of next color etc.

By carrying out above-mentioned operation successively, can make colour filter of the present invention.

In addition,, successively each color (3 looks or 4 looks) is repeated above-mentioned each operation, can make the colour filter of the painted cured film (colored pattern) that is formed with multiple color thus according to desirable form and aspect number.

Embodiment

Below, by embodiment the present invention is carried out more specific description, but only otherwise exceeding purport of the present invention just is not limited to following embodiment.In addition, if not otherwise specified, " part " expression " mass parts ".

At first, employed composition in embodiment and the comparative example is described.

Synthesizing of＜resin B 〉

7.5 parts above-mentioned illustrative monomer M-11,31.25 parts of methyl methacrylates, 11.25 parts of methacrylic acids and MPEG 167 mass parts are imported the there-necked flask that nitrogen has been replaced, with stirrer (new eastern science Co., Ltd.: Three-One Motor) stir, heat while nitrogen is flowed in flask, be warming up to 78 ℃.To wherein adding 2,0.1 part of two (2 Methylpropionic acid) dimethyl ester (the pure medicine of trade(brand)name: V-601 and light Co., Ltd. system) of 2 '-azo carry out 2 hours heated and stirred under 78 ℃.After 2 hours, further add 0.1 part of V-601, carry out 3 hours heated and stirred, obtain 30% solution of resin B.The resin B that obtains be salt when grinding before the drying process of pigment employed resin.

Synthesizing of＜Resin A 〉

Except the monomer that will use in above-mentioned resin B synthetic and add-on thereof are replaced by the monomer and add-on of record in the following table 1, similarly synthesized Resin A.The resin that before the drying process of pigment, uses when the Resin A that obtains is the salt grinding.

Used monomer and add-on thereof when following table 1 has been represented synthetic resins A, B, the weight-average molecular weight and the acid number of institute's synthetic Resin A, resin B.Here, weight-average molecular weight is used is to measure and value that the value that obtain is tried to achieve with polystyrene conversion at the GPC of following condition (gel permeation chromatography).

Use post: TSKgel Multipore HXL-M

(pore polydispersion type linear columns) TOSOH system

Elutriant: THF

Flow: 1.0ml/min

Temperature: 40 ℃

Testing conditions: RI

System: the high speed GPC device same form (TOSOH makes HLC-8220)

In addition, acid number is to measure the value that obtains by following method.

(measuring method of acid number)

KOH ethanolic soln with 0.1N carries out titration, and calculates.The acid number of solution is based on the measuring method of the acid number of JISK0070:1992 " test method of the acid number of chemical preparations, saponification value, ester value, iodine number, hydroxyl value and unsaponifiables ", a certain amount of resin of dissolving in 1-methoxyl group-2-propyl alcohol acetic ester, with phenolphthalein as indicator, utilize the KOH/ ethanolic soln to carry out titration, thereby measure.

[table 1]

Grind the resin that use the back at salt	Form (quality %)	Weight-average molecular weight	Acid number (mgKOH/g)
				Resin A	St/BzMA/MAA ＝22.5/50/22.5	12000	150
Resin B	Monomer M-11/MMA/MAA=15/62.5/22.5	12000	150

In the above-mentioned table 1, monomer M-11 is meant the illustration monomer that lists as the preferred concrete example of monomer, maleimide and the maleimide derivatives of above-mentioned general formula (1) expression.In addition, in the table 1, monomeric details used in Resin A synthetic is as follows.

St: vinylbenzene

BzMA: benzyl methacrylate

MAA: methacrylic acid

MMA: methyl methacrylate

Secondly, employed various dispersion agents describe during to conditioned pigment dispersive composition in embodiment and comparative example.

Resin (1): * AA-6/ monomer M-11/ styrene/methacrylic acid

The multipolymer of=55/10/20/15 (quality %)

(weight-average molecular weight 20,000)

(* AA-6: single terminal methyl group propylene acidylate polymethyl methacrylate oligomer

(Mn=6000, East Asia synthetic chemical industry Co., Ltd. system))

Resin (2): maleimide/styrene/methacrylic acid=20/65/15 (quality %)

Multipolymer (weight-average molecular weight 20,000)

In addition, the structure of employed pigment derivative is as follows in the modulation of salt grinding and pigment dispensing composition.

[embodiment 1]

(having used the manufacturing process of the processing pigment of salt grinding)

With (A) diketopyrrolo-pyrrole pigment among the present invention is that イ Le ガ Off オ ア レ Star De BT-CF (Ciba Japan Co., Ltd. system, Pigment red 254) 50g, water-soluble inorganic salt are that sodium-chlor 500g (median size 10 μ m) and water-miscible organic solvent are that glycol ether (Tokyo changes into corporate system) 150g adds in 1 gallon of kneader of stainless steel (aboveground making institute corporate system), mixes under 50 ℃ 10 hours.

Then, in this mixture, add synthetic Resin A solution (solids component is 30 quality %) 25g and mixing as described above, this mixture is dropped in about 3 liters hot water, Yi Bian be heated to about 70 ℃, use high-speed mixer stir about 1 hour, finish mix pulpous state on one side.Then, filter, wash, remove sodium-chlor and solvent, with dry about 24 hours of 60 ℃ hot-air ovens, obtained surperficial at least a portion be stained with Resin A surface treatment (A) diketopyrrolo-pyrrole pigment.

By transmission electron microscope the particle diameter of resulting processing pigment is measured, the result is that average primary particle diameter is 30nm.In the mensuration of particle, use be the mean value of the multiplying power with 100,000 times, the major diameter of measuring 500 pigment and minor axis the time mean value.

(embodiment 1)

The modulation of＜pigment dispensing composition 〉

The composition that mixes following composition (1) utilizes homogenizer with revolution 3, and 000r.p.m. stirred 1 hour and mixed, and had modulated the mixing solutions that comprises pigment.

(forming (1))

The surface treatment diketopyrrolo-pyrrole pigment that in aforesaid method, obtains ((A) composition)

86 parts

10 parts of pigment derivative (1) (said structure)

Pigment derivative (3) (said structure: (B) composition) 10 parts

(is 13.4 parts with respect to 100 parts of (A) compositions)

5 parts of pigment derivative (4) (said structure: (C) composition))

(is 6.69 parts with respect to 100 parts of (A) compositions)

33 parts of Disperbyk-2001 (BYKChemie corporate system)

50 parts of the 30%1-methoxyl groups of resin (1)-2-propyl alcohol acetate solution

50 parts of the 30%1-methoxyl groups of resin (2)-2-propyl alcohol acetate solution

767 parts of 1-methoxyl groups-2-propyl alcohol acetic ester

Then, will use the bead dispersion machine (DISPERMAT, GETZMANN corporate system) of 0.8mm φ zirconium oxide bead (Nikkato of Co., Ltd. system) to carry out 20 minutes pre-dispersed by the above-mentioned mixing solutions utilization that obtains.Then, the main dispersion of utilizing the bead dispersion machine ULTRAAPEXMILL (longevity Industrial Co., Ltd's system) that has used 0.10mm φ zirconium oxide bead (Nikkato of Co., Ltd. system) to carry out 2 hours, obtained the red pigment dispersive composition of embodiment 1.

(evaluation of pigment dispensing composition)

Dispersiveness, dispersion stabilization to the pigment dispensing composition that obtains are estimated.

For the pigment dispensing composition of having modulated, use E type viscometer determining modulation after just having finished viscosities il 1 (25 ℃) and modulate after through the viscosities il after the week 2 (25 ℃).η 1 and η 2 are 9cp, have confirmed to demonstrate good dispersiveness and dispersion stabilization.

(embodiment 2)

The modulation of＜coloured polymerized composition 〉

The pigment dispensing composition that use obtains in the foregoing description 1 has been made the coloured polymerized composition of following composition (2).

In addition, red pigment dispersive composition A and yellow ultramarine dispersive composition A modulate as described below.

(red pigment dispersive composition A)

In the manufacturing process of above-mentioned processing pigment, use except substituting " ィ Le ガ Off オ ア レ Star De BT-CF " " red pigment (チ バ ジ ヤ パ Application Co., Ltd. system " Network ロ モ Off Le レ Star De A2B ": PR177) ", carry out salt similarly to Example 1 and grind, the processing pigment that to have obtained median size be 28nm.Then, use resulting processing pigment, use except substituting " pigment derivative (1) " " pigment derivative (5) ", obtained red pigment dispensing composition A similarly to Example 1.

In addition, yellow ultramarine dispersive composition A modulates as described below.

(yellow ultramarine dispersive composition A)

In the manufacturing process of above-mentioned processing pigment, use except substituting " イ Le ガ Off オ ア レ Star De BT-CF " " yellow ultramarine (LANXESS corporate system " E4GN-GT ") ", carry out salt similarly to Example 1 and grind, the processing pigment that to have obtained median size be 30nm.Then, use resulting processing pigment, use except substituting " pigment derivative (1) " " pigment derivative (6) ", obtained yellow ultramarine dispersive composition A similarly to Example 1.

(forming (2))

800 parts of the red pigment dispersive compositions that in embodiment 1, obtains

800 parts of above-mentioned red pigment dispersive composition A

400 parts of above-mentioned yellow ultramarine dispersive composition A

80 parts of Dipentaerythritol five or six acrylate (optical polymerism compound)

4-[o-bromo-p-N, N-two (ethoxy carbonyl) aminophenyl]-2,30 parts of 6-two (trichloromethyl)-S-triazine (Photoepolymerizationinitiater initiater)

Benzyl methacrylate/methacrylic acid (=70/30[mass ratio]) multipolymer (weight-average molecular weight: propylene glycol monomethyl ether solution 10,000) (solids component is 30%) (alkali soluble resins) 300 parts

590 parts of 1-methoxyl groups-2-propyl alcohol acetic ester (solvent)

400 parts of 3-ethoxyl ethyl propionates (solvent)

Wherein, Dipentaerythritol five or six acrylate are represented KAYARAD DPHA (Japanese chemical drug company).

＜used the making of the colour filter of coloured polymerized composition 〉

The coloured polymerized composition (colored resist liquid) that obtains is coated on the glass substrate (1737, CORNING corporate system) of 100mm * 100mm, make that the x value as the index of color depth is 0.650,60 seconds (prebake conditions) of drying in 90 ℃ baking oven.Then, to film whole with 200mJ/cm ²(illumination 20mW/cm ²) expose, with filming after the exposure with 1% aqueous solution covering of alkaline-based developer CDK-1 (FUJIFILM Electronic Materials Co., Ltd. system), static 60 seconds.After static, pure water is scattered wash-out developer with the shower shape.Then, implemented that photocuring is handled and filming of development treatment carried out 30 minutes heat treated (back baking) in 220 ℃ baking oven like that with above-mentioned, on glass substrate, form the painted epithelium that the formation colour filter is used, made the colouring filter device substrate (colour filter) that possesses unicolor painted areas.

Further using glass substrate scrubber (LC4000, the electronics エ of Hitachi Application ジ ニ ア リ Application グ Co., Ltd. system) to carry out UV to the substrate of making cleans (with 20mW/cm ², 500mJ/cm ²) after, implement above-mentioned prebake conditions, above-mentioned development, the baking of above-mentioned back once more.Then, implement further that above-mentioned UV cleans, above-mentioned prebake conditions, above-mentioned development, the baking of above-mentioned back, obtained estimating with colouring filter device substrate (colour filter).

The evaluation of making for synthetic coloured polymerized composition (colored resist liquid) as described above and by this coloured polymerized composition is estimated in the following manner with colouring filter device substrate (colour filter).The results are shown in table 2.

-1. the mensuration of viscosity-

For synthetic coloured polymerized composition (colored resist liquid), with E type viscometer determining modulation after just having finished viscosities il 1 (25 ℃) and modulate after through the viscosities il after the week 2 (25 ℃).

-2. the mensuration, evaluation of contrast gradient-

Measured the contrast gradient of the evaluation of made as described below with colouring filter device substrate (colour filter).

Promptly, to estimate with colouring filter device substrate and be placed between 2 pieces of polaroids, utilize the BM-5 of TOPCON Co., Ltd. corporate system to measure the brightness of brightness when vertical when polarization axle is parallel, the brightness when parallel when vertical brightness and the value that obtains (brightness during=brightness when parallel/vertical) as the index that is used to estimate contrast gradient.(this evaluation method is with reference to " nineteen ninety the 7th color light association view, 512 looks show 10.4 " size TFT-LCD colour filter, plant wooden, Xiao Seki, good fortune forever, in the mountain ").

-3. the mensuration of surfaceness-

Evaluation colouring filter device substrate (colour filter) to made utilizes atomic force microscope (NanoScope IIIa, NanoWorld corporate system) to measure the surfaceness on painted epithelium surface.

[embodiment 3]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (1) 0.8g, carry out salt similarly to Example 1 and grind, obtain handling pigment.The average primary particle diameter of resulting processing pigment is 26nm.Then, use resulting processing pigment, obtained red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[embodiment 4]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (2) 0.9g, carry out salt similarly to Example 1 and grind, obtain handling pigment.The average primary particle diameter of resulting processing pigment is 23nm.Then, use resulting processing pigment, obtained red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[embodiment 5]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (2) 0.9g, carry out salt similarly to Example 1 and grind.In addition, use " resin B solution (solids component is 30 quality %) " that obtains in the above-mentioned synthesis example, obtained processing pigment similarly to Example 1 except " Resin A solution (solids component is 30 quality %) " that substitute after mixing.The average primary particle diameter of resulting processing pigment is 23nm.Then, use resulting processing pigment, obtained red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[embodiment 6]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (2) 0.9g, carry out salt similarly to Example 1 and grind.In addition, use " resin B solution (solids component is 30 quality %) ", obtained processing pigment similarly to Example 1 except " Resin A solution (solids component is 30 quality %) " that substitute after mixing.The average primary particle diameter of resulting processing pigment is 23nm.Then, use resulting processing pigment, use except substituting " (1) 10 part of pigment derivative " " (2) 10 parts of pigment derivative ", obtained red pigment dispensing composition similarly to Example 2.And then, obtain red coloured polymerized composition similarly to Example 1 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[embodiment 7]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (2) 0.9g, carry out salt similarly to Example 1 and grind.In addition, use " resin B solution (solids component is 30 quality %) ", obtained processing pigment similarly to Example 1 except " Resin A solution (solids component is 30 quality %) " that substitute after mixing.The average primary particle diameter of resulting processing pigment is 23nm.Then, use resulting processing pigment, use except substituting " (1) 10 part of pigment derivative, (3) 10 parts of pigment derivative, (4) 5 parts of pigment derivative " " (2) 11 parts of pigment derivative, (3) 7 parts of pigment derivative, (4) 7 parts of pigment derivative ", obtained red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[comparative example 1]

Carry out salt similarly to Example 1 and grind, obtain handling pigment.The average primary particle diameter of resulting processing pigment is 30nm.Then, use resulting processing pigment, use " 103 parts of the processing pigment that in aforesaid method, obtains " except substituting " 86 parts of the processing pigment that in aforesaid method, obtains " and do not use " pigment derivative (3) " and " pigment derivative (4) ", obtain red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[comparative example 2]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (1) 0.8g, carry out salt similarly to Example 1 and grind, obtain handling pigment.The average primary particle diameter of resulting processing pigment is 26nm.Then, use resulting processing pigment, use " 103 parts of the processing pigment that in aforesaid method, obtains " except substituting " 86 parts of the processing pigment that in aforesaid method, obtains " and do not use " pigment derivative (3) " and " pigment derivative (4) ", obtained red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[comparative example 3]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (1) 0.8g, carry out salt similarly to Example 1 and grind, obtain handling pigment.The average primary particle diameter of resulting processing pigment is 26nm.Then, use resulting processing pigment, use except substituting " (3) 10 parts of pigment derivative, (4) 5 parts of pigment derivative " " (3) 15 parts of pigment derivative ", obtained red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[comparative example 4]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (1) 0.8g, carry out salt similarly to Example 1 and grind, obtain handling pigment.The average primary particle diameter of resulting processing pigment is 26nm.Then, use resulting processing pigment, use except substituting " (3) 10 parts of pigment derivative, (4) 5 parts of pigment derivative " " (4) 15 parts of pigment derivative ", obtained red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[comparative example 5]

Except in embodiment 1, carrying out further adding when salt grinds pigment derivative (4) 1g, carry out salt similarly to Example 1 and grind, obtain handling pigment.The average primary particle diameter of resulting processing pigment is 24nm.Then, use resulting processing pigment, use " 103 parts of the processing pigment that in aforesaid method, obtains " except substituting " 86 parts of the processing pigment that in aforesaid method, obtains " and do not use " pigment derivative (3) " and " pigment derivative (4) ", obtained red pigment dispensing composition similarly to Example 1.And then, obtain red coloured polymerized composition similarly to Example 2 after, carried out evaluation similarly to Example 2.The results are shown in table 2.

[table 2]

	Initial stage viscosities il 1 (cp)	Through the time viscosities il 2 (cp)	Contrast gradient	Surfaceness (nm)
					Embodiment 2	5	5	3000	4
Embodiment 3	5	6	3200	4
					Embodiment 4	5	6	3400	5
Embodiment 5	4	5	3500	4
					Embodiment 6	4	4	3700	5
Embodiment 7	5	5	3600	5
					Comparative example 1	5	5	1500	20
Comparative example 2	5	5	1000	25
					Comparative example 3	5	6	2600	11
Comparative example 4	15	50	2500	9
					Comparative example 5	8	15	1200	23

As known from Table 2, use the pigment dispensing composition of the present invention of embodiment 1 and the viscosity of the coloured polymerized composition of synthetic embodiment 2～embodiment 7 after not finding to preserve rises, therefore the dispersion stabilization of contained pigment dyestuff is good.In addition we know, use this coloured polymerized composition and the colouring filter device (colour filter) that forms can form excellent contrast, painted epithelium that surfaceness is little.

Can infer from these results to draw,, can obtain having high-contrast and reduce resulting from the colour filter of picture element flaw of surfaceness etc. according to coloured polymerized composition of the present invention.

Claims (9)

1. pigment dispensing composition, it contains the diketopyrrolo-pyrrole series pigments, with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts, with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts be 0.1～20 mass parts O-phthalic imide alkylation quinoline a word used for translation ketone and at least a organic solvent.

2. pigment dispensing composition according to claim 1, wherein, the average primary particle diameter of described diketopyrrolo-pyrrole series pigments is 10nm～30nm.

3. pigment dispensing composition according to claim 1, wherein, described diketopyrrolo-pyrrole series pigments is the diketopyrrolo-pyrrole series pigments that obtains by the method with following operation, described operation is:

To diketopyrrolo-pyrrole series pigments, water-soluble inorganic salt and the water-miscible organic solvent that do not dissolve this water-soluble inorganic salt in fact carry out mechanically mixing operation,

Remove this water-soluble inorganic salt and described water-miscible organic solvent operation,

To this diketopyrrolo-pyrrole series pigments carry out the exsiccant operation,

And the operation that described diketopyrrolo-pyrrole series pigments is contacted with resin.

4. pigment dispensing composition according to claim 3, wherein, described resin is that acid number is the macromolecular compound of 50～300mgKOH/g.

5. the manufacture method of a pigment dispensing composition, it has:

To average primary particle diameter be add in the diketopyrrolo-pyrrole series pigments of 10nm～30nm at least a portion with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts and with respect to the operation of these diketopyrrolo-pyrrole series pigments 100 mass parts O-phthalic imide alkylation quinoline a word used for translation ketone that is 0.1～20 mass parts,

With the diketopyrrolo-pyrrole series pigments, with respect to this diketopyrrolo-pyrrole series pigments of per 100 mass parts O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts and with respect to this diketopyrrolo-pyrrole series pigments of per 100 mass parts O-phthalic imide alkylation quinoline a word used for translation ketone that is 0.1～20 mass parts with organic solvent dispersive operation.

6. coloured polymerized composition, it contains the described pigment dispensing composition of claim 1, optical polymerism compound and Photoepolymerizationinitiater initiater.

7. coloured polymerized composition according to claim 6, it further contains alkali soluble resins.

8. colour filter, it is to use the described coloured polymerized composition of claim 6 to form.

9. manufacturing method of color filter, it comprises the steps: the coating described coloured polymerized composition of claim 6 on substrate and forms and film, with formed film exposure, develops then.