CN101555362B - 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, the coloured polymerized composition that comprises this pigment dispensing composition, use this coloured polymerized composition and the colour filter that forms and the manufacture method of this colour filter.

Background technology

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

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

For above-mentioned requirements, use primary particle size by miniaturization pigment be effective.As by the method for the primary particle size miniaturization of pigment, for example there is following method: will under pigment and room temperature, be solid and water-insoluble synthetic resins, the 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 is reinstated kneader (kneader) etc. and is carried 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) "), then by washing, remove water-soluble inorganic salt and water-miscible organic solvent (for example, with reference to Japanese kokai publication hei 7-13016 communique).In the method, because pulverizing and the crystal growth of the primary particle of pigment are carried out simultaneously, therefore be applicable to obtaining final size narrowly distributing, median size is little but pigment that surface-area is little, be applicable to obtaining as colour filter needs by the pigment high density of fine particle size the method for pigment in the purposes of disperseing.

But the pigment of making like this, owing to causing fierce cohesion in the drying process after desalination, is the bad situation of dispersiveness and dispersion stabilization mostly.Use such pigment, be difficult to obtain dispersiveness, the good colo(u)rant dispersion thing of dispersion stabilization.In the inadequate situation of dispersiveness of pigment, on the colored pattern forming by the Polymerizable composition that comprises colo(u)rant dispersion thing, there is striped (fringe, the problems such as edge section unevenly) or concave-convex surface, colourity or the dimensional precision with the colour filter manufacturing declines, contrast gradient is significantly deteriorated.

In addition, in the situation that the dispersion stabilization of pigment is poor, be accompanied by the passage of time, the constituent of coloured polymerized composition causes cohesion, and viscosity rise exists the problem that working life, (potlife) became extremely short.In addition, in the situation that manufacture colour filter with such coloured polymerized composition, the film uniformity in painting process declines, and easily causes thus the problems such as sensitivity change, the caustic solubility in developing procedure in exposure process changes, inhomogeneous.Particularly when forming coloring film with coloured polymerized composition in order to form large-area colour filter on glass substrate, carry out in the situation of slot coated (slit coating) (or also referred to as " mouthful mould coating (die coating) "), there is following problems point: coated face easily produces the defects such as bar muscle, the surface texture of coating reduces, and this becomes the picture element flaw of colour filter.

Therefore,, as improving the dispersiveness of pigment and the method for dispersion stabilization, propose to have 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 diketopyrrolo-pyrrole series pigments, propose to have and when salt grinds, add pigment derivative and promote micronize, make the method (for example, with reference to TOHKEMY 2001-220520 communique and JP 2007-31539 communique) of contrast gradient raising.

But, according to above-mentioned technology in the past, when being only conceived to the miniaturization of pigment particles and the contrast gradient of image, although can obtain the effect of improving to a certain degree, but in miniaturization diketopyrrolo-pyrrole series pigments in, for make the operation of colour filter, particularly repeatedly developing, rear baking, UV be clean in the situation that, has the withered such problem points in surface.

Summary of the invention

Therefore, the present invention puts in view of the above problems and completes, and usings and reaches following object as problem.

That is, the 1st object of the present invention is to provide 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 object of the present invention is to provide the epithelium that can form excellent contrast and then the coloured polymerized composition that can form the colour filter of surface smoothing.

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

As follows for solving the means of above-mentioned problem.

; pigment dispensing composition of the present invention is characterised in that, contains: diketopyrrolo-pyrrole series pigments, 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, O-phthalic imide alkylation quinacridone and at least one organic solvent that is 0.1～20 mass parts with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts.

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

Can for the diketopyrrolo-pyrrole series pigments of pigment dispensing composition of the present invention, preferably by having, the method for following operation obtain, described operation is: the operation of diketopyrrolo-pyrrole series pigments, water-soluble inorganic salt and the water-miscible organic solvent that do not dissolve in fact this water-soluble inorganic salt being carried out to 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 to dry operation; And the operation that makes described diketopyrrolo-pyrrole series pigments contact with resin before this drying process.

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

The manufacture method of pigment dispensing composition of the present invention has following operation: the operation of at least a portion in the O-phthalic imide alkylation diketopyrrolo-pyrrole that in the diketopyrrolo-pyrrole series pigments that is 10nm～30nm to average primary particle diameter, interpolation is 0.1～30 mass parts with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts and the O-phthalic imide alkylation quinacridone that is 0.1～20 mass parts with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts; With the operation that diketopyrrolo-pyrrole series pigments, the O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts with respect to this diketopyrrolo-pyrrole series pigments of every 100 mass parts and the O-phthalic imide alkylation quinacridone that is 0.1～20 mass parts with respect to this diketopyrrolo-pyrrole series pigments of every 100 mass parts are disperseed together with organic solvent.

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

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

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

Pigment dispensing composition of the present invention is with respect to diketopyrrolo-pyrrole series pigments, the O-phthalic imide alkylation diketopyrrolo-pyrrole of specified quantitative and O-phthalic imide alkylation quinacridone are disperseed and formed in organic solvent.

In the present invention, by also with O-phthalic imide alkylation diketopyrrolo-pyrrole and O-phthalic imide alkylation quinacridone, accessing the pigment dispensing composition of dispersion stabilization and excellent contrast with respect to diketopyrrolo-pyrrole series pigments; Viscosity stability is good, can form the coloured polymerized composition of the high and then colour filter that surface smoothness is good of contrast gradient; The colour filter that contrast gradient is high and surface smoothness is good.

By also using O-phthalic imide alkylation diketopyrrolo-pyrrole and O-phthalic imide alkylation quinacridone, can bring into play the larger synergy of the stability of improving diketopyrrolo-pyrrole series pigments, therefore the composition forming by containing this pigment, can form excellent contrast, coloring film that surface smoothness is high.Its mechanism of action is still uncertain, but can think: the surperficial different position respectively of 2 kinds of O-phthalic imide alkylation pigment derivative with different parent nucleus and diketopyrrolo-pyrrole pigment has strong interaction, thus, unsettled diketopyrrolo-pyrrole surface is protected, compare with situation about using separately separately, by their synergy, can obtain unforeseeable good stability, by containing the coloured polymerized composition of this pigment, can form pigment and evenly and stably disperse, contrast gradient is high, the coloring film that surface smoothness is good.

According to the present invention, can provide 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 excellent contrast and the good epithelium of surface smoothness, this coloured polymerized composition is suitable for manufacturing colour filter.

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

embodiment

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

< pigment dispensing composition >

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

((A) diketopyrrolo-pyrrole series pigments)

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

In 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, such as listing halogen atom, alkenyl, aryl, hydroxyl, alkoxyl group etc., as the substituting group that can import aryl, such as listing halogen atom, alkyl, alkoxyl group etc.

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

In order to obtain the colour filter of high-contrast, in the present invention, the particle diameter of DPP series pigments used is preferably small size and narrowly distributing, and preferably 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 to the image obtaining with transmission electron microscope with 100,000 times of multiplying powers.In addition, for median size, for example, can measure the major diameter of particle and the mean value of minor axis, the particles of 500 be carried out to this mensuration, using its mean value as median size.Average primary particle diameter in the present invention is measured and is obtained by the method.

The 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 in order to obtain the minuteness particle of narrow diameter distribution, preferably by salt, grind and carry out miniaturization in the present invention.Below, to by salt, grind obtain miniaturization the situation of diketopyrrolo-pyrrole series pigments be elaborated.

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

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

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

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

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

Below they are described in detail respectively.

(DPP series pigments)

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

In the present invention, in grinding, DPP series pigments used can be synthetic by known method for salt, also can use commercially available commodity.As concrete trade(brand)name, can list (being Ciba Specialty Chemicals company 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 RED 2030, CROMOPHTAL DPP RED BP.

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

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

, 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, 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 is 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 DPP series pigments, more preferably following pigment.

, 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, in the situation that 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 more than 0.1 quality % and lower than 100 quality %.

(water-soluble inorganic salt)

The water-soluble inorganic salt using during salt grinds so long as the inorganic salt that are dissolved in water just without particular limitation of, can use sodium-chlor, bariumchloride, Repone K, sodium sulfate etc., but from the viewpoint of price, preferably use sodium-chlor or sodium sulfate.

The particle diameter of water-soluble inorganic salt is more little more can obtain high micronize effect, but because undersized inorganic salt price is high, 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 using in salt grinding step is from processing efficiency and this two aspect of production efficiency, 1～30 quality that is preferably the whole pigment dyestuffs that comprise DPP series pigments doubly, be particularly preferably 5～25 amounts times.With respect to pigment dyestuff, the amount of inorganic salt is than larger, and miniaturization efficiency is higher, but because the pigment treatment capacity of 1 time 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 to wetting action, so long as dissolve (mixing) and do not dissolve in fact the solvent of used water-soluble inorganic salt in water, just without particular limitation of.

But temperature rises when salt grinds, solvent becomes the evaporable state of appearance, and therefore from the viewpoint of security, preferably using boiling point is 120 ℃ of above high boiling solvents.

As water-miscible organic solvent, such as using 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-methoxy-2-propanol, 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, with respect to above-mentioned water-soluble inorganic salt, be preferably 5 quality %～80 quality %.More preferably with respect to water-soluble inorganic salt, be 10 quality %～60 quality %, optimal is to be 15 quality %～50 quality % with respect to water-soluble inorganic salt.

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

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

(resin)

In the manufacture of miniaturization diketopyrrolo-pyrrole series pigments in the present invention, for prevent miniaturization the strong cohesion of diketopyrrolo-pyrrole series pigments when dry, can easily disperse, 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, diketopyrrolo-pyrrole series pigments is contacted with resin.

Here, DPP series pigments is contacted refer to resin to stick to the meaning on surperficial at least one of DPP series pigments with resin.

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

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

The acid number using in 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 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 epoxy resin, acrylic resin, maleic acid resin, butyral resin, vibrin, melamine resin, resol, urethane resin, polyamide resin etc.

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

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

By acid number is adjusted within the scope of this, 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 and below 50000 with weight-average molecular weight, and more preferably, more than 3000 and below 30000, optimal is more than 4000 and below 25000.By molecular weight is adjusted within the scope of this, can reach the good caustic solubility of miniaturization DPP series pigments, agglomeration preventing effect, dispersiveness when dry.

(macromolecular compound that contains pigment adsorption base)

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

As the macromolecular compound with pigment adsorption base, be preferably particularly the polymkeric substance (following, to be called " particular polymers ") containing from the polymerized unit of a kind of monomer among the choosing group that freely monomer shown in following general formula (1), maleimide and maleimide derivatives form.Wherein, as particular polymers, be particularly preferably the polymkeric substance containing from the polymerized unit of the monomer shown in following general formula (1).

general formula (1)

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

As R ¹the alkyl representing, is preferably carbonatoms and is 1～12 alkyl, and the alkyl that more preferably carbonatoms is 1～8 is particularly preferably carbonatoms and is 1～4 alkyl.

At R ¹the alkyl representing has in substituent situation, as this substituting group, can list alkoxyl groups such as hydroxyl or methoxyl group, oxyethyl group, cyclohexyloxy.As this alkoxyl group, being preferably carbonatoms is 1～5 alkoxyl group, the alkoxyl group that more preferably carbonatoms is 1～3.

As R ¹the preferred alkyl representing, 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 general formula (1) ²the concatenating group of the divalent representing, the divalent group that is preferably alkylidene group or contains alkylidene group.As this alkylidene group, be preferably carbonatoms and be 1～12 alkylidene group, the alkylidene group that more preferably carbonatoms is 1～10, the alkylidene group that more preferably carbonatoms is 1～8, is particularly preferably carbonatoms and is 1～4 alkylidene group.

In addition, at this alkylidene group, have in substituent situation, as this substituting group, such as listing hydroxyl etc.

As R ²the preferred alkylidene group representing, can list methylene radical, ethylidene, propylidene, trimethylene, tetramethylene particularly.

As R ²the divalent group that comprises alkylidene group representing can be the divalent group that 2 above above-mentioned alkylidene groups are situated between and for example, are formed by connecting by heteroatoms (Sauerstoffatom, nitrogen-atoms or sulphur atom).

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

The nitrogen heterocyclic ring structure of the nitrogen heterocycle representing as the Z forming in general formula (1), can list particularly and have 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 such as 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 more than 6 nitrogen heterocyclic ring structures, is particularly preferably and has the group that carbonatoms is 6～12 nitrogen heterocyclic ring structure.

As carbonatoms, it is more than 6 nitrogen heterocyclic ring structures, be preferably particularly 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, be particularly preferably the structure shown in following general formula (2), (3) or (4).

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

In general formula (2), X represents to be selected from singly-bound, alkylidene group (such as methylene radical, ethylidene, propylidene, trimethylene, tetramethylene etc.) ,-O-,-S-,-NR ^a-and-C (=O)-in any.R wherein ^arepresent hydrogen atom or alkyl.R ^ait is 1～18 alkyl, the alkyl that more preferably carbonatoms is 1～6 that alkyl in expression alkyl situation is preferably carbonatoms, such as 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 general formula (2), be preferably singly-bound, methylene radical ,-O-or-C (=O)-, be particularly preferably-C (=O)-.

In general formula (4), represent independently of one another-N=of Y and Z ,-NH-,-N (R ^b)-,-S-or-O-.R ^brepresent alkyl, it is 1～18 alkyl, the alkyl that more preferably carbonatoms is 1～6 that this alkyl is preferably carbonatoms, such as 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 general formula (4), be particularly preferably-N=,-NH-and-N (R ^b)-.As the combination of Y and Z, can list either party in Y and Z and be-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 such as 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 particularly preferably phenyl ring, naphthalene nucleus, pyridine ring.

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

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

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

In the structure representing in general formula (2), (3) or (4), viewpoint from 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 in the present invention refers to the maleimide that N position has been replaced by substituting groups such as alkyl or aryls.

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

Particular polymers in the present invention can only contain a kind from the polymerized unit that is selected from a kind of monomer in monomer, maleimide and the maleimide derivatives that general formula (1) represents, also can contain two or more.

Among monomer, maleimide and maleimide derivatives that general formula (1) represents, the monomer representing due to general formula (1) is high to the adsorptivity of pigment, so preferably.

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

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

Particular polymers in the present invention preferably comprises from the polymerized unit with the monomer of acidic group.By particular polymers is comprised from the polymerized unit with the monomer of acidic group, in the situation that pigment dispensing composition is applicable to optical polymerism composition, the development removability of unexposed portion is good.

As the monomer with acidic group, can exemplify out the unsaturated monocarboxylic classes such as vinylformic acid, methacrylic acid, β-crotonic acid, α-chloro-acrylicacid, styracin; 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; 3 yuan of above unsaturated polycarboxylic acid or its anhydrides; List ((methyl) acryloxyalkyl) the ester class of 2 yuan of above polycarboxylic acids such as mono succinate (2-acryloxy ethyl ester), mono succinate (2-methacryloxy ethyl ester), edicarboxylic acid list (2-acryloxy ethyl ester), edicarboxylic acid list (2-methacryloxy ethyl ester); List (methyl) esters of acrylic acid of the 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 polymerized unit with the monomer of acidic group, also can comprise two or more.

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

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

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

Here, as operable vinyl monomer, have no particular limits, be preferably ester class such as (methyl) esters of acrylic acid, crotonate class, vinyl ester, maleic acid diester class, dimethyl ester class, methylene-succinic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol, styrenic, (methyl) vinyl cyanide etc.As the concrete example of such vinyl monomer, for example, can list following compound.In addition, in this specification sheets, in the situation that represent any or both of " propenyl, methylpropenyl ", be sometimes recited as " (methyl) propenyl ".

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, the tertiary monooctyl ester of (methyl) vinylformic acid, (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) tribromophenyl acrylate, (methyl) vinylformic acid tribromophenoxy ethyl ester etc.

As the example of crotonate class, can list butyl crotonate and the own ester of β-crotonic acid 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 (such as t-Boc etc.) protection.

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

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

That is to say, from being the generation of 2 aggregates or the viewpoint that effectively weakens the cohesive force of 2 aggregates in order effectively to suppress the aggregate of 1 particle of pigment, the weight-average molecular weight of particular polymers (Mw) is preferably more than 1000.In addition, the viewpoint of the developability while manufacturing colour filter from process the optical polymerism composition of pigment by containing, the weight-average molecular weight of particular polymers (Mw) is preferably below 50000.

Particular polymers can utilize the monomer that for example general formula (1) represents and manufacture 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 adopting during as synthetic such particular polymers, for example can list ethylene dichloride, pimelinketone, methyl ethyl ketone, acetone, methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, 2-methyl cellosolve acetic ester, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetic ester, N, dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), toluene, vinyl acetic monomer, methyl lactate, ethyl lactate etc.These solvents can be used separately or mix two or more.

In addition, when 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 contacting with DPP series pigments in these operations in the manufacturing process of miniaturization DPP series pigments, before dry, preferably adds 1 quality %～80 quality % with respect to the total amount of the pigment dyestuff that comprises DPP series pigments.Preferred addition is that the total amount with respect to the pigment dyestuff that comprises DPP series pigments is 5 quality %～60 quality %, and optimal addition is that the total amount with respect to the pigment dyestuff that comprises DPP series pigments is 7 quality %～35 quality %.

When addition is in the scope of 1 quality %～80 quality %, can obtains preventing fully flocculating result when dry, and can obtain the colour filter of preferred form and aspect.

(pigment derivative)

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

The preferred skeleton having as pigment derivative, can list the skeletons such as quinacridine ketone pigment, phthalocyanine pigment, azo pigment, quinophthalone class pigment, isoindoline class pigment, isoindoline ketone pigment, diketopyrrolo-pyrrole pigment, Benzimidazolinone pigment.In addition, preferably in skeleton, also comprise the flaxen aromatic series polynuclear compounds such as naphthalene system, anthraquinone system, triazine system, quinoline system.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 the pigment derivative of recording in Japanese kokai publication hei 11-49974 communique, Unexamined Patent 11-189732 communique, Unexamined Patent 10-245501 communique, JP 2006-265528 communique, Unexamined Patent 8-295810 communique, Unexamined Patent 11-199796 communique, JP 2005-234478 communique, JP 2003-240938 communique, JP 2001-356210 communique, JP 2001-220520 communique, JP 2007-186681 communique etc.

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

The in the situation that of adding pigment derivative in the present invention when salt grinds, general before mixing, by DPP series pigments and pigment derivative, the form with powder coordinates and uses, 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.

The in the situation that of adding pigment derivative in the present invention when salt grinds, an example of the compound that can use is expressed as follows.

(salt grinding step with and subsequent operation)

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

In this operation; the any device such as micro-granulating device of the 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 applicable preferably 30 ℃～90 ℃.If carry out micronize under the condition higher than 150 ℃, the speed of growth of particle is faster than micronize speed sometimes, and it is difficult that micronize becomes.In addition, if carry out micronize at the temperature lower than 10 ℃, the heating during due to micronize, becomes difficult to the control of temperature, manufactures stability and produces fluctuation, therefore not preferred.Salt milled processed can carry out obtaining the random time of object particle diameter, but be generally 2 hours～24 hours, if the productivity of considering is preferably 2 hours～15 hours.

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

First, after salt grinding step, generally the thing that mixes obtaining is carried out to desalting treatment.

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

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

Generally make the pigment after desalting treatment and filtration dry.For dry, conventionally mostly use baking oven, but also can use dry (spray dry) method or the boulton process of spraying.Particularly in spray-drying process, known can obtain dry cohesion weak, disperse to be easy to powder pigment.

In the situation that using oven drying, temperature is generally 30 ℃～150 ℃, is preferably 30 ℃～120 ℃, and optimal is 40 ℃～90 ℃.If be dried at the temperature higher than 150 ℃, cause fierce dry cohesion, it is difficult sometimes to disperse to become.In addition, long-time lower than the dry needs at the temperature of 30 ℃, not preferred from productive viewpoint.

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

Pigment dispensing composition of the present invention contains DPP series pigments, but preferably by least one of above-mentioned miniaturization DPP series pigments, forms.

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

For example, as red pigment, can use diketopyrrolo-pyrrole series pigments at least one (comprising above-mentioned miniaturization DPP 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 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 from the viewpoint of form and aspect, dichroism, be preferably C.I. Pigment red 254.As anthraquione pigmentss, preferably can list C.I. pigment Red 89, C.I. Pigment red 177 etc., but from the viewpoint of form and aspect, dichroism, preferably use C.I. Pigment red 177.

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 by the yellow ultramarines such as C.I. Pigment red 254 and C.I. Pigment red 177 and C.I. Pigment Yellow 73 150 or C.I. pigment yellow 13 9, C.I. pigment yellow 13 8 use.Wherein, the combination of C.I. Pigment red 254 and C.I. Pigment red 177 and C.I. Pigment Yellow 73 150 use is from the viewpoint of contrast gradient, particularly preferably.

As can with the pigment of pigment dispensing composition of the present invention use, have no particular limits, can use a series of known pigment already described in the project of above-mentioned diketopyrrolo-pyrrole series pigments, as preferably combination also as mentioned above.From the viewpoint of contrast gradient, the pigment optimization can be used together 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 use, have no particular limits colour filter purposes before can being used as and the known dyestuff that uses.It is for example Japanese kokai publication sho 64-90403 communique, JP 64-91102 communique, Unexamined Patent 1-94301 communique, Unexamined Patent 6-11614 communique, 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, Unexamined Patent 6-35183 communique, Unexamined Patent 6-51115 communique, Unexamined Patent 6-194828 communique, Unexamined Patent 8-211599 communique, Unexamined Patent 4-249549 communique, Unexamined Patent 10-123316 communique, Unexamined Patent 11-302283 communique, Unexamined Patent 7-286107 communique, JP 2001-4823 communique, Unexamined Patent 8-15522 communique, Unexamined Patent 8-29771 communique, Unexamined Patent 8-146215 communique, Unexamined Patent 11-343437 communique, Unexamined Patent 8-62416 communique, JP 2002-14220 communique, JP 2002-14221 communique, JP 2002-14222 communique, JP 2002-14223 communique, Unexamined Patent 8-302224 communique, Unexamined Patent 8-73758 communique, Unexamined Patent 8-179120 communique, the pigment of recording in Unexamined Patent 8-151531 communique etc.

As chemical structure, can use the 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 two or more are used.

As in pigment dispensing composition comprise DPP series pigments and according to hope and and the total content of the pigment of other pigment of use, ratio as 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, color depth fully and can effectively guarantee good colour characteristics.

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

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

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

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

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

General formula (B)

In 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, represents 1～3 integer.X in above-mentioned general formula (B) and Y are identical with X and Y implication in above-mentioned general formula (A), and preferred form is also identical.

(B) O-phthalic imide alkylation diketopyrrolo-pyrrole can be by known manufacturing process, such as by being that red pigment is reacted with paraformaldehyde and adjacent phthalic imidine or hydroxymethyl phthalic imidine etc. and easily manufactured in sulfuric acid by diketopyrrolo-pyrrole.For this synthetic method, be at length recorded in JP 62-149759 communique etc., can be with reference to the document.As the diketopyrrolo-pyrrole using in this is synthetic, it is red pigment, such as listing C.I. Pigment red 254,255,264 and C.I. pigment orange 71,73 etc., from synthetic easness and the viewpoint of form and aspect, particularly preferably use C.I. Pigment red 255.

As (B) O-phthalic imide alkylation diketopyrrolo-pyrrole, the phthalimidomethyl diketopyrrolo-pyrrole that the replacement number that can use phthalimidomethyl is 1～3 with by the diketopyrrolo-pyrrole of O-phthalic imide, be not the mixture of red pigment.As diketopyrrolo-pyrrole now, be red pigment, such as listing 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.

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

General formula (C)

In 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, represents 1～3 integer.

As said structure representative can be for (C) of the present invention O-phthalic imide alkylation quinacridone, such as listing phthalimidomethyl without replacing quinacridone, phthalimidomethyl dimethylquinacridone, phthalimidomethyl dichloro quinacridone etc.

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

(C) O-phthalic imide alkylation quinacridone can be by easily manufacturing such as quinacridone red pigment being reacted with paraformaldehyde and phthalic imidine or hydroxymethyl phthalic imidine in sulfuric acid etc.For the method, be recorded in JP 55-108466 communique etc., can be with reference to the document.

As (C) O-phthalic imide alkylation quinacridone, the phthalimidomethyl quinacridone that the replacement number that can use phthalimidomethyl is 1～3 with not by O-phthalic imide the mixture of quinacridone red pigment.As quinacridone red pigment now, such as can list C.I. pigment violet 19 such without replacing the such dichloro quinacridone pigment of quinacridone pigment, C.I. pigment red 122 such dimethylquinacridone pigment, C.I. Pigment red 202, C.I. Pigment red 209 etc.

In 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, it is 0.1 mass parts～25 mass parts, optimal is 0.5 mass parts～20 mass parts.In addition, as the particularly preferred content of (C) O-phthalic imide alkylation quinacridone, with respect to diketopyrrolo-pyrrole series pigments 100 mass parts, be 0.1 mass parts～15 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 the O-phthalic imide alkylation diketopyrrolo-pyrrole and the O-phthalic imide alkylation quinacridone that contain this scope, can obtain the good surface smoothness 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 respectively separately a kind, also can two or more are used.

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 preferably at least a portion (preferably becoming after 10nm～30nm at average primary particle diameter) after the miniaturization of diketopyrrolo-pyrrole is carried out is added.Specifically, such as can list to salt, grind in the thing that mixes after finishing add, the interpolation of desalination while disperseing, interpolation to adding in the powder pigment after drying and crushing, to adding in the pigment dispensing composition before disperseing, in colo(u)rant dispersion way etc.By the O-phthalic imide alkylation diketopyrrolo-pyrrole of at least a portion and O-phthalic imide alkylation quinacridone are added after the miniaturization of diketopyrrolo-pyrrole, can obtain the good surface smoothness of high pigment-dispersing, high-contrast and colour filter.

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

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

Can and the preferred pigments derivative of use be to using pigment dyestuff as precursor skeleton, imported acidic groups or basic group, aromatic series base as substituent compound at side chain specifically.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 there is the skeleton of diketopyrrolo-pyrrole series pigments but be not included in the pigment derivative in above-mentioned (B) composition or there is 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 the flaxen aromatic series polynuclear compounds such as the naphthalene system that is not generally called pigment, anthraquinone system, triazine system, quinoline system.

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

As can be preferably in the present invention and the pigment derivative of use, can list the pigment derivative of recording such as in Japanese kokai publication hei 3-153780 communique, Unexamined Patent 11-49974 communique, Unexamined Patent 11-189732 communique, Unexamined Patent 10-245501 communique, JP 2006-265528 communique, Unexamined Patent 8-295810 communique, Unexamined Patent 11-199796 communique, JP 2005-234478 communique, JP 2003-240938 communique, JP 2001-356210 communique, JP 2007-186681 communique etc.

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

((D) organic solvent)

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

(D) organic solvent used in modulation as pigment dispensing composition of the present invention, can list 1-methoxy-2-propanol acetic ester, 1-methoxy-2-propanol, ethylene glycol monomethyl 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, in composition, can only use a kind, and also two or more kinds may be used.

In addition, the addition of organic solvent can be according to purposes of pigment dispensing composition etc. and suitable selection, but in the situation that for the modulation of coloured polymerized composition described later, from the viewpoint of operability, can be so that the solid component concentration that comprises pigment etc. becomes the mode of 5～50 quality % and adds.

(other compositions)

-dispersion agent-

In pigment dispensing composition of the present invention, from improving the dispersed viewpoint of contained pigment, preferably add dispersion agent.

As dispersion agent used in the present invention, can list macromolecule dispersing agent (such as, daiamid and salt, 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, from its structure, can further be categorized into straight chain-like macromolecule compound, terminal-modified type macromolecular compound, graft type macromolecular compound and block type polymer compound.

Macromolecule dispersing agent is adsorbed on the surface of pigment, has played and has prevented from condensing such effect again.Therefore,, as preferred structure, can list the terminal-modified type macromolecular compound, graft type macromolecular compound, the block type polymer compound that have to the position of anchoring in surface of pigments.

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

(block type polymer compound)

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

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

Below, for be suitable as the monomer that forms pigment adsorption block the monomer with organic pigment structure or heterocycle structure, there is the monomer of acidic groups and there is the monomer of basic nitrogen atom and describe.

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

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

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

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

In addition, also can utilize (methyl) vinylformic acid 2-hydroxy methacrylate etc. to there is 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, from viewpoints such as copolymerizable or cost, solvabilities, be particularly preferably (methyl) vinylformic acid.

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

As the monomer with basic nitrogen atom, as the monomer with heterocycle, can list vinyl pyridine, vinyl imidazole, vinyl triazole etc., as (methyl) acrylate, can list (methyl) vinylformic acid N, N-dimethylamino ethyl ester, (methyl) vinylformic acid N, N-dimethylamino propyl ester, (methyl) vinylformic acid 1-(N, 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, N-dimethylamino) ethyl (methyl) acrylamide, 2-(N, N-diethylamino) ethyl (methyl) acrylamide, 3-(N, N-diethylamino) propyl group (methyl) acrylamide, 3-(N, N-dimethylamino) propyl group (methyl) acrylamide, 1-(N, 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 the monomer of more than 4 alkyl, alkoxysilyl, epoxy group(ing), isocyanate group, 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 anionic property vinyl monomer, can list the above-mentioned vinyl monomer with acidic groups an alkali metal salt or with salt of organic amine (such as 3 grades of amine such as, triethylamine, dimethylaminoethanols) etc.As cationic vinyl monomer, can list above-mentioned nitrogenous haloalkyl (alkyl: C1～18, halogen atom: chlorine atom, bromine atoms or iodine atom) for vinyl monomer; The benzyl halides such as zephiran chloride, bromination benzyl; The alkyl sulfonic esters such as methanesulfonic (alkyl: C1～18); The aryl sulfonic acid such as Phenylsulfonic acid, toluenesulphonic acids alkyl ester (alkyl: C1～18); C1～4) etc. sulfuric acid dialkyl (alkyl: carry out 4 grades of cationic vinyl monomers of changing and obtaining and dialkyldiallyl ammonium salt etc.

Above-mentioned such having can be adsorbed on the monomer of the functional group on pigment can be according to the pigment type that will disperse and suitable selection, and they can use separately, also can two or more are used.

As forming the monomer that is not adsorbed on the block on pigment, have no particular limits, such as listing (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., do not there is the monomer of pigment adsorption base.

Form these monomers be not adsorbed on the block on pigment, can use separately, also can two or more are used.

In addition, in the situation that be applicable to need the pigment dispensing composition of alkaline development processing, the monomer that above-mentioned formation is not adsorbed on the block on pigment also can be used together with the vinyl monomer with acidic groups.

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, the tertiary monooctyl ester of (methyl) vinylformic acid, (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) tribromophenyl acrylate, (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 β-crotonic acid 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 (such as 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, N-cyclohexylmaleimide, phenyl maleimide etc.

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

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

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

In addition, can also use (methyl) vinylformic acid 2-hydroxy methacrylate etc. to there is 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 be used as the monomer that contains the acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride of carboxyl precursor.

In addition, from viewpoints such as copolymerizable or cost, solvabilities, (methyl) vinylformic acid wherein particularly preferably.

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

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

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

Such as known, there are 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: when the monomer that has the monomer of pigment adsorption base or do not have a pigment adsorption base is carried out to radical polymerization, will with thiol carboxylic acid, or 2-ethanoyl sulfenyl ethyl ether, the compound that 10-ethanoyl sulfenyl decane mercaptan etc. contain thioesters and thiol group at molecule coexists and polymkeric substance that polymerization obtains is processed with alkali such as sodium hydroxide or ammonia, make the polymkeric substance on single end with thiol group, on resulting single end, have under the existence of polymkeric substance of thiol group, make the method for the monomer component generation radical polymerization of another block.In these methods, living polymerization method is preferred.

Weight-average molecular weight to 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, can more effectively obtain stabilization effect, in addition, if, below 100,000, can more effectively adsorbing, weight-average molecular weight brings into play good dispersiveness.

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

(graft type macromolecular compound)

For the graft type macromolecular compound using as macromolecule dispersing agent, have no particular limits, can preferably exemplify out JP 54-37082 communique, that records in JP 61-174939 communique etc. making polyalkyleneimine react with petchem and the compound that obtains, that in Unexamined Patent 9-169821 communique, records modifies the amino of the side chain of PAH and the compound that obtains with polyester, the polyester polyol of recording in JP 60-166318 communique adds generating polyurethane etc., and then can also preferably exemplify out Unexamined Patent 9-171253 communique, " chemistry and industry of macromonomer " (IPC publishing department, 1989) etc. in, using 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.The graft type macromolecular compound wherein, more preferably in branch portion with the structural unit of following general formula (5) expression.

general formula (5)

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

In general formula (5), R ⁷⁴the alkyl representing also can have substituting group, is preferably carbonatoms and is 1～6 alkyl, is particularly preferably methyl.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 particularly preferably hydrogen atom, methyl.

In general formula (5), the aryl that Q represents also can have substituting group, is preferably carbonatoms and is 6～20 aryl, is particularly preferably carbonatoms 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 without substituted aryl or by the aryl that halogen atom, alkyl or alkoxyl group have replaced, be particularly preferably without substituted aryl or by alkyl substituted aryl.

Q at general formula (5) is-COOR ⁷⁵situation under, R ⁷⁵the alkyl representing also can have substituting group, is preferably carbonatoms and is 1～12 alkyl, is particularly preferably carbonatoms 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, 2-chloroethyl, 2-bromotrifluoromethane, 2-dion e, 2-methoxy ethyl, 2-bromopropyl, crotyl, pentenyl, 3-methyl-pentenyl, 2-hexenyl, 4-methyl-2-hexenyl, benzyl, styroyl, 3-phenyl propyl, menaphthyl, 2-naphthalene ethyl, chlorobenzyl, bromobenzyl, methyl-benzyl, Ethylbenzyl, methoxy-benzyl, dimethyl benzyl, dimethoxy-benzyl, cyclohexyl, 2-cyclohexyl ethyl, 2-cyclopentyl ethyl, dicyclo (3.2.1) is pungent-2-base, 1-adamantyl, dimethylaminopropyl, acetylamino ethyl, N, N-dibutylamino carbamyl ylmethyl etc.

In such alkyl, be preferably without substituted alkyl or by the alkyl that halogen atom, aryl or hydroxyl have replaced, be particularly preferably without substituted alkyl.

Q at general formula (5) is-COOR ⁷⁵situation under, R ⁷⁵the aryl representing also can have substituting group, is preferably carbonatoms and is 6～20 aryl, is particularly preferably carbonatoms 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 without substituted aryl or by the aryl that halogen atom, alkyl or alkoxyl group have replaced, be particularly preferably by alkyl substituted aryl.

At such R ⁷⁵in, the alkyl that to be preferably hydrogen atom, carbonatoms be 1～22, the alkyl that to be particularly preferably hydrogen atom, carbonatoms be 1～12.

As the object lesson of the branch portion of such graft type macromolecular compound in branch portion with the structural unit that general formula (5) represents, 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 in branch portion with the structural unit that general formula (5) represents also can utilize known any method.

Specifically, can list the macromonomer with the structural unit that general formula (5) represents 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 that preferably following general formula (6) represents.

general formula (6)

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

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

The object lesson of the macromonomer representing as such general formula (6), can list macromonomer as follows.

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

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

As the molecular weight of above-mentioned macromonomer, with the number-average molecular weight (Mn) of polystyrene conversion, be preferably 1,000～20,000, more preferably 2,000～15,000.If above-mentioned number-average molecular weight, in above-mentioned scope, 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 dispersiveness, the dispersion stabilization of pigment, preferably use above-mentioned " forming the monomer of pigment adsorption block ".In addition, as other copolymer compositions, also can make above-mentioned " forming the monomer that is not adsorbed on the block on 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, can more effectively obtain stabilization effect, in addition, if, below 100,000, can more effectively adsorbing, weight-average molecular weight brings into play good dispersiveness.

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 company systems " Disperbyk-161,171,174 " etc.

(terminal-modified type macromolecular compound)

As the terminal-modified type macromolecular compound as macromolecule dispersing agent, such as the end at polymkeric substance that can list record in Unexamined Patent 9-77994 communique, JP 2002-273191 communique etc., there is the macromolecular compound of functional group.

The method to synthesizing end at polymkeric substance with the macromolecular compound of functional group has no particular limits, such as method that can list following method or they are combined etc.

1. the polymerization of the polymerization starter that contains functional group by use (such as radical polymerization, anionoid polymerization, cationoid polymerisation etc.) and synthetic method

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

Here, as the functional group importing, 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 coordination Sauerstoffatom is the position in more than 4 alkyl, alkoxysilyl, epoxy group(ing), isocyanate group, hydroxyl and ionic functional groups etc.In addition, can be also the functional group that can be derivatized to these adsorption sites.

As what adopt in the synthetic method above-mentioned 1., can import in polymer ends the polymerization starter (polymerization starter that contains functional group) of functional group, 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 what adopt in the synthetic method above-mentioned 2., can in polymer ends, import the chain-transfer agent (chain-transfer agent that contains functional group) of functional group, for example can list sulfhydryl compound (Thiovanic acid for example, mercaptosuccinic acid, thiosalicylic acid, 2 mercaptopropionic acid, 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-thiohydracrylic acid, 4-sulfydryl fourth sulfonic acid, 2 mercapto ethanol, 3-sulfydryl-1,2-propane diol, 1-sulfydryl-2-propyl alcohol, 3-sulfydryl-2-butanols, mercapto-phenol, 2-mercaptoethyl amine, 2-mercaptoimidazole, 2-sulfydryl-3-pyridone, benzenethiol, toluenethiol, sulfydryl methyl phenyl ketone, naphthyl mercaptan, naphthalene methyl mercaptan etc.), the oxide compound of these sulfhydryl compounds is disulphide, and halogenide (2-iodo ethyl sulfonic acid for example, 3-iodo propanesulfonic acid etc.).

The monomer of use while carrying out polymerization as the macromolecular compound the end of polymkeric substance being had to functional group, for example, as free radical polymerization monomer, can be used above-mentioned " forming the monomer that is not adsorbed on the block on 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, can more effectively obtain the steric repulsion effect as dispersion agent, if below 50,000, can more effectively suppress stereoeffect, further shorten the 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, it is particularly preferred containing from the graft type macromolecular compound, the terminal-modified type macromolecular compound that has organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups or a carbamate groups as terminal group of copolymerization units with the monomer of organic pigment structure or heterocycle structure.

In addition, in the present invention, can use dispersion resin as required.By using dispersion resin, can improve dispersion stabilization, the keeping quality of processing pigment.

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

As the polymkeric substance at side chain with carboxylic acid, such as having the Sipacril 2739OF recorded in JP 59-44615 communique, examined patent publication 54-34327 communique, examined patent publication 58-12577 communique, examined patent publication 54-25957 communique, JP 59-53836 communique, JP 59-71048 communique, acrylic copolymer, itaconic acid copolymer, β-crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc., similarly at side chain, there is in addition in addition the acid cellulose derivative of carboxylic acid.

The polymkeric substance at side chain with carboxylic acid for example can list (methyl) vinylformic acid, toxilic acid (acid anhydride), β-crotonic acid, methylene-succinic acid, fumaric acid etc. have 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, ethylacrylic acid glycidyl esters, β-crotonic acid glycidyl ether, (methyl) acrylate chloride, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) Hydroxyethyl Acrylate, N hydroxymethyl acrylamide, N, N DMAA, N-methacryloyl morpholine, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethyl aminoethyl acrylamide, maleimide, in N-phenylmaleimide etc. a kind above copolymer composition copolymerization and the polymkeric substance that obtains.Wherein preferably at least comprise (methyl) vinylformic acid or (methyl) alkyl acrylate as (methyl) acrylic resin of structural unit, also preferably comprise (methyl) vinylformic acid and cinnamic (methyl) acrylic resin.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 give two keys on side chain, can improve light solidified, further improve resolution, adaptation.

As the synthesizing mean that imports the two keys of ethylenic, such as listing the middle method of recording such as examined patent publication 50-34443 communique, examined patent publication 50-34444 communique etc.Specifically, can list carboxyl or hydroxyl and the method that there is the compound of glycidyl, epoxycyclohexyl and (methyl) acryl or acrylate chloride etc. and react.For example use (methyl) glycidyl acrylate, allyl glycidyl ether, α-ethylacrylate glycidyl ester, crotonyl glycidyl ether, (different) β-crotonic acid glycidyl ether, (3; 4-epoxycyclohexyl) compound such as (methyl) methyl acrylate, (methyl) acrylate chloride, (methyl) acryloyl chloride; by the resin reaction with thering is carboxyl or hydroxyl, thereby can access the resin at side chain with polymer-based group.

The resin that particularly preferably makes the reaction of (3,4-epoxycyclohexyl) (methyl) methyl acrylate and obtain.As these concrete compounds, such as listing DIANAL NR series (Mitsubishi Rayon Co., Ltd. system), Photomer 6173 (the Polyurethane acrylic oligopolymer that contains COOH, Diamond Shamrock Co.Ltd. system), 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.

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

H ₂c=CRC (=O) OCR ⁴r ⁵c (=R ³)=CR ²r ¹general formula (7)

In above-mentioned general formula (7), R represents hydrogen atom or methyl, R ¹～R ⁵represent to be selected from independently of one another 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, such as listing methyl, n-propyl, sec.-propyl, the tertiary butyl etc., be preferably carbonatoms, is 1～7 alkyl.

As above-mentioned aryl, such as listing phenyl, furyl, naphthyl etc.

In above-mentioned, as dispersion resin, can select various monomers, control solubleness and acid number, be therefore preferably the multipolymer of (methyl) vinylformic acid and (methyl) acrylate.The preferable range of the weight-average molecular weight that these dispersion resins are measured by gel permeation chromatography (GPC) is 1,000～80,000, 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 developability.

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

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

If the addition of dispersion agent, within the scope of this, can obtain sufficient colo(u)rant dispersion effect.But the optimum addition of dispersion agent can pass through the combination such as used pigment, solvent etc. and suitable adjustment.

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

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

By utilizing pigment dispensing composition of the present invention to modulate coloured polymerized composition, and be applicable to, in the manufacture of colour filter, can access the colour filter that contrast gradient is high, surface smoothness is good.

(modulation of pigment dispensing composition)

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

In addition, blending dispersion operation preferably includes to mix disperses and in micro-dispersion treatment of carrying out continuously thereafter, but also can omit the dispersion of mixing.

In the manufacture method of pigment dispensing composition of the present invention, preferably implement following operation: first implement 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 predetermined addition, be preferably whole (B) O-phthalic imide alkylation diketopyrrolo-pyrroles and (C) operation of O-phthalic imide alkylation quinacridone; Then implement (A) diketopyrrolo-pyrrole series pigments, (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and operation that (C) O-phthalic imide alkylation quinacridone disperses together with organic solvent.Although reach at the average primary particle diameter of (A) diketopyrrolo-pyrrole series pigments, also can add (B) O-phthalic imide alkylation diketopyrrolo-pyrrole and (C) part for O-phthalic imide alkylation quinacridone before the scope of 10nm～30nm, 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.

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

If manufacture method of the present invention is specifically described, be for example by (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 use be pre-mixed.Further will to this mixture, disperse in advance with homogenizer etc., dispersed this mixture is in advance utilized together with organic solvent to have used the medium stirring-type dispersion machine (such as the デ イ ス パ mono-マ Star ト of GETZMANN company system) etc. of zirconium oxide bead etc. to carry out differential loose, can modulate pigment dispensing composition of the present invention thus.

In the present invention, in the situation that utilizing medium stirring-type dispersion machine to carry out micro-dispersion treatment, in order not carry out gentle dispersion to being dispersed body at short notice, preferably use median size for the medium more than 0.01mm and below 0.2mm with causing damage.Here, the median size in the present invention refers to 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 to bust shot with stereomicroscope, from its image, can obtain particle diameter.

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

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

In addition, about the detailed content of mixing, disperseing, 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, because dispersiveness and the dispersion stabilization of diketopyrrolo-pyrrole pigment are good, is suitable for containing diketopyrrolo-pyrrole pigment as in the various uses of tinting material, routine coloured polymerized composition as described below 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 composition contained in coloured polymerized composition of the present invention is described in detail.

(pigment dispensing composition)

At least one of the pigment dispensing composition of the present invention that coloured polymerized composition use of the present invention is above-mentioned forms.For the detailed content that forms the pigment dispensing composition of the present invention of coloured polymerized composition, as mentioned above.

Content as the pigment dispensing composition in 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 within the scope of this, color depth fully and can effectively guarantee good colour characteristics.

(optical polymerism compound)

The optical polymerism compound that coloured polymerized composition of the present invention contains at least a kind.

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

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

The object lesson of the monomer of the ester forming as aliphatic polyol compound and unsaturated carboxylic acid, as acrylate, has glycol diacrylate, triethylene glycol diacrylate, 1,3 butyleneglycol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, Viscoat 295, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylate, hexanediyl ester, Isosorbide-5-Nitrae-cyclohexanediol diacrylate, Viscoat 335HP, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, Dipentaerythritol diacrylate, dipentaerythritol acrylate, Sorbitol Powder triacrylate, Sorbitol Powder tetraacrylate, Sorbitol Powder five acrylate, Sorbitol Powder six acrylate, three (acryloxy ethyl) isocyanuric acid ester, 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-butyleneglycol 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 [p-(3-methacryloxy-2-hydroxyl propoxy-) phenyl] dimethylmethane, two-[p-(methacryloxy oxyethyl group) phenyl] dimethylmethanes etc.

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

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

Example as other ester, can suitably use the fatty alcohol of for example recording in examined patent publication 51-47334, JP 57-196231 is ester class, or the ester with aromatic series pastern bone frame of recording in JP 59-5240, JP 59-5241, Unexamined Patent 2-226149, that in Unexamined Patent 1-165613, records contains amino ester etc.And then above-mentioned ester monomer can also be used as mixture.

In addition, the object lesson of the monomer of the acid amides forming as aliphatic polyamine compound and unsaturated carboxylic acid, there are methylene diacrylamine, methylene radical two (Methacrylamide), 1,6-hexa-methylene diacrylamine, 1,6-hexa-methylene two (Methacrylamide), Diethylenetriamine three acrylamides, benzene two methylene diacrylamines, benzene two methylenes two (Methacrylamide) etc.The example of preferred amide class monomer as other, can list the acid amides with cyclohexylidene structure of recording in examined patent publication 54-21726.

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

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

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

In addition, in No. 2-16765, No. 51-37193, JP, No. 2-32293, JP, JP, record such urethane acrylate class, the carbamate compounds class with ethylene oxide skeleton of recording in No. 62-39418, No. 58-49860, examined patent publication, No. 56-17654, examined patent publication, No. 62-39417, examined patent publication, examined patent publication is also preferred.And then, by use the addition polymerization compounds in the molecule of recording with amino structure or sulfide based structural in No. 1-105238, No. 63-277653, JP, No. 63-260909, JP, Unexamined Patent, also can obtain the optical polymerism composition that film speed is very good.

As other example, can list and record such polyester acrylate class in each communique of No. 48-64183, JP, No. 49-43191, examined patent publication, No. 52-30490, examined patent publication, epoxy resin reacts with (methyl) vinylformic acid polyfunctional acrylate or the methacrylic esters such as Epoxy Acrylates forming.In addition, can also list the specific unsaturated compound of recording in No. 1-40336, No. 46-43946, examined patent publication, No. 1-40337, JP, JP, the vinyl phosphonic acid compounds of recording etc. in No. 2-25493, Unexamined Patent.In addition, in some cases, can suitably use the structure that contains perfluoroalkyl of recording in No. 61-22048, JP.And then, can also use in Japan and follow in the will Vol.20 of association, No.7,300th～308 pages (1984) as light solidified monomer and oligopolymer and the compound of introducing.

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

For example, can select according to following such viewpoint.Aspect sensitivity, preferred many structures of the unsaturated group content in every 1 molecule, at most cases, be preferably 2 officials can more than.In addition, in order to improve curing film strength, also can be the compound that 3 officials can be above, and then, by and for example, with (thering is different functional number, different polymerizable group, acrylate, methacrylic ester, styrene compound, vinyl ethers compound) addition polymerization compound, be also 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 the binder polymers such as alkali soluble resins, Photoepolymerizationinitiater initiater, tinting material (pigment), the selection of addition polymerization compound, using method are also important factors, for example,, sometimes by with low-purity compound or and improve consistency with two or more.

In addition, also can be in order to improve with the adaptation of substrate etc. and to select specific structure.Addition polymerization Compound Phase is for the non-volatility composition in 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 two or more is also used.In addition, for the using method of addition polymerization compound, can go out to send to select suitable structure, cooperation, addition from viewpoints such as the size of the encumbering property of polymerization to oxygen, exploring degree, photographic fog (fogging), variations in refractive index, surface adhesives.

(Photoepolymerizationinitiater initiater)

As Photoepolymerizationinitiater initiater, can list the Lu that records in Japanese kokai publication sho 60-3626 communique for example for Jia oxadiazole; Halogenated methyl-s-triazine isoreactivity halogen compounds of recording in JP 59-1281 communique, JP 53-133428 communique etc.; No. 4318791st, United States Patent (USP), european patent application disclose the aromatic carbonyls such as ketal, acetal or benzoin alkylether class of recording in each specification sheets such as the 88050th; The aromatic ketone compounds such as benzophenone of recording in No. 4199420 specification sheets of United States Patent (USP); (sulfo-) xanthene ketone or the acridine compound in No. 2456741 specification sheets of French Patent invention, recorded; The compounds such as the coumarins of recording in Japanese kokai publication hei 10-62986 communique or 2,4,5-triphenyl imidazole dimer class; The sulfonium Organic Bor Complex of Unexamined Patent 8-015521 communique etc. etc.

As the Photoepolymerizationinitiater initiater in 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, it 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, be Photoepolymerizationinitiater initiater, can preferably list such as benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl acetal etc.

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

As above-mentioned bitter almond oil camphor system or benzoyl, be Photoepolymerizationinitiater initiater, can preferably list such as 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, be Photoepolymerizationinitiater initiater, can preferably list such as diethyl thioxanthone, di-isopropyl thioxanthone, single isopropyl thioxanthone, clopenthixal ketone etc.

As above-mentioned active halogen compound (triazine Xi ， oxadiazole system, coumarin series), for example can preferably list 2, two (the trichloromethyl)-6-p-methoxyphenyl-s-triazines of 4-, two (the trichloromethyl)-6-of 2,4-are to methoxyl-styrene-s-triazine, two (trichloromethyl)-6-(1-is to the dimethylaminophenyl)-1,3-butadiene base-s-triazines of 2,4-, two (the trichloromethyl)-6-xenyl-s-triazines of 2,4-, two (trichloromethyl)-6-(to the methyl biphenyl)-s-triazines of 2,4-, to hydroxyl-oxethyl styryl-2,6-bis-(trichloromethyl)-s-triazine, methoxyl-styrene-2,6-bis-(trichloromethyl-s-triazine, 3,4-dimethoxy-styryl-2,6-bis-(trichloromethyl)-s-triazine, 4-benzo tetrahydrofuran-2,6-bis-(trichloromethyl)-s-triazine, 4-(the bromo-p-N of o-, N-bis-(ethoxy carbonyl is amino)-phenyl)-2,6-bis-(chloromethyl)-s-triazine, 4-(p-N, N-bis-(ethoxy carbonyl is amino)-phenyl)-2,6-bis-(chloromethyl)-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(cyano-styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4-oxadiazole, 3-methyl-5-amino-((s-triazine-2-yl) amino)-3-phenyl tonka bean camphor, the chloro-5-diethylamino of 3--((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, be Photoepolymerizationinitiater initiater, can preferably list for example 9-phenylacridine, 1, two (9-acridyl) heptane of 7-etc.

As above-mentioned bisglyoxaline, it 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-(2,4-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-one oxime, 2,4,6-trimethylphenyl carbonyl-diphenylphosphine acyl-oxygen, the even phosphorus-trialkyl Ben of hexafluoro Ji phosphonium salt etc.

In 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 recording in No. 2367660 specification sheets of United States Patent (USP), the alpha-carbonyl compound of recording in No. 2367661st, United States Patent (USP) and No. 2367670 specification sheets, the acyloin ether of recording in No. 2448828 specification sheets of United States Patent (USP), the aromatic series acyloin compound being replaced by α-alkyl of recording in No. 2722512 specification sheets of United States Patent (USP), the multinuclear naphtoquinone compounds of recording in No. 3046127th, United States Patent (USP) and No. 2951758 specification sheets, the combination of triallyl imidazole dimer/p-aminophenyl ketone of recording in No. 3549367 specification sheets of United States Patent (USP), benzothiazole based compound/trihalomethyl group-s-triazine based compound of recording in examined patent publication 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 oxime ester compound that JP 2000-66385 communique is recorded etc.

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

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

(alkali soluble resins)

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

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

For the manufacture of alkali soluble resins, can suitably use the method for for example using known radical polymerization.The polymerizing conditions such as kind of the kind of the temperature while manufacturing alkali soluble resins with radical polymerization, pressure, radical initiator and amount thereof, solvent, 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 at side chain, there is the polymkeric substance of carboxylic acid.For example, can list as No. 59-44615, JP, No. 54-34327, examined patent publication, No. 58-12577, examined patent publication, No. 54-25957, examined patent publication, No. 59-53836, JP, the Sipacril 2739OF of recording in No. 59-71048 each communique of JP, acrylic copolymer, itaconic acid copolymer, β-crotonic acid multipolymer, maleic acid, partial esterification maleic acid etc., and the acid cellulose derivative at side chain with carboxylic acid, there is the polymkeric substance of hydroxyl and material that acid anhydrides addition obtains etc., in addition, as preferred compound, also can list the high molecular polymer at side chain with (methyl) acryl.

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

In addition,, as useful compound, also can enumerate material of sening as an envoy to HEMA copolymerization and obtaining etc.

Except above-mentioned, also can list methacrylic acid 2-hydroxypropyl acrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/Sipacril 2739OF of recording in Unexamined Patent 7-140654 communique, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester/polymethylmethacrylate macromonomer/benzyl methacrylate/Sipacril 2739OF, HEMA/Group-capped Polystyrene Macromer/methyl methacrylate/Sipacril 2739OF, HEMA/Group-capped Polystyrene Macromer/benzyl methacrylate/Sipacril 2739OF etc.

As the preferred resin of the alkali soluble resins in the present invention, can list especially (methyl) vinylformic acid with can with the multipolymer of other monomers of its copolymerization.Here, (methyl) vinylformic acid is by 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 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, NVP, tetrahydrofurfuryl methacrylate, Group-capped Polystyrene Macromer, polymethylmethacrylate macromonomer, CH ₂=CR ¹r ², CH ₂=C (R ¹) (COOR ³) (wherein, R ¹represent the alkyl that hydrogen atom or carbonatoms are 1～5, R ²represent the aromatic hydrocarbons ring that carbonatoms is 6～10, R ³the aralkyl that the alkyl that expression carbonatoms is 1～8 or carbonatoms are 6～12) etc.

These can copolymerization other monomer can use separately a kind of or combine two kinds of above uses.

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 one in (methyl) phenyl acrylate, (methyl) benzyl acrylate and vinylbenzene, be particularly preferably CH ₂=CR ¹r ²and/or CH ₂=C (R ¹) (COOR ³).

Content as alkali soluble resins in coloured polymerized composition, with respect to the total solids composition of said composition, is preferably 1～30 quality %, and more preferably 1～20 quality %, is particularly preferably 2～15 quality %.

(solvent)

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

As operable solvent, can list: ester class, for example pentyl formate, the 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, Butyl Glycolate, Methoxy Methyl Acetate, Methoxy acetic acid ethyl ester, Methoxy acetic acid butyl ester, oxyethyl group ritalin, oxyethyl group vinyl acetic monomer, the 3-hydroxyalkyl propionate classes such as 3-hydroxy methyl propionate and 3-hydroxy-propionic acid ethyl ester, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid propyl ester, 2-methoxy methyl propionate, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, 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-Oxobutyric acid methyl esters, 2-Oxobutyric acid ethyl ester etc., ethers, such as 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, such as methylethylketone, pimelinketone, 2-heptanone, 3-heptanone etc., aromatic hydrocarbon based, such as 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-methoxy methyl propionate, 2-heptanone, pimelinketone, ethyl carbitol acetic ester, diethylene glycol monobutyl ether acetic ester, 1-Methoxy-2-propyl acetate etc.

Solvent, except can using separately, can also combine two kinds of above uses.

(other composition)

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

(sensitizing coloring matter)

In coloured polymerized composition of the present invention, can add as required sensitizing coloring matter.Sensitizing coloring matter exposes through the wavelength that can be 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 light splitting sensitizing coloring matter or dyestuff or absorb light and the interactional dyestuff of Photoepolymerizationinitiater initiater or pigment.

(light splitting sensitizing coloring matter or dyestuff)

As the sensitizing coloring matter using in the present invention and preferred light splitting sensitizing coloring matter or dyestuff, (for example can list the polynuclear aromatic same clan, pyrene, perylene, benzophenanthrene), xanthene class (for example, fluorescein, eosin, tetraiodofluorescein, rhodamine B, rose-red), cyanine class (for example, thia-carbonyl cyanine (thiacarbocyanine), oxa-carbocyanine (oxacarbocyanine)), 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), porphyrin (for example, tetraphenylporphyrin, the porphyrin of central metal displacement), chlorophyll class (for example, chlorophyll, CHLOROPHYLLINE, the chlorophyll of central metal displacement), metal complex (for example following compound), Anthraquinones (for example anthraquinone), squaric acid inner salt (squaryliums) class (for example, squaric acid inner salt) etc.

Exemplified the example of preferred light splitting sensitizing coloring matter or dyestuff below.

Can list the cationic dyestuff of recording in JP 62-143044 communique; The quinoxaline salt of recording in examined patent publication 59-24147 communique, the new methylene blue compound of recording in JP 64-33104 communique; The Anthraquinones of recording in JP 64-56767 communique; The benzoxanthene dye of recording in Unexamined Patent 2-1714 communique; The acridine of recording in Unexamined Patent 2-226148 communique and Unexamined Patent 2-226149 communique; The pyrans salt of recording in examined patent publication 40-28499 communique; The cyanine class of recording in examined patent publication 46-42363 communique; The cumarone pigment of recording in Unexamined Patent 2-63053 communique; Conjugation ketone pigment at Unexamined Patent 2-85858 communique, Unexamined Patent 2-216154 communique; The pigment of recording in JP 57-10605 communique; The azo cinnamylidene derivative of recording in JP 2-30321 communique; The anthocyanins of recording in Unexamined Patent 1-287105 communique; The xanthene class pigment of recording in JP 62-31844 communique, JP 62-31848 communique, JP 62-143043 communique; The amino-benzene vinyl ketone of recording in examined patent publication 59-28325 communique; The pigment of recording in Unexamined Patent 2-179643 communique; The merocyanine pigment of recording in Unexamined Patent 2-244050 communique; The merocyanine pigment of recording in examined patent publication 59-28326 communique; The merocyanine pigment of recording in JP 59-89303 communique; The merocyanine pigment of recording in Unexamined Patent 8-129257 communique; The benzo pyran pigment of recording in Unexamined Patent 8-334897 communique.

(pigment at 350～450nm with maximum absorption wavelength)

As other preferred configuration of sensitizing coloring matter, can list pigment compound group and there is maximum absorption wavelength at 350～450nm belonging to below.

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

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

general formula (XIV)

(in general formula (XIV), A ¹represent sulphur atom or-NR ⁶⁰-, R ⁶⁰represent alkyl or aryl, L ⁰¹represent the A with adjacency ¹form the nonmetallic atom group of the alkaline core of pigment together with carbon atom, R ⁶¹, R ⁶²represent independently of one another hydrogen atom or monovalence nonmetallic atom group, 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 that general formula (XIV) represents.

general formula (XV)

(in general formula (XV), Ar ¹and Ar ²represent independently of one another aryl, 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 general formula (XIV).)

The preference of the compound representing as general formula (XV), can list ((A-6)～(A-8)) below.

general formula (XVI)

(in general formula (XVI), A ²represent sulphur atom or-NR ⁶⁹-, L ⁰³represent the A with adjacency ²form the nonmetallic atom group of the alkaline core of pigment together with carbon atom, R ⁶³, R ⁶⁴, R ⁶⁵, R ⁶⁶, R ⁶⁷and R ⁶⁸the nonmetallic atom group that represents independently of one another monovalence, R ⁶⁹represent alkyl or aryl.)

The preference of the compound representing as general formula (XVI), can list compound below ((A-9)～(A-11)).

general formula (XVII)

(in general formula (XVII), A ³, A ⁴independently of one another expression-S-or-NR ⁷³-, R ⁷³represent substituted or non-substituted alkyl or substituted or non-substituted aryl, L ⁰⁴, L ⁰⁵represent independently of one another the A with adjacency ³, A ⁴form the nonmetallic atom group of the alkaline core of pigment together with carbon atom, R ⁷¹, R ⁷²represent independently of one another monovalence nonmetallic atom group, also can interosculate and form the ring of aliphatics or aromatic series.)

The preference of the compound representing as general formula (XVII), can list compound below ((A-12)～(A-15)).

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

general formula (XVIII)

(in 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 independently of one another hydrogen atom or monovalence nonmetallic atom group, 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 ⁷⁶while representing monovalence nonmetallic atom group, R ⁷⁴, R ⁷⁵, R ⁷⁶preferably represent to replace or without the alkyl or aryl replacing.

Below, to R ⁷⁴, R ⁷⁵, R ⁷⁶preference specifically narrate.Example as preferred alkyl, can list carbonatoms and be the alkyl of 1～20 straight chain shape, a chain and ring-type, 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.The alkyl of the ring-type that the chain that straight chain shape, the carbonatoms that wherein, more preferably carbonatoms is 1～12 is 3～12 and carbonatoms are 5～10.

As the substituting group of 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, alkyl disulfide group, aryl disulfide group, amino, N-alkylamino, N, N-dialkyl amido, N-arylamino, N, 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, alkyl sulfinyl, aryl sulfinyl, acyl sulfenyl, amido, N-alkyl amido, N-aryl amido, 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 is amino, N-alkyl-N-alkoxycarbonyl amino, N-alkyl-N-aryloxycarbonyl is amino, N-aryl-N-alkoxycarbonyl amino, N-aryl-N-aryloxycarbonyl is amino, formyl radical, ethanoyl, carboxyl, alkoxy carbonyl, aryloxycarbonyl, formamyl, N-alkyl-carbamoyl, N, N-dialkyl amido formyl radical, 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 (be hereinafter 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 (be hereinafter 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 (be hereinafter called " alkyl phosphonic acid alkali), single aryl phosphine acyl group (PO ₃h (aryl)) and its conjugation base (be hereinafter called " arylphosphonic acid alkali), phosphonato (OPO ₃h ₂) and its conjugation base (be hereinafter 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 (be hereinafter called " alkyl phosphonate oxygen base), single aryl phosphine acyloxy (OPO ₃h (aryl)) and its conjugation base (be hereinafter 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, sym-trimethylbenzene base, isopropyl phenyl, chloro-phenyl-, bromophenyl, chloromethyl phenyl, hydroxy phenyl, p-methoxy-phenyl, ethoxyl phenenyl, Phenoxyphenyl, acetoxyl group phenyl, benzoyloxy phenyl, methylthio group phenyl, thiophenyl phenyl, methylamino-phenyl, dimethylamino phenyl, acetylamino phenyl, carboxyl phenyl, methoxycarbonyl phenyl, ethoxyl phenenyl carbonyl, phenyloxycarbonyl phenyl, N-phenyl amino formyl radical phenyl, phenyl, cyano-phenyl, sulfo group phenyl, sulphonate-base phenyl, 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 sulphur atom, or the group that derives of Ppolynuclear aromatic ring, example as the hetero-aromatic ring in particularly preferred heteroaryl, for example can list, thiophene, thianthrene, furans, pyrans, isobenzofuran, chromene (chromene), xanthene, phenoxazine, pyrroles, pyrazoles, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, different indolizine, indoles, indazole, purine, quinolizine, isoquinoline 99.9, 2, 3-naphthyridine, naphthyridines, quinazoline, quinoline, pteridine, carbazole, carboline, luxuriant and rich with fragrance, acridine, perimidine (Perimidine), phenanthroline, 2, 3-naphthyridine, phenarsazine, furazan etc., they can also be fused benzo rings, can also there is substituting group.

In addition, as the example of the alkenyl in the substituting group of above-mentioned substituted alkyl, can list vinyl, 1-propenyl, 1-butylene base, cinnamyl, the chloro-1-vinyl of 2-etc.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, N-alkylamino, N, N-dialkyl amido, acyloxy, N-alkyl carbamoyloxy base, N-arylamino methanoyl, amido, formyl radical, acyl group, carboxyl, alkoxy carbonyl, aryloxycarbonyl, formamyl, N-alkyl-carbamoyl, N, N-dialkyl amido formyl radical, N-aryl-amino-carbonyl, N-alkyl-N-aryl-amino-carbonyl, sulfo group, sulphonate-base, sulfamyl, N-alkylsulfamoyl group, N, N-dialkyl sulfamine, N-ammonia aryl sulfonyl, N-alkyl-N-ammonia aryl sulfonyl, phosphono, phosphonic acids alkali, dialkyl phosphine acyl group, diaryl phosphono, monoalkyl phosphono, alkyl phosphonic acid alkali, single aryl phosphine acyl group, arylphosphonic acid alkali, phosphonato, phosphonate oxygen base, aryl, alkenyl.

As by the R that 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, 2-chloroethyl, trifluoromethyl, methoxymethyl, methoxyethoxyethyl, allyl group oxygen ylmethyl, phenoxymethyl, methylthiomethyl, toluene sulfenyl methyl, ethylamino ethyl, 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, kharophen ethyl, N-methyl benzoyl aminopropyl, 2-oxoethyl, 2-oxopropyl, carboxyl propyl group, dion e, allyl group oxygen base carbonyl butyl, chlorophenoxy carbonyl methyl, 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, sulfo group butyl, sulphonate-base propyl group, sulphonate-base butyl, 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, phosphono butyl, phosphonic acids alkali hexyl, diethyl phosphonyl butyl, diphenylphosphine acyl propyl, methylphosphine acyl group butyl, methyl-phosphorous acid alkali butyl, tolylphosphine acyl group hexyl, tolylphosphine hydrochlorate base hexyl, phosphonato propyl group, phosphonic acids alkali oxygen Ji Dingji, benzyl, styroyl, α-methylbenzyl, 1-methyl isophthalic acid-phenylethyl, to methyl-benzyl, cinnamyl, allyl group, 1-propenyl methyl, crotyl, 2-methacrylic, 2-methacrylic ylmethyl, 2-propynyl, 2-butyne base, 3-butynyl etc.

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

In addition, as R ⁷⁵and R ⁷⁶more preferably example, can list and replace or without the alkyl replacing.In addition, as R ⁷⁴more preferably example, can list and replace or without the aryl replacing.Its reason is not yet definite, but infer be due to, by having such substituting group, the electron excitation state producing because of photoabsorption and the interaction of initiator compounds become large especially, thereby have improved the cause that initiator compounds produces the efficiency of free radical, acid or alkali.

Below, the A in mutual-through type (XVIII) ⁵be explained.A ⁵expression can have substituent aromatic nucleus or heterocycle, as the concrete example can with substituent aromatic nucleus or heterocycle, 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 there is alkoxyl group, sulfanyl, amino aryl, as particularly preferred A ⁵, can list and there is amino aryl.

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

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

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

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 independently of one another hydrogen atom or monovalence nonmetallic atom group, 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 Ar skeleton (Hammett ' substituent constant) need be larger than 0.Here, " summation of Hammett value is larger than 0 " refers to have a substituting group, and this substituent Hammett value is larger than 0, also can have a plurality of substituting groups, and the summation of these substituent Hammett values is larger than 0.

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

As the substituting group that can import on the Ar of 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.What represent in bracket is that this substituting group imports to position and its Hammett value on aryl skeleton, (m:0.50) represent this substituting group import between Hammett value during position (meta position) be 0.50.Wherein, as the preference of Ar, can list and there is substituent phenyl, as the preferred substituents on Ar skeleton, can list ester group, cyano group.Position as replacing, is particularly preferably positioned at the ortho position (ortho position) on Ar skeleton.

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

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

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

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

By making the content of sensitizing coloring matter within the scope of this, exposure wavelength with respect to ultrahigh pressure mercury lamp is high sensitivity, therefore makes film be cured to deep, from then on viewpoint,, from Development margin (margin), viewpoint that pattern formative is good, be simultaneously preferred.

(epoxy resin)

In coloured polymerized composition of the present invention, in order to improve formed painting film strength, can use epoxy resin as thermopolymerization composition.

As epoxy resin, it is the compound that bisphenol A-type, cresols phenolic varnish type, biphenyl type, alicyclic epoxy compound etc. have more than 2 oxirane ring in molecule.

For example, as bisphenol A-type, can list (above for Nagase changes into system) such as EPOTOHTO YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170 etc. (above for Dongdu changes into system), DENACOLE EX-1101, EX-1102, EX-1103, PLACCEL GL-61, GL-62, G101, G102 (being DAICEL chemistry system above) 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 for DAICEL UCB system) etc.

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

In addition, can also use 1,1,2,2-tetra-(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 EPOTOHTO YH-434, the YH-434L of amine type epoxy resin, the skeleton of 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, and solidified nature is high, and the contraction while solidifying is large; 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, by containing fluorine class organic compound, can improve the characteristics of liquids (particularly mobility) while making coating fluid, 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 coating fluid, improvement is to the wettability (wettability) of applied, raising is to the coating of applied, therefore, even in the situation that form the film of several μ m left and right thicknesses with a small amount of liquid measure, also can effectively form the film of the uniform thickness that uneven thickness is less.

Fluorine containing ratio in fluorine class organic compound is preferably 3～40 quality %, more preferably 5～30 quality %, particularly preferably 7～25 quality %.Fluorine containing ratio is in above-mentioned scope time, 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 (being Dainippon Ink. & Chemicals Inc's system above), Fluorad FC430, Fluorad FC431, Fluorad FC171 (being Sumitomo ス リYiエム Co., Ltd. system above), 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 (being Asahi Glass Co., Ltd's system above) etc.

Particularly, when forming thin filming with coloured polymerized composition of the present invention, fluorine class organic compound can effectively prevent crawling or uneven thickness.In addition, even in easily there is the slot coated of liquid cutout, when applicable coloured polymerized composition of the present invention, be also 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 is also effective in coloured polymerized composition of the present invention, containing thermal polymerization.

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

As above-mentioned azo compound; can list 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 coloured polymerized composition of the present invention, from the viewpoint of improvement coating, also can add various tensio-active agents.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 in tensio-active agent with perfluoroalkyl is tensio-active agent.

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

In addition, as positively charged ion, it is tensio-active agent, specifically, can list phthalocyanine derivates (commercially available product EFKA-745 (Sen Xia industry company system)), organosiloxane polymer KP341 (chemical industrial company of SHIN-ETSU HANTOTAI system), (methyl) acrylic acid series (being total to) polymkeric substance Port リ Off ロ mono-No.75, No.90, No.95 (chemical industrial company of GongSakae company system), W001 (Yu Shang company system) etc.

As nonionic, it 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, as negatively charged ion, be tensio-active agent, specifically, can list W004, W005, W017 (Yu Shang company system) etc.

(other additives)

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

As the concrete example of additive, can list the weighting agents such as glass, aluminum oxide; The soluble resin of the alkali such as phenoxy resin that the polymkeric substance of the maleic acid of itaconic acid copolymer, β-crotonic acid 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; The macromolecule dispersing agents such as EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (above Wei Senxia industry company system); SOLSPERSE3000,5000,9000,12000,13240,13940,17000,24000,26000, the 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 company system) and IONET S-20 (Sanyo Chemical Industries, Ltd.'s system); The UV light absorber such as 2-(the 3-tertiary butyl-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; And the anti-flocculation agent such as sodium polyacrylate.

In addition, in the situation that wish promote uncured portion caustic solubility, further improve the developability of coloured polymerized composition, can in coloured polymerized composition of the present invention, add organic carboxyl acid, preferably adding molecular weight is the lower molecular weight organic carboxyl acid below 1000.

Specifically, can list such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, PIVALIC ACID CRUDE (25), caproic acid, diethylacetic acid, enanthic acid, the aliphatic monocarboxylic acid such as sad; The 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; The aliphatic tricarboxylic acids such as tricarballylic acid, equisetic acid, camphoronic acid; Phenylformic acid, tolyl acid, isopropyl acid, 2，3-xylic acid, 3, the aromatic monocarboxylates such as 5-mesitylenic acid; The aromatic 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, phenylsuccinic 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 preventing agent.

As thermopolymerization preventing agent, 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-butylphenol), 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 the additives such as alkali soluble resins or solvent, tensio-active agent, thereby modulate.

Because coloured polymerized composition of the present invention comprises pigment dispensing composition of the present invention, the dispersion stabilization of the pigment therefore containing as tinting material is good.In addition, use coloured polymerized composition of the present invention and the painted epithelium made, because look material evenly and is stably dispersed, so contrast gradient is high, surface smoothness 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 on substrate, to have the colored pattern that uses the coloured polymerized composition of the invention described above and form.Below, for colour filter of the present invention, by its manufacture method (manufacture method of colour filter of the present invention), describe in detail.

The manufacture method of colour 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, be secondly that exposure and the order of developing are carried out.

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

Below, each operation is elaborated.

(coating)

In the present invention, when manufacturing colour filter, by being coated with the film that forms coloured polymerized composition.As coating process, can utilize the known methods such as spin coating, slit-spin coating, slot coated, but from productive viewpoint, preferably utilize slot coated.

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

On these substrates, can be formed with the black matrix" of each pixel of isolation or for promoting closely sealed etc. transparent resin layer.

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

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

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

In the present invention, as coloured polymerized composition of the present invention is coated on to the method on substrate, preferably use slot coated.Condition as this slot coated, size condition difference because of coated substrates, for example, in the situation that the glass substrate (1100mm * 1250mm) of the 5th generation is coated with, the amount of the coloured polymerized composition penetrating from gap nozzle was preferably for 500～3000 microlitre/seconds conventionally, 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 using in this slot coated operation, is generally 10～23%, is preferably 13～20%.

By coloured polymerized composition of the present invention, on substrate, formed while filming, the thickness of filming as this (prebake conditions process after), is generally 0.3～5.0 μ m, is preferably 0.5～4.0 μ m, most preferably is 0.5～3.0 μ m.

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

(prebake conditions)

Preferably forming by coating method after the film of coloured polymerized composition of the present invention as described above, preferably carry out prebake conditions on substrate.

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

Vacuum drying condition is that vacuum tightness is generally 0.1～1.0torr (13～133Pa), is preferably 0.2～0.5torr (27～67Pa) left and right.

In addition, when carrying out prebake conditions according to hope while processing, can use hot plate, baking oven etc. the temperature range of 50～140 ℃, be preferably under the condition of 70～110 ℃ of left and right and carry out 10～300 seconds.In addition, prebake conditions is processed also and can and be used with high frequency processing etc.Also can use separately high frequency to process.

(exposure)

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

As the radioactive rays that use in when exposure, the particularly preferably ultraviolet ray such as g line, h line, i line, j line.

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

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

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

(development)

After above-mentioned exposure, develop.By this, develop, the uncured portion of filming after exposure is dissolved in developing solution, only make cured portion remain on substrate.

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

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

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

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

In addition, as alkaline aqueous solution, for example can list, sodium hydroxide, potassium hydroxide, sodium carbonate, 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 take concentration as 0.001～10 quality %, be preferably 0.01～1 quality % and dissolve the alkaline aqueous solution form.

In alkaline aqueous solution, also can add appropriate water-miscible organic solvents such as methyl alcohol, ethanol or tensio-active agent etc.

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

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

After development treatment, through remaining developing solution being cleaned to the drip washing of removing, process, and be dried, then for completion of cure, according to hope, implement heat treated (baking afterwards).

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

Drip washing after moisture is removed and is dried, is carried out the heat treated of 100～250 ℃ after processing conventionally.Rear baking is like this heating after the development of carrying out in order to make completion of cure, preferably at 200～250 ℃, heats (baking firmly, hard bake).

This heat treated (baking afterwards) can be carried out the heater meanses such as using under these conditions hot-plate or convection oven (hot air circulation type drying machine), high frequency heating machine of filming after developing with continous way or intermittent type.

Preferably after rear baking, carry out UV before the coating of next color and clean.UV cleans and can for example, by (LC4000, the electronics エ of Hitachi Application ジ ニアリン グ Co., Ltd. systems) such as glass substrate scrubbers, be undertaken, as UV irradiation dose, and 100mJ/cm normally ²～1000mJ/cm ²left and right.By carrying out UV, clean, can remove development residue, improve the pattern formative of next color etc.

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

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

Embodiment

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

First, the composition using in embodiment and comparative example is described.

The synthetic > of < resin B

Above-mentioned illustrative monomer M-11 of 7.5 parts, 31.25 parts of methyl methacrylates, 11.25 parts of methacrylic acids and MPEG 167 mass parts are imported to the there-necked flask that nitrogen have been replaced, with stirrer (Xin Dong science Co., Ltd.: Three-One Motor) stir, while making nitrogen flow and heat, be warming up to 78 ℃ in flask.Add wherein 2, two (2 Methylpropionic acid) dimethyl ester (trade(brand)names: V-601 ,He Guangchun medicine Co., Ltd. system) 0.1 part, carry out the heated and stirred of 2 hours at 78 ℃ of 2 '-azo.After 2 hours, further add 0.1 part of V-601, carry out the heated and stirred of 3 hours, obtain 30% solution of resin B.The resin using before the drying process of pigment when the resin B obtaining is salt grinding.

The synthetic > of < Resin A

Except the monomer using in above-mentioned resin B synthetic and add-on thereof being replaced by the monomer and add-on of recording in following table 1, similarly synthesized Resin A.The resin using before the drying process of pigment when the Resin A obtaining is salt grinding.

Monomer and add-on thereof used when following table 1 has represented synthetic resins A, B, the Resin A of synthesized, the weight-average molecular weight of resin B and acid number.Here, weight-average molecular weight is used is the GPC of the condition following (gel permeation chromatography) to be measured and value that the value that obtains is tried to achieve by polystyrene conversion.

Use post: TSKgel Multipore HXL-M

(pore polydispersion Linear post) TOSOH system

Elutriant: THF

Flow: 1.0ml/min

Temperature: 40 ℃

Testing conditions: RI

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

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

(measuring method of acid number)

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

[table 1]

The resin using after salt grinds	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 above-mentioned table 1, monomer M-11 refer to the illustration monomer listing as the preferred concrete example of monomer, maleimide and the maleimide derivatives of above-mentioned general formula (1) expression.In addition, in table 1, in Resin A synthetic, the details of monomer used is as follows.

St: vinylbenzene

BzMA: benzyl methacrylate

MAA: methacrylic acid

MMA: methyl methacrylate

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

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)

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

(pigment derivative 1)

(pigment derivative 2)

(pigment derivative 3:(B) composition)

(pigment derivative 4:(C) composition)

(pigment derivative 5)

(pigment derivative 6)

[embodiment 1]

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

By (A) diketopyrrolo-pyrrole pigment in the present invention, be 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 company's system) 150g adds in 1 gallon of kneader of stainless steel (aboveground manufacturing company system), at 50 ℃, mix 10 hours.

Then, in this mixture, add synthetic as described above Resin A solution (solids component is 30 quality %) 25g and mix, this mixture being dropped in the hot water of approximately 3 liters, Yi Bian be heated to approximately 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 the hot-air ovens of 60 ℃ dry approximately 24 hours, 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, result is that average primary particle diameter is 30nm.In the mensuration of particle, use be multiplying power with 100,000 times, the mean value while measuring the major diameter of 500 pigment and the mean value of minor axis.

(embodiment 1)

The modulation > of < pigment dispensing composition

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

(forming (1))

The surface treatment diketopyrrolo-pyrrole pigment obtaining in aforesaid method ((A) composition)

86 parts

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

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

(with respect to 100 parts of (A) compositions, being 13.4 parts)

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

(with respect to 100 parts of (A) compositions, being 6.69 parts)

33 parts of Disperbyk-2001 (BYKChemie company system)

50 parts of the 30%1-methoxy-2-propanol acetate solution of resin (1)

50 parts of the 30%1-methoxy-2-propanol acetate solution of resin (2)

767 parts of 1-methoxy-2-propanol acetic ester

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

(evaluation of pigment dispensing composition)

The dispersiveness of the pigment dispensing composition obtaining, dispersion stabilization are evaluated.

For the pigment dispensing composition of having modulated, the viscosities il 1 (25 ℃) of modulation after just having finished of having used E type viscometer determining and modulate after viscosities il 2 (25 ℃) after one week.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 above-described embodiment 1, has 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, except substituting " イ Le ガ Off オ ア レ Star De BT-CF ", use " red pigment (チバ ジヤパン Co., Ltd. system " Network ロ モ Off タ Le レ Star De A2B ": PR177) ", carry out similarly to Example 1 salt grinding, the processing pigment that to have obtained median size be 28nm.Then, use resulting processing pigment, except substituting " pigment derivative (1) ", use " pigment derivative (5) ", obtained similarly to Example 1 red pigment dispensing composition A.

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

(forming (2))

800 parts of the red pigment dispersive compositions obtaining in embodiment 1

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)

The bromo-p-N of 4-[o-, N-bis-(ethoxy carbonyl) aminophenyl]-2,30 parts of 6-bis-(trichloromethyl)-S-triazines (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-methoxy-2-propanol acetic ester (solvent)

400 parts of 3-ethoxyl ethyl propionates (solvent)

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

< has been used the making > of the colour filter of coloured polymerized composition

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

To the substrate of making, further using glass substrate scrubber (LC4000, the electronics エ of Hitachi Application ジ ニアリン グ Co., Ltd. system) to carry out UV cleans (with 20mW/cm ², 500mJ/cm ²) after, again implement above-mentioned prebake conditions, above-mentioned development, above-mentioned rear baking.Then, further implement that above-mentioned UV cleans, above-mentioned prebake conditions, above-mentioned development, above-mentioned rear baking, obtained evaluating with colouring filter device substrate (colour filter).

For the coloured polymerized composition (colored resist liquid) of modulation as described above and the colouring filter device substrate (colour filter) for evaluation of being made by this coloured polymerized composition, evaluate in the following manner.The results are shown in table 2.

-1. the mensuration of viscosity-

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

-2. the mensuration, evaluation of contrast gradient-

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

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

-3. the mensuration of surfaceness-

Colouring filter device substrate (colour filter) for evaluation to made, utilizes atomic force microscope (NanoScope IIIa, NanoWorld company system) to measure the surfaceness on painted epithelium surface.

[embodiment 3]

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

[embodiment 4]

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

[embodiment 5]

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

[embodiment 6]

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

[embodiment 7]

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

[comparative example 1]

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

[comparative example 2]

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

[comparative example 3]

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

[comparative example 4]

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

[comparative example 5]

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

[table 2]

	Initial stage viscosities il 1 (cp)	Through 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 rise of the coloured polymerized composition of embodiment 2～embodiment 7 of modulating after not finding to preserve, 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.

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

Claims (9)

1. a pigment dispensing composition, it contains diketopyrrolo-pyrrole series pigments, 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, O-phthalic imide alkylation quinacridone and at least one organic solvent that is 0.1～20 mass parts with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts

Described diketopyrrolo-pyrrole series pigments is red～orange pigment of the structure of following general formula (A) expression,

In described general formula (A), X, Y represent hydrogen atom, cyano group or halogen group independently of one another;

Described O-phthalic imide alkylation diketopyrrolo-pyrrole is the diketopyrrolo-pyrrole series pigments derivative of the structure of following general formula (B) expression,

In described general formula (B), X and Y represent hydrogen atom, cyano group or halogen group independently of one another; N represents 1～3 integer;

Described O-phthalic imide alkylation quinacridone is the quinacridone pigment derivative of the structure of following general formula (C) expression,

In described general formula (C), X and Y represent hydrogen atom, methyl or chlorine atom independently of one another; N represents 1～3 integer.

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 obtaining by having the method for following operation, described operation is:

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

And the operation that makes described diketopyrrolo-pyrrole series pigments contact with resin before this drying process.

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

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

The operation of the O-phthalic imide alkylation quinacridone that adds 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 of at least a portion in the diketopyrrolo-pyrrole series pigments that is 10nm～30nm to average primary particle diameter and be 0.1～20 mass parts with respect to these diketopyrrolo-pyrrole series pigments 100 mass parts,

The operation that the mixture of the diketopyrrolo-pyrrole series pigments obtaining in above-mentioned operation, the O-phthalic imide alkylation diketopyrrolo-pyrrole that is 0.1～30 mass parts with respect to this diketopyrrolo-pyrrole series pigments of every 100 mass parts and the O-phthalic imide alkylation quinacridone that is 0.1～20 mass parts with respect to this diketopyrrolo-pyrrole series pigments of every 100 mass parts is disperseed together with organic solvent;

Described diketopyrrolo-pyrrole series pigments is red～orange pigment of the structure of following general formula (A) expression,

In described general formula (A), X, Y represent hydrogen atom, cyano group or halogen group independently of one another;

Described O-phthalic imide alkylation diketopyrrolo-pyrrole is the diketopyrrolo-pyrrole series pigments derivative of the structure of following general formula (B) expression,

In described general formula (B), X and Y represent hydrogen atom, cyano group or halogen group independently of one another; N represents 1～3 integer;

Described O-phthalic imide alkylation quinacridone is the quinacridone pigment derivative of the structure of following general formula (C) expression,

In described general formula (C), X and Y represent hydrogen atom, methyl or chlorine atom independently of one another; N represents 1～3 integer.

6. a coloured polymerized composition, it contains pigment dispensing composition claimed in claim 1, optical polymerism compound and Photoepolymerizationinitiater initiater.

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

8. a colour filter, its right to use requires the coloured polymerized composition described in 6 to form.

9. a manufacture method for colour filter, it comprises the steps: on substrate, to be coated with coloured polymerized composition claimed in claim 6 and forms and film, and by formed film exposure, then develops.