CN101276147A - Compound for forming colored pattern, method of forming colored pattern, color filter, method of manufacturing the color filter and liquid crystal display element - Google Patents

Abstract

The invention provides a filter coloring pattern forming compound which comprises: (A) pigment; (B) a compound provided with alkenes unsaturated radical; (C) a photopolymerization initiator; and (D) a coloring pattern forming compound which disperses resin. The invention is characterized in satisfying that Eta*Theta a is more than or equal to 30 and less than or equal to 40 when arranging viscosity of the coloring pattern forming compound under the temperature of 23 Deg C as Eta (mPa.s) and arranging an advanced contact angle of the coloring pattern forming compound relative to a glass substrate as Theta a(Deg), wherein, Eta is more than or equal to 2 and less than or equal to 3. Moreover, the invention provides a coloring pattern forming method comprising a working procedure of coating the compound, a manufacturing method of the filter using the forming method, the filter manufactured via the manufacturing method, and a liquid crystal display element.

Description

Colored pattern forms with composition, colored pattern formation method, color filter and manufacture method and liquid crystal display cells

Technical field

The present invention relates to colored pattern forms with composition, colored pattern formation method, manufacturing method of color filter, color filter and liquid crystal display cells.

Background technology

Color filter is to contain other composition such as polyfunctional monomer, Photoepolymerizationinitiater initiater and adhesive resin and form coloring photosensitive combination in the dispersive composition of colorants such as organic pigment, inorganic pigment, and uses this coloring photosensitive combination to wait by photoetch method and make.

In recent years, color filter is in liquid crystal display cells (Liquid Crystal Display:LCD) purposes, have not only to monitor but also purposes enlarges in televisor (TV) trend,, in colourity, contrast etc., also require the color characteristics of height gradually along with the trend that this purposes enlarges.In addition, in solid-state imager (Image sensor, image sensor) purposes, also require the high color filter of color characteristics gradually equally.

In addition, along with the maximization of substrate, in order to boost productivity, the technology that the coating process of coloring photosensitive combination is also carrying out (being also referred to as a mouthful mould (die) coating, curtain coating coating) from spin coating (spin coat) method to slit (slit) rubbing method shifts.Wherein, seek to be suitable for the composition of this coating process,, disclose the composition (for example the spy opens 2004-318111 number) of the static contact angle of controlling viscosity and measuring under given conditions as such composition.The coating process (for example the spy opens 2004-212944 number) of the dimensionless group (being also referred to as capillary number) that control forms by surface tension, viscosity, the coating speed of composition has also been proposed in addition.

In recent years, along with popularizing of large-scale LCD etc., the maximization of substrate further develops, and also requires the high-speed coating that did not in the past have in the slot coated method.Yet, the present situation of these technology is, in order to make color filter, be under the situation of high speed of 200mm/ second in the slot coated speed on the glass substrate set, still there are the many problems of coating defects, in addition, can't reach the desired high colour purity of pixel of the color filter that forms and the such color characteristics of high-contrast and satisfy practical level.

Summary of the invention

The present invention considers that the problems referred to above point forms, its purpose is to provide a kind of colored pattern to form with composition and colored pattern formation method, this colored pattern forms good with the coating of composition when carrying out slot coated in order to make color filter on glass substrate, and the color filter of gained can have good color characteristics.

In addition, the present invention also provides the colored pattern that uses the invention described above to form the color filter with high-contrast, its manufacture method that forms with composition and the liquid crystal display cells with this color filter.

In order to realize above-mentioned problem, technical scheme of the present invention is as follows.

＜1〉a kind of color filter forms with colored pattern and uses composition, its be contain compound that (A) pigment, (B) has the olefinic unsaturated group, (C) Photoepolymerizationinitiater initiater and (D) colored pattern of dispersion resin form and use composition, it is characterized in that, this colored pattern under with 23 ℃ form viscosity with composition be set at η (mPas), with this colored pattern formation with composition with respect to the advancing contact angle of glass substrate be set at θ a (°) time, satisfy following formula (1):

30≤η * θ a≤40 (2≤η≤3) formulas (1).

＜2〉as＜1〉described color filter forms with colored pattern and uses composition, it is characterized in that the primary particle size of above-mentioned (A) pigment is 8nm～15nm.

＜3〉as＜1〉or＜2〉described color filter form with colored pattern and to use composition, it is characterized in that, also contain (E) adhesive resin, and the mass ratio that contains that above-mentioned (B) has a compound of olefinic unsaturated group/should (E) adhesive resin is more than 1.2.

＜4〉as＜1 〉～＜3 each described color filter form with colored pattern and use composition, it is characterized in that solid component concentration is 9-12 weight %.

＜5〉as＜1 〉～＜4 each described color filter form with colored pattern and use composition, it is characterized in that above-mentioned (D) dispersion resin contains and is selected from following at least a in any:

(D-1) have nitrogen heterocyclic ring as containing of dispersion resin and have the macromolecular compound of the monomer of olefinic unsaturated group as copolymerization units.

(D-2) has the macromolecular compound of 2～100 pigment adsorption bases as dispersion resin at the macromolecule end.

＜6〉as＜1 〉～＜5 each described color filter form with colored pattern and use composition, it is characterized in that, also contain and be selected from surfactant and the silane coupling agent more than one.

＜7〉a kind of colored pattern formation method is characterized in that, contains＜1 〉～＜6 each described colored pattern form the operation that is coated with the coating speed of second 200mm/ second～400mm/ by the slot coated method with composition.

＜8〉a kind of manufacturing method of color filter is characterized in that, uses＜7〉described colored pattern formation method.

＜9〉a kind of color filter is characterized in that, by＜8〉described manufacture method is made, and contrast is more than 5000.

＜10〉a kind of liquid crystal display cells, it has used＜and 9〉described color filter.

Be under the situation at a high speed with the slot coated speed setting, also can considering to eliminate coating defects by reducing coating fluid viscosity.Yet, in the present invention, by viscosity is controlled in the particular range, and makes between the viscosity of composition and the advancing contact angle and satisfy specified conditions with respect to glass substrate, suppressed coating defects.In addition, even satisfied this condition,,, can not suppress coating defects being under the situation of the high speed of 200mm/ more than second with the slot coated speed setting if the scope of the viscosity ratio afore mentioned rules of composition is also low.In addition, in the present invention, do not improve the viscosity of composition and high concentration ground uses the little pigment of primary particle size, viscosity is risen and it is disperseed, realize the high colour purity and the high-contrast of color filter thus.

The invention provides colored pattern forms with composition and colored pattern formation method, this colored pattern forms good with the coating of composition when carrying out slot coated speed in order to make color filter on glass substrate, and the color filter of gained can have good color characteristics.

In addition, the invention provides the colored pattern that uses the invention described above and form the color filter with high-contrast, its manufacture method that forms with composition and liquid crystal display cells with this color filter.

Description of drawings

The illustraton of model of the drop state when Fig. 1 is illustrated in the assay method that carries out dynamic contact angle.

Embodiment

Below, the present invention is described in detail.

＜colored pattern forms uses composition 〉

It is to contain compound that (A) pigment, (B) has the olefinic unsaturated group, (C) Photoepolymerizationinitiater initiater and (D) the colored pattern formation composition of dispersion resin that colored pattern of the present invention forms with composition, it is characterized in that, this colored pattern under with 23 ℃ form viscosity with composition be set at η (mPas), with this colored pattern formation with composition with respect to the advancing contact angle of glass substrate be set at θ a (°) time, satisfy following formula (1).

30≤η * θ a≤40 (2≤η≤3) formula 1

At first, colored pattern formation of the present invention is specifically described with the condition that composition satisfied.

Usually, the viscosimetric analysis that contains the composition of pigment etc. as described above can be carried out with any method in method, the method for using the capillary type viscosity meter of using rotational viscosimeter, the method for using oscillatory viscometer etc., but preferably uses known method that BM type rotational viscosimeter measures or the method for using the flow graph (rheometer) that can carry out determination of viscoelasticity etc.

In the present invention, the viscosities il (mPas) that colored pattern forms with composition is to use flow graph AR-2000 (TA イ Application ス Star Le メ Application ト company (TA instruments) system), is that 60 μ m, rotating speed are equivalent to the value measured under 100rpm, 23 ℃ the condition at parallel-plate (parallel plate), gap (gap) of 20mm.

For viscosity, in the present invention, the viscosity of composition need be in the scope of 2mPas～3mPas.The adjusting of viscosity, the amount of kind of polymerizable compound that can be by containing in the composition, solvent etc. and amount, pigment, the kind of pigment dispersing agent and amount etc. are suitably regulated.As the example that is used for this modulation means, the solid component concentration that can enumerate in the composition of sening as an envoy to is 9～12 weight %, and means such as the molecular weight of adjusting pigment dispersing agent, composition, acid number, ammonia value, composition distribution, terminal functional group or the degree of branching etc.

In addition, colored pattern form with composition with respect to the advancing contact angle θ a of glass substrate (°) can measure by the assay method of dynamic contact angle.

That is, dynamic contact angle is meant the contact angle in interface when motion of liquid and solid, is useful for the detection of moving when the such coating of the present invention.Dynamic contact angle has advancing contact angle and receding contact angle, can think, the advancing contact angle that the present invention adopts is subjected to the influence of solid to the wetting difficulty or ease of this liquid.As the mensuration of advancing contact angle, for example can measure with landing method (falling method), tilt to make drop to slide by the solid sample (being glass substrate in the present invention) that makes the carrying drop, measure thereby measure contact angle.In addition, can also measure by the expansion/contraction method.By the liquid drip expansion or the suction that contact with solid surface are contracted, can be respectively as the drop interface advance, advancing contact angle when retreating, receding contact angle and obtain.Fig. 1 is the illustraton of model of the drop state of expression when carrying out the assay method of dynamic contact angle.θ a represents advancing angle among Fig. 1, and θ r represents receding angle, and α represents to fall the angle.

Show the concrete condition determination of the advancing contact angle among the present invention below.

It is according to known base plate glass wettability of the surface test method that the advancing contact angle of composition of the present invention is measured, the substrate that tilts on one side Yi Bian begin landing, is taken a picture to drop with video camera, use the software of Young-Laplace method then, thereby obtain by image analysis.

Advancing contact angle θ a on the glass substrate can regulate by means such as the kind of adding fluorine class surfactant, interpolation silane coupling agent, selective solvent, the molecular weight of regulating pigment dispersing agent, composition distribution, terminal functional group, the degrees of branching.

In the present invention, viscosity and advancing contact angle need satisfy the relation of above-mentioned formula (1), and composition of the present invention preferably is 10 °～20 ° scope under 23 ℃ with respect to the advancing contact angle θ a of glass substrate itself.

In the present invention, in order to satisfy above-mentioned condition, can suitably regulate the kind, amount of the necessary composition of (A)～(D) that constitute composition or various optional members etc., specifically, preference is as being the adjusting following.

As one of this regulating measure, can list following means: promptly use primary particle size as the atomic thin pigment of 8nm～15nm as (A) pigment, use compound described later as (D) dispersion resin, this pigment homogeneous disperseed and cooperate.By these means, can not make the viscosity of composition cooperate a large amount of micro pigments with rising, by satisfying above-mentioned rerum natura, can improve coating, realize excellent colour developing and contrast simultaneously.

Promptly, as colored pattern formation one of preferred configuration of composition of the present invention, can list following form, promptly as (D) dispersion resin, select (D-1) to contain and have nitrogen heterocyclic ring and have the dispersion resin of the monomer of olefinic unsaturated group, or (D-2) have the dispersion resin of the macromolecular compound of 2～100 pigment adsorption bases at the macromolecule end as the macromolecular compound of copolymerization units.

Below, be the pigment of 8nm～15nm, compound, (C) Photoepolymerizationinitiater initiater, the so necessary composition of (D) dispersion resin that (B) has the olefinic unsaturated group not only, but also the adhesive resin of preferred use, organic solvent, other optional member are elaborated constituting (A) primary particle size that colored pattern of the present invention forms with composition.

[(D) dispersion resin]

At first (D) dispersion resin that uses among the present invention is illustrated.

Dispersion resin among the present invention is the compound that has as the function of (A) dispersing of pigments agent, and as its rerum natura, preferred acid number is 20～300mg/g, and weight-average molecular weight is in 3,000～100,000 the scope.

(D) dispersion resin there is not particular determination, but owing to preferably have specific acid number as described above, so preferably have the macromolecular compound of acidic groups.

As the macromolecular scaffold of this macromolecular compound, be preferably and be selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, ammonia esters polymer, acylamide polymer, epoxide polymer, type siloxane polymkeric substance and their modification body or multipolymer and [comprise that multipolymer of for example polyethers/polyurethane copolymer, polyethers/polymer of vinyl monomer etc. (can be in random copolymers, segmented copolymer, the graft copolymer any.)。] in any, more preferably be selected from least a in polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, ammonia esters polymer and their modification body or the multipolymer, be preferably polymer of vinyl monomer or multipolymer especially.

In addition,, for example can list when the above-mentioned macromolecular scaffold of polymerization, make the method for the monomer copolymerization that contains acidic groups as the method that imports acidic groups to macromolecular scaffold as described above; And after above-mentioned macromolecular scaffold polymerization, the method that imports by high molecular weight reactive.

As the monomer that contains acidic groups, for example can list (methyl) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, acrylic acid dimer, vinyl benzoic acid, styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, mono phosphoric acid ester (methyl) acryloyl group ethyl ester or contain monomer that reactions such as cyclic acid anhydride such as the monomer of alcohol hydroxyl group and maleic anhydride, phthalic anhydride obtain etc. by methacrylic acid 2-hydroxyl ethyl ester etc.

Wherein, as preferred monomer example, can list (methyl) acrylic acid, contain monomer that reactions such as cyclic acid anhydride such as the monomer of alcohol hydroxyl group and maleic anhydride, phthalic anhydride obtain etc. by methacrylic acid 2-hydroxyl ethyl ester etc.As cyclic acid anhydride used herein, can list for example itaconic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, trimellitic anhydride etc., preferred especially phthalic anhydride, succinic anhydride etc.

And then the macromolecular compound with acidic groups can also make the copolymerization of vinyl monomer composition form.

As above-mentioned vinyl monomer, do not have particular determination, but be preferably ester class, phenylethylene, (methyl) vinyl cyanide of for example (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol etc.

As such vinyl monomer, can list for example following such compound.

As the example of (methyl) esters of acrylic acid, can list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) 2-EHA, (methyl) acrylic acid uncle monooctyl ester, (methyl) acrylic acid dodecane ester, (methyl) acrylic acid octadecane ester, (methyl) acrylic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxypropyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid diethylene glycol monomethyl ether ester, (methyl) acrylic acid diethylene glycol monoethyl ether ester, (methyl) acrylic acid triethylene glycol monomethyl ether ester, (methyl) acrylic acid triethylene glycol monoethyl ether ester, (methyl) polyalkylene glycol acrylate monomethyl ether ester, (methyl) polyalkylene glycol acrylate monoethyl ether ester, (methyl) acrylic acid beta-phenoxy ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy macrogol ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid tribromo phenyl oxygen base ethyl ester etc.

As the example of crotonates class, can list butyl crotonate and the own ester of crotonic acid etc.

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

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

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

As the example of itaconic acid diester class, can list dimethyl itaconate, diethyl itaconate, 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-isopropyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tert-butyl group (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 phenylethylene, can list styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorobenzene ethene, bromostyrene, 1-chloro-4-methyl-benzene, by can be by hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. of the group of acidic materials deprotection (for example t-Boc etc.) protection.

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

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

And then, can also use the vinyl monomer of functional groups such as for example having urethano, urea groups, sulfoamido, phenylol, imide.As such monomer with urethano or urea groups, for example, it is suitably synthetic to utilize isocyanate group and hydroxyl or amino addition reaction.Specifically, monomer that can be by containing isocyanate group with contain the compound of 1 hydroxyl or contain the addition reaction of the compound of 1 uncle or secondary amino group, or contain the monomer of hydroxyl or contain uncle or the monomer of secondary amino group and the addition reaction of monoisocyanates etc. are suitably synthesized.

Following such polyreactive oligomers can also be seen that making vinyl monomer uses.

Polyreactive oligomers (following be called sometimes " macromonomer ") is the oligomer that end has the group that contains ethylenical unsaturated double bonds.In the present invention, in above-mentioned polyreactive oligomers, preferably only has the above-mentioned group that contains ethylenical unsaturated double bonds in two ends of this oligomer.

From the steric repulsion effect of spreading agent and to the viewpoint of colorant (pigment) adsorption time, the molecular weight of above-mentioned polyreactive oligomers is 1000～20000 in the number-average molecular weight (Mn) of polystyrene conversion preferably, more preferably 2000～15000.

As above-mentioned oligomer, for example generally can list the homopolymer that forms by at least a monomer that is selected from (methyl) alkyl acrylate, styrene, vinyl cyanide, vinyl acetate and the butadiene or multipolymer etc., wherein homopolymer or multipolymer, the polystyrene etc. of preferred (methyl) alkyl acrylate.In the present invention, these oligomer also can be substituted base and replace, and as this substituting group, do not have particular determination, can list for example hydroxyl, halogen atom etc.

Above-mentioned vinyl monomer can only a kind ofly carry out polymerization, also can and carry out copolymerization with two or more, such free radical polyalcohol can by will be separately accordingly vinyl monomer obtain according to the well-established law polymerization with known method.

For example, can utilize these vinyl monomers, chain-transferring agent are dissolved in the appropriate solvent, to wherein adding radical polymerization initiator, under about 50 ℃～220 ℃, in solution, make the method (solution polymerization process) of its polymerization thus obtain.

As the example of the appropriate solvent of in solution polymerization process, using, can select arbitrarily according to the dissolubility of monomer that uses and the multipolymer that generates.Can list for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, acetone, MEK, methyl isobutyl ketone, acetate methoxyl propyl ester, ethyl lactate, ethyl acetate, vinyl cyanide, tetrahydrofuran, dimethyl formamide, chloroform, toluene.These solvents can mix two or more uses.

In addition, as radical polymerization initiator, can use 2,2 '-azoisobutyronitrile (AIBN), 2, two (2,4 '-methyl pentane nitrile) the such azo-compounds of 2 '-azo, the persulfate that superoxide that benzoyl peroxide is such and potassium persulfate, ammonium persulfate are such etc.

(D) dispersion resin among the present invention, as described above, preferred acid number is the scope of 20～300mg/g, more preferably the scope of 30～250mg/g, the further scope of preferred 30～200mg/g.

When the acid number of (D) dispersion resin during in this scope, (A) dispersiveness of pigment (pigment), dispersion stabilization excellence, alkali-developable is also excellent in addition.

In addition, (D) weight-average molecular weight of dispersion resin is preferably 3,000～100,000 scope, more preferably 3,000～70,000 scope, more preferably 5,000～50,000 scope.

When the weight-average molecular weight of (D) dispersion resin during, be preferred from shortening (A) dispersing of pigments time and disperseing the viewpoint of the ageing stability of thing in this scope.

In addition, as (D) dispersion resin among the present invention, be preferably and be selected from (D-1) and contain the monomer that has nitrogen heterocyclic ring and have an olefinic unsaturated group and have resin in the dispersion resin of macromolecular compound of 2～100 pigment adsorption bases at the macromolecule end as the dispersion resin of the macromolecular compound of copolymerization units with (D-2).

Below these two macromolecular compounds are specifically described.

Contain as (D-1) of (D) dispersion resin and to have nitrogen heterocyclic ring and to have the macromolecular compound of the monomer of olefinic unsaturated group as copolymerization units, so long as have specific acid number as described above and weight-average molecular weight, contain and have nitrogen heterocyclic ring and have the macromolecular compound of the monomer of olefinic unsaturated group simultaneously as copolymerization units, just do not have particular determination, preferably have following nitrogen heterocyclic ring.

As preferred nitrogen heterocyclic ring, can list pyrroles, pyrrolin, pyrrolidine, pyrazoles, pyrazoline, pyrazolidine, imidazoles, triazole, pyridine, piperidines, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, Benzimidazolinone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoins, carbazole.

Wherein, be preferably the polymkeric substance that contains from the copolymerization units of monomer shown in the following general formula (I), or contain the polymkeric substance of the structural unit shown in the general formula (a).

The macromolecular compound that has 2～100 pigment adsorption bases as (D-2) of (D) dispersion resin at the macromolecule end, so long as have specific acid number as described above and weight-average molecular weight and have the macromolecular compound of 2～100 pigment adsorption bases at the macromolecule end, just do not have particular determination, but be preferably following macromolecular compound.

That is, be preferably the macromolecular compound that has 4～70 pigment adsorption bases at the macromolecule end, more preferably have the macromolecular compound of 5～50 pigment adsorption bases at the macromolecule end.In addition, as the pigment adsorption base, be preferably organic pigment structure, heterocycle structure, acidic groups, basic group etc.Wherein, be preferably the macromolecular compound shown in the aftermentioned general formula (1).

Below, the conduct (D-1) that is suitable as (D) dispersion resin among the present invention is contained the polymkeric substance that the monomer that has nitrogen heterocyclic ring and have an olefinic unsaturated group contains to come polymkeric substance, the macromolecular compound shown in (D-1-2) general formula (1) of the copolymerization units of monomer shown in the self-drifting (I) as (D-1-1) of the dispersion resin of the macromolecular compound of copolymerization units and (D-1-3) contain the structural unit shown in the general formula (a) illustrated.

[(D-1-1) containing to come the polymkeric substance of the copolymerization units of the monomer shown in the self-drifting (I): (D-1-1) specific dispersion resin]

Then to containing polymkeric substance (following suitably be called " (D-1-1) specific dispersion resin " from the copolymerization units of the monomer shown in the following general formula (I).) illustrated.

General formula (I)

In general formula (I), R ⁰¹Expression hydrogen atom or replace or do not have the alkyl of replacement.R ⁰²The expression alkylidene.W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene.X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.Y represents-NR ⁰³-,-O-,-S-or-N=, form ring texture thereby link to each other with the N atom by the atomic group that is adjacent.R ⁰³Expression hydrogen atom, alkyl or aryl.M1 and n1 represent 0 or 1 respectively independently.

Below, to as the necessary copolymerization units of (D-1-1) the specific dispersion resin among the present invention, be that the monomer shown in the general formula (I) is elaborated.

In general formula (I), R ⁰¹Expression hydrogen atom or replace or do not have the alkyl of replacement.

As R ⁰¹The alkyl of expression, preferred carbon number is 1～12 alkyl, and more preferably carbon number is 1～8 alkyl, and preferred especially carbon number is 1～4 alkyl.

At R ⁰¹The alkyl of expression is under the situation of substituted alkyl, as the substituting group that can introduce, can list for example hydroxyl, alkoxy, aryloxy group, acyloxy, halogen etc.

As R ⁰¹The preferred alkyl of expression specifically can list methyl, ethyl, propyl group, normal-butyl, isobutyl, the tert-butyl group, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 2-methoxy ethyl etc.

R ⁰²The expression alkylidene.

As R ⁰²The alkylidene of expression is preferably carbon number and is 1～12 alkylidene, and more preferably carbon number is 1～8 alkylidene, is preferably carbon number especially and is 1～4 alkylidene.

R ⁰²The alkylidene of expression can have substituting group under the situation that can import, as this substituting group, can list for example hydroxyl, alkoxy, aryloxy group, acyloxy etc.

As R ⁰²The preferred alkylidene of expression can list methylene, ethylidene, propylidene, 1,3-propylidene, 1,4-butylidene etc. particularly.

W represents-CO-,-C (=O) O-,-CONH-,-OC (=O)-or phenylene, be preferably-C (=O) O-or-CONH-.

Y represents-NR ⁰³-,-O-,-S-or-N=, form ring texture thereby link to each other with the N atom by the atomic group that is adjacent.

R ⁰³Expression hydrogen atom, alkyl or aryl are preferably hydrogen atom or methyl.

As Y, be preferably especially-S-,-NH-or-N=.

The ring texture that links to each other and form by the atomic group that is adjacent and N atom as Y, can list single ring architectures such as imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, and fused rings structures such as benzimidazole ring, benzothiazole ring, benzoxazole ring, purine ring, quinazoline ring, uncle's pyridine (Perimidine) ring, from with the viewpoint of the compatibility of pigment, be preferably the fused rings structure.In addition, in the fused rings structure, especially preferably list benzimidazole ring, benzothiazole ring, benzoxazole ring.

X represents-O-,-S-,-C (=O) O-,-CONH-,-C (=O) S-,-NHCONH-,-NHC (=O) O-,-NHC (=O) S-,-OC (=O)-,-OCONH-or-NHCO-.

As X, be preferably especially-O-,-S-,-CONH-,-NHCONH-and-NHC (=O) S-.

M1 and n1 represent 0 or 1 respectively independently, and preferred especially m1 and n1 are 1 simultaneously.

List the preferred concrete example (monomer M-1～monomer M-18) of the monomer shown in the general formula (I) below, but the present invention is not limited.

From giving the viewpoint of dispersing of pigments stability, (D-1-1) the specific dispersion resin among the present invention is preferably especially and contains from the copolymerization units of monomer shown in the above-mentioned general formula (I), also contains the graft copolymer from the copolymerization units of the polyreactive oligomers that has ethylenic unsaturated bond endways simultaneously.

The polyreactive oligomers that has ethylenic unsaturated bond endways like this is the compound with molecular weight of regulation, so be also referred to as macromonomer.In the following description, sometimes " polyreactive oligomers that has ethylenic unsaturated bond endways " among the present invention suitably is called " polyreactive oligomers " or " macromonomer ".

The polyreactive oligomers that uses according to hope is formed by the polymerisable functional moieties with ethylenical unsaturated double bonds of polymer chain part and its end in the present invention.From obtaining the viewpoint of desirable graft polymer, the end that such group with ethylenical unsaturated double bonds only is preferably at polymer chain has.Group as having ethylenical unsaturated double bonds is preferably (methyl) acryloyl group, vinyl, is preferably (methyl) acryloyl group especially.

In addition, the number-average molecular weight in polystyrene conversion of this macromonomer (Mn) is preferably 1000～10000 scope, is preferably 2000～9000 scope especially.

The part of above-mentioned polymer chain generally is homopolymer or the multipolymer that is formed by at least a monomer that is selected from (methyl) alkyl acrylate, styrene and derivant thereof, vinyl cyanide, vinyl acetate, the butadiene, or polyoxyethylene, PPOX, polycaprolactone.

Above-mentioned polyreactive oligomers is preferably the oligomer shown in the following general formula (II).

General formula (II)

In the general formula (II), R ¹¹And R ¹³Represent hydrogen atom or methyl respectively independently.

R ¹²Expression contains the connection base that carbon number is 1～12 alkylidene, and this connection base can be that carbon number is 1～12 alkylidene, also can be the group that a plurality of these alkylidenes are formed by connecting by ester bond, ehter bond, amido link etc.As R ¹², be preferably carbon number and be 1～4 alkylidene, or carbon number is the group that 1～4 alkylidene is formed by connecting by ester bond.R ¹²The alkylidene of expression also can have substituting group (for example hydroxyl).

Y ¹¹Expression do not have substituent phenyl, have phenyl that a carbon number is 1～4 alkyl or-COOR ¹⁴Here R ¹⁴The expression carbon number is that 1～6 alkyl, phenyl or carbon number are 7～10 aralkyl.Y be preferably phenyl or-COOR ¹⁴, the R here wherein ¹⁴The expression carbon number is 1～12 alkyl.

Q represents 20～200 integer.

Preferred example as the polyreactive oligomers (macromonomer) that uses in (D-1-1) specific dispersion resin that can be in the present invention synthetic can list poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate and poly-(methyl) isobutyl acrylate, combine the polymkeric substance of (methyl) acryloyl group in a molecular end of polystyrene.As such polyreactive oligomers that can on market, obtain; can list the polystyrene oligomer (Mn=6000 that has carried out the metering system acidylate at an end; trade name: AS-6; East Asia synthetic chemical industry (strain) system); carried out the polymethyl methacrylate oligomer (Mn=6000 of metering system acidylate at an end; trade name: AA-6; East Asia synthetic chemical industry (strain) system); and the positive butyl ester oligomer of the polyacrylic acid (Mn=6000 that has carried out the metering system acidylate at an end; trade name: AB-6, East Asia synthetic chemical industry (strain) system).

(D-1-1) of the present invention specific dispersion resin is owing to having specific acid number, so more preferably contain the copolymerization units from the monomer with acidic group.

As monomer, can list unsaturated monocarboxylic classes such as acrylic acid, methacrylic acid, crotonic acid, α-Lv Daibingxisuan, cinnamic acid with acidic group; Unsaturated dicarboxylic or its acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, lemon health are antiacid, citraconic anhydride, mesaconic acid; Unsaturated polybasic carboxylic acid more than 3 yuan or its acid anhydrides; List [(methyl) acryloxyalkyl] the ester class of mono succinate (2-acryloxy ethyl) ester, mono succinate (2-methacryloxyethyl) ester, fumaric acid list (2-acryloxy ethyl) ester, the fumaric acid list polybasic carboxylic acids more than 2 yuan such as (2-methacryloxyethyl); Two ends such as ω-carboxyl-polycaprolactone single-acrylate, ω-carboxyl-polycaprolactone monomethacrylates have list (methyl) esters of acrylic acid of the polymkeric substance of carboxyl etc.

(D-1-1) of the present invention specific dispersion resin is in the scope of not damaging its effect, but the vinyl monomer that can also contain copolymerization is as copolymer composition.

Here as spendable vinyl monomer, do not have particular determination, for example be preferably ester class, styrene, (methyl) vinyl cyanide of (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, vinyl ethers, vinyl alcohol etc.As the concrete example of such vinyl monomer, can list following such compound.

Promptly, as the example of (methyl) esters of acrylic acid, can list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) 2-EHA, (methyl) acrylic acid uncle monooctyl ester, (methyl) acrylic acid dodecane ester, (methyl) acrylic acid octadecane ester, (methyl) acrylic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxypropyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid diethylene glycol monomethyl ether ester, (methyl) acrylic acid diethylene glycol monoethyl ether ester, (methyl) acrylic acid triethylene glycol monomethyl ether ester, (methyl) acrylic acid triethylene glycol monoethyl ether ester, (methyl) polyalkylene glycol acrylate monomethyl ether ester, (methyl) polyalkylene glycol acrylate monoethyl ether ester, (methyl) acrylic acid beta-phenoxy ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy macrogol ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid tribromophenoxy ethyl ester etc.

In addition, in this manual, under any in expression " acrylic acid, methacrylic acid " or both situations, put down in writing " (methyl) acrylic acid " sometimes.

As the example of crotonates class, can list butyl crotonate and the own ester of crotonic acid etc.

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

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

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

As the example of itaconic acid diester class, can list dimethyl itaconate, diethyl itaconate, 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-isopropyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tert-butyl group (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 phenylethylene, can list styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorobenzene ethene, bromostyrene, 1-chloro-4-methyl-benzene, by can be by hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. of the group of acidic materials deprotection (for example tert-butyl group oxygen base carbonyl (t-Boc) etc.) protection.

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

As the preferred configuration of (D-1-1) of the present invention specific dispersion resin, can list contain 2～50 quality % from the copolymerization units of the monomer of above-mentioned general formula (I) expression and contain the multipolymer of the copolymerization units from monomer, 0～20 quality % of the copolymerization units from the polyreactive oligomers that has ethylenic unsaturated bond endways, 1～30 quality % of 10～90 quality % from the copolymerization units of vinyl monomer with acidic group.

Below, enumerated concrete example [exemplary compounds 1～exemplary compounds 16] and weight-average molecular weight thereof that colored pattern of the present invention forms (D-1-1) the specific dispersion resin that can preferably use with composition simultaneously, but the present invention is not limited to these.

Exemplary compounds (1): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-2/ methacrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 10/25/65 (quality %), weight-average molecular weight are 50000, and acid number is 163mg/g)

Exemplary compounds (2): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-2/ methacrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 10/15/75 (quality %), weight-average molecular weight are 35000, and acid number is 98mg/g)

Exemplary compounds (3): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-3/ methacrylic acid/methacrylic acid 2-hydroxyl ethyl ester/terminal methyl group propylene acidylate (copolymerization ratio 5/5/10/80 (quality %), weight-average molecular weight are 40000, and acid number is 33mg/g)

Exemplary compounds (4): the multipolymer (copolymerization ratio 15/10/10/65 (quality %) of the polymethylmethacrylate of above-mentioned monomer M-3/ methacrylic acid/benzyl methacrylate multipolymer/terminal methyl group propylene acidylate; weight-average molecular weight is 60000, and acid number is 65mg/g)

Exemplary compounds (5): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-4/ methacrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 10/30/60 (quality %), weight-average molecular weight are 80000, and acid number is 195mg/g)

Exemplary compounds (6): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-4/ methacrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 10/15/75 (quality %), weight-average molecular weight are 20000, and acid number is 98mg/g)

Exemplary compounds (7): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-5/ acrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 25/15/60 (quality %), weight-average molecular weight are 60000, and acid number is 117mg/g)

Exemplary compounds (8): the multipolymer of the butyl polyacrylate of above-mentioned monomer M-5/ acrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 15/5/80 (quality %), weight-average molecular weight are 45000, and acid number is 39mg/g)

Exemplary compounds (9): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-6/ acrylic acid/methacrylic acid 2-hydroxyl ethyl ester/terminal methyl group propylene acidylate (copolymerization ratio 15/10/5/70 (quality %), weight-average molecular weight are 80000, and acid number is 78mg/g)

Exemplary compounds (10): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-6/ acrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 12/18/70 (quality %), weight-average molecular weight are 50000, and acid number is 140mg/g)

Exemplary compounds (11): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-7/ methacrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 10/18/72 (quality %), weight-average molecular weight are 15000, and acid number is 117mg/g)

Exemplary compounds (12): the multipolymer of above-mentioned monomer M-7/ methacrylic acid/benzyl methacrylate/methoxy polyethylene glycol methacrylate-styrene polymer (copolymerization ratio 10/10/50/30 (quality %), weight-average molecular weight are 50000, and acid number is 65mg/g)

Exemplary compounds (13): the multipolymer of the polystyrene of above-mentioned monomer M-10/ acrylic acid/methacrylic acid 2-hydroxyl ethyl ester/terminal methyl group propylene acidylate (copolymerization ratio 5/35/10/50 (quality %), weight-average molecular weight are 20000, and acid number is 272mg/g)

Exemplary compounds (14): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-10/ methacrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 10/12/78 (quality %), weight-average molecular weight are 10000, and acid number is 78mg/g)

Exemplary compounds (15): the multipolymer of above-mentioned monomer M-10/ acrylic acid/methoxy polyethylene glycol methacrylate-styrene polymer (copolymerization ratio 15/3/82 (quality %), weight-average molecular weight are 15000, and acid number is 23mg/g)

Exemplary compounds (16): the multipolymer of the polymethylmethacrylate of above-mentioned monomer M-13/ methacrylic acid/terminal methyl group propylene acidylate (copolymerization ratio 10/25/65 (quality %), weight-average molecular weight are 20000, and acid number is 163mg/g)

The physical property measurement method of above-mentioned specific dispersion resin is as follows.If not special record, the physics value of described resin etc. also can be measured with the method identical with following method in this manual.

The assay method of＜weight-average molecular weight and number-average molecular weight 〉

The assay method of weight-average molecular weight and number-average molecular weight is measured by GPC (gel permeation chromatography) respectively under the following conditions, is expressed as the polystyrene conversion value.

Use post: TSK gel Multipore HXL-M (pore polydispersion type linear columns (linearcolumn)), TOSOH CORPORATION system

Eluent: THF (tetrahydrofuran)

Flow: 1.0mL/ branch

Temperature: 40 ℃

Testing conditions: RI (reflectivity index) detects

GPC apparatus system: the high speed GPC device same form (HLC-8220, TOSOHCORPORATION system)

The assay method of＜acid number 〉

In the solution that obtains in that sample (resin) is dissolved in 1-methoxyl-2-propyl alcohol, further add entry, the solution that obtains is carried out acid-base titration with the potassium hydroxide aqueous solution of 1 equivalent, measure acid number thus.

(D-1-1) specific dispersion resin among the present invention be multipolymer as described above be by make the represented monomer of above-mentioned general formula (I), according to hope and and the polyreactive oligomers of usefulness or other monomer in solvent, carry out free radical polymerization and obtain.As radical polymerization initiator, can use known compound, example as this compound of preferred use, can list azo-initiator (for example 2,2 '-azo two (2 Methylpropionic acid) dimethyl ester, azoisobutyronitrile, 2,2 '-azo two (2-amidine propane) dihydrochloride etc.), superoxide (benzoyl peroxide, potassium persulfate etc.).Except initiating agent, can also add chain-transferring agent (for example, 2 mercapto ethanol, 3-mercaptopropionic acid, 2-mercaptoacetic acid, dodecyl mercaptans etc.) and synthesize.

In addition, as described later about concrete synthesis example.

[(D-1-2) macromolecular compound shown in the general formula (1): (D-1-2) specific dispersion resin]

At first, the macromolecular compound shown in the following general formula (1) (following suitably be called " (D-1-2) specific dispersion resin ") is illustrated.

General formula (1)

In above-mentioned general formula (1), A ¹Expression contains and is selected from the 1 valency organic group that organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, urethano, the group with coordination oxygen atom, carbon number are at least a position in alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4.N A ¹Can be identical, also can be different.

That is to say above-mentioned A ¹Expression contain organic pigment structure, heterocycle structure such pigment is had the structure of energy of adsorption; Or acidic groups, group, urea groups, urethano, group, carbon number with coordination oxygen atom with basic nitrogen atom be alkyl, alkoxysilyl, epoxy radicals, isocyanate group and hydroxyl more than 4 such pigment is had 1 at least a valency organic group among the functional group of energy of adsorption.

In addition, below this is had adsorbing position (said structure and functional group) to pigment and suitably be generically and collectively referred to as " adsorption site ", illustrated.

Above-mentioned adsorption site is at 1 A ¹As long as in contain at least a kind, also can contain more than 2 kinds.

" the 1 valency organic group that contains at least 1 adsorption site " is above-mentioned adsorption site and the organic 1 valency organic group that is connected the base be combined into that is formed by 1～200 carbon atom, 0～20 nitrogen-atoms, 0～100 oxygen atom, 1～400 hydrogen atom and 0～40 sulphur atom in addition, in the present invention.In addition, be that adsorption site itself also can be A under the situation about constituting of the organic group by 1 valency at adsorption site itself ¹1 valency organic group of expression.

At first, to constituting above-mentioned A ¹Adsorption site carry out following explanation.

As above-mentioned " organic pigment structure ", as preference, can list for example phthalocyanines, insoluble azo class, the azo lake class, the anthraquinone class, quinacridone dioxazines, the diketopyrrolo-pyrrole class, anthra pyridine (anthrapyridine) class, two and anthrone (anthanthrone) class, the indanthrone class, flavanthrones, purple perilla ketone; perylene class, thioindigo (thioindigoid) class pigment structure, phthalocyanines more preferably, the azo lake class, anthraquinone class dioxazines, the pigment structure of diketopyrrolo-pyrrole class is preferably phthalocyanines especially, the anthraquinone class, the pigment structure of diketopyrrolo-pyrrole class.

In addition, as above-mentioned " heterocycle structure ", for example can list as preference, thiophene, furans, xanthene, the pyrroles, pyrrolin, pyrrolidine, dioxolanes, pyrazoles, pyrazoline, pyrazolidine, imidazoles oxazole, thiazole oxadiazole, triazole, thiadiazoles, pyrans, pyridine, piperidines diox, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, Benzimidazolinone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoins, indoles, quinoline, carbazole, acridine, acridone, anthraquinone, more preferably pyrrolin, pyrrolidine, pyrazoles, pyrazoline, pyrazolidine, imidazoles, triazole, pyridine, piperidines, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, Benzimidazolinone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoins, carbazole, acridine, acridone, anthraquinone.

In addition, above-mentioned " organic pigment structure " or " heterocycle structure " can also have substituting group.As this substituting group, can list the carbon number of methyl, ethyl etc. for example and be 1～20 alkyl; Carbon number such as phenyl, naphthyl is 6～16 aryl; Carbon numbers such as hydroxyl, amino, carboxyl, sulfonamido, N-sulfonamido, acetoxyl group are that carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy are that carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyl oxygen base carbonyl such as 1～20 alkoxy, chlorine, bromine are carbonate groups such as 2 to 7 alkoxy carbonyl, cyano group, tert-butyl group carbonic ester etc.Here, these substituting groups also can combine with organic pigment structure or heterocycle by the connection base that following structural unit or this structural unit constitute.

As above-mentioned " acidic groups ", as preference, can list for example carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, phosplate base, boronate, more preferably carboxylic acid group, sulfonic group, sulfate mono ester group, phosphate, phosplate base are preferably carboxylic acid group, sulfonic group, phosphate especially.

In addition, as above-mentioned " group ",, can list for example amino (NH as preference with basic nitrogen atom ₂), substituted imido (NHR ⁸,-NR ⁹R ¹⁰, R here ⁸, R ⁹And R ¹⁰Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.), the guanidine radicals of following formula (a1) expression, the amidino groups of following formula (a2) expression etc.

In formula (a1), R ¹¹And R ¹²Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl more than 6 or carbon number are the aralkyl more than 7.

In formula (a2), R ¹³And R ¹⁴Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl more than 6 or carbon number are the aralkyl more than 7.

Wherein, more preferably amino (NH ₂), substituted imido (NHR ⁸,-NR ⁹R ¹⁰, R here ⁸, R ⁹And R ¹⁰Represent that independently of one another carbon number is 1～10 alkyl, phenyl, benzyl.), the guanidine radicals of following formula (a1) expression [in formula (a1), R ¹¹And R ¹²Represent that independently of one another carbon number is 1～10 alkyl, phenyl, benzyl.], the amidino groups of following formula (a2) expression [in formula (a2), R ¹³And R ¹⁴Represent that independently of one another carbon number is 1～10 alkyl, phenyl, benzyl.] etc.

Can preferably use amino (NH especially ₂), substituted imido (NHR ⁸,-NR ⁹R ¹⁰, R here ⁸, R ⁹And R ¹⁰Represent that independently of one another carbon number is 1～5 alkyl, phenyl, benzyl.), the guanidine radicals of following formula (a1) expression [in formula (a1), R ¹¹And R ¹²Represent that independently of one another carbon number is 1～5 alkyl, phenyl, benzyl.], the amidino groups of following formula (a2) expression [in formula (a2), R ¹³And R ¹⁴Represent that independently of one another carbon number is 1～5 alkyl, phenyl, benzyl.] etc.

As above-mentioned " urea groups ",, for example can list-NR as preference ¹⁵CONR ¹⁶R ¹⁷(R here ¹⁵, R ¹⁶And R ¹⁷Represent that independently of one another hydrogen atom or carbon number are that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.), more preferably-NR ¹⁵CONHR ¹⁷(R here, ¹⁵And R ¹⁷Represent that independently of one another hydrogen atom or carbon number are that 1～10 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.), be preferably especially-NRCONHR ¹⁷(R here, ¹⁷Expression hydrogen atom or carbon number are that 1～10 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.)。

As above-mentioned " urethano ", for example can list-NHCOOR as preference ¹⁸,-NR ¹⁹COOR ²⁰,-OCONHR ²¹,-OCONR ²²R ²³(R here ¹⁸, R ¹⁹, R ²⁰, R ²¹, R ²²And R ²³Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.) etc., more preferably-NHCOOR ¹⁸,-OCONHR ²¹(R here ¹⁸, R ²¹Represent that independently of one another carbon number is that 1～20 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.) etc., be preferably especially-NHCOOR ¹⁸,-OCONHR ²¹(R here ¹⁸, R ²¹Represent that independently of one another carbon number is that 1～10 alkyl, carbon number are that aryl, carbon number more than 6 is the aralkyl more than 7.) etc.

As above-mentioned " group ", can list for example acetylacetone based, crown ether etc. with coordination oxygen atom.

As above-mentioned " carbon number is the alkyl more than 4 ", as preference, aryl, the carbon number that can list carbon number and be alkyl, carbon number more than 4 and be more than 6 are aralkyl more than 7 etc., more preferably carbon number is that 4～20 alkyl, carbon number are that 6～20 aryl, carbon number are aralkyl of 7～20 etc., and being preferably carbon number especially and being 4～15 alkyl (for example octyl group, dodecyl etc.), carbon number and be 6～15 aryl (for example phenyl, naphthyl etc.), carbon number is aralkyl (for example benzyl etc.) of 7～15 etc.

As above-mentioned " alkoxysilyl ", can list for example trimethoxysilyl, triethoxysilyl etc.

As with organic base that is connected of above-mentioned adsorption site combination, be preferably singly-bound, or the organic base that is connected that forms by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 sulphur atoms.This organic connection base can not replace, and can also have substituting group.

As the concrete example of this organic connection base, the group that can list following structural unit or constitute by this structural unit.

Have under the substituent situation at above-mentioned organic connection base,, can list carbon number such as methyl, ethyl for example and be 1～20 alkyl as this substituting group; Carbon number such as phenyl, naphthyl is 6～16 aryl; Carbon numbers such as hydroxyl, amino, carboxyl, sulfonamido, N-sulfonamido, acetoxyl group are that carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy are that carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyl oxygen base carbonyl such as 1～6 alkoxy, chlorine, bromine are carbonate groups such as 2～7 alkoxy carbonyl, cyano group, tert-butyl group carbonic ester etc.

In above-mentioned group, above-mentioned A ¹Be preferably to contain and be selected from the 1 valency organic group that organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups and carbon number are at least a kind of position in the alkyl more than 4.

Above-mentioned A ¹1 valency organic group of more preferably following general formula (4) expression.

General formula (4)

In above-mentioned general formula (4), B ¹Represent above-mentioned adsorption site (promptly being selected from organic pigment structure, heterocycle structure, acidic groups, group, urea groups, urethano, group, carbon number and being the position in alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4), R with coordination oxygen atom with basic nitrogen atom ²⁴Expression singly-bound or (a+1) organic connection base of valency.A represents 1～10 integer, a B ¹Can be identical, also can be different.

As above-mentioned B ¹The example of the adsorption site of expression can list and the A that constitutes above-mentioned general formula (1) ¹The same position of adsorption site, preference is too.

Wherein, be preferably that to be selected from organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups and carbon number be position in the alkyl more than 4.

R ²⁴Expression singly-bound or (a+1) organic connection base of valency, a represents 1～10.Preferred a is 1～7, and more preferably a is 1～5, and preferred especially a is 1～3.

(a+1) organic connection base of valency contains by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom, 0～20 group that sulphur atom forms, and can not have replacement, also can have substituting group.

As the concrete example of organic connection base of above-mentioned (a+1) valency, the group that can list following structural unit or constitute (also can form ring structure) by this structural unit.

As R ²⁴, be preferably singly-bound, or organic base that is connected of (a+1) valency that forms by 1～50 carbon atom, 0～8 nitrogen-atoms, 0～25 oxygen atom, 1～100 hydrogen atom and 0～10 sulphur atom; Singly-bound more preferably, or organic base that is connected of (a+1) valency that forms by 1～30 carbon atom, 0～6 nitrogen-atoms, 0～15 oxygen atom, 1～50 hydrogen atom and 0～7 sulphur atom; Be preferably singly-bound especially, or organic base that is connected of (a+1) valency that forms by 1～10 carbon atom, 0～5 nitrogen-atoms, 0～10 oxygen atom, 1～30 hydrogen atom and 0～5 sulphur atom.

In above-mentioned connection base, have under the substituent situation at organic connection base of (a+1) valency, as this substituting group, can list carbon number such as methyl, ethyl for example and be 1～20 alkyl; Carbon number such as phenyl, naphthyl is 6～16 aryl; Carbon numbers such as hydroxyl, amino, carboxyl, sulfonamido, N-sulfonamido, acetoxyl group are that carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy are that carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyl oxygen base carbonyl such as 1～6 alkoxy, chlorine, bromine are carbonate groups such as 2～7 alkoxy carbonyl, cyano group, tert-butyl group carbonic ester etc.

In the above-mentioned general formula (1), R ²Organic connection base of expression singly-bound or divalent.N R ²Can be identical, also can be different.

In organic connection base of divalent, contain by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 group that sulphur atom forms, can there be replacement, also can have substituting group.

As the concrete example of organic connection base of above-mentioned divalent, the group that can list following structural unit or constitute by this structural unit.

As R ², be preferably singly-bound, or organic base that is connected of the divalent that forms by 1～50 carbon atom, 0～8 nitrogen-atoms, 0～25 oxygen atom, 1～100 hydrogen atom and 0～10 sulphur atom; Singly-bound more preferably, or organic base that is connected of the divalent that forms by 1～30 carbon atom, 0～6 nitrogen-atoms, 0～15 oxygen atom, 1～50 hydrogen atom and 0～7 sulphur atom; Be preferably singly-bound especially, or organic base that is connected of the divalent that forms by 1～10 carbon atom, 0～5 nitrogen-atoms, 0～10 oxygen atom, 1～30 hydrogen atom and 0～5 sulphur atom.

In above-mentioned connection base, have under the substituent situation at organic connection base of divalent, as this substituting group, can list carbon number such as methyl, ethyl for example and be 1～20 alkyl; Carbon number such as phenyl, naphthyl is 6～16 aryl; Carbon numbers such as hydroxyl, amino, carboxyl, sulfonamido, N-sulfonamido, acetoxyl group are that carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy are that carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyl oxygen base carbonyl such as 1～6 alkoxy, chlorine, bromine are carbonate groups such as 2～7 alkoxy carbonyl, cyano group, tert-butyl group carbonic ester etc.

In above-mentioned general formula (1), R ¹Organic connection base of expression (m+n) valency.M+n satisfies 3～10 scope.

As above-mentioned R ¹Organic connection base of (m+n) valency of expression contains by 1～100 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～200 hydrogen atom and 0～20 group that sulphur atom forms, and can not have replacement, also can have substituting group.

As the concrete example of organic connection base of above-mentioned (m+n) valency, the group that can list following structural unit or constitute (also can form ring structure) by this structural unit.

As organic connection base of (m+n) valency, be preferably by 1～60 carbon atom, 0～10 nitrogen-atoms, 0～40 oxygen atom, 1～120 hydrogen atom and 0～10 group that sulphur atom forms; More preferably by 1～50 carbon atom, 0～10 nitrogen-atoms, 0～30 oxygen atom, 1～100 hydrogen atom and 0～7 group that sulphur atom forms; Be preferably especially by 1～40 carbon atom, 0～8 nitrogen-atoms, 0～20 oxygen atom, 1～80 hydrogen atom and 0～5 group that sulphur atom forms.

In above-mentioned connection base, have under the substituent situation at organic connection base of (m+n) valency, as this substituting group, can list carbon number such as methyl, ethyl for example and be 1～20 alkyl; Carbon number such as phenyl, naphthyl is 6～16 aryl; Carbon numbers such as hydroxyl, amino, carboxyl, sulfonamido, N-sulfonamido, acetoxyl group are that carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy are that carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyl oxygen base carbonyl such as 1～6 alkoxy, chlorine, bromine are carbonate groups such as 2～7 alkoxy carbonyl, cyano group, tert-butyl group carbonic ester etc.

Show above-mentioned R below ¹The concrete example [concrete example (1)～(17)] of organic connection base of (m+n) valency of expression.But be not limited to these in the present invention.

In above-mentioned concrete example, from acquired, the synthetic difficulty or ease of raw material, the deliquescent viewpoint all kinds of solvents, the organic connection base of most preferred (m+n) valency is a following radicals.

In above-mentioned general formula (1), m represents 1～8 integer.M preferably represents 1～5 integer, and more preferably 1～4 integer is preferably 1～3 integer especially.

In addition, in above-mentioned general formula (1), n represents 2～9 integer.As n, preferably represent 2～8 integer, more preferably 2～7 integer is preferably 3～6 integer especially.

In above-mentioned general formula (1), P ¹The expression macromolecular scaffold can be from known polymkeric substance etc. be selected according to purpose etc.M P ¹Can be identical, also can be different.

In polymkeric substance, be selected from polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, ammonia esters polymer, acylamide polymer, epoxide polymer, type siloxane polymkeric substance and their modification body or multipolymer and [comprise that multipolymer of for example polyethers/polyurethane copolymer, polyethers/polymer of vinyl monomer etc. (can be in random copolymers, segmented copolymer, the graft copolymer any in order to constitute macromolecular scaffold, to be preferably.)。] in any, more preferably be selected from least a in polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, ammonia esters polymer and their modification body or the multipolymer, be preferably polymer of vinyl monomer or multipolymer especially.

And then, be the viewpoint of the adsorbed layer of necessity from guaranteeing for decentralized stabilization, preferred above-mentioned polymkeric substance is solvable in organic solvent.

As above-mentioned vinyl monomer, do not have particular determination, for example be preferably (methyl) esters of acrylic acid, crotonates class, vinyl ester, maleic acid diester class, dimethyl ester class, itaconic acid diester class, (methyl) acrylic amide, phenylethylene, vinyl ethers, vinyl ketones, olefines, maleimide, (methyl) vinyl cyanide, have the vinyl monomer of acidic groups etc.

Below, the preference of these vinyl monomers is illustrated.

Example as (methyl) esters of acrylic acid, can list (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid pentyl ester, the just own ester of (methyl) acrylic acid, (methyl) cyclohexyl acrylate, (methyl) acrylic acid tert-butyl group cyclohexyl, (methyl) 2-EHA, (methyl) acrylic acid uncle monooctyl ester, (methyl) acrylic acid dodecane ester, (methyl) acrylic acid octadecane ester, (methyl) acrylic acid acetoxyl group ethyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 4-hydroxy butyl ester, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-ethoxy ethyl ester, (methyl) acrylic acid 2-(2-methoxy ethoxy) ethyl ester, (methyl) acrylic acid 3-phenoxy group-2-hydroxypropyl acrylate, (methyl) acrylic acid 2-chloroethene ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxy radicals cyclohexyl methyl esters, (methyl) acrylic acid vinyl esters, (methyl) acrylic acid 2-phenyl vinyl ester, (methyl) acrylic acid 1-propenyl ester, (methyl) allyl acrylate, (methyl) acrylic acid 2-allyloxy ethyl ester, (methyl) acrylic acid alkynes propyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid diethylene glycol monomethyl ether ester, (methyl) acrylic acid diethylene glycol monoethyl ether ester, (methyl) acrylic acid triethylene glycol monomethyl ether ester, (methyl) acrylic acid triethylene glycol monoethyl ether ester, (methyl) polyalkylene glycol acrylate monomethyl ether ester, (methyl) polyalkylene glycol acrylate monoethyl ether ester, (methyl) acrylic acid beta-phenoxy ethoxy ethyl ester, (methyl) acrylic acid Nonylphenoxy macrogol ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid trifluoro ethyl ester, (methyl) acrylic acid octafluoro pentyl ester, (methyl) acrylic acid perfluoro capryl ethyl ester, (methyl) acrylic acid two cyclopentene esters, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid tribromophenoxy ethyl ester, (methyl) acrylic acid gamma-butyrolacton etc.

As the example of crotonates class, can list butyl crotonate and the own ester of crotonic acid etc.

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

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

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

As the example of itaconic acid diester class, can list dimethyl itaconate, diethyl itaconate, dibutyl itaconate etc.

Example as (methyl) acrylic amide; can list (methyl) acrylamide; N-methyl (methyl) acrylamide; N-ethyl (methyl) acrylamide; N-propyl group (methyl) acrylamide; N-isopropyl (methyl) acrylamide; N-normal-butyl (methyl) acrylamide; the N-tert-butyl group (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-nitrobenzophenone 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 (methyl) acrylamide etc.

As the example of phenylethylene, can list styrene, methyl styrene, dimethyl styrene, trimethylbenzene ethene, ethyl styrene, cumene ethene, butylstyrene, hydroxy styrenes, methoxy styrene, butyl phenyl ether ethene, acetoxy-styrene, chlorostyrene, dichlorobenzene ethene, bromostyrene, 1-chloro-4-methyl-benzene, by can be by hydroxy styrenes, vinyl benzoic acid methyl esters and the α-Jia Jibenyixi etc. of the group of acidic materials deprotection (for example t-Boc etc.) protection.

As the example of vinyl ethers, can list methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl group vinyl ether, methoxy ethyl 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, isobutylene, butadiene, isoprene etc.

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

Can also use hetero ring type base (for example vinylpyridine, N-vinyl pyrrolidone, vinylcarbazole etc.), N-vinyl formamide, N-vinyl acetamide, N-vinyl imidazole, vinyl caprolactone of (methyl) vinyl cyanide, vinyl substituted etc.

Except above-claimed cpd, can also use the vinyl monomer of functional groups such as for example having urethano, urea groups, sulfonamido, phenylol, imide.As such monomer, for example can utilize isocyanate group and hydroxyl or amino addition reaction suitably to synthesize with urethano or urea groups.Specifically, monomer that can be by containing isocyanate group with contain the compound of 1 hydroxyl or contain the addition reaction of the compound of 1 uncle or secondary amino group, or contain the monomer of hydroxyl or contain uncle or the monomer of secondary amino group and the addition reaction of monoisocyanates etc. are suitably synthesized.

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

As the example of vinyl monomer, can list (methyl) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer etc. with carboxyl.In addition, can also use (methyl) acrylic acid 2-hydroxyl ethyl ester etc. to have addition reaction, ω-carboxyl-polycaprolactone list (methyl) acrylate of the such cyclic anhydride of the monomer of hydroxyl and maleic anhydride or phthalic anhydride, cyclohexane cyclohexanedimethanodibasic acid anhydride etc.In addition, as the precursor of carboxyl, can also use maleic anhydride, itaconic anhydride, citraconic anhydride etc. to contain the monomer of acid anhydrides.In addition, wherein, the viewpoint from copolymerization, cost, dissolubility etc. is preferably (methyl) acrylic acid especially.

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

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

In the macromolecular compound shown in the above-mentioned general formula (1), be preferably the represented macromolecular compound of following general formula (2).

General formula (2)

In above-mentioned general formula (2), A ²Expression contains and is selected from the 1 valency organic group that organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, urethano, the group with coordination oxygen atom, carbon number are at least a position in alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4.N A ²Can be identical, also can be different.

In addition, A ²With the above-mentioned A in the above-mentioned general formula (1) ¹Same meaning, preferred configuration are also identical.

In above-mentioned general formula (2), R ⁴, R ⁵Organic connection base of representing singly-bound or divalent independently of one another.N R ⁴Can be identical, also can be different.In addition, m R ⁵Can be the same or different.

As R ⁴, R ⁵The organic connection base of represented divalent, can use with as the R of above-mentioned general formula (1) ²The listed identical connection base of enumerating of organic connection base of the organic connection base of divalent of expression, preferred configuration too.

In above-mentioned general formula (2), R ³Organic connection base of expression (m+n) valency.M+n satisfies 3～10 scope.

As above-mentioned R ³Organic connection base of (m+n) valency of expression contains by 1～60 carbon atom, 0～10 nitrogen-atoms, 0～50 oxygen atom, 1～100 hydrogen atom and 0～20 group that sulphur atom forms, and can not have replacement, also can have substituting group.

As above-mentioned R ³Organic connection base of (m+n) valency of expression specifically, can use and R as above-mentioned general formula (1) ¹The listed identical connection base of enumerating of organic connection base of organic connection base of (m+n) valency of expression, preferred configuration too.

In above-mentioned general formula (2), m represents 1～8 integer.M preferably represents 1～5 integer, and more preferably 1～4 integer is preferably 1～3 integer especially.

In addition, in the above-mentioned general formula (2), n represents 2～9 integer.N represents 2～8 integer, and more preferably 2～7 integer is preferably 3～6 integer especially.

In addition, the P in the general formula (2) ²The expression macromolecular scaffold can be from known polymkeric substance etc. be selected according to purpose etc.M P ²Can be identical, also can be different.About the preferred configuration of polymkeric substance, with the P in the above-mentioned general formula (1) ¹Equally.

In the macromolecular compound shown in the above-mentioned general formula (2), the R shown in below most preferably all satisfying ³, R ⁴, R ⁵, P ², m and n macromolecular compound.

R ³: above-mentioned concrete example (1), (2), (10), (11), (16) or (17)

R ⁴: singly-bound, or following structural unit or (can have substituting group by the organic base that is connected of divalent that forms by " 1～10 carbon atom, 0～5 nitrogen-atoms, 0～10 oxygen atom, 1～30 hydrogen atom and 0～5 sulphur atom " that following structural unit constitutes, as this substituting group, can list the carbon number of methyl, ethyl etc. for example and be 1～20 alkyl; Carbon number such as phenyl, naphthyl is 6～16 aryl; Carbon numbers such as hydroxyl, amino, carboxyl, sulfonamido, N-sulfonamido, acetoxyl group are that carbon numbers such as 1～6 acyloxy, methoxyl, ethoxy are that carbon numbers such as halogen atom, methoxycarbonyl, ethoxy carbonyl, cyclohexyl oxygen base carbonyl such as 1～6 alkoxy, chlorine, bromine are carbonate groups such as 2 to 7 alkoxy carbonyl, cyano group, tert-butyl group carbonic ester etc.).

R ⁵: singly-bound, ethylidene, propylidene, following radicals (a) or following radicals (b)

In addition, in following radicals, R ²⁵Expression hydrogen atom or methyl, 1 expression 1 or 2.

P ²: polymer of vinyl monomer or multipolymer, esters polymer, ether polymer, ammonia esters polymer and their modification body

m：1～3

n：3～6

(synthetic method)

Macromolecular compound shown in the above-mentioned general formula (1) (comprising the macromolecular compound shown in the general formula (2)) there is not particular determination, can be synthetic by following method etc.

1. the polymkeric substance that end has been introduced be selected from the functional group in carboxyl, hydroxyl, the amino etc. and the carboxylic acid halides with a plurality of above-mentioned adsorption sites, the isocyanates etc. that has the alkyl halide of a plurality of above-mentioned adsorption sites or have a plurality of above-mentioned adsorption sites carry out the method for high molecular weight reactive.

2. the method that makes the end polymkeric substance of having introduced carbon-to-carbon double bond and mercaptan carry out reversal of the Michael addition with a plurality of above-mentioned adsorption sites.

3. the method that the end polymkeric substance of having introduced carbon-to-carbon double bond and the mercaptan with above-mentioned adsorption site are reacted in the presence of radical initiator.

4. the method that the end polymkeric substance of having introduced a plurality of mercaptan and the compound with carbon-to-carbon double bond and above-mentioned adsorption site are reacted in the presence of radical initiator.

5. in the presence of mercaptan compound, make the method for polyvinyl generation free radical polymerization with a plurality of above-mentioned adsorption sites.

In said method, from the difficulty or ease of synthesizing, preferred 2,3,4,5 the synthetic method of (D-1-2) specific dispersion resin among the present invention, more preferably 3,4,5 synthetic method.Particularly, have at (B-1) specific dispersion resin under the situation of the structure shown in the general formula (2),, most preferably synthesize with 5 synthetic method from the difficulty or ease of synthesizing.

Synthetic method as above-mentioned 5 more particularly, is preferably in the presence of the compound shown in the following general formula (3) and makes vinyl monomer carry out the method for free radical polymerization.

General formula (3)

In above-mentioned general formula (3), R ⁶, R ⁷, A ³, m and n can be respectively with above-mentioned general formula (2) in R ³, R ⁴, A ², m and n same meaning, its preferred configuration is too.

Compound shown in the above-mentioned general formula (3) can wait synthetic in the following method, from the difficulty or ease of synthesizing, more preferably following 7 method.

From the halogenide with a plurality of above-mentioned adsorption sites change into mercaptan compound method (can list with the method for thiocarbamide reaction and hydrolysis, with the NaSH directly method and the CH of reaction ₃The method of COSNa reaction and hydrolysis etc.)

7. make the compound that has 3～10 sulfydryls in a part and have above-mentioned adsorption site and have the method that to carry out addition reaction with the functional group's of sulfydryl reaction compound

" can with the functional group of sulfydryl reaction " as in the above-mentioned synthetic method 7 preferably lists carboxylic acid halides, alkyl halide, isocyanates, carbon-to-carbon double bond etc.

Preferred especially " can with the functional group of sulfydryl reaction " be carbon-to-carbon double bond, and addition reaction is the free radical addition reaction.In addition, as carbon-to-carbon double bond, from reactive viewpoint of sulfydryl, more preferably 1 replaces or 2 vinyl that replace.

Concrete example [concrete example (18)～(34)] as the compound that has 3～10 sulfydryls in a part can list following compound.

In above-claimed cpd, from acquired, the synthetic difficulty or ease of raw material, the deliquescent viewpoint all kinds of solvents, preferred especially following compound.

As the compound that has above-mentioned adsorption site and have a carbon-to-carbon double bond (specifically, have that to be selected from organic pigment structure, heterocycle structure, acidic groups, the group with basic nitrogen atom, urea groups, urethano, the group with coordination oxygen atom, carbon number be at least a position in alkyl, alkoxysilyl, epoxy radicals, isocyanate group and the hydroxyl more than 4, and the compound with carbon-to-carbon double bond), do not have particular determination, can list following such compound.

Above-mentioned " compound that has 3～10 sulfydryls in a part ", can utilize following method to obtain with the free radical addition resultant of reaction of " have above-mentioned adsorption site and have the compound of carbon-to-carbon double bond ", promptly for example, above-mentioned " compound that has 3～10 sulfydryls in a part " and " have above-mentioned adsorption site and have the compound of carbon-to-carbon double bond " are dissolved in the appropriate solvent, to wherein adding radical initiator, under about 50 ℃～100 ℃, carry out method (the mercaptan-alkene reaction method: thiol-ene reaction) of addition.

As the appropriate solvent example that can in above-mentioned mercaptan-alkene reaction method, use, can select arbitrarily according to employed " compound that has 3～10 sulfydryls in a part ", " have above-mentioned adsorption site and have the compound of carbon-to-carbon double bond " and the dissolubility of " the free radical addition resultant of reaction of generation ".

Can list for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, acetone, MEK, methyl isobutyl ketone, acetate methoxyl propyl ester, ethyl lactate, ethyl acetate, vinyl cyanide, tetrahydrofuran, dimethyl formamide, chloroform, toluene.These solvents can mix two or more uses.

In addition, as radical polymerization initiator, can use 2,2 '-azoisobutyronitrile (AIBN), 2,2 '-azo two (2,4 '-methyl pentane nitrile), 2, persulfate that superoxide that such azo-compound, the benzoyl peroxide (Benzoyl Peroxide) of 2 '-azo-bis-iso-dimethyl is such and potassium persulfate, ammonium persulfate are such etc.

As employed vinyl monomer in above-mentioned 5 the synthetic method, do not have particular determination, for example can use with at the P that obtains above-mentioned general formula (1) ¹The same vinyl monomer of employed vinyl monomer during shown macromolecular scaffold.

Above-mentioned vinyl monomer can be only carries out polymerization with a kind of, also can and carry out copolymerization with two or more.

In addition, (D-1-2) specific dispersion resin more preferably makes vinyl monomer with acidic groups more than a kind and the vinyl monomer that does not have acidic groups more than a kind carry out copolymerization.

As (D-1-2) the specific dispersion resin among the present invention, preferably by using the compound shown in these vinyl monomers and the above-mentioned general formula (3) to utilize known method to carry out the resin that polymerization obtains according to well-established law.In addition, the compound shown in the above-mentioned general formula (3) among the present invention is the compound with chain-transferring agent function, abbreviates " chain-transferring agent " below sometimes as.

For example utilize following method to obtain, that is, these vinyl monomers and above-mentioned chain-transferring agent are dissolved in the appropriate solvent,, under about 50 ℃～220 ℃, in solution, make the method (solution polymerization process) of its polymerization to wherein adding radical polymerization initiator.

The appropriate solvent that uses in the solution polymerization process can be selected arbitrarily according to the dissolubility of monomer that uses and the multipolymer that generates.Can list for example methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, acetone, MEK, methyl isobutyl ketone, acetate methoxyl propyl ester, ethyl lactate, ethyl acetate, vinyl cyanide, tetrahydrofuran, dimethyl formamide, chloroform, toluene.These solvents can mix two or more uses.

In addition, as radical polymerization initiator, can use 2,2 '-azoisobutyronitrile (AIBN), 2,2 '-azo two (2,4 '-methyl pentane nitrile), 2, persulfate that superoxide that such azo-compound, the benzoyl peroxide of 2 '-azo-bis-iso-dimethyl is such and potassium persulfate, ammonium persulfate are such etc.

Vinyl monomer as using in above-mentioned 5 the synthetic method does not have particular determination, for example can use with at the P that obtains above-mentioned general formula (1) ¹The same vinyl monomer of vinyl monomer that uses during shown macromolecular scaffold.

(D-1-2) specific dispersion resin among the present invention is preferably by using the compound shown in these vinyl monomers and the above-mentioned general formula (3) to utilize known method to carry out the resin that polymerization obtains according to well-established law.In addition, the compound shown in the above-mentioned general formula (3) among the present invention is the compound with chain-transferring agent function, abbreviates " chain-transferring agent " below sometimes as.

For example utilize following method to obtain, that is, these vinyl monomers and above-mentioned chain-transferring agent are dissolved in the appropriate solvent,, under about 50 ℃～220 ℃, in solution, make the method (solution polymerization process) of its polymerization to wherein adding radical polymerization initiator.

For the appropriate solvent that uses in the solution polymerization process, can select arbitrarily according to the dissolubility of monomer that uses and the multipolymer that generates.For example can list methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, acetone, MEK, methyl isobutyl ketone, acetate methoxyl propyl ester, ethyl lactate, ethyl acetate, vinyl cyanide, tetrahydrofuran, dimethyl formamide, chloroform, toluene.These solvents can mix two or more uses.

In addition, as radical polymerization initiator, can use 2,2 '-azoisobutyronitrile (AIBN), 2,2 '-azo two (2,4 '-methyl pentane nitrile), 2, persulfate that superoxide that such azo-compound, the benzoyl peroxide of 2 '-azo-bis-iso-dimethyl is such and potassium persulfate, ammonium persulfate are such etc.

＜synthesis example 〉

[employed chain-transferring agent is synthetic when obtaining (D-1-2) specific dispersion resin]

As follows, synthesized employed chain-transferring agent 1～13 when obtaining (D-1-2) specific dispersion resin.

[synthesis example: chain-transferring agent 1 synthetic]

The compound (m-1) that 7.83 parts dipentaerythritols six (3-mercaptopropionic acid ester) [DPMP: Sakai Chemical Industry Co., Ltd.'s system] and 15.57 parts following is had adsorption site and have a carbon-to-carbon double bond is dissolved in 93.60 parts the dimethyl formamide, is heated to 70 ℃ under stream of nitrogen gas.To wherein add 0.06 part 2, two (2, the 4-methyl pentane nitrile) [V-65, Wako Pure Chemical Industries, Ltd.'s systems] of 2 '-azo also heated 3 hours.The V-65 that further adds 0.06 part reacted 3 hours down at 70 ℃ under stream of nitrogen gas.Be cooled to room temperature, obtained 20% solution of sulfhydryl compound of the present invention shown below (chain-transferring agent 1) thus.

[synthesis example: chain-transferring agent 2 synthetic]

Except with 15.57 parts in above-mentioned chain-transferring agent 1 synthetic have adsorption site and have the compound (m-1) of carbon-to-carbon double bond and 93.60 parts dimethyl formamide change to 14.61 parts have adsorption site and have the compound (m-2) of carbon-to-carbon double bond and 89.78 parts dimethyl formamide, with synthetic 20% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 2) of above-mentioned chain-transferring agent 1.

[synthesis example: chain-transferring agent 3 synthetic]

Except with 15.57 parts in above-mentioned chain-transferring agent 1 synthetic have adsorption site and have the compound (m-1) of carbon-to-carbon double bond and 93.60 parts dimethyl formamide change to 10.06 parts have adsorption site and have the compound (m-3) of carbon-to-carbon double bond and 41.75 parts propylene glycol monomethyl ether, with synthetic 30% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 3) of above-mentioned chain-transferring agent 1.

[synthesis example: chain-transferring agent 4 synthetic]

Except with 15.57 parts in above-mentioned chain-transferring agent 1 synthetic have adsorption site and have the compound (m-1) of carbon-to-carbon double bond and 93.60 parts dimethyl formamide change to 5.26 parts have adsorption site and have the compound (m-4) of carbon-to-carbon double bond and 30.54 parts propylene glycol monomethyl ether, with synthetic 30% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 4) of above-mentioned chain-transferring agent 1.

[synthesis example: chain-transferring agent 5 synthetic]

Except with 15.57 parts in above-mentioned chain-transferring agent 1 synthetic have adsorption site and have the compound (m-1) of carbon-to-carbon double bond and 93.60 parts dimethyl formamide change to 4.71 parts have adsorption site and have the compound (m-5) of carbon-to-carbon double bond and 29.25 parts propylene glycol monomethyl ether, with synthetic 30% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 5) of above-mentioned chain-transferring agent 1.

[synthesis example: chain-transferring agent 6 synthetic]

The compound (m-6) that 7.83 parts dipentaerythritols six (3-mercaptopropionic acid ester) [DPMP: Sakai Chemical Industry Co., Ltd.'s system] and 6.51 parts following is had adsorption site and have a carbon-to-carbon double bond is dissolved in 33.45 parts the propylene glycol monomethyl ether, is heated to 70 ℃ under stream of nitrogen gas.To wherein add 0.06 part 2, two (2, the 4-methyl pentane nitrile) [V-65, Wako Pure Chemical Industries, Ltd.'s systems] of 2 '-azo also heated 3 hours.The V-65 that further adds 0.06 part reacted 3 hours down at 70 ℃ under stream of nitrogen gas.Be cooled to room temperature, obtained 30% solution of sulfhydryl compound of the present invention shown below (chain-transferring agent 6) thus.

[synthesis example: chain-transferring agent 7 synthetic]

Except with 6.51 parts in above-mentioned chain-transferring agent 6 synthetic have adsorption site and have the compound (m-6) of carbon-to-carbon double bond and 33.45 parts propylene glycol monomethyl ether change to 5.80 parts following have adsorption site and have the compound (m-7) of carbon-to-carbon double bond and 31.81 parts propylene glycol monomethyl ether, with synthetic 30% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 7) of above-mentioned chain-transferring agent 6.

[synthesis example: chain-transferring agent 8 synthetic]

Except with 6.51 parts in above-mentioned chain-transferring agent 6 synthetic have adsorption site and have the compound (m-6) of carbon-to-carbon double bond and 33.45 parts propylene glycol monomethyl ether change to 12.46 parts following have adsorption site and have the compound (m-8) of carbon-to-carbon double bond and 47.35 parts dimethyl formamide, with synthetic 30% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 8) of above-mentioned chain-transferring agent 6.

[synthesis example: chain-transferring agent 9 synthetic]

Except with 6.51 parts in above-mentioned chain-transferring agent 6 synthetic have adsorption site and have the compound (m-6) of carbon-to-carbon double bond and 33.45 parts propylene glycol monomethyl ether change to 10.46 parts following have adsorption site and have the compound (m-9) of carbon-to-carbon double bond and 42.67 parts dimethyl formamide, with synthetic 30% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 9) of above-mentioned chain-transferring agent 6.

[synthesis example: chain-transferring agent 10 synthetic]

Except with 6.51 parts in above-mentioned chain-transferring agent 6 synthetic have adsorption site and have the compound (m-6) of carbon-to-carbon double bond and 33.45 parts propylene glycol monomethyl ether change to 7.86 parts following have adsorption site and have the compound (m-10) of carbon-to-carbon double bond and 36.61 parts propylene glycol monomethyl ether, with synthetic 30% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 10) of above-mentioned chain-transferring agent 6.

[synthesis example: chain-transferring agent 11 synthetic]

Except with 6.51 parts in above-mentioned chain-transferring agent 6 synthetic have adsorption site and have the compound (m-6) of carbon-to-carbon double bond and 33.45 parts propylene glycol monomethyl ether change to 11.72 parts following have adsorption site and have the compound (m-11) of carbon-to-carbon double bond and 45.61 parts propylene glycol monomethyl ether, with synthetic 30% solution that has similarly obtained sulfhydryl compound of the present invention shown below (chain-transferring agent 11) of above-mentioned chain-transferring agent 6.

[synthesis example: chain-transferring agent 12 synthetic]

The compound (m-6) that 4.89 parts pentaerythrites four (3-mercaptopropionic acid ester) [PEMP: Sakai Chemical Industry Co., Ltd.'s system] and 3.90 parts following is had adsorption site and have a carbon-to-carbon double bond is dissolved in 20.51 parts the propylene glycol monomethyl ether, is heated to 70 ℃ under stream of nitrogen gas.To wherein add 0.04 part 2, two (2, the 4-methyl pentane nitrile) [V-65, Wako Pure Chemical Industries, Ltd.'s systems] of 2 '-azo also heated 3 hours.The V-65 that further adds 0.04 part reacted 3 hours down at 70 ℃ under stream of nitrogen gas.Be cooled to room temperature, obtained 30% solution of sulfhydryl compound of the present invention shown below (chain-transferring agent 12) thus.

[synthesis example: chain-transferring agent 13 synthetic]

The compound (m-6) that 7.83 parts dipentaerythritols six (3-mercaptopropionic acid ester) [DPMP: Sakai Chemical Industry Co., Ltd.'s system] and 4.55 parts following is had adsorption site and have a carbon-to-carbon double bond is dissolved in 28.90 parts the propylene glycol monomethyl ether, is heated to 70 ℃ under stream of nitrogen gas.To wherein add 0.04 part 2, two (2, the 4-methyl pentane nitrile) [V-65, Wako Pure Chemical Industries, Ltd.'s systems] of 2 '-azo also heated 3 hours.The V-65 that further adds 0.04 part reacted 3 hours down at 70 ℃ under stream of nitrogen gas.Be cooled to room temperature, obtained 30% solution of sulfhydryl compound of the present invention shown below (chain-transferring agent 13) thus.

Show the synthesis example of (D-1-2) specific dispersion resin below.

[synthesis example: B-1-1's is synthetic]

With 20% solution of 23.37 parts the chain-transferring agents that obtain as described above 1,18 parts methyl methacrylate (MMA; Monomer) and 2 parts methacrylic acid (MAA; Monomer) mixed solution flows down at nitrogen and is heated to 80 ℃.To wherein add 0.007 part 2,2 '-azoisobutyronitrile [the pure pharmaceutical worker of AIBN and light industry (strain) system] also heats 3 hours, and then adds 0.007 part AIBN, flows down 80 ℃ of reactions 3 hours at nitrogen.And then add 0.007 part AIBN, flow down 80 ℃ of reactions 3 hours at nitrogen.Be chilled to room temperature then, use acetone diluted.Use a large amount of methanol (1/1 weight ratio) to precipitate again, carry out vacuum drying then, obtain the solid of (B-1) the specific dispersion resin (B-1-1: the weight-average molecular weight in polystyrene conversion is 32000) among the present invention shown below of 21 parts thus.Wherein, weight-average molecular weight is to measure by GPC (gel permeation chromatography) under the following conditions, is expressed as the polystyrene conversion value.

Use post: TSK gel Multipore HXL-M (pore polydispersion type linear columns (linearcolumn)), TOSOH CORPORATION system

Eluent: THF (tetrahydrofuran)

Flow: 1.0mL/ branch

Temperature: 40 ℃

Testing conditions: RI (reflectivity index) detects

GPC apparatus system: the high speed GPC device same form (HLC-8220, TOSOHCORPORATION system)

In addition, further add entry in the solution that obtains in that (B-1) specific dispersion resin B-1-1 is dissolved in 1-methoxyl-2-propyl alcohol, the solution that obtains is carried out acid-base titration with the potassium hydroxide aqueous solution of 1 equivalent, measure acid number thus.The acid number that is somebody's turn to do (B-1) specific dispersion resin B-1-1 is 60mg/g.

[synthesis example: B-1-2～B-1-5's is synthetic]

And then, except with the amount of the kind of chain-transferring agent, monomer and amount, AIBN, and intermediate processing is changed as following table 1 again, other and above-mentioned B-1-1's is synthetic same, thereby has obtained the illustration dispersion resin B-1-2～B-1-5 as the concrete example of (D-1-1) specific dispersion resin.In addition, in table 1, show the acid number of each (B-1) specific dispersion resin in the lump.

Table 1

(B-1) specific dispersion resin	Chain-transferring agent	Monomer	AIBN	Intermediate processing again	The receipts amount	Weight-average molecular weight	Acid number (mg/g)
								B-1-2	22.45 the solution of part 2	1 part of 19 parts of MAA of MMA	0.007 part	Precipitate again with methanol (1/1)	21 parts	31000	30
B-1-3	11.93 the solution of part 3	2 parts of 18 parts of MAA of MMA	0.007 part	Precipitate again with methanol (1/1)	20 parts	30000	62
								B-1-4	8.73 the solution of part 4	1 part of 19 parts of MAA of MMA	0.007 part	Precipitate again with methanol (1/1)	16 parts	26000	31
B-1-5	8.36 the solution of part 5	2 parts of 18 parts of MAA of MMA	0.007 part	Precipitate again with methanol (1/1)	18 parts	32000	63

MMA ... methyl methacrylate

MAA ... methacrylic acid

Show the structure of synthetic (B-1) specific dispersion resin B-1-2～B-1-5 below.

[synthesis example: B-1-6's is synthetic]

30% solution of 19.11 parts the chain-transferring agents that obtain as described above 6,20 parts the mixed solution of methyl methacrylate flowed down at nitrogen be heated to 80 ℃.To wherein add 0.013 part 2,2 '-azoisobutyronitrile [the pure pharmaceutical worker of AIBN and light industry (strain) system] also heated 3 hours.And then add 0.013 part AIBN, flow down 80 ℃ of reactions 3 hours at nitrogen.Be cooled to room temperature then, use acetone diluted.Use a large amount of methyl alcohol that it is precipitated again, carry out vacuum drying then, obtain the solid of (B-1) the specific dispersion resin (B-1-6: the weight-average molecular weight in polystyrene conversion is 12000) among the present invention shown below of 13 parts thus.

The acid number that is somebody's turn to do (B-1) specific dispersion resin B-1-6 is 47mg/g.

[synthesis example: B-1-7's is synthetic]

Except in above-mentioned B-1-6 synthetic, 30% solution of 19.11 parts chain-transferring agents 6 is modified to 9.56 parts, 0.013 part AIBN is modified to beyond 0.007 part, other and above-mentioned B-1-6's is synthetic same, thereby obtains the solid of 14 parts of macromolecular compounds of the present invention shown below (B-1-7: the weight-average molecular weight in polystyrene conversion is 20000).

The acid number that is somebody's turn to do (B-1) specific dispersion resin B-1-7 is 28mg/g.

[synthesis example: B-1-8's is synthetic]

Except in above-mentioned B-1-6 synthetic, 20 parts methyl methacrylates are modified to beyond the methacrylic acid 2-hydroxyl ethyl ester of 19.5 parts butyl methacrylate and 8.5 parts, other and above-mentioned B-1-6's is synthetic same, thereby obtains the solid of 13 parts of (B-1) of the present invention specific dispersion resins shown below (B-1-8: the weight-average molecular weight in polystyrene conversion is 13000).

The acid number that is somebody's turn to do (B-1) specific dispersion resin B-1-8 is 43mg/g.

[synthesis example: B-1-9～B-1-20's is synthetic]

And then, except with the amount of the kind of chain-transferring agent, monomer and amount, AIBN, and intermediate processing was changed as following table 2 again, other was equally synthetic with above-mentioned B-1-6's, thereby obtains (B-1) the specific dispersion resin B-1-9～B-1-20 among the present invention.In addition, in table 2, show the acid number of each (B-1) specific dispersion resin in the lump.

Table 2

(B-1) specific dispersion resin	Chain-transferring agent	Monomer	AIBN	Intermediate processing again	The receipts amount	Weight-average molecular weight	Acid number (mg/g)
								B-1-9	9.56 the solution of part 6	1 part of 19 parts of MAA of MMA	0.007 part	Precipitate again with methanol (1/1)	15 parts	23000	55
B-1-10	9.56 the solution of part 6	2 parts of 18 parts of MAA of MMA	0.007 part	Precipitate again with methanol (1/1)	15 parts	24000	85
								B-1-11	9.94 the solution of part 6	2 parts of 18 parts of AA of MMA	0.007 part	Precipitate again with methanol (1/1)	17 parts	20000	102
B-1-12	9.03 the solution of part 6	2 parts of 18 parts of MK エ of MMA ス テ Le-SA	0.007 part	Precipitate again with methanol (1/1)	16 parts	23000	36
								B-1-13	18.18 the solution of part 7	20 parts of MMA	0.013 part	Precipitate again with methyl alcohol	11 parts	13000	43
B-1-14	9.09 the solution of part 7	20 parts of MMA	0.007 part	Precipitate again with methyl alcohol	12 parts	23000	24
								B-1-15	18.18 the solution of part 7	8.5 parts of 19.5 parts of HEMA of BMA	0.013 part	Precipitate again with methyl alcohol	11 parts	16000	35
B-1-16	13.53 the solution of part 8	20 parts of MMA	0.007 part	Precipitate again with methyl alcohol	13 parts	27000	21
								B-1-17	12.19 the solution of part 9	20 parts of MMA	0.007 part	Precipitate again with methyl alcohol	11 parts	26000	43
B-1-18	10.46 the solution of part 10	1 part of 19 parts of MAA of MMA	0.007 part	Precipitate again with methanol (1/1)	17 parts	30000	31
								B-1-19	8.69 the solution of part 11	1 part of 19 parts of MAA of MMA	0.007 part	Precipitate again with methanol (1/1)	18 parts	31000	27
B-1-20	11.72 the solution of part 12	20 parts of MMA	0.013 part	Precipitate again with methyl alcohol	11 parts	11000	41

MMA ... methyl methacrylate

MAA ... methacrylic acid

AA ... acrylic acid

BMA ... n-BMA

HEMA ... methacrylic acid 2-hydroxyl ethyl ester

MK エ ス テ Le-SA (Xin Zhong village chemical industry system)

Show the structure of synthetic (B-1) specific dispersion resin B-1-9～B-1-20 below.

[synthesis example: B-1-21's is synthetic]

The methacrylic acid of 30% solution of 4.99 parts the chain-transferring agents that obtain as described above 13,19.0 parts methyl methacrylate and 1.0 parts, 4.66 parts the mixed solution of propylene glycol monomethyl ether flowed down at nitrogen be heated to 90 ℃.Stir on one side this mixed solution, on one side with dripped in 2.5 hours 0.139 part 2,2 '-azo-bis-iso-dimethyl [the pure pharmaceutical worker's industry of V-601 and light (strain) is made], 5.36 parts propylene glycol monomethyl ether, 9.40 parts the mixed solution of propylene glycol methyl ether acetate.After drip finishing,, add 2,2 '-azo-bis-iso-dimethyl of 0.046 part, 4.00 parts the mixed solution of propylene glycol methyl ether acetate then 90 ℃ of reactions 2.5 hours down.And then reacted again 2 hours.In reactant liquor, add 1.52 parts propylene glycol monomethyl ether, 21.7 parts propylene glycol methyl ether acetate, be cooled to room temperature, obtain the solution (propylene glycol methyl ether acetates of the specific dispersion resin of 30 quality %, the propylene glycol monomethyl ether of 21 quality %, 49 quality %) of (B-1) specific dispersion resin involved in the present invention shown below (B-1-21: the weight-average molecular weight in polystyrene conversion is 24000) thus.

The acid number that is somebody's turn to do (B-1) specific dispersion resin B-1-21 is 48mg/g.

[synthesis example: B-1-22's is synthetic]

Except 30% solution that synthesizes middle 4.99 parts the chain-transferring agent of putting down in writing 13 with above-mentioned B-1-21,19.0 the methyl methacrylate of part, methacrylic acid with 1.0 parts, 4.66 the mixed solution of the propylene glycol monomethyl ether of part is modified to 30% solution of 5.03 parts chain-transferring agent 13,18.0 the methyl methacrylate of part, methacrylic acid with 2.0 parts, 4.66 beyond the mixed solution of the propylene glycol monomethyl ether of part, other and the synthetic of above-mentioned B-1-21 similarly make it react solution (the specific dispersion resin of 30 quality % of (B-1) the of the present invention specific dispersion resin shown below (B-1-22: the weight-average molecular weight in polystyrene conversion is 25000) that obtains thus, the propylene glycol monomethyl ether of 21 quality %, the propylene glycol methyl ether acetate of 49 quality %).

The acid number that is somebody's turn to do (B-1) specific dispersion resin B-1-22 is 78mg/g.

[(D-1-3) containing the polymkeric substance of the structural unit shown in the general formula (a): (D-1-3) specific dispersion resin]

Then, the polymkeric substance (following suitably be called " (D-1-3) specific dispersion resin ") that contains the structural unit shown in the following general formula (a) is illustrated.

General formula (a)

In general formula (a), R ¹Expression hydrogen or methyl, R ^2aThe expression alkylidene, Z ¹Expression nitrogen heterocyclic ring structure.

As R ^2aThe alkylidene of expression, can list methylene, ethylidene, 1,3-propylidene, 1,4-butylidene, 1,6-hexylidene, 2-hydroxy propylidene, inferior methoxyl, inferior ethoxyl, inferior methoxycarbonyl, methylene sulfenyl etc. wherein are preferably methylene, inferior methoxyl, inferior methoxycarbonyl, methylene sulfenyl.

In above-mentioned general formula (a), Z ¹Expression nitrogen heterocyclic ring structure can list the nitrogen heterocyclic ring structure that for example has pyridine ring, pyridazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, quinoline ring, acridine ring, benzothiazine ring, benzoxazine ring, acridone ring, anthraquinone ring, benzimidazole ring structure, benzotriazole ring structure, benzothiazole ring structure, cyclic amide structure, ring-type urea structure, cyclic imide structure particularly.

Wherein, Z ¹Shown nitrogen heterocyclic ring structure optimization is following general formula (b) or the represented structure of general formula (c).

General formula (b) general formula (c)

In above-mentioned general formula (b), X ¹Expression be selected from singly-bound, alkylidene (for example methylene, ethylidene, propylidene, 1,3-propylidene, 1,4-butylidene etc.) ,-O-,-S-,-NR-and-C (=O)-in any.In addition, R represents hydrogen atom or alkyl here, represents the alkyl under the situation of alkyl as R, can list for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, n-octyl, 2-ethylhexyl, n-octadecane base etc.

Wherein, X ¹Be preferably singly-bound, methylene ,-O-,-C (=O)-, be preferably especially-C (=O)-.

In above-mentioned general formula (b) and general formula (c), ring A, ring B and ring C represent aromatic rings respectively independently.As this aromatic rings, for example can list, phenyl ring, naphthalene nucleus, indenes ring, azulenes ring, fluorenes ring, anthracene nucleus, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, benzothiazine ring, benzoxazine ring, acridone ring, anthraquinone ring etc., wherein be preferably phenyl ring, naphthalene nucleus, anthracene nucleus, pyridine ring, benzoxazine ring, acridine ring, benzothiazine ring, benzoxazine ring, acridone ring, anthraquinone ring, be preferably phenyl ring, naphthalene nucleus, pyridine ring especially.

Listed the preferred concrete example [illustration structural unit (M '-1)～(M '-7)] of structural unit shown in the general formula (a) below, but the present invention is not limited to these.

Structural unit shown in the above-mentioned general formula (a) in (D-1-3) specific dispersion resin, preferably contains 2～50 quality %, more preferably contains 4～30 quality %, especially preferably contains 5～20 quality %.

(D-1-3) specific dispersion resin among the present invention is preferably especially except containing the structural unit shown in the above-mentioned general formula (a), also contain the polyreactive oligomers that the has ethylenical unsaturated double bonds endways graft copolymer as copolymerization units.

As such polyreactive oligomers that has ethylenical unsaturated double bonds endways, can list and the same oligomer of polyreactive oligomers that uses as copolymer composition in above-mentioned (B-2) specific dispersion resin, its preferred configuration (oligomer shown in the general formula (II)), preference (concrete example) are too.

In order to obtain specific acid number, (D-1-3) the specific dispersion resin among the present invention more preferably contain have acidic group monomer (structural unit) as copolymer composition.

As monomer, can list (methyl) acrylic acid, to the succinic anhydride addition product of vinyl benzoic acid, maleic acid, fumaric acid, itaconic acid, (methyl) acrylic acid 2-hydroxyl ethyl ester, the phthalic anhydride addition product of (methyl) acrylic acid 2-hydroxyl ethyl ester etc. with acidic group.

(D-1-3) specific dispersion resin among the present invention, in the scope of not damaging its effect, but the vinyl monomer that can also contain copolymerization is as copolymer composition.

As spendable vinyl monomer here, can list and the same monomer of vinyl monomer that in above-mentioned (B-2) specific dispersion resin, uses as copolymer composition, its preferred preference is too.

In addition, as the preferred configuration of specific dispersion resin involved in the present invention, can preferably list the structural unit shown in the above-mentioned general formula (a) that contains 2～50 quality % and contain the multipolymer of vinyl monomer of the structural unit with acidic group, 0～20 quality % of the polyreactive oligomers that has ethylenical unsaturated double bonds endways, 1～30 quality % of 10～90 quality %.

Listed together below and can be suitable for concrete example [exemplary compounds (I)～(XV)] and the weight-average molecular weight thereof that colored pattern of the present invention forms (D-1-3) the specific dispersion resin that uses with composition, but the present invention is not limited to these.

Exemplary compounds (I): the multipolymer (copolymerization ratio 10/4/86 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-1); weight-average molecular weight is 50000, and acid number is 26mg/g)

Exemplary compounds (II): the multipolymer (copolymerization ratio 10/33/57 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-1); weight-average molecular weight is 30000, and acid number is 214mg/g)

Exemplary compounds (III): the multipolymer (copolymerization ratio 5/28/10/57 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/methacrylic acid 2-hydroxyl ethyl ester/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-1); weight-average molecular weight is 40000, and acid number is 182mg/g)

Exemplary compounds (IV): the multipolymer (copolymerization ratio 15/5/10/70 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/benzyl methacrylate multipolymer/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-1); weight-average molecular weight is 60000, and acid number is 33mg/g)

Exemplary compounds (V): the multipolymer (copolymerization ratio 20/20/60 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-5); weight-average molecular weight is 80000, and acid number is 130mg/g)

Exemplary compounds (VI): the multipolymer (copolymerization ratio 10/20/70 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-5); weight-average molecular weight is 30000, and acid number is 130mg/g)

Exemplary compounds (VII): the multipolymer (copolymerization ratio 25/20/55 (quality %) of polymethylmethacrylate that can form the monomer/acrylic/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-5); weight-average molecular weight is 60000, and acid number is 156mg/g)

Exemplary compounds (VIII): the multipolymer (copolymerization ratio 15/15/70 (quality %), weight-average molecular weight are 40000, and acid number is 117mg/g) of butyl polyacrylate that can form the monomer/acrylic/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-5)

Exemplary compounds (IX): the multipolymer (copolymerization ratio 15/5/5/75 (quality %) of polymethylmethacrylate that can form the monomer/acrylic/methacrylic acid 2-hydroxyl ethyl ester/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-5); weight-average molecular weight is 80000, and acid number is 39mg/g)

Exemplary compounds (X): the multipolymer (copolymerization ratio 12/17/71 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-6); weight-average molecular weight is 50000, and acid number is 110mg/g)

Exemplary compounds (XI): the multipolymer (copolymerization ratio 10/12/78 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-6); weight-average molecular weight is 20000, and acid number is 78mg/g)

Exemplary compounds (XII): the multipolymer (copolymerization ratio 10/10/50/30 (quality %) that can form the monomer/methacrylic acid/benzyl methacrylate/methoxy polyethylene glycol methacrylate-styrene polymer of above-mentioned illustration structural unit (M '-6), weight-average molecular weight is 35000, and acid number is 65mg/g)

Exemplary compounds (XIII): the multipolymer (copolymerization ratio 5/5/10/80 (quality %) of polystyrene that can form the monomer/acrylic/methacrylic acid 2-hydroxyl ethyl ester/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-6); weight-average molecular weight is 20000, and acid number is 39mg/g)

Exemplary compounds (XIV): the multipolymer (copolymerization ratio 8/12/10/70 (quality %) of polymethylmethacrylate that can form the monomer/methacrylic acid/methyl methacrylate/terminal methyl group propylene acidylate of above-mentioned illustration structural unit (M '-7); weight-average molecular weight is 70000, and acid number is 78mg/g)

Exemplary compounds (XV): the multipolymer (copolymerization ratio 15/20/65 (quality %), weight-average molecular weight are 15000, and acid number is 156mg/g) that can form the monomer/acrylic/methoxy polyethylene glycol methacrylate-styrene polymer of above-mentioned illustration structural unit (M '-7)

As the multipolymer as described above of (D-1-3) the specific dispersion resin among the present invention, can be by obtaining with the monomer of the become formation unit shown in the above-mentioned general formula (a) and according to the polyreactive oligomers and the free radical polymerization in solvent of other monomer of hope and usefulness.In this free radical polymerization, can use and the same radical polymerization initiator, the chain-transferring agent that when synthesizing (D-1-2) specific dispersion resin, use.

The content of (D) dispersion resin is preferably 15～30 quality % with respect to all solids composition (quality) of said composition in colored pattern of the present invention forms with composition, more preferably 18～27 quality %.When the content of (B) dispersion resin is in above-mentioned scope, can shorten (A) dispersing of pigments time, so the stability after can guaranteeing for a long time to disperse in addition is preferred.

[other spreading agent]

Colored pattern of the present invention forms with in the composition, as (D) dispersion resin, except above-mentioned preferred dispersion resin (D-1-1), (D-1-2) or (D-1-3), can also and with present known spreading agent (pigment dispersing agent).

As known spreading agent (pigment dispersing agent), [for example can list macromolecule dispersing agent, daiamid and salt thereof, high molecular unsaturated acid ester, modified polyurethane, modified poly ester, poly-(methyl) acrylate of modification, (methyl) acrylic copolymer], and polyxyethylated phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc.

Macromolecule dispersing agent can also be categorized into straight chain shape macromolecule, terminal-modified type macromolecule, graft type macromolecule, block type polymer from its structure.

Macromolecule dispersing agent has on the surface that is adsorbed on pigment, prevent to condense such effect again.Therefore, as the preferred structure of macromolecule dispersing agent, can list the terminal-modified type macromolecule, graft type macromolecule, the block type polymer that have to the position of surface of pigments anchoring.On the other hand, by to the surface of pigments modification, pigment derivative has the effect that promotes macromolecule dispersing agent absorption.

As the concrete example of the spendable known spreading agent of the present invention (pigment dispersing agent), can list BYK Chemie corporate system " Disperbyk-107 (carboxylate); 130 (polyamide); 161; 162; 163; 164,165,166,170 (high-molecular copolymers) "; EFKA corporate system " EFKA4047,4050,4010,4165 (polyurethaness), EFKA4330,4340 (segmented copolymers), 4400,4402 (modified polyacrylates), 5010 (polyesteramides), 6220 (fatty acid polyesters), 6745 (phthalocyanine derivates), 6750 (azo derivatives) "; system " ア ジ ス パ one (Ajisper) PB821 of monosodium glutamate Off ア イ Application テ Network ノ company (Ajinomoto Fine-Techno.Co.Inc), PB822 "; chemical company of common prosperity society system " Off ロ one レ Application (FLOWLEN) TG-710 (ammonia ester oligomer) "; " Port リ Off ロ one (POLYFLOW) No.50E, No.300 (acrylic copolymer) " nanmu originally changes into corporate system " デ イ ス パ ロ Application (DISPERON) #7004 (polyether ester), DA-703-50, DA-705, DA-725 "; KAO. Corp. SA's system " エ マ Le ゲ Application (EMULGEN) 920,930,935,985 (polyoxyethylene nonylplenyl ethers) "; " ア セ ミ Application (ACETAMIN) 86 (stearic amine acetic acid esters) "; system " ソ Le ス パ one ス (SOLSPERSE) 5000 (phthalocyanine derivates) of Le one Block リ ヅ, one Le company (Lubrizol Corporation), 22000 (AZO pigments derivants, 13240 (polyesteramines), 3000,17000,27000 (terminal part has the macromolecule of function portion) "; 24000; 28000; 32000; 38500 (graft type macromolecules); daylight ケ ミ カ Le corporate system " ニ Star コ one Le (NIKKOL) T106 (polyoxyethylene sorbitan monoleate), MYS-IEX (polyoxyl 40 stearate) " etc.

And situation with known spreading agent as described above under, with respect to (D-1) and content (D-2) as above-mentioned preferred dispersion resin, can be preferably in the scope use of 10～100 quality %.

[(A) pigment]

Colored pattern of the present invention forms with in the composition, as (A) pigment, can suitably select to use from present known various inorganic pigments or organic pigment, but the pigment of primary particle size as 8nm～15nm is used in preferred selection.

That is to say, no matter (A) pigment that uses in color filter forms with composition is inorganic pigment or organic pigment, if consider preferred high permeability, it is little then preferably to use granularity to try one's best, in addition, even from the viewpoint of adding, viscosity does not also raise, the primary particle size of pigment (mean grain size) also needs to be 8nm～15nm, more preferably 8nm～12nm.

In addition, here the primary particle size of pigment can use following method to measure, promptly the method for taking a picture, the method for taking a picture by transmission electron microscope (TEM) by high resolution scanning Electronic Speculum (SEM), measure particle specific surface area and the method that converts, in dispersion medium, use small angle X ray scattering to carry out method for measuring, be embedded in the binder film and and carry out method for measuring etc. by gas absorption by the reflective film X ray, wherein, from the viewpoint of precision, preferably use high-resolution SEM method, use the method for TEM, the method by gas absorption.The present invention adopts the value of using high-resolution SEM to measure.

As above-mentioned inorganic pigment, can list represented metallic compounds such as metal oxide, metal complex salts, as concrete example, can enumerate tap a blast furnace, the metal oxide of cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony etc. and composite oxides of above-mentioned metal etc.

As above-mentioned organic pigment, for example can list,

C.I. pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;

C.I. pigment orange 36,38,43,71;

C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;

C.I. pigment violet 19,23,32,37,39;

C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66;

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

C.I. pigment brown 25,28;

C.I. pigment black 1,7;

Carbon black etc.

Though do not have particular determination among the present invention, more preferably following pigment.

C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185,

C.I. pigment orange 36,71,

C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264,

C.I. pigment violet 19,23,37,

C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66,

C.I. pigment black 7.

These organic pigments can use separately, perhaps can be used in combination various in order to improve colour purity.Show the concrete example of combination below.

For example, as red pigment, can use separately or the pigment that mixes of at least a and diazonium class yellow uitramarine wherein, isoindoline class yellow uitramarine, quinophthalone class yellow uitramarine Huo perylene class red pigment anthraquinone class pigment, perylene class pigment, diketopyrrolo-pyrrole (Diketopyrrolopyrrole) class pigment.For example as anthraquinone class pigment, can list C.I. paratonere 177 Zuo Wei perylene class pigment, can list C.I. paratonere 155, C.I. paratonere 224, as diketopyrrolo-pyrrole class pigment, can list C.I. paratonere 254, they mix use with C.I. pigment yellow 13 9, are preferred from the good this point of colorrendering quality.In addition, from obtaining sufficient colour purity and suppressing that (the NTSC standard: the viewpoint that aim colour National Television Standards Committee standard) departs from mutually, the mass ratio of red pigment and yellow uitramarine be preferably 100: 5～100: 50 from NTSC.Particularly, as above-mentioned mass ratio, only is 100: 10～100: 30 scope.In addition, under situation, can contrast colourity and regulate the red pigment combination with one another.

In addition,, halogenated phthalocyanines class pigment can be used separately, maybe it use can be mixed with diazonium class yellow uitramarine, quinophthalone class yellow uitramarine, azomethine class yellow uitramarine or isoindoline class yellow uitramarine as viridine green.For example, be preferably C.I. pigment Green 7,36,37 and the pigment that mixes of C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, fast yellow (FAST YELLOW) Y-5688, pigment yellow E4GN, Huang (YELLOW) 5GN-01, C.I. pigment yellow 180 or C.I. pigment yellow 185.From the viewpoint that obtains sufficient colour purity and suppress to depart from mutually from the aim colour of NTSC, the mass ratio of viridine green and yellow uitramarine is preferably 100: 5～and 100: 150.Mass ratio is preferably 100: 30～100: 120 scope especially.

As blue pigment, can use phthalocyanine pigment separately, maybe it can be mixed use Yu the dioxazines violet pigment.For example be preferably the C.I. pigment blue 15: 6 pigment that mix with the C.I. pigment Violet 23.The mass ratio of blue pigment and violet pigment is preferably 100: 0～and 100: 50, more preferably 100: 5～100: 30.

In addition, as the pigment that black matrix" is used, can list that independent carbon black, titanium are black, iron oxide, titanium dioxide, or their pigment of mixing, be preferably the black combination of carbon black and titanium.In addition, from the viewpoint of dispersion stabilization, the mass ratio that carbon black and titanium are black is preferably 100: 0～100: 60 scope.

These pigment can be according to regulating purpose such as form and aspect and with more than 2 kinds.As obtaining the example of the method for the micro pigment of the particle diameter of preferred configuration in the present invention, can list following 3 kinds of methods etc.

(1) material that will become piece (bulk) carries out machinery and grinds by pulverizing to wait, thus the method for miniaturization (routing (Break down) method)

(2) pigment particles is become molecular state by dissolving or temporary transient returning such as distillation, the method for separating out with graininess (making up (Build up) method)

(3), when synthetic, generate the method for particulate pigment by the control reaction conditions

Rout method as above-mentioned (1), can list " the 4th edition experimental chemistry lecture " the 12nd volume of for example writing in Japanization association, year, 411～488 pages, the method for record during (strain) ball is kind.

As above-mentioned (2) structure method, can list and slowly make the solution contact aqueous medium that is dissolved with organic pigment, thereby make the method that pigment separates out (so-called coprecipitation (reprecipitation method): open in 2003-26972 communique put down in writing for example spy), use the method (open in No. 2002138216 communiques put down in writing for example spy) of supercritical fluid, subcritical fluids etc.

As the method for above-mentioned (3), can list the method for using microreactor (for example spy open 2005-307154 number, spy open 2006-193651 number, spy open 2006-193652 number, spy open 2006-193654 number, spy open 2006-193655 number, the spy opens 2006-263538 number and the spy open in 2006-272962 number each communique put down in writing) etc.

Colored pattern of the present invention forms with in (A) pigment in the composition, preferably, be the content of the pigment of 8nm～15nm as primary particle size, with respect to all solids composition (quality) of said composition, be preferably 40～60 quality %, more preferably 45～55 quality %.When the content of (A) pigment is in above-mentioned scope, can effectively guarantee the color characteristics that color depth is abundant and excellent, viscosity, the rerum natura with composition maintains in the scope of the present invention's regulation easily.

The compound of olefinic unsaturated group [(B) have]

Colored pattern of the present invention forms and contains the compound (the following polymerizable compound that suitably is called) that at least a (B) has the olefinic unsaturated group with composition.

Operable in the present invention polymerizable compound is the addition polymerization compound with at least one ethylenical unsaturated double bonds, is selected from the compound that has at least 1, is preferably the terminal ethylenic unsaturated bond more than 2.Such compounds is widely known by the people in this industrial field, and the present invention can not have particular determination ground to use these compounds.They can be for example monomer, and prepolymer i.e. 2 polymers, 3 polymers and oligomer, or their potpourri, and their chemical forms such as multipolymer.

As the example of monomer and multipolymer thereof, can list unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.), its ester class, amide-type.The amide-type that preferred ester, unsaturated carboxylic acid and the aliphatic polyamine compound that uses unsaturated carboxylic acid and aliphatic polyol compound to form forms.In addition, the also preferred addition reaction that uses the substituent esters of unsaturated carboxylic acids of nucleophilicity such as having hydroxyl, amino, sulfydryl or amide-type and simple function or polyfunctional isocyanates or epoxies, and with the dehydration condensation thing of simple function or polyfunctional carboxylic acid etc.In addition, also preferably have the addition reaction of substituent esters of unsaturated carboxylic acids of electrophilicity such as isocyanate group or epoxy radicals or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol, and then also preferably have the substituted reactant of the esters of unsaturated carboxylic acids of the substituents of leaving away such as halogen radical, tosyloxy or amide-type and simple function or polyfunctional alcohols, amine, thio-alcohol.In addition, as other example, can also use by the compound group of replacements such as unsaturated phosphonic acids, styrene, vinyl ether to replace above-mentioned unsaturated carboxylic acid.

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

As methacrylate, have 1,4-butylene glycol two (methacrylic acid) ester, triethylene glycol two (methacrylic acid) ester, neopentyl glycol two (methacrylic acid) ester, trimethylolpropane tris (methacrylic acid) ester, trimethylolethane trimethacrylate (methacrylic acid) ester, ethylene glycol bisthioglycolate (methacrylic acid) ester, 1,3 butylene glycol two (methacrylic acid) ester, hexanediol two (methacrylic acid) ester, pentaerythrite two (methacrylic acid) ester, pentaerythrite three (methacrylic acid) ester, pentaerythrite four (methacrylic acid) ester, dipentaerythritol two (methacrylic acid) ester, dipentaerythritol six (methacrylic acid) ester, D-sorbite three (methacrylic acid) ester, D-sorbite four (methacrylic acid) ester, two [right-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl] dimethylmethane, two-[right-(methacryloxy ethoxy) phenyl] dimethylmethanes etc.

As itaconate, ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1 are arranged, 3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc.As crotonates, ethylene glycol bisthioglycolate crotonates, tetramethylene glycol two crotonatess, pentaerythrite two crotonatess, D-sorbite four crotonatess etc. are arranged.As the iso-crotonic acid ester, ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, D-sorbite four iso-crotonic acid esters etc. are arranged.As maleate, ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc. are arranged.

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

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

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

CH ₂＝C(R)COOCH ₂CH(R’)OH (A)

(wherein, R and R ' expression H or CH ₃)

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

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

About the structure of these optical polymerism polymkeric substance (addition polymerization compound), use still separately and, can set arbitrarily according to the performance design of finished pigmented pattern with detailed using method such as, additions.For example, can select according to following such viewpoint.

Aspect sensitivity, the structure that the unsaturated group content of preferred per 1 molecule is many at most cases, is preferably more than 2 official's energy.In addition, promptly solidify film strength in order to improve colored pattern, it also can be the above compound of 3 officials energy, and then, and (for example with different functional number, different polymerism base, acrylate, methacrylate, styrene compound, vinyl ethers compound) compound, also be effectively to regulate the two method of sensitivity and intensity.From solidifying the viewpoint of sensitivity, the preferred compound that contains (methyl) acrylate structural more than 2 that uses more preferably uses the compound that contains more than 3, most preferably uses the compound that contains more than 4.In addition, the viewpoint from the development of solidifying sensitivity and unexposed portion preferably contains EO modification body.In addition, the viewpoint from the intensity of solidifying sensitivity and exposed portion preferably contains ammonia ester bond.

In addition, the selection of polyaddition compounds, using method, colored pattern of the present invention with other composition in the composition (is for example formed, (A) have specific primary particle size pigment, (C) Photoepolymerizationinitiater initiater, and according to hope and and (E) adhesive resin (alkali soluble resin) of usefulness) compatibility, dispersiveness also be key factor, for example, sometimes by using the low-purity compound or, can improving compatibility also with more than 2 kinds.In addition, colored pattern is being formed when being applied on the substrate etc. with composition,, can select ad hoc structure in order to improve the adaptation with substrate etc.

For above viewpoint, as preferred compound, can list bisphenol a diacrylate, bisphenol a diacrylate EO modification body, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acryloxy ethyl) isocyanuric acid ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc., in addition, as commercially available product, be preferably ammonia ester oligomer UAS-10, UAB-140 (adret state basic policy パ Le プ corporate system), DPHA-40H (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity corporate system).

Wherein, more preferably bisphenol a diacrylate EO modification body, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylate, dipentaerythritol acrylate, three (acryloxy ethyl) isocyanuric acid ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc., in addition, as commercially available product, more preferably DPHA-40H (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity corporate system).

In the present invention, (B) polymerizable compound can also be used in combination more than 2 kinds except a kind of independent use.

Form the content of using (B) polymerizable compound in the composition as colored pattern of the present invention, with respect to all solids composition of said composition, be preferably 1～90 quality %, more preferably 5～80 quality %, more preferably 10～70 quality %.When the content of polymerizable compound was in above-mentioned scope, curing reaction can fully carry out.

Particularly, when colored pattern of the present invention being formed the colored pattern that is used for color filter with composition and form, the scope of above-mentioned content is preferably 5～50 quality %, more preferably 7～50 quality %, more preferably 10～50 quality %.

[(C) Photoepolymerizationinitiater initiater]

Colored pattern of the present invention forms and contains at least a (C) Photoepolymerizationinitiater initiater with composition.

Photoepolymerizationinitiater initiater among the present invention is a polymeric compounds of decomposing and cause and promote the following compound that contains ethylenic unsaturated bond by light.Be preferably the material that has absorption in the zone of wavelength 300～500nm.In addition, Photoepolymerizationinitiater initiater can use separately, and also two or more kinds may be used.

As Photoepolymerizationinitiater initiater; for example can list organohalogen compounds, oxadiazole compound, carbonyls, acetal compound, benzoin compound, acridine compound, organic peroxide, azo-compound, coumarin compound, triazo-compound, Metallocenic compound, six aryl united imidazoles, organic boronic compound, disulfonic acid compound, oxime ester compound, salt compound, acylphosphanes (oxide) compound.

Below these all cpds are elaborated.

As organohalogen compounds, can list the compound of putting down in writing in the following document particularly, described document is: if " Bull Chem Soc Japan " 42 such as woodss, 2924 (1969), United States Patent (USP) the 3rd, 905, No. 815 instructionss, special public clear 46-4605 number, the spy opens clear 48-36281 number, the spy opens clear 55-32070 number, the spy opens clear 60-239736 number, the spy opens clear 61-169835 number, the spy opens clear 61-169837 number, the spy opens clear 62-58241 number, the spy opens clear 62-212401 number, the spy opens clear 63-70243 number, the spy opens clear 63-298339 number, M.P.Hutt " Journal of HeterocyclicChemistry " 1 (No3), (1970), can list trihalomethyl especially and replace De oxazole compound, s-triazine.

As s-triazine, more preferably on the s-triazine ring, combine at least 1 list, two, or three Striazine derivative of forming of halogen substituent methyl, for example can list 2 particularly, 4,6-three (monochloro methyl) s-triazine, 2,4,6-three (dichloromethyl) s-triazine, 2,4,6-three (trichloromethyl) s-triazine, 2-methyl-4,6-two (trichloromethyl) s-triazine, 2-n-pro-pyl-4,6-two (trichloromethyl) s-triazine, 2-(α, α, β-three chloroethyl)-4,6-two (trichloromethyl)-s-triazine, 2-phenyl-4,6-two (trichloromethyl) s-triazine, 2-(p-methoxyphenyl)-4,6-two (trichloromethyl) s-triazine, 2-(3, the 4-epoxy-phenyl)-4,6-two (trichloromethyl) s-triazine, 2-(rubigan)-4,6-two (trichloromethyl) s-triazine, 2-[1-(p-methoxyphenyl)-2, the 4-butadienyl]-4,6-two (trichloromethyl) s-triazine, 2-styryl-4,6-two (trichloromethyl) s-triazine, 2-(to methoxyl-styrene)-4,6-two (trichloromethyl) s-triazine, 2-(to the isopropoxystyrene base)-4,6-two (trichloromethyl) s-triazine, 2-(p-methylphenyl)-4,6-two (trichloromethyl) s-triazine, 2-(4-methoxyl naphthyl)-4,6-two (trichloromethyl) s-triazine, 2-thiophenyl-4,6-two (trichloromethyl) s-triazine, 2-benzylthio-4,6-two (trichloromethyl) s-triazine, 2,4,6-three (two bromomethyls) s-triazine, 2,4,6-three (trisbromomethyl) s-triazine, 2-methyl-4,6-two (trisbromomethyl) s-triazine, 2-methoxyl-4,6-two (trisbromomethyl) s-triazine etc.

Zuo Wei oxadiazole compound, can list 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 etc.

As carbonyls, can list benzophenone derivates such as benzophenone, Michler's keton, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl benzophenone; 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-methyl phenyl ketone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl-(4 '-(methyl mercapto) phenyl)-2-morpholinyl-1-acetone, 1,1,1-trichloromethyl-(to butyl phenyl) ketone, 2-benzyl-2-dimethylamino-acetophenone derivs such as 4-morpholinyl bromo benzophenone; Thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2, thioxanthone derivates such as 4-diisopropyl thioxanthones; The ESCAROL 507 ethyl ester, to benzoate derivatives such as diethylamino ethyl benzoate etc.

As acetal compound, can list benzyl dimethoxym ethane, benzyl-'beta '-methoxy ethyl acetal etc.

As the benzoin compound, can list benzoin iso-propylether, benzoin isobutyl ether, benzoin methylether, methyl o-benzoyl yl benzoic acid ester etc.

As the acridine compound, can list 9-phenylacridine, 1,7-two (9-acridinyl) heptane etc.

As the organic peroxy compound; for example can list; the peroxidating trimethylcyclohexanone; diacetone peroxide; 1; 1-two (tert-butyl hydroperoxide)-3; 3; the 5-trimethyl-cyclohexane; 1; 1-two (tert-butyl hydroperoxide) cyclohexane; 2; 2-two (tert-butyl hydroperoxide) butane; tert-butyl hydroperoxide; cumyl hydroperoxide; the diisopropyl benzene hydrogen peroxide; 2; 5-dimethylhexane-2; 5-diperoxy hydrogen; 1; 1; 3; the 3-tetramethyl butyl hydroperoxide; the tert-butyl peroxide cumyl; dicumyl peroxide; 2; 5-dimethyl-2; 5-two (tert-butyl hydroperoxide) hexane; 2; 5-oxalyl superoxide (oxanoylperoxide); succinic acid peroxide; benzoyl peroxide; peroxidating 2; 4-dichloro-benzoyl base; diisopropyl peroxydicarbonate; two-2-ethylhexyl peroxy dicarbonate; two-2-ethoxyethyl group peroxy dicarbonate; dimethoxy isopropyl peroxycarbonates; two (3-methyl-3-methoxyl butyl) peroxy dicarbonate; the tert-butyl hydroperoxide acetic acid esters; t-butylperoxy pivarate; tert-butyl hydroperoxide neodecanoic acid ester; the tert-butyl hydroperoxide caprylate; the tert-butyl hydroperoxide laurate; tertiary carbon acid esters ( one シ Le カ one ボ ネ one ト; tertial carbonate); 3; 3 '; 4; 4 '-four-(tert-butyl hydroperoxide carbonyl) benzophenone; 3; 3 '; 4; 4 '-four-(uncle's hexyl peroxidating carbonyl) benzophenone; 3; 3 '; 4,4 '-four-(p-isopropyl cumyl peroxidating carbonyl) benzophenone; carbonyl two (tert-butyl hydroperoxide dihydro two phthalic esters); carbonyl two (uncle's hexyl peroxidating dihydro two phthalic esters) etc.

As azo-compound, for example can list, open azo-compound of putting down in writing in the flat 8-108621 communique etc. the spy.

As coumarin compound, for example can list 3-methyl-5-amino-((guanamine-yl) amino)-3-phenyl cumarin, 3-chloro-5-diethylamino-((guanamine-yl) amino)-3-phenyl cumarin, 3-butyl-5-dimethylamino-((guanamine-yl) amino)-3-phenyl cumarin etc.

As triazo-compound, can list the organic azide of in No. 2848328 instructions of United States Patent (USP), No. 2852379 instructions of United States Patent (USP) and No. 2940853 instructions of United States Patent (USP), putting down in writing, 2,6-two (4-nitrine benzal base)-4-ethyl cyclohexanone (BAC-E) etc.

As Metallocenic compound, can list the spy and open clear 59-152396 communique, the spy opens clear 61-151197 communique, the spy opens clear 63-41484 communique, Te Kaiping 2-249 communique, Te Kaiping 2-4705 communique, various two cyclopentadiene titanium compounds of putting down in writing in the Te Kaiping 5-83588 communique, for example, the two phenyl titaniums of dicyclopentadienyl, dicyclopentadienyl two (2,6-two fluorobenzene-1-yl) titanium, dicyclopentadienyl two (2,4-two fluorobenzene-1-yl) titanium, dicyclopentadienyl two (2,4,6-trifluoro-benzene-1-yl) titanium, dicyclopentadienyl two (2,3,5,6-phenyl tetrafluoride-1-yl) titanium, dicyclopentadienyl two (2,3,4,5,6-phenyl-pentafluoride-1-yl) titanium, two (methyl cyclopentadienyl) two (2,6-two fluorobenzene-1-yl) titanium, two (methyl cyclopentadienyls) two (2,4,6-trifluoro-benzene-1-yl) titanium, two (methyl cyclopentadienyl) two (2,3,5,6-phenyl tetrafluoride-1-yl) titanium, two (methyl cyclopentadienyl) two (2,3,4,5,6-phenyl-pentafluoride-1-yl) titanium, and open flat 1-304453 communique the spy, the iron of putting down in writing in the Te Kaiping 1-152109 communique-aromatic hydrocarbons complex etc.

As six aryl united imidazoles, for example can list, at the fair 6-29285 communique of spy, United States Patent (USP) the 3rd, 479, No. 185, United States Patent (USP) the 4th, 311, No. 783, United States Patent (USP) the 4th, 622, wait all cpds of putting down in writing in each instructions No. 286, can list particularly, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-bromophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (neighbours, right-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,5 '-four (m-methoxyphenyl) bisglyoxaline, 2,2 '-two (neighbour, neighbour '-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (ortho-nitrophenyl base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (o-methyl-phenyl-)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-two (adjacent trifluorophenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline etc.

As the organic boronic salt compound, as object lesson, for example can list and open clear 62-143044 number the spy, the spy opens clear 62-150242 number, Te Kaiping 9-188685 number, Te Kaiping 9-188686 number, Te Kaiping 9-188710 number, the spy opens 2000-131837 number, the spy opens 2002-107916 number, specially permit No. 2764769, special hope waits each communique 2000-310808 number, and Kunz, the organic borate of Martin record in " Rad Tech ' 98.Proceeding April 19-22; 1998; Chicago " etc., open flat 6-157623 communique the spy, Te Kaiping 6-175564 communique, organic boron sulfonium complex of putting down in writing in the Te Kaiping 6-175561 communique or organic boron oxygen sulfonium complex, open flat 6-175554 communique the spy, organic boron iodine complex of putting down in writing in the Te Kaiping 6-175553 communique, open the You Ji Peng Phosphonium complex of putting down in writing in the flat 9-188710 communique the spy, open flat 6-348011 communique the spy, Te Kaiping 7-128785 communique, Te Kaiping 7-140589 communique, Te Kaiping 7-306527 communique, organic boron transition-metal coordination complex such as Te Kaiping 7-292014 communique etc.

As two sulphones, can list the spy and open the compound put down in writing in clear 61-166544 communique, the special 2001-132318 of the hope communique etc. etc.

As oxime ester compound, can list 1653-1660 at J.C.S.Perkin II (1979)), J.C.S.Perkin II (1979) 156-162, Journal of PhotopolymerScience and Technology (1995) 202-232, spy open the compound of putting down in writing in the 2000-66385 communique, opens the compound put down in writing in 2000-80068 communique, the special table 2004-534797 communique etc. the spy.

As salt compound, for example can list, at S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal etc., Polymer, 21, the diazo salt of record in 423 (1980), at United States Patent (USP) the 4th, 069, No. 055 instructions, the ammonium salt of putting down in writing in the Te Kaiping 4-365049 grade, at United States Patent (USP) the 4th, 069, No. 055, United States Patent (USP) the 4th, 069, record De phosphonium salt in No. 056 each instructions, at European patent the 104th, No. 143, No. the 339th, 049, United States Patent (USP), the 410th, No. 201 each instructions of United States Patent (USP), Te Kaiping 2-150848 number, salt compounded of iodine of putting down in writing in Te Kaiping 2-296514 number each communique etc.

The salt compounded of iodine that can be suitable for the present invention's use is a diaryl group iodized salt, and from the viewpoint of stability, it is preferably replaced by sub-property groups of power supply such as the alkyl more than 2, alkoxy, aryloxy group.In addition, as other the form of preferred salt compounded of iodine, preferably the triaryl salt compounded of iodine substituting group has cumarin, anthraquinone ring, and has salt compounded of iodine of absorption etc. more than 300nm.

The sulfonium salt that the present invention uses can be suitable for, European patent can be listed the 370th, No. 693, European patent the 390th, No. 214, No. the 233rd, 567, European patent, No. the 297th, 443, European patent, European patent the 297th, No. 442, United States Patent (USP) the 4th, 933, No. 377, No. the 161st, 811, United States Patent (USP), United States Patent (USP) the 410th, No. 201, United States Patent (USP) the 339th, No. 049, United States Patent (USP) the 4th, 760, No. 013, United States Patent (USP) the 4th, 734, No. 444, United States Patent (USP) the 2nd, 833, No. 827, Deutsche Bundespatent the 2nd, 904, No. 626, Deutsche Bundespatent the 3rd, 604, No. 580, Deutsche Bundespatent the 3rd, 604, the sulfonium salt of putting down in writing in No. 581 each instructionss, from the viewpoint of the sensitivity of stability, preferably they are replaced by the electrophilic group.It is bigger than 0 that the electrophilic group is preferably Hammett (Hammett) value.As preferred electrophilic group, can list halogen atom, carboxylic acid etc.

In addition, as other preferred sulfonium salt, a substituting group that can list triarylsulfonium salt has cumarin, anthraquinone ring, and has the sulfonium salt of absorption more than 300nm.As other preferred sulfonium salt, can list triarylsulfonium salt has aryloxy group, arylthio and have absorption more than 300nm in substituting group sulfonium salt.

In addition, as salt compound, can list people such as J.V.Crivello at Macromolecules, 10 (6), 1307 (1977), people such as J.V.Crivello is at J.PolymerSci., Polymer Chem.Ed., 17, the selenium salt of record in 1047 (1979), C.S.Wen etc. are at Teh, Proc.Conf.Rad.Curing ASIA, 478 pages, Tokyo, salt such as the middle record of Oct (1988) De Arsenic salt etc.

As acylphosphanes (oxide) compound, can list IRGACURE 819, Dalocure4265, the Dalocure TPO of Ciba Specialty Chemicals company (Ciba Specialty Chemicals Inc.) system etc.

As spendable Photoepolymerizationinitiater initiater among the present invention; viewpoint from the exposure sensitivity is preferably and is selected from the trihalomethyl compound in triazine class; the benzyl dimethyl acetal compound; alpha-hydroxyacetone compounds; the alpha-amido ketonic compound; the acylphosphanes compounds; the phosphinoxides compound; Metallocenic compound; oxime compound; the bisglyoxaline compounds; compounds; benzothiazole compound; benzophenone compound; acetophenone compounds and derivant thereof; cyclopentadiene-benzene-iron complex and salt thereof; halogen Jia oxadiazole compound; compound in the 3-aryl substituted cumarin compound.

More preferably trihalomethyl compound in triazine class, alpha-amido ketonic compound, acylphosphanes compounds, phosphinoxides compound, oxime compound, bisglyoxaline compounds, compounds, benzophenone compound, acetophenone compounds most preferably are at least a compound that is selected from trihalomethyl compound in triazine class, alpha-amido ketonic compound, oxime compound, bisglyoxaline compounds, the benzophenone compound.In addition, most preferably be the bisglyoxaline compounds.

The content of (C) Photoepolymerizationinitiater initiater is preferably 0.1～50 quality % with respect to all solids composition of said composition in colored pattern of the present invention forms with composition, and more preferably 0.5～30 quality % is preferably 1～20 quality % especially.In this scope, can obtain good sensitivity and pattern formation property.

In addition, (C) content of the Photoepolymerizationinitiater initiater weight that has the compound of ethylenical unsaturated double bonds with respect to above-mentioned (B) is preferably 5～100 quality %, and more preferably 10～60 quality % are preferably 15～50 quality % especially.In the time of in this scope, can obtain good curing characteristics.

[(E) adhesive resin (alkali soluble resin)]

Formed by the viewpoint of membrane property from improving, colored pattern of the present invention forms and preferably contains at least a alkali soluble resin as adhesive resin with composition.

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

As above-mentioned wire organic high molecular polymer, be preferably the polymkeric substance that has carboxylic acid at side chain.For example can list; open clear 59-44615 number the spy; special public clear 54-34327 number; special public clear 58-12577 number; special public clear 54-25957 number; the spy opens clear 59-53836 number; the spy opens the such methacrylic acid copolymer of record in each communique of clear 59-71048 number; acrylic copolymer; itaconic acid copolymer; the crotonic acid multipolymer; maleic acid; the maleic acid of partial esterification; and the acid cellulose derivant that has carboxylic acid at side chain; have the polymkeric substance of hydroxyl and the polymkeric substance of acid anhydrides addition etc., and then can also list the high molecular polymer that has (methyl) acryloyl group at side chain as preference.

Wherein, specially suitable is (methyl) benzyl acrylate/(methyl) acrylic copolymer or by multiple copolymer that (methyl) benzyl acrylate/(methyl) acrylic acid/other monomer forms.

In addition, as useful polymkeric substance, can also enumerate the multipolymer that the methacrylic acid 2-hydroxyl ethyl ester copolymerization of sening as an envoy to forms.This polymkeric substance can mix use with optional amount.

Except above-mentioned polymkeric substance, can also list the spy and open (methyl) acrylic acid 2-hydroxypropyl acrylate/polystyrene macromolecular monomer/methacrylic acid benzyl ester/methacrylic acid copolymer of putting down in writing in the flat 7-140654 communique, 2-hydroxyl-3-phenoxy propyl acrylate/polymethylmethacrylate macromonomer/methacrylic acid benzyl ester/methacrylic acid copolymer, methacrylic acid 2-hydroxyl ethyl ester/polystyrene macromolecular monomer/methyl methacrylate/methacrylic acid copolymer, methacrylic acid 2-hydroxyl ethyl ester/polystyrene macromolecular monomer/methacrylic acid benzyl ester/methacrylic acid copolymer etc.

About the concrete formation unit of alkali soluble resin, specially suitable be (methyl) acrylic acid and can with the multipolymer of other monomer of its copolymerization.

As above-mentioned can with other monomer of (methyl) acrylic acid copolymer, can list the compound of following (1)～(12).

(1) acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate, acrylic acid 3-hydroxypropyl acrylate, acrylic acid 4-hydroxy butyl ester, methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, methacrylic acid 3-hydroxypropyl acrylate, methacrylic acid 4-hydroxy butyl ester etc. have the esters of acrylic acid and the methyl acrylic ester of aliphatic hydroxyl.

(2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, acrylic acid pentyl ester, Hexyl 2-propenoate, 2-EHA, 2-ethyl hexyl acrylate, benzyl acrylate, acrylic acid 2-chloroethene ester, acrylic acid glycidyl esters, acrylic acid 3, alkyl acrylates such as 4-epoxycyclohexyl methyl esters, acrylic acid vinyl esters, acrylic acid 2-phenyl vinyl ester, acrylic acid 1-propenyl ester, allyl acrylate, acrylic acid 2-allyloxy ethyl ester, acrylic acid alkynes propyl ester.

(3) methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, the methacrylic acid pentyl ester, hexyl methacrylate, methacrylic acid 2-Octyl Nitrite, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid 2-chloroethene ester, methyl propenoic acid glycidyl base ester, methacrylic acid 3,4-epoxycyclohexyl methyl esters, the methacrylic acid vinyl esters, methacrylic acid 2-phenyl vinyl ester, methacrylic acid 1-propenyl ester, allyl methacrylate, methacrylic acid 2-allyloxy ethyl ester, alkyl methacrylates such as methacrylic acid alkynes propyl ester.

(4) acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-ethyl acrylamide, N-hexyl methyl acrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N phenyl acrylamide, N-nitrobenzophenone acrylamide, N-ethyl-N phenyl acrylamide, vinyl acrylamide, vinyl Methacrylamide, N, N-diallyl acrylamide, N, acrylamide or Methacrylamides such as N-diallyl Methacrylamide, allyl acrylamide, allyl methyl acrylamide.

(5) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ether and Vinyl phenyl ether.

(6) vinyl esters such as vinyl-acetic ester, chloroacetic acid vinyl esters, butyric acid vinyl esters, benzoic acid vinyl esters.

(7) styrene, α-Jia Jibenyixi, methyl styrene, 1-chloro-4-methyl-benzene, to phenylethylenes such as acetoxy-styrene.

(8) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone.

(9) olefines such as ethene, propylene, isobutylene, butadiene, isoprene.

(10) N-vinyl pyrrolidone, vinyl cyanide, methacrylonitrile etc.

(11) unsaturated amides such as maleimide, N-acryloyl group acrylamide, N-vinyl Methacrylamide, N-propiono Methacrylamide, N-(to chlorobenzene formacyl) Methacrylamide.

(12) be combined with heteroatomic methacrylic monomer in the α position.Can list the compound of putting down in writing in for example special 2001-115595 of hope instructions, the special 2001-115598 of the hope instructions.

Wherein, side chain have allyl, vinyl ester group and carboxyl (methyl) acrylate resin and the spy open 2000-187322 communique, spy open put down in writing in the 2002-62698 communique side chain have two keys alkali soluble resin or the spy open put down in writing in the 2001-242612 communique have film strength, the sensitivity of the alkali soluble resin of amide group, the balance excellence of development at side chain, so be suitable.

In addition, the fair 7-12004 of spy number, special fair 7-120041 number, special fair 7-120042 number, special fair 8-12424 number, spy open clear 63-287944 number, spy open clear 63-287947 number, spy open flat 1-271741 number, special be willing to flat 10-116232 number etc. in record the ammonia ester class binder polymer that contains acidic group or the spy open put down in writing among the 2002-107918 to have the intensity of ammonia ester class binder polymer of acidic group and two keys at side chain very excellent, so at anti-brush with hang down that to expose aspect adaptive be favourable.

In addition, open the film strength of the ethylidene ether modification polyvinyl alcohol binder polymer with acidic group of record among the 2001-318463 etc., the balance excellence of development European patent 993966, European patent 1204000, spy, so suitable.

And then as other water-soluble wire organic polymer, polyvinyl pyrrolidone, polyoxyethylene etc. is useful.In addition, for the intensity that improves cured film, pure soluble nylon, 2, the polyethers of 2-two (4-hydroxy phenyl) propane and chloropropylene oxide etc. also is useful.

These alkali soluble resins can be in atactic polymers, block polymer, the graft polymer etc. any.

The spendable alkali soluble resin of the present invention can synthesize by present known method.Specifically, can use the method for utilizing known radical polymerization.The kind of the temperature when preparing alkali soluble resin with radical polymerization, pressure, radical initiator and polymerizing conditions such as amount, solvent types can be set easily for those skilled in the art, also can determine condition by test.

As the solvent that uses when the synthetic alkali soluble resin, for example can list, tetrahydrofuran, ethylene dichloride, cyclohexanone, MEK, acetone, methyl alcohol, ethanol, glycol monoethyl ether, ethylene glycol monoethyl ether, 2-methoxy ethyl acetic acid esters, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, N, dinethylformamide, N,N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water etc.These solvents can use separately, or mix more than 2 kinds and use.

When synthesizing the alkali soluble resin that can use in the present invention,, can list known compounds such as azo-initiator, peroxide initiator as spendable radical polymerization initiator.

As (E) adhesive resin (alkali soluble resin) that uses in the present invention, preferably using acid number is 50～400mg/g, and weight-average molecular weight is 3,000～100,000 compound, more preferably acid number is at 50～300mg/g, further preferably in the scope of 50～200mg/g.In addition, (E) weight-average molecular weight of adhesive resin (alkali soluble resin) more preferably 3,000～70,000, and more preferably 4,000～50,000.

Polydispersity (weight-average molecular weight/number-average molecular weight) is preferably 1.0～10 scope, more preferably 1.0～5 scope.

Colored pattern of the present invention forms the content with (E) adhesive resin (alkali soluble resin) in the composition, is preferably 1～20 quality % with respect to all solids composition of said composition, and more preferably 2～15 quality % are preferably 3～12 quality % especially.

In addition, from making composition reach the viewpoint of physics value given to this invention easily, the mass ratio that contains that the content of preferred (E) adhesive resin that uses satisfies the compound that above-mentioned (B) have the olefinic unsaturated group/should (E) adhesive resin is a condition more than 1.2.

[organic solvent]

In order to regulate physics value etc., colored pattern of the present invention forms can contain organic solvent with composition.

As organic solvent, can enumerate the ester output class, ethyl acetate for example, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, the oxo methyl acetate, oxo ethyl acetate, the oxo butyl acetate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, and 3-oxo alkyl propionates class (for example, 3-methoxypropionic acid methyl esters such as 3-oxo methyl propionate and 3-oxo ethyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate), and 2-oxo methyl propionate, ethyl 2-oxopropanoate, with 2-oxo alkyl propionates such as 2-oxo propyl propionate (2-methoxypropionic acid methyl esters for example, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-oxo-2 Methylpropionic acid methyl esters, 2-oxo-2 Methylpropionic acid ethyl ester, 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester), and methyl pyruvate, ethyl pyruvate, Propyl pyruvate, the acetate methyl acetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, 2-ketobutyric acid ethyl ester etc.;

Ethers, for example diethylene glycol dimethyl ether, tetrahydrofuran, glycol monoethyl ether, ethylene glycol monoethyl ether, methylcellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol propyl ether acetic acid esters etc.;

Ketone, for example MEK, cyclohexanone, 2-heptanone, 3-heptanone etc.;

Aromatic hydrocarbon based, for example toluene, dimethylbenzene etc.

Wherein, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, ethyl carbitol acetic acid esters, acetate of butyl carbitol, propylene glycol methyl ether acetate etc. are suitable.

Solvent can also be used in combination more than 2 kinds except can using separately.

[other composition]

Colored pattern of the present invention forms uses composition, above-mentioned except containing (A)～(D), (E) composition and solvent as the preferred optional composition, can also contain fluorine class organic compound as required, thermal polymerization prevents agent, various adjuvants such as other filling agent, other spreading agent except above-mentioned (D) dispersion resin and the macromolecular compound except (E) adhesive resin (alkali soluble resin), surfactant, adhesion promotor, antioxidant, ultraviolet light absorber, anti-polycoagulant.

(fluorine class organic compound)

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

That is to say, by containing fluorine class organic compound, can reduce the surface tension of substrate and coating fluid, improvement is to the wetting state of substrate, raising is to the coating of substrate, even so under the situation of the film that forms several μ m degree with a spot of liquid measure, also can effectively form the film of the little homogeneous thickness of uneven thickness.

The fluorine containing ratio of fluorine class organic compound is that 3～40 quality % are suitable, and more preferably 5～30 quality % are preferably 7～25 quality % especially.The fluorine class organic compound of fluorine containing ratio in above-mentioned scope is being that effectively the dissolubility in composition is also good aspect coating thickness homogeneity and the province's fluidity.

As fluorine class organic compound, can list for example メ ガ Off ア Star Network (Megafac) F171, メ ガ Off ア Star Network F 172, メ ガ Off ア Star Network F 173, メ ガ Off ア Star Network F 177, メ ガ Off ア Star Network F 141, メ ガ Off ア Star Network F 142, メ ガ Off ア Star Network F 143, メ ガ Off ア Star Network F 144, メ ガ Off ア Star Network R30, メ ガ Off ア Star Network FF437 (above is big Japanese ink chemical industry (strain) system), Off ロ ラ one De (Fluorad) FC430, Off ロ ラ one De FC 431, Off ロ ラ one De FC 171 (above is Sumitomo 3M (strain) system), サ one Off ロ Application (Surflon) S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC1068, サ one Off ロ Application SC-381, サ one Off ロ Application SC-383, サ one Off ロ Application S393, サ one Off ロ Application KH-40 (above is Asahi Glass (strain) system) etc.

Particularly for example when the coated film attenuation that coating is formed, fluorine class organic compound can effectively prevent crawling and uneven thickness.In addition, even in the narrow slit coating that occurs the liquid cutout easily, also be effective.

Colored pattern of the present invention forms the addition with fluorine class organic compound in the composition, is preferably 0.001～2.0 quality % with respect to the all-mass of composition, more preferably 0.005～1.0 quality %.

(thermal polymerization)

It also is effective that colored pattern of the present invention forms with containing thermal polymerization in the composition.As thermal polymerization; can list for example various azo compounds, superoxide compounds; as above-mentioned azo compound; can list azo two and replace (ア ゾ PVC ス, azobis) compounds; as above-mentioned superoxide compounds, can list ketone peroxide, peroxidating acetal, hydroperoxides, dialkyl, peroxidating diacyl, peroxyester, peroxy dicarbonate etc.

(surfactant)

Colored pattern of the present invention forms with in the composition, from the viewpoint of improvement coating, preferably uses various surfactants to constitute, and can use the various surfactants of nonionic class, cationic, anionic species.Wherein, be preferably the fluorine class surfactant that has perfluoroalkyl in the nonionic class surfactant.

As the concrete example of fluorine class surfactant, can list メ ガ Off ア Star Network (registered trademark) series of big Japanese ink chemical industry (strain) system, Off ロ ラ one De (registered trademark) series of 3M corporate system etc.

In addition, the surfactant of nonionic, cationic, anionic species can list particularly, phthalocyanine derivates (commercially available product EFKA-745 (gloomy industry corporate system down)); The cationic surfactant of organic siloxane polymer KP341 (chemical industrial company of SHIN-ETSU HANTOTAI system), (methyl) acrylic compounds (being total to) polymkeric substance Port リ Off ロ one No.75, No.90, No.95 (oil chemistry industrial group of common prosperity society system), WO01 (abundant merchant's corporate system) etc.; Polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether, NONIN HS 240, polyoxyethylene nonylplenyl ether, polyethylene glycol dilaurate, polyglycol distearate, sorbitan fatty ester (nonionic class surfactants such as the system プ of BASF AG Le ロ ニ Star Network L10, L31, L61, L62,10R5,17R2,25R2, テ ト ロ ニ Star Network 304,701,704,901,904,150R1; WO04, WO05, WO17 anionic species surfactants such as (abundant merchant's corporate systems) etc.

(silane coupling agent)

As silane coupling agent, can list for example γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) aminopropyl dimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane), the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl-triethoxysilicane, γ-isocyanate group propyl trimethoxy silicane, γ-isocyanate group propyl-triethoxysilicane, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane hydrochloride, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, amino silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, methyltrimethoxy silane, methyl triethoxysilane, vinyltriacetoxy silane, γ-r-chloropropyl trimethoxyl silane, hexamethyldisilazane, γ-phenylamino propyl trimethoxy silicane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (beta-methoxy-ethoxy) silane, octadecyl dimethyl [3-(trimethoxysilyl) propyl group] ammonium chloride, gamma-chloropropylmethyldimethoxysilane, γ-sulfydryl propyl group methyl dimethoxysilane, methyl trichlorosilane, dimethyldichlorosilane, trimethyl chlorosilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the diallyl trimethoxy silane, tetraethoxysilane, two (trimethoxysilyl) hexane, phenyltrimethoxysila,e, N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxywerene werene, N-(3-methacryloxy-2-hydroxypropyl)-3-aminopropyltriethoxywerene werene, (methacryloxy methyl) methyldiethoxysilane, (acryloyl-oxy ylmethyl) methyl dimethoxysilane etc.

Wherein, be preferably γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl-triethoxysilicane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-An Jibingjisanyiyangjiguiwan, phenyltrimethoxysila,e, most preferably be γ-methacryloxypropyl trimethoxy silane.

In above-mentioned adjuvant, contain be selected from surfactant and the silane coupling agent more than a kind, be preferred from the viewpoint of may command advancing contact angle and viscosity, more preferably contain more than at least a kind of both sides of surfactant and silane coupling agent.

Except above-mentioned adjuvant, as the concrete example of the additive that can in colored pattern of the present invention forms with composition, use, can list filling agent (for example glass, aluminium oxide etc.) and alkali soluble resin (for example the phenoxy resin of the polymkeric substance of the maleic acid of itaconic acid copolymer, crotonic acid multipolymer, maleic acid, partial esterification, acid cellulose derivant, polymkeric substance and acid anhydrides addition, pure soluble nylon, bisphenol-A and chloropropylene oxide formation etc.) with hydroxyl.

As other the example of additive etc., can list EFKA-46, EFKA-47, EFKA-47EA, EFKA polymkeric substance 100, EFKA polymkeric substance 400, EFKA polymkeric substance 401, EFKA polymkeric substance 450 (above be gloomy industry corporate system down), デ イ ス パ one ス エ イ De (Disperseaid) 6, デ イ ス パ one ス エ イ De 8, デ イ ス パ one ス エ イ De 15, デ イ ス パ one ス エ イ De 9100 macromolecule dispersing agents such as (サ Application ノ プ コ (SAN NOPCO) corporate systems); Various ソ Le ス パ one ス spreading agents (ゼ ネ カ corporate system) such as ソ Le ス パ one ス 3000,5000,9000,12000,13240,13940,17000,24000,26000,28000; ア デ カ プ Le ロ ニ Star Network (Adeka Pluronic) L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (rising sun electrification corporate system) and イ ソ ネ Star ト (Isonet) S-20 (Sanyo changes into corporate system); Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy benzophenone; And anti-polycoagulant such as sodium polyacrylate.

In addition, promote under the alkali-soluble of uncured portion, the situation that can add organic carboxyl acid in Photocurable composition, be preferably molecular weight is low-molecular-weight organic carboxyl acid below 1000 with the development of further raising Photocurable composition in desire.As the concrete example of low-molecular-weight organic carboxyl acid, can list formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, diethacetic acid, enanthic acid, aliphatic monocarboxylic acid such as sad; Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, tridecandioic acid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid; Benzoic acid, methyl benzoic acid, isopropyl acid, 2,3-mesitylenic acid, 3, aromatic monocarboxylates such as 5-mesitylenic acid; Aromatic series polybasic carboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA), trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid; Other carboxylic acids such as phenylacetic acid, phenylpropionic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, benzene acrol acetate, coumaric acid, umbellic acid.

(thermal polymerization prevents agent)

In the present invention, in order stoping in the preparation of Photocurable composition or the unnecessary thermal polymerization of polymerizable compound in preserving, to add a spot of thermal polymerization and prevent that agent from being desirable.

Prevent agent as the thermal polymerization that can use in the present invention, quinhydrones, p methoxy phenol, BHT, 1,2,3,-thrihydroxy-benzene, the tert-butyl group be can list and benzenediol, benzoquinones, 4 connected, 4 '-sulfo-two (3 methy 6 tert butyl phenol), 2,2 '-methylene two (4-methyl-6-tert butyl phenol), 2-mercaptobenzimidazole, N-nitroso-phenyl hydramine cerium (III) salt etc.

The addition that thermal polymerization prevents agent is about 0.01 quality %～about 5 quality % with respect to the quality optimization of whole compositions.In addition, as required,, can add the such advanced higher fatty acid derivative of mountain Yu acid, mountain Yu acid acid amides etc., and make and concentrate the surface that is present in photographic layer in its dry run after coating in order to prevent to encumber because of the polymerization that oxygen causes.The addition of advanced higher fatty acid derivative is preferably about 0.5 quality %～about 10 quality % of whole compositions

[colored pattern forms the modulation with composition]

Colored pattern of the present invention form with composition can be as described as follows by conditioned pigment in advance disperse thing, in this pigment dispersing thing, contain (B) polymerizable compound and (C) Photoepolymerizationinitiater initiater (preferably with organic solvent), also modulate to adjuvants such as mixed surfactants wherein as required.

Here, the modulator approach that colored pattern of the present invention is formed with the pigment dispersing thing that uses in the composition is illustrated.

Pigment dispersing thing among the present invention, can be by for example being the potpourri of pigment, (D) dispersion resin and the organic solvent of 10nm～15nm with above-mentioned (A) primary particle size, the sand mill (sand grinder) of use longitudinal type or horizontal type, needle mill (pin mill), slit grinding machine (slit mill), ultrasonic dispersing machine etc., the pearl that is formed by glass, zirconia etc. with 0.01～1mm particle diameter carries out the diffusing processing of differential, thereby obtains.

In addition, before carrying out the pearl dispersion, two rollers, three rollers, bowl mill (ball mill), cylinder grinding machine (Trom mel (rotary shieve)), dispersion machine (disper), kneader (kneader) be can use, kneader (Co-kneader), homogenizer (homogenizer), mixer (blender), single screw rod or double screw extrusion machine etc. are total to, apply strong shearing force on one side, Yi Bian the dispersion treatment of mixing.

In addition, about the detailed content of mixing, disperseing, on the books in T.C.Patton work " Paint Flowand Pigment Dispersion " (John Wiley and Sons society published in 1964) etc.

The colored pattern of the present invention that so obtains forms uses composition, by containing above-mentioned each composition, can keep (A) primary particle size is the pigment of 10nm～15nm good disperse state in composition, obtain good color characteristics, when using said composition configuration example such as color filter, can obtain high-contrast simultaneously.

Formation method, manufacturing method of color filter and the color filter of＜colored pattern 〉

Formation method, manufacturing method of color filter and color filter to colored pattern of the present invention illustrated below.

The formation method of colored pattern of the present invention comprises that being coated with colored pattern of the present invention by the slot coated method with the coating speed of second 200mm/ second～400mm/ forms operation with composition, can form desirable colored pattern thus.The colored pattern of the invention described above forms with composition owing to have the rerum natura of defined, even so carrying out under the situation of slot coated with the high speed of second coating speed 200mm/ second～400mm/, also can suppress coating defects and produce, prepare flawless light-sensitive surface efficiently.

The formation method of this colored pattern is preferably used in manufacturing method of color filter.

Below, the manufacturing method of color filter (manufacturing method of color filter of the present invention) of the formation method of having used colored pattern of the present invention is illustrated.

Manufacturing method of color filter of the present invention comprises following operation, thereby that is: colored pattern of the present invention is formed with composition directly or by other layer give the operation that on substrate, forms photosensitive film (below, be called for short aptly and make " photosensitive film formation operation ".); The photosensitive film that forms is carried out the operation (below, be called for short aptly and make " exposure process ") of pattern exposure (exposing) by mask; Photosensitive film after the exposure is developed, thus form colored pattern operation (below, be called for short aptly and make " developing procedure ".)。

Below, each operation in the manufacture method of the present invention is illustrated.

(photosensitive film formation operation)

In photosensitive film forms operation, directly or having on the substrate of other layer coating (giving) colored pattern of the present invention form and use composition, thus the formation photosensitive film.

As the substrate that uses in this operation, can list the soda-lime glass that for example is used for liquid crystal display cells etc., send lachs (PYREX

) glass, quartz glass and the glass that on them, attached nesa coating, the photo-electric conversion element substrate that in imaging apparatus etc., uses, siloxane substrate etc. for example, complementary burning film semiconductor (Complementary MetalOxide Semiconductor:CMOS) etc.On these substrates, be formed with the blackstreak of isolating each pixel sometimes.

In addition, on these substrates, can be provided for improveing with the driving fit of the layer on top as required, prevent the material diffusion or be used for the undercoat (other layer) of the planarization of substrate surface.

In manufacturing method of color filter of the present invention, coating colored pattern of the present invention forms with comprising the operation that use slot coated method was coated with second coating speed 200mm/ second～400mm/ in the method for compositions on substrate.According to colored pattern formation composition of the present invention, but owing to form the light-sensitive surface of the homogeneous that does not have coating defects by the slot coated high productivity ground of such high speed, thereby its effect is remarkable when using in manufacturing method of color filter of the present invention, but undoubtedly be to use other various coating processes such as ink-jet method, spin coating, flow coat, roller coat, silk screen print method to form light-sensitive surface.

Form the coating film thickness of using composition as colored pattern, be preferably 0.1～10 μ m, more preferably 0.2～5 μ m, more preferably 0.2～3 μ m.

Be coated on the drying (prebake conditions: prebaking) can under 50 ℃～140 ℃ temperature, carry out 10～300 seconds of the photosensitive film on the substrate by electric hot plate, baking oven etc.

(exposure process)

In exposure process, make to form the mask that the photosensitive film that forms in the operation is situated between by the mask pattern with regulation at above-mentioned photosensitive film and expose, be pattern exposure.

In this operation, be that photosensitive film exposes by being situated between to coated film by the mask pattern of stipulating, only can make and partly be solidified by light-struck coated film.

As spendable radiant rays in exposure, be preferably ultraviolet rays such as g line, i line especially.Exposure is preferably 5～1500mJ/cm ², 10～1000mJ/cm more preferably ², most preferably be 10～500mJ/cm ²

When the color filter of making is used for liquid crystal display element, be preferably 5～200mJ/cm in the above range ², 10～150mJ/cm more preferably ², most preferably be 10～100mJ/cm ²In addition, be the solid-state imager time spent at the color filter of making, be preferably 30～1500mJ/cm in the above range ², 50～1000mJ/cm more preferably ², most preferably be 80～500mJ/cm ²

(developing procedure)

Then,, make the unexposed portion stripping in developer solution in exposure process, only the part of remaining photocuring by carrying out development treatment.As developer solution, if the film of the Photocurable composition in uncured of the solubilized, and do not dissolve solidified portion, just can use any.Specifically, can use the combination or the alkaline aqueous solution of various organic solvents.

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

As above-mentioned organic solvent, can list the operable solvent of having narrated when modulation colored pattern of the present invention forms with composition.

Aqueous solution as above-mentioned alkalescence, preferred for example NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, choline, pyrroles, the piperidines, 1 of using, 8-diaza-bicyclo-[5,4,0]-to be diluted to concentration with pure water be 0.001～10 quality % to alkali compounds such as 7-hendecene, be preferably the alkaline aqueous solution that 0.01～1 quality % forms.

In addition, when using the developer solution that forms by such alkaline aqueous solution, generally after development, clean (drip washing) with pure water.

Behind developing procedure, clean and remove remaining developer solution, carry out drying, carry out heat treated (back baking: post baking) then.

The back baking is the heat treated of carrying out after development in order to make completion of cure, carries out 100 ℃～240 ℃ heat curing usually and handles.When substrate is glass substrate or siloxane substrate, in the said temperature scope, be preferably 200 ℃～240 ℃.

This back baking processing be the coated film after developing is used under condition as described above firing equipment continous way such as electric hot plate (hot plate) or convection baking oven (heated air circulation type dryer), high frequency heating machine or in batches (batch) formula carry out.

Photosensitive film described above is formed operation, exposure process and developing procedure (and then comprising the heat treated of carrying out as required) only repeat desirable form and aspect number, thereby make the color filter (color filter of the present invention) that constitutes by desirable form and aspect.

The color filter that obtains by above such manufacturing method of color filter of the present invention has the formation of using colored pattern of the present invention to form the colored pattern that forms with composition on substrate, can make contrast is more than 5000.

Here, contrast is meant for the R (red), the G (green) that constitute color filter, the contrast that every kind of color of B (indigo plant) is estimated.

The assay method of contrast is as described below.Overlapping polaroid on the both sides of measured object under the polarization direction of polaroid state parallel to each other, from a side polaroid side irradiation rear-projection light, is measured the briliancy Y1 by the light behind the opposing party's the polaroid.Then, under the state of polaroid mutually orthogonal,, measure briliancy Y2 by the light behind the opposing party's the polaroid from a side polaroid side irradiation rear-projection light (back light).Use the measured value of gained, calculate contrast with Y1/Y2.Here, as polaroid, use a day eastern electrician G1220DUN, analyzer uses color brightness photometer BM-5 ((strain) ト プ コ Application (Topcon Co) system).

Give when forming film on the substrate colored pattern of the present invention being formed,, be generally 0.3～5.0 μ m, be preferably 0.5～3.5 μ m, most preferably be 1.0～2.5 μ m as the dry thickness of film with composition.

As substrate, for example can list the alkali-free glass, the soda-lime glass that in liquid crystal display cells etc., use, send lachs (registered trademark) glass, quartz glass and their are attached the glass of the nesa coating of knowing clearly, the photo-electric conversion element substrate that in solid-state imager etc., uses, for example siloxane substrate etc., and plastic base.On these substrates, be formed with the blackstreak (black stripe) of isolating each pixel usually.

Plastic base preferably has gas barrier (gas barrier) layer and/or solvent resistance layer in its surface.

Form the purposes of using composition as colored pattern of the present invention, mainly can tell the purposes in the pixel of color filter, but undoubtedly be, also be applicable to the black matrix" that between the pixel of color filter, is provided with.Black matrix" is to use to add carbon black, titanium and deceive material that black colorants such as (titanium black) forms as colorant in colored pattern of the present invention forms with composition, in addition, similarly carry out pattern exposure with the method for making of above-mentioned pixel, alkali develops, and then carry out the curing of back baking after this, thereby form with the promotion film.

＜liquid crystal display cells 〉

Liquid crystal display cells of the present invention is to possess the liquid crystal display cells that color filter of the present invention forms.

More particularly, can make alignment films relative with electrode base board by forming alignment films at the medial surface of color filter, fill up liquid crystal and seal at gap portion, be panel thereby obtain liquid crystal display cells of the present invention.

Embodiment

Below, be described more specifically the present invention by embodiment, but the present invention does not limit the following examples.In addition, short of specified otherwise, " % " " part " is a quality criteria.

(embodiment 1)

The composition that mixes following composition uses homogenizer to stir with rotating speed 3000r.p.m. and mixed in 3 hours, the modulation mixed solution.

[composition]

(A) pigment: 254 50 parts of C.I. paratoneres

(method of opening 2005-307154 communique embodiment 9 by the spy prepares,

Primary particle size: be determined as 9nm) by the SEM method

(A) pigment: 14 parts of C.I. pigment red 122s

(method of opening 2005-307154 communique embodiment 12 by the spy prepares,

Primary particle size: be determined as 12nm) by the SEM method

(D-1-1) specific dispersion resin: 112 parts of the solution of above-mentioned exemplary compounds (1)

(solid constituent 30%)

(E) organic solvent: 520 parts of propylene glycol methyl ether acetates

Then, will stir in the grinding machine (ス one ミ Le) (ア シ ザ ワ Off ア イ Application テ Star Network company (Ashizawa Finetech Ltd.) system) at the pearl dispersion machine, use the zirconium oxide bead of 0.3mm Φ to carry out 3 hours dispersion treatment by the mixed solution that said method obtains.And then use the zirconium oxide bead of 0.03mm Φ to carry out 1 hour dispersion treatment, thereby obtain red pigment dispersing thing at the same grinding machine that stirs.

In the pigment dispersing thing that obtains, further add the composition of following composition, mix, form with composition (colored resist liquid) thereby modulate colored pattern of the present invention.

[composition]

(C) optical polymerism compound:

25 parts of DPHA (dipentaerythritol five or six acrylate, Japanese chemical drug system)

(D) Photoepolymerizationinitiater initiater:

2,2 '-two (Chloro-O-Phenyl)-4,4 ', 5,6 parts of 5 '-tetraphenyl bisglyoxalines

3 parts of the compd As of following structural formula

(F) adhesive resin: methacrylic acid benzyl ester/methacrylic acid (=70/30[mol ratio]) multipolymer (acid number: 110mg/g, weight-average molecular weight: 37 parts of propylene glycol methyl ether acetate solution 5000) (solid constituent 45%)

2 parts of エ ピ Network ロ Application (EPICLON) N-695 (big Japanese ink system epoxy resin)

2 parts of エ マ Le ゲ Application A-60 (the flower king makes non-ionic surfactant)

(E) organic solvent: 580 parts of propylene glycol methyl ether acetates

1 part of the propylene glycol methyl ether acetate solution of p methoxy phenol (solid constituent 1%)

2 parts of γ-acryloxy propyl trimethoxy silicane

2 parts of the propylene glycol methyl ether acetate solution (solid constituent 10%) of メ ガ Off ア Star Network F-781 (big Japan system fluorine class surfactant)

Compd A

(physical property measurement)

Colored pattern formation to gained is carried out following physical property measurement with composition.

(1) mensuration of viscosity, surface tension, advancing contact angle (23 ℃, 50%RH)

Colored pattern formation composition to gained uses E type viscosity meter (RE550L, eastern machine industry corporate system), measures the viscosities il after composition is modulated, and the result is 3.0mPa second, and with William's method (Wilhelmy method) mensuration surface tension, the result is 27mN/m.

In addition, use automatic contact angle meter (consonance interface science corporate system) to be determined at advancing contact angle (landing method) on the glass substrate (1737, コ one ニ Application グ company (Corning Inc.) system), the result is 10.6 °.

(estimating 1)

Colored pattern formation composition to gained, use apparatus for coating (Hirata Spinning Ltd.'s system dispense tip coating machine (head coater) of slit coater (slit coater), carried the dispense tip of Off ア ス one (Faster) corporate system), go up 150 pieces of the coating speed coatings (every piece coating is spaced apart 30 seconds: empty (dummy) sprays 2 seconds) of second at the glass substrate (1737, コ one ニ Application グ corporate system) of 550mm * 650mm with 200mm/.Then, dry 60 seconds (prebake conditions) in 90 ℃ baking oven.The thickness of desciccator diaphragm is 1.5 μ m.

The coating surface proterties that visualization is the 150th piece.

Metewand is as described below, and △ is the lower limit of the allowed band in the practicality.

◎: per 0.25 square metre number of defects is less than 0.5.

Zero: per 0.25 square metre number of defects is less than 1.

△: per 0.25 square metre number of defects is more than 1, but is less than 2.

*: per 0.25 square metre number of defects is more than 2

(estimating 2)

Use the colored pattern formation composition of gained, glass substrate (1737 at 550mm * 650mm, コ one ニ Application グ corporate system) on, forms with the coating speed of 200mm/ second by slit coater (head coater has carried the dispense tip of Off ア ス -corporate system) and to film.

With 200mJ/cm ²(illumination is 20mW/cm ²) the whole face of filming is exposed, with alkaline developer CDK-1 (the Off イ of Fuji Le system エ レ Network ト ロ ニ Network ス マ テ リ ア Le ズ (strain) (FUJIFILM Electronic Materials Co., Ltd.) 1% aqueous solution system) covers films static 60 seconds after the exposure.After static, scatter pure water, flush away developer solution with the spray shape.Then with the above-mentioned film that has carried out exposure like that and developed heat treated 1 hour (back baking) in 220 ℃ baking oven, on glass substrate, form color filter with pigmentary resin tunicle (colored pattern), thereby make painted filter substrate (color filter).

Polaroid is placed on the pigmentary resin tunicle (colored pattern) of painted filter substrate, clamping pigmentary resin tunicle, use the BM-5 of ト プ コ Application corporate system to measure the briliancy of polaroid when parallel and the briliancy during quadrature, the briliancy institute value of the briliancy when parallel during divided by quadrature (briliancy during=briliancy when parallel/quadrature) be the index estimated of degree as a comparison.

(embodiment 2～16)

Except the exemplary compounds 2～16 of the above-mentioned exemplary compounds (1) of (D-1-1) specific dispersion resin being used (D-1-1) the specific dispersion resin shown in the following table 3 in embodiment 1 respectively replaces, beyond silane coupling agent replaced with the silane coupling agent shown in the table 3 too, other modulates red pigment dispersing thing similarly to Example 1, and then modulate colored pattern formation and use composition, estimate similarly to Example 1.

(embodiment 17～31)

Except the exemplary compounds I～XV (making the solid component content unanimity by the concentration of propylene glycol methyl ether acetate solution is regulated) that the above-mentioned exemplary compounds (1) of (D-1-1) specific dispersion resin is used (D-1-3) the specific dispersion resin shown in the following table 4 in embodiment 1 respectively replaces, beyond silane coupling agent replaced with the silane coupling agent shown in the table 4 too, other modulates red pigment dispersing thing similarly to Example 1, and then modulate colored pattern formation and use composition, estimate similarly to Example 1.

(embodiment 32～53)

Except the above-mentioned illustration dispersion resin B-1-1～B-1-22 (making the solid component content unanimity by the concentration of propylene glycol methyl ether acetate solution is regulated) that the above-mentioned exemplary compounds (1) of (D-1-1) specific dispersion resin is used (D-1-2) the specific dispersion resin shown in the following table 5 in embodiment 1 respectively replaces, beyond silane coupling agent replaced with the silane coupling agent shown in the table 5 too, other modulates red pigment dispersing thing similarly to Example 1, and then modulate colored pattern formation and use composition, estimate similarly to Example 1.

(comparative example 1)

Except in embodiment 1, the solution of the exemplary compounds (1) of (D-1-1) specific dispersion resin being replaced with the solution (making the solid component content unanimity by the concentration of propylene glycol methyl ether acetate solution is regulated) of dispersion resin 1 with following comparative example, other similarly to Example 1 conditioned pigment composition, colored pattern form and use composition, estimate similarly to Example 1.

Comparative example is with the solution of dispersion resin 1: the solution after the solution that will contain the ammonia ester class dispersion resin that obtains in the synthesis example 14 of record in the 97th～99 page of WO2004/081070 communique (in table 3, be recited as " WO2004/081070 synthesis example 14) carries out concentration adjustment.

(comparative example 2)

Except in embodiment 1, the solution of the exemplary compounds (1) of (D-1-1) specific dispersion resin being replaced with the solution (making the solid component content unanimity by the concentration of propylene glycol methyl ether acetate solution is regulated) of dispersion resin 2 with following comparative example, other similarly to Example 17 conditioned pigment composition, colored pattern form and use composition, estimate similarly to Example 1.

Comparative example is with the solution of dispersion resin 2: will contain the dispersant A that obtains in the synthesis example 17 of record in the 100th page of WO2004/081070 communique ' solution after the solution of (in table 3, be recited as " WO2004/081070 synthesis example 17) carries out concentration adjustment.

(comparative example 3)

Except in embodiment 32, the solution of the exemplary compounds (1) of (D-1-1) specific dispersion resin being replaced with dispersion resin 3 (making the solid component content unanimity by the concentration of propylene glycol methyl ether acetate solution is regulated) with following comparative example, other and embodiment 32 similarly conditioned pigment composition, colored pattern formation use composition, estimate similarly to Example 1.

The comparative example dispersant A of putting down in writing in the 103rd page the table-4 of dispersion resin 3:WO2004/081070 communique " (in table 3, being recited as " dispersant A of WO2004/081070 ")

In addition, the concrete condition of the silane coupling agent in the following table 1～table 3 is following like that.

A γ-acryloxy propyl trimethoxy silicane

B γ-methacryloxypropyl trimethoxy silane

C gamma-amino propyl trimethoxy silicane

Table 3

	Dispersion resin	Silane coupling agent	Viscosities il (mPa.s)	Advancing contact angle θ a (°)	η×θa	Coating defects	Contrast
								Embodiment 1	Exemplary compounds (1)	a	3.0	10.6	31.7	◎	5990
Embodiment 2	Exemplary compounds (2)	b	2.9	13.7	39.9	○	6961
								Embodiment 3	Exemplary compounds (3)	c	2.7	13.4	36.1	○	5893
Embodiment 4	Exemplary compounds (4)	a	2.9	10.4	30.2	◎	5681
								Embodiment 5	Exemplary compounds (5)	b	2.9	13.4	38.5	○	6062
Embodiment 6	Exemplary compounds (6)	c	2.2	16.3	36.5	○	6237
								Embodiment 7	Exemplary compounds (7)	a	2.7	12.5	34.1	◎	5875
Embodiment 8	Exemplary compounds (8)	b	2.3	14.3	32.9	◎	5141
								Embodiment 9	Exemplary compounds (9)	c	2.2	13.8	30.2	◎	5270
Embodiment 10	Exemplary compounds (10)	a	2.5	13.8	34.5	◎	6917
								Embodiment 11	Exemplary compounds (11)	b	2.8	12.3	34.3	◎	5215
Embodiment 12	Exemplary compounds (12)	c	2.5	14.5	36.7	○	6611
								Embodiment 13	Exemplary compounds (13)	a	2.0	14.8	30.0	◎	5677
Embodiment 14	Exemplary compounds (14)	b	2.2	14.1	31.6	◎	5753
								Embodiment 15	Exemplary compounds (15)	c	2.4	14.5	34.4	◎	6789
Embodiment 16	Exemplary compounds (16)	a	2.9	12.3	36.2	○	6247

Table 4

	Dispersion resin	Silane coupling agent	Viscosities il (mPa.s)	Advancing contact angle θ a (°)	η×θa	Coating defects	Contrast
								Embodiment 17	Exemplary compounds (I)	a	2.8	10.9	30.6	◎	5696
Embodiment 18	Exemplary compounds (II)	b	2.8	13.3	37.4	○	5461
								Embodiment 19	Exemplary compounds (III)	c	2.2	16.8	36.7	○	6504
Embodiment 20	Exemplary compounds (IV)	a	2.3	16.0	37.4	○	6842
								Embodiment 21	Exemplary compounds (V)	b	2.2	16.5	36.0	○	5662
Embodiment 22	Exemplary compounds (VI)	c	2.9	13.1	38.6	○	5099
								Embodiment 23	Exemplary compounds (VII)	a	2.8	12.9	36.2	○	5037
Embodiment 24	Exemplary compounds (VIII)	b	2.5	14.5	36.7	○	5985
								Embodiment 25	Exemplary compounds (IX)	c	2.6	11.6	30.8	◎	6572
Embodiment 26	Exemplary compounds (X)	a	2.9	13.1	38.2	○	5442
								Embodiment 27	Exemplary compounds (XI)	b	2.0	18.0	36.9	○	5257
Embodiment 28	Exemplary compounds (XII)	c	2.5	14.7	36.2	○	6376
								Embodiment 29	Exemplary compounds (XIII)	a	2.5	14.7	36.7	○	5865
Embodiment 30	Exemplary compounds (XIV)	b	2.4	16.2	39.3	○	6645
								Embodiment 31	Exemplary compounds (XV)	c	2.4	13.5	32.5	◎	5126

Table 5

	Dispersion resin	Silane coupling agent	Viscosities il (mPa.s)	Advancing contact angle θ a (°)	η×θa	Coating defects	Contrast
								Embodiment 32	B-1-1	a	2.0	14.8	30.0	◎	5056
Embodiment 33	B-1-2	b	3.0	13.3	39.9	○	5335
								Embodiment 34	B-1-3	c	2.4	14.4	35.1	○	6404
Embodiment 35	B-1-4	a	2.8	13.7	38.2	○	5692
								Embodiment 36	B-1-5	b	2.1	16.5	33.9	◎	5091
Embodiment 37	B-1-6	c	2.6	12.3	32.1	◎	6301
								Embodiment 38	B-1-7	a	2.6	11.9	31.2	◎	6638
Embodiment 39	B-1-8	b	2.3	15.7	36.3	○	5230
								Embodiment 40	B-1-9	c	2.6	12.7	33.5	◎	6297
Embodiment 41	B-1-10	a	2.7	12.5	33.8	◎	5964
								Embodiment 42	B-1-11	b	2.7	13.6	37.1	○	6243
Embodiment 43	B-1-12	c	2.2	17.6	39.0	○	5706
								Embodiment 44	B-1-13	a	2.7	14.6	39.4	○	5297
Embodiment 45	B-1-14	b	2.2	13.9	30.8	◎	6772
								Embodiment 46	B-1-15	c	2.3	16.0	36.8	○	6372
Embodiment 47	B-1-16	a	2.3	15.6	35.5	○	6345
								Embodiment 48	B-1-17	b	2.2	17.9	39.8	○	6153
Embodiment 49	B-1-18	c	2.2	18.1	39.0	○	6447
								Embodiment 50	B-1-19	a	2.2	15.8	34.6	◎	6641
Embodiment 51	B-1-20	b	2.4	13.6	32.5	◎	5221
								Embodiment 52	B-1-21	c	2.7	13.6	36.9	○	5071
Embodiment 53	B-1-22	a	2.5	12.1	30.4	◎	6205
								Comparative example 1	WO04/81070 synthesis example 14	Do not have	3.1	13.5	42.0	×	5500
Comparative example 2	WO04/81070 synthesis example 17	Do not have	2.5	11.2	28.0	×	4900
								Comparative example 3	WO04/81070 dispersant A "	Do not have	2.8	10.4	29.0	×	4500

Shown in the result of table 3～table 5, form with under the situation of composition at the colored pattern that uses embodiment 1～53, defective when using this colored pattern formation to carry out slot coated with composition is few, the good coating surface proterties that the defective that can be inhibited produces.In addition, with the contrast of comparative example 1～3 in can know, use the colored pattern that satisfies physics value of the present invention to form and compare with prior composition with the situation of composition, can obtain the coating surface proterties of excellence.Therefore can know to have the colored pattern formation of using embodiment 1～53 and compare the contrast excellence with existing product with the color filter of the present invention of the colored pattern of composition formation.

Claims (11)

1. a color filter forms with colored pattern and uses composition, its be contain compound that (A) pigment, (B) has the olefinic unsaturated group, (C) Photoepolymerizationinitiater initiater and (D) colored pattern of dispersion resin form and use composition, it is characterized in that, described colored pattern under with 23 ℃ form viscosity with composition be set at η (mPas), with described colored pattern formation with composition with respect to the advancing contact angle of glass substrate be set at θ a (°) time, satisfy following formula (1):

30≤η * θ a≤40, formula (1)

In the formula (1), 2≤η≤3.

2. color filter as claimed in claim 1 forms with colored pattern and uses composition, it is characterized in that the primary particle size of described (A) pigment is 8nm～15nm.

3. color filter as claimed in claim 1 forms with colored pattern and uses composition, it is characterized in that, also contains (E) adhesive resin, and the mass ratio that contains that described (B) has compound/described (E) adhesive resin of olefinic unsaturated group is more than 1.2.

4. color filter as claimed in claim 1 forms with colored pattern and uses composition, it is characterized in that solid component concentration is 9-12 weight %.

5. color filter as claimed in claim 1 forms with colored pattern and uses composition, it is characterized in that, described (D) dispersion resin contain be selected from following (D-1) and (D-2) at least a:

(D-1) contain and have nitrogen heterocyclic ring and have the macromolecular compound of the monomer of olefinic unsaturated group as copolymerization units;

(D-2) has the macromolecular compound of 2～100 pigment adsorption bases at the macromolecule end.

6. color filter as claimed in claim 1 forms with colored pattern and uses composition, it is characterized in that, also contains to be selected from surfactant and the silane coupling agent more than one.

7. color filter as claimed in claim 1 forms with colored pattern and uses composition, it is characterized in that, satisfy following (i)～(at least one vi):

(i) primary particle size of described (A) pigment is 8nm～15nm;

(ii) also contain (E) adhesive resin, and the mass ratio that contains that described (B) has compound/described (E) adhesive resin of olefinic unsaturated group is more than 1.2;

(iii) solid component concentration is 9～12 weight %;

(iv) described (D) dispersion resin is that (D-1) contains and have nitrogen heterocyclic ring and have the macromolecular compound of the monomer of olefinic unsaturated group as copolymerization units;

(v) described (D) dispersion resin is the macromolecular compound that (D-2) macromolecule end has 2～100 pigment adsorption bases;

(vi) also contain be selected from surfactant and the silane coupling agent more than a kind.

8. colored pattern formation method is characterized in that containing following operation: each described colored pattern of claim 1～7 is formed with composition be coated with by the coating speed of slot coated method with second 200mm/ second～400mm/.

9. a manufacturing method of color filter is characterized in that, has used the described colored pattern of claim 8 formation method.

10. a color filter is characterized in that, it is made by the described manufacture method of claim 9, and contrast is more than 5000.

11. a liquid crystal display cells, it has used the described color filter of claim 10.

Images