JP5036269B2 - Composition for forming colored pattern, method for forming colored pattern, method for producing color filter, color filter, and liquid crystal display element - Google Patents

Description

  The present invention relates to a colored pattern forming composition, a colored pattern forming method, a color filter manufacturing method, a color filter, and a liquid crystal display element.

  A color filter contains a polyfunctional monomer, a photopolymerization initiator, a binder resin, and other components in a dispersion composition of a colorant such as an organic pigment and an inorganic pigment to form a colored photosensitive composition, which is used as a photolithographic method. It is manufactured by.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required. In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

In response to the above requirements, it is required to disperse the pigment in a finer state (good dispersibility) and to disperse in a stable state (good dispersion stability).
If the dispersibility is insufficient, fringes (jagged edges) and surface irregularities occur in the formed colored resist film, the chromaticity and dimensional accuracy of the produced color filter are reduced, and the contrast is remarkably high. There is a problem of deterioration. Further, when the dispersion stability is insufficient, in the color filter manufacturing process, in particular, the uniformity of the film thickness in the coating process of the colored photosensitive composition is reduced, or the photosensitive sensitivity in the exposure process is low. The problem that it falls, or the alkali solubility in a image development process falls easily arises. Further, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored photosensitive composition are aggregated with the passage of time, the viscosity is increased, and the pot life is extremely shortened.
In particular, when the particle size of the pigment is reduced, the surface area of the pigment particle increases, so the cohesive force between the pigment particles increases, and it is difficult to achieve both dispersibility and dispersion stability at a high level. Many.

In order to solve such problems, various pigment dispersants have been developed.
For example, Patent Document 1 discloses a dispersant into which a dye structure, an acidic group, and a macromonomer are introduced. This is because the interaction between the organic pigment introduced into the dispersant and the pigment particles becomes strong, and the effect of the macromonomer promotes the adsorption of the polymer pigment dispersant to the pigment particles, thereby improving the dispersibility. It is considered that the alkali solubility is improved by the acid group.
However, the colored pattern forming composition of Patent Document 1 is prone to defects such as streaks on the coated surface when slit coating (also referred to as die coating) is performed on a glass substrate for producing a color filter. There is a problem that this becomes a pixel defect of the color filter.

Therefore, for example, in Patent Document 2, a specific binder resin is used, and the weight ratio of the dispersant to the colorant is set to a specific range, whereby a slit is formed on the glass substrate for the production of a color filter. A technique for reducing pixel defects in a color filter is disclosed even when coating is performed.
JP 2003-238837 A WO 2004/091070

However, the above-mentioned composition for forming a colored pattern in Patent Document 2 is used when a slit coating speed is set to 200 mm / sec on a glass substrate for the production of a color filter, or when the number of coatings is large. From the viewpoint of reducing pixel defects in the color filter, it has become clear that the performance is insufficient.
In addition, there is a problem in that there is a restriction in manufacturing the composition that it is necessary to use a binder resin having a specific structure.

Therefore, the present invention has been made in view of the above, and a composition for forming a colored pattern capable of obtaining a high contrast without using a special binder and suppressing coating defects when applied to a high speed and a large amount of coating. It is an object to provide an object and a coloring pattern forming method, and to achieve the object.
Another object of the present invention is to provide a color filter having high contrast, a method for producing the same, and a liquid crystal display device including the color filter, and to achieve the object.

  Specific means for achieving the above object are as follows. That is, the present invention

<1> (A) a pigment, (B) a polymer comprising a polymer compound represented by the following general formula (2), a copolymer unit derived from a monomer represented by the following general formula (I), or Dispersion resin which is any one of polymers containing a structural unit represented by the following general formula (a) and has an acid value of 20 to 300 mg / g and a weight average molecular weight of 3,000 to 100,000. C) A photopolymerizable compound, (D) a photopolymerization initiator, and (E) an organic solvent, wherein the composition satisfies the following conditions.
Conditions: The composition is coated on a glass substrate, dried to form a film having a thickness of 2 μm, and the main organic solvent constituting the composition is formed on the film surface obtained by tilting the glass substrate by 45 degrees. As a test solution, 0.1 ml droplets prepared by the method of 9.3.1 of JIS K 5600-6-1 are continuously dropped at the same location at intervals of 1 second, and the film surface is dissolved within 5 droplets. To do

In general formula (2), A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a group having 4 or more carbon atoms. A monovalent organic group containing at least one site selected from the group consisting of a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ² may be the same or different. R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different. R ³ represents an (m + n) -valent organic linking group. P ² represents a polymer skeleton of a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, or a modified product thereof. m represents an integer of 1 to 8, n represents an integer of 2 to 9, and m + n satisfies 3 to 10.

In general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m1 and n1 are each independently 0 or 1.

In general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.
<2> The colored pattern forming composition according to <1>, wherein P ² in the general formula (2) is a polymer or copolymer skeleton of a vinyl monomer.

< 3 > The mass ratio mb of (C) the photopolymerizable compound to all components having a weight average molecular weight of 3,000 or more in the composition is 0.2 to 3.0, and (B) the acid value of the dispersed resin. <1> or <2> , wherein the relationship between av1 and the mb satisfies any of the following formulas (a-1), (a-2), and (a-3): It is a composition for pattern formation.
(A) When the pigment is red: 150 <(av1) / (mb) <250 Formula (a-1)
(A) When the pigment is green: 100 <(av1) / (mb) <200 Formula (a-2)
(A) When the pigment is blue: 50 <(av1) / (mb) <150 Formula (a-3)

< 4 > Further, (F) a binder resin having an acid value of 50 to 400 mg / g and a weight average molecular weight of 3,000 to 100,000, and (B) a mass ratio db of the (F) binder resin to the dispersed resin 0.2 to 3.0, and the relationship between the acid value av2 of the binder resin (F) and the above db is represented by the following formulas (b-1), (b-2), and (b-3): The colored pattern forming composition according to any one of <1> to <3>, wherein any one of the above is satisfied.
(A) When the pigment is red: 200 <(av2) / (db) <250 Formula (b-1)
(A) When the pigment is green: 175 <(av2) / (db) <220 Formula (b-2)
(A) When the pigment is blue: 125 <(av2) / (db) <175 Formula (b-3)

< 5 > A colored pattern forming method comprising a step of applying the colored pattern forming composition according to any one of <1> to < 4 > by a slit coating method.

< 6 > A method for producing a color filter, wherein the method for forming a colored pattern according to < 5 > is used.

< 7 > A color filter produced by the production method according to < 6 >, wherein the contrast is 5000 or more.

< 8 > A liquid crystal display element using the color filter of < 7 >.

According to the present invention, a composition for forming a colored pattern and a method for forming a colored pattern that can obtain high contrast without using a special binder and can suppress coating defects when applied to a large amount of coating at high speed are provided. can do.
In addition, a color filter having high contrast, a manufacturing method thereof, and a liquid crystal display element including the color filter can be provided.

Hereinafter, the present invention will be described in detail.
<Colored pattern forming composition>
The colored pattern forming composition of the present invention comprises (A) a pigment, (B) a polymer compound represented by the general formula (2), and a copolymer derived from the monomer represented by the general formula (I). It is any one of a polymer containing a polymer unit or a polymer containing a structural unit represented by the general formula (a), and has an acid value of 20 to 300 mg / g and a weight average molecular weight of 3,000 to 100 The composition for coloring pattern formation characterized by containing the dispersion resin which is 1,000, (C) a photopolymerizable compound, (D) a photoinitiator, and (E) the organic solvent, and satisfy | filling the following conditions.
Conditions: The composition is coated on a glass substrate, dried to form a film having a thickness of 2 μm, and the main organic solvent constituting the composition is formed on the film surface obtained by tilting the glass substrate by 45 degrees. As a test solution, 0.1 ml droplets prepared by the method of 9.3.1 of JIS K 5600-6-1 are continuously dropped at the same location at intervals of 1 second, and the film surface is dissolved within 5 droplets. To do

First, the conditions satisfied by the colored pattern forming composition of the present invention will be specifically described.
The colored pattern forming composition of the present invention is applied onto a glass substrate and dried to form a film having a thickness of 2 μm. At this time, the liquid temperature of the composition is 23 ° C., and the coating speed is preferably 200 mm / sec. Further, an oven is used for drying, the drying temperature is preferably 90 ° C., and the drying time is preferably 60 seconds.
Next, the glass substrate having the film dried as described above is inclined 45 degrees to incline the film surface.
Subsequently, the main organic solvent constituting the composition for forming a colored pattern of the present invention is used as a test solution for the inclined film surface, and the method of 9.3.1 of JIS K 5600-6-1: 1999. The droplets (0.1 ml) produced in step 1 are continuously dropped at the same location at 1 second intervals.
At this time, it is determined as follows that the film surface dissolves within 5 drops.
That is, when the state of the film surface is visually observed for each droplet, the portion where the droplet is dropped dissolves, the glass substrate is exposed, and the state where the color of the film surface is not recognized is formed. Then, it is judged as “dissolved”.

  Here, the main organic solvent which comprises the composition for colored pattern formation of this invention is used for the droplet dripped on a film surface on said conditions. This "main organic solvent" refers to an organic solvent having the largest proportion in mass in the organic solvent (E) constituting the colored pattern forming composition of the present invention, and is an industrially available organic solvent. It is preferable that there is, for example, propylene glycol monomethyl ether acetate.

As described above, in the present invention, it is necessary to satisfy the condition that the film surface dissolves within 5 drops, preferably within 3 drops, and more preferably within 1 drop.
It can be seen that the smaller the number of drops at which dissolution of the film surface is confirmed, the higher the redissolvability of the dried product of the colored pattern forming composition of the present invention.

The colored pattern forming composition of the present invention has a high redissolvability of the dried product, so that, for example, when applied to a coating apparatus, it is newly supplied even when it is dried and cured in the apparatus. When contacted with the composition, the dried product is re-dissolved by the organic solvent in the composition, and fluidity is reproduced.
As a result, the composition for forming a colored pattern of the present invention can suppress coating defects even when applied to high-speed and large-scale intermittent application. Moreover, the resolution and visibility of the color filter manufactured using this composition for colored pattern formation can be improved.

In the present invention, in order to satisfy the above-described conditions, the essential components (A) to (E) constituting the composition and the types and amounts of various optional components may be appropriately adjusted. For example, it is preferable to adjust as follows.
In addition, it is a more preferable aspect to adjust the quantity of another component according to the hue of (A) pigment.

That is, in the composition for forming a colored pattern of the present invention, the mass ratio mb of the photopolymerizable compound (C) to all components having a weight average molecular weight of 3,000 or more in the composition is 0.2 to 3.0, And it is preferable that the relationship between the acid value av1 of the (B) dispersion resin and the mb satisfies any of the following formulas (a-1), (a-2), and (a-3).
(A) When the pigment is red: 150 <(av1) / (mb) <250 Formula (a-1)
(A) When the pigment is green: 100 <(av1) / (mb) <200 Formula (a-2)
(A) When the pigment is blue: 50 <(av1) / (mb) <150 Formula (a-3)

When the pigment (A) is red, it is more preferable that 150 <(av1) / (mb) <225, and it is more preferable that 175 <(av1) / (mb) <225.
(A) When the pigment is green, it is more preferable to satisfy 125 <(av1) / (mb) <200, and it is even more preferable to satisfy 125 <(av1) / (mb) <175.
(A) When the pigment is blue, it is more preferable to satisfy 75 <(av1) / (mb) <150, and it is even more preferable to satisfy 75 <(av1) / (mb) <125.

The colored pattern forming composition of the present invention includes (F) a binder resin having an acid value of 50 to 400 mg / g and a weight average molecular weight of 3,000 to 100,000. F) The mass ratio db of the binder resin is 0.2 to 3.0, and (F) the relationship between the acid value av2 of the binder resin and the db is represented by the following formulas (b-1) and (b-2). ) And (b-3) are more preferably satisfied.
(A) When the pigment is red: 200 <(av2) / (db) <250 Formula (b-1)
(A) When the pigment is green: 175 <(av2) / (db) <220 Formula (b-2)
(A) When the pigment is blue: 125 <(av2) / (db) <175 Formula (b-3)

In addition, when (A) a pigment is red, it is more preferable to satisfy | fill 210 <(av2) / (db) <250, and it is still more preferable to satisfy | fill 210 <(av2) / (db) <240.
When the pigment is green, it is more preferable to satisfy 175 <(av2) / (db) <200, and it is even more preferable to satisfy 190 <(av2) / (db) <200.
When the pigment is blue, it is more preferable to satisfy 125 <(av2) / (db) <160, and it is even more preferable to satisfy 140 <(av2) / (db) <160.

Hereinafter, (A) a pigment constituting the colored pattern forming composition of the present invention, (B) a polymer compound represented by the general formula (2), and a monomer represented by the general formula (I). It is any one of a polymer containing a derived copolymer unit or a polymer containing a structural unit represented by the general formula (a), and has an acid value of 20 to 300 mg / g, a weight average molecular weight of 3, A dispersion resin (hereinafter, simply referred to as “(B) dispersion resin”) , (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) organic In addition to the essential components of the solvent, the (F) binder resin that is preferably used will be described in detail.

[(B) component dispersed Resin
First, a description about the (B) component Chitty fat used in the present invention.
The (B) dispersion resin in the present invention is a compound that can function as a dispersant for the (A) pigment.

(B) Since the dispersion resin needs to have a specific acid value as described above, the dispersion resin is preferably a polymer compound having an acidic group.
Examples of the polymer skeleton of the polymer compound include polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and modified products thereof. Or a copolymer [for example, a polyether / polyurethane copolymer, a copolymer of a polyether / vinyl monomer polymer, etc. (any of a random copolymer, a block copolymer, and a graft copolymer) Good). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.

Examples of a method for introducing an acidic group into the polymer skeleton as described above include, for example, a method of copolymerizing a monomer containing an acidic group when polymerizing the polymer skeleton, and the polymer described above. There is a method of introducing a skeleton by polymer reaction after polymerization.
Examples of the monomer containing an acidic group include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid, acrylic acid dimer, vinyl benzoic acid, styrene sulfonic acid, 2-acrylamide-2- It is obtained by reacting an alcoholic hydroxyl group-containing monomer such as methylpropanesulfonic acid, mono (meth) acryloylethyl phosphate, or 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride or phthalic anhydride. And monomers.
Among these, examples of preferable monomers are obtained by reacting an alcoholic hydroxyl group-containing monomer such as (meth) acrylic acid or 2-hydroxyethyl methacrylate with a cyclic acid anhydride such as maleic anhydride or phthalic anhydride. And the like. Examples of the cyclic acid anhydride used here include itaconic anhydride, maleic anhydride, phthalic anhydride, succinic anhydride, glutaric anhydride, trimetic anhydride, etc., and particularly phthalic anhydride, succinic anhydride, etc. Is preferred.

Furthermore, the polymer compound having an acidic group may further be obtained by copolymerizing a vinyl monomer component.
Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides , Vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable.

Examples of such vinyl monomers include the following compounds.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with a vinyl group (for example, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, Vinyl caprolactone can also be used.
Furthermore, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Further, polymerizable oligomers as shown below may be used as vinyl monomers.
The polymerizable oligomer (hereinafter sometimes referred to as “macromonomer”) is an oligomer having a group having an ethylenically unsaturated double bond at the terminal. In the present invention, among the polymerizable oligomers, it is preferable to have a group having the ethylenically unsaturated double bond only at one of both ends of the oligomer.

  The molecular weight of the polymerizable oligomer is preferably a polystyrene-equivalent number average molecular weight (Mn) of 1000 to 20000, more preferably 2000 to 15000. If the number average molecular weight is less than 1000, the steric repulsion effect as a dispersant may not be sufficient, and if it exceeds 20000, it may take time to adsorb to the colorant (pigment) due to the steric effect. .

  The oligomer generally includes, for example, a homopolymer or copolymer formed from at least one monomer selected from alkyl (meth) acrylate, styrene, acrylonitrile, vinyl acetate and butadiene, Among these, alkyl (meth) acrylate homopolymers or copolymers, polystyrene, and the like are preferable. In the present invention, these oligomers may be substituted with a substituent, and the substituent is not particularly limited, and examples thereof include a hydroxyl group and a halogen atom.

The above vinyl monomers may be polymerized by only one kind, or may be copolymerized by using two or more kinds together. Such a radical polymer is prepared by a known method in accordance with a conventional method for each corresponding vinyl monomer. It is obtained by polymerizing.
For example, a method in which these vinyl monomer and chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in solution at about 50 ° C. to 220 ° C. (solution polymerization method) Can be obtained using

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene Can be mentioned. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

As described above, the dispersion resin (B) in the present invention requires an acid value in the range of 20 to 300 mg / g, preferably in the range of 30 to 250 mg / g, more preferably 30. It is in the range of ~ 200 mg / g.
When the acid value of the (B) dispersion resin is within this range, the dispersibility and dispersion stability of the (A) pigment (pigment) are excellent, and the alkali developability is also excellent.

Moreover, the weight average molecular weight of (B) dispersion resin needs to be in the range of 3,000 to 100,000, preferably in the range of 3,000 to 70,000, more preferably 5, It is in the range of 000 to 50,000.
When the weight average molecular weight of the (B) dispersion resin is within this range, it is preferable from the viewpoint of shortening the dispersion time of the (A) pigment and stability with time of the dispersion.

In addition, the (B) dispersion resin in the present invention has a polymer compound having 2 to 100 pigment-adsorptive groups at the polymer terminal, or a nitrogen-containing heterocyclic ring, and an ethylenically unsaturated group. A polymer compound containing a monomer as a copolymer unit is preferable.
Hereinafter, these two polymer compounds will be specifically described.

(B) The polymer compound having 2 to 100 pigment-adsorptive groups as the dispersion resin at the polymer terminal has a specific acid value and a weight average molecular weight as described above, and the pigment-adsorptive group has Although it will not restrict | limit especially if it is a high molecular compound which has 2-100 in the polymer terminal, It is preferable that it is the following.
That is, a polymer compound having 4 to 70 pigment adsorbing groups at the polymer terminal is preferable, and a polymer compound having 5 to 50 pigment adsorbing groups at the polymer terminal is more preferable. The pigment adsorbing group is preferably an organic dye structure, a heterocyclic structure, an acidic group, a basic group, or the like. Among these, a polymer compound represented by the general formula (1) described later is preferable.

(B) As a polymer compound having a nitrogen-containing heterocycle as a dispersion resin and a monomer having an ethylenically unsaturated group as a copolymer unit, the specific acid value and weight average as described above The polymer compound is not particularly limited as long as it is a polymer compound having a molecular weight, a nitrogen-containing heterocyclic ring, and a monomer having an ethylenically unsaturated group as a copolymerization unit. What has is preferable.
Preferred nitrogen-containing heterocycles include pyrrole, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, triazole, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzo Examples include thiazole, succinimide, phthalimide, naphthalimide, hydantoin, and carbazole.
Especially, it is preferable that it is a polymer containing the copolymer unit derived from the monomer represented by the below-mentioned general formula (I), or the polymer containing the structural unit represented by general formula (a).

Hereinafter, derived from (B-1) the polymer represented by the general formula ( 2 ), (B-2) the monomer represented by the general formula (I), which is the (B) dispersion resin in the present invention. polymers containing copolymerized units, and, for a polymer containing a structural unit represented by (B-3) the general formula (a), will be described respectively.

[(B-1) Polymer Compound Represented by General Formula ( 2 ): (B-1) Specific Dispersion Resin]
First, a description of the polymer compound represented by the following general formula (1), then the general formula (2) polymer compounds represented by (hereinafter to as "(B-1) a specific dispersion resin" Will be described.

In the general formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ¹ may be the same or different.

That is, the A ¹ has a structure capable of adsorbing to a pigment such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen atom. And a monovalent organic group containing at least one functional group capable of adsorbing to a pigment, such as a group, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group.
Hereinafter, the site having the ability to adsorb to the pigment (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.

The adsorption sites are in one A ^1, it may be contained at least one, may contain two or more kinds.
Further, in the present invention, the “monovalent organic group containing at least one kind of adsorption site” means the above-mentioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to It is a monovalent organic group formed by bonding up to 100 oxygen atoms, 1 to 400 hydrogen atoms, and an organic linking group consisting of 0 to 40 sulfur atoms. In the case where adsorption sites themselves may constitute a monovalent organic group, adsorption sites itself may be a monovalent organic group represented by A ^1.
First, the adsorption site constituting A ¹ will be described below.

  Examples of the “organic dye structure” include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone, indanthrone, flavan. Examples of preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone. A diketopyrrolopyrrole dye structure is particularly preferred.

  Examples of the “heterocyclic structure” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine. , Piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, Anthraquinone is mentioned as a preferred example, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, Riazor, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone, anthraquinone are more preferable.

  The “organic dye structure” or “heterocyclic structure” may further have a substituent. Examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group. An acyloxy group having 1 to 6 carbon atoms, such as an aryl group having 6 to 16 carbon atoms such as a hydroxyl group, a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group. Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group , A cyano group, a carbonate group such as t-butyl carbonate, and the like. Here, these substituents may be bonded to the organic dye structure or the heterocyclic ring through the following structural unit or a linking group constituted by combining the structural units.

  Preferred examples of the “acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. A sulfate group, a phosphate group, and a monophosphate group are more preferable, and a carboxylic acid group, a sulfonic acid group, and a phosphate group are particularly preferable.

Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), Preferred examples include the amidinyl group represented by a2).

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group and a benzyl group), a guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, phenyl Represents a benzyl group. Amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.

Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number) Preferred examples include 6 or more aryl groups and an aralkyl group having 7 or more carbon atoms. —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or 1 carbon atom) More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms), -NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 1 to 10 carbon atoms). An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (wherein R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (here And R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like, more preferably —NHCOOR ¹⁸ , -OCONHR ^{21 (wherein,} R ^{18, R 21} each independently represents an alkyl group having from 1 to 10 carbon atoms, 6 or more arylene carbon Group, the number 7 or aralkyl group having a carbon.), Etc. are particularly preferred.

  Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.

  Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferred are an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and an aryl having 6 to 15 carbon atoms. A group (for example, phenyl group, naphthyl group, etc.), an aralkyl group having 7 to 15 carbon atoms (for example, benzyl group, etc.) and the like are particularly preferable.

  Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

The organic linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. An organic linking group consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
Specific examples of the organic linking group include the following structural units or groups constituted by combining the structural units.

  When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 acyloxy group, methoxy group, ethoxy group, etc. Group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.

In the above, as A ¹ , at least one site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is used. It is preferable that it is a monovalent organic group to contain.

The A ¹ is more preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ represents the adsorption site (that is, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, or a group having a coordinating oxygen atom). , A moiety selected from a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group), and R ²⁴ represents a single bond or an (a + 1) -valent organic linking group. a represents an integer of 1 to 10, and a number of B ¹ may be the same or different.

Examples of the adsorption site represented by B ¹ include the same adsorption sites that constitute A ¹ in the general formula (1), and preferred examples are also the same.
Among these, a site selected from an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms is preferable.

R ²⁴ represents a single bond or an (a + 1) -valent organic linking group, and a represents 1 to 10. Preferably, a is 1-7, more preferably, a is 1-5, and particularly preferably, a is 1-3.
(A + 1) valent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And a group consisting of 0 to 20 sulfur atoms, which may be unsubstituted or further substituted.

  Specific examples of the (a + 1) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

R ²⁴ may be a single bond, or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and An (a + 1) valent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent organic linking groups consisting of up to 1 oxygen atom, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 (A + 1) valence consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The organic linking group is particularly preferred.

  Among the above, when the (a + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

In the general formula (1), R ² represents a single bond or a divalent organic linking group. n R ² may be the same or different.
Divalent organic linking groups include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

  Specific examples of the divalent organic linking group include the following structural units or groups formed by combining the structural units.

R ² may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and A divalent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond, or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 And more preferably a divalent organic linking group comprising 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, A divalent organic linking group consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms, in particular preferable.

  Among the above, when the divalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In the general formula (1), R ¹ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
The (m + n) -valent organic linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 200 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the (m + n) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

  (M + n) -valent organic linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, And groups consisting of 0 to 10 sulfur atoms are preferred, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 More preferred are groups consisting of up to 5 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms. Particularly preferred are groups consisting of 1 to 80 hydrogen atoms and 0 to 5 sulfur atoms.

  Among the above, when the (m + n) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

Specific examples (specific examples (1) to (17)) of the (m + n) -valent organic linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

  Among the above specific examples, the most preferable (m + n) -valent organic linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (1), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (1), P ¹ represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. The m P ¹ may be the same or different.
Among polymers, in order to constitute a polymer skeleton, a polymer or copolymer of vinyl monomers, ester polymers, ether polymers, urethane polymers, amide polymers, epoxy polymers, silicone polymers, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). At least one selected from the group consisting of vinyl monomers, selected from the group consisting of polymers or copolymers of vinyl monomers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferable, and a polymer or copolymer of vinyl monomers is particularly preferable.
Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.

Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having an acidic group, and the like are preferable.
Hereinafter, preferable examples of these vinyl monomers will be described.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, (meth) acrylic acid-2-hydroxypropyl, (meth ) Acrylic acid-3-hydroxypropyl, (meth) acrylic acid-4-hydroxybutyl, (meth) acrylic acid 2-methoxyethyl, (meth) acrylic acid 2-ethoxyethyl, (meth) acrylic acid 2- (2- Methoxyethoxy) ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylic acid-3,4-epoxycyclohexylmethyl, (Meth) vinyl acrylate, (meth) acrylic acid-2-phenylvinyl, (meth) acrylic acid-1-propenyl, (meth) acrylic acid allyl, (meth) acrylic acid-2-allyloxyethyl, (meth) Propargyl acrylate, benzyl (meth) acrylate, diethylene glycol (meth) acrylate Methyl ether, (meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic Polyethylene glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth ) Trifluoroethyl acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, Meth) acrylic acid tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid -γ- butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. are also used. it can.

  In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

Examples of the vinyl monomer having an acidic group include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferred from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  Furthermore, a vinyl monomer containing a phenolic hydroxyl group or a vinyl monomer containing a sulfonamide group can be used as the vinyl monomer having an acidic group.

Among the polymer compounds represented by the general formula (1), in the colored pattern forming composition of the present invention, (B-1) a polymer represented by the following general formula (2) used as the specific dispersion resin. The compounds will be described below .

In the general formula (2), A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ² may be the same or different.
Incidentally, A ² has the same meaning as the A ¹ in the general formula (1), a preferable embodiment thereof is also the same.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different.
As the divalent organic linking group represented by R ⁴ and R ⁵ , the same ones as those mentioned as the divalent organic linking group represented by R ² in the general formula (1) are used, The preferred embodiment is also the same.

In the general formula (2), R ³ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
Examples of the (m + n) -valent organic linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
Specifically, the (m + n) -valent organic linking group represented by R ³ is the same as the (m + n) -valent organic linking group represented by R ¹ in the general formula (1). The preferred embodiments are the same.

In said general formula (2), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (2), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In addition, P ² in the general formula (2) represents a polymer skeleton of a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, or a modified product thereof. Can be selected according to the purpose. the m P ² can be the same or different. The preferred embodiment of the polymer is the same as P ¹ in Formula (1).

Among the polymer compounds represented by the general formula (2), those satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below are most preferable.
R ³ : Specific examples (1), (2), (10), (11), (16), or (17)
R ⁴ : A single bond or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygens” A divalent organic linking group comprising an atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, C1-C20 alkyl group such as methyl group and ethyl group, aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide Groups, acyloxy groups having 1 to 6 carbon atoms such as acetoxy groups, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups, etho Aryloxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, carbonate group, such as t- butyl carbonate, and the like.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)
In the following groups, R ²⁵ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer, ester polymer, ether polymer, urethane polymer, and polymer skeleton of these modified products m: 1 to 3
n: 3-6

(Synthesis method)
The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group, or the like is introduced at the terminal; an acid halide having a plurality of the adsorption sites; an alkyl halide having a plurality of the adsorption sites; or a plurality of the adsorption sites. A method of polymerizing the isocyanate and the like.
2. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of the adsorption sites are subjected to a Michael addition reaction.
3. A method of reacting a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having the adsorption site in the presence of a radical generator.
4). A method in which a polymer having a plurality of mercaptans introduced at its terminal is reacted with a compound having a carbon-carbon double bond and the adsorption site in the presence of a radical generator.
5. A method of radical polymerizing a vinyl monomer in the presence of a mercaptan compound having a plurality of the adsorption sites.

  Among the above, the (B-1) specific dispersion resin in the present invention is preferably a synthesis method of 2, 3, 4, 5 and more preferably a synthesis method of 3, 4, 5 because of ease of synthesis. In particular, when (B-1) the specific dispersion resin has a structure represented by the general formula (2), it is most preferable to synthesize by the synthesis method 5 in view of ease of synthesis.

  More specifically, the synthesis method 5 is preferably a method in which a vinyl monomer is radically polymerized in the presence of a compound represented by the following general formula (3).

In the general formula (3), R ⁶ , R ⁷ , A ³ , m, and n have the same meanings as R ³ , R ⁴ , A ² , m, and n in the general formula (2), respectively. The preferred embodiment is also the same.

The compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
6). A method of converting a halide compound having a plurality of adsorption sites into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, a method of reacting with CH ₃ COSNa and hydrolyzing, etc.) )
7). Method of addition reaction of a compound having 3 to 10 mercapto groups in one molecule and a compound having the adsorption site and having a functional group capable of reacting with a mercapto group

Preferable examples of the “functional group capable of reacting with a mercapto group” in the synthesis method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the compound having 3 to 10 mercapto groups in one molecule [specific examples (18) to (34)] include the following compounds.

  Among the above, the following compounds are particularly preferable from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

  A compound having the adsorption site and having a carbon-carbon double bond (specifically, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a coordination group) A group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group; and a carbon-carbon double bond Although it does not restrict | limit especially as a compound which has, The following are mentioned.

  The radical addition reaction product of the “compound having 3 to 10 mercapto groups in one molecule” and the “compound having the adsorption site and having a carbon-carbon double bond” is, for example, The above-mentioned “compound having 3 to 10 mercapto groups in one molecule” and “compound having the adsorption site and having a carbon-carbon double bond” are dissolved in a suitable solvent, It is obtained using a method (thiol-ene reaction method) in which a radical generator is added and added at about 50 ° C. to 100 ° C.

Examples of suitable solvents used in the thiol-ene reaction method include “compound having 3 to 10 mercapto groups in one molecule”, “having the adsorption site, and carbon-carbon double. It can be arbitrarily selected according to the solubility of the “compound having a bond” and the “radical addition reaction product to be produced”.
For example, methanol, ethanol, propanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene Can be mentioned. These solvents may be used as a mixture of two or more.

  In addition, as radical generators, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate An azo compound such as benzoyl peroxide, a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.

The vinyl monomer used in the synthesis method of 5 is not particularly limited, for example, those similar to the vinyl monomers used in obtaining the polymer skeleton represented by P ¹ of the general formula (1) is used It is done.

The above vinyl monomers may be polymerized alone or in combination of two or more.
Further, (B-1) the specific dispersion resin is more preferably copolymerized with a vinyl monomer having one or more acidic groups and a vinyl monomer having no one or more acidic groups.

As (B-1) specific dispersion resin in this invention, what is obtained by polymerizing according to a conventional method by a well-known method using these vinyl monomers and the compound represented by the said General formula (3). preferable. In addition, the compound represented by the general formula (3) in the present invention functions as a chain transfer agent, and may be simply referred to as “chain transfer agent” hereinafter.
For example, a method in which these vinyl monomers and the chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto, and the mixture is polymerized in a solution at about 50 ° C. to 220 ° C. (solution polymerization method) ) To obtain.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene Can be mentioned. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), and 2,2′-azobisisobutyric acid. Azo compounds such as dimethyl, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate can be used.

[(B-2) Polymer containing copolymer units derived from the monomer represented by formula (1): (B-2) specific dispersion resin]
Next, a polymer containing a copolymer unit derived from a monomer represented by the following general formula (I) (hereinafter, appropriately referred to as “(B-2) specific dispersion resin”) will be described.

In the general formula (1), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —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═, and is linked to an N atom via an adjacent atomic group to form a cyclic structure. R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. m1 and n1 each independently represents 0 or 1.

  Hereinafter, the monomer represented by the general formula (1), which is an essential copolymer unit of the (B-2) specific dispersion resin in the present invention, will be described in detail.

In the general formula (1), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
The alkyl group represented by R ⁰¹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.
When the alkyl group represented by R ⁰¹ is a substituted alkyl group, examples of the substituent that can be introduced include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and a halogen group.
Specifically, preferred examples of the alkyl group represented by R ⁰¹ include methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, 2-hydroxy group. Examples thereof include an ethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.

R ⁰² represents an alkylene group.
The alkylene group represented by R ⁰² is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 1 to 4 carbon atoms.
The alkylene group represented by R ⁰² may have a substituent when it can be introduced, and examples of the substituent include a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, and the like. It is done.
Specific examples of the preferable alkylene group represented by R ⁰² include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.

  W represents —CO—, —C (═O) O—, —CONH—, —OC (═O) —, or a phenylene group, and is —C (═O) O— or —CONH—. Is preferred.

Y represents —NR ⁰³ —, —O—, —S—, or —N═, and is linked to an N atom via an adjacent atomic group to form a cyclic structure.
R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom or a methyl group.
Y is particularly preferably -S-, -NH-, or -N =.

  Examples of the cyclic structure formed by linking Y with an N atom through an atomic group adjacent thereto include imidazole ring, pyrimidine ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, and the like, and , A condensed ring structure such as a benzimidazole ring, a benzthiazole ring, a benzoxazole ring, a purine ring, a quinazoline ring, and a perimidine ring, and a condensed ring structure is preferable from the viewpoint of affinity with a pigment. Of the condensed ring structures, a benzimidazole ring, a benzthiazole ring, and a benzoxazole ring are particularly preferred.

X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (= O) S-, -OC (= O)-, -OCONH-, or -NHCO-.
X is particularly preferably —O—, —S—, —CONH—, —NHCONH—, and —NHC (═O) S—.

  m1 and n1 each independently represents 0 or 1, and it is particularly preferable that both m1 and n1 are 1.

  Preferred specific examples (monomer M-1 to monomer M-18) of the monomer represented by the general formula (1) are listed below, but the present invention is not limited thereto.

  The specific dispersion resin (B-2) in the present invention is further ethylenically terminated with a copolymer unit derived from the monomer represented by the general formula (1) from the viewpoint of imparting dispersion stability of the pigment. A graft copolymer containing a copolymer unit derived from a polymerizable oligomer having an unsaturated bond is particularly preferred.

  Such a polymerizable oligomer having an ethylenically unsaturated bond at the terminal is also called a macromonomer because it is a compound having a predetermined molecular weight. In the following description, the “polymerizable oligomer having an ethylenically unsaturated bond at the terminal” in the present invention may be appropriately referred to as “polymerizable oligomer” or “macromonomer”.

  The polymerizable oligomer optionally used in the present invention comprises a polymer chain part and a part of a polymerizable functional group having an ethylenically unsaturated double bond at its terminal. It is preferable from the viewpoint of obtaining a desired graft polymer that such a group having an ethylenically unsaturated double bond is present only at one end of the polymer chain. As the group having an ethylenically unsaturated double bond, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is particularly preferable.

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
The polymer chain portion is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used.

  The polymerizable oligomer is preferably an oligomer represented by the following general formula (II).

In general formula (II), R ¹¹ and R ¹³ each independently represent a hydrogen atom or a methyl group.
R ¹² represents a linking group containing an alkylene group having 1 to ¹² carbon atoms, and the linking group may be an alkylene group having 1 to 12 carbon atoms, or a plurality of the alkylene groups may be ester bonds or ethers. It may be linked via a bond, an amide bond or the like. R ¹² is preferably a group in which an alkylene group having 1 to 4 carbon atoms or an alkylene group having 1 to 4 carbon atoms is linked by breaking an ester bond. The alkylene group represented by R ¹² may further have a substituent (for example, a hydroxyl group).
Y ¹¹ represents a phenyl group having no substituent, a phenyl group having one alkyl group having 1 to 4 carbon atoms, or —COOR ¹⁴ . Here, R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms. Y is preferably a phenyl group or —COOR ¹⁴ where R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms.
q represents an integer of 20 to 200.

  Preferred examples of the polymerizable oligomer (macromonomer) that can be used in the synthesis of the (B-2) specific dispersion resin in the present invention include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and poly-i-. A polymer in which a (meth) acryloyl group is bonded to one molecular end of butyl (meth) acrylate or polystyrene can be exemplified. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

In order to obtain a specific acid value, the (B-2) specific dispersion resin according to the present invention preferably further includes a copolymer unit derived from a monomer having an acid group.
As monomers having an acid group, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monoacrylate Mono (meth) acrylates such as both terminal carboxy polymers methacrylate and the like.

The (B-2) specific dispersion resin according to the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Although it does not restrict | limit especially as a vinyl monomer which can be used here, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, ( Preference is given to meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like. Specific examples of such vinyl monomers include the following compounds.

That is, examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid n. -Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxy (meth) acrylate Ethyl, 2-methoxyethyl (meth) acrylate, 2-ethoxy (meth) acrylate Chill, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) Acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether , Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dimethacrylate Cyclopentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyl and tribromophenyloxyethyl (meth) acrylate.
In addition, in this specification, when showing either or both of "acryl and methacryl", it may describe as "(meth) acryl".

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, etc. are mentioned.

Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

  As a preferable aspect of the (B-2) specific dispersion resin according to the present invention, it contains 2 to 50% by mass of a copolymer unit derived from the monomer represented by the general formula (1), and further, at the terminal. 10 to 90% by mass of copolymer units derived from a polymerizable oligomer having an ethylenically unsaturated bond, 1 to 30% by mass of copolymer units derived from a monomer having an acid group, and copolymerization derived from a vinyl monomer The copolymer containing 0-20 mass% of a unit can be mentioned preferably.

  Specific examples (B-2) of specific dispersion resins [Exemplary Compound 1 to Exemplified Compound 16] that can be suitably used in the colored pattern forming composition of the present invention are listed below together with their weight average molecular weights. It is not limited to.

Exemplary compound (1): monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/25/65 mass%, weight average molecular weight 50000, acid value 163 mg / g)
Exemplary compound (2): Monomer M-2 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75% by mass, weight average molecular weight 35000, acid value 98 mg / g)
Exemplary compound (3): monomer M-3 / methacrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (5/5/10/80 mass%, weight average molecular weight 40000, acid (Value 33 mg / g)
Illustrative compound (4): monomer M-3 / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/10/10/65 mass%, weight average molecular weight 60000, acid (Value 65 mg / g)
Exemplary compound (5): monomer M-4 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/30/60 mass%, weight average molecular weight 80000, acid value 195 mg / g)

Exemplary compound (6): monomer M-4 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/15/75 mass%, weight average molecular weight 20000, acid value 98 mg / g)
Exemplary compound (7): Monomer M-5 / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/15/60 mass%, weight average molecular weight 60000, acid value 117 mg / g)
Exemplary compound (8): Monomer M-5 / acrylic acid / terminated methacryloylated polybutyl acrylate copolymer (15/5/80 mass%, weight average molecular weight 45000, acid value 39 mg / g)
Illustrative compound (9): monomer M-6 / acrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polymethyl methacrylate copolymer (15/10/5/70 mass%, weight average molecular weight 80,000, acid (Value 78 mg / g)
Exemplary Compound (10): Monomer M-6 / Acrylic acid / Terminal methacryloylated polymethyl methacrylate copolymer (12/18/70 mass%, weight average molecular weight 50000, acid value 140 mg / g)

Exemplary compound (11): monomer M-7 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/18/72% by mass, weight average molecular weight 15000, acid value 117 mg / g)
Illustrative compound (12): monomer M-7 / methacrylic acid / benzyl methacrylate / methoxypolyethylene glycol methacrylate copolymer (10/10/50/30 mass%, weight average molecular weight 50000, acid value 65 mg / g)
Illustrative compound (13): monomer M-10 / acrylic acid / 2-hydroxyethyl methacrylate / terminal methacryloylated polystyrene copolymer (5/35/10/50 mass%, weight average molecular weight 20000, acid value 272 mg) / G)
Exemplary compound (14): monomer M-10 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/12/78 mass%, weight average molecular weight 10,000, acid value 78 mg / g)
Illustrative compound (15): Monomer M-10 / acrylic acid / methoxypolyethylene glycol methacrylate copolymer (15/3/82 mass%, weight average molecular weight 15000, acid value 23 mg / g)
Exemplary compound (16): monomer M-13 / methacrylic acid / terminated methacryloylated polymethyl methacrylate copolymer (10/25/65 mass%, weight average molecular weight 20000, acid value 163 mg / g)

The copolymer as described above, which is (B-2) the specific dispersion resin in the present invention, includes the monomer represented by the general formula (1), a polymerizable oligomer used in combination as desired, and other monomers. It can be obtained by radical polymerization in a solvent. As the radical polymerization initiator, a known compound is used, and an azo initiator (for example, dimethyl-2,2′-azobis (2-methylpropionate), azobisisobutyronitrile, 2,2′- Azobis (2-amidinopropane) dihydrochloride, etc.) and peroxides (benzoyl peroxide, potassium persulfate, etc.) are preferably used. In addition to the initiator, a chain transfer agent (for example, 2-mercaptoethanol, 3-mercaptopropionic acid, 2-mercaptoacetic acid, dodecyl mercaptan) may be added and synthesized.
A specific synthesis example will be described later.

[(B-3) Polymer containing structural unit represented by general formula (a): (B-3) specific dispersion resin]
Subsequently, a polymer containing a structural unit represented by the following general formula (a) (hereinafter, appropriately referred to as “(B-3) specific dispersion resin”) will be described.

In the general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure.
^Examples of the alkylene group represented by R ^2a include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a 2-hydroxypropylene group, a methyleneoxy group, an ethyleneoxy group, a methyleneoxycarbonyl group, a methylenethio group, Among them, a methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, and a methylenethio group are preferable.

In the general formula (a), Z ¹ represents a nitrogen-containing heterocyclic structure, specifically, for example, a pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, Examples thereof include quinoline ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone ring, benzimidazole structure, benztriazole structure, benzthiazole structure, cyclic amide structure, cyclic urea structure, and cyclic imide structure.
Among these, the nitrogen-containing heterocyclic structure represented by Z ¹ is preferably a structure represented by the following general formula (b) or general formula (c).

In the general formula (b), X ¹ represents a single bond, an alkylene group (for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, etc.), —O—, —S—, —NR—, and , -C (= O)-. Here, R represents a hydrogen atom or an alkyl group. When R represents an alkyl group, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , T-butyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group and the like.
Among these, X ¹ is preferably a single bond, a methylene group, —O— or —C (═O) —, and particularly preferably —C (═O) —.

  In the general formula (b) and the general formula (c), the ring A, the ring B, and the ring C each independently represent an aromatic ring. Examples of the aromatic ring include a benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrrole ring, imidazole ring, indole ring, quinoline ring, acridine ring, Examples include phenothiazine ring, phenoxazine ring, acridone ring and anthraquinone ring. Among them, benzene ring, naphthalene ring, anthracene ring, pyridine ring, phenoxazine ring, acridine ring, phenothiazine ring, phenoxazine ring, acridone ring, anthraquinone A ring is preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

  Preferred specific examples of the structural unit represented by the general formula (a) [Exemplary structural units (M′-1) to (M′-7)] are listed below, but the present invention is not limited thereto. .

The structural unit represented by the general formula (a) is preferably contained in the specific dispersed resin (B-3) in an amount of 2 to 50% by mass, more preferably 4 to 30% by mass, and more preferably 5 to 20%. It is particularly preferable that it be contained by mass%.
The (B-3) specific dispersion resin in the present invention is a graft containing, in addition to the structural unit represented by the general formula (a), a polymerizable oligomer having an ethylenically unsaturated double bond at the terminal as a copolymer unit. A copolymer is particularly preferred.
Examples of the polymerizable oligomer having an ethylenically unsaturated double bond at the terminal include those similar to the polymerizable oligomer used as a copolymerization component in the above-mentioned (B-2) specific dispersion resin. The same applies to (oligomer represented by formula (II)) and preferred examples (specific examples).

In order to obtain a specific acid value, the (B-3) specific dispersion resin in the present invention preferably further contains a monomer having an acid group (structural unit) as a copolymerization component.
Examples of the monomer having an acid group include (meth) acrylic acid, p-vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, succinic anhydride adduct of 2-hydroxyethyl (meth) acrylate, (meth) And phthalic anhydride adduct of 2-hydroxyethyl acrylate.

The (B-3) specific dispersion resin in the present invention may further contain a copolymerizable vinyl monomer as a copolymer component as long as the effect is not impaired.
Examples of the vinyl monomer that can be used here include those similar to the vinyl monomer used as a copolymerization component in the above-mentioned (B-2) specific dispersion resin, and preferred examples thereof are also the same.

  In addition, as a preferable aspect of the specific dispersion resin according to the present invention, polymerization containing 2 to 50% by mass of the structural unit represented by the general formula (a) and further having an ethylenically unsaturated double bond at the terminal Preferred examples include a copolymer containing 10 to 90% by mass of a functional oligomer, 1 to 30% by mass of a structural unit having an acid group, and 0 to 20% by mass of a vinyl monomer.

  Specific examples (B-3) of specific dispersion resins [Exemplary compounds (I) to (XV)] that can be suitably used for the colored pattern forming composition of the present invention are listed below together with their weight average molecular weights. Is not limited to these.

Exemplary Compound (I): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (Copolymerization Ratio = 10/4/86 Mass%, Weight) that can Form the Exemplary Structural Unit (M′-1) (Average molecular weight 50000, acid value 26 mg / g)
Exemplary Compound (II): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/33/57% by Mass, Weight Average Molecular Weight 30000, Forming the Exemplary Structural Unit (M′-1)) Acid value 214mg / g)
Exemplary Compound (III): Monomer / Methacrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (5/28/10 /) that can Form the Exemplary Structural Unit (M′-1) 57 mass%, weight average molecular weight 40000, acid value 182 mg / g)
Exemplary compound (IV): monomer capable of forming the exemplary structural unit (M′-1) / methacrylic acid / benzyl methacrylate copolymer / terminal methacryloylated polymethyl methacrylate copolymer (15/5/10 / 70 mass%, weight average molecular weight 60000, acid value 33 mg / g)
Exemplary Compound (V): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (20/20/60% by Mass, Weight Average Molecular Weight 80000, Forming the Exemplary Structural Unit (M′-5) Acid value 130mg / g)

Exemplary Compound (VI): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/20/70% by Mass, Weight Average Molecular Weight 30000, Forming the Exemplary Structural Unit (M′-5) Acid value 130mg / g)
Exemplary compound (VII): monomer / acrylic acid / terminal methacryloylated polymethyl methacrylate copolymer (25/20/55 mass%, weight average molecular weight 60000, which can form the exemplary structural unit (M′-5) Acid value 156 mg / g)
Exemplary compound (VIII): monomer / acrylic acid / terminated methacryloylated polybutyl acrylate copolymer (15/15/70% by mass, weight average molecular weight 40000, which can form the exemplary structural unit (M′-5) Acid value 117mg / g)
Exemplary Compound (IX): Monomer / Acrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (15/5/5 /) capable of Forming the Exemplary Structural Unit (M′-5) 75% by mass, weight average molecular weight 80000, acid value 39 mg / g)
Exemplary Compound (X): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (12/17/71% by Mass, Weight Average Molecular Weight 50000, Forming the Exemplary Structural Unit (M′-6)) Acid value 110mg / g)

Exemplary Compound (XI): Monomer / Methacrylic Acid / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (10/12/78% by Mass, Weight Average Molecular Weight 20000, which can Form Exemplary Structural Unit (M′-6)) Acid value 78 mg / g)
Exemplary Compound (XII): Monomer / Methacrylic Acid / Benzyl Methacrylate / Methoxypolyethylene Glycol Methacrylate Copolymer (10/10/50/30% by Weight, Can Form the Exemplary Structural Unit (M′-6)) (Average molecular weight 35000, acid value 65 mg / g)
Exemplary Compound (XIII): Monomer / Acrylic Acid / 2-Hydroxyethyl Methacrylate / Terminal Methacryloylated Polystyrene Copolymer (5/5/10/80 Mass) that can Form the Exemplary Structural Unit (M′-6) %, Weight average molecular weight 20000, acid value 39 mg / g)
Exemplary Compound (XIV): Monomer / Methacrylic Acid / Methyl Methacrylate / Terminal Methacryloylated Polymethyl Methacrylate Copolymer (8/12/10/70% by Mass) that can Form the Exemplary Structural Unit (M′-7) , Weight average molecular weight 70000, acid value 78 mg / g)
Exemplary compound (XV): monomer / acrylic acid / methoxypolyethylene glycol methacrylate copolymer (15/20/65% by mass, weight average molecular weight 15000, acid value) capable of forming the exemplary structural unit (M′-7) 156 mg / g)

The copolymer as described above, which is (B-3) the specific dispersion resin in the present invention, is a monomer that can be a structural unit represented by the general formula (a), a polymerizable oligomer used in combination as desired, Other monomers can be obtained by radical polymerization in a solvent. In this radical polymerization, the same radical polymerization initiator and chain transfer agent as those used when (B-2) the specific dispersion resin is synthesized are used.
A specific synthesis example will be described later.

  As content of (B) dispersion resin in the composition for colored pattern formation of this invention, 15-30 mass% is preferable with respect to the total solid (mass) of this composition, and 18-27 mass% is More preferred. When the content of the (B) dispersion resin is within the above range, the dispersion time of the (A) pigment can be shortened, and the stability after dispersion is kept long, which is preferable.

[Other dispersants]
The composition for forming a colored pattern of the present invention can be used in combination with a conventionally known dispersant (pigment dispersant) in addition to the (B) dispersion resin.

Known dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic types. Copolymers], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of known dispersants (pigment dispersants) that can be used in the present invention include "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166" manufactured by BYK Chemie. , 170 (polymer copolymer) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide) manufactured by EFKA ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) ”,“ Ajisper PB821, PB822 ”manufactured by Ajinomoto Fan Techno Co.,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Polif No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ”manufactured by Enomoto Kasei Co., Ltd.,“ “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “acetamine 86 (stearylamine acetate)”, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester) manufactured by Lubrizol Corporation Amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate) "manufactured by Nikko Chemical Co., Ltd. , MY S-IEX (polyoxyethylene monostearate) "and the like.

  The known dispersing agents as described above can be used in the range of 10 to 100% by mass as the (B) dispersing resin.

[(A) Pigment]
In the composition for forming a colored pattern of the present invention, conventionally known various inorganic pigments or organic pigments can be appropriately selected and used as the (A) pigment.
(A) The pigment as the pigment is preferably an inorganic pigment or an organic pigment, preferably having a high transmittance, and preferably has a particle size as small as possible. As an average particle diameter, 0.01-0.1 micrometer is preferable and 0.01-0.05 micrometer is more preferable.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, Examples thereof include metal oxides such as antimony, and complex oxides of the above metals.

Examples of the organic pigment include:
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;
Examples thereof include carbon black.

Although it does not specifically limit in this invention, The following pigment is more preferable.
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 be used alone or in various combinations in order to increase color purity. Specific examples of combinations are shown below.
For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a bisazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment A mixture of these can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In addition, in the case of the combination of red pigments, it can adjust according to chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a bisazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150 from the viewpoint of obtaining sufficient color purity and suppressing deviation from the NTSC target hue. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment and the purple pigment is preferably 100: 0 to 100: 50, more preferably 100: 5 to 100: 30.

  Examples of the pigment for the black matrix include carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60 from the viewpoint of dispersion stability.

  As content of (A) pigment (pigment) in the composition for colored pattern formation of this invention, 40-90 mass% is preferable with respect to the total solid (mass) of this composition, and 50-80 mass % Is more preferable. (A) When the content of the pigment (pigment) is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

[(C) Photopolymerizable compound]
The colored pattern forming composition of the present invention contains (C) at least one photopolymerizable compound.
The photopolymerizable compound that can be used in the present invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, and a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. Chosen from. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

  Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

_{CH 2 = C (R) COOCH} 2 CH (R ') OH (A)
(However, R and R ′ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these photopolymerizable compounds (addition polymerizable compounds), the details of usage, such as the structure, single use or combined use, and addition amount, can be arbitrarily set according to the performance design of the final coloring pattern. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the colored pattern, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers / different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether). It is also effective to adjust both sensitivity and strength by using a compound of the type). From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
Also, compatibility with other components (for example, (A) pigment (pigment), (D) photopolymerization initiator, (F) binder resin (alkali-soluble resin)) in the colored pattern forming composition of the present invention. The selection and use method of the addition polymerization compound is also an important factor for the dispersibility. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. Further, when the composition for forming a colored pattern is applied to a substrate or the like, a specific structure may be selected for the purpose of improving the adhesion to the substrate or the like.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

  In the present invention, the photopolymerizable compound (C) can be used in combination of two or more, in addition to being used alone.

As content of (C) photopolymerizable compound in the composition for colored pattern formation of this invention, it is preferable that it is 1-90 mass% with respect to the total solid of this composition, and 5-80 mass % Is more preferable, and 10 to 70% by mass is even more preferable. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently performed.
In particular, when the composition for forming a colored pattern of the present invention is used for forming a colored pattern of a color filter, the content is preferably 5 to 50% by mass, and 7 to 40% by mass. More preferably, it is more preferably 10 to 35% by mass.

[(D) Photopolymerization initiator]
The colored pattern forming composition of the present invention contains (D) at least one photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates polymerization of a compound containing an ethylenically unsaturated bond, which will be described later, and has absorption in a wavelength region of 300 to 500 nm. Is preferred. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryls. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.
Hereinafter, each of these compounds will be described in detail.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, and methyl o-benzoylbenzoate.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. et al. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As a photopolymerization initiator used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, and a phosphine oxide compound , Metallocene compounds, oxime compounds, biimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds And compounds selected from the group consisting of 3-aryl-substituted coumarin compounds are preferred.

  More preferably, they are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, biimidazole compounds, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. More preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a biimidazole compound, and a benzophenone compound. Biimidazole compounds are most preferred.

  As content of (D) photoinitiator in the composition for colored pattern formation of this invention, it is preferable that it is 0.1-50 mass% with respect to the total solid of this composition, More preferably Is 0.5 to 30% by mass, particularly preferably 1 to 20% by mass. Within this range, good sensitivity and pattern formability can be obtained.

[(E) Organic solvent]
The composition for forming a colored pattern of the present invention contains (E) an organic solvent.
Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-oxypropionate and 3-oxypropionic acid 3-oxypropionic acid alkyl esters such as ethyl (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-oxypropionate 2-oxypropionic acid alkyl esters such as methyl 2-ethylpropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid) Propyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2 -Ethyl ethoxy-2-methylpropionate), and methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve 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 acetate, propylene glycol propyl ether acetate, etc .;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using independently.

  The content of the (E) photopolymerization initiator in the colored pattern forming composition of the present invention is 5 to 100% by mass with respect to the weight of the (C) photopolymerizable compound of the composition. More preferably, it is 10-60 mass%, Most preferably, it is 15-50 mass%. In this range, good curing characteristics can be obtained.

[(F) Binder resin (alkali-soluble resin)]
The colored pattern forming composition of the present invention preferably contains at least one alkali-soluble resin as a binder resin.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxylic acid, polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
Of these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are particularly suitable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.

As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.
Examples of other monomers copolymerizable with the (meth) acrylic acid include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  These alkali-soluble resins may be random polymers, block polymers, graft polymers or the like.

  The alkali-soluble resin that can be used in the present invention can be synthesized by a conventionally known method. Specifically, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

Examples of the solvent used for synthesizing the alkali-soluble resin include tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether. , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, water and the like. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the alkali-soluble resin that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.

In the present invention, the binder resin (alkali-soluble resin) is preferably a compound having an acid value of 50 to 400 mg / g and a weight average molecular weight of 3,000 to 100,000.
In addition, the acid value of (F) binder resin (alkali-soluble resin) has the more preferable range of 50-300 mg / g, and the range of 50-200 mg / g is still more preferable.
The weight average molecular weight of the (F) binder resin (alkali-soluble resin) is more preferably 3,000 to 70,000, still more preferably 4,000 to 50,000.
The polydispersity (weight average molecular weight / number average molecular weight) is preferably in the range of 1.0 to 10, more preferably in the range of 1.0 to 5.

  As content of (F) binder resin (alkali-soluble resin) in the composition for colored pattern formation of this invention, 1-20 mass% is preferable with respect to the total solid of this composition, More preferably, 2 It is -15 mass%, Most preferably, it is 3-12 mass%.

[Other ingredients]
In addition to the above components (A) to (F), the colored pattern forming composition of the present invention includes, as necessary, a fluorine-based organic compound, a thermal polymerization inhibitor, other fillers, and the aforementioned (B) dispersion resin. , Other dispersants, and (F) polymer additives other than binder resins (alkali-soluble resins), surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and other various additives. be able to.

(Fluorine organic compounds)
In the present invention, by containing a fluorinated organic compound, the liquid properties (particularly fluidity) when used as a coating liquid can be improved, and the uniformity of coating thickness and the liquid-saving property can be improved.
In other words, the interfacial tension between the substrate and the coating liquid is lowered to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  3-40 mass% is suitable for the fluorine content rate of a fluorine-type organic compound, More preferably, it is 5-30 mass%, Most preferably, it is 7-25 mass%. A fluorine-based organic compound having a fluorine content within the above range is effective in terms of coating thickness uniformity and liquid-saving properties, and has good solubility in the composition.

  Examples of the fluorinated organic compound include MegaFuck F171, F172, F173, F177, F141, F142, F143, F144, R30, and F437 (above, Dainippon Ink and Chemicals, Inc.) Manufactured), FLORARD FC430, FC431, FC171 (above, manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (manufactured by Asahi Glass Co., Ltd.).

The fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness, for example, when a coating film to be formed is thinned. It is also effective in slit coating that easily causes liquid breakage.
0.001-2.0 mass% is preferable with respect to the total mass of a composition, and, as for the addition amount of the fluorine-type organic compound in the composition for colored pattern formation of this invention, More preferably, 0.005-1. 0% by mass.

(Thermal polymerization initiator)
It is also effective to contain a thermal polymerization initiator in the colored pattern forming composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

(Surfactant)
The colored pattern forming composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability, and various nonionic, cationic and anionic surfactants can be used. . Among these, a nonionic surfactant and a fluorosurfactant having a perfluoroalkyl group are preferable.
Specific examples of the fluorosurfactant include Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc., and Fluorard (registered trademark) series manufactured by 3M.

  In addition to the above, the colored pattern forming composition of the present invention includes, as specific examples of additives, fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial Non-ionic resin such as esterified maleic acid copolymer, acidic cellulose derivative, polymer having hydroxyl group added with acid anhydride, alcohol-soluble nylon, phenoxy resin formed from bisphenol A and epichlorohydrin; , Kachin, anionic surfactants, specifically phthalocyanine derivatives (commercially available product EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (Co) polymer polyflow No. 75, no. 90, no. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.);

  Examples of other additives include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Sorbitan fatty acid esters (nonionic surfactants such as Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1 manufactured by BASF; W004, W005, W017 ( Anionic surfactants such as EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, Polymer dispersing agents such as FKA Polymer 401, EFKA Polymer 450 (manufactured by Morishita Sangyo Co., Ltd.), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000 , 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Geneca); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei); 2- (3-t-butyl-5-methyl-2- Hydroxyphenyl) -5-chlorobenzo Examples thereof include ultraviolet absorbers such as triazole and alkoxybenzophenone; and aggregation preventing agents such as sodium polyacrylate.

  Further, when the alkali solubility of the uncured part is promoted and the developability of the photocurable composition is further improved, the photocurable composition is an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

(Thermal polymerization inhibitor)
In the present invention, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the photocurable composition.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% by mass to about 10% by mass of the total composition.

[Preparation of colored pattern forming composition]
In the colored pattern forming composition of the present invention, as shown below, a pigment dispersion is prepared in advance, and (C) a photopolymerizable compound and (D) a photopolymerization initiator are added to this pigment dispersion (preferably Can be prepared by mixing (with an organic solvent) and, if necessary, an additive such as a surfactant.

Here, the preparation method of the pigment dispersion used for the composition for colored pattern formation of this invention is demonstrated.
The pigment dispersion in the present invention is, for example, a mixture of the above-mentioned (A) pigment (pigment), (B) dispersion resin, and (E) organic solvent, a vertical or horizontal sand grinder, pin mill, slit mill, It can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm using a sonic disperser or the like.
In addition, before carrying out bead dispersion, while applying a strong shear force using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also possible to perform a kneading and dispersing process.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

  The colored pattern forming composition of the present invention thus obtained contains the above-mentioned components, so that (A) the pigment (pigment) is kept in a good dispersion state in the composition, and good color characteristics are obtained. With this composition, for example, when a color filter is constructed, a high contrast can be obtained.

<Coloring Pattern Forming Method, Color Filter Manufacturing Method, and Color Filter>
Next, the colored pattern forming method, the color filter manufacturing method, and the color filter of the present invention will be described.
The coloring pattern formation method of this invention can form a desired coloring pattern by including the process of apply | coating the composition for coloring pattern formation of this invention by the slit coat method.
This colored pattern forming method is preferably applied to a method for producing a color filter.
Hereinafter, a color filter manufacturing method (a color filter manufacturing method of the present invention) to which the colored pattern forming method of the present invention is applied will be described.

The method for producing a color filter of the present invention comprises a step of forming a photosensitive film by applying the colored pattern forming composition of the present invention directly or via another layer (hereinafter referred to as “photosensitive film” as appropriate). Abbreviated as “formation step”), a step of pattern exposure (exposed through a mask) of the formed photosensitive film (hereinafter abbreviated as “exposure step” as appropriate), and photosensitivity after exposure. A step of developing the film to form a colored pattern (hereinafter abbreviated as “development step” as appropriate).
Hereafter, each process in the manufacturing method of this invention is demonstrated.

(Photosensitive film forming process)
In the photosensitive film forming step, the colored film forming composition of the present invention is applied (applied) directly or on a substrate having another layer to form a photosensitive film.

Examples of the substrate that can be used in this step include soda glass, Pyrex (registered trademark) glass, quartz glass, and those in which a transparent conductive film is attached to these substrates, photoelectric sensors used for imaging devices, and the like. Examples of the conversion element substrate include a silicone substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, if necessary, an undercoat layer (other layers) may be provided on these substrates for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface.

In the method for producing a color filter of the present invention, as a method for applying the colored pattern forming composition of the present invention onto a substrate, it is necessary to use a slit coating method, but in addition, an inkjet method, a spin coating, a casting coating. Various coating methods such as roll coating and screen printing can be applied.
As a coating film thickness of the composition for coloring pattern formation, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is still more preferable.

  The photosensitive film coated on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven, or the like.

(Exposure process)
In the exposure step, the photosensitive film formed in the photosensitive film forming step is exposed through a mask having a predetermined mask pattern, that is, pattern exposure is performed.
In this step, only the coating film portion irradiated with light can be cured by exposing the photosensitive film as the coating film through a predetermined mask pattern.

As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.
If the color filter to be manufactured is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter to be manufactured is a solid-state imaging device, it is more preferably preferably 50~1000mJ / cm ² 30~1500mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

(Development process)
Next, by performing development processing, the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains. Any developer can be used as long as it dissolves the film of the photocurable composition in the uncured part while not dissolving the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

Examples of the organic solvent include the solvents described above that can be used in preparing the colored pattern forming composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution diluted with pure water so as to be 1% by mass is preferably used as the developer.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

After the development step, excess developer is washed away and dried, followed by heat treatment (post-bake).
The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicone substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coating film after development is in the above-mentioned condition. be able to.

  By repeating the photosensitive film formation step, the exposure step, and the development step (and heat treatment if necessary) as described above for the desired number of hues, a color filter having the desired hue (the color filter of the present invention) is produced. Is done.

The color filter obtained by the method for producing a color filter of the present invention as described above has a color pattern formed on the substrate using the composition for forming a color pattern of the present invention, and has a contrast of 5000 or more. can do.
Here, the contrast means a contrast that is individually evaluated for each color of R (red), G (green), and B (blue) constituting the color filter.
The contrast measurement method is as follows. In the state where the polarizing plates are overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other, the backlight Y is applied from the side of one polarizing plate, and the luminance Y1 of the light passing through the other polarizing plate is obtained. taking measurement. Next, in a state where the polarizing plates are orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. The contrast is calculated by Y1 / Y2 using the obtained measurement value. Here, Nitto Denko G1220DUN was used as the polarizing plate, and a color luminance meter BM-5 (manufactured by Topcon Corporation) was used as the measuring instrument.

  When the colored pattern forming composition of the present invention is applied onto a substrate to form a film, the dry thickness of the film is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm. Most preferably, the thickness is 1.0 to 2.5 μm.

As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, solid-state imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicone substrate and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  The use of the composition for forming a colored pattern of the present invention has mainly been described mainly for use in pixels of a color filter, but it goes without saying that the composition can also be applied to a black matrix provided between pixels of a color filter. As for the black matrix, except that a black colorant such as carbon black or titanium black is added to the composition for forming a colored pattern of the present invention as a colorant, pattern exposure, It can be formed by alkali development and then post-baking to accelerate the curing of the film.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter, is opposed to the electrode substrate, and the gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display element of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

<Synthesis example>
[(B-1) Synthesis of chain transfer agent used in obtaining specific dispersion resin]
In the following manner, chain transfer agents 1 to 13 used to obtain (B-1) specific dispersion resin were synthesized.

[Synthesis Example: Synthesis of Chain Transfer Agent 1]
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] 7.83 parts, and a compound having the following adsorption site and having a carbon-carbon double bond (m -1) 15.57 parts was dissolved in 93.60 parts of dimethylformamide and heated to 70 ° C under a nitrogen stream. To this, 0.06 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.06 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 20% solution of the mercaptan compound (chain transfer agent 1) according to the present invention shown below was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 2]
In the synthesis of the chain transfer agent 1, 15.57 parts of the compound (m-1) having an adsorption site and having a carbon-carbon double bond, 93.60 parts of dimethylformamide, having an adsorption site, carbon -The mercaptan according to the present invention shown below in the same manner as in the synthesis of the chain transfer agent 1 except that 14.61 parts of the compound (m-2) having a carbon double bond and 89.78 parts of dimethylformamide were used. A 20% solution of the compound (chain transfer agent 2) was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 3]
In the synthesis of the chain transfer agent 1, 15.57 parts of the compound (m-1) having an adsorption site and having a carbon-carbon double bond, 93.60 parts of dimethylformamide, having an adsorption site, carbon -In the present invention shown below, in the same manner as in the synthesis of the chain transfer agent 1, except that the compound (m-3) having carbon double bond (10.06 parts) and propylene glycol monomethyl ether (41.75 parts) were used. A 30% solution of the mercaptan compound (chain transfer agent 3) was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 4]
In the synthesis of the chain transfer agent 1, 15.57 parts of the compound (m-1) having an adsorption site and having a carbon-carbon double bond, 93.60 parts of dimethylformamide, having an adsorption site, carbon -Except having changed into 5.26 parts of compound (m-4) which has a carbon double bond, and 30.54 parts of propylene glycol monomethyl ethers, it carries out to this invention shown below similarly to the synthesis | combination of the said chain transfer agent 1. A 30% solution of the mercaptan compound (chain transfer agent 4) was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 5]
In the synthesis of the chain transfer agent 1, 15.57 parts of the compound (m-1) having an adsorption site and having a carbon-carbon double bond, 93.60 parts of dimethylformamide, having an adsorption site, carbon -In the present invention shown below, in the same manner as in the synthesis of the chain transfer agent 1, except that the compound (m-5) having carbon double bond (4.71 parts) and propylene glycol monomethyl ether (29.25 parts) were used. A 30% solution of the mercaptan compound (chain transfer agent 5) was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 6]
7.83 parts of dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] and the following compound having an adsorption site and having a carbon-carbon double bond ( m-6) 6.51 parts was dissolved in 33.45 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this, 0.06 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.06 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 30% solution of the mercaptan compound (chain transfer agent 6) according to the present invention shown below was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 7]
In the synthesis of the chain transfer agent 6, 6.51 parts of the compound (m-6) having an adsorption site and having a carbon-carbon double bond and 33.45 parts of propylene glycol monomethyl ether were adsorbed to the following adsorption site. And the compound (m-7) having a carbon-carbon double bond is changed to 5.80 parts and propylene glycol monomethyl ether 31.81 parts in the same manner as in the synthesis of the chain transfer agent 6, A 30% solution of the mercaptan compound (chain transfer agent 7) according to the present invention shown below was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 8]
In the synthesis of the chain transfer agent 6, 6.51 parts of the compound (m-6) having an adsorption site and having a carbon-carbon double bond and 33.45 parts of propylene glycol monomethyl ether were adsorbed to the following adsorption site. And the compound (m-8) having a carbon-carbon double bond (12.46 parts) and dimethylformamide (47.35 parts). A 30% solution of the mercaptan compound (chain transfer agent 8) according to the present invention is obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 9]
In the synthesis of the chain transfer agent 6, 6.51 parts of the compound (m-6) having an adsorption site and having a carbon-carbon double bond and 33.45 parts of propylene glycol monomethyl ether were adsorbed to the following adsorption site. And having the carbon-carbon double bond (m-9) 10.46 parts and dimethylformamide 42.67 parts. A 30% solution of the mercaptan compound (chain transfer agent 9) according to the present invention is shown.

[Synthesis Example: Synthesis of Chain Transfer Agent 10]
In the synthesis of the chain transfer agent 6, 6.51 parts of the compound (m-6) having an adsorption site and having a carbon-carbon double bond and 33.45 parts of propylene glycol monomethyl ether were adsorbed to the following adsorption site. And the compound (m-10) having a carbon-carbon double bond (7.86) and propylene glycol monomethyl ether (36.61 parts), except that the chain transfer agent 6 was synthesized, A 30% solution of the mercaptan compound (chain transfer agent 10) according to the present invention shown below was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 11]
In the synthesis of the chain transfer agent 6, 6.51 parts of the compound (m-6) having an adsorption site and having a carbon-carbon double bond and 33.45 parts of propylene glycol monomethyl ether were adsorbed to the following adsorption site. The compound (m-11) having a carbon-carbon double bond is changed to 11.72 parts and propylene glycol monomethyl ether 45.61 parts in the same manner as in the synthesis of the chain transfer agent 6, A 30% solution of the mercaptan compound (chain transfer agent 11) according to the present invention shown below was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 12]
4.89 parts of pentaerythritol tetrakis (3-mercaptopropionate) [PEMP; manufactured by Sakai Chemical Industry Co., Ltd.] and the following compound having an adsorption site and having a carbon-carbon double bond (m- 6) 3.90 parts was dissolved in 20.51 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this, 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, the following 30% solution of the mercaptan compound (chain transfer agent 12) according to the present invention was obtained.

[Synthesis Example: Synthesis of Chain Transfer Agent 13]
7.83 parts of dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd.] and the following compound having an adsorption site and having a carbon-carbon double bond ( m-6) 4.55 parts was dissolved in 28.90 parts of propylene glycol monomethyl ether and heated to 70 ° C. under a nitrogen stream. To this, 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, the following 30% solution of the mercaptan compound (chain transfer agent 13) according to the present invention was obtained.

[(B-1) Synthesis of specific dispersion resin]
Subsequently, as shown below, (B-1) specific dispersion resins B-1-1-1 to B-1-22 in the present invention were synthesized.

[Synthesis Example: Synthesis of B-1-1]
A mixed solution of 23.37 parts of a 20% solution of chain transfer agent 1 obtained as described above, 18 parts of methyl methacrylate (MMA; monomer) and 2 parts of methacrylic acid (MAA; monomer) was placed under a nitrogen stream. And heated to 80 ° C. To this was added 2,7'-azobis (isobutyronitrile) [AIBN, Wako Pure Chemical Industries, Ltd.] 0.007 part, heated for 3 hours, then added AIBN 0.007 part again, under nitrogen flow And reacted at 80 ° C. for 3 hours. Further, 0.007 part of AIBN was added, and the mixture was reacted at 80 ° C. for 3 hours under a nitrogen stream. Then, it cooled to room temperature and diluted with acetone. After reprecipitation using a large amount of methanol / water (1/1 weight ratio), vacuum drying is carried out, whereby (B-1) specific dispersion resin (B-1-1: polystyrene conversion) in the present invention shown below. 21 parts of a solid having a weight average molecular weight of 32000) was obtained.
The acid value of this (B-1) specific dispersion resin B-1-1 was 60 mg / g.

[Synthesis Example: Synthesis of B-1-2 to B-1-5]
Furthermore, except that the chain transfer agent, the type and amount of monomer, the amount of AIBN, and the reprecipitation method were changed as shown in Table 1 below, the same as in the synthesis of B-1-1 in the present invention ( B-1) Specific dispersion resins B-1-2 to B-1-5 were obtained. In Table 1, the acid value of each (B-1) specific dispersion resin is also shown.

  Hereinafter, the structures of synthesized (B-1) specific dispersion resins B-1-2 to B-1-5 are shown.

[Synthesis Example: Synthesis of B-1-6]
A mixed solution of 19.11 parts of a 30% solution of chain transfer agent 6 and 20 parts of methyl methacrylate obtained as described above was heated to 80 ° C. in a nitrogen stream. To this, 0.013 part of 2,2′-azobis (isobutyronitrile) [AIBN, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.013 part of AIBN was added and reacted at 80 ° C. for 3 hours under a nitrogen stream. Then, it cooled to room temperature and diluted with acetone. After reprecipitation using a large amount of methanol, vacuum drying is carried out to obtain the following (B-1) specific dispersion resin (B-1-6: weight average molecular weight 12,000 in terms of polystyrene) according to the present invention. 13 parts of a solid were obtained.
The acid value of this (B-1) specific dispersion resin B-1-6 was 47 mg / g.

[Synthesis Example: Synthesis of B-1-7]
In the synthesis of B-1-6, except that 19.11 parts of 30% solution of chain transfer agent 6 was changed to 9.56 parts and 0.013 parts of AIBN were changed to 0.007 parts, B-1-6 In the same manner as in the above synthesis, 14 parts of a solid compound (B-1-7: weight average molecular weight in terms of polystyrene of 20000) according to the present invention shown below was obtained.
The acid value of this (B-1) specific dispersion resin B-1-7 was 28 mg / g.

[Synthesis Example: Synthesis of B-1-8]
In the synthesis of B-1-6, except that 20 parts of methyl methacrylate was changed to 19.5 parts of butyl methacrylate and 8.5 parts of 2-hydroxyethyl methacrylate, the synthesis of B-1-6 In the same manner as above, 13 parts of the solid (B-1) specific dispersion resin (B-1-8: polystyrene-equivalent weight average molecular weight 13000) according to the present invention shown below was obtained.
The acid value of this (B-1) specific dispersion resin B-1-8 was 43 mg / g.

[Synthesis Examples B-1-9 to B-1-20]
Furthermore, except that the chain transfer agent, the type and amount of monomer, the amount of AIBN, and the reprecipitation method were changed as shown in Table 2 below, the same as in the synthesis of B-1-6 in the present invention ( B-1) Specific dispersion resins B-1-9 to B-1-20 were obtained. In Table 2, the acid value of each (B-1) specific dispersion resin is also shown.

  Hereinafter, the structures of the synthesized (B-1) specific dispersion resins B-1-9 to B-1-20 are shown.

[Synthesis Example: Synthesis of B-1-21]
A mixed solution of 4.99 parts of a 30% solution of chain transfer agent 13 obtained as described above, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether, It heated at 90 degreeC under nitrogen stream. While stirring this mixed solution, 0.139 part of dimethyl 2,2′-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.], 5.36 parts of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate 9 40 parts of the mixed solution was added dropwise over 2.5 hours. After the completion of the dropwise addition, the mixture was reacted at 90 ° C. for 2.5 hours, and then a mixed solution of 0.046 parts of dimethyl 2,2′-azobisisobutyrate and 4.00 parts of propylene glycol monomethyl ether acetate was added, and further 2 hours. Reacted. By adding 1.52 parts of propylene glycol monomethyl ether and 21.7 parts of propylene glycol monomethyl ether acetate to the reaction liquid and cooling to room temperature, the following (B-1) specific dispersion resin (B- 1-21: Polystyrene equivalent weight average molecular weight 24000) solution (specific dispersion resin 30% by mass, propylene glycol monomethyl ether 21% by mass, propylene glycol monomethyl ether acetate 49% by mass).
The acid value of this (B-1) specific dispersion resin B-1-21 was 48 mg / g.

[Synthesis Example: Synthesis of B-1-22]
Mixing of 4.99 parts of 30% solution of chain transfer agent 13 described in the synthesis of B-1-21, 19.0 parts of methyl methacrylate, 1.0 part of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether Except that the solution was changed to a mixed solution of 5.03 parts of a 30% solution of chain transfer agent 13, 18.0 parts of methyl methacrylate, 2.0 parts of methacrylic acid, and 4.66 parts of propylene glycol monomethyl ether. By making it react like the synthesis | combination of B-1-21, the solution (specific) of the (B-1) specific dispersion resin (B-1-22: polystyrene conversion weight average molecular weight 25000) which concerns on this invention shown below is shown. Dispersion resin 30 mass%, propylene glycol monomethyl ether 21 mass%, propylene glycol monomethyl ether acetate 49 mass%) was obtained.
The acid value of this (B-1) specific dispersion resin B-1-22 was 78 mg / g.

[(B-2) Synthesis of specific dispersion resin]
The (B-2) specific dispersion resin [Exemplary compounds (2), (6), (14)] in the present invention was synthesized as follows.

[Synthesis Example B-2-1]
(Synthesis of monomer 1)
9.51 parts of 2-aminopyrimidine are dissolved in 30 parts of pyridine and heated to 45 ° C. To this, 17.1 parts of 2-methacryloyloxyethyl isocyanate is dropped, and the mixture is further stirred with heating at 50 ° C. for 5 hours. The reaction solution was poured into 200 parts of distilled water while stirring, and the resulting precipitate was filtered and washed to obtain 23.8 parts of monomer 1.

(Synthesis of Exemplary Compound (2))
5.0 parts of the monomer 1, 37.5 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 7.5 parts of methacrylic acid, and 167 parts by weight of methoxypropylene glycol Then, the mixture is introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated to 78 ° C. while flowing nitrogen into the flask. 0.07 part of dimethyl-2,2′-azobis (2-methylpropionate) (Wako Pure Chemical Industries, Ltd. V-601) was added thereto, and the mixture was stirred with heating at 78 ° C. for 2 hours. Two hours later, 0.07 part of V-601 was further added, and the mixture was heated and stirred for 3 hours to obtain a 30% solution of the exemplified compound (2).

[Synthesis Example B-2-2]
(Synthesis of Exemplary Compound (6))
Synthesis Example B-2-1: “9.51 parts of 2-aminopyrimidine” used in the synthesis of Monomer 1 was changed to “13.3 parts of 2-aminobenzimidazole”, and dimethyl-2,2′- Exemplified compound described above in the same manner as in Synthesis Example B-2-1 except that the amount of azobis (2-methylpropionate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) was 0.15 part. A 30% solution of (6) was obtained.

[Synthesis Example B-2-3]
(Synthesis of monomer 3)
13.3 parts of 2-aminobenzimidazole and 13.8 parts of potassium carbonate are dissolved in 30 parts of dimethyl sulfoxide and heated to 45 ° C. To this, 22.9 parts of chloromethylstyrene is dropped, and the mixture is further heated and stirred at 50 ° C. for 5 hours. The reaction solution was poured into 200 parts of distilled water while stirring, and the resulting precipitate was filtered and washed to obtain 25.6 parts of monomer 3.

(Synthesis of Exemplary Compound (14))
Monomer 1 in Synthesis Example B-2-1 was changed to monomer 3, 39 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), and 6 parts of methacrylic acid All except that the amount of addition of dimethyl-2,2′-azobis (2-methylpropionate) (V-601 manufactured by Wako Pure Chemical Industries, Ltd.) was changed to 0.30 part. In the same manner as in the synthesis of the exemplary compound (2) in 2-1, a 30% solution of the above-described exemplary compound (14) was obtained.

[(B-3) Synthesis of specific dispersion resin]
The (B-3) specific dispersion resin [Exemplary compounds (II), (VI), (XI)] in the present invention was synthesized as follows.

[Synthesis Example B-3-1]
(Synthesis of monomer 1)
9.76 parts of 9 (10H) acridone and 5.94 parts of potassium t-butoxy are dissolved in 30 parts of dimethyl sulfoxide and heated to 45 ° C. To this, 15.26 parts of chloromethylstyrene is dropped, and the mixture is further heated and stirred at 50 ° C. for 5 hours. The reaction solution was poured into 200 parts of distilled water while stirring, and the resulting precipitate was filtered and washed to obtain 11.9 parts of monomer 1.

(Synthesis of Exemplified Compound (II))
5.0 parts of the monomer 1, 28.5 parts of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 16.5 parts of methacrylic acid, and 50 parts by weight of methoxypropylene glycol It introduce | transduces into the substituted three necked flask, and stirs with a stirrer (Shinto Kagaku Co., Ltd .: Three-one motor), heats up, flowing nitrogen in a flask, and heats up to 78 degreeC. To this, 0.07 part of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was heated and stirred at 78 ° C. for 2 hours. Two hours later, 0.07 part of V-65 was further added, and after 3 hours of heating and stirring, 66.7 parts of propylene glycol monomethyl ether acetate was added to the resulting reaction solution, and 30% of the above exemplified compound (II) was added. A solution was obtained.

[Synthesis Example B-3-2]
(Synthesis of Exemplified Compound (VI))
Synthesis Example B-3-1: “9 (10H) Acridone 9.76 parts” used in the synthesis of monomer 1 was changed to “7.8 parts of phthalimide”, and polymethyl methacrylate having a methacryloyl group at the terminal (AA- 6: Toa Gosei Co., Ltd.) was changed to 35 parts and methacrylic acid was changed to 10 parts, respectively, in the same manner as in Synthesis Example B-3-1 to obtain a 30% solution of the exemplified compound (VI) described above. .

[Synthesis Example B-3-3]
(Synthesis of Exemplified Compound (XI))
Synthesis Example B-3-1: “9 (10H) Acridone 9.76 parts” used in the synthesis of Monomer 1 was changed to “1,8-naphthalimide 9.52 parts”, and a poly having a methacryloyl group at the terminal Methyl methacrylate (AA-6: manufactured by Toa Gosei Co., Ltd.) was changed to 39 parts and methacrylic acid was changed to 6.0 parts, respectively. 2,2-azobis (2,4-dimethylvaleronitrile) (Wako Pure Chemical Industries, Ltd.) Except that V-65) was changed to 0.15 parts, a 30% solution of the exemplified compound (XI) was obtained in the same manner as the synthesis of the exemplified compound (II) in Synthesis Example B-3-1. .

Example 1
Ingredients having the following composition were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 3 hours to prepare a mixed solution.
〔composition〕
(A) Pigment: C.I. I. Pigment Red 254: 51 parts (A) Pigment: C.I. I. Pigment Red 177 ... 13 parts (B-2) Specific Dispersing Resin: Exemplified Compound (1) Solution (solid content 30%) ... 113 parts (E) Organic solvent: Propylene glycol monomethyl ether acetate ... 310 parts

  Subsequently, the mixed solution obtained above was subjected to a dispersion treatment using 0.3 mmφ zirconia beads for 3 hours with a bead disperser Star Mill (manufactured by Ashizawa Finetech). Furthermore, a dispersion treatment using 0.03 mmφ zirconia beads was carried out for 1 hour in the same machine to obtain a red pigment dispersion.

Components of the following composition were further added to the obtained pigment dispersion and mixed by stirring to prepare a colored pattern forming composition (color resist solution) of the present invention.
〔composition〕
・ (C) Photopolymerizable compound: DPHA (dipentaerythritol pentahexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 25 parts ・ (D) Photopolymerization initiator: 4- [o-bromo-pN, N-di (Ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -S-triazine 5 parts- (F) Binder resin: benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer Propylene glycol monomethyl ether acetate solution (solid content 45%) of coalescence (acid value: 110 mg / g, weight average molecular weight: 5,000): 37 parts, Epicron N-695 (Dainippon Ink Epoxy Resin): 5 parts Emulgen A-60 (Kao nonionic surfactant) ... 2 parts (E) Organic solvent: Propylene glycol monomethyl ether acetate ... 50 parts · (E) organic solvent: ethyl 3-ethoxypropionate · · 84 parts · propylene glycol monomethyl ether acetate solution of p-methoxyphenol (solid content 1%) · · · 1 part · MegaFuck F-781 (Dainippon Ink) Fluorine surfactant) in propylene glycol monomethyl ether acetate (solid content 10%)… 1 part

(Physical property measurement)
The following physical property measurement was performed on the obtained composition for forming a colored pattern.

(1) Measurement of viscosity, surface tension and contact angle (23 ° C., 50% RH)
About the obtained composition for forming a colored pattern, the viscosity η after composition preparation was measured using an E-type viscometer (RE550L, manufactured by Toki Sangyo Co., Ltd.), which was 3.5 mPa · sec. The surface tension measured was 27 mN / m.
Further, the contact angle to the glass substrate (1737, manufactured by Corning) was measured by an automatic contact angle meter (DropMaster DM500, manufactured by Kyowa Interface Science Co., Ltd.) and found to be 18 °.

(2) Solvent solubility measurement The obtained colored pattern forming composition was applied on a 550 mm × 650 mm glass substrate (1737, Corning) using a slit coater (head coater, head mounted by Faster). Application was performed at a speed of 200 mm / sec. Thereafter, it was dried in an oven at 90 ° C. for 60 seconds (pre-baking). The film thickness of the dry film was 2 μm.
The substrate having the dry film was fixed at an inclination of 45 degrees, and propylene glycol monomethyl ether acetate droplets (0.1 ml) were dropped at 1 second intervals, and dissolution of the film surface was visually observed.
The evaluation index is as follows.
◎: The film dissolves in 1 drop ○: The film dissolves in 2 to 3 drops △: The film dissolves in 4 to 5 drops x: The film does not dissolve in 5 drops

(Evaluation 1)
Using the obtained colored pattern forming composition, slit coater coating was performed under the same conditions as the solubility measurement film. Application of 150 sheets (application interval 30 seconds for each sheet: dummy discharge 2 seconds) was performed, and the surface of the 150th sheet was visually observed.
The evaluation index is as follows, and Δ is the lower limit of the practical allowable range.
◎: The number of defects is less than 0.5 per 0.25 square meter. ○: The number of defects is less than 1 per 0.25 square meter. △: The number of defects is 1 or more and less than 2 per 0.25 square meter. ×: The number of defects is 2 or more per 0.25 square meters

(Evaluation 2)
Using the resulting colored pattern forming composition, a slit coater (head coater, equipped with a head manufactured by Faster Corp.) was applied onto a 550 mm × 650 mm glass substrate (1737, manufactured by Corning) at a coating speed of 200 mm / sec. A coating film was formed.
The entire surface of the coating film is exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film is exposed to a 1% aqueous solution of an alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials). Covered and rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. The film exposed and developed as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored resin film (colored pattern) for the color filter on the glass substrate. A filter substrate (color filter) was produced.
A polarizing plate is placed on the colored resin film (colored pattern) of the colored filter substrate, the colored resin film is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal are measured using BM-5 manufactured by Topcon Corporation. Then, a value obtained by dividing the parallel brightness by the orthogonal brightness (= the brightness when parallel / the brightness when orthogonal) was used as an index for contrast evaluation.

(Examples 2 to 16)
In Example 1, (B-2) The exemplified compound 1 of the specific dispersion resin is replaced with (B-2) Exemplified compounds 2 to 16 of the specific dispersion resin shown in Table 3 below, respectively, and (B-2) Specific dispersion resin amount (in the table, the solid content amount is displayed: actually, a solution having a solid content concentration of 30% is used), (C) photopolymerizable compound amount, (D) photopolymerization initiator amount, and (F) binder resin ( In the table, the amount of the solid content is displayed (actually, a solution having a solid content concentration of 45% is used), except that the amount is changed as shown in Table 3, respectively. The composition for color pattern formation was further prepared, and the same evaluation as Example 1 was performed.

(Example 17)
A green pigment dispersion was prepared in the same manner as in Example 1 except that the red pigment dispersion was replaced with a green pigment dispersion having the following composition in Example 1. The green pigment dispersion Further, a colored pattern forming composition was prepared in the same manner as in Example 1 except that components having the following composition were additionally added, and the same evaluation as in Example 1 was performed.

〔composition〕
(A) Pigment: C.I. I. Pigment Green 36: 37 parts (A) Pigment: C.I. I. Pigment Yellow 150: 24 parts. (B-3) Specific Dispersing Resin: The above-mentioned Exemplified Compound (I) Solution (Solid Content 30%) ... 103 Parts. (E) Organic Solvent: Propylene Glycol Monomethyl Ether Acetate ... 228 Parts

[Additional composition]
・ (C) Photopolymerizable compound: DPHA (dipentaerythritol pentahexaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 23 parts ・ (D) Photopolymerization initiator: 2,2′-bis (o-chlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole 6 partsCompound of the following structural formula 3 partsF (F) Binder resin: benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Acid value: 113 mg / g, weight average molecular weight: 5,000) propylene glycol monomethyl ether acetate solution (solid content 45%) ... 41 parts, Epicron N-695 (Epoxy resin made by Dainippon Ink) ... 5 parts, Emulgen A-60 (Kao nonionic surfactant) 2 parts (E) Organic solvent: propylene glycol monomethyl ether acetate 360 parts (E) Organic solvent: Ethyl 3-ethoxypropionate: 170 parts ・ Propylene glycol monomethyl ether acetate solution of p-methoxyphenol (solid content: 1%): 1 part ・ Megafac F-781 (fluorine surfactant manufactured by Dainippon Ink) Propylene glycol monomethyl ether acetate solution (solid content 10%) ... 1 part

(Examples 18 to 31)
In Example 17, (B-3) The exemplified compound I of the specific dispersion resin is replaced with (B-3) Exemplified compounds II to XV of the specific dispersion resin shown in Table 4 below, respectively, and (B-3) Specific dispersion resin amount (in the table, the solid content amount is displayed: actually, a solution having a solid content concentration of 30% is used), (C) photopolymerizable compound amount, (D) photopolymerization initiator amount, and (F) binder resin ( In the table, the amount of the solid content is displayed (actually, a solution having a solid content concentration of 45% is used). The composition for color pattern formation was further prepared, and the same evaluation as Example 1 was performed.

(Example 32)
A blue pigment dispersion was prepared in the same manner as in Example 1 except that the red pigment dispersion was replaced with a blue pigment dispersion having the following composition in Example 1. The blue pigment dispersion Further, a colored pattern forming composition was prepared in the same manner as in Example 1 except that components having the following composition were additionally added, and the same evaluation as in Example 1 was performed.

〔composition〕
(A) Pigment: C.I. I. Pigment Blue 15; 6... 46 parts (A) Pigment: C.I. I. Pigment Violet 23 1 part (B-1) specific dispersion resin: B-1-1 obtained in the above synthesis example 25 parts (E) Organic solvent: propylene glycol monomethyl ether acetate 290 parts

[Additional composition]
(C) Photopolymerizable compound: DPHA (dipentaerythritol pentahexaacrylate, Nippon Kayaku) 37 parts (D) Photopolymerization initiator: 2,2′-bis (o-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole / 4,4′-bis (diethylamino) benzophenone = 70/30 (mass ratio) mixture 7.4 parts (F) Binder resin: benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (acid value: 113 mg / g, weight average molecular weight: 5,000) in propylene glycol monomethyl ether acetate solution (solid content 45%) ... 56 parts / Epicron N-695 (Epoxy resin made by Dainippon Ink) ... 5 parts, Emulgen A-60 (Nonionic surfactant made by Kao) ... 2 parts, (E) Organic solvent: propylene glycol 490 parts · (E) organic solvent: ethyl 3-ethoxypropionate · 43 parts · propylene glycol monomethyl ether acetate solution of p-methoxyphenol (solid content 1%) · · · 1 part · Megafac F- 781 (Dainippon Ink fluorine surfactant) propylene glycol monomethyl ether acetate solution (solid content 10%) ... 1 part

(Examples 33-53)
In Example 32, (B-1) B-1-1 of the specific dispersion resin is replaced with B-1-2 to B-1-22 of (B-1) specific dispersion resin shown in Table 5 below, respectively. Furthermore, (B-1) the amount of the specific dispersion resin (in the table, the amount of solid content is displayed: actually, a solution having a solid content concentration of 30% is used), (C) the amount of photopolymerizable compound, (D) the amount of photopolymerization initiator, And (F) In the same manner as in Example 32, except that the amount of the binder resin (in the table, the solid content is displayed: actually, a solution having a solid content of 45% is used) was changed as shown in Table 3. A blue pigment dispersion was prepared, a colored pattern forming composition was further prepared, and the same evaluation as in Example 1 was performed.

(Comparative Example 1)
In Example 1, (B-2) Except that the solution of the specific compound (1) of the specific dispersion resin was replaced with the following solution of the dispersion resin 1 for comparative example (solid content 30%), the same as in Example 1. A pigment composition and a colored pattern forming composition were prepared and evaluated in the same manner as in Example 1.
Dispersion Resin 1 Solution for Comparative Example: Concentration-adjusted solution containing urethane-based dispersion resin obtained in Synthesis Example 14 described in p97 to 99 of WO2004 / 081070

(Comparative Example 2)
In Example 17, (B-3) The same procedure as in Example 17 except that the solution of the exemplified compound (I) of the specific dispersion resin was replaced with the following solution of the dispersion resin 2 for comparative example (solid content 30%). A pigment composition and a colored pattern forming composition were prepared and evaluated in the same manner as in Example 1.
Dispersion Resin 2 Solution for Comparative Example: Concentration-adjusted solution containing Dispersant A ′ obtained in Synthesis Example 17 described in p100 of WO2004 / 081070

(Comparative Example 3)
In Example 32, (B-1) Pigment composition and colored pattern formation were performed in the same manner as in Example 32 except that B-1-1 of the specific dispersion resin was replaced with the following dispersion resin 3 for comparative example. A composition for preparation was prepared and evaluated in the same manner as in Example 1.
Dispersion Resin 3 for Comparative Example: Dispersant A ″ described in Table 4-4 of WO103 / 081070, p103

  As is apparent from Tables 3 to 5, the colored pattern forming compositions of Examples 1 to 53 are excellent in solvent solubility, and also when slit coater coating is performed using the colored pattern forming composition, A defect-coated surface was obtained. Furthermore, it turns out that the color filter which uses the composition for colored pattern formation of Examples 1-53 is excellent in contrast.

Claims (8)

(A) a pigment, (B) a polymer compound represented by the following general formula (2), a polymer containing a copolymer unit derived from a monomer represented by the following general formula (I), or the following general formula ( C) a dispersion resin which is any one of the polymers containing the structural unit represented by (a) and has an acid value of 20 to 300 mg / g and a weight average molecular weight of 3,000 to 100,000. A colored pattern forming composition comprising a polymerizable compound, (D) a photopolymerization initiator, and (E) an organic solvent, and satisfying the following conditions.
Conditions: The composition is coated on a glass substrate, dried to form a film having a thickness of 2 μm, and the main organic solvent constituting the composition is formed on the film surface obtained by tilting the glass substrate by 45 degrees. As a test solution, 0.1 ml droplets prepared by the method of 9.3.1 of JIS K 5600-6-1 are continuously dropped at the same location at intervals of 1 second, and the film surface is dissolved within 5 droplets. To do

In general formula (2), A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a group having 4 or more carbon atoms. A monovalent organic group containing at least one site selected from the group consisting of a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, and a hydroxyl group. The n A ² may be the same or different. R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. The n R ^{4 s} may be the same or different. The m R ^{5 s} may be the same or different. R ³ represents an (m + n) -valent organic linking group. P ² represents a polymer skeleton of a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, or a modified product thereof. m represents an integer of 1 to 8, n represents an integer of 2 to 9, and m + n satisfies 3 to 10.

In general formula (I), R ⁰¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ⁰² represents an alkylene group. W represents -CO-, -C (= O) O-, -CONH-, -OC (= O)-, or a phenylene group. X is —O—, —S—, —C (═O) O—, —CONH—, —C (═O) S—, —NHCONH—, —NHC (═O) O—, —NHC (═O ) Represents one selected from S-, -OC (= O)-, -OCONH-, and -NHCO-. Y represents any one selected from NR ⁰³ , O, and S, and R ⁰³ represents a hydrogen atom, an alkyl group, or an aryl group. In the formula, N and Y are connected to each other to form a cyclic structure. m1 and n1 are each independently 0 or 1.

In general formula (a), R ^1a represents hydrogen or a methyl group, R ^2a represents an alkylene group, and Z ¹ represents a nitrogen-containing heterocyclic structure. P in the general formula (2) ² The composition for forming a colored pattern according to claim 1, wherein is a polymer or copolymer skeleton of a vinyl monomer. The mass ratio mb of (C) the photopolymerizable compound to all components having a weight average molecular weight of 3,000 or more in the composition is 0.2 to 3.0, and (B) the acid value av1 of the dispersion resin and the above The relationship with mb satisfies any of the following formulas (a-1), (a-2), and (a-3): The coloring pattern forming method according to claim 1 or 2 , Composition.
(A) When the pigment is red: 150 <(av1) / (mb) <250 Formula (a-1)
(A) When the pigment is green: 100 <(av1) / (mb) <200 Formula (a-2)
(A) When the pigment is blue: 50 <(av1) / (mb) <150 Formula (a-3) Further, (F) a binder resin having an acid value of 50 to 400 mg / g and a weight average molecular weight of 3,000 to 100,000 is included, and (B) the mass ratio db of the (F) binder resin to the dispersed resin is 0.00. 2 to 3.0, and the relationship between the acid value av2 of the binder resin (F) and the db is any of the following formulas (b-1), (b-2), and (b-3): The colored pattern forming composition according to any one of claims 1 to 3, wherein the composition is satisfied.
(A) When the pigment is red: 200 <(av2) / (db) <250 Formula (b-1)
(A) When the pigment is green: 175 <(av2) / (db) <220 Formula (b-2)
(A) When the pigment is blue: 125 <(av2) / (db) <175 Formula (b-3) A colored pattern forming method comprising a step of applying the colored pattern forming composition according to any one of claims 1 to 4 by a slit coating method. A method for producing a color filter, comprising using the colored pattern forming method according to claim 5 . A color filter manufactured by the manufacturing method according to claim 6 and having a contrast of 5000 or more. A liquid crystal display element using the color filter according to claim 7 .