KR20130054175A - Phosphoric group-containing block copolymer, pigment dispersant, and pigment-based colorant composition - Google Patents

Abstract

PURPOSE: A phosphoric acid-containing block copolymer is provided to finely disperse pigment microparticles and to manufacture a pigment colorant composition with excellent spreadability and long term stability. CONSTITUTION: A phosphoric acid-containing block copolymer is an A-B block copolymer which contains 90 wt% or more of a structure unit originated from a methacrylic acid-based monomer and consists of an A polymer block and a B polymer block. Only the B polymer block includes a structure unit originated from a phosphate-containing methacrylic acid-based monomer. A pigment colorant composition contains a pigment dispersant which contains the phosphate-containing methacrylic acid-based monomer as a main ingredient and pigment of which number average particle diameter is 10-150 nm.

Description

Phosphoric acid group-containing block copolymers, pigment dispersants, and pigment colorant compositions {PHOSPHORIC GROUP-CONTAINING BLOCK COPOLYMER, PIGMENT DISPERSANT, AND PIGMENT-BASED COLORANT COMPOSITION}

The present invention relates to a novel phosphoric acid group-containing block copolymer useful as a pigment dispersant and a method for producing the same, and a pigment dispersant and a pigment colorant composition using the phosphoric acid group-containing block copolymer.

In recent years, with the rapid development of information equipment, liquid crystal color displays are being used as various information display members of information equipment. Examples of applications of the liquid crystal color display include display screens such as TVs, projectors, personal computers, mobile information devices, monitors, vehicle navigation systems, mobile phones, electronic calculators, and electronic dictionaries; Displays such as information boards, information boards, function signs and signs; Shooting screens, such as a digital camera and a video camera, are mentioned. The color filter is normally mounted in the liquid crystal color display. This color filter is required to be excellent in color characteristics and optical characteristics of image performance such as fineness, color density, light transmittance, and contrast.

The dispersion stabilizer is used with the pigment for the color filter coloring agent (henceforth "color filter color") used for the conventional color filter trichromatic pixel. As the dispersion stabilizer, (a) a pigment derivative having a skeleton similar to a pigment, usually referred to as a 'synergy', and having an acidic group such as a sulfonic acid group introduced therein (hereinafter, a 'pigment derivative' is also referred to as a 'synergy'). And (b) a combination of a basic polymer type pigment dispersant having an amino group paired with the acidic group of this synergy, is often used (for example, refer to Patent Document 1). Dispersion stability of the pigment in an organic solvent can be improved by using combining (a) synergy and (b) basic polymer type pigment dispersing agent. Moreover, the viscosity of the pigment ink obtained can be reduced and the long-term storage stability of an ink can be improved.

However, for color filters for liquid crystal color televisions, for example, it is required to further improve color display performance (performance of pixels) such as color density, light transmittance, and contrast ratio. It does not correspond. In response to such a demand, there is a tendency to improve the performance of a pixel by reducing the particle diameter of the pigment to be used and making it ultrafine. However, since the number of particles increases even if the ultrafine particles are equal in mass to the pigments that are not ultrafine particles, the surface area is also expanded. For this reason, with the conventional technique, it is difficult to fully maintain the dispersion stability of the ultrafine particle | grains.

As a method of improving the dispersion stability of the ultrafine particle | grains, there exists a method of increasing the usage-amount of the synergist which has an acidic group, and a pigment dispersant (for example, refer patent document 2). However, when the usage-amount of synergy and a pigment dispersant increases, since a pigment concentration falls comparatively, color density (high color density of a pixel) will fall. In other words, it is very difficult to provide an ink in which the pigment content ratio and the dispersion stability of the pigment are both compatible in order to make the pixel have a high color density to obtain an appropriate pixel coating film composition.

Moreover, there exists a method of introducing an acidic group in the molecular structure of a pigment dispersant as a method of suppressing the relative fall of a pigment concentration (for example, refer patent document 3). However, this method is difficult to apply to the basic pigment dispersant having an amino group. This is because when an acidic group is introduce | transduced into the molecular structure of the basic polymer type pigment dispersant used with the synergy which has an acidic group, an acidic group and an amino group may ion-bond. When the acidic group and the amino group are ionically bound, the pigment dispersant gels in or between the molecules in the organic solvent. In addition, even when the pigment dispersant does not gel, since the ionic bond exists in the molecule | numerator or between molecules of a pigment dispersant, it becomes difficult for the pigment dispersant and synergy to ion-bond. For this reason, the pigment dispersant which has an ionic bond may not fully function as a pigment dispersant.

By the way, a color filter usually applies a color filter color to glass, and then exposes only the necessary part using a photo mask or the like to insolubilize it, and then removes the unexposed part (unnecessary part) with an alkaline developer. Thus prepared. On the other hand, the developing polymer which has acidic groups, such as a carboxyl group, is generally added to the color for color filters. The alkaline developing solution neutralizes the acidic groups of the developing polymer and removes the developing polymer by solubilizing it in water. However, since the basic pigment dispersant which has an amino group cannot introduce an acidic group in the molecular structure, it does not melt | dissolve in alkaline developing solution. For this reason, a basic pigment dispersing agent has become a cause which deteriorates developability, such as long developing time or a sharp edge of a pixel.

Under these circumstances, a method for producing a block copolymer by living radical polymerization has recently been developed. Moreover, various polymerization methods which can easily control a structure and molecular weight using such a manufacturing method are developed. Specifically, methods listed below have been researched and developed widely.

Nitroxide method (NMP method) using dissociation and bonding of amine oxide radicals (see Non-Patent Document 1)

Atom transfer radical polymerization (ATRP) in which heavy metals such as copper, ruthenium, nickel, and iron, and ligands that form complexes with these heavy metals are polymerized using halogen compounds as starting compounds. Method) (See Patent Documents 4 and 5, Non-Patent Document 2)

Reversible addition-fragmentation chain using a dithiocarboxylic acid ester or a xanthate compound as an initiating compound and polymerizing using an addition polymerizable monomer and a radical initiator. transfer: RAFT method) (see Patent Document 6), and Macromolecular Design via Interchange of Xanthate (MADIX method) (See Patent Document 7)

-Method using heavy metals, such as organic tellurium, organic bismuth, organic antimony, antimony halide, organic germanium, and germanium halide (Degenerative transfer: DT method) (refer patent document 8, nonpatent literature 3).

Patent Document 1: Japanese Patent Application Laid-Open No. 9-176511 Patent Document 2: Japanese Patent Application Laid-Open No. 2001-240780 Patent Document 3: Japanese Unexamined Patent Publication No. 2008-298967 Patent Document 4: Japanese Patent Application Publication No. 2000-500516 Patent Document 5: Japanese Patent Application Publication No. 2000-514479 Patent Document 6: Japanese Patent Application Publication No. 2000-515181 Patent Document 7: International Publication No. 1999-05099 Patent Document 8: Japanese Unexamined Patent Publication No. 2007-277533

Non Patent Literature 1: Chemical Review (2001) 101, p3661 Non Patent Literature 2: Chemical Review (2001) 101, p3689 Non-Patent Document 3: Journal of American Chemical Society (2002) 124, p2874, East (2002) 124, p13666 East (2003) 125, p8720

According to the method of the said patent documents 5-8 and the nonpatent literatures 2 and 3, the structure and molecular weight of resin can be controlled easily. However, in living radical polymerization, there exists a practical problem as shown below. For example, in NMP method, tetramethyl piperidine oxide radical is used, but it is necessary to superpose | polymerize on high temperature conditions 100 degreeC or more. Moreover, in order to raise a polymerization rate, it is necessary to superpose | polymerize with a monomer alone without using a solvent. For this reason, polymerization conditions become more severe. Moreover, when a methacrylate type monomer is used, there also exists a problem that superposition | polymerization does not advance. On the other hand, although it is also possible to lower the polymerization temperature or polymerize the methacrylate monomer, it is necessary to use a special nitroxide compound.

In addition, in the ATRP method, it is necessary to use a heavy metal. For this reason, it is necessary to remove heavy metals from a polymer and refine | purify a polymer even if it is a trace amount after superposition | polymerization. In addition, since heavy metals with a high load on the environment are contained in the waste water and waste solvent produced by refining the polymer, it is necessary to remove and purify the heavy metals. On the other hand, in the ATRP method using copper as a catalyst, deactivation of the catalyst by oxygen must be prevented and it is necessary to polymerize under an inert gas. There is also a method of preventing deactivation of the catalyst by adding a reducing agent such as a second tin compound or ascorbic acid. However, only by adding the reducing agent may cause the polymerization to stop in the middle, and it is essential to sufficiently remove oxygen from the polymerization atmosphere. In addition, in the method of polymerizing a amine compound by forming a complex as a ligand, formation of the complex is inhibited when an acidic substance is present in the polymerization system, and therefore it is difficult to polymerize an addition polymerizable monomer having an acid group. . On the other hand, in order to introduce an acid group into a polymer by the ATRAP method, it is necessary to superpose | polymerize the monomer which protected the acid group with the protecting group, and to remove | desorb the protecting group after superposition | polymerization. For this reason, it is not easy to introduce an acidic radical into a polymer block. As described above, in the ATRP method, since heavy metals such as copper are used, it is necessary to remove such heavy metals and to purify the polymer after polymerization. In addition, since the polymerization does not proceed when an acid that inhibits the complex formation of the heavy metal and the ligand is present, there is a problem that the ATRP method cannot directly polymerize a monomer having an acid group.

Moreover, in RAFT method and MADIX method, it is necessary to synthesize | combine special compounds, such as a dithiocarboxylic acid ester and a xanthate compound, and to use these synthesized compounds first. Moreover, since such a special compound is a sulfur compound, sulfur-like unpleasant odor is easy to remain in the polymer obtained, and may be colored. For this reason, it is necessary to remove odor and coloring from the obtained polymer.

In addition, in the DT method, it is necessary to use a heavy metal similarly to the ATRP method. For this reason, there is a problem that it is necessary to remove the heavy metals from the obtained polymer and to purify the waste water containing the generated heavy metals.

This invention is made | formed in view of the problem which this prior art has, and it makes the subject the microparticles | fine-particles to finely disperse | distribute a finely divided pigment, and also the coating property and long-term storage stability It is providing the novel phosphoric acid group containing block copolymer which can prepare this excellent pigment colorant composition. Furthermore, the object of the present invention is to provide a method for producing a phosphate group-containing block copolymer which is free of odors or coloring, does not require heavy metals, has a narrow molecular weight distribution (PDI), and is advantageous in terms of cost and ease. It is to offer. Moreover, the subject of this invention is providing the pigment dispersant which can prepare the pigment colorant composition which is excellent in coating property and long-term storage stability.

Moreover, the subject of this invention is excellent in coating property and long-term storage stability, and excellent in optical characteristics, such as color density, definition, contrast, and transparency of the pixel equipped with information display apparatuses, such as a liquid crystal color television. It is to provide a pigment colorant composition suitable for producing a color filter.

MEANS TO SOLVE THE PROBLEM As a result of earnestly research, the polymer structure is made into the AB block type which consists of A polymer block and B polymer block, and is made into the AB block type which consists of a solvent-soluble chain | strand and an adsorptive chain, and only a B-phosphate group By including a structural unit derived from a phosphate group-containing methacrylic acid-based monomer having a polymer, the A polymer block functions as a solvent-soluble chain and the B polymer block functions as an adsorptive chain, thereby completing the present invention. .

That is, according to this invention, the phosphoric acid group containing block copolymer shown below is provided.

[1] An AB block type copolymer comprising an A polymer block and a B polymer block, containing 90% by mass or more of a structural unit derived from a methacrylic acid monomer, wherein, in the A polymer block and the B polymer block, the B Only the polymer block contains the structural unit derived from the phosphate group containing methacrylic acid type monomer which has a phosphate group, The phosphoric acid group containing block copolymer characterized by the above-mentioned.

[2] The above-mentioned [1], wherein the A polymer block contains a structural unit derived from a carboxyl group-containing methacrylic acid monomer having a carboxyl group, wherein the acid value of the A polymer block is 10 to 200 mgKOH / g. The phosphoric acid group containing block copolymer of description.

[3] The phosphoric acid group-containing block copolymer according to the above [2], wherein the carboxyl group-containing methacrylic acid monomer is methacrylic acid.

[4] The number average molecular weight of the polymer A blocks is 3,000 to 20,000, the molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.6 or less, and the number average molecular weight of the polymer B blocks is 200 to 3,000. The phosphate group containing block copolymer in any one of said [1]-[3] whose number average molecular weights are 4,000-23,000, and whose molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.6 or less.

[5] The phosphate group-containing block copolymer according to any one of [1] to [4], wherein the acid value of the B polymer block is 50 to 500 mgKOH / g and the content of the B polymer block is 5 to 40 mass%. .

Moreover, according to this invention, the manufacturing method of the phosphoric acid group containing block copolymer shown below is provided.

[6] A method for producing the phosphate group-containing block copolymer according to any one of [1] to [5], wherein living radical polymerization of a monomer component containing the methacrylic acid monomer in the presence of a polymerization initiation compound and a catalyst is carried out. A process for producing a phosphate group-containing block copolymer, comprising the step, wherein the polymerization starting compound is at least one of iodine and an iodine compound.

[7] The catalyst may be a halogenated phosphite compound, a phosphinate compound, an imide compound, a phenol compound, a diphenylmethane compound, or a cyclopentadiene compound. The manufacturing method of the phosphoric acid group containing block copolymer as described in said [6] which is at least 1 sort (s) of compound chosen from the group which consists of.

[8] The method for producing a phosphoric acid group-containing block copolymer according to the above [6] or [7], wherein the polymerization temperature at the time of the living radical polymerization is 30 to 50 ° C.

Moreover, according to this invention, the pigment dispersant shown below is provided.

[9] A pigment dispersant comprising the phosphoric acid group-containing block copolymer according to any one of the above [1] to [5] as a main component.

Moreover, according to this invention, the pigment colorant composition shown below is provided.

[10] A pigment colorant composition comprising the pigment dispersant according to the above [9] and a pigment having a number average particle diameter of 10 to 150 nm.

[11] The pigment colorant composition according to the above [10], further containing a dye derivative having a basic functional group.

[12] The pigment colorant according to the above [11], wherein the content of the phosphate group-containing block copolymer with respect to 100 parts of the pigment is 10 to 100 parts, and the content of the pigment derivative with respect to 100 parts of the pigment is 5 to 100 parts. Composition.

[13] The pigment colorant composition according to any one of the above [10] to [12], which is used as a colorant for a color filter.

The phosphoric acid group-containing block copolymer of the present invention is a polymer block in which the A polymer block has a compatibility with the dispersion medium, and a B polymer block has a strong acidic phosphoric acid group. That is, since the phosphate group of the B polymer block strongly ionically bonds with an active hydrogen group (hydroxyl group, amide group, carboxyl group, thiol group, urethane group, etc.) basic group in the structure of the pigment, the phosphate group of the present invention is contained. The block copolymer adsorbs steadily on the pigment. Moreover, when the phosphoric acid group containing block copolymer of this invention is used, the resin process pigment in which the pigment was processed by resin can be obtained easily. That is, according to the phosphate group containing block copolymer of this invention, the pigment colorant composition which can highly disperse | distribute microparticles | fine-particles to pigment | dye, and is excellent in coating property and long-term storage stability can be prepared. On the other hand, various uses, such as an ion exchange resin, can be considered as a use of the phosphate group containing block copolymer of this invention. Especially, what sets it as a pigment dispersant is especially suitable. That is, since the pigment dispersant of this invention contains the said phosphate group containing block copolymer as a main component, the pigment colorant composition excellent in the coating property and long-term storage stability can be prepared.

The pigment colorant composition of the present invention is one capable of keeping low viscosity stable for a long time and is excellent in coating properties and long-term storage stability. The pigment colorant composition of the present invention can be used for paints, inks, coating agents, stationery, toners, plastics and the like. Especially, it is especially suitable as a coloring agent for color filters. That is, when the pigment coloring agent composition of this invention is used as a coloring agent for color filters, the color equipped with information display apparatuses, such as a liquid crystal color television, which is excellent in optical characteristics, such as color density, the fineness, contrast property, and transparency of a pixel. Filters can be prepared. And when the pigment colorant composition of this invention is used, the resist for color filters excellent in the developability at the time of alkali image development can be obtained.

In the production method of the phosphoric acid group-containing block copolymer of the present invention, the use of a heavy metal compound is not essential, the purification of a polymer is not essential, and no special compound needs to be synthesized. For this reason, according to the manufacturing method of the phosphate group containing block copolymer of this invention, only the relatively cheap material on the market can be used, and the phosphate group containing block copolymer which is a target object can be manufactured easily. Moreover, the manufacturing method of the phosphoric acid group containing block copolymer of this invention has the advantage shown below. The polymerization conditions are mild and can be polymerized under the same conditions as in the conventional radical polymerization method. That is, since a conventional radical polymerization installation can be used, a special installation is unnecessary. In addition, they are not significantly affected by oxygen, water, and light during the polymerization. Moreover, the monomer to be used, a solvent, etc. do not need to be refine | purified, and the monomer which has various functional groups can be used. For this reason, various functional groups desired can be introduced into a polymer. Furthermore, since the polymerization rate is also very high, the phosphoric acid group-containing block copolymer can be produced in large quantities easily.

1. Phosphoric acid group containing block copolymer

(Phosphate-containing block copolymer)

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated to the example about the detail of this invention. The phosphoric acid group containing block copolymer of this invention is an A-B block type copolymer which consists of A polymer block and B polymer block containing 90 mass% or more of structural units derived from a methacrylic acid type monomer. And, among the A polymer block and the B polymer block, only the B polymer block includes a structural unit derived from a methacrylic acid monomer (phosphate group-containing methacrylic acid monomer) having a phosphate group. Hereinafter, a phosphate group containing block copolymer is also described as "A-B block copolymer."

The phosphoric acid group-containing block copolymer of the present invention is an A-B block type copolymer.

A polymer block can be considered as a block which shows the function melt | dissolved or compatible with the medium to disperse | distribute. On the other hand, since the B polymer block has a phosphate group in its structure, it can be considered that this phosphate group has a function of binding to and adsorbing to a pigment treated with a pigment or a basic group-containing dye derivative. The adsorption of the pigment and the B polymer block is, for example, a hydrogen bond between an active hydrogen group (hydroxyl group, amide group, carboxyl group, thiol group, urethane group, etc.) and phosphoric acid group in the structure of the pigment, or a basic pigment or basic group. It is guessed that it is by the ionic bond of the basic group and the phosphoric acid group of the pigment processed with the containing pigment derivative. By the structure and action peculiar to such an AB block type copolymer, the B polymer block is adsorbed on the surface of the finely divided pigment by ionic bond or the like, while the A polymer block is dissolved or used in a dispersion medium, A three-dimensional or electrical repulsion of the polymer block prevents the aggregation of the pigment. For this reason, it can be considered that the phosphate group-containing block copolymer of the present invention can prepare a pigment colorant composition which can highly finely disperse the finely divided pigment and has excellent coating properties and long-term storage stability. On the other hand, hereafter, only "pigment" means any one of (i) the pigment itself and (ii) the pigment surface-treated with the basic group containing pigment derivative.

In the case where the phosphate group-containing block copolymer is composed of an A polymer block having a carboxyl group and a B polymer block having a phosphate group, speculation that any acid groups may be ionically adsorbed to the pigment may be established. have. However, a phosphoric acid group is group which shows acidity stronger than a carboxyl group. That is, since the pKa value of a phosphate group is low compared with pKa of a carboxyl group, it can be considered that the B polymer block which has a phosphate group adsorb | sucks selectively to a pigment.

The phosphate group-containing block copolymer contains 90% by mass or more, preferably 95% by mass or more of the structural unit derived from the methacrylic acid monomer, and more preferably consists of 100% of the structural unit derived from the methacrylic acid monomer. will be. In the manufacturing method (polymerization method) of the phosphoric acid group containing block copolymer of this invention mentioned later, a methacrylic acid type monomer is especially preferable as a monomer. Vinyl monomers, such as styrene, acrylate monomers, and vinyl ether monomers, such as iodine bound to the polymerization terminal is too stabilized, it is necessary to warm in order to dissociate or do not dissociate There is a possibility of problems. For this reason, when a large amount of monomers other than methacrylic acid-based monomers are used, there is a possibility that problems such as not forming a specific structure of the target or widening molecular weight distribution may occur. However, you may use monomers other than methacrylic acid type monomer in the range which does not impair the objective of this invention as needed.

(A polymer block)

As methacrylic acid type monomers used in order to form A polymer block, a conventionally well-known thing is mentioned, There is no special limitation. Specific examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 2-methylpropane methacrylate, t-butyl methacrylate, pentyl methacrylate, hexyl Methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, octadecyl methacrylate , Behenyl methacrylate, isostearyl methacrylate, cyclohexyl methacrylate, t-butylcyclohexyl methacrylate, isobornyl methacrylate, trimethylcyclohexyl methacrylate, cyclodecyl methacrylate, cyclodecyl (Cyclo) alkyl methacrylates such as methyl methacrylate, tricyclodecyl methacrylate and benzyl methacrylate Acrylates; aryl methacrylates such as phenyl methacrylate and naphthyl methacrylate; alkenyl methacrylates such as allyl methacrylate; (poly) ethylene glycol monomethyl ether methacrylate, (poly) ethylene glycol Glycol monoalkyl ether methacrylates such as monolauryl ether methacrylate and (poly) propylene glycol monomethyl ether methacrylate;

Glycidyl group-containing methacrylates such as glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacryloyloxyethylglycidyl ether and methacryloyloxyethoxyethylglycidyl ether (Meth) acryloyloxyethyl isocyanate, 2- (2-isocyanate ethoxy) ethyl methacrylate, and isocyanate with isocyanate groups of these compounds blocked with ε-caprolactone, MEK oxime, pyrazole and the like Group-containing methacrylates; cyclic methacrylates such as tetrahydrofurfuryl methacrylate and oxetanylmethyl methacrylate; halogens such as octafluorooctyl methacrylate and tetrafluoroethyl methacrylate Element-containing methacrylate; 2- (4-benzooxy-3-hydroxyphenoxy) ethyl methacrylate, 2- (2'-hydroxy-5-methacryloyloxyethylphenyl) -2H-benzotri Methacrylates of absorbing ultraviolet light, such as sol; and the like trimethoxysilyl group or dimethyl silicon atom-containing methacrylate with a silicone chain. Moreover, the macromonomer etc. which are obtained by introduce | transducing a (meth) acryl group into the single terminal end of the oligomer obtained by superposing | polymerizing such a monomer can be used.

However, methacrylate which has amino groups, such as dimethylaminoethyl methacrylate, is easy to ion-bond with a carboxyl group or a phosphate group. For this reason, gelatinization etc. occur, or the adsorption property with the basic group etc. of a pigment is impaired, and it should not be used.

It is preferable that A polymer block contains the structural unit derived from the methacrylic acid type monomer (carboxyl group-containing methacrylic acid type monomer) which has a carboxyl group.

The A polymer block into which the carboxyl group is introduced is ionized by neutralizing with an alkali and dissolved in water. For this reason, it can use suitably in alkali image development in the manufacturing process of a color filter. Specific examples of the carboxyl group-containing methacrylic acid-based monomers include methacrylic acid; methacrylate obtained by reacting 2-hydroxyethyl methacrylate with a dibasic acid such as phthalic acid; a hydroxyl group obtained by reacting phthalic acid with glycidyl methacrylate. Methacrylate which has a carboxyl group, etc. are mentioned. Especially, methacrylic acid with a small molecular weight and high polymerizability is preferable. If methacrylic acid is used as the carboxyl group-containing methacrylic acid monomer, problems such as remaining without polymerization are unlikely to occur.

When A polymer block of a phosphoric acid group containing block copolymer has a carboxyl group, it is preferable that the acid value of A polymer block is 10-200 mgKOH / g, and it is more preferable that it is 20-150 mgKOH / g. If the acid value of A polymer block is in the said numerical range, it can use as a component suitable for alkali image development in the manufacturing process of a color filter, for example. If the acid value of the A polymer block is less than 10 mgKOH / g, there is a tendency that it does not dissolve or the dissolution rate is slow even when neutralized with alkali. On the other hand, when the acid value of A polymer block is more than 200 mgKOH / g, even the hydrophilicity of an exposure hardening part may improve, water resistance may fall, and the formed pixel may become messy.

It is preferable that it is 3,000-20,000, and, as for the number average molecular weight of A polymer block, it is more preferable that it is 4,000-10,000. When the number average molecular weight of A polymer block is less than 3,000, the three-dimensional repulsion of A polymer block does not work in the phosphate group containing block copolymer adsorbed to the pigment, and stability may be insufficient. On the other hand, when the number average molecular weight of A polymer block is more than 20,000, since the part which melt | dissolves or dissolves in a dispersion medium will increase, viscosity may increase too much or developability may fall.

It is preferable that it is 1.6 or less, and, as for the molecular weight distribution (PDI = weight average molecular weight / number average molecular weight) of A polymer block, it is more preferable that it is 1.5 or less. According to the manufacturing method of the phosphate group containing block copolymer of this invention mentioned later, it is possible to manufacture the phosphate group containing block copolymer of such narrow molecular weight distribution. When the molecular weight distribution (PDI) of the A polymer block is more than 1.6, the number average molecular weight reaches less than 3,000 components or more than 20,000 components, so that the stability and developability are lowered or the viscosity is excessively increased. I may do it.

(B polymer block)

As methacrylic acid type monomer (phosphate group containing methacrylic acid type monomer) which has a phosphoric acid group used in order to comprise B polymer block, a conventionally well-known thing is mentioned, There is no special limitation. Specific examples include 2- (methacryloyloxy) ethyl phosphate, 3-chloro-2- (phosphonooxy) propyl methacrylate, 2- (methacryloyloxy) propyl phosphate, 2- (phenoxy) Ciphosphonyloxy) ethyl, an acid phosphooxy polyoxyethylene glycol monomethacrylate, an acid phosphooxy polyoxypropylene glycol monomethacrylate, etc. are mentioned. Moreover, bifunctional methacrylates, such as bis (2-methacryloyloxyethyl) phosphate, can also be used in the range which does not gelatinize the obtained phosphate group containing block copolymer. In addition, you may copolymerize 1 or more types of monomers (other monomer) used in order to comprise the above-mentioned A polymer block, and the phosphate group containing methacrylic acid type monomer. Since a phosphoric acid group containing methacrylic acid type monomer has low polymerizability compared with another monomer, it is more preferable to copolymerize with another monomer.

Moreover, after preparing the polymer block which has a hydroxyl group using the methacrylic acid type monomer which has a hydroxyl group, you may make a B polymer block which has a phosphoric acid group by introducing a phosphoric acid group by making a phosphorylation reagent react with this hydroxyl group. Furthermore, you may manufacture B polymer block by superposing | polymerizing the phosphoric acid group containing methacrylic acid type monomer obtained by making methacrylic acid type monomer which has a hydroxyl group, and the phosphorylation reagent react. As a specific example of the methacrylic acid type monomer which has a hydroxyl group, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, polyethyleneglycol monomethacrylate, etc. are mentioned. As a specific example of a phosphorylation reagent, phosphorus pentaoxide, phosphorus oxychloride, polyphosphoric acid, phosphoric acid, etc. are mentioned.

It is preferable that it is 200-3,000, and, as for the number average molecular weight of B polymer block, it is more preferable that it is 500-2,000. In addition, the number average molecular weight of B polymer block is represented by the value which subtracted the number average molecular weight of A polymer block from the number average molecular weight of a phosphoric acid group containing block copolymer (A-B block copolymer). If the number average molecular weight of B polymer block is less than 200, the adsorption force with respect to a pigment may be weak and stability may be insufficient. On the other hand, when the number average molecular weight of B polymer block is more than 3,000, since it is too large, particle | grains of pigment may adsorb | suck and stability may be insufficient.

It is preferable that it is 50-500 mgKOH / g, and, as for the acid value of B polymer block, it is more preferable that it is 100-350 mgKOH / g. If the acid value of the B polymer block is less than 50 mgKOH / g, the adsorbability to the pigment may be insufficient. On the other hand, when the acid value of B polymer block is more than 500 mgKOH / g, since the part adsorb | sucked to a pigment becomes excess, a pigment may aggregate rather.

It is preferable that it is 5-40 mass%, and, as for content of B polymer block in a phosphoric acid group containing block copolymer, it is more preferable that it is 10-30 mass%. When content of B polymer block is less than 5 mass%, since the part adsorb | sucked to a pigment is too small, it is easy to detach | desorb and there exists a tendency for the dispersibility of a pigment to fall. On the other hand, when content of B polymer block is more than 40 mass%, since content of the A polymer block which is a part melt | dissolved or compatible with a dispersion medium becomes comparatively small, there exists a tendency for dispersion stability to fall.

As mentioned above, it is preferable that it is 4,000-23,000, and, as for the number average molecular weight of a phosphoric acid group containing block copolymer, it is more preferable that it is 5,000-14,000. Moreover, it is preferable that it is 1.6 or less, and, as for the molecular weight distribution (PDI) of a phosphoric acid group containing block copolymer, it is more preferable that it is 1.5 or less.

Since the phosphate group containing block copolymer of this invention has a phosphate group, it is expected to apply for various uses. Specifically, it can use suitably as a resin component for pigment dispersants and resin treatment pigments.

2. Process for producing phosphate group-containing block copolymer

The manufacturing method of the phosphate group containing block copolymer of this invention is a method of manufacturing the above-mentioned phosphate group containing block copolymer, The process of living radically polymerizing the monomer component containing a methacrylic acid type monomer in presence of a polymerization start compound and a catalyst. (Polymerization step). And a polymerization start compound is at least one of an iodine and an iodine compound. In addition, the phosphoric acid group containing block copolymer of this invention can also be synthesize | combined (manufacturing) according to the conventional living radical polymerization method. However, it is preferable to manufacture according to the manufacturing method of the phosphoric acid group containing block copolymer of this invention.

(Polymerization step)

In a polymerization process, at least any one of an iodine and an iodine compound is used as a polymerization start compound, and it is a process of superposing | polymerizing the monomer component containing a methacrylic acid type monomer by living radical polymerization. When heat or light is applied to the iodine or the iodine compound used as the polymerization start compound, the iodine radical dissociates. After the monomer is inserted in the dissociated state of the iodine radical, the iodine radical immediately bonds with the polymer terminal radical again to stabilize, and the polymerization reaction proceeds while preventing the stop reaction.

Specific examples of the iodine compound include alkyl iodides such as 2-iodine-1-phenylethane and 1-iodine-1-phenylethane; 2-cyano-2-iodine propane, 2-cyano-2-iodobutane, 1 Cyano groups such as cyano-1-iodinecyclohexane, 2-cyano-2-iodine-2,4-dimethylpentane, and 2-cyano-2-iodine-4-methoxy-2,4-dimethylpentane Containing iodide, and the like.

Although a commercial item may be used as it is, such an iodine compound can also use what was prepared by the conventionally well-known method. For example, an iodine compound can be obtained by making an azo compound, such as azobisisobutyronitrile, react with iodine. The iodine compound is also reacted by reacting an organic halide in which iodine of the iodine compound is substituted with a halogen atom such as bromine or chlorine and reacting an iodide salt such as quaternary ammonium iodide or sodium iodide to halogen exchange You can get it.

In a polymerization process, the catalyst which can extract the iodine of a polymerization start compound is used with a polymerization start compound. Examples of the catalyst include phosphorus compounds such as phosphorus halides, phosphite compounds and phosphinate compounds; nitrogen compounds such as imide compounds; oxygen compounds such as phenol compounds; diphenylmethane compounds and cyclopentadiene compounds. It is preferable to use a hydrocarbon compound. In addition, such a catalyst can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the phosphorus compound include phosphorus triiodide, diethyl phosphite, dibutyl phosphite, ethoxyphenyl phosphinate, phenylphenoxy phosphinate and the like. Specific examples of the nitrogen-based compound include succinimide, 2,2-dimethylsuccinimide, maleimide, phthalimide, N-iodine succinimide, hydantoin, and the like. Specific examples of the oxygen compound include phenol, hydroquinone, methoxyhydroquinone, t-butylphenol, catechol, di-t-butylhydroxytoluene, and the like. Cyclohexadiene, diphenylmethane, etc. are mentioned as a specific example of a hydrocarbon type compound.

It is preferable to make the usage-amount (mole number) of this catalyst less than the usage-amount (mole number) of a polymerization start compound. If the amount of use (molar number) of the catalyst is too large, the polymerization may be controlled so much that the polymerization may be difficult to proceed. Moreover, it is preferable to make temperature (polymerization temperature) at the time of living radical polymerization into 30-50 degreeC. If the polymerization temperature is too high, iodine at the end of the polymerization may be decomposed by methacrylic acid, and the end may not be stable and living polymerization may not be performed.

In addition, in the polymerization step, a polymerization initiator capable of generating radicals is usually added. As the polymerization initiator, conventionally known azo initiators and peroxide initiators are used. On the other hand, it is preferable to use the polymerization initiator which generate | occur | produces radical sufficiently in the range of the said polymerization temperature. Specifically, it is preferable to use an azo initiator such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). The amount of the polymerization initiator to be used is preferably 0.001 to 0.1 mole times with respect to the monomer, and more preferably 0.002 to 0.05 mole times. When the usage-amount of a polymerization initiator is too small, a polymerization reaction may not fully advance. On the other hand, when the usage-amount of a polymerization initiator is too large, a normal radical polymerization reaction rather than a living radical polymerization reaction may advance as a side reaction.

The living radical polymerization may be bulk polymerization without using an organic solvent, but it is preferable to use solution polymerization using an organic solvent. As an organic solvent, what can melt | dissolve components, such as a polymerization initiator compound, a catalyst, a monomer component, and a polymerization initiator, is preferable. Specific examples of the organic solvent include hydrocarbon solvents such as hexane, octane, decane, isodecane, cyclohexane, methylcyclohexane, toluene, xylene and ethylbenzene; methanol, ethanol, propanol, isopropanol, butanol, isobutanol, hexanol, Alcohol solvents such as benzyl alcohol and cyclohexanol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol propyl ether, diglyme, triglyme, diprophylline glycol dimethyl ether, butyl carbitol, butyl triethylene glycol, methyl dipropylene glycol, methyl cellosolve acetate, propylene glycol To monomethyl ether acetate, dipropylene glycol butyl ether acetate, diethylene glycol monobutyl Glycol solvents such as Le acetate;

Ether solvents such as diethyl ether, dipropyl ether, methylcyclopropyl ether, tetrahydrofuran, dioxane and anisole; methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, acetophenone Ketone solvents such as methyl acetate, ethyl acetate, butyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, caprolactone, ester solvents such as methyl lactate and ethyl lactate; halogenated solvents such as chloroform and dichloroethane; Other than amide solvents such as dimethylformamide, dimethylacetamide, pyrrolidone, N-methylpyrrolidone and caprolactam, dimethyl sulfoxide, sulfolane, tetramethyl urea, ethylene carbonate, propylene carbonate and carbonic acid Dimethyl etc. are mentioned. In addition, such an organic solvent can be used individually by 1 type or in combination of 2 or more type.

In the case of solution polymerization, the solid content concentration (monomer concentration) of the polymerization liquid is preferably 5 to 80% by mass, more preferably 20 to 60% by mass. When solid content concentration of a polymerization liquid is less than 5 mass%, monomer concentration may be too low and superposition | polymerization may not be completed. On the other hand, when solid content concentration of a polymerization liquid is more than 80 mass% or bulk polymerization, the viscosity of a polymerization liquid will become high too much, and stirring becomes difficult and there exists a tendency for a polymerization yield to fall. It is preferable to perform living radical polymerization until a monomer disappears. Specifically, the polymerization time is preferably 0.5 to 48 hours, more preferably substantially 1 to 24 hours. Moreover, polymerization atmosphere is not specifically limited, The atmosphere which oxygen exists in a normal range may be sufficient, or a nitrogen-airflow atmosphere may be sufficient. In addition, the material (monomer etc.) used for superposition | polymerization may use what remove | eliminated an impurity by distillation, activated carbon treatment, or alumina treatment, etc., and may use a commercial item as it is. In addition, polymerization may be performed under light shielding, or polymerization may be performed in a transparent container such as glass.

As a polymerization sequence of an A-B block copolymer, it is preferable to polymerize (i) the monomer which comprises A polymer block, to form A polymer block, and to further polymerize by adding the monomer which comprises (ii) B polymer block. If the monomers constituting the B polymer block are first polymerized, the polymerization may not be completed and a monomer having a phosphate group may remain in the reaction system. In such a case, the monomer having a phosphate group may be easily introduced into the A polymer block. On the other hand, if the monomer constituting the A polymer block is first polymerized, even if the polymerization is not completed and the monomer remains in the reaction system, 90 mass% or more of the constituent components of the obtained AB block copolymer are (meth) acrylate-based. When the B polymer block is introduced so as to be a monomer, the AB block copolymer can be easily obtained. On the other hand, it is preferable to polymerize the monomers constituting the A polymer block until the polymerization rate is 50% or more, more preferably 80% or more, and particularly preferably 100%, to form the A polymer block. It is good to form the B polymer block by adding the monomer which comprises the B polymer block.

The molecular weight of the A-B block copolymer obtained can be controlled by adjusting the usage-amount of a polymerization start compound. Specifically, the A-B block copolymer of arbitrary molecular weight can be obtained by setting the number-of-moles of a monomer suitably with respect to the number-of-moles of a polymerization start compound. For example, when 1 mol of a polymerization start compound is used and 500 mol of monomers having a molecular weight of 100 are used to polymerize, an A-B block copolymer having a theoretical molecular weight of '1 × 100 × 500 = 50,000' can be obtained. That is, the theoretical molecular weight of A-B block copolymer can be computed by following formula (1). In addition, said "molecular weight" is a concept containing both a number average molecular weight (Mn) and a weight average molecular weight (Mw).

'Theoretical molecular weight of A-B block copolymer' = '1 mole of polymerization start compound' × 'monomer molecular weight' x 'mole number of monomer / polymerization start compound'. ... ... (One)

On the other hand, in a polymerization process, since it may be accompanied by side reaction of 2 molecule stop and disproportionation, the A-B block copolymer which has said theoretical molecular weight may not be obtained. The A-B block copolymer is preferably one obtained without such side reactions. However, even if the molecular weight of the A-B block copolymer obtained by coupling increases to some extent, the molecular weight of the A-B block copolymer obtained by stopping the polymerization reaction may be slightly reduced. In addition, the polymerization rate may not be 100%. In addition, after completion | finish of superposition | polymerization, you may add superposition | polymerization start compound and a catalyst, and consume the remaining monomer, and complete superposition | polymerization. That is, what is necessary is just to produce | generate A-B block copolymer.

Although the obtained A-B block copolymer may be in the state which the iodine atom derived from a polymerization start compound has couple | bonded, it is preferable to remove an iodine atom. The method of detaching the iodine atom from the A-B block copolymer is not particularly limited as long as it is a conventionally known method. Specifically, the A-B block copolymer may be heated or treated with an acid or an alkali. In addition, the A-B block copolymer may be treated with sodium thiosulfate or the like. The iodine desorbed may be removed by treatment with an iodine adsorbent such as activated carbon or alumina.

3. Pigment Dispersant and Pigment Colorant Composition

The pigment dispersant of this invention contains the above-mentioned phosphoric acid group containing block copolymer as a main component. On the other hand, it is preferable that a pigment dispersant consists essentially of a phosphoric acid group containing block copolymer. Moreover, the pigment colorant composition of this invention contains this pigment dispersant and the pigment whose number average particle diameter is 10-150 nm. The phosphate group in the structure of the phosphate group-containing block copolymer (in the B polymer block) is strongly bound to the basic group of the pigment treated with the basic pigment or the basic group-containing pigment derivative, and the B polymer block adsorbs onto the pigment, Demonstrates the effect of improving dispersibility. That is, since the pigment dispersant of this invention is a component which disperse | distributes a pigment by this effect | action, there is no special limitation about the kind of pigment to disperse.

(Pigment)

As the pigment, metal pigments such as organic pigments, inorganic pigments, metal powders or fine particles, inorganic fillers and the like can be used. Specific examples of organic pigments and inorganic pigments include quinacridone pigments, anthraquinone pigments, diketopyrrolopyrrole pigments, perylene pigments, and phthalocyanine blue. Pigments, phthalocyanine green pigments, isoindolinone pigments, indigo thioindigo pigments, dioxazine pigments, quinophthalone pigments, nickel Azo (nickel azo) pigments, insoluble azo pigments, soluble azo pigments, high molecular weight azo pigments, carbon black pigments, complex oxide black pigments, iron oxide black pigments, titanium oxide black pigments, azomethine azo compounds And red, green, blue, yellow, orange, purple, black, and white pigments selected from the group consisting of black pigments and titanium oxide pigments. Specific examples of the metal pigments include copper powder, aluminum flakes, and the like. Moreover, a mica pigment, a natural mineral, a silica etc. are mentioned as a specific example of an inorganic filler.

On the other hand, as a pigment for color filters, it is preferable to use an organic pigment and the inorganic pigment for black matrices. Examples of the red pigment include color index (hereinafter C.I.) Pigment Red (PR) 56, 58, 122, 166, 168, 176, 177, 178, 224, 242, 254, 255. As the green pigment, C.I. Pigment green (PG) 7, 36, 58, poly (14-16) bromine copper phthalocyanine, poly (12-15) bromination-poly (4-1) crawling copper phthalocyanine. As the blue pigment, C.I. Pigment blue (PB) 15: 1, 15: 3, 15: 6, 60, 80, etc. are mentioned.

Moreover, the following are mentioned as a complementary pigment or a pigment for a pixel of a multicolor type with respect to the pigment for said color filters. As the yellow pigment, C.I. Pigment Yellow (PY) 12, 13, 14, 17, 24, 55, 60, 74, 83, 90, 93, 126, 128, 138, 139, 150, 154, 155, 180, 185, 216, 219, CI Pigment violet (PV) 19, 23 is mentioned. Moreover, as a black pigment for black matrices, C.I. Pigment black (PBK) 6, 7, 11, 26, copper-manganese-iron type complex oxide is mentioned.

The number average particle diameter of a pigment is 10-150 nm, Preferably it is 20-80 nm. The pigment colorant composition obtained by disperse | distributing the finely divided pigment is especially suitable as a coloring agent which can manufacture the color filter which has high transparency and high contrast property. Moreover, the pigment colorant composition of this invention contains the pigment dispersing agent (phosphate group containing block copolymer) which can stabilize and highly disperse | distribute the finely divided pigment. For this reason, the pigment coloring agent composition of this invention disperse | distributes in the state with such extremely fine pigments, and is excellent also in long-term storage stability. On the other hand, when the ratio of the pigment contained in a pigment colorant composition makes 100 mass% of the whole pigment colorant composition, it is preferable that it is 5-40 mass%, and it is more preferable that it is 10-30 mass%.

(Pigment derivative)

It is preferable to contain the basic pigment derivative which has a basic functional group in a pigment colorant composition, in order to make it adsorb by ionic bond with the phosphate group in the phosphate group containing block copolymer used for a pigment dispersant. This pigment derivative introduce | transduces a basic functional group in a pigment | dye skeleton. As the dye skeleton, a skeleton which is the same as or similar to the pigment, or a skeleton which is the same as or similar to the compound used as the raw material of the pigment is preferable. Specific examples of the dye skeleton include an azo dye skeleton, a phthalocyanine dye skeleton, an anthraquinone dye skeleton, a triazine dye skeleton, an acridine dye skeleton, a perylene dye skeleton, and the like.

As a basic functional group introduce | transduced into a dye skeleton, an amino group is preferable. As the amino group to be introduced, any of primary, secondary, and tertiary amino groups may be used, or may be a quaternary ammonium salt. Moreover, although basic functional groups, such as an amino group, may couple | bond directly with the pigment | dye frame | skeleton, hydrocarbon groups, such as an alkyl group and an aryl group; may be couple | bonded with the pigment | dye skeleton through ester, ether, sulfonamide, a urethane bond. On the other hand, from the convenience of the synthesis and the strength of the bond, it is preferable that the basic functional group is bonded to the dye skeleton through the sulfonamide.

It is preferable that it is 10-100 mass parts with respect to 100 mass parts of pigments, and, as for content of the phosphoric acid group containing block copolymer in a pigment colorant composition, it is more preferable that it is 10-50 mass parts. When content of a phosphoric acid group containing block copolymer is less than 10 mass parts, the dispersibility of a pigment may become inadequate. On the other hand, when content of a phosphoric acid group containing block copolymer is more than 100 mass parts, resin which does not contribute to dispersion | distribution may produce. Moreover, it is preferable that it is 5-100 mass parts with respect to 100 mass parts of pigments, and, as for content of the pigment derivative in a pigment colorant composition, it is more preferable that it is 10-30 mass parts. When content of a pigment derivative is less than 5 mass parts, since the basic group which covers the surface of a pigment will become small, adsorption of a pigment dispersant may become inadequate. On the other hand, when content of a pigment derivative is more than 100 mass parts, the color of a pigment derivative tends to come out, and it may not become the target color.

(Alkali Developable Polymer)

The pigment colorant composition of this invention is obtained by disperse | distributing a pigment and the pigment derivative used as needed to a liquid medium using the above-mentioned phosphate group containing block copolymer as a pigment dispersing agent. On the other hand, when using a pigment coloring agent composition as a coloring agent for color filters, it is preferable to add an alkali developable polymer. Since the phosphoric acid group containing block copolymer used as a pigment dispersing agent has a carboxyl group in its structure, since it neutralizes and ionizes and becomes soluble in water, alkali development is possible.

An alkali developable polymer has acidic radicals, such as a carboxyl group, in the structure, acidic radicals are neutralized with aqueous alkali solution, it becomes soluble in water, and can develop. For this reason, it is conceivable that the alkali developable polymer may be ionically bonded to the surface of the pigment and adsorbed in the same manner as the phosphate group-containing block copolymer. However, the phosphate group in a phosphoric acid group containing block copolymer is group which shows strong acidity compared with a carboxyl group. For this reason, even when the phosphoric acid group containing block copolymer and the alkali developable polymer which has a carboxyl group coexist, it can be considered that a phosphoric acid group selectively ionically bonds with the surface of a pigment. Therefore, even when there exists an alkali developable polymer etc. which have acid groups other than a phosphoric acid group in the structure, a phosphoric acid group containing block copolymer can highly disperse | distribute the finely divided pigment.

As an alkali developable polymer, photosensitive resin which has photosensitive groups, such as an unsaturated bond group, and non-photosensitive resin can be used. Specific examples of the photosensitive resin include photosensitive cyclized rubber resins, photosensitive phenolic resins, photosensitive polyacrylate resins, photosensitive polyamide resins, photosensitive polyimide resins, and unsaturated polyester resins and polyester acrylates. Resin, polyepoxy acrylate resin, polyurethane acrylate resin, polyether acrylate resin, polyol acrylate resin and the like. Specific examples of the non-photosensitive resins include cellulose acetate resins, nitrocellulose resins, styrene (copolymer) polymers, polyvinyl butyral resins, amino alkyd resins, polyester resins and amino resin modified polyester resins. , Polyurethane resins, acrylic polyol urethane resins, soluble polyamide resins, soluble polyimide resins, soluble polyamideimide resins, soluble polyesterimide resins, hydroxyethyl cellulose, styrene-maleic acid ester copolymers, ( And meta) acrylic acid ester-based (co) polymers. Such alkali developable polymers can be used individually by 1 type or in combination of 2 or more types. On the other hand, it is preferable that it is 5-300 mass parts with respect to 100 mass parts of pigments, and, as for content of the alkali developable binder in a pigment colorant composition, it is more preferable that it is 10-100 mass parts.

Moreover, it is preferable to make the pigment colorant composition contain the unsaturated bond group containing block copolymer obtained by reacting the (meth) acrylate which has glycidyl group or an isocyanate group. This unsaturated bond group containing block copolymer is a component which can photocure and form a film | membrane. For this reason, the intensity (resistant) of the pixel of a color filter can be improved. Moreover, the edge of a pixel can be formed sharply, and the solvent tolerance of the formed pixel can be improved. On the other hand, the unsaturated bond group in an unsaturated bond group containing block copolymer is suitable for an acryl group or a methacryl group. Such an unsaturated bond group is introduce | transduced in an unsaturated bond group containing block copolymer by a conventionally well-known method.

As a liquid medium used for a pigment colorant composition, an organic solvent is preferable. Specific examples of the organic solvent include hydrocarbon solvents such as hexane and toluene; alcohol solvents such as butanol; ester solvents such as propyl acetate and butyl acetate; ketone solvents such as cyclohexanone and methyl isobutyl ketone; diethylene glycol Glycol solvents such as monobutyl ether and propylene glycol monomethyl ether; glycol esters or ether solvents such as propylene glycol monomethyl ether acetate and dipropylene glycol dibutyl ether; amides such as N-methylpyrrolidone and dimethylacetamide Solvents; carbonate solvents such as ethylene carbonate and propion carbonate; and the like. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

In addition, you may add a conventionally well-known additive to a pigment colorant composition. As a specific example of an additive, a ultraviolet absorber, a leveling agent, an antifoamer, a photoinitiator, etc. are mentioned. Moreover, you may add the monomer which has unsaturated bonds, such as methacrylate and an acrylate, as a reactive diluent.

(Method of producing a pigment colorant composition)

At the time of manufacture of a pigment colorant composition, each component may be mix | blended at once and may be mix | blended individually. On the other hand, it is preferable to add a pigment derivative when pigmentizing a raw material compound of a pigment to make a pigment or when making a pigment fine. Thereby, the pigment (surface treatment pigment) whose surface became basic by the action of a pigment derivative can be obtained. In addition, when using the resin treatment pigment mentioned later, components, such as a liquid medium and an alkali developable polymer, are added and disperse | distributed to a resin treatment pigment. In addition, you may add another pigment dispersant as needed.

The method of disperse | distributing a pigment should just be a conventionally well-known method, and it does not specifically limit. Specific examples of the apparatus used to disperse the pigment include vertical and horizontal media mills, sand mills, attritors, microfluidizers, ultrasonic dispersers, and three roll mills. three roll mill). Using such a device, it is preferable to disperse the pigment until it reaches a predetermined number average particle diameter.

When refine | miniaturizing a pigment, a pigment dispersant (phosphate group containing block copolymer) can also be used. Specifically, the phosphoric acid group-containing block copolymer is added during the kneading of the pigment, and by kneading, the phosphate group of the phosphoric acid group-containing block copolymer is ion-bonded to the pigment to adsorb the pigment dispersant to the pigment. It does not specifically limit as a kneading method of a pigment. Specifically, conventionally known kneaders such as a kneader, an extruder, a ball mill, two roll mills, three roll mills, a flasher, and the like are used, and are usually 0.5 to 60 hours under normal temperature or heating conditions, preferably Knead for 1 to 12 hours. Moreover, it is preferable to use together salts, such as a carbonate and a chloride salt, as a medium for refine | miniaturizing a pigment as needed. The amount of the salt to be used is preferably 1 to 30 mass times, more preferably 2 to 20 mass times, with respect to the pigment.

Moreover, it is preferable to use together the organic solvent which has viscosity, such as glycerin, ethylene glycol, diethylene glycol, and provide lubricity. Since a phosphate group containing block copolymer melt | dissolves in the organic solvent which has such a viscosity, a pigment can be refined without depositing a phosphate group containing block copolymer. What is necessary is just to adjust the usage-amount of the organic solvent which has a viscosity according to the viscosity of a kneaded material. The resin treatment pigment thus obtained may be a water paste after desalting, or may be ground to powder. Moreover, the obtained resin process pigment can be disperse | distributed to a liquid medium and can be used as a pigment dispersion.

The pigment colorant composition of this invention can be used as a coloring agent of various articles. For example, the pigment colorant composition of the present invention can be used as gravure ink, offset ink, UV inkjet ink, or the like. In particular, since it is possible to make low viscosity and high fineness of a pigment and to have favorable long-term storage stability, it is suitable as a coloring agent for color filters (pigment colorant composition for color filters).

[ Example ]

Next, an Example is given and this invention is demonstrated in detail. Hereinafter, "part" and "%" in a door are a mass reference | standard unless there is particular limitation.

Synthesis Example 1: PP-1

230 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as 'PGMAc') in a 1 L separable flask provided with a reflux tube, a gas introduction device, a thermometer, and a stirring device, 4.1 parts of iodine, 2,2 9.7-azobis (4-methoxy-2,4-dimethylvaleronitrile) (hereinafter referred to as 'V-70') 19.7 parts, methyl methacrylate (hereinafter referred to as 'MMA') 57.6 parts, meta 57.6 parts of butyl methacrylate (hereinafter referred to as 'BMA'), 28.8 parts of 2-ethylhexyl methacrylate (hereinafter referred to as 'EHMA'), methacrylic acid methoxypolyethylene glycol (n = 3 to 5) (hereinafter 28.8 parts of methacrylic acid benzyl (hereinafter referred to as 'BzMA'), 20 parts of methacrylic acid (hereinafter referred to as 'MAA'), and 3,5-dit-butyl 0.9 parts of -4-hydroxytoluene (hereinafter referred to as 'BHT') was added thereto. It superposed | polymerized at 40 degreeC for 7 hours, flowing nitrogen, and obtained the solution of the A polymer block. The polymerization rate of the A polymer block calculated from the solid content was 87.2%. In addition, Mn measured by GPC was 4,800, PDI was 1.25, and the molecular weight of the peak top was 6,000. Moreover, the acid value was 61.7 mgKOH / g.

26.0 parts of MMA and 2- (methacryloyloxy) ethyl phosphate (it writes brand name "light ester P-1M", the Kyoeisha Chemical Co., Ltd. product, hereinafter, "P1M") in the solution of the obtained A polymer block 13.4 To V-70, 0.9 part of the mixture and 39 parts of PGMAc were added. The polymerization was carried out for 4 hours to form a B polymer block. After stopping distribution of nitrogen, it heated at 80 degreeC, the iodine couple | bonded with the terminal of a polymer chain was liberated, and the polymer solution containing an A-B block copolymer was obtained. On the other hand, it was confirmed that iodine was free because the polymer solution became a brown transparent liquid.

Solid content of the obtained polymer solution was 48.3%. Moreover, the polymerization rate of the B polymer block computed from solid content was nearly 100%. Mn of the A-B block copolymer was 5,500, PDI was 1.35, the peak top molecular weight was 7,400, and the acid value was 80.5 mgKOH / g. In addition, Mn of the B polymer block ('Mn' of the A-B block copolymer-'Mn' of the A polymer block) was 700. The obtained A-B block copolymer is called "PP-1."

(Synthesis example 2: PP-2)

As above, except that 280 parts of PGMAc, 3.6 parts of iodine, 17.7 parts of V-70, M7.7 77.7 parts, BMA 77.7 parts, EHMA 38.8 parts, PME200 38.8 parts, BzMA 19.4 parts, MAA 27.0 parts, and BHT 0.9 parts In the same manner as in Synthesis Example 1, a solution of the A polymer block was obtained. The polymerization rate of the A polymer block calculated from the solid content was 90.1%. Moreover, Mn of the A polymer block was 7,000, PDI was 1.36, the peak top molecular weight was 9,500, and the acid value was 62.2 mgKOH / g.

Subsequently, a B polymer block was formed in the same manner as in Synthesis Example 1 except that 23.1 parts of MMA, 12.0 parts of P1M, 0.8 parts of V-70, and 35 parts of PGMAc were used to form a B block copolymer. A polymer solution containing was obtained. Solid content of the obtained polymer solution was 48.5%, and the polymerization rate of B polymer block computed from solid content was nearly 100%. Mn of the A-B block copolymer was 7,500, PDI was 1.40, the peak top molecular weight was 10,500, and the acid value was 76.3 mgKOH / g. Moreover, Mn of the B polymer block was 500. The obtained A-B block copolymer is called "PP-2".

(Synthesis example 3: PP-3)

As above, except that 280 parts of PGMAc, 3.6 parts of iodine, 17.7 parts of V-70, M7.7 77.7 parts, BMA 77.7 parts, EHMA 38.8 parts, PME200 38.8 parts, BzMA 19.4 parts, MAA 27.0 parts, and BHT 0.9 parts In the same manner as in Synthesis Example 1, a solution of the A polymer block was obtained. The polymerization rate of the A polymer block calculated from the solid content was 90.4%. Moreover, Mn of the A polymer block was 7,000, PDI was 1.36, the peak top molecular weight was 9,500, and the acid value was 62.0 mgKOH / g.

Subsequently, a B polymer block was formed in the same manner as in Synthesis Example 1 above except that 28.9 parts of MMA, 18.0 parts of P1M, 0.9 part of V-70, and 46.9 parts of PGMAc were used, and an AB block copolymer was formed. A polymer solution containing was obtained. Solid content of the obtained polymer solution was 48.8%, and the polymerization rate of B polymer block computed from solid content was nearly 100%. Mn of the A-B block copolymer was 8,500, PDI of 1.44, peak top molecular weight of 11,200, and acid value of 82.9 mgKOH / g. Moreover, Mn of the B polymer block was 1,500. The obtained A-B block copolymer is called "PP-3".

(Synthesis example 4: PP-4)

As above, except that 280 parts of PGMAc, 3.6 parts of iodine, 17.7 parts of V-70, M7.7 77.7 parts, BMA 77.7 parts, EHMA 38.8 parts, PME200 38.8 parts, BzMA 19.4 parts, MAA 27.0 parts, and BHT 0.9 parts In the same manner as in Synthesis Example 1, a solution of the A polymer block was obtained. The polymerization rate of the A polymer block calculated from the solid content was 90.9%. Moreover, Mn of the A polymer block was 6,900, PDI was 1.34, the peak top molecular weight was 9,500, and the acid value was 61.9 mgKOH / g.

Subsequently, a B polymer block was formed in the same manner as in Synthesis Example 1 above except that 34.7 parts of MMA, 24.0 parts of P1M, 1.2 parts of V-70, and 58.7 parts of PGMAc were used to form an AB block copolymer. A polymer solution containing was obtained. Solid content of the obtained polymer solution was 48.6%, and the polymerization rate of B polymer block computed from solid content was nearly 100%. Mn of the A-B block copolymer was 9,600, PDI was 1.45, the peak top molecular weight was 14,000, and the acid value was 89.9 mgKOH / g. Moreover, Mn of the B polymer block was 2,700. The obtained A-B block copolymer is called "PP-4".

(Synthesis example 5: PP-5)

Synthesis Example 1 described above, except that 280 parts of PGMAc, 3.6 parts of iodine, 17.7 parts of V-70, M7.7 77.7 parts, BMA 77.7 parts, EHMA 38.8 parts, PME200 was used 38.8 parts, BzMA 19.4 parts, and BHT 0.9 parts In the same manner as in the case of, a solution of the A polymer block was obtained. The polymerization rate of the A polymer block calculated from the solid content was 88.5%. Moreover, Mn of the A polymer block was 6,500, PDI was 1.33, and the peak top molecular weight was 8,600.

Subsequently, a B polymer block was formed in the same manner as in Synthesis Example 1 except that 23.1 parts of MMA, 12.0 parts of P1M, 0.8 parts of V-70, and 35 parts of PGMAc were used to form a B block copolymer. A polymer solution containing was obtained. Solid content of the obtained polymer solution was 48.4%, and the polymerization rate of B polymer block computed from solid content was nearly 100%. Mn of the A-B block copolymer was 7,000, PDI of 1.40, peak top molecular weight of 9,800, and acid value of 22.1 mgKOH / g. Moreover, Mn of the B polymer block was 500. The obtained A-B block copolymer is called "PP-5".

(Comparative Synthesis Example 1: HG-1)

300 parts of PGMAc was thrown into the 1 L separable flask which installed the reflux tube, the thermometer, and the stirring apparatus, and it heated at 80 degreeC. 7.5 parts of 2,2'- azobisisobutyronitrile prepared in another container previously, and 6 parts of lauryl mercaptan dissolved as a chain transfer agent, 95 parts of MMA, 74 parts of BMA, 37 parts of EHMA, The monomer solution containing 37 parts of PME200, 18 parts of BzMA, 27 parts of MAA, and 12 parts of P1M was dripped in the said 1 L separable flask for 1.5 hours. After completion of dropwise addition, the mixture was polymerized at the same temperature for 5 hours to obtain a polymer solution containing a polymer. Solid content of the obtained polymer solution was 50.3%. Mn of the polymer was 6,300, PDI was 1.92 and the acid value was 79.5 mgKOH / g. The obtained polymer is called "HG-1".

(Comparative Synthesis Example 2: HG-2)

As above, except using 154 parts of PGMAc, 3.6 parts of iodine, 17.7 parts of V-70, 42.3 parts of MMA, 42.3 parts of BMA, 21.3 parts of EHMA, 21.3 parts of BMEMA, 12 parts of BzMA, 15 parts of MAA, and 0.9 parts of BHT. In the same manner as in Synthesis Example 1, a solution of the A polymer block was obtained. The polymerization rate of the A polymer block calculated from the solid content was 93.2%. Moreover, Mn of the A polymer block was 4,500, PDI was 1.26, the peak top molecular weight was 5,700, and the acid value was 59.2 mgKOH / g.

Subsequently, except for using 67.5 parts of MMA, 11.9 parts of 2-methacryloyloxyethyl phthalic acid (hereinafter, referred to as 'MEPA'), 1.6 parts of V-70, and 79.4 parts of PGMAc, the above-described synthesis example 1 In the same manner as in the case of the B polymer block, a polymer solution containing an AB block copolymer was obtained. Solid content of the obtained polymer solution was 48.3%, and the polymerization rate of B polymer block computed from solid content was nearly 100%. Mn of the A-B block copolymer was 7,300, PDI was 1.45, the peak top molecular weight was 12,000, and the acid value was 52.1 mgKOH / g. Moreover, Mn of the B polymer block was 2,800. The obtained A-B block copolymer is called "HG-2".

The composition and physical properties of the polymer obtained in each synthesis example described above are shown in Tables 1-3.

(Examples 1-6, Comparative Examples 1 and 2: Pigment Coloring Agent Composition)

(a) Refinement of Pigment

PR254, PG58, PY138, PY150, PB15-6, and PV23 were prepared as a pigment for color filters, and the refinement | miniaturization process was performed by the method shown below. 100 parts of pigment, 400 parts of sodium chloride, and 130 parts of diethylene glycol were placed in a kneader equipped with a pressure lid. Premixing was carried out until a uniformly wet mass appeared in the kneader. The pressurized lid was closed, and the mixture was kneaded and ground for 7 hours while pressing the contents at a pressure of 6 kg / cm 2 to obtain a ground product. The obtained ground product was poured into 3,000 parts of 2% sulfuric acid and stirred for 1 hour. After filtration to remove sodium chloride and diethylene glycol, the mixture was washed with water sufficiently, then dried and pulverized to obtain a pigment powder. The number average particle diameter of the obtained pigment powder was about 30 nm.

(b) Preparation of Pigment Colorant Compositions

Each component shown in Table 4 was mix | blended with the quantity (part) shown in Table 4, and it stirred for 2 hours by the dissolver. After confirming that the ingot of the pigment disappeared, dispersion treatment was carried out using a horizontal media disperser to prepare a pigment colorant composition (pigment dispersion). In Table 4, 'synergy 1' is represented by the following structural formula (1) (n = 1 to 2 (substantially 1.5)), 'synergy 2' is represented by the following structural formula (2), and 'synergy 3' is represented by All are pigment derivatives each having an amino group represented by the following structural formula (3) (n = 1 to 2 (substantially 1.5)). The acrylic resin in Table 4 has a monomer composition of BzMA / MAA = 80/20 (mass ratio), Mn of 5,500 and PDI of 2.02 by GPC measurement (PGMAc solution (solid content concentration: 30%)). Was used.

(Evaluation (1) of pigment colorant composition)

The measurement result of the number average particle diameter of the pigment contained in the obtained pigment colorant composition (pigment dispersion liquid), the viscosity of the initial stage of a pigment dispersion liquid, and the viscosity (viscosity after storage) after leaving it for 3 days at 45 degreeC are shown in Table 5 Indicates.

As shown in Table 5, the number average particle diameter of the pigment contained in the pigment colorant composition (pigment dispersion liquid) of Examples 1-6 was 50 nm or less, and it turned out that the micronized pigment is fully disperse | distributed. Moreover, the initial viscosity of all the pigment dispersion liquids of Examples 1-6 was 10 mPa * s or less. Moreover, when comparing an initial viscosity and the viscosity after storage, it turns out that a viscosity change is very small. As mentioned above, it is clear that the pigment dispersion liquid of Examples 1-6 has sufficient dispersion stability.

On the other hand, when the pigment dispersion liquid of the comparative example 1 is compared with the pigment dispersion liquid of Example 1, it turns out that the number average particle diameter of a pigment is large and it is not fully disperse | distributing. In addition, since the viscosity after storage is greatly increased, it can be seen that dispersion stability is also insufficient. Moreover, since the pigment dispersion liquid of the comparative example 2 does not contain the phosphate group containing methacrylate as a structural component of the polymer block of B, the adsorption power to a pigment is weak, and the viscosity of an initial stage of dispersion is good, but the aggregation of a pigment during storage It turned out that dispersion stability was inadequate.

(Examples 7-9: the pigment colorant composition for color filters)

Each component shown in Table 6 was mix | blended with the quantity (part) shown in Table 6, and it fully mixed with the mixer, and obtained the pigment colorant composition (color pigment ink) for color filters of each color which is a color resist. In addition, the "photosensitive acrylic resin varnish" in Table 6 is a varnish containing the acrylic resin obtained by making glycidyl methacrylate react with BzMA / MAA copolymer. This acrylic resin had a Mn of 6,000 and a PDI of 2.38 and an acid value of 110 mgKOH / g. 'TMPTA' represents trimethylolpropanetriacrylate, 'HEMPA' represents 2-hydroxyethyl-2-methylpropionic acid, and 'DEAP' represents 2,2-diethoxyacetophenone.

The glass substrate processed with the silane coupling agent was set to the spin coater. The red pigment ink-1 of Example 7 was spin-coated on the glass substrate at 300 rpm for 5 second conditions. After prebaking at 80 degreeC for 10 minutes, it exposed to light quantity of 100mJ / cm <2> using the ultrahigh pressure mercury lamp, and manufactured the red glass substrate. In addition, except having used the green pigment ink-1 of Example 8 and the blue pigment ink-1 of Example 9 respectively, it carried out similarly to the case where said red glass substrate was manufactured, A green glass substrate and a blue glass substrate Prepared.

The obtained glass substrate (color glass substrate) of each color had the outstanding spectral curve characteristic, and was excellent also in fastness, such as light resistance and heat resistance. Moreover, any color glass substrate was excellent also in optical characteristics, such as light transmittance and contrast ratio.

(Comparative examples 3 and 4: pigment colorant composition for color filters)

(i) A polyester-based dispersant having no phosphoric acid group in place of 'PP-2' (condensation product of polyε-caprolactone and polyethyleneimine having 12-hydroxystearic acid as a starting compound, Mn: 12,000, amine Value: 12 mgKOH / g) and (ii) except for using the monosulfonated diketopyrrolopyrrole in place of 'Synergy 1', in the same manner as in Example 1 described above for comparison A red pigment dispersion liquid was prepared. In addition, except the (i) using the said polyester type dispersing agent instead of "PP-4", and (ii) using the monosulfonated copper phthalocyanine instead of "synergy 3", the above-mentioned implementation is carried out. In the same manner as in Example 5, a comparative blue pigment dispersion was prepared.

And except having used the prepared pigment dispersion for comparison, it carried out similarly to the case of Example 7, and prepares a red pigment ink (comparative example 3) and a blue pigment ink (comparative example 4), and compares The red glass substrate and the blue glass substrate were manufactured.

(Alkali Developability Test)

A 0.1 N tetramethylammonium hydroxide aqueous solution was spotted every 5 seconds on each of the color glass substrates produced using the pigment inks of Examples 7 to 9 and Comparative Examples 3 and 4. And it was confirmed by visual observation about "how many seconds the exposure part of a coating film melt | dissolves." The results are shown in Table 7.

As shown in Table 7, in the glass substrate manufactured using the red pigment ink-1 of Example 7, the green pigment ink-1 of Example 8, and the blue pigment ink-1 of Example 9, all exposed in a short time. A negative coating film melt | dissolved, and melt | dissolution residue (film-like sediment) did not generate | occur | produce and showed favorable developability. On the other hand, when the edge part (edge) of the coating film which remained without melt | dissolution was observed under the microscope, it was confirmed that both were sharp. That is, when using the pigment colorant composition (pigment ink) of Examples 7-9, since image development time can be shortened, productivity improvement is anticipated.

On the other hand, in the glass substrate manufactured using the manufactured red pigment ink of the comparative example 3, and the blue pigment ink of the comparative example 4, 60 second or more was required for all the exposure part of a coating film to disappear completely. Thus, it can be considered that the development time is long because a pigment dispersant suitable for alkali development is used. Moreover, also about any glass substrate, the exposure part of the coating film was detach | desorbed in the film form, and the residue was produced. This is considered to be because a pigment dispersant is not alkali solubility. As mentioned above, it turned out that the coating film formed using the pigment ink of Examples 7-9 using the pigment dispersant of Examples 1, 2, and 5 was excellent in alkali developability.

(Reference Examples 1-3: Preparation of Pigment Powder Treated with Resin)

100 parts of PR254 (pigment), 400 parts of sodium chloride, and 130 parts of diethylene glycol were put into the kneader with a pressurized lid. Premixing was carried out until a uniformly wet mass appeared in the kneader. Subsequently, 61.5 parts of 'PP-2' was added, the pressure lid was closed, and the mixture was kneaded and ground for 7 hours while pressing the contents at a pressure of 6 kg / cm 2 to obtain a ground material. The obtained ground product was poured into 3,000 parts of 2% sulfuric acid and stirred for 1 hour. After filtration to remove sodium chloride and diethylene glycol, the mixture was washed with water sufficiently, then dried and pulverized to obtain a red pigment powder (Reference Example 1). The number average particle diameter of the obtained pigment powder was 30 nm.

A green pigment powder (Reference Example 2) was obtained in the same manner as in Reference Example 1, except that PR254 was replaced with PG58, and 'PP-2' was replaced with 'PP-1'. The number average particle diameter of the obtained pigment powder was 35 nm. A blue pigment powder (Reference Example 3) was prepared in the same manner as in Reference Example 1, except that PR254 was replaced with PB15: 6 and 'PP-2' was replaced with 'PP-4'. Got it. The number average particle diameter of the obtained pigment powder was 30 nm.

(Examples 10-12: Pigment colorant composition)

Each component shown in Table 8 was mix | blended with the quantity (part) shown in Table 8, and it stirred with the resolver for 2 hours. After confirming that the ingot of the pigment disappeared, it was dispersed using a horizontal media disperser to prepare a pigment colorant composition (pigment dispersion).

(Evaluation (2) of pigment colorant composition)

The measurement result of the number average particle diameter of the pigment contained in the obtained pigment colorant composition (pigment dispersion liquid), the viscosity of the initial stage of a pigment dispersion liquid, and the viscosity (viscosity after storage) after leaving it for 3 days at 45 degreeC are shown in Table 9 Indicates.

As shown in Table 9, the pigment colorant composition (pigment dispersion liquid) of Examples 10-12 had the favorable viscosity after initial stage and storage. As mentioned above, it was confirmed that the pigment dispersant of this invention can exhibit sufficient pigment dispersibility even when it adds and uses at the time of refine | miniaturizing a pigment.

(Examples 13-15: the pigment colorant composition for color filters)

Each component shown in Table 10 was mix | blended with the quantity (part) shown in Table 10, it mixed sufficiently by the mixer, and the pigment colorant composition for color filters (pigment ink) of each color which is a color resist was obtained.

The glass substrate processed with the silane coupling agent was set by the spin coater. The red pigment ink-2 of Example 13 was spin-coated on a glass substrate at 300 rpm for 5 seconds. After prebaking at 80 degreeC for 10 minutes, it exposed at the light quantity of 100mJ / cm <2> using the ultrahigh pressure mercury lamp, and manufactured the red glass substrate. In addition, except having used the green pigment ink-2 of Example 14 and the blue pigment ink-2 of Example 15 similarly to the case where said red glass substrate was manufactured, a green glass substrate and a blue glass substrate Prepared.

Since the glass substrate (color glass substrate) of each color obtained does not perform color adjustment at all, it cannot be called a reliable filter color. However, any color glass substrate had excellent spectral curve characteristics and was excellent in fastness such as light resistance and heat resistance. Moreover, any color glass substrate was excellent also in optical characteristics, such as light transmittance and contrast ratio.

The phosphoric acid group containing block copolymer of this invention has the outstanding characteristic especially as a pigment dispersant. For this reason, when the phosphate group containing block copolymer of this invention is used, the pigment colorant composition excellent in long-term storage stability at low viscosity can be prepared. And since this pigment colorant composition (pigment ink) is excellent in coating property and developability, it is a material for manufacturing the color filter which was excellent in optical characteristics, such as fineness, color density, light transmittance, and contrast property. Useful as On the other hand, the pixel display device provided with the color filter manufactured in this way is excellent in image performance such as fineness, color density, light transmittance, and contrast property.

Claims (13)

It is the AB block type copolymer which consists of A polymer block and B polymer block containing 90 mass% or more of structural units derived from a methacrylic acid type monomer,
The phosphate group containing block copolymer of the said A polymer block and the said B polymer block only the B polymer block contains the structural unit derived from the phosphate group containing methacrylic acid type monomer which has a phosphate group. The method of claim 1,
The said A polymer block contains the structural unit derived from the carboxyl group-containing methacrylic acid type monomer which has a carboxyl group,
A phosphoric acid group containing block copolymer whose acid value of the said A polymer block is 10-200 mgKOH / g. 3. The method of claim 2,
The phosphoric acid group containing block copolymer whose said carboxyl group-containing methacrylic acid type monomer is methacrylic acid. The method according to any one of claims 1 to 3,
The number average molecular weight of the said A polymer block is 3,000-20,000, molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.6 or less,
The number average molecular weight of the said B polymer block is 200-3,000,
The phosphoric acid group containing block copolymer whose number average molecular weights are 4,000-23,000, and whose molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.6 or less. The method according to any one of claims 1 to 3,
The acid value of the said B polymer block is 50-500 mgKOH / g,
The phosphoric acid group containing block copolymer whose content of the said B polymer block is 5-40 mass%. As a manufacturing method of the phosphoric acid group containing block copolymer of any one of Claims 1-3,
A living radical polymerization of a monomer component containing the methacrylic acid monomer in the presence of a polymerization initiating compound and a catalyst,
The said polymerization start compound is at least one of an iodine and an iodine compound, The manufacturing method of the phosphate group containing block copolymer characterized by the above-mentioned. The method according to claim 6,
Phosphoric acid group which the said catalyst is at least 1 sort (s) of compound chosen from the group which consists of a halogenated, phosphite type compound, a phosphinate compound, an imide type compound, a phenol type compound, a diphenylmethane type compound, and a cyclopentadiene type compound. Process for the preparation of containing block copolymers. The method according to claim 6,
The manufacturing method of the phosphate group containing block copolymer whose polymerization temperature at the time of the said living radical polymerization is 30-50 degreeC. A pigment dispersant comprising the phosphoric acid group-containing block copolymer according to any one of claims 1 to 3 as a main component. The pigment dispersant of Claim 9 and the pigment whose number average particle diameter is 10-150 nm are contained, The pigment colorant composition characterized by the above-mentioned. 11. The method of claim 10,
The pigment colorant composition which further contains the pigment derivative which has a basic functional group. The method of claim 11,
Content of the said phosphate group containing block copolymer with respect to 100 mass parts of said pigments is 10-100 mass parts,
The pigment colorant composition whose content of the said pigment derivative with respect to 100 mass parts of said pigments is 5-100 mass parts. 11. The method of claim 10,
Pigment colorant composition used as a colorant for color filters.