JP2019099801A - Polymer product containing block copolymer and manufacturing method of polymer product - Google Patents

Abstract

To provide a polymer product having excellent dispersion performance and excellent storage stability when used as a dispersant.SOLUTION: There is provided a polymer product containing a block copolymer having an A block with a structural unit derived from a (meth)acrylic monomer, and a B block with a structural unit represented by the following general formula (1), and having molecular weight distribution (PDI) of the polymer product of 2.0 or less and percentage content of the block copolymer of 75 mass% or more in 100 mass% of the polymer product. Rand Rrepresent chain or cyclic hydrocarbon group, Xrepresents a bivalent connection group, and Rrepresents a hydrogen atom or a methyl group.SELECTED DRAWING: None

Description

  The present invention relates to a polymerization product containing a block copolymer and a method for producing the polymerization product.

  Coloring compositions obtained by mixing colorants (pigments, dyes, etc.), dispersants, dispersion media (solvents) and dispersing colorants are used in a wide range of fields such as color filters for liquid crystal displays etc. . For example, in a color filter, in order to apply a coloring material to a substrate, a coating film made of a coloring composition is formed on the substrate, exposed through a photomask having a desired pattern shape, and alkaline development is performed. .

  In the manufacture of a liquid crystal display, after forming a pattern shape of a coloring material, a transparent electrode for driving liquid crystal is formed thereon by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. It is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, their formation is generally performed at a high temperature of 200 ° C. or more. A resin type dispersant is used as the dispersant of the coloring composition because the structure design is easy, but when many resin type dispersants are used, the contrast ratio of the color filter before and after the process involving high heat The heat resistance such as the decrease of the color and the change of the color becomes a problem. Therefore, in order to obtain a pigment dispersion composition in which heat resistance and dispersibility are compatible, in Patent Document 1, from the A block having a quaternary ammonium base in the side chain and the B block not having a quaternary ammonium base It is disclosed that the AB block copolymer is used as a pigment dispersant for color filters (see Patent Document 1 (claim 1, paragraphs 0049 to 0058)).

  The coloring composition is required to be excellent in various characteristics such as sharpness and high transparency, and the coloring material is made into fine particles and the like. When the colorant is in the form of fine particles, the surface energy is increased to cause aggregation of the colorant, the storage stability is poor, and the viscosity of the colorant dispersion becomes high. Therefore, in order to further improve the colorant dispersibility, Patent Document 2 is composed of an A block having a polyalkylene glycol chain in a side chain and a B block having a primary to tertiary amino group in a side chain, (Meth) An acrylic block copolymer is disclosed (see Patent Documents 2 (paragraphs 0039 to 0049)).

  On the other hand, it is known to use a living polymerization method for the preparation of the A-B block copolymer (see, for example, Patent Document 3 (claim 1, page 20, lines 18 to 23)). Living polymerization methods include living anion polymerization method, living cation polymerization method, living radical polymerization method, etc. However, living anion polymerization method and living cation polymerization method require strict polymerization conditions, and functional groups capable of coexistence are limited. However, living radical polymerization is characterized by its ability to precisely control molecular weight distribution and produce polymers of uniform composition while maintaining versatility and compatibility with polar functional groups and simplicity not affected by the purity of monomers and solvents, etc. There is. Therefore, living radical polymerization is used for producing a block copolymer having a polar group and a narrow molecular weight distribution with a controlled molecular weight and a uniform composition.

  In addition, when manufacturing a block copolymer, the polymer impurity byproduced at the time of superposition | polymerization will be contained unavoidable. Therefore, methods for reducing the content of such polymer impurities have been proposed. For example, Patent Document 4 describes a purification method in which polymer impurities are selectively removed by liquid-liquid extraction of a block copolymer after polymerization using a specific solvent (Patent Document 4 See paragraphs 0017 to 0024)). However, Patent Document 4 discusses the purification and removal of the styrene homopolymer, but the method of removing the (meth) acrylic homopolymer is not examined.

JP, 2012-068559, A JP, 2014-167636, A WO 2004/096870 JP, 2015-113444, A

  In recent years, as the characteristics required for coloring compositions become more advanced, conventional dispersants have the problem that the viscosity and storage stability of the coloring compositions are not sufficient. In addition, if the amount of the dispersant used is increased to improve the dispersibility of the coloring material, the heat resistance such as the decrease in the contrast ratio of the color filter and the change in the hue becomes a problem, so even a small amount has excellent dispersibility. Dispersants are needed. However, when the block copolymer contains a polymer impurity, the dispersibility and the dispersion stability tend to be lowered.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a block copolymer which can be used, for example, as a dispersant and has excellent dispersibility and dispersion stability, and a method for producing the same.

  The polymerization product of the present invention, which has been able to solve the above problems, is a polymerization product obtained by polymerizing the monomer composition, and A having a structural unit derived from a (meth) acrylic vinyl monomer. A block copolymer having a block and a B block having a structural unit represented by the following general formula (1), wherein the molecular weight distribution (PDI) of the polymerization product is 2.0 or less, and The content of the block copolymer is 75% by mass or more in 100% by mass of the polymerization product.

〔式（１）において、Ｒ¹¹およびＲ¹²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹およびＲ¹²が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を示す。Ｒ¹³は水素原子またはメチル基を示す。〕

[In formula (1), R ¹¹ and R ¹² each independently represent a linear or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹³ represents a hydrogen atom or a methyl group. ]

  The polymerization product of the present invention contains a block copolymer having an A block having a structural unit derived from a (meth) acrylic vinyl monomer and a B block having a structural unit represented by the general formula (1) Do. This block copolymer has excellent dispersion performance by having the A block and the B block. Thus, the polymerization product of the present invention can be used as a dispersant. In the polymerization product of the present invention, the content of the block copolymer is 75% by mass or more. In other words, the content of polymer impurities such as a polymer consisting only of A block and a polymer consisting only of B block is 25% by mass or less. Therefore, the polymerization product of the present invention exhibits excellent storage stability when used as a dispersant.

The method for producing a polymerization product of the present invention comprises the first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator, or the organic tellurium compound represented by the general formula (3) A block polymerization step of polymerizing a first monomer composition containing a (meth) acrylic vinyl monomer using a second mixture of an azo polymerization initiator and an organic ditelluride compound represented by the general formula (4) B block polymerization step of polymerizing a second monomer composition containing a vinyl monomer forming a structural unit represented by the general formula (1) using the first mixture or the second mixture, In all the polymerization steps, the difference (T _1/2 -Tr) between the 10 hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) is 10 ° C. to 60 ° C. It is characterized by

〔一般式（３）中、Ｒ³¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を表す。Ｒ³²およびＲ³³は、それぞれ、水素原子または炭素数１〜８のアルキル基を表す。Ｒ³⁴は、炭素数１〜８のアルキル基、アリール基、芳香族へテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を表す。
一般式（４）中、Ｒ³¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を表す。〕

[In general formula (3), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. R ³² and R ³³ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
In formula (4), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]

The method for producing a polymerization product of the present invention comprises the first mixture of an organic tellurium compound and an azo polymerization initiator, or the second mixture of an organic tellurium compound, an azo polymerization initiator and an organic ditelluride compound. By polymerizing the monomer composition, a block copolymer having precise molecular weight and molecular weight distribution can be synthesized under mild conditions. In the block copolymer production method of the present invention, the difference between the 10 hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) in the polymerization step of all the blocks T _1/2 -Tr) is adjusted to 10 ° C. to 60 ° C. By adjusting the reaction temperature to the above range, purification of polymer impurities can be suppressed. Therefore, if the method for producing a polymerization product of the present invention is adopted, a polymerization product having a high content of a desired block copolymer and a low content of polymer impurities can be obtained.

  The polymerization product of the present invention has excellent dispersion performance and exhibits excellent storage stability when used as a dispersant. The method for producing a polymerization product of the present invention provides a polymerization product having a high content of a desired block copolymer and a low content of polymer impurities.

  The polymerization product of the present invention is a polymerization product obtained by polymerizing a monomer composition, which comprises an A block having a structural unit derived from a (meth) acrylic vinyl monomer, and a general formula (1) described later A block copolymer having a B block having a structural unit represented by), a molecular weight distribution (PDI) of the polymerization product is 2.0 or less, and a content of the block copolymer However, it is characterized by being 75 mass% or more in 100 mass% of said polymerization products.

  The polymerization product of the present invention contains a block copolymer having an A block having a structural unit derived from a (meth) acrylic vinyl monomer and a B block having a structural unit represented by the general formula (1) Do. This block copolymer has excellent dispersion performance by having the A block and the B block. Thus, the polymerization product of the present invention can be used as a dispersant. In the polymerization product of the present invention, the content of the block copolymer is 75% by mass or more. In other words, the content of polymer impurities such as a polymer consisting only of A block and a polymer consisting only of B block is 25% by mass or less. Therefore, the polymerization product of the present invention exhibits excellent storage stability when used as a dispersant.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiments are merely illustrative. The present invention is not at all limited to the following embodiments.

<Polymerization product>
The polymerization product of the present invention contains a block copolymer having an A block and a B block, and a polymer impurity.

  In the present invention, “A block” can be rephrased as “A segment”, and “B block” can be rephrased as “B segment”. In the present invention, the "vinyl monomer" refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule. The “structural unit derived from a vinyl monomer” refers to a structural unit in which a radical polymerizable carbon-carbon double bond of a vinyl monomer is polymerized to form a carbon-carbon single bond. "(Meth) acrylic" refers to "at least one of acrylic and methacrylic". "(Meth) acrylate" refers to "at least one of acrylate and methacrylate". "(Meth) acryloyl" refers to "at least one of acryloyl and methacryloyl".

  In the present invention, the "polymerization product" refers to a product obtained when a polymerization operation (if necessary, a quaternization treatment) is performed to obtain the block copolymer. The “polymerization product” includes a desired block copolymer and a polymer impurity by-produced when synthesizing this block copolymer.

  In the present invention, "polymer impurities" are other polymers which are inevitably by-produced when synthesizing a desired block copolymer. For example, as a polymer impurity by-produced when synthesizing an AB diblock copolymer, a random polymer having the same composition as the A block and a random polymer having the same composition as the B block can be mentioned. As a polymer impurity by-produced when synthesizing an A-B-A triblock copolymer or a B-A-B triblock copolymer, a random polymer having the same composition as that of the A block, and the same as the B block And random polymers having the following composition. The “polymer impurity” is a polymer by-produced when synthesizing a desired block copolymer, and does not include a separately added polymer.

(Block copolymer)
The various components of the block copolymer and the like will be described below.

(A block)
The A block is a polymer block containing a structural unit derived from a (meth) acrylic vinyl monomer. The structural unit derived from the (meth) acrylic vinyl monomer in the A block may be only one type or may have two or more types. By setting it as a structural unit derived from a (meth) acrylic vinyl monomer, high affinity with the dispersion medium (solvent) and the binder resin can be maintained.

  The content of the structural unit derived from the (meth) acrylic vinyl monomer is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more in 100% by mass of the A block. Particularly preferably, it is 100% by mass.

  The (meth) acrylic vinyl monomer is a (meth) acrylate having a linear alkyl group (a linear alkyl group or a branched alkyl group), a (meth) acrylate having a cyclic alkyl group, or a polycyclic structure (meth ) Acrylate, (meth) acrylate having aromatic group, (meth) acrylate having polyalkylene glycol structural unit, (meth) acrylate having hydroxy group, (meth) acrylate having lactone modified hydroxy group, having alkoxy group And (meth) acrylates, (meth) acrylates having an oxygen-containing heterocyclic group, (meth) acrylates having an acid group, (meth) acrylic acid and the like can be mentioned, and one or two or more of these may be combined It can be used.

  The (meth) acrylate having a linear alkyl group is preferably a (meth) acrylate having a linear alkyl group in which the carbon number of the linear alkyl group is 1 to 20, and the carbon number of the linear alkyl group is 1 to 1 More preferred is a (meth) acrylate having a linear alkyl group of 10. Examples of the (meth) acrylate having a linear alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, decyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate and the like can be mentioned.

  The (meth) acrylate having a branched alkyl group is preferably a (meth) acrylate having a branched alkyl group in which the carbon number of the branched alkyl group is 1 to 20, and the carbon number of the branched alkyl group is preferably 1 to 1 (Meth) acrylates having a branched alkyl group of 10 are preferred. Examples of the (meth) acrylate having a branched alkyl group include isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isooctyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate and the like can be mentioned.

  The (meth) acrylate having a cyclic alkyl group is preferably a (meth) acrylate having a cyclic alkyl group having 6 to 12 carbon atoms. Examples of the cyclic alkyl group include cyclic alkyl groups having a single ring structure (eg, cycloalkyl group). Specific examples of the (meth) acrylate having a cyclic alkyl group having a single ring structure include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate and the like.

  The (meth) acrylate having a polycyclic structure is preferably a (meth) acrylate having a polycyclic structure having 6 to 12 carbon atoms. The polycyclic structure includes a cyclic alkyl group having a bridged ring structure (for example, an adamantyl group, a norbornyl group, an isobornyl group). Specific examples of (meth) acrylates having a polycyclic structure include isobornyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, 2-methyl-2-adamantyl Examples include (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate and the like.

  The (meth) acrylate having an aromatic group is preferably a (meth) acrylate having an aromatic group having 6 to 12 carbon atoms. The aromatic group may, for example, be an aryl group, an alkylaryl group, an aralkyl group, an aryloxy group, an aryloxyalkyl group, an alkylaryloxy group or an aralkyloxy group, and in particular, a phenyl group, a benzyl group, a tolyl group, a phenoxyethyl group. Groups are preferred. Specific examples of the (meth) acrylate having an aromatic group include benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.

  Examples of the (meth) acrylate having a polyalkylene glycol structural unit include polyethylene glycol (degree of polymerization = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization = 2 to 10) ethyl ether (meth) acrylate, polyethylene Glycol (polymerization degree = 2 to 10) (meth) acrylate having polyethylene glycol structural unit such as propyl ether (meth) acrylate; polypropylene glycol (polymerization degree = 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree = 2 to 10) (meth) acrylate having a polypropylene glycol structural unit such as ethyl ether (meth) acrylate, polypropylene glycol (degree of polymerization = 2 to 10) propyl ether (meth) acrylate Relate; and the like.

  Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxy lauryl (meth) acrylate and the like can be mentioned.

  Examples of the (meth) acrylate having a lactone-modified hydroxy group include those obtained by adding a lactone to the (meth) acrylate having a hydroxy group, and those having a caprolactone added are preferable. The addition amount of caprolactone is preferably 1 mol to 10 mol, and more preferably 1 mol to 5 mol. As the (meth) acrylate having a lactone modified hydroxy group, 1 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, 2 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 3 mol adduct of caprolactone, 4 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, 5 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, 10 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, etc. are preferable .

  Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.

  The (meth) acrylate having an oxygen-containing heterocyclic group is preferably a (meth) acrylate having a 4- to 6-membered oxygen-containing heterocyclic group. Specific examples of the (meth) acrylate having an oxygen-containing heterocyclic group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (3-ethyl oxetan-3-yl) methyl (meth) acrylate, (2-) Methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2-[(2-tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-Dioxane- (meth) acrylate etc. are mentioned.

Examples of the acidic group include carboxy group (—COOH), sulfonic acid group (—SO ₃ H), phosphoric acid group (—OPO ₃ H ₂ ), phosphonic acid group (—PO ₃ H ₂ ), phosphinic acid group (— PO ₂ H ₂₎ can be mentioned. As the (meth) acrylate having an acidic group, a (meth) acrylate having a carboxy group such as a monomer obtained by reacting an hydroxy anhydride (meth) acrylate with an acid anhydride such as maleic anhydride, succinic anhydride, or phthalic anhydride (Meth) acrylate having a sulfonic acid group such as ethyl sulfonate (meth) acrylate; (meth) acrylate having a phosphoric acid group such as 2- (phosphonooxy) ethyl (meth) acrylate; Is a (meth) acrylate having a carboxy group.

  The (meth) acrylic vinyl monomer preferably contains a (meth) acrylate having a polyalkylene glycol structural unit and / or a (meth) acrylate having a lactone-modified hydroxy group. When these monomers are used, the total content of structural units derived from (meth) acrylate having a polyalkylene glycol structural unit in A block and structural units derived from (meth) acrylate having a lactone modified hydroxy group is In 100% by mass of the A block, 5% by mass or more is preferable, more preferably 10% by mass or more, further preferably 20% by mass or more, particularly preferably 30% by mass or more, and 80% by mass or less is preferable More preferably, it is 70 mass% or less, More preferably, it is 50 mass% or less, Especially preferably, it is 40 mass% or less.

  It is also preferable to use only one of these (meth) acrylates having a polyalkylene glycol structural unit and / or (meth) acrylates having a lactone-modified hydroxy group.

  As one aspect of the (meth) acrylic vinyl monomer, a (meth) acrylate having a linear alkyl group (a linear alkyl group or a branched alkyl group), a cyclic alkyl group, and the like. (Meth) acrylate having a polycyclic structure, (meth) acrylate having an aromatic group, (meth) acrylate having a hydroxy group, (meth) acrylate having an alkoxy group, an oxygen-containing heterocyclic group It is preferable to contain only (meth) acrylate having an acid group, (meth) acrylate having an acid group, one or more selected from (meth) acrylic acid, and (meth) acrylate having a polyalkylene glycol structural unit . By using these (meth) acrylic vinyl monomers, the dispersibility and the dispersion stability can be further improved. In this case, the content of structural units derived from (meth) acrylate having a polyalkylene glycol structural unit is preferably 5% by mass or more, more preferably 10% by mass or more, in 100% by mass of the A block. Is 20% by mass or more, preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

  As another embodiment of the (meth) acrylic vinyl monomer, a (meth) acrylate having a linear alkyl group (a linear alkyl group or a branched alkyl group), a cyclic alkyl group, and the like. (Meth) acrylate having a polycyclic structure, (meth) acrylate having an aromatic group, (meth) acrylate having an aromatic group, (meth) acrylate having a hydroxy group, (meth) acrylate having an alkoxy group, an oxygen-containing heterocyclic ring It is preferable to contain only (meth) acrylate having a group, (meth) acrylate having an acid group, one or more selected from (meth) acrylic acid, and (meth) acrylate having a lactone modified hydroxy group . By using these (meth) acrylic vinyl monomers, the dispersibility, heat resistance and alkali developability can be improved. In this case, the total content of structural units derived from (meth) acrylate having a lactone-modified hydroxyalkyl group in the A block is preferably 5% by mass or more, more preferably 30% by mass in 100% by mass of the A block. % Or more, preferably 80% by mass or less, and more preferably 70% by mass or less.

  As a structural unit derived from the (meth) acrylate which has the said polyalkylene glycol structural unit, the structural unit represented, for example by following General formula (7) can be mentioned.

〔一般式（７）において、ｎ７は２〜１５０の整数を表す。Ｒ⁷¹は水素原子又は炭素数が１〜６のアルキル基を表す。Ｒ⁷²は炭素数が１〜６のアルキレン基を表す。Ｒ⁷³は水素原子またはメチル基を表す。〕

[In general formula (7), n7 represents the integer of 2-150. R ⁷¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁷² represents an alkylene group having 1 to 6 carbon atoms. R ⁷³ represents a hydrogen atom or a methyl group. ]

N7 in the formula (7) is preferably an integer of 2 to 50, and more preferably an integer of 2 to 10.
The alkyl group having 1 to 6 carbon atoms represented by R ⁷¹ may be linear or branched, but is preferably linear. Specific examples of the alkyl group of carbon number 1 to 6 represented by R ⁷¹ include methyl group, ethyl group, n- propyl group, n- butyl group, a pentyl group, a hexyl group. R ⁷¹ is preferably an alkyl group having 1 to 3 carbon atoms.
The alkylene group having 1 to 6 carbon atoms represented by R ⁷² may be linear or branched, but linear is preferable. Specific examples of the above alkylene group having a carbon number represented by R ⁷² is 1-6, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like. R ⁷² is preferably an alkylene group having 2 to 4 carbon atoms.

  As a structural unit derived from the (meth) acrylate which has the said lactone modified | denatured hydroxy group, the structural unit represented, for example by following General formula (8) can be mentioned.

〔一般式（８）において、ｎ８は１〜１０の整数を表す。Ｒ⁸¹は炭素数が１〜１０のアルキレン基を表す。Ｒ⁸²は炭素数が１〜１０のアルキレン基を表す。Ｒ⁸³は水素原子またはメチル基を表す。〕

[In the general formula (8), n8 represents an integer of 1 to 10. R ⁸¹ represents an alkylene group having 1 to 10 carbon atoms. R ⁸² represents an alkylene group having 1 to 10 carbon atoms. R ⁸³ represents a hydrogen atom or a methyl group. ]

It is preferable that n8 of said Formula (8) is an integer of 1-7, and it is more preferable that it is an integer of 1-5.
The C 1-10 alkylene group represented by R ⁸¹ may be linear or branched, but linear is preferable. As a specific example of a C1-C10 alkylene group shown by said R ⁸¹ , a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Nonamethylene group, decamethylene group etc. are mentioned. R ⁸¹ is preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 3 to 8 carbon atoms.
The alkylene group having 1 to 10 carbon atoms represented by R ⁸² may be linear or branched, but is preferably linear. As a specific example of a C1-C10 alkylene group shown by said R ⁸² , a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, Nona methylene group, decamethylene group, 1-methyl ethylene group etc. are mentioned. It is preferable that R ^<82> is a C1-C5 alkylene group.

  The said A block may have other structural units other than the structural unit derived from a (meth) acrylic-type vinyl monomer. Other structural units that can be included in the A block are particularly limited as long as they are formed of a (meth) acrylic vinyl monomer and a vinyl monomer copolymerizable with both of the vinyl monomers forming the B block described later. Absent. The vinyl monomers capable of forming other structural units of the A block may be used alone or in combination of two or more.

  Specific examples of the vinyl monomer which can form another structural unit of A block include α-olefin, aromatic vinyl monomer, vinyl monomer containing a heterocycle, vinylamide, vinyl carboxylate, dienes and the like. These vinyl monomers may have a hydroxy group or an epoxy group.

As an alpha-olefin, 1-hexene, 1-octene, 1-decene etc. are mentioned.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene and the like.
As a vinyl monomer containing a heterocycle, 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine, N-phenylmaleimide, N-benzyl Maleimide, N-cyclohexyl maleimide, etc. are mentioned.
As vinylamide, N-vinylformamide, N-vinylacetamide, N-vinyl-ε-caprolactam and the like can be mentioned.
Examples of vinyl carboxylates include vinyl acetate, vinyl pivalate and vinyl benzoate.
Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like.

  The A block preferably has a structural unit derived from a vinyl monomer having an acidic group (preferably a (meth) acrylate having an acidic group, (meth) acrylic acid). By having a structural unit derived from a vinyl monomer having an acidic group, the solubility in an alkali developer can be increased, and the alkali developability can be improved. However, if the ratio increases, the affinity with the solvent and the alkali-soluble resin may be lowered. Therefore, the proportion of structural units derived from a vinyl monomer having an acidic group is preferably such that the total acid value of the block copolymer becomes lower than the amine value.

  When the structural unit derived from the vinyl monomer having an acidic group is contained, the content is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more in 100% by mass of the A block. 20 mass% or less is preferable, More preferably, it is 18 mass% or less, More preferably, it is 16 mass% or less. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate at the time of neutralization with alkali in alkali development becomes fast, and if 20% by mass or less, the hydrophilicity is high It is possible to suppress the randomness of the formed pixels.

  In the block A, the content of structural units represented by the general formula (1) described later is less than 5% by mass, preferably 3% by mass or less, more preferably 1% by mass or less, and in the general formula (1) It is further preferred not to contain the structural units represented. The lower the content of the structural unit represented by the general formula (1) in the A block, the better the dispersion performance of the colorant.

  It is preferred that the A block does not have an amino group. That is, it is preferable not to contain the vinyl monomer which has an amino group in the vinyl monomer which comprises A block. When a large amount of amino groups is present in the A block, the colorant is adsorbed to both the A block and the B block when used as a dispersant, and the dispersion performance of the colorant is degraded. 2 mass% or less is preferable, and, as for the content rate of the structural unit derived from the vinyl monomer which has an amino group in A block (The thing whose amino group is quaternized is included.), More preferably, it is 1 mass% or less. More preferably, it is 0.1% by mass or less, most preferably 0% by mass.

  When two or more types of structural units are contained in the A block, various structural units contained in the A block may be contained in any mode such as random copolymerization or block copolymerization in the A block. It is preferable to contain in the aspect of random copolymerization from the viewpoint of uniformity. For example, the A block may be formed of a copolymer of a structural unit consisting of a1 block and a structural unit consisting of a2 block.

(B block)
B block is a polymer block containing B block containing the structural unit represented by following General formula (1).

(Structural unit represented by the general formula (1))
The structural unit represented by the general formula (1) may be only one type or may have two or more types. By setting it as a structural unit represented by General formula (1), adsorptivity with a coloring material is high and heat resistance can be made high.

〔式（１）において、Ｒ¹¹およびＲ¹²は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ¹¹およびＲ¹²が互いに結合して環状構造を形成していてもよい。Ｘ¹は２価の連結基を示す。Ｒ¹³は水素原子またはメチル基を示す。〕

[In formula (1), R ¹¹ and R ¹² each independently represent a linear or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹³ represents a hydrogen atom or a methyl group. ]

The linear hydrocarbon group represented by R ¹¹ or R ¹² includes both linear and branched. Examples of the substituent groups of the chain hydrocarbon group represented by R ¹¹ or R ^12, a halogen group, an alkoxy group, a benzoyl group (-COC ₆ H _5), hydroxy group, and the like. The substituent having a hydrocarbon group of cyclic represented by R ¹¹ or R ^12, chain alkyl group, a halogen group, an alkoxy group, hydroxy group, and the like.

Examples of the group represented by R ¹¹ or R ¹² include an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent. preferably, a methyl group, an ethyl group, a propyl group, a benzyl group (-CH ₂ C ₆ H ₅₎ is more preferable.

Examples of the cyclic structure formed by bonding R ¹¹ or R ¹² to each other include a 5-membered to 7-membered nitrogen-containing heterocyclic ring or a fused ring formed by condensing two of these. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, structures represented by the following formulas (1-1), (1-2) and (1-3) can be mentioned.

〔一般式（１−１）、（１−２）、（１−３）において、Ｒ¹⁴は、炭素数１〜６のアルキル基を示す。ｌは０〜５の整数を表す。ｍは０〜４の整数を表す。ｎは０〜４の整数を表す。＊は結合手を表す。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ¹⁴は、それぞれ同一でも異なっていてもよい。〕

[Formula (1-1), (1-2), in (1-3), R ¹⁴ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4; n represents an integer of 0 to 4; * Represents a bond. When l is 2 to 5, m is 2 to 4 and n is 2 to 4, a plurality of R ¹⁴ may be the same or different. ]

In the general formula (1), as the divalent linking group X ¹ , for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-R ¹⁵ -group (amide group), -COO-R ^16- group (ester group) and the like, preferably -COO-R ¹⁶ - a group - group and / or -CONH-R ¹⁵ - a group, more preferably -COO-R ^16. Incidentally, an amide group, the binding direction of the ester group is not particularly limited, but is preferably ^{C-CO-NH-R 15} -NR 11 R 12 is as a bonding aspect of the amide groups, as a binding aspect of ester groups include, C-CO -O-R ¹⁶ -NR ¹¹ R ¹² are preferred.
R ¹⁵ is a single bond, an alkylene group of 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) of 1 to 10 carbon atoms, preferably an alkylene group of 1 to 10 carbon atoms, more preferably Is an alkylene group having 1 to 4 carbon atoms. As a specific example, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group etc. can be mentioned.
R ¹⁶ is a single bond, an alkylene group of 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) of 1 to 10 carbon atoms, preferably an alkylene group of 1 to 10 carbon atoms, and more preferably Is an alkylene group having 1 to 4 carbon atoms. As a specific example, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group etc. can be mentioned.

  Specific examples of the vinyl monomer forming the structural unit represented by the general formula (1) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) 2.) Acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide and the like.

  15 mass% or more is preferable in 100 mass% of B blocks, as for the content rate of the structural unit represented by General formula (1), More preferably, it is 20 mass% or more, More preferably, it is 25 mass% or more, 98 mass % Or less is preferable, more preferably 70% by mass or less, still more preferably 65% by mass or less, and particularly preferably 60% by mass or less. By setting the content of the structural unit represented by the general formula (1) in this range, it is considered to have high affinity with the colorant.

  The B block may have a structural unit represented by the following general formula (2). The structural unit represented by General formula (2) in B block may be only 1 type, and may have 2 or more types. If the B block has a structural unit represented by the general formula (2), strong adsorption to the surface of the coloring material can be maintained for a long time, and storage stability is further improved.

〔式（２）において、Ｒ²¹、Ｒ²²およびＲ²³は、それぞれ独立して、置換基を有していてもよい鎖状もしくは環状の炭化水素基を示す。Ｒ²¹、Ｒ²²およびＲ²³のうち２つ以上が互いに結合して環状構造を形成していてもよい。Ｘ²は２価の連結基を示す。Ｒ²⁴は水素原子またはメチル基を示す。Ｙ^-は対イオンを示す。〕

[In formula (2), R ²¹ , R ²² and R ²³ each independently represent a linear or cyclic hydrocarbon group which may have a substituent. Two or more of R ²¹ , R ²² and R ²³ may be bonded to each other to form a cyclic structure. X ² represents a divalent linking group. R ²⁴ represents a hydrogen atom or a methyl group. Y ^- represents a counter ion. ]

The linear hydrocarbon groups represented by R ^{21 to} R ²³ include both linear and branched ones. As a substituent which the chain-like hydrocarbon group represented by said R < ²¹ > -R < ²³ > has, a halogen group, an alkoxy group, a benzoyl group, a hydroxy group etc. are mentioned. As a substituent which the cyclic hydrocarbon group represented by said R < ²¹ > -R < ²³ > has, a chain | strand-shaped alkyl group, a halogen atom, an alkoxy group, a hydroxyl group etc. are mentioned.

The group represented by R ^{21 to} R ²³ includes an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent. Preferably, a methyl group, an ethyl group, a propyl group and a benzyl group are more preferable.

Examples of the cyclic structure formed by bonding two or more of R ^{21 to} R ²³ to each other include a 5- to 7-membered nitrogen-containing heterocyclic ring or a fused ring formed by condensing two of these. Be The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, structures represented by the following formulas (2-1), (2-2) and (2-3) can be mentioned.

〔一般式（２−１）、（２−２）、（２−３）において、Ｒ²⁵は、Ｒ²¹〜Ｒ²³のいずれかである。Ｒ²⁶は、炭素数１〜６のアルキル基を示す。ｌは０〜５の整数を表す。ｍは０〜４の整数を表す。ｎは０〜４の整数を表す。＊は結合手を表す。ｌが２〜５、ｍが２〜４、ｎが２〜４の場合、複数存在するＲ²⁶は、それぞれ同一でも異なっていてもよい。〕

[In the general formulas (2-1), (2-2), (2-3), R ²⁵ is any one of R ^{21 to} R ²³ . R ²⁶ represents an alkyl group having 1 to 6 carbon atoms. l represents an integer of 0 to 5; m represents an integer of 0 to 4; n represents an integer of 0 to 4; * Represents a bond. When l is 2 to 5, m is 2 to 4 and n is 2 to 4, plural R ^{26 s} may be the same or different. ]

In General Formula (2), as the divalent linking group X ² , for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-R ²⁷ -group (amide group), -COO-R ²⁸ -group (ester group) and the like, preferably -CONH-R ²⁷ - a group - groups and / or -COO-R ²⁸ - a group, more preferably -COO-R ^28. Although the bonding direction of the amido group and the ester group is not particularly limited, C-CO-NH-R ²⁷ -N ⁺ R ²¹ R ²² R ²³ is preferable as a bonding mode of the amido group, and as a bonding mode of the ester group And C—CO—O—R ²⁸ —N ⁺ R ²¹ R ²² R ²³ is preferable.
R ²⁷ is a single bond, an alkylene group of 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) of 1 to 10 carbon atoms, preferably an alkylene group of 1 to 10 carbon atoms, and more preferably Is an alkylene group having 1 to 4 carbon atoms. As a specific example, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group etc. can be mentioned.
R ²⁸ is a single bond, an alkylene group of 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) of 1 to 10 carbon atoms, preferably an alkylene group of 1 to 10 carbon atoms, more preferably Is an alkylene group having 1 to 4 carbon atoms. As a specific example, a methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group etc. can be mentioned.

Examples of Y ^- include halogen anions, carboxylate anions, nitroxide anions, sulfate anions, sulfonate anions, phosphate anions, alkyl phosphate anions and the like.
Examples of the halogen anion include fluoroanion, chloroanion, bromoanion and iodoanion.
Examples of the alkyl carboxylate anion include alkyl carboxylate anions such as alkyl carboxylate anions such as acetate anion and propionate anion; and aromatic carboxylate anions such as benzoate anion.
Examples of the sulfate anion include alkyl sulfate anions such as methyl sulfate anion and ethyl sulfate anion; and aromatic sulfate anions such as phenyl sulfate anion and benzyl sulfate anion.
Examples of the sulfonate anion include alkyl sulfonate anions such as methane sulfonate anion and ethane sulfonate anion; and aromatic sulfonate anions such as benzene sulfonate anion and toluene sulfonate anion.

  As a specific example of the vinyl monomer which forms the structural unit shown by said Formula (2), (meth) acryloyloxyethyl trimethyl ammonium chloride, (meth) acryloyl oxypropyl trimethyl ammonium chloride, (meth) acryloyl oxy butyl trimethyl ammonium chloride (Meth) acryloyloxyethyl benzyldimethyl ammonium chloride, (meth) acryloyloxypropyl benzyl dimethyl ammonium chloride, (meth) acryloyloxy butyl benzyl dimethyl ammonium chloride, (meth) acryloyl oxyethyl benzyl diethyl ammonium chloride, (meth) acryloyloxy Propyl benzyl diethyl ammonium chloride, (meth) acryloyloxy butyl benzyl diethyl Ammonium chloride, (meth) acryloylamidopropyl benzyldimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium bromide, (meth) acryloyloxypropyltrimethylammonium bromide, (meth) acryloyloxybutyltrimethylammonium bromide, (meth) acryloyloxyethyl Benzyldimethyl ammonium bromide, (meth) acryloyloxypropyl benzyl dimethyl ammonium bromide, (meth) acryloyloxy butyl benzyl dimethyl ammonium bromide, (meth) acryloyloxy ethyl benzyl diethyl ammonium bromide, (meth) acryloyloxy propyl benzyl diethyl ammonium bromide, ( Meta) Acryloyl Cyclobutylbenzyldiethylammonium bromide, (meth) acryloylamidopropyl benzyldimethylammonium bromide, (meth) acryloyloxyethyltrimethylammonium iodide, (meth) acryloyloxypropyltrimethylammonium iodide, (meth) acryloyloxybutyltrimethylammonium iodide (Meth) acryloyloxyethyl benzyldimethyl ammonium iodide, (meth) acryloyloxy propyl benzyl dimethyl ammonium iodide, (meth) acryloyloxy butyl benzyl dimethyl ammonium iodide, (meth) acryloyl oxyethyl benzyl diethyl ammonium iodide ( Meta) acryloyloxypropyl benzyl diethyl ammonium iodide, (Meth) acryloyloxybutylbenzyldiethylammonium iodide, (meth) acryloyloxyethyltrimethylammonium fluoride, (meth) acryloyloxypropyltrimethylammonium fluoride, (meth) acryloyloxybutyltrimethylammonium fluoride, (meth) acryloyloxy Ethyl benzyl dimethyl ammonium fluoride, (meth) acryloyloxy propyl benzyl dimethyl ammonium fluoride, (meth) acryloyl oxy butyl benzyl dimethyl ammonium fluoride, (meth) acryloyl oxy ethyl benzyl diethyl ammonium fluoride, (meth) acryloyl oxy propyl benzyl Diethyl ammonium fluoride, (meth) acryloyloxybutyl benzyl diethyl Ammonium fluoride, (meth) acryloyloxyethyl trimethyl ammonium = methyl sulfate, (meth) acryloyloxy propyl trimethyl ammonium = methyl sulfate, (meth) acryloyloxy butyl trimethyl ammonium = methyl sulfate, (meth) acryloyl oxyethyl dimethyl Ethylammonium = ethylsulfate, (meth) acryloyloxypropyldimethylethylammonium = ethylsulfate, (meth) acryloyloxybutyldimethylethylammonium = ethylsulfate, (meth) acryloyloxyethyltrimethylammonium = toluene-4-sulfonate, (Meth) acryloyloxypropyltrimethylammonium = toluene-4-sulfonate (( Data) acryloyloxybutyl trimethylammonium = toluene-4-sulfonate, (meth) acryloyl amidopropyl trimethylammonium = methyl sulfate, and (meth) acryloyl amidopropyl dimethylammonium = ethyl sulfate and the like.

  When the structural unit represented by the general formula (2) is contained, its content is preferably 15% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more in 100% by mass of the B block. 99 mass% or less is preferable, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less. By setting the content of the structural unit represented by the general formula (2) in this range, it is considered to have high affinity with the colorant.

  The B block may be only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or other structural units may be included. From the viewpoint of maintaining the affinity to the colorant, the total content of the structural unit represented by the general formula (1) in the B block and the structural unit represented by the general formula (2) is 80% by mass or more Is more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 98% by mass or more. Moreover, it is preferable that B block does not substantially contain the structural unit derived from the vinyl monomer which has an acidic group. That is, 5 mass% or less is preferable in 100 mass% of B blocks, as for the content rate of the structural unit derived from the vinyl monomer which has an acidic group, 2 mass% or less is more preferable, and 1 mass% or less is more preferable.

  Specific examples of the vinyl monomer that can form the other structural unit of the B block can be the same as those exemplified as specific examples of the vinyl monomer that can form the other structural unit of the A block.

  When two or more structural units are contained in the B block, various structural units contained in the B block may be contained in any mode such as random copolymerization or block copolymerization in the B block. It is preferable to contain in the aspect of random copolymerization from the viewpoint of uniformity. For example, the B block may be formed of a copolymer of a structural unit consisting of b1 block and a structural unit consisting of b2 block.

(Block copolymer)
The structure of the block copolymer is preferably a linear block copolymer. The linear block copolymer may have any structure (arrangement), but from the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A, and the B block is B. when expressed as, _{(a-B) m} type, _(a-B) m -A type, the group consisting of _(B-a) m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) It is preferable that it is a copolymer having at least one kind of structure selected from Among these, from the viewpoint of handleability at the time of processing and physical properties of the composition, an AB diblock copolymer is preferable. The structural unit derived from the (meth) acrylic vinyl monomer contained in the A block and the structural unit represented by the general formula (1) contained in the B block by constituting the A-B type diblock copolymer It is believed that the localized can be efficiently interacted with the colorant, the solvent, and the binder resin (alkali-soluble resin). The block copolymer may have other blocks other than the A block and the B block.

  The content of the block A is preferably 35% by mass or more, more preferably 40% by mass or more, and still more preferably 45% by mass or more, and preferably 85% by mass or less in 100% by mass of the whole block copolymer. More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less. The content of B block is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and preferably 65% by mass or less in 100% by mass of the whole block copolymer. More preferably, it is 60 mass% or less, more preferably 55 mass% or less. By adjusting the content of A block and B block within the above range, the dispersion performance when used as a dispersant is further improved.

  The mass ratio of A block to B block (A block / B block) in the block copolymer is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, 95 / 5 or less is preferable, More preferably, it is 90/10 or less, More preferably, it is 80/20 or less. If the mass ratio of the A block to the B block is within the above range, the dispersion performance when used as a dispersant is further improved.

  1 mass% or more is preferable, as for the content rate of the structural unit derived from the vinyl monomer which has an acidic group in the said block copolymer, More preferably, it is 2 mass% or more, More preferably, it is 3 mass% or more, 10 mass% The following is preferable, More preferably, it is 9 mass% or less, More preferably, it is 8 mass% or less.

  The total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the block copolymer is preferably 5% by mass or more, more preferably 10% by mass The content is more preferably 20% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less.

  The content of the block copolymer in the polymerization product is 75% by mass or more, preferably 80% by mass or more, and more preferably 82% by mass or more in 100% by mass of the polymerization product. When the content of the block copolymer in the polymerization product is 75% by mass or more, the storage stability is improved when the polymerization product is used as a dispersant.

  When the polymerization product is obtained for the purpose of synthesizing an A-B diblock copolymer, the content of the A-B diblock copolymer in the polymerization product is the polymerization product In 100 mass%, it is 75 mass% or more, preferably 80 mass% or more, more preferably 82 mass% or more.

  When the polymerization product is obtained for the purpose of synthesizing an A-B-A triblock copolymer or a B-A-B triblock copolymer, A-B in a polymerization product The total content of -A triblock copolymer and A-B diblock copolymer is 75% by mass or more, preferably 80% by mass or more, more preferably 82% by mass or more in 100% by mass of the polymerization product is there.

  The weight average molecular weight (Mw) of the polymerization product is preferably 5,000 or more, more preferably 6,000 or more, still more preferably 7,000 or more, and preferably 40,000 or less, more preferably 30,000. Or less, more preferably 20,000 or less. When the weight average molecular weight is in the above range, the dispersion performance when used as a dispersant becomes better. The molecular weight of the polymerization product is measured by gel permeation chromatography (hereinafter referred to as "GPC").

  The molecular weight distribution (PDI) of the polymerization product is 2.0 or less, more preferably 1.6 or less, and still more preferably 1.4 or less. In the present invention, the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of polymerization product) / (number average molecular weight (Mn) of polymerization product). The smaller the PDI, the narrower the range of the molecular weight distribution, and the polymerization product with uniform molecular weight. When the value is 1.0, the range of the molecular weight distribution is the narrowest. When the molecular weight distribution (PDI) of the polymerization product exceeds 2.0, those having a small molecular weight and those having a large molecular weight are included.

  The amine value of the polymerization product is preferably 3 mg KOH / g or more, more preferably 10 mg KOH / g or more, still more preferably 20 mg KOH / g or more, particularly preferably 30 mg KOH / g or more, and preferably 180 mg KOH / g or less. It is preferably 140 mg KOH / g or less, more preferably 120 mg KOH / g or less, particularly preferably 100 mg KOH / g or less. By setting the amine value in the above range, the dispersion performance when used as a dispersant is further improved.

  The acid value of the polymerization product is preferably less than 35 mg KOH / g. When the acid value exceeds the above range, the dispersibility may be deteriorated due to the interaction between the block copolymers.

<Method of producing polymerization product>
In the polymerization product of the present invention, the A block is produced first by sequentially polymerizing the vinyl monomers constituting the block, and the B block monomer is produced on the A block; B block is produced first, A method of polymerizing a monomer of A block to B block; Obtained by polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (1) in B block by preparing A block first A method of quaternizing the tertiary amine structure of a part of the structural unit represented by the formula (1) in the polymerized product; a vinyl monomer capable of forming the structural unit represented by the formula (1) in the B block The monomer composition containing A is polymerized, the monomer of A block is polymerized to this polymer, and the tertiary amine structure of a part of the structural unit represented by the formula (1) in the polymer obtained is quaternary. How to It is.

  Examples of the method for producing a polymerization product by polymerization reaction of a vinyl monomer include living polymerization methods such as living anion polymerization method, living cation polymerization method, living radical polymerization method, and in the present invention, polymerization generation is performed by living radical polymerization method. It is preferable to manufacture a product. The living anionic polymerization method and the living cationic polymerization method require strict polymerization conditions, and the functional groups that can coexist are limited. However, the living radical polymerization method has versatility such as coexistence with polar functional groups, purity of monomers and solvents, etc. It is preferable because precise control of molecular weight distribution and polymer of uniform composition can be produced while maintaining the simplicity not influenced by the above. That is, as said block copolymer, what was superposed | polymerized by living radical polymerization is preferable.

  In addition, in conventional radical polymerization methods, not only initiation reaction and growth reaction but also termination reaction and chain transfer reaction cause deactivation of the growth end, and tend to be a mixture of polymers of various molecular weights and heterogeneous compositions. . On the other hand, in the living radical polymerization method, the termination reaction and chain transfer hardly occur while maintaining the simplicity and versatility of the conventional radical polymerization method, and the growth terminal grows without being inactivated, so It is preferable at the point which manufacture of the polymer of precise control and a uniform composition is easy.

  In the living radical polymerization method, a method using a transition metal catalyst (ATRP method); a method using a sulfur-based reversible chain transfer agent (RAFT method); an organic tellurium compound depending on the method of stabilizing the polymerization growth terminal There are methods such as the method used (TERP method); Since the ATRP method uses an amine complex, it may not be possible to use without protecting the acid group of the vinyl monomer having an acid group. The RAFT method is less likely to have a low molecular weight distribution when various monomers are used, and may have problems such as sulfur odor and coloring. Among these methods, it is preferable to use the TERP method from the viewpoint of the variety of usable monomers, molecular weight control in the polymer region, uniform composition, or coloring.

  The TERP method is a method of polymerizing a radically polymerizable compound (vinyl monomer) using an organic tellurium compound as a chain transfer agent, and, for example, WO 2004/14848, WO 2004/14962, WO No. 2004/072126 and WO 2004/096870.

Specific examples of the polymerization method of the TERP method include the following (a) to (d).
(A) A vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (3).
(B) A vinyl monomer is polymerized using a first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator.
(C) The vinyl monomer is polymerized using a mixture of the organic tellurium compound represented by the general formula (3) and the organic ditelluride compound represented by the general formula (4).
(D) A vinyl monomer is polymerized using a second mixture of an organic tellurium compound represented by the general formula (3), an azo polymerization initiator and an organic ditelluride compound represented by the general formula (4).

〔一般式（３）中、Ｒ³¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を表す。Ｒ³²およびＲ³³は、それぞれ、水素原子または炭素数１〜８のアルキル基を表す。Ｒ³⁴は、炭素数１〜８のアルキル基、アリール基、芳香族へテロ環基、アルコキシ基、アシル基、アミド基、オキシカルボニル基、シアノ基、アリル基またはプロパルギル基を表す。
一般式（４）中、Ｒ³¹は、炭素数１〜８のアルキル基、アリール基または芳香族ヘテロ環基を表す。〕

[In general formula (3), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. R ³² and R ³³ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
In formula (4), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]

The group represented by R ³¹ is an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group, and specifically, it is as follows.
As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group And linear or branched alkyl groups such as octyl group and cyclic alkyl groups such as cyclohexyl group. It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
As an aryl group, a phenyl group, a naphthyl group, etc. can be mentioned.
As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group etc. can be mentioned.

The groups represented by R ³² and R ³³ are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.
As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group And linear or branched alkyl groups such as octyl group and cyclic alkyl groups such as cyclohexyl group. It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.

The group represented by R ³⁴ is an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an allyl group or It is a propargyl group, specifically as follows.
As the alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group And linear or branched alkyl groups such as octyl group and cyclic alkyl groups such as cyclohexyl group. It is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
As an aryl group, a phenyl group, a naphthyl group, etc. can be mentioned. Preferably it is a phenyl group.
As a substituted aryl group, a phenyl group having a substituent, a naphthyl group having a substituent, and the like can be mentioned. Examples of the substituent of the aryl group having a substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by -COR ³¹¹ (R ³¹¹ is carbon An alkyl group of the number 1 to 8, an aryl group, an alkoxy group having 1 to 8 carbon atoms or an aryloxy group), a sulfonyl group, a trifluoromethyl group and the like can be mentioned. In addition, one or two of these substituents may be substituted.
As an aromatic heterocyclic group, a pyridyl group, a furyl group, a thienyl group etc. can be mentioned.
The alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert- group. Examples include butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like.
As an acyl group, an acetyl group, a propionyl group, a benzoyl group etc. can be mentioned.
Examples of the amido group include -CONR ³²¹ R ³²² (R ³²¹ and R ³²² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
The oxycarbonyl group is preferably a group represented by -COOR ³³¹ (R ³³¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group), and examples thereof include a carboxy group, a methoxycarbonyl group, an ethoxycarbonyl group and a propoxycarbonyl group. Groups, n-butoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, n-pentoxycarbonyl group, phenoxycarbonyl group and the like can be mentioned. Preferred oxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl groups.
As an allyl group, -CR ³⁴¹ R ³⁴² -CR ³⁴³ = CR ³⁴⁴ R ³⁴⁵ (R ³⁴¹ and R ³⁴² each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³⁴³ , R ³⁴⁴ and R ³⁴⁵ are And each of which is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and the respective substituents may be connected by a cyclic structure) and the like.
As a propargyl group, -CR ³⁵¹ R ³⁵² -C≡CR ³⁵³ (R ³⁵¹ , R ³⁵² is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ³⁵³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms , An aryl group or a silyl group) and the like.

  Specifically, the organic tellurium compound represented by the general formula (3) is (methyl teranyl methyl) benzene, (methyl teranyl methyl) naphthalene, ethyl 2-methyl 2-methyl teranyl-propionate, ethyl 2- Methyl-2-n-butyl-teranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methyl-teranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methyl-teranyl-propionate or (3-trimethylsilylpropargyl Organic compounds described in WO 2004/14848, WO 2004/14962, WO 2004/072126, and WO 2004/096870). All of the tellurium compounds It can Shimesuru.

  Specific examples of the organic ditelluride compound represented by the general formula (4) include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, and dicyclopropyl ditelluride. -N-butyl ditelluride, di-s-butyl ditelluride, di-tert-butyl ditelluride, dicyclobutyl ditelluride, diphenyl ditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, bis -(P-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride, dipyridyl ditelluride, and the like can be exemplified.

The azo-based polymerization initiator can be used without particular limitation as long as it is an azo-based polymerization initiator used in conventional radical polymerization. For example, 2,2′-azobis (isobutyronitrile) (AIBN) (65 ° C., toluene), 2,2′-azobis (2-methylbutyronitrile) (AMBN) (67 ° C., toluene), 2, 2'-azobis (2,4-dimethylvaleronitrile) (ADVN) (52 ° C., toluene), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN) (88 ° C., toluene), dimethyl-2, 2, 2′-Azobisisobutyrate (MAIB) (66 ° C., toluene), 4,4′-azobis (4-cyanovaleric acid) (ACVA) (69 ° C., water (as Na salt)), 1,1 ′ -Azobis (1-acetoxy-1-phenylethane) (61 ° C., toluene), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (V-70) (30 ° C., toluene) 2,2'-azobis (2-methylamidinopropane) dihydrochloride (56 ° C, water), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] (61 ° C, methanol), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] (86 ° C., water),
Exemplifying 2,2′-azobis (N-butyl-2-methylpropionamide) (110 ° C., ethylbenzene) or dimethyl 1,1′-azobis (1-cyclohexanecarboxylate) (73 ° C., toluene) etc. Can. Among these, an oil-soluble azo polymerization initiator is preferable as the azo polymerization initiator, and AIBN, AMBN, ADVN, ACHN, and V-70 are more preferable. The numerical value described in the parenthesis after the compound name of the azo polymerization initiator is the solvent used for the measurement of the 10 hour half-life temperature and the 10 hour half-life temperature. The 10-hour half-life temperature of the azo polymerization initiator refers to a temperature at which the concentration of the azo group in the solvent becomes half in 10 hours. As a solvent used for measurement of half-life temperature, toluene, ethylbenzene, etc. are mentioned as an oil-soluble azo polymerization initiator, and water, methanol, etc. are mentioned as a water-soluble azo polymerization initiator.

  The polymerization step is a container substituted with an inert gas, and the vinyl monomer and the organic tellurium compound of the general formula (3) are further added according to the type of vinyl monomer for the purpose of reaction promotion, control of molecular weight and molecular weight distribution, etc. An azo polymerization initiator and / or an organic ditelluride compound of the general formula (4) are mixed. At this time, nitrogen, argon, helium etc. can be mentioned as an inert gas. Preferably, argon and nitrogen are good.

  The use amount of the vinyl monomer in the above (a), (b), (c) and (d) may be appropriately adjusted according to the physical properties of the target copolymer. It is preferable to make a vinyl monomer into 5 mol-10000 mol with respect to 1 mol of organic tellurium compounds of General formula (3).

  When using together the organic tellurium compound of General formula (3) of said (b), and an azo polymerization initiator, an azo compound shall be 0.01 mol-10 mol with respect to 1 mol of organic tellurium compounds of General formula (3) Is preferred.

  When the organic tellurium compound of the general formula (3) of (c) and the organic ditelluride compound of the general formula (4) are used in combination, the organic compound of the general formula (4) relative to 1 mol of the organic tellurium compound of the general formula (3) It is preferable to make a ditelluride compound into 0.01 mol-100 mol.

  When the organic tellurium compound of the general formula (3) of (d), the organic ditelluride compound of the general formula (4) and the azo polymerization initiator are used in combination, 1 mol of the organic tellurium compound of the general formula (3) The organic ditelluride compound of the formula (4) is preferably 0.01 mol to 100 mol, and the azo polymerization initiator is preferably 0.01 mol to 10 mol based on 1 mol of the organic tellurium compound of the general formula (3).

  The polymerization reaction may be carried out without a solvent, but may be carried out by stirring the mixture using an aprotic solvent or a protic solvent generally used in radical polymerization. Aprotic solvents which can be used are, for example, anisole, benzene, toluene, N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform And carbon tetrachloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate, trifluoromethylbenzene and the like. Moreover, as a protic solvent, water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, diacetone alcohol etc. can be illustrated, for example.

  The amount of the solvent used may be appropriately adjusted, and is, for example, preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, per 1 g of the monomer composition. 50 ml or less is preferable, more preferably 10 ml or less, and still more preferably 1 ml or less.

  The reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the resulting copolymer, but the reaction is usually stirred at 0 ° C. to 150 ° C. for 1 minute to 100 hours. The TERP method can obtain high yields and precise molecular weight distributions even at low polymerization temperatures and short polymerization times. At this time, the pressure is usually performed at normal pressure, but may be increased or decreased.

  After completion of the polymerization reaction, the solvent used, residual vinyl monomer, and the like are removed from the obtained reaction mixture by conventional separation and purification means, and the target copolymer can be separated.

The growth end of the copolymer obtained by the polymerization reaction is in the form of -TeR ³¹ derived from the tellurium compound (wherein R ³¹ is the same as R ³¹ in the general formula (3)), and the polymerization reaction is completed. It will be deactivated by the later operation in air, but the tellurium atom may remain. It is preferable to remove the tellurium atom because the copolymer in which the tellurium atom remains at the end is colored or has poor thermal stability.

  As a method of removing tellurium atoms, a radical reduction method using tributylstannane or a thiol compound; a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbents, etc .; ion exchange resin etc. Method of adsorbing metal; Oxidative decomposition of tellurium terminal of copolymer end by adding peroxide such as hydrogen peroxide solution or benzoyl peroxide or blowing air or oxygen into the system, washing with water A liquid-liquid extraction method or solid-liquid extraction method for removing residual tellurium compounds by combining solvents; a purification method in a solution state such as ultrafiltration which extracts and removes only those having a specific molecular weight or less; Also, these methods can be used in combination.

  When the tertiary amine group of the structural unit represented by the formula (1) is quaternized, alkyl halides such as methyl chloride, ethyl chloride, methyl bromide and methyl iodide as quaternizing agents; benzyl chloride Halogenated aralkyls such as benzyl bromide and benzyl iodide; Diaryl sulfates such as diphenyl sulfate; Dialkyl sulfates such as dimethyl sulfate, diethyl sulfate and di-n-propyl sulfate; p-toluenesulfonic acid methyl, p-toluenesulfonic acid And alkyl aromatic sulfonates such as ethyl; and the like. Among these, preferred are halogenated aralkyl such as benzyl chloride, benzyl bromide and benzyl iodide, dimethyl sulfate, diethyl sulfate, dialkyl sulfate such as di-n-propyl sulfate, methyl p-toluenesulfonate, p-toluene sulfone It is an aromatic sulfonic acid alkyl such as ethyl acid, more preferably benzyl chloride, dimethyl sulfate, methyl p-toluenesulfonate. In the structure after quaternization, an alkyl group and an aralkyl group derived from a quaternizing agent are introduced. Therefore, the amount of the structural unit represented by Formula (2) can be estimated by measuring the amount of the alkyl group, the aralkyl group, etc. which were introduce | transduced by quaternization.

  As a method of quaternizing a part of the tertiary amine structure of the structural unit represented by the formula (1) in the polymer, a method of contacting the polymer with a quaternizing agent may be mentioned. Specifically, after polymerizing a monomer composition containing a vinyl monomer capable of forming a structural unit represented by the formula (1), a method of adding a quaternizing agent to the reaction liquid and stirring it may be mentioned. . The temperature of the reaction solution to which the quaternizing agent is added is preferably 25 ° C to 65 ° C, and the stirring time is preferably 1 hour to 40 hours. It is also preferable to dilute the reaction solution after polymerization when adding the quaternizing agent. The solvent to be added for dilution includes a solvent that can be used for the polymerization reaction, a protic solvent, and a mixed solvent of a solvent that can be used for the polymerization reaction and the protic solvent, and the solubility of the target block copolymer It may be selected as appropriate. Methanol is preferred as the protic solvent.

(Preferred embodiment of the method for producing a polymerization product)
Hereinafter, one aspect of the method for producing the polymerization product will be described.

The production method is a first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator, or an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator A block polymerization step of polymerizing a first monomer composition containing a (meth) acrylic vinyl monomer using a second mixture with an organic ditelluride compound represented by the general formula (4), the first mixture or the first mixture or B block polymerization step of polymerizing a second monomer composition containing a vinyl monomer forming a structural unit represented by the general formula (1) using the second mixture, and in all the polymerization steps, The difference (T _1/2 -Tr) between the 10 hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) is preferably 10 ° C. to 60 ° C., more preferably 10 ° C to 50 ° C, more preferred Or 10 ° C. to 40 ° C., particularly preferably 10 ° C. to 30 ° C.

  Generally, in the TERP method, when the monomer has an amino group or an acidic group, the amino group or the acidic group tends to deactivate the polymerization terminal radical. For example, in the case of an amino group, the polymerization terminal radical may be provided with a hydrogen radical to be inactivated. In addition, in the acidic group, proton coordination occurs to the organic tellurium which forms dormant species, which may inhibit formation of dormant species and inactivate the polymerization terminal. Therefore, when the monomer has an amino group or an acidic group, the content of the polymer ("non-connected component") to which each block component in the polymerization product is not bonded tends to increase. However, by setting the polymerization temperature to a temperature 10 ° C. or more lower than the 10-hour half-life temperature of the azo polymerization initiator to be added, the formation of the unconnected component can be suppressed.

  In the preferred embodiment, a first mixture or a second mixture is used during polymerization. The first mixture or the second mixture is common to the A block polymerization step and the B block polymerization step. That is, for example, in the case of producing an A-B diblock copolymer, after performing the first polymerization step, this reaction liquid (the first polymerization product and the first mixture or the second mixture) And the second stage monomer composition is added to the second stage polymerization step.

  The amount of the azo polymerization initiator used in the first mixture is preferably 0.01 mol or more, more preferably 0.05 mol or more, and still more preferably 0. 1 mol or more per 1 mol of the organic tellurium compound of the general formula (3). It is 1 mol or more, preferably 10 mol or less, more preferably 2 mol or less, and still more preferably 1 mol or less.

  The amount of the azo polymerization initiator used in the second mixture is preferably 0.01 mol or more, more preferably 0.05 mol or more, and still more preferably 0. 1 mol or more per 1 mol of the organic tellurium compound of the general formula (3). It is 1 mol or more, preferably 10 mol or less, more preferably 2 mol or less, and still more preferably 1 mol or less.

  The amount of the organic ditelluride compound of the general formula (4) in the second mixture is preferably 0.01 mol or more, more preferably 0.1 mol or more, more preferably 1 mol of the organic tellurium compound of the general formula (3). Preferably it is 0.2 mol or more, 100 mol or less is preferable, More preferably, it is 5 mol or less, More preferably, it is 3 mol or less.

  In the A block polymerization step, the first mixture of the organic tellurium compound represented by the general formula (3) and the azo polymerization initiator, or the organic tellurium compound represented by the general formula (3) and the azo polymerization initiation The first monomer composition containing a (meth) acrylic vinyl monomer is polymerized using a second mixture of the agent and the organic ditelluride compound represented by the general formula (4).

  In the A block polymerization step, the amount of the vinyl monomer used is preferably 5 mol or more, more preferably 10 mol or more, still more preferably 20 mol or more, and preferably 10000 mol or less, per 1 mol of the organic tellurium compound of the general formula (3). More preferably, it is 300 mol or less, further preferably 100 mol or less.

  In the B block polymerization step, the first mixture of the organic tellurium compound represented by the general formula (3) and the azo polymerization initiator, or the organic tellurium compound represented by the general formula (3) and the azo polymerization initiation Polymerizing a second monomer composition containing a vinyl monomer forming a structural unit represented by the general formula (1), using a second mixture of the agent and the organic ditelluride compound represented by the general formula (4) .

  The amount of the vinyl monomer used in the B block polymerization step is preferably 5 mol or more, more preferably 7 mol or more, still more preferably 10 mol or more, and preferably 10000 mol or less, per 1 mol of the organic tellurium compound of the general formula (3). More preferably, it is 300 mol or less, further preferably 100 mol or less.

In the preferred embodiment, the difference (T _1/2 -Tr) between the 10 hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) of all the polymerization steps is 10 ° C. or more The temperature is 60 ° C. or less, preferably 50 ° C. or less, more preferably 40 ° C. or less, and particularly preferably 30 ° C. or less. In addition, when using two or more azo polymerization initiators, it is preferable to satisfy the said range about 10 hour half life temperature of all the azo polymerization initiators.

  In the preferred embodiment, the reaction temperature is preferably 0 ° C. or more, more preferably 10 ° C. or more, still more preferably 20 ° C. or more, particularly preferably 30 ° C. or more, preferably 70 ° C. or less, more preferably 60 C. or less, more preferably 55 ° C. or less. The reaction time is preferably 1 hour or more, more preferably 3 hours or more, still more preferably 5 hours or more, preferably 100 hours or less, more preferably 50 hours or less, still more preferably 30 hours or less.

  In the above-mentioned preferred embodiment, the polymerization rate (monomer conversion rate) of the monomer in the monomer composition serving as the raw material in each polymerization step is preferably 90% by mass or more, more preferably 96% by mass or more, and still more preferably 97 % By mass or more, particularly preferably 98% by mass or more.

  The preferred embodiment has at least an A block polymerization step and a B block polymerization step. The order of these polymerization steps is not particularly limited, and the A block polymerization step may be performed first and the B block polymerization step may be performed later, or the B block polymerization step is performed first and the A block polymerization step is performed later. It is also good. Moreover, the said preferable aspect may have the process of polymerizing other blocks other than A block and B block. Moreover, the said preferable aspect may have the process of quaternizing the structural unit represented by General formula (1).

<Dispersing agent>
The dispersant of the present invention contains the above-mentioned polymerization product as the main component (50% by mass or more), preferably 75% by mass or more of the above-mentioned polymerization product, and more preferably the above-mentioned polymerization formation It consists only of things. The block copolymer contained in the polymerization product is, for example, a coloring material in which the tertiary amino group in the structure (B block) and the quaternary ammonium base are treated with an acidic coloring material or an acidic group-containing dye derivative. It is thought that the effect of enhancing the dispersibility of the colorant is exhibited by strongly bonding to the acidic group and the B block adsorbs to the colorant. That is, since the dispersing agent of the present invention is a component that causes the colorant to be well dispersed by this action, the type of colorant to be dispersed is not particularly limited. The dispersant of the present invention can be suitably used as a dispersant for color filters. The dispersant of the present invention can be further suitably used as a dispersant for color filters by having alkali developability.

(Coloring composition)
The coloring composition of the present invention contains the above-mentioned dispersant, colorant, dispersion medium and binder resin.

(Colorant)
The type of the colorant may be appropriately selected depending on the application, and examples include pigments and dyes. It is preferable that the said coloring composition contains a pigment as a coloring material from a light resistance and a heat resistant viewpoint. The pigment may be either an organic pigment or an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferable. As a pigment, the pigment of each color, such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, a purple pigment, is mentioned, for example. The structure of the pigment is azo based pigments such as monoazo based pigments, diazo based pigments, condensed diazo based pigments, diketopyrrolopyrrole based pigments, phthalocyanine based pigments, isoindolinone based pigments, isoindoline based pigments, quinacridone based pigments, indigo based pigments And pigments such as system pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and polycyclic pigments such as perinone pigments. The coloring material contained in the coloring composition may be only one kind, or may be plural kinds for adjustment of chromaticity and the like.

  Specific examples of the pigment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 168, 177, Red pigments such as 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264; I. Pigment Yellow 1, 3, 5, 6, 14, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 93, 97, 98, 104, 108, 110, 138, 139, 147, Yellow pigments such as 150, 151, 154, 155, 166, 167, 168, 170, 180, 185, 188, 193, 194, 213; I. Pigment Orange 36, 38, 43, etc .; I. Pigment Blue 15, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, etc. blue pigments; C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, aluminum phthalocyanine, polyhalogenated aluminum phthalocyanine, aluminum phthalocyanine hydroxide, diphenoxyphosphinyl oxyaluminum phthalocyanine, diphenyl phosphinyl oxyaluminum phthalocyanine, polyhalogenated diphenoxy Green pigments such as phosphinyl oxyaluminum phthalocyanine, polyhalogenated diphenyl phosphinyl oxyaluminum phthalocyanine; C.I. I. Pigment Violet 23, 29, 32, 50, and the like. Among these, pigments are C.I. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, C.I. I. Pigment Green 59 is preferred.

  When using the coloring composition of the present invention to form a light shielding material such as a black matrix of a color filter, a black pigment can be used. The black pigment may be used alone, or the red pigment, the green pigment, the blue pigment and the like may be mixed and used. Examples of black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black and the like. Among these, carbon black and titanium black are preferable from the viewpoint of light blocking ratio and image characteristics.

  The number average particle diameter of the coloring material may be appropriately selected according to the application, and is not particularly limited. It is preferable that the said coloring composition contains a coloring material with a number average particle diameter of 10 nm-150 nm from a viewpoint of high transparency and high contrast property.

  The colorant may contain a dye derivative as a dispersion aid. The dye derivative preferably contains an acidic dye derivative having an acidic group in order to cause it to be ionically bonded to a tertiary amino group and a quaternary ammonium base in the block copolymer contained in the dispersant and to cause adsorption. . This dye derivative is one in which an acidic functional group is introduced into the dye skeleton. As a pigment | dye frame | skeleton, the frame | skeleton same as or similar to the coloring material which comprises the coloring composition, and frame | skeleton identical or similar to the compound used as the raw material of this pigment are 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 an acidic group introduce | transduced into pigment | dye frame | skeleton, a carboxy group, a phosphoric acid group, and a sulfonic acid group are preferable. Sulfonic acid groups are preferred for the convenience of synthesis and for the degree of acidity. The acidic group may be directly bonded to the dye skeleton, but may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, an ether, a sulfonamide or a urethane bond. Although the usage-amount of a pigment derivative does not have limitation in particular, For example, it is preferable that they are 4 mass parts-17 mass parts with respect to 100 mass parts of coloring materials.

  The upper limit of the content of the coloring material in the coloring composition is usually 80% by mass, preferably 70% by mass, and preferably 60% by mass, in the total solid content of the coloring composition, from the viewpoint of brightness. Is more preferred. The lower limit of the content of the coloring material in the coloring composition is usually 10% by mass, preferably 20% by mass, and more preferably 30% by mass, in the total solid content of the coloring composition. preferable. Here, the solid content is a component other than the dispersion medium described later.

  The content of the dispersant relative to the colorant in the coloring composition is preferably 5 parts by mass to 200 parts by mass, preferably 10 parts by mass to 100 parts by mass, with respect to 100 parts by mass of the colorant, and 10 parts by mass More preferably, it is from 80 to 80 parts by weight.

(Dispersion medium)
The coloring composition is appropriately selected so long as it disperses or dissolves the other components constituting the coloring composition as a dispersion medium, and does not react with these components and has appropriate volatility. Can be used. For example, conventionally known organic solvents can be used, and glycol monoalkyl ethers, glycol dialkyl ethers, glycol alkyl ether acetates, glycol diacetates, alkyl acetates, ethers, ketones, monohydric or polybasic Alcohols, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, linear or cyclic esters, alkoxycarboxylic acids, halogenated hydrocarbons, ether ketones, nitriles, etc. .

  As glycol monoalkyl ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene Glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl- 3-methoxy Pentanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether, and the like. Examples of glycol dialkyl ethers include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and the like. As glycol alkyl ether acetates, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol mono Chill ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate and the like. Examples of glycol diacetates include ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate and the like. Examples of alkyl acetates include cyclohexanol acetate and the like. Examples of the ethers include amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether and the like. As ketones, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy Methyl pentanone and the like can be mentioned. As monohydric or polyhydric alcohols, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1-methoxy-2-propanol, methoxymethyl Pentanol, glycerin, benzyl alcohol and the like can be mentioned. Examples of aliphatic hydrocarbons include n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane and the like. Cycloaliphatic hydrocarbons include cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl and the like. Examples of aromatic hydrocarbons include benzene, toluene, xylene and cumene. As chain or cyclic esters, amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate Isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxy Propyl propionate, butyl 3-methoxypropionate, γ-butyrolactone and the like can be mentioned. Examples of the alkoxycarboxylic acids include 3-methoxypropionic acid and 3-ethoxypropionic acid. Examples of halogenated hydrocarbons include butyl chloride and amyl chloride. Examples of ether ketones include methoxymethyl pentanone and the like. Examples of nitriles include acetonitrile and benzonitrile. The organic solvent is a glycol alkyl ether acetate, a glycol monoalkyl ether, or a monohydric or polyhydric alcohol from the viewpoint of the dispersibility of a coloring material, the solubility of a dispersant, the coatability of a coloring composition, etc. Is preferred. The solvent contained in the coloring composition may be only one type or a plurality of types.

  When forming the pixels of the color filter by photolithography, the boiling point of the dispersion medium is preferably 100 ° C. to 200 ° C. (pressure 1013.25 hPa conditions. Hereinafter, all the same with regard to the boiling point), and 120 ° C. to 170 ° C. More preferable. Among the above-mentioned dispersion media, glycol alkyl ether acetates are preferable in terms of good balance of coating properties, surface tension and the like and relatively high solubility of the component in the coloring composition. The glycol alkyl ether acetates may be used alone or in combination with other dispersion media. In this case, it is also preferable to use a dispersion medium having a boiling point of 150 ° C. or more in combination. By using such a dispersion medium having a high boiling point in combination, the colored composition becomes difficult to dry, and the destruction of the mutual relationship of the colored composition due to rapid drying can be suppressed. The content of the dispersion medium having a boiling point of 150 ° C. or more is preferably 3% by mass to 50% by mass with respect to 100% by mass of the whole dispersion medium. When the content ratio is 3% by mass or more, it is possible to suppress that a coloring material or the like precipitates and solidifies at the tip of the slit nozzle to generate foreign matter defects. If the content is 50% by mass or less, the drying speed of the coloring composition becomes slow, and the occurrence of problems such as prolongation of the drying time and pin marks of prebaking can be suppressed in color filter production described later. The dispersion medium having a boiling point of 150 ° C. or more may be a glycol alkyl ether acetate, and in this case, a dispersion medium having a boiling point of 150 ° C. or more may not be separately contained.

  When forming the pixel of a color filter by the inkjet method, 130 degreeC-300 degreeC of the boiling point of a dispersion medium is preferable, and 150 degreeC-280 degreeC are more preferable. By setting the boiling point to 130 ° C. or more, the uniformity of the obtained coating film is improved. Further, by setting the boiling point to 300 ° C. or less, it is possible to reduce the residual solvent in the coating film after the thermal baking, and it is possible to suppress the quality problems and the prolongation of the drying time. Further, the vapor pressure of the dispersion medium may be generally 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the obtained coating film.

  In the color filter production by the ink jet method, since the ink emitted from the nozzles is extremely fine such as several pL to several tens pL, the dispersion medium evaporates before the ink lands around the nozzle opening or in the pixel bank. Tend to concentrate and dry. In order to avoid this, the boiling point of the dispersion medium is preferably high, and specifically, it is preferable to include a dispersion medium having a boiling point of 180 ° C. or more. More preferably, it contains a dispersion medium having a boiling point of 200 ° C. or more, particularly preferably 220 ° C. or more. The high boiling point solvent having a boiling point of 180 ° C. or more is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass with respect to 100% by mass of the whole dispersion medium contained in the coloring composition. The above is the most preferable. By setting the content to the above lower limit value or more, there is a tendency that the effect of preventing evaporation of the solvent from droplets can be sufficiently exhibited.

  The content of the dispersion medium in the coloring composition is not particularly limited, and can be appropriately adjusted. The upper limit value of the content of the dispersion medium in the coloring composition is usually 99% by mass. The lower limit value of the content of the dispersion medium in the coloring composition is usually 70% by mass and preferably 75% by mass in consideration of the viscosity suitable for application of the coloring composition. The dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the coloring composition.

(Binder resin)
The coloring composition of the present invention contains a binder resin (except for the above-mentioned block copolymer). Thereby, the alkali developability of the coloring composition and the binding property to the substrate can be enhanced. Such a binder resin is not particularly limited, but is preferably a resin having an acidic group such as a carboxy group or a phenolic hydroxy group. As the binder resin, for example, with respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, an unsaturated single base at least a part of the epoxy group which the copolymer has A resin obtained by adding an acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxy group generated by the addition reaction; a linear alkali-soluble resin containing a carboxy group in the main chain Resin; resin in which epoxy group-containing unsaturated compound is added to carboxy group part of carboxy group-containing resin; (meth) acrylic resin; epoxy (meth) acrylate resin having carboxy group; Can be used alone or in combination of two or more.

  As a preferred embodiment of the binder resin, a random copolymer containing a structural unit derived from a carboxy group-containing vinyl monomer, a structural unit derived from (meth) acrylate and styrene, a structural unit derived from a carboxy group-containing vinyl monomer And random copolymers containing a structural unit derived from (meth) acrylate and (meth) acrylate. As the carboxy group-containing vinyl monomer, (meth) acrylic acid is preferable. As said (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono ( Meta) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. That.

  The total content of the structural unit derived from the carboxy group-containing vinyl monomer and the structural unit derived from (meth) acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably It is 70 mass% or more. The content of the structure derived from the carboxy group-containing vinyl monomer is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more, and 90% by mass or less. Is preferable, and more preferably 70% by mass or less.

  Among these, a random copolymer of a carboxy group-containing vinyl monomer and (meth) acrylate is preferable. Specific examples of such a copolymer include a random copolymer of (meth) acrylic acid and butyl (meth) acrylate, a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate, (meth And the like) and random copolymers of acrylic acid, butyl (meth) acrylate and benzyl (meth) acrylate, and the like. From the viewpoint of the affinity between the binder resin and the colorant, the binder resin is particularly preferably a random copolymer of (meth) acrylic acid and benzyl (meth) acrylate.

  In the copolymer of a carboxy group-containing vinyl monomer and (meth) acrylate, the content of (meth) acrylic acid is usually 5% by mass to 90% by mass, and 10% by mass to 70% by mass, based on all the monomer components. Is preferably 20% by mass to 70% by mass.

  The binder resin may have a radically polymerizable carbon-carbon double bond in a side chain. By having a double bond in the side chain, the photocurability of the coloring composition according to the present invention is enhanced, and thus resolution and adhesion can be further improved. As a method for introducing a radically polymerizable carbon-carbon double bond into a side chain, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m- or p-) A method of reacting a compound such as vinyl benzyl glycidyl ether with the acid group of the binder resin can be mentioned.

  The Mw of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance, film strength and the like of the colored layer formed from the coloring composition become good, and when the Mw is 100,000 or less, the alkali developability of this coating film Become even better.

  The acid value of the binder resin is preferably 20 mg KOH / g to 170 mg KOH / g, more preferably 50 mg KOH / g to 150 mg KOH / g, and still more preferably 90 mg KOH / g to 150 mg KOH / g. When the acid value of the binder resin is 20 mg KOH or more / g, the alkali developability when the colored composition is a colored layer is further improved, and when it is 170 mg KOH / g or less, the heat resistance is improved.

  The binder resin contained in the coloring composition may be only one type or a plurality of types. In the coloring composition, the content of the binder resin is preferably 3 parts by mass to 200 parts by mass, and more preferably 10 parts by mass to 100 parts by mass, with respect to 100 parts by mass of the colorant. More preferably, it is from 80 to 80 parts by weight.

(Crosslinking agent)
The coloring composition may contain a crosslinking agent. The crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. The crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups. The said crosslinking agent can be used individually or in mixture of 2 or more types.

  Specific examples of the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, and caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide modified polyfunctional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having hydroxy group with polyfunctional isocyanate, (meth) acrylate having hydroxy group The polyfunctional (meth) acrylate etc. which have a carboxy group obtained by making and an acid anhydride react can be mentioned.

  Examples of the aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; and trivalent or more such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Aliphatic polyhydroxy compounds of the formula: Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and di Pentaerythritol hexa (meth) acrylate, glycerol dimethacrylate and the like can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate and the like. Examples of the acid anhydrides include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, etc .; pyromellitic anhydride, biphenyl tetracarboxylic acid And tetrabasic acid dianhydrides such as acid dianhydride and benzophenone tetracarboxylic acid dianhydride.

  In the coloring composition of the present invention, the content of the crosslinking agent is preferably 10 parts by mass to 1,000 parts by mass, and particularly preferably 20 parts by mass to 500 parts by mass with respect to 100 parts by mass of the colorant. If the content of the crosslinking agent is too low, sufficient curability may not be obtained. On the other hand, when the amount of the crosslinking agent is too large, the alkali developability of the coloring composition of the present invention is lowered, and there is a tendency that background stains, film residue and the like tend to occur on the unexposed area substrate or light shielding layer. .

(Photopolymerization initiator)
The coloring composition preferably contains a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The said photoinitiator is a compound which generate | occur | produces the active species which can start superposition | polymerization of a crosslinking agent by exposure of radiations, such as a visible ray, an ultraviolet-ray, a far infrared ray, an electron beam, X ray.

  Examples of the photopolymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, and α-diketones. There can be mentioned, for example, based compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds and the like. A photoinitiator can be used individually or in mixture of 2 or more types.

  In the coloring composition of the present invention, the content of the photopolymerization initiator is preferably 0.01 parts by mass to 120 parts by mass, and particularly preferably 1 part by mass to 100 parts by mass, with respect to 100 parts by mass of the crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, curing may be insufficient due to exposure, while if it is too large, the formed colored layer tends to fall off the substrate during development. .

(Other additives)
In the coloring composition, other additives can be blended in addition to the additives as long as the preferred physical properties of the present invention are not impaired. Other additives include dispersants other than the block copolymer, sensitizing dyes, thermal polymerization inhibitors, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, Plasticizers, organic carboxylic acid compounds, organic carboxylic acid anhydrides, pH adjusters, antioxidants, UV absorbers, light stabilizers, preservatives, fungicides, anticoagulants, adhesion improvers, development improvers, A storage stabilizer etc. can be mentioned.

  As the dispersant excluding the block copolymer, a urethane based dispersant, a polyethyleneimine based dispersant, a polyoxyethylene alkyl ether based dispersant, a polyoxyethylene glycol diester based dispersant, a sorbitan aliphatic ester based dispersant, a fat Group modified polyester type dispersing agent etc. are mentioned.

  As the sensitizing dye, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3 2,4-diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- ( p-Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p -Diethylaminophenyl) benzothiazo , 2- (p-Dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) Pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine and the like can be mentioned.

  Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like.

  As a nonionic surfactant, a fluorinated surfactant (1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetra) Fluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol Di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1, 2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane etc.), sili Surfactants, polyoxyethylene surfactants (polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene Fatty acid esters, glycerine fatty acid esters, polyoxyethylene glycerine fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid ester And polyoxyethylene sorbite fatty acid esters and the like).

As an anionic surfactant, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfates, higher alcohol sulfates, aliphatic Alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer based surfactant Agents and the like.
Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like.
Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, amino acids and the like.

  Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like.

  Examples of organic carboxylic acid compounds include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid and methacrylic acid, oxalic acid, malonic acid, succinic acid and glutaric acid , A carboxyl group is directly bonded to a phenyl group such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, tricarballylic acid, aconitic acid, benzoic acid and phthalic acid Examples thereof include carboxylic acids, and carboxylic acids in which a carboxyl group is bonded to a phenyl group via a carbon bond.

  Examples of organic carboxylic acid anhydrides include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2- anhydride, and the like. Cyclohexene dicarboxylic acid, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride and the like can be mentioned.

<Production method of coloring composition and color filter>
The coloring composition can be prepared by mixing a dispersant (polymerization product), a colorant, a dispersion medium, a binder resin, and if necessary, a crosslinking agent, a photopolymerization initiator, other additives and the like. For mixing, for example, a mixing and dispersing machine such as a paint shaker, bead mill, ball mill, dissolver, kneader can be used.

  The colored composition can be suitably used for a color filter because it has alkali developability.

  The color filter of the present invention is provided with a colored layer formed using the above-mentioned coloring composition. As a method of manufacturing a color filter, the following method is mentioned, for example. First, thermoplastic resin sheets such as polyester resins, polyolefin resins, polycarbonate resins and polymethyl methacrylate resins, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins and poly (meth) acrylic resins, various glasses For example, after applying a coloring composition of the present invention in which a red pigment is dispersed, on a transparent substrate such as, for example, prebaking is performed to evaporate a solvent (dispersion medium) to form a coating film. Next, the coating film is exposed to light through a photomask and then developed using an alkaline developer (an organic solvent or an aqueous solution containing a surfactant and an alkaline compound, etc.) to dissolve and remove the unexposed area of the coating film. Do. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement. Then, using each green or blue coloring composition and applying, prebaking, exposing, developing and postbaking each coloring composition in the same manner as above, the green pixel array and the blue pixel array are the same substrate Form sequentially on top. As a result, a color filter in which pixel arrays of three primary colors of red, green and blue are disposed on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above. In addition, a black matrix may be provided on a transparent substrate used to form a red, green and blue three primary color pixel array.

When the coloring composition is applied to the substrate, an appropriate application method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method can be employed. In particular, spin coating or slit die coating is preferably employed.
A protective film is formed on the pixel pattern thus obtained, if necessary, and then a transparent conductive film (ITO or the like) is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter.

  The color filter of the present invention has high dimensional accuracy and the like, and can be suitably used for a color liquid crystal display device, a color imaging tube device, a color sensor, an organic EL display device, an electronic paper, and the like.

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these specific examples. Moreover, the various physical-property measurement measured with the following apparatuses. The meanings of the abbreviations are as follows.
MMA: methyl methacrylate BMA: n-butyl methacrylate BzMA: benzyl methacrylate EHMA: 2-ethylhexyl methacrylate MA: methyl acrylate BA: n-butyl acrylate M4 EGM: methoxypolyethylene glycol monomethacrylate (addition molar number of ethylene oxide: 4) (trade name: Blemmer (Registered trademark) PME-200, manufactured by NOF Corporation
MAA: Methacrylic acid PCL5: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (manufactured by Daicel Chemical Co., Ltd., Plaxel® FM5)
DMAEMA: 2- (dimethylamino) ethyl methacrylate DMAPAAm: N- (3-dimethylaminopropyl) acrylamide BzCl: benzyl chloride BTEE: ethyl-2-methyl-2-n-butyl-teranyl-propionate DBDT: dibutyl ditelluride AIBN: 2,2'-azobis (isobutyronitrile)
ADVN: azobis (2,4-dimethyl valeronitrile)
PMA: Propylene glycol monomethyl ether acetate MeOH: Methanol

[Evaluation method]
(Polymerization rate)
¹ H-NMR was measured (solvent: deuterated chloroform, internal standard: tetramethylsilane) using a nuclear magnetic resonance (NMR) measurement apparatus (manufactured by Bruker, model: AVANCE 500 (frequency 500 MHz)). With respect to the obtained NMR spectrum, the integral ratio of the vinyl group derived from the monomer and the peak of the ester side chain derived from the polymer was determined to calculate the polymerization rate of the monomer.

(Weight average molecular weight (Mw) and molecular weight distribution (PDI))
It was determined by gel permeation chromatography (GPC) using a high performance liquid chromatograph (manufactured by Tosoh Corporation, model: HLC-8320). Column: One SHODEX GPC KF-603 (Φ 6.0 mm × 150 mm) (manufactured by Showa Denko KK), mobile phase: 30 mmol / L lithium bromide-30 mmol / L acetic acid-N-methyl pyrrolidone solution, detector with differential refraction I used a meter. As the measurement conditions, the column temperature was 40 ° C., the sample concentration was 10 mg / mL, the sample injection amount was 10 μL, and the flow rate was 0.2 mL / min. Prepare a calibration curve (calibration curve) using polystyrene (molecular weight 70, 500, 37, 900, 19, 920, 10, 200, 4, 290, 2, 630, 1, 150) as a standard substance, and weight average Molecular weight (Mw) and number average molecular weight (Mn) were measured. The molecular weight distribution (PDI = Mw / Mn) was calculated from these measured values.

(Amine value)
The amine value is represented by the mass of potassium hydroxide (KOH) equivalent to the basic component per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, and the obtained solution was subjected to neutralization titration with a 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: GT-200, manufactured by Mitsubishi Chemical Corporation). The amine value (B) was calculated by the following equation, with the inflection point of the titration pH curve as the titration end point.
B = 56. 11 x Vs x 0.1 x f / w
B: Amine value (mg KOH / g)
Vs: Use amount (mL) of 0.1 mol / L hydrochloric acid / 2-propanol solution required for titration
f: titer of 0.1 mol / L hydrochloric acid / 2-propanol solution w: mass of measurement sample (g) (solid content conversion)

(Acid number)
An acid value represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of solid content. The measurement sample was dissolved in tetrahydrofuran, several drops of a phenolphthalein ethanol solution were added as an indicator, and neutralization titration was performed with a 0.1 mol / L potassium hydroxide / 2-propanol solution. The acid value (A) was calculated by the following equation.
A = 56. 11 x Vs x 0.1 x f / w
A: Acid value (mg KOH / g)
Vs: Use amount (mL) of 0.1 mol / L potassium hydroxide / 2-propanol solution required for titration
f: titer of 0.1 mol / L potassium hydroxide / propanol solution w: mass of measurement sample (g) (solid content conversion)

(Content of block copolymer)
High performance liquid chromatography (trade name: HPLC 11 Series, manufactured by Agilent Technologies), column (trade name: L-Column 2 ODS 5 μm, 4.6 × 150 mm, manufactured by CERI), column temperature 40 ° C., detector (ELSD PL-ELS2100 Manufactured by Polymer Laboratory, evaporator temperature 80 ° C., nebulizer temperature 70 ° C., gas flow rate 1.1 SLM), mobile phase A (acetonitrile: water: trifluoroacetic acid = 80: 20: 0.1 volume ratio), mobile phase B (tetrahydrofuran) It analyzed on the gradient conditions which become mobile phase B 100% from mobile phase A 100% in 10 minutes using :: trifluoroacetic acid = 100: 0.1 volume ratio) at the flow rate of 1 mL / min. The sample was bombarded with 5 μL of a 7 mg / mL solution of acetonitrile: THF: water = 4: 1: 1 (volume ratio). A calibration curve was prepared using each unligated component of each block synthesized separately, and quantified. Moreover, the remainder which remove | eliminated the amount of unconnected components from the whole was made into the content rate of the block copolymer.

(viscosity)
The viscosity was measured at 25 ° C. using an E-type viscometer (trade name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.) using a cone rotor (0.8 ° × R24). In addition, the initial measurement was performed about the coloring composition immediately after preparation. Storage stability was performed on a coloring composition stored at 23 ° C. for one week or a coloring composition stored at 40 ° C. for one week after preparation.

(Pigment particle size)
5.4 g of PMA was added to 0.6 g of the coloring composition, and measurement was performed using a particle size distribution analyzer (FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) to obtain an average particle diameter as a result of cumulant analysis. In addition, the initial measurement was performed about the coloring composition immediately after preparation. Storage stability was performed on the colored composition stored for 1 week at 40 ° C. after preparation.

<Production of block copolymer>
(Manufacturing method No. 1)
In a 1 L reactor equipped with a stirrer with argon substitution, 39.5 g of MMA, 19.0 g of BMA, 13.2 g of BzMA, 17.9 g of EHMA, 6.91 g of M4EGM, 6.91 g of MAA, 6.91 g of MAA in a 1 L reactor equipped with a stirrer and stirred in advance. 43 g, DBDT 3.96 g, AIBN 0.70 g, and PMA 69.0 g were charged and reacted at 54 ° C. for 19 hours. The polymerization rate was 99%.

  To this reaction solution, 46.5 g of DMAEMA previously purged with argon and 31.0 g of PMA were added, and reacted at 54 ° C. for 22 hours. The polymerization rate was 98%. In addition, the monomers of the first stage of polymerization remaining in the reaction solution were also polymerized, and the polymerization rate of the monomers of the first stage of polymerization remaining in these reaction solutions was 100%.

  13.1 g of BzCl and 216.0 g of MeOH which were previously purged with argon were added to the reaction solution, and reacted at 60 ° C. for 20 hours.

  After completion of the reaction, the reaction solution was diluted with tetrahydrofuran (THF) and poured into heptane under stirring. The precipitated polymer was filtered by suction and dried, and polymerization product No. 1 was obtained. I got one. The polymerization product has a Mw of 7,599, a PDI of 1.3, an amine value of 67 mg KOH / g, an acid value of 31 mg KOH / g, an unconnected component at the first stage of polymerization (a random polymer having the same composition as the A block) 9% by mass, the content of unconnected components in the second polymerization stage (random polymer having the same composition as B block) is 7% by mass, and the content of block copolymer is 84% by mass The In addition, the content rate of each structural unit in a copolymer was computed from the preparation ratio and the polymerization rate of the monomer used for the polymerization reaction.

(Manufacturing method No. 2)
In an argon-purged, 3 L reactor equipped with stirring, 163.2 g of MMA, 78.5 g of BMA, 55.3 g of BzMA, 75.6 g of EHMA, 29.0 g of M4EGM, 28.9 g of MAA, 28.9 g of MAA, were previously purged with argon. 0 g, 15.5 g of DBDT, 2.7 g of AIBN, and 268.6 g of PMA were charged and reacted at 60 ° C. for 15 hours. The polymerization rate was 98%.

  To this reaction solution, 192.3 g of DMAEMA previously purged with argon and 128.0 g of PMA were added, and reacted at 60 ° C. for 7 hours. The polymerization rate was 97%. In addition, the monomers of the first stage of polymerization remaining in the reaction solution were also polymerized, and the polymerization rate of the monomers of the first stage of polymerization remaining in these reaction solutions was 100%.

  To this reaction solution, 54.8 g of BzCl previously purged with argon and 878.9 g of MeOH were added, and reacted at 60 ° C. for 20 hours.

  After completion of the reaction, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was filtered by suction and dried, and polymerization product No. 1 was obtained. I got two. The polymerization product has a Mw of 7,644, a PDI of 1.3, an amine value of 64 mg KOH / g, an acid value of 29 mg KOH / g, a content of unconnected components in the first stage of polymerization of 21% by mass, and a second stage of polymerization. The content of the unconnected component in the eye was 9% by mass, and the content of the block copolymer was 70% by mass. In addition, the content rate of each structural unit in a copolymer was computed from the preparation ratio and the polymerization rate of the monomer used for the polymerization reaction.

(Manufacturing method No. 3)
In a 500 mL reactor equipped with a stirrer and charged with argon, 36.8 g of BMA, 110.4 g of PCL5, 5.99 g of BTEE, 3.69 g of DBDT, 0.7 g of AIBN, and 98.1 g of PMA were charged beforehand. The reaction was allowed to proceed at 23 ° C for 23 hours. The polymerization rate was 99%.

  To this reaction solution, 46.4 g of DMAEMA previously purged with argon and 30.9 g of PMA were added, and reacted at 54 ° C. for 21 hours. The polymerization rate was 98%. In addition, the monomers of the first stage of polymerization remaining in the reaction solution were also polymerized, and the polymerization rate of the monomers of the first stage of polymerization remaining in these reaction solutions was 100%.

  After completion of the reaction, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was filtered by suction and dried, and polymerization product No. 1 was obtained. I got three. The polymerization product has an Mw of 15,434, a PDI of 1.5, an amine value of 83 mg KOH / g, a content of the unconnected component of the first stage of polymerization of 5% by mass, and a content of the unconnected component of the second stage of polymerization The rate was 3% by mass, and the content of the block copolymer was 92% by mass.

(Manufacturing method No. 4)
A stirrer is placed in a 60 mL screw-head test tube and argon-replaced, then BMA 2.30 g, PCL 5 6.90 g, BTEE 0.375 g, DBDT 0.231 g, AIBN 0.04 g, PMA 6.13 g containing argon are pre-argonized. Charge and react at 65 ° C. for 29 hours. The polymerization rate was 99%.

  To this reaction solution were added 2.90 g of DMAEMA and 1.93 g of PMA, which were previously purged with argon, and reacted at 65 ° C. for 16 hours. The polymerization rate was 99%. In addition, the monomers of the first stage of polymerization remaining in the reaction solution were also polymerized, and the polymerization rate of the monomers of the first stage of polymerization remaining in these reaction solutions was 100%.

  After completion of the reaction, the reaction solution was diluted with THF and poured into heptane under stirring. The precipitated polymer was filtered by suction and dried, and polymerization product No. 1 was obtained. I got four. The polymerization product has a Mw of 20,363, a PDI of 1.9, an amine value of 85 mg KOH / g, a content of the unconnected component of the first stage of polymerization of 18% by mass, and a content of the unconnected component of the second stage of polymerization The rate was 8% by mass, and the content of the block copolymer was 74% by mass.

(Manufacturing method No. 5)
In a 500 mL reactor equipped with a stirrer and charged with argon, previously charged with argon 53.71 g of MA, 30.08 g of BA, 3.00 g of BTEE, 2.48 g of ADVN, and 56.0 g of ethyl acetate are added. It was made to react. The polymerization rate was 97%.

  To this reaction solution, 30.61 g of DMAPAAm, which had been previously purged with argon, and 20.40 g of ethyl acetate were added, and reacted at 30 ° C. for 48 hours. The polymerization rate was 96%. In addition, the monomers of the first stage of polymerization remaining in the reaction solution were also polymerized, and the polymerization rate of the monomers of the first stage of polymerization remaining in these reaction solutions was 100%.

  To this reaction solution, 12.1 g of diethyl sulfate previously substituted with argon and 63.4 g of MeOH were added, and reacted at 30 ° C. for 20 hours. After completion of the reaction, the reaction solution was diluted with tetrahydrofuran (THF) and poured into heptane under stirring. The precipitated polymer was filtered by suction and dried, and polymerization product No. 1 was obtained. I got five. The polymerization product has an Mw of 11,936, a PDI of 1.2, an amine value of 52 mg KOH / g, a content of the unconnected component of the first stage of polymerization of 3% by mass, and a content of the unconnected component of the second stage of polymerization The content of the block copolymer was 95% by mass.

Production method No. The reaction temperature of the first polymerization step and the second polymerization step is 54 ° C., and the difference (T) with the 10 hour half-life temperature (65 ° C.) of the azo polymerization initiator (AIBN) _2/1- Tr) is at 11 ° C. This manufacturing method No. The content of the desired block copolymer of the polymerization product obtained in 1 is as high as 84% by mass, and polymer impurities are reduced.

Production method No. The reaction temperature of the first polymerization step and the second polymerization step is 60 ° C., and the difference (T) with the 10 hour half-life temperature (65 ° C.) of the azo polymerization initiator (AIBN) _2/1- Tr) is 5 ° C. This manufacturing method No. The polymerization product obtained in 2 has a low content of the desired block copolymer of 70% by mass and a high content of polymer impurities.

Production method No. The reaction temperature of the first polymerization step and the second polymerization step is 54 ° C., and the difference (T) with the 10 hour half-life temperature (65 ° C.) of the azo polymerization initiator (AIBN) _2/1- Tr) is at 11 ° C. This manufacturing method No. In the polymerization product obtained in 3, the content of the desired block copolymer is as high as 92% by mass, and polymer impurities are reduced.

Production method No. The reaction temperature of the first polymerization step and the second polymerization step is 65 ° C., and the difference (T) with the 10 hour half-life temperature (65 ° C.) of the azo polymerization initiator (AIBN) _2/1- Tr) is at 0 ° C. This manufacturing method No. The polymerization product obtained in 4 has a low content of the desired block copolymer of 74% by mass and a high content of polymer impurities.

Production method No. The reaction temperature of the first polymerization step and the second polymerization step is 30 ° C., and the difference (T) with the 10 hour half-life temperature (52 ° C.) of the azo polymerization initiator (ADVN) is 5 _2/1- Tr) is 22 ° C. This manufacturing method No. In the polymerization product obtained in 5, the content of the desired block copolymer is as high as 95% by mass, and polymer impurities are reduced.

<Coloring composition>
C. I. 12 parts by mass of Pigment Red 254 (trade name: BKCF, manufactured by Ciba Specialty Chemicals), 3.6 parts by mass of a polymerization product, and a binder resin (benzyl methacrylate / methacrylic acid copolymer = 60/40 (mass ratio) ), An acid value of 128 mg KOH / g, weight average molecular weight of 9,150), 3.6 parts by mass, 80.8 parts by mass of PMA, 100 parts by mass of 0.3 mm zirconia beads, and adding a bead mill (trade name: DISPERMAT CA, VMA-GETZMANN) The mixture was mixed for 2 hours and thoroughly dispersed. After completion of the dispersion, the beads were separated by filtration and filtered through a 5 μm pore size PTFE membrane filter to obtain a pigment dispersion (pigment composition).

  Coloring composition No. No. 1 is the above-mentioned polymerization product No. 1 as a dispersant. This is the case where 1 is used. The coloring composition No. 1 In No. 1, the viscosity in the initial evaluation is low, and the average particle size of the pigment is also small, and the pigment dispersibility is excellent. Moreover, the viscosity in the storage stability (40 ° C., 1 week) evaluation is also low, and the average particle size of the pigment is also substantially the same as the initial evaluation. Therefore, the storage stability of the dispersant is also excellent.

  Coloring composition No. No. 2 is the above-mentioned polymerization product No. 1 as a dispersant. This is the case where 2 is used. The coloring composition No. 1 No. 2 has a high viscosity in the initial evaluation, a large average particle size of the pigment, and a poor pigment dispersibility. Moreover, the viscosity in storage stability (40 degreeC, 1 week) evaluation is increasing to 4 times or more of initial evaluation, and the average particle diameter of a pigment is also increasing rather than initial evaluation. Therefore, when the content rate of the polymer impurity of the polymerization product used as a dispersing agent is high, it turns out that it is inferior to storage stability.

  Coloring composition No. No. 3 is the above-mentioned polymerization product No. 1 as a dispersant. This is the case where 3 is used. The coloring composition No. 1 No. 3 has a low viscosity in the initial evaluation, a small average particle size of the pigment, and is excellent in the dispersibility of the pigment. Moreover, coloring composition No. Compared with 4, the viscosity in storage stability (23 ° C., 1 week) evaluation is also low. Therefore, the storage stability of the dispersant is also excellent.

  Coloring composition No. No. 4 represents the above polymerization product No. 4 as a dispersant. It is a case where 4 is used. The coloring composition No. 1 In No. 4, the obtained pigment dispersion was gelled, and the pigment could not be dispersed sufficiently. The viscosity in the initial evaluation is very high, and the average particle size of the pigment is large, and the dispersibility of the pigment is poor.

  Coloring composition No. No. 5 represents the above polymerization product No. 5 as a dispersant. 5 is used. The coloring composition No. 1 No. 5 has a low viscosity in the initial evaluation, a small average particle size of the pigment, and is excellent in the dispersibility of the pigment. Moreover, the viscosity in the storage stability (40 ° C., 1 week) evaluation is also low, and the average particle size of the pigment is also substantially the same as the initial evaluation. Therefore, the storage stability of the dispersant is also excellent.

  The polymerization product of the present invention can be used as a dispersant for the colorant of the coloring composition. The said coloring composition can be used conveniently for color filters. The color filter has high dimensional accuracy and the like, and can be suitably used for a color liquid crystal display device, a color imaging tube device, a color sensor, an organic EL display device, an electronic paper, and the like.

Claims (12)

A polymerization product obtained by polymerizing a monomer composition,
A block copolymer having an A block having a structural unit derived from a (meth) acrylic vinyl monomer and a B block having a structural unit represented by the following general formula (1),
The molecular weight distribution (PDI) of the polymerization product is 2.0 or less, and
The polymerization product characterized in that the content of the block copolymer is 75% by mass or more in 100% by mass of the polymerization product.

[In formula (1), R ¹¹ and R ¹² each independently represent a linear or cyclic hydrocarbon group which may have a substituent. R ¹¹ and R ¹² may be bonded to each other to form a cyclic structure. X ¹ represents a divalent linking group. R ¹³ represents a hydrogen atom or a methyl group. ]   The polymerization product according to claim 1, wherein the weight average molecular weight of the polymerization product is 5,000 to 40,000.   The polymerization product according to claim 1 or 2, wherein the amine value of the polymerization product is 3 mg KOH / g to 180 mg KOH / g.   The polymerization product according to any one of claims 1 to 3, wherein the polymerization product is produced by living radical polymerization.   The polymerization product according to any one of claims 1 to 4, wherein the mass ratio of A block to B block (A block / B block) in the block copolymer is 50/50 to 95/5. .   The polymerization product according to any one of claims 1 to 5, wherein the block copolymer is an A-B type diblock copolymer.   A dispersant comprising the polymerization product according to any one of claims 1 to 6.   The dispersant according to claim 7, which is for color filters.   A coloring composition comprising the dispersant according to claim 7 or 8, a colorant, a dispersion medium, and a binder resin.   A color filter comprising a colored layer formed using the coloring composition according to claim 9. The method for producing a polymerization product according to any one of claims 1 to 6, wherein
A first mixture of an organic tellurium compound represented by the general formula (3) and an azo polymerization initiator, or an organic tellurium compound represented by the general formula (3), an azo polymerization initiator and a general formula (4) A block polymerization step of polymerizing a first monomer composition containing a (meth) acrylic vinyl monomer using a second mixture with an organic ditelluride compound represented by
B block polymerization step of polymerizing a second monomer composition containing a vinyl monomer forming a structural unit represented by the general formula (1) using the first mixture or the second mixture,
In all the polymerization steps, the difference (T _1/2 -Tr) between the 10 hour half-life temperature (T _1/2 ) of the azo polymerization initiator and the reaction temperature (Tr) is 10 ° C. to 60 ° C. A method of producing a polymerization product characterized by

[In general formula (3), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. R ³² and R ³³ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R ³⁴ represents an alkyl group having 1 to 8 carbon atoms, an aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amido group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
In formula (4), R ³¹ represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group. ]   The method for producing a polymerization product according to claim 11, wherein the polymerization rate of the monomer composition is 96% or more in all the polymerization steps.