JP2010099593A - Dispersant and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersant which is used for preparing compositions e.g ink, coating material, adhesive, photoresist ink, etc., which are curable by active energy radiations such as ultraviolet rays and electron radiations, or raw materials for manufacturing color filter, dry film, etc., and is best-suited for dispersion of pigments etc. in the medium e.g. organic solvent, as well as a method of manufacturing the dispersant. <P>SOLUTION: This dispersant includes a polymer block (X) with an amino group and/or a carboxyl group, and a polymer block (Y) whose affinity with the medium is higher than that of the polymer block (X), when the polymer block (Y) is dissolved or dispersed in the medium. Further, the dispersant is characterized in that at least, either the polymer block (X) or the polymer block (Y) contains a block copolymer with an active energy radiations-curable functional group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dispersant and a method for producing the same. More specifically, the present invention is suitable for preparing various compositions such as inks, paints, adhesives, and photoresist inks that are cured with active energy rays such as ultraviolet rays and electron beams, and manufacturing raw materials such as color filters and dry films. The present invention relates to a dispersant used and a method for producing the same.

Conventionally, paints, adhesives, photoresist inks, etc. used by curing with active energy rays such as ultraviolet rays (light energy), electron rays, X-rays, α rays, β rays, γ rays, neutron rays, etc. Active energy ray-curable compositions containing pigments, dispersants, acrylic oligomers, and the like have been used as the raw materials for producing these compositions, color filters, dry films and the like. In recent years, development of an active energy ray-curable composition containing an acrylic oligomer having the action of a dispersant has been advanced.
Patent Document 1 discloses an active energy ray-curable graft copolymer having a polymer having an amino group as a trunk and a polymer having an active energy ray-curable functional group as a branch, and a polymer having an amino group. At least one active energy ray-curable graft copolymer selected from active energy ray-curable graft copolymers having as a trunk a polymer having an active energy ray-curable functional group as a branch, and (meth) acryloyl An active energy ray-curable graft copolymer composition containing an active energy ray-curable compound having one or more groups and a molecular weight of 100 to 5,000 is disclosed.
Patent Document 2 discloses an active energy ray in which any one of a polymer having an amino group and a carboxyl group and a polymer having an active energy ray-curable functional group is a trunk and the other is a branch. An active energy ray-curable composition containing a curable graft copolymer and an active energy ray-curable compound having a molecular weight of 100 to 5,000 having one or more (meth) acryloyl groups is disclosed.

JP 2001-261726 A JP 2001-288229 A

Although the active energy ray-curable graft copolymer contained in the compositions disclosed in Patent Documents 1 and 2 above has a certain performance in the dispersibility of the pigment, a more excellent dispersant has been demanded. .
The present invention is used for preparing various compositions such as inks, paints, adhesives, photoresist inks and the like, which are cured with active energy rays such as ultraviolet rays and electron beams, and raw materials for producing color filters, dry films, etc. It is an object of the present invention to provide a dispersant suitable for dispersing pigments in a medium such as a solvent and a method for producing the same.

〔式中、Ｒ^１は水素原子又は炭素数１〜２のアルキル基であり、Ｒ^２は炭素数１〜２のアルキル基又はニトリル基であり、Ｒ^３は−（ＣＨ_２）_ｍ−（ｍは０〜２の整数である。）であり、Ｒ^４は水素原子又は炭素数１〜４のアルキル基であり、Ｒ^５は互いに独立して炭素数１〜４のアルキル基であり、Ｒ^６は互いに独立して炭素数１〜４のアルキル基であり、Ｒ^７は互いに独立して炭素数１〜４のアルキル基である。〕
［７］上記官能基がエポキシ基である上記［６］に記載の分散剤の製造方法。
［８］上記ブロック共重合体に上記カルボキシル基を導入するための単量体が下記一般式（２）により表される化合物である上記［６］又は［７］に記載の分散剤の製造方法。

〔式中、Ｒ^８は水素原子又はメチル基であり、Ｒ^９はあってもなくてもよく、Ｒ^９を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ_６Ｈ_４−であり、Ｒ^１０はＲ^１１−Ｏ−（Ｒ^１１は炭素数２〜４のアルキル基）、Ｒ^１２−Ｃ（Ｏ）−Ｏ−（Ｒ^１２は炭素数１〜８のアルキル基）、Ｒ^１３−Ｏ−Ｃ（Ｏ）−Ｒ^１４−（Ｒ^１３は炭素数１〜８のアルキル基、Ｒ^１４は炭素数１〜８のアルキル基）、−Ｃ_６Ｈ_４−又は−ＣＨ_２＝ＣＨ_２−であり、ｎは０〜４である。〕
［９］上記活性エネルギー線硬化性官能基がアクリロイル基及びメタクリロイル基のうちの少なくとも一方である上記［６］乃至［８］のうちのいずれか１項に記載の分散剤の製造方法。 The present invention is shown below.
[1] A polymer block (X) having an amino group and / or a carboxyl group, and a polymer block (A) having a higher affinity with the medium than the polymer block (X) when dissolved or dispersed in the medium Y), and at least one of the polymer block (X) and the polymer block (Y) contains a block copolymer having an active energy ray-curable functional group.
[2] The dispersant according to [1], wherein the active energy ray-curable functional group is at least one of an acryloyl group and a methacryloyl group.
[3] The dispersant according to [1] or [2] above, wherein the block copolymer is dissolved in the medium.
[4] The dispersant according to any one of [1] to [3], wherein the block copolymer has a number average molecular weight of 2,000 to 70,000.
[5] The dispersant according to any one of [1] to [4], which is used as a pigment dispersant.
[6] The method for producing a dispersant according to any one of [1] to [5] above,
In the presence of a living radical polymerization initiator represented by the following general formula (1), a first step of producing a block copolymer containing a polymer block having at least a carboxyl group among an amino group and a carboxyl group;
Dispersion characterized by comprising the second step of reacting the block copolymer with a monomer having a functional group that reacts with a carboxyl group of the block copolymer and an active energy ray-curable functional group. Manufacturing method.

[Wherein, R ¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ² is an alkyl group having 1 to ² carbon atoms or a nitrile group, and R ³ is — (CH ₂ ) _m — (m Is an integer of 0 to 2.), R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms independently of each other, and R ⁶ Are each independently an alkyl group having 1 to 4 carbon atoms, and R ⁷ is independently an alkyl group having 1 to 4 carbon atoms. ]
[7] The method for producing a dispersant according to [6], wherein the functional group is an epoxy group.
[8] The method for producing a dispersant as described in [6] or [7] above, wherein the monomer for introducing the carboxyl group into the block copolymer is a compound represented by the following general formula (2): .

Wherein, ^{R 8} is a hydrogen atom or a methyl group, may or may not be ^{R 9} is a, if with ^{R 9} is, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —, R ¹⁰ is R ¹¹ —O— (R ¹¹ is an alkyl group having 2 to 4 carbon atoms), and R ¹² —C (O) —O— (R ¹² is carbon number) 1-8 alkyl ^{group), R 13 -O-C (} O) -R 14 - (R 13 represents an alkyl group having 1 to 8 carbon ^{atoms, R 14} is an alkyl group having 1 to 8 carbon atoms), - _{C 6} H ₄ — or —CH ₂ ═CH ₂ —, and n is 0 to 4. ]
[9] The method for producing a dispersant according to any one of [6] to [8], wherein the active energy ray-curable functional group is at least one of an acryloyl group and a methacryloyl group.

The dispersant of the present invention is used for preparing various compositions such as inks, paints, adhesives and photoresist inks that are cured with active energy rays such as ultraviolet rays and electron beams, and manufacturing raw materials such as color filters and dry films. It is suitable for dispersing pigments in a medium such as an organic solvent.
Moreover, according to the manufacturing method of the dispersing agent of this invention, the dispersing agent which has the said effect can be manufactured efficiently.

  The present invention will be described in detail below. In this specification, “(meth) acryl” means acryl and methacryl, “(meth) acrylate” means acrylate and methacrylate, and “(meth) acryloyl” means acryloyl and methacryloyl.

The dispersant of the present invention has a polymer block (X) having an amino group and / or a carboxyl group and a polymer block (X) having a higher affinity with the medium than the polymer block (X) when dissolved or dispersed in the medium. A block copolymer (hereinafter referred to as “block copolymer (Y)), wherein at least one of the polymer block (X) and the polymer block (Y) has an active energy ray-curable functional group. A) ").
The dispersant of the present invention may be only the block copolymer (A) or a composition containing the block copolymer (A) and other components.

  The polymer block (X) in the block copolymer (A) functions as an adsorbing unit to the dispersoid in the dispersion containing a dispersoid such as a pigment obtained using the dispersant of the present invention. On the other hand, the polymer block (Y) functions as an affinity unit for a medium such as water or an organic solvent in the dispersion.

  The polymer block (X) is a polymer block having an amino group and / or a carboxyl group, and may be a polymer block having any one of an amino group and a carboxyl group, It may be a polymer block having both. In the present invention, from the viewpoint of dispersibility of pigments and the like, the polymer block (X) is preferably a polymer block having both an amino group and a carboxyl group.

  The polymer block (X) preferably contains mainly (preferably 80% by mass or more) structural units derived from a polymerizable unsaturated compound having a carboxyl group, a polymerizable unsaturated compound having an amino group, and the like. In addition, the density | concentration of the amino group in this polymer block (X) and a carboxyl group, and its coupling | bonding position are not specifically limited. The concentration of the amino group is preferably 1 to 8 meq, more preferably 2 to 5 meq per 1 g of the polymer block (X). Moreover, the density | concentration of a carboxyl group becomes like this. Preferably it is 1-8 meq per 1g of said polymer blocks (X), More preferably, it is 2-5 meq. When the amino group and carboxyl group concentrations are in the above ranges, the adsorptivity to dispersoids such as pigments is excellent.

  The polymer block (X) may have a functional group other than an amino group and a carboxyl group. Examples of monomers that give structural units having other functional groups include (meth) acrylic acid alkyl ester compounds in which the alkyl moiety of the alkyl ester is a hydrocarbon group having 1 to 14 carbon atoms, aromatic vinyl compounds; hydroxyl groups, Examples thereof include polymerizable unsaturated compounds having a functional group such as an acid anhydride group, an amide group, an alkoxyl group, and a cyano group.

  The number average molecular weight (hereinafter also referred to as “Mn”) of the polymer block (X) is preferably 200 to 15,000, more preferably, in terms of standard polystyrene by gel permeation chromatography (GPC) measurement. 800-5,000. When Mn is in the above range, the adsorptivity and wettability to dispersoids such as pigments are excellent.

  When the polymer block (Y) is dissolved or dispersed in a medium, the polymer block (Y) has a higher affinity with the medium than the polymer block (X). That is, regardless of whether the block copolymer (A) is dissolved in the medium or not, the polymer block (Y) has a higher affinity for the medium than the polymer block (X). This medium is, for example, alkylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol isoamyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether or the like. Alkyl ether; alkylene glycol polyalkyl ether such as ethylene glycol diethyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, etc. Alkylene glycol monoacetate such as ethylene glycol monoacetate; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate Alkylene glycol (poly) alkyl ether acetate such as diethylene glycol monomethyl ether acetate, dialkylene glycol (poly) alkyl ether acetate such as diethylene glycol monoethyl ether acetate; lactic acid ester such as methyl lactate and ethyl lactate; methoxymethoxy ether, diethylene glycol, Lopylene glycol, 1-butoxyethoxypropanol, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, methyl amyl ketone, methyl-α-hydroxyisobutyrate, methyl-β-methoxyisobutyrate, etc. Is mentioned.

The polymer block (Y) has a structure derived from a (meth) acrylic acid alkyl ester compound in which the alkyl moiety of the alkyl ester is a hydrocarbon group having 1 to 14 carbon atoms, an aromatic vinyl compound having no functional group, or the like. It is preferable that the unit is mainly contained (preferably 80% by mass or more).
The polymer block (Y) is usually a polymer block that does not have an amino group and a carboxyl group, but an amino group and / or a carboxyl group as long as the relationship with the polymer block (X) is satisfied. It may be a polymer block having a group. Moreover, you may have other functional groups, such as a hydroxyl group, an acid anhydride group, an amide group, an alkoxyl group, and a cyano group. Examples of monomers that give these functional groups include polymerizable unsaturated compounds having functional groups such as hydroxyl groups, acid anhydride groups, amide groups, alkoxyl groups, and cyano groups.

  When the polymer block (Y) is a polymer block having an amino group and / or a carboxyl group, the concentration of amino group and carboxyl group and the bonding position thereof are not particularly limited. The concentration of the amino group is preferably 0.2 meq or less, more preferably 0.1 meq or less, per 1 g of the polymer block (Y). Moreover, the density | concentration of a carboxyl group becomes like this. Preferably it is 0.2 meq or less per 1 g of said polymer blocks (Y), More preferably, it is 0.1 meq or less. When the concentration of the amino group and the carboxyl group is in the above range, the affinity for the medium is excellent.

  Mn of the polymer block (Y) is preferably 1,000 to 45,000, more preferably 3,000 to 30,000. When Mn is in the above range, the affinity for the medium is excellent.

  Although the manufacturing method of the said block copolymer (A) is mentioned later, in the obtained block copolymer (A), the residue (organic group etc.) based on raw material components, such as a polymerization initiator used in the manufacture. It may be bonded to the polymer block (X) and / or (Y).

When the block copolymer (A) has an amino group and does not have a carboxyl group, the concentration of the amino group is preferably 0.01 to 3 meq per 1 g of the block copolymer (A). Is 0.2-1 meq.
When the block copolymer (A) has a carboxyl group and does not have an amino group, the concentration of the carboxyl group is preferably 0.01 to 3 meq per 1 g of the block copolymer (A). Is 0.2-1 meq.
Further, when the block copolymer (A) has an amino group and a carboxyl group, the concentration of the amino group and the carboxyl group is preferably 0.1 to 3 meq and 1 g per 1 g of the block copolymer (A), respectively. It is 0.1-3 meq, More preferably, it is 0.2-1 meq and 0.2-1 meq.
In the said description, the dispersing agent containing the block copolymer (A) in which the density | concentration of an amino group and a carboxyl group exists in said each range is excellent in dispersibility, such as a pigment.

In the block copolymer (A), the polymer block (X) and / or the polymer block (Y) have an active energy ray-curable functional group.
The active energy ray-curable functional group is preferably an acryloyl group and a methacryloyl group. When the block copolymer (A) has a plurality of active energy ray-curable functional groups, they may all be the same functional group or a combination of different functional groups.
The position of the active energy ray-curable functional group is not particularly limited, and may be one end or both ends of the main chain constituting the polymer, or the side chain of the polymer.

  The number of the active energy ray-curable functional group is not particularly limited, but the content of the active energy ray-curable functional group is a double bond equivalent per 1 g of the block copolymer (A), preferably 0. 0.01 to 10 meq, more preferably 0.05 to 5 meq, and still more preferably 0.2 to 1 meq. The dispersant containing the block copolymer (A) having a content in the above range is particularly excellent in dispersibility of pigments and the like.

  The number average molecular weight (Mn) of the block copolymer (A) is preferably 2,000 to 70,000, more preferably 3,000 to 50,000. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), that is, the polydispersity is preferably 3 or less, more preferably 1.1 to 2.5, and still more preferably. 1.3 to 2.2. The dispersant containing the block copolymer (A) having the polydispersity is excellent in dispersibility of pigments and the like.

The monomer which forms the structural unit which the said block copolymer (A) has is illustrated below.
Examples of the polymerizable unsaturated compound having an amino group include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, (meth) 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl (meth) acrylate, 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, (meth) acrylic 2-diethylaminopropyl acid, 2- (di-n-propylamino) propyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, (meth) acrylic acid 3 -(Di-n-propylamino) propyl, (meth) acrylic acid 2- ert-butylaminoethyl, phenylaminoethyl (meth) acrylate, 4-aminostyrene, 4-dimethylaminostyrene, N-vinyldiethylamine, N-acetylvinylamine, (meth) acrylamine, N-methyl (meth) acrylic An amine etc. are mentioned. These compounds can be used alone or in combination of two or more.

〔式中、Ｒ^８は水素原子又はメチル基であり、Ｒ^９はあってもなくてもよく、Ｒ^９を有する場合は、−Ｃ（Ｏ）−Ｏ−、−ＯＣ（Ｏ）−、−ＮＨ−又は−Ｃ_６Ｈ_４−であり、Ｒ^１０はＲ^１１−Ｏ−（Ｒ^１１は炭素数２〜４のアルキル基）、Ｒ^１２−Ｃ（Ｏ）−Ｏ−（Ｒ^１２は炭素数１〜８のアルキル基）、Ｒ^１３−Ｏ−Ｃ（Ｏ）−Ｒ^１４−（Ｒ^１３は炭素数１〜８のアルキル基、Ｒ^１４は炭素数１〜８のアルキル基）、−Ｃ_６Ｈ_４−又は−ＣＨ_２＝ＣＨ_２−であり、ｎは０〜４である。〕 Examples of the polymerizable unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and compounds represented by the following general formula (2). Can be mentioned. These compounds can be used alone or in combination of two or more.

Wherein, ^{R 8} is a hydrogen atom or a methyl group, may or may not be ^{R 9} is a, if with ^{R 9} is, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —, R ¹⁰ is R ¹¹ —O— (R ¹¹ is an alkyl group having 2 to 4 carbon atoms), and R ¹² —C (O) —O— (R ¹² is carbon number) 1-8 alkyl ^{group), R 13 -O-C (} O) -R 14 - (R 13 represents an alkyl group having 1 to 8 carbon ^{atoms, R 14} is an alkyl group having 1 to 8 carbon atoms), - _{C 6} H ₄ — or —CH ₂ ═CH ₂ —, and n is 0 to 4. ]

  Examples of the (meth) acrylic acid alkyl ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, ( Amyl acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Examples include isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, and the like. In these compounds, one or more hydrogen atoms contained in the hydrocarbon group may be substituted with a halogen atom. The said (meth) acrylic-acid alkylester can be used individually or in combination of 2 or more.

  Examples of the aromatic vinyl compound include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, and 4-tert-butylstyrene. , Vinyl toluene, vinyl naphthalene and the like. In addition, halogenated styrene etc. by which the one or more hydrogen atom contained in the said compound is substituted by the halogen atom can also be used. These compounds can be used alone or in combination of two or more.

  Examples of the polymerizable unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth) acrylic acid 2- Hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7- (meth) acrylic acid 7- Hydroxyheptyl, 8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 11-hydroxyundecyl (meth) acrylate, (meth) acrylic 12 -Hydroxydodecyl, (meth) acrylic acid 2- (6- Droxyethylhexanoyloxy) ethyl, 3- (6-hydroxyethylhexanoyloxy) propyl (meth) acrylate, 4- (6-hydroxyethylhexanoyloxy) butyl (meth) acrylate, (meth) acrylic acid 5- (6-hydroxyethylhexanoyloxy) pentyl, 6- (6-hydroxyethylhexanoyloxy) hexyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth ) A (meth) acrylic acid ester compound having a hydroxyl group such as a compound obtained by adding ε-caprolactone to 2-hydroxyethyl acrylate (for example, trade name “PLAXEL”, manufactured by Daicel Chemical Industries, Ltd.); -Hydroxystyrene, m-hydro Xylstyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α -Methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1 -Isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8-hydroxymethyl-1-isopropenylnaphthalene, p-vinylbenzyl alcohol and the like. These compounds can be used alone or in combination of two or more.

  Examples of the polymerizable unsaturated compound having an acid anhydride group include maleic anhydride, itaconic anhydride, and citraconic anhydride. These compounds can be used alone or in combination of two or more.

  Examples of the polymerizable unsaturated compound having an amide group include (meth) acrylamide, N-methylol (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide, vinylpyrrolidone and the like. These compounds can be used alone or in combination of two or more.

  Examples of the polymerizable unsaturated compound having an alkoxyl group include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl (meth) acrylate, (meth) acrylic acid 2 -(N-butoxy) ethyl, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2- (n-propoxy) propyl (meth) acrylate, 2- (meth) acrylic acid 2- ( n-butoxy) propyl and the like. These compounds can be used alone or in combination of two or more.

  Examples of the polymerizable unsaturated compound having a cyano group include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, cyanomethyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 1-cyanopropyl (meth) acrylate, 2-cyanopropyl (meth) acrylate, 3-cyanopropyl (meth) acrylate, (meth ) 4-cyanobutyl acrylate, 6-cyanohexyl (meth) acrylate, 2-ethyl-6-cyanohexyl (meth) acrylate, 8-cyanooctyl (meth) acrylate, and the like. These compounds can be used alone or in combination of two or more.

In the present invention, a preferable block copolymer (A) is shown below.
[1] The polymer block (X) is a polymer block having an amino group and an active energy ray-curable functional group, and the polymer block (Y) has an amino group, a carboxyl group and an active energy ray-curable functional group. The aspect which is a polymer block which does not have.
[2] The polymer block (X) is a polymer block having a carboxyl group and an active energy ray-curable functional group, and the polymer block (Y) has an amino group, a carboxyl group and an active energy ray-curable functional group. The aspect which is a polymer block which does not have.
[3] The polymer block (X) is a polymer block having an amino group, a carboxyl group and an active energy ray-curable functional group, and the polymer block (Y) is an amino group, a carboxyl group and an active energy ray-curable material. The aspect which is a polymer block which does not have a functional group.
[4] The polymer block (X) is a polymer block having an amino group and an active energy ray-curable functional group, and the polymer block (Y) does not have an amino group and a carboxyl group and is active energy ray-cured. The mode which is a polymer block which has a functional functional group.
[5] The polymer block (X) is a polymer block having a carboxyl group and an active energy ray-curable functional group, and the polymer block (Y) does not have an amino group and a carboxyl group and is active energy ray-cured. The mode which is a polymer block which has a functional functional group.
[6] The polymer block (X) is a polymer block having an amino group, a carboxyl group and an active energy ray-curable functional group, and the polymer block (Y) has no amino group and a carboxyl group and is active. The aspect which is a polymer block which has an energy-beam curable functional group.
[7] The polymer block (X) is a polymer block having an amino group, and the polymer block (Y) does not have an amino group and a carboxyl group and has an active energy ray-curable functional group. The aspect which is.
[8] The polymer block (X) is a polymer block having a carboxyl group, and the polymer block (Y) does not have an amino group or a carboxyl group and has an active energy ray-curable functional group. The aspect which is.
[9] The polymer block (X) is a polymer block having an amino group and a carboxyl group, and the polymer block (Y) does not have an amino group and a carboxyl group and has an active energy ray-curable functional group. An embodiment that is a polymer block.
In addition, when any one or both of the polymer blocks (X) and (Y) have a hydroxyl group, the polymer blocks (X) and (Y) according to the present invention are also handled.

  Among the above embodiments, [3], [6], [7], [8] and [9] are preferable.

As described above, the dispersant of the present invention may be only the block copolymer (A), or may be a composition containing this block copolymer (A) and other components. Good. In the latter case, the other component is preferably an organic solvent. Examples of the organic solvent include linear or branched aliphatic hydrocarbons; alicyclic hydrocarbons; aromatic hydrocarbons such as toluene and xylene; one or more hydrogen atoms in these hydrocarbons are substituted with halogen atoms. Alkylene glycol monoalkyl ether; alkylene glycol polyalkyl ether; dialkylene glycol (poly) alkyl ether; alkylene glycol monoacetate; alkylene glycol (poly) alkyl ether acetate such as propylene glycol monomethyl ether acetate; Glycol (poly) alkyl ether acetate; lactate ester; acetate ester such as ethyl acetate, methyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate Ketone compounds such as ruketone and cyclohexanone; methoxymethoxy ether, diethylene glycol, propylene glycol, 1-butoxyethoxypropanol, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, methyl-α-hydroxyisobutyrate And methyl-β-methoxyisobutyrate. Of these, propylene glycol monomethyl ether acetate and acetates such as ethyl acetate, methyl acetate, and butyl acetate are preferred.
The block copolymer (A) may be dissolved or dispersed in the organic solvent as a medium. Further, when the block copolymer (A) has an amino group, it is quaternized with an organic halide such as epichlorohydrin, methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, benzyl bromide or methyl iodide. And may be dissolved or dispersed in the organic solvent. The quaternization rate of nitrogen in the amino group is preferably 50 to 100%, more preferably 80 to 100%, from the viewpoint of dispersibility of pigments and the like.

  When the dispersant of the present invention contains the block copolymer (A) and the organic solvent, the content of the block copolymer (A) is usually based on 100 parts by mass of the organic solvent. It is 40-90 mass parts, Preferably it is 50-80 mass parts. If it is a dispersant with the above ratio, it is excellent in dispersibility of pigments, etc., each composition such as ink, paint, adhesive, photoresist ink etc. that is cured with active energy rays such as ultraviolet rays and electron beams, color filters, Preparation of manufacturing raw materials such as dry film can be efficiently advanced.

  The manufacturing method of the dispersing agent of this invention containing the said block copolymer (A) is not specifically limited. Moreover, the introduction method of the active energy ray-curable functional group in the block copolymer (A) is not particularly limited.

〔式中、Ｒ^１は水素原子又は炭素数１〜２のアルキル基であり、Ｒ^２は炭素数１〜２のアルキル基又はニトリル基であり、Ｒ^３は−（ＣＨ_２）_ｍ−（ｍは０〜２の整数である。）であり、Ｒ^４は水素原子又は炭素数１〜４のアルキル基であり、Ｒ^５は互いに独立して炭素数１〜４のアルキル基であり、Ｒ^６は互いに独立して炭素数１〜４のアルキル基であり、Ｒ^７は互いに独立して炭素数１〜４のアルキル基である。〕 The method for producing a dispersant of the present invention comprises a block copolymer containing a polymer block having at least a carboxyl group among an amino group and a carboxyl group in the presence of a living radical polymerization initiator represented by the following general formula (1). A first step of producing a coalescence; a second step of reacting the block copolymer with a monomer having a functional group that reacts with a carboxyl group of the block copolymer and an active energy ray-curable functional group; It is characterized by providing.

[Wherein, R ¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ² is an alkyl group having 1 to ² carbon atoms or a nitrile group, and R ³ is — (CH ₂ ) _m — (m Is an integer of 0 to 2.), R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms independently of each other, and R ⁶ Are each independently an alkyl group having 1 to 4 carbon atoms, and R ⁷ is independently an alkyl group having 1 to 4 carbon atoms. ]

The living radical polymerization initiator represented by the general formula (1) is a nitroxide compound. By using this living radical polymerization initiator, a stable nitroxy free radical is generated in the reaction system, whereby the terminal is in an inactive state and the active state is in an equilibrium state, It is possible to efficiently produce a living polymer which is polymerized and has a polydispersity adjusted.
Incidentally, the substituents R ¹ to R ⁷ in the general formula (1) is as described above, R ⁴ is hydrogen atom, without using a polymerizable unsaturated compound having a carboxyl group, a carboxyl group A polymer having (—COOH) can be produced.

  In the present invention, the first step is a step of producing a block copolymer containing a polymer block having at least a carboxyl group among an amino group and a carboxyl group in the presence of the living radical polymerization initiator. This block copolymer usually comprises a polymer block having at least a carboxyl group of an amino group and a carboxyl group, and another polymer block. And by a 2nd process, these polymer blocks are converted and formed into polymer block (X) and (Y) in the block copolymer (A) based on the said invention. In addition, the other polymer block in the first block copolymer may have an amino group and / or a carboxyl group depending on how to use the monomer.

The block copolymer produced by the first step is a precursor in the block copolymer (A) according to the present invention, and is usually produced by a two-stage polymerization step. The specific method is illustrated below.
(1-1) A polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is a hydrogen atom. Polymerization of the monomer (m1) not containing, then, in the presence of the resulting polymer having one carboxyl group, a polymerizable unsaturated compound containing a carboxyl group-containing polymerizable unsaturated compound and having an amino group A method of polymerizing a monomer (m2) containing no compound.
(1-2) A polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is a hydrogen atom. Polymerization of the monomer (m3) not containing, then, in the presence of the resulting polymer having one carboxyl group, the polymerizable unsaturated compound containing the amino group-containing polymerizable unsaturated compound and having the carboxyl group A method of polymerizing a monomer (m4) containing no compound.
(1-3) A polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is a hydrogen atom. The monomer (m5) not containing was polymerized, and then the polymerizable unsaturated compound having an amino group and the polymerizable unsaturated compound having a carboxyl group were obtained in the presence of the obtained polymer having one carboxyl group. A method of polymerizing a monomer (m6) containing the polymer.
(1-4) A polymerizable unsaturated compound containing a polymerizable unsaturated compound having an amino group and having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is a hydrogen atom. A monomer (m7) containing no compound is polymerized, and then the resulting polymerizable unsaturated compound and carboxyl having an amino group in the presence of a polymer having one or more amino groups and one carboxyl group. A method of polymerizing a monomer (m8) not containing a polymerizable unsaturated compound having a group.
(1-5) A polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is a hydrogen atom. A polymerizable unsaturated compound having an amino group and a carboxyl group in the presence of the resulting polymer having one or more amino groups and two or more carboxyl groups. A method for polymerizing a monomer (m10) that does not contain a polymerizable unsaturated compound.
(1-6) Polymerizable unsaturated compound containing a polymerizable unsaturated compound having a carboxyl group and having an amino group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is a hydrogen atom The monomer (m11) not containing a compound is polymerized, and then, in the presence of the obtained polymer having one or more carboxyl groups, the polymerizable unsaturated compound having an amino group and the polymerizability having a carboxyl group A method of polymerizing a monomer (m12) not containing an unsaturated compound.
(1-7) A polymerizable unsaturated compound containing a polymerizable unsaturated compound having a carboxyl group and having an amino group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is a hydrogen atom The monomer (m13) not containing a compound is polymerized, and then, in the presence of the obtained polymer having one or more carboxyl groups, it contains a polymerizable unsaturated compound having an amino group and has a carboxyl group A method of polymerizing a monomer (m14) not containing a polymerizable unsaturated compound.
(1-8) A polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is the alkyl group. And then the polymerizable unsaturated compound having an amino group in the presence of the obtained polymer having one or more amino groups and two or more carboxyl groups, and A method of polymerizing a monomer (m16) not containing a polymerizable unsaturated compound having a carboxyl group.
(1-9) A polymerizable group containing a polymerizable unsaturated compound having a carboxyl group and having an amino group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is the alkyl group. A monomer (m17) not containing a saturated compound is polymerized, and then, in the presence of the obtained polymer containing two or more carboxyl groups, the polymerizable unsaturated compound having an amino group and the carboxyl group are contained. A method of polymerizing a monomer (m14) not containing a polymerizable unsaturated compound.
(1-10) A polymerizable group containing a polymerizable unsaturated compound having a carboxyl group and having an amino group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is the alkyl group. The monomer (m19) containing no saturated compound is polymerized, and then, in the presence of the obtained polymer containing two or more carboxyl groups, the polymerizable unsaturated compound containing an amino group is contained and the carboxyl group A method of polymerizing a monomer (m20) that does not contain a polymerizable unsaturated compound.
(1-11) A polymerizable radical containing a polymerizable unsaturated compound having an amino group and having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is the alkyl group. The monomer (m21) containing no saturated compound is polymerized, and then, in the presence of the obtained polymer containing one or more amino groups, the polymerizable unsaturated compound having a carboxyl group is contained and the amino group A method of polymerizing a monomer (m22) that does not contain a polymerizable unsaturated compound.
(1-12) A polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is the alkyl group. A monomer that does not contain a polymerizable unsaturated compound having a carboxyl group and does not contain a polymerizable unsaturated compound having an amino group in the presence of the resulting polymer. A method for polymerizing the body (m24).
(1-13) A polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group in the presence of a living radical polymerization initiator in which the substituent R ⁴ in the general formula (1) is the alkyl group. A monomer (m26) containing no polymerizable group, and then in the presence of the obtained polymer, a monomer (m26) containing a polymerizable unsaturated compound having a carboxyl group and a polymerizable unsaturated compound having an amino group. ).

  In the above-exemplified method, since the polymerization of each monomer can be carried out continuously only by sequentially adding the predetermined monomer in the two-stage polymerization process to the reaction system, the living radical polymerization described above. Usually, the initiator may be used only in the reaction system in the first polymerization, and does not need to be replenished during the polymerization.

In addition, the two-stage polymerization process can proceed continuously in the same reaction system, and the polymerization can be performed using the same polymerization solvent. In the first stage and the second stage, different polymerization solvents can be used.
Examples of the polymerization solvent include linear or branched aliphatic hydrocarbons; alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; one or more hydrogen atoms in these hydrocarbons being halogen atoms Substituted halogen-substituted compounds; cyclic ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate, methyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; methyl orthoformate and methyl orthoacetate Orthocarboxylic acid esters such as methanol; alcohols such as methanol, ethanol and isopropanol; These solvents may be used alone or in combination of two or more.

In the above embodiment (1-1), the monomer (m1) is preferably the above (meth) acrylic acid alkyl ester compound and / or an aromatic vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited. Moreover, it is preferable that a monomer (m2) contains 80 mass% or more of the polymerizable unsaturated compound which has a carboxyl group with respect to the whole monomer (m2). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds.
In addition, the usage ratio of the monomers (m1) and (m2) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 50 to 99% by mass and 1 to 50% by mass, preferably 70 to 95% by mass and 5 to 30% by mass.

In the polymerization of the monomer (m1), the amount of the living radical polymerization initiator used is preferably 0.3 to 10 parts by mass, more preferably 100 parts by mass based on the total amount of the monomer (m1). 1 to 6 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m1) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m2) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the embodiment (1-1), the polymer block having one carboxyl group derived from the monomer (m1), and the monomer (m2), The Mn of the polymer block having two or more carboxyl groups is preferably 1,000 to 45,000 and 500 to 10,000, more preferably 3,000 to 30,000 and 1,000 to 7, respectively. 000.

In the above embodiment (1-2), the monomer (m3) is preferably the above (meth) acrylic acid alkyl ester compound and / or an aromatic vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited. Moreover, it is preferable that a monomer (m4) contains 80 mass% or more of the polymerizable unsaturated compound which has an amino group with respect to the whole monomer (m4). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds.
In addition, the usage ratio of the monomers (m3) and (m4) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 50 to 99% by mass and 1 to 50% by mass, preferably 70 to 95% by mass and 5 to 30% by mass.

In the polymerization of the monomer (m3), the amount of the living radical polymerization initiator used is preferably 0.3 to 10 parts by mass, more preferably 100 parts by mass with respect to the total amount of the monomer (m3). 1 to 6 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m3) is 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m4) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-2), the polymer block having one carboxyl group derived from the monomer (m3), and the monomer (m4), The Mn of the polymer block having two or more amino groups is preferably 1,000 to 45,000 and 500 to 10,000, more preferably 3,000 to 30,000 and 1,000 to 7, respectively. 000.

  In the above aspect (1-3), the monomer (m5) is preferably the above (meth) acrylic acid alkyl ester compound and / or an aromatic vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited. In the monomer (m6), the total amount of the polymerizable unsaturated compound having an amino group and the polymerizable unsaturated compound having a carboxyl group is 80% by mass or more based on the entire monomer (m6). It is preferable that Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. In addition, the use ratio of the polymerizable unsaturated compound which has an amino group, and the polymerizable unsaturated compound which has a carboxyl group is not specifically limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 40 to 95% by mass and 5 to 60% by mass, preferably 50 to 90% by mass and 10 to 50% by mass.

In the above aspect (1-3), the use ratio of the monomers (m5) and (m6) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 50 to 99% by mass and 1 to 50% by mass, preferably 70 to 95% by mass and 5 to 30% by mass.
In the polymerization of the monomer (m5), the amount of the living radical polymerization initiator used is preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer (m5). Preferably it is 1-6 mass parts.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m5) is 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m6) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-3), the polymer block having one carboxyl group derived from the monomer (m5), and the monomer (m6), The Mn of the polymer block having two or more carboxyl groups and amino groups is preferably 1,000 to 45,000 and 500 to 10,000, more preferably 3,000 to 30,000 and 1,000, respectively. ~ 7,000.

In said aspect (1-4), it is preferable that a monomer (m7) contains 80 mass% or more of the polymerizable unsaturated compound which has an amino group with respect to the whole monomer (m7). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. Further, the monomer (m8) does not include a polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group, and preferably the (meth) acrylic acid alkyl ester compound and / or aromatic. Vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited.
In addition, the usage ratio of the monomers (m7) and (m8) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total amount is 100% by mass, they are usually 1 to 50% by mass and 50 to 99% by mass, preferably 5 to 30% by mass and 70 to 95% by mass.

In the polymerization of the monomer (m7), the amount of the living radical polymerization initiator used is preferably 5 to 80 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer (m7). 50 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m7) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m8) is preferably 90 ° C to 150 ° C, more preferably 90 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-4), a polymer block having one carboxyl group and a plurality of amino groups derived from the monomer (m7), and the monomer (m8) Mn of the polymer block consisting of a structural unit having no amino group and carboxyl group derived from) is preferably 500 to 10,000 and 1,000 to 45,000, more preferably 1,000 to 7, respectively. , 3,000 and 3,000 to 30,000.

In the case of the above embodiment (1-5), in the monomer (m9), the total amount of the polymerizable unsaturated compound having an amino group and the polymerizable unsaturated compound having a carboxyl group is the entire monomer (m9). It is preferable that it is 80 mass% or more. Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. In addition, the use ratio of the polymerizable unsaturated compound which has an amino group, and the polymerizable unsaturated compound which has a carboxyl group is not specifically limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 40 to 95% by mass and 5 to 60% by mass, preferably 50 to 90% by mass and 10 to 50% by mass. In addition, the monomer (m10) does not include a polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group, and is preferably the (meth) acrylic acid alkyl ester compound and / or aromatic. Vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited.
In addition, the use ratio of the monomers (m9) and (m10) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total amount is 100% by mass, they are usually 1 to 50% by mass and 50 to 99% by mass, preferably 5 to 30% by mass and 70 to 95% by mass.

In the polymerization of the monomer (m9), the amount of the living radical polymerization initiator used is preferably 5 to 80 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer (m9). 50 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m9) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m10) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above embodiment (1-5), a polymer block having two or more carboxyl groups and amino groups derived from the monomer (m9), and the monomer (m10) Mn of the polymer block consisting of a structural unit having no amino group and carboxyl group derived from) is preferably 500 to 10,000 and 1,000 to 45,000, more preferably 1,000 to 7, respectively. , 3,000 and 3,000 to 30,000.

In said aspect (1-6), it is preferable that a monomer (m11) contains 80 mass% or more of the polymerizable unsaturated compound which has a carboxyl group with respect to the whole monomer (m11). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. Further, the monomer (m12) does not include a polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group, and preferably the (meth) acrylic acid alkyl ester compound and / or aromatic. Vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited.
In addition, the usage ratio of the monomers (m11) and (m12) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total amount is 100% by mass, they are usually 1 to 50% by mass and 50 to 99% by mass, preferably 5 to 30% by mass and 70 to 95% by mass.

In the polymerization of the monomer (m11), the amount of the living radical polymerization initiator used is preferably 5 to 80 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer (m11). 50 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m11) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m12) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-6), the polymer block having two or more carboxyl groups derived from the monomer (m11), and the monomer (m12) Mn of the polymer block consisting of a structural unit having no amino group and carboxyl group is preferably 500 to 10,000 and 1,000 to 45,000, more preferably 1,000 to 7,000, respectively. 3,000 to 30,000.

In said aspect (1-7), it is preferable that a monomer (m13) contains 80 mass% or more of the polymerizable unsaturated compound which has a carboxyl group with respect to the whole monomer (m13). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. Moreover, it is preferable that a monomer (m14) contains 80 mass% or more of the polymerizable unsaturated compound which has an amino group with respect to the whole monomer (m14). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds.
In addition, the usage ratio of the monomers (m13) and (m14) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 40 to 90% by mass and 10 to 60% by mass, preferably 60 to 80% by mass and 20 to 40% by mass.

In the polymerization of the monomer (m13), the amount of the living radical polymerization initiator used is preferably 5 to 80 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer (m13). 50 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m13) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m14) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-7), the polymer block having two or more carboxyl groups derived from the monomer (m13), and the monomer (m14) The Mn of the polymer block having an amino group is preferably 1,000 to 45,000 and 500 to 10,000, more preferably 3,000 to 30,000 and 1,000 to 7,000, respectively. is there.

In the case of the above embodiment (1-8), in the monomer (m15), the total amount of the polymerizable unsaturated compound having an amino group and the polymerizable unsaturated compound having a carboxyl group is the whole of the monomer (m15). It is preferable that it is 80 mass% or more. Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. In addition, the use ratio of the polymerizable unsaturated compound which has an amino group, and the polymerizable unsaturated compound which has a carboxyl group is not specifically limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 40 to 95% by mass and 5 to 60% by mass, preferably 50 to 90% by mass and 10 to 50% by mass. Further, the monomer (m16) does not include a polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group, and preferably the (meth) acrylic acid alkyl ester compound and / or aromatic. Vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited.
In addition, the usage ratio of the monomers (m15) and (m16) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total amount is 100% by mass, they are usually 1 to 50% by mass and 50 to 99% by mass, preferably 5 to 30% by mass and 70 to 95% by mass.

In the polymerization of the monomer (m15), the amount of the living radical polymerization initiator used is preferably 5 to 80 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer (m15). 50 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m15) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m16) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-8), a polymer block having two or more carboxyl groups and amino groups derived from the monomer (m15), and the monomer (m16) Mn of the polymer block consisting of a structural unit having no amino group and carboxyl group derived from) is preferably 500 to 10,000 and 1,000 to 45,000, more preferably 1,000 to 7, respectively. , 3,000 and 3,000 to 30,000.

In said aspect (1-9), it is preferable that a monomer (m17) contains the polymerizable unsaturated compound which has a carboxyl group 80 mass% or more with respect to the whole monomer (m17). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. In addition, the monomer (m18) does not include a polymerizable unsaturated compound having an amino group and a polymerizable unsaturated compound having a carboxyl group, and is preferably the above (meth) acrylic acid alkyl ester compound and / or aromatic. Vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited.
In addition, the usage ratio of the monomers (m17) and (m18) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total amount is 100% by mass, they are usually 1 to 50% by mass and 50 to 99% by mass, preferably 5 to 30% by mass and 70 to 95% by mass.

In the polymerization of the monomer (m17), the amount of the living radical polymerization initiator used is preferably 5 to 80 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer (m17). 50 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m17) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m18) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-9), the polymer block having two or more carboxyl groups derived from the monomer (m17) and the monomer (m18) Mn of the polymer block consisting of a structural unit having no amino group and carboxyl group is preferably 500 to 10,000 and 1,000 to 45,000, more preferably 1,000 to 7,000, respectively. 3,000 to 30,000.

In said aspect (1-10), it is preferable that a monomer (m19) contains 80 mass% or more of the polymerizable unsaturated compound which has a carboxyl group with respect to the whole monomer (m19). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. Moreover, it is preferable that a monomer (m20) contains 80 mass% or more of the polymerizable unsaturated compound which has an amino group with respect to the whole monomer (m20). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds.
In addition, the usage ratio of the monomers (m19) and (m20) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 40 to 80% by mass and 20 to 60% by mass, preferably 60 to 80% by mass and 20 to 40% by mass.

In the polymerization of the monomer (m19), the amount of the living radical polymerization initiator used is preferably 0.3 to 10 parts by mass, more preferably 100 parts by mass based on the total amount of the monomer (m19). 1 to 8 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m19) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m20) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-10), the polymer block having two or more carboxyl groups derived from the monomer (m19), and the monomer (m20) The Mn of the polymer block having an amino group is preferably 1,000 to 45,000 and 500 to 10,000, more preferably 3,000 to 30,000 and 1,000 to 7,000, respectively. is there.

In said aspect (1-11), it is preferable that a monomer (m21) contains the polymerizable unsaturated compound which has an amino group 80 mass% or more with respect to the whole monomer (m21). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. Moreover, it is preferable that a monomer (m20) contains 80 mass% or more of the polymerizable unsaturated compound which has a carboxyl group with respect to the whole monomer (m22). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds.
In addition, the usage-ratio of a monomer (m21) and (m22) is not specifically limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 10 to 60% by mass and 40 to 90% by mass, preferably 20 to 40% by mass and 60 to 80% by mass.

In the polymerization of the monomer (m21), the amount of the living radical polymerization initiator used is preferably 5 to 90 parts by mass, more preferably 10 to 10 parts by mass with respect to 100 parts by mass of the total amount of the monomer (m21). 50 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m21) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m22) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above embodiment (1-11), a polymer block having an amino group derived from the monomer (m21) and two derived from the monomer (m22) Mn of the polymer block having the above carboxyl group is preferably 500 to 10,000 and 1,000 to 45,000, more preferably 1,000 to 7,000 and 3000 to 30,000, respectively.

In the above embodiment (1-12), the monomer (m23) is preferably the above (meth) acrylic acid alkyl ester compound and / or an aromatic vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited. Moreover, it is preferable that a monomer (m24) contains 80 mass% or more of the polymerizable unsaturated compound which has a carboxyl group with respect to the whole monomer (m24). Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds.
In addition, the usage ratio of the monomers (m23) and (m24) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 50 to 99% by mass and 1 to 50% by mass, preferably 70 to 95% by mass and 5 to 30% by mass.

In the polymerization of the monomer (m23), the amount of the living radical polymerization initiator used is preferably 0.3 to 10 parts by mass, more preferably 100 parts by mass relative to the total amount of the monomer (m23). 1 to 6 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m23) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m24) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above embodiment (1-12), the polymer block derived from the monomer (m23) and having no carboxyl group and amino group, and the monomer (m2) The Mn of the polymer block having two or more carboxyl groups derived from is preferably 1,000 to 45,000 and 500 to 10,000, more preferably 3,000 to 30,000 and 1,000, respectively. ~ 7,000.

  In the above embodiment (1-13), the monomer (m25) is preferably the above (meth) acrylic acid alkyl ester compound and / or an aromatic vinyl compound. When using the said (meth) acrylic-acid alkylester compound and an aromatic vinyl compound together, the use ratio is not specifically limited. In the monomer (m26), the total amount of the polymerizable unsaturated compound having an amino group and the polymerizable unsaturated compound having a carboxyl group is 80% by mass or more based on the entire monomer (m26). It is preferable that Examples of other monomers include the above (meth) acrylic acid alkyl ester compounds and aromatic vinyl compounds. In addition, the use ratio of the polymerizable unsaturated compound which has an amino group, and the polymerizable unsaturated compound which has a carboxyl group is not specifically limited. From the viewpoint of dispersibility of pigments and the like, when the total amount is 100% by mass, they are usually 40 to 95% by mass and 5 to 60% by mass, preferably 50 to 90% by mass and 10 to 50% by mass.

  In the above aspect (1-13), the use ratio of the monomers (m25) and (m26) is not particularly limited. From the viewpoint of dispersibility of pigments and the like, when the total of these is 100% by mass, they are usually 50 to 99% by mass and 1 to 50% by mass, preferably 70 to 95% by mass and 5 to 30% by mass.

In the polymerization of the monomer (m25), the amount of the living radical polymerization initiator used is preferably 0.3 to 10 parts by mass, more preferably 100 parts by mass with respect to the total amount of the monomer (m25). 1 to 6 parts by mass.
Polymerization solvents include cyclic ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; acetate esters such as ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and cyclohexanone; methyl orthoformate and ortho Orthocarboxylic acid esters such as methyl acetate; alcohols such as methanol, ethanol and isopropanol are preferred. These solvents may be used alone or in combination of two or more.
The polymerization temperature of the monomer (m25) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C. The polymerization temperature of the monomer (m26) is preferably 90 ° C to 150 ° C, more preferably 105 ° C to 130 ° C.

  In the copolymer obtained by the above aspect (1-13), the polymer block derived from the monomer (m25) and having no carboxyl group and amino group, and the monomer (m2) The Mn of the polymer block having two or more carboxyl groups and amino groups derived from is preferably 1,000 to 45,000 and 500 to 10,000, more preferably 3,000 to 30,000, respectively. 1,000 to 7,000.

  In the above embodiments (1-1) to (1-13), the polymerizable unsaturated compound having an amino group includes 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, dimethylamino. Propyl (meth) acrylamide and the like are preferable. As the polymerizable unsaturated compound having a carboxyl group, a compound represented by the above general formula (2), (meth) acrylic acid and the like are preferable. Moreover, as said (meth) acrylic-acid alkylester compound, isobutyl acrylate, isobutyl methacrylate, methyl acrylate, methyl methacrylate, benzyl methacrylate, etc. are preferable.

  In the present invention, the second step is a monomer having a functional group that reacts with a carboxyl group of the block copolymer and an active energy ray-curable functional group in the block copolymer obtained in the first step. Thus, the block copolymer (A) according to the present invention, that is, the dispersant of the present invention can be produced.

The functional group that reacts with the carboxyl group is preferably an epoxy group. Therefore, a polymerizable unsaturated compound having an epoxy group can be used as the monomer having a functional group that reacts with a carboxyl group and an active energy ray-curable functional group.
Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, 3-methyl-3 (meth) acrylate, 4-epoxybutyl, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 2,3-epoxycyclohexylmethyl (meth) acrylate, (Meth) acrylic acid 3,4-epoxycyclohexylmethyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 2-vinylcyclohexene oxide, 3-vinylcyclohexene oxide, 4-vinylcyclohexene Oxide, Allyl Glycidi And ruether. These can be used alone or in combination of two or more. Of these compounds, glycidyl (meth) acrylate is preferred.

  The usage-amount of the polymerizable unsaturated compound which has the said epoxy group is selected by the molar concentration of the carboxyl group which the block copolymer obtained by the 1st process has. In this second step, all the carboxyl groups may be eliminated or an arbitrary number may remain. However, when the block copolymer obtained in the first step has a carboxyl group and does not have an amino group, in the second step, a polymerization having an epoxy group so that at least one carboxyl group remains. The amount of the unsaturated compound used is selected.

The reaction in the second step may be performed in the presence of a medium or in the absence. Moreover, in this 2nd process, since the polymerizable unsaturated compound which has an epoxy group is used, it is preferable to use a polymerization inhibitor together. Examples of the polymerization inhibitor include phenol compounds such as hydroquinone, methyl hydroquinone, ethyl hydroquinone, tert-butyl hydroquinone, hydroquinone methyl ether, hydroquinone ethyl ether, di-tert-butyl-p-cresol, catechol, tert-butyl catechol; phenothiazine And nitrogen-containing compounds such as diphenylamine. These can be used alone or in combination of two or more.
The usage-amount of the said polymerization inhibitor is 0.01-1 mass part normally with respect to 100 mass parts of polymerizable unsaturated compounds which have an epoxy group.

  As described above, depending on the structure of the block copolymer obtained in the first step, and depending on the amount of the polymerizable unsaturated compound having an epoxy group used in the second step, the amino group and A block copolymer (A) having various arrangements of carboxyl groups can be produced.

  In the first step, when a block copolymer having one or more amino groups and one carboxyl group is produced, one or more amino groups and one active energy ray-curable functional group are produced by the second step. The block copolymer (A) which has can be manufactured.

Specific examples of the block copolymer (A) obtained by the production method of the present invention are as follows.
In the first step, when a block copolymer having one or more amino groups and one carboxyl group is produced, one or more amino groups and one active energy ray-curable functional group are produced by the second step. The block copolymer (A1-1) which has can be manufactured.
In the first step, when a block copolymer having one or more amino groups and two or more (x) carboxyl groups is produced, one or more amino groups, s Block copolymer (A1-2) having 1 (1 ≦ s ≦ x-1) active energy ray-curable functional groups and (xs) carboxyl groups, or one or more amino groups and x A block copolymer (A1-3) having one active energy ray-curable functional group and no carboxyl group can be produced.
Furthermore, in the first step, when the first block copolymer having two or more (x) carboxyl groups is produced, the second step performed so that at least one carboxyl group remains, s A block copolymer (A1-4) having 1 (1 ≦ s ≦ x−1) active energy ray-curable functional groups and (xs) carboxyl groups can be produced.

In the block copolymer (A1-1), when one polymer block has one or more amino groups, the polymer block is the above-mentioned book regardless of the presence or absence of the active energy ray-curable functional group. It corresponds to the polymer block (X) constituting the block copolymer (A) according to the invention, and the other polymer block corresponds to the polymer block (Y). And the block copolymer provided with the polymer block which contains one or more amino groups and active energy ray hardening functional groups simultaneously is an example of the said aspect [1]. A block copolymer containing one or more amino groups and an active energy ray-curable functional group in different polymer blocks is an example of the above aspect [7].
In the block copolymer (A1-2), when one polymer block has one or more amino groups, the polymer block is present regardless of the presence or absence of a carboxyl group and an active energy ray-curable functional group. These correspond to the polymer block (X) constituting the block copolymer (A) according to the present invention, and the other polymer blocks correspond to the polymer block (Y). And this block copolymer (A1-2) is an example of the said aspect [3], [4], [6], and [9].
In the block copolymer (A1-3), when one polymer block has one or more amino groups, the polymer block is the above-mentioned book regardless of the presence or absence of the active energy ray-curable functional group. It corresponds to the polymer block (X) constituting the block copolymer (A) according to the invention, and the other polymer block corresponds to the polymer block (Y). And the block copolymer provided with the polymer block which contains an at least 1 amino group and an active energy ray hardening functional group simultaneously is an example of the said aspect [1] and [4]. A block copolymer containing one or more amino groups and an active energy ray-curable functional group in different polymer blocks is an example of the above aspect [7].
Moreover, in the said block copolymer (A1-4), when the density | concentration of the carboxyl group contained in one polymer block is higher than the density | concentration of the carboxyl group contained in the other polymer block, the polymer block is The polymer block (X) constituting the block copolymer (A) according to the present invention, regardless of the presence or absence of the active energy ray-curable functional group, corresponds to the polymer block (X). Y). This block copolymer (A1-4) is an example of the above embodiments [2], [5] and [8].

  According to the present invention, a block copolymer (A) having an Mn of preferably 2,000 to 70,000 and a polydispersity of preferably 3 or less can be produced efficiently.

As described above, the dispersant of the present invention can be dissolved or dispersed in an organic solvent.
For example, a step of mixing the block copolymer (A) obtained in the second step with an organic solvent or the like can be further provided. In this step, a known mixing apparatus can be used, and heating or the like may be performed as necessary.
Also, the block copolymer (A) obtained in the second step is reacted with an organic halide such as epichlorohydrin, methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, benzyl bromide, methyl iodide, etc. The process of making it further can be provided.

The dispersant of the present invention is a block copolymer containing a polymer block having an amino group and / or a carboxyl group and a hydroxyl group in the presence of the living radical polymerization initiator represented by the general formula (1). After the combination is produced, the block copolymer can also be produced by a method in which a monomer having a functional group that reacts with the hydroxyl group of the block copolymer and an active energy ray-curable functional group is reacted. .
In this production method, the functional group that reacts with a hydroxyl group is preferably an isocyanate group.
As the polymerizable unsaturated compound having a hydroxyl group, the compounds exemplified above can be used.
Examples of the polymerizable unsaturated compound having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 3- (meth) acryloyloxypropyl isocyanate. These may be used alone or in combination of two or more. Can be used.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to this Example, unless the main point of this invention is exceeded. In the following, “part” and “%” are based on mass unless otherwise specified.

その後、このＩＢＡマクロ開始剤６．７ｇ、メタクリル酸ジメチルアミノエチル（以下、「ＤＭＡ」ともいう）１．１ｇ、下記式により表される東亞合成社製ω−カルボキシポリカプロラクトンモノアクリレート（商品名「アロニックス Ｍ５３００」、以下、「ＣＰＬＡ」という）２．１ｇ及び酢酸ブチル１０．０ｇを混合した。そして、この混合物を容量１００ミリリットルのナスフラスコに仕込み、窒素ガスにより十分にバブリングさせ、脱気した。次いで、上記混合物を攪拌しながら、１１２℃に昇温し、重合を開始した。３時間反応させた後、ＤＭＡ及びＣＰＬＡの重合率を測定したところ、それぞれ、９２％及び８３％であった。そして、得られた重合体分散液（約２０ｇ）を、８００ｇのヘプタン中に投入して、ブロック共重合体を再沈殿させ、上澄み液をデカンテーションした。その後、沈殿物を回収し、６０℃で２４時間真空乾燥させることにより、アミノ基及びカルボキシル基を有するブロック共重合体（ａ１）を得た。

〔式中、ｎ＝２である。〕 1. Production of Dispersant Example 1 (Production of Dispersant Containing Block Copolymer Comprising Polymer Block Having Amino Group and Carboxyl Group)
27.6 g of isobutyl acrylate (hereinafter also referred to as “IBA”), 0.6 g of a living radical polymerization initiator represented by the following formula, and 11.8 g of butyl acetate were mixed. Thereafter, this mixture was charged into a eggplant flask having a capacity of 100 ml, sufficiently bubbled with nitrogen gas, and deaerated. Next, while stirring the above mixture, the temperature was raised to 112 ° C. to initiate polymerization. After reacting for 6 hours, the polymerization rate of IBA was measured and found to be 76%. And the remaining IBA and butyl acetate contained in the obtained polymer dispersion liquid were distilled off by evaporation. Thereby, an IBA macroinitiator having a carboxyl group was obtained. This IBA macroinitiator has a GPC number average molecular weight (Mn) of 12,270 and a dispersity represented by a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 1. 28.

Thereafter, 6.7 g of this IBA macroinitiator, 1.1 g of dimethylaminoethyl methacrylate (hereinafter also referred to as “DMA”), ω-carboxypolycaprolactone monoacrylate (trade name “Made by Toagosei Co., Ltd.” represented by the following formula: Aronix M5300 ”(hereinafter referred to as“ CPLA ”) 2.1 g and butyl acetate 10.0 g were mixed. Then, this mixture was charged into a eggplant flask having a capacity of 100 ml, sufficiently bubbled with nitrogen gas, and deaerated. Next, while stirring the above mixture, the temperature was raised to 112 ° C. to initiate polymerization. After reacting for 3 hours, the polymerization rates of DMA and CPLA were measured and found to be 92% and 83%, respectively. The obtained polymer dispersion (about 20 g) was put into 800 g of heptane to reprecipitate the block copolymer, and the supernatant liquid was decanted. Thereafter, the precipitate was collected and vacuum-dried at 60 ° C. for 24 hours to obtain a block copolymer (a1) having an amino group and a carboxyl group.

[Wherein n = 2. ]

  The composition of the block copolymer (a1) was IBA / DMA / CPLA = 71/11/18 (%). Moreover, Mn was 17,400.

  Next, 5 g of the block copolymer (a1), 0.082 g of glycidyl methacrylate, 5 g of butyl acetate and 0.0015 g of hydroquinone monomethyl ether were charged into an eggplant flask having a capacity of 100 ml. Thereafter, air was blown into the flask, the temperature was raised to 110 ° C. while stirring, the reaction was allowed to proceed for 5 hours, and the nonvolatile content was removed by evaporation. The reaction rate of glycidyl methacrylate calculated based on the reduction rate of the acid value was 99%. Moreover, the block copolymer (A1) by which 19% was converted into the double bond by the glycidyl methacrylate among this carboxyl group based on the CPLA unit in the said block copolymer (a1) by this reaction was obtained. This block copolymer (A1) has a polymer block derived from IBA and a polymer block derived from DMA and CPLA and having an amino group and a carboxyl group, and contains an active energy ray-curable functional group. It is a block copolymer. The amino group and carboxyl group concentrations per gram of the block copolymer (A1) are 0.75 meq and 0.49 meq, respectively, and the content of the active energy ray-curable functional group is 0 in terms of double bond equivalent. .11 meq. Moreover, Mw and Mn by GPC were 26,300 and 17,500, respectively.

  The dispersant containing the block copolymer (A1) was produced as follows. First, 2.25 g of the block copolymer (A1) was dissolved in 13.9 g of propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMAC”). Thereafter, 0.21 g of benzyl chloride was added, and this mixture was heated to 85 ° C. with stirring to be reacted. A dispersant solution (D1) having a solid content concentration of about 15% was obtained.

Example 2 (Production of a dispersant containing a block copolymer having a polymer block having an amino group)
405.8 g of IBA, 12.1 g of the above living radical polymerization initiator, and 173.9 g of butyl acetate were mixed. Thereafter, this mixture was charged into a 1-liter separable flask, sufficiently bubbled with nitrogen gas, and degassed. Next, while stirring the above mixture, the temperature was raised to 112 ° C. to initiate polymerization. After reacting for 6 hours, the polymerization rate of IBA was measured and found to be 99%. And the remaining IBA and butyl acetate contained in the obtained polymer dispersion liquid were distilled off by evaporation. Thereby, an IBA macroinitiator having a carboxyl group was obtained. This IBA macroinitiator had a Mn of 9,750 and a Mw / Mn of 1.52.
Thereafter, 11.8 g of this IBA macroinitiator, 3.2 g of DMA, and 10.3 g of butyl acetate were mixed. This mixture was charged into a eggplant flask having a capacity of 100 ml, sufficiently bubbled with nitrogen gas, and degassed. Next, while stirring the above mixture, the temperature was raised to 112 ° C. to initiate polymerization. After reacting for 3 hours, the polymerization rate of DMA was measured and found to be 71%. And the block copolymer (a2) which has an amino group and a carboxyl group was obtained by vacuum-drying the obtained polymer dispersion liquid at 140 degreeC for 24 hours.

  The composition of the block copolymer (a2) was IBA / DMA = 84/16 (%). Moreover, Mn was 11,640.

  Next, 10 g of the block copolymer (a2), 0.12 g of glycidyl methacrylate, 10 g of butyl acetate and 0.0015 g of hydroquinone monomethyl ether were charged into an eggplant flask having a capacity of 100 ml. Thereafter, air was blown into the flask, the temperature was raised to 110 ° C. while stirring, the reaction was allowed to proceed for 5 hours, and the nonvolatile content was removed by evaporation. The reaction rate of glycidyl methacrylate calculated based on the reduction rate of the acid value was 99%. Moreover, the block copolymer (A2) by which the carboxyl group couple | bonded with the terminal of the IBA unit in the said block copolymer (a2) was converted into the double bond with the glycidyl methacrylate by this reaction was obtained. This block copolymer (A2) is a block copolymer having a polymer block derived from IBA and a polymer block derived from DMA and having an amino group and containing an active energy ray-curable functional group. is there. The amino group concentration per gram of the block copolymer (A2) was 1.1 meq, and the content of the active energy ray-curable functional group was 0.086 meq in terms of double bond equivalent. Moreover, Mw and Mn by GPC were 18,500 and 12,300, respectively.

  The dispersant containing the block copolymer (A2) was produced as follows. First, 2.25 g of the block copolymer (A2) was dissolved in 13.9 g of propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMAC”). Thereafter, 0.31 g of benzyl chloride was added, and this mixture was heated to 85 ° C. with stirring to be reacted. And the dispersing agent solution (D2) of solid content concentration about 15% was obtained.

Example 3 (Production of a dispersant containing a block copolymer having a polymer block having an amino group and a carboxyl group)
6.1 g of dimethylaminoethyl acrylate (hereinafter also referred to as “DA”), 12.7 g of CPLA, 1.2 g of the above living radical polymerization initiator, and 20.0 g of butyl acetate were mixed. Thereafter, this mixture was charged into a separable flask having a capacity of 300 ml, sufficiently bubbled with nitrogen gas, and deaerated. Next, while stirring the above mixture, the temperature was raised to 112 ° C. to initiate polymerization. After reacting for 6 hours, the polymerization rates of DA and CPLA were measured to be 93% and 96%, respectively. Further, 41.6 g of IBA and 82.7 g of butyl acetate were added and reacted at 112 ° C. for 6 hours. The polymerization rates of DA, CPLA and IBA at this point were 99%, 99% and 85%, respectively. Thereafter, the obtained polymer dispersion (about 160 g) was put into 2,500 g of heptane to reprecipitate the block copolymer, and the supernatant was decanted. Next, the precipitate was collected and vacuum-dried at 60 ° C. for 24 hours to obtain a block copolymer (a3) having an amino group and a carboxyl group.

  The composition of the block copolymer (a3) was DA / CPLA / IBA = 11/23/66 (%). Moreover, Mn was 16,360.

  Next, 50 g of the block copolymer (a3), 0.88 g of glycidyl methacrylate, 50 g of butyl acetate and 0.0015 g of hydroquinone monomethyl ether were charged into a eggplant flask having a capacity of 300 ml. Thereafter, air was blown into the flask, the temperature was raised to 110 ° C. while stirring, the reaction was allowed to proceed for 5 hours, and the nonvolatile content was removed by evaporation. The reaction rate of glycidyl methacrylate calculated based on the reduction rate of the acid value was 99%. Moreover, the block copolymer (A3) by which 16% was converted into the double bond by the glycidyl methacrylate among this carboxyl group based on the CPLA unit in the said block copolymer (a3) by this reaction was obtained. This block copolymer (A3) has a polymer block derived from IBA and a polymer block derived from DMA and CPLA and having an amino group and a carboxyl group, and contains an active energy ray-curable functional group. It is a block copolymer. The amino group and carboxyl group concentrations per 1 g of this block copolymer (A3) are 0.83 meq and 0.64 meq, respectively, and the content of the active energy ray-curable functional group is 0 in terms of double bond equivalent. .12 meq. Moreover, Mw and Mn by GPC were 24,800 and 16,500, respectively.

  The dispersant containing the block copolymer (A3) was produced as follows. First, 2.25 g of the block copolymer (A3) was dissolved in 13.9 g of propylene glycol monomethyl ether acetate (hereinafter also referred to as “PGMAC”). Thereafter, 0.23 g of benzyl chloride was added, and this mixture was heated to 85 ° C. with stirring to be reacted. And the dispersing agent solution (D3) of solid content concentration about 15% was obtained.

Comparative Example 1 (Production of a dispersant containing a graft copolymer having an active energy ray-curable functional group in the trunk and an amino group in the branch)
First, 95.28 parts of propylene glycol monomethyl ether acetate was charged into a flask and heated at 93 ° C. with stirring. Thereafter, under a nitrogen stream, a mixed solution (r) of 1.0 part of azobismethylisobutyronitrile and 30 parts of propylene glycol monomethyl ether acetate was added over 5 hours, and at the same time, 84 parts of benzyl methacrylate, N, N- Polymerization was performed by adding a mixed solution (s) of 16 parts of dimethylaminoethyl methacrylate and 1.5 parts of 3-mercaptopropionic acid over 3 hours. After completion of the addition of the mixed solution (r), the polymerization was completed while stirring at the same temperature for 2 hours to obtain a polymer (a41) (total mass including solvent: 227.78 parts). As a result of analyzing the polymer (a41), Mw and Mn by GPC are 4,400 and 2,100, respectively, and the acid value of the solution has a carboxyl group at one end of 0.060 meq / g. It was a polymer.
Next, the reaction system containing the polymer (a41) was switched to air bubbling, and continuously in the same flask, 2.21 parts of glycidyl methacrylate, 0.046 parts of methoxyphenol, and 2.28 parts of dimethylbenzylamine as a catalyst. Then, 2.71 parts of propylene glycol monomethyl ether acetate was added and reacted at 110 ° C. with stirring for 6 hours. The acid value of the reaction product (a42) thus obtained (total mass 235.03 parts including the solvent) was measured and found to be 0.001 meq / g or less, and the acid reaction rate was 98% or more. Ended.
Thereafter, as a result of analysis of the reaction product (a42), Mw and Mn by GPC were 4,650 and 2,200, respectively, and an amino group (N, N-dimethylaminoethyl group) was removed. It was a macromonomer having in the molecular chain and having a methacryloyl group at one end.
The solution containing the macromonomer (a42) was heated at 200 ° C. for 20 minutes to remove volatile components, and the solid content was measured and found to be 44.7%.
Next, 66.67 parts of the above macromonomer (a42) solution, 20.33 parts of methyl methacrylate and 57.44 parts of propylene glycol monomethyl ether acetate were charged into a flask and heated at 85 ° C. with stirring. , 40.67 parts of methyl methacrylate, 9 parts of methacrylic acid and 0.5 part of 3-mercaptopropionic acid were added over 3 hours, and at the same time, 1 part of azobismethylisobutyronitrile and propylene glycol monomethyl ether acetate Polymerization was carried out by adding 29.33 parts of the mixed solution over 5 hours. Thereafter, the temperature is raised to 110 ° C. and held for 1 hour to complete the polymerization, and contains a graft copolymer (a43) having a polymer having a carboxyl group as a trunk and a polymer having an amino group as a branch. (Total polymerization time 6.5 hours, total mass including solvent, 224.94 parts). When the acid value of the solution containing this graft copolymer (a43) was measured, it was 0.485 meq / g. Moreover, when the GPC analysis of the graft copolymer (a43) was conducted, Mw and Mn were 25,800 and 9,800, respectively.
Thereafter, 15.5 parts of glycidyl methacrylate, 2.25 parts of dimethylbenzylamine, 0.045 parts of methoxyphenol, and 14.80 parts of propylene glycol monomethyl ether acetate were added to the solution of the graft copolymer (a43) while air bubbling. Then, the mixture was heated at 110 ° C. for 6 hours with stirring to add glycidyl methacrylate to the carboxyl group of the graft copolymer (a43). Then, propylene glycol monomethyl ether acetate was further added to the solid content. The concentration was adjusted to 15%. As described above, a light red solution containing a graft copolymer (a44) having a polymer part having an active energy ray-curable functional group (methacryloyl group) as a trunk and a polymer part having an amino group as a branch is obtained. It was. As a result of GPC analysis, Mw and Mn of the graft copolymer (a44) were 26,800 and 10,600, respectively.
Thereafter, 3.86 g of benzyl chloride was added, and this mixture was heated to 85 ° C. with stirring and reacted. And the dispersing agent solution (D4) of solid content concentration about 15% was obtained.

2. Evaluation of Dispersant The dispersant solutions (D1) to (D4) obtained above were evaluated for the dispersibility of the pigment.
6 g of a dispersant solution (solid concentration 15%), 11 g of PGMAC, and 3 g of pigment (phthalocyanine green) are mixed, 40 g of zirconia beads having a diameter of 0.3 mm are added, and dispersed for 1 hour using a paint shaker manufactured by Asada Steel To prepare a pigment dispersion. Thereafter, 0.1 g of the pigment dispersion was diluted with 9.9 g of PGMAC, and the pigment dispersion in each pigment dispersion after being left at 60 ° C. for 24 hours at the initial stage of dispersion using a Microtrac UPA particle size distribution meter manufactured by Nikkiso Co., Ltd. The particle size distribution (50% average particle size) was measured. The results are shown in Table 1.
The comprehensive evaluation in Table 1 is based on the following description.
A: The particle size distribution is 200 nm or less in both the initial stage of dispersion and after standing for 24 hours, and the difference between the two is small.
○: The particle size distribution is 200 nm or less in both the initial stage of dispersion and after standing for 24 hours, and the difference between the two is small, or the initial stage of dispersion is 200 nm or less, and is larger after standing for 24 hours.
X: The particle size distribution is 400 nm or less at the initial stage of dispersion, and is larger after standing for 24 hours.

  The dispersant of the present invention is used in combination with a medium such as an organic solvent, and is cured with active energy rays such as ultraviolet rays and electron beams. Compositions such as inks, paints, adhesives, and photoresist inks, color filters, and dry films It is suitable for preparation of manufacturing raw materials and the like.

Claims (9)

  A polymer block (X) having an amino group and / or a carboxyl group, and a polymer block (Y) having an affinity for the medium higher than that of the polymer block (X) when dissolved or dispersed in the medium; And at least one of the polymer block (X) and the polymer block (Y) contains a block copolymer having an active energy ray-curable functional group.   The dispersant according to claim 1, wherein the active energy ray-curable functional group is at least one of an acryloyl group and a methacryloyl group.   The dispersing agent according to claim 1 or 2, wherein the block copolymer is dissolved in the medium.   The dispersant according to any one of claims 1 to 3, wherein the block copolymer has a number average molecular weight of 2,000 to 70,000.   The dispersant according to any one of claims 1 to 4, which is used as a pigment dispersant. A method for producing a dispersant according to any one of claims 1 to 5,
In the presence of a living radical polymerization initiator represented by the following general formula (1), a first step of producing a block copolymer containing a polymer block having at least the carboxyl group of an amino group and a carboxyl group;
A second step of reacting the block copolymer with a monomer having a functional group that reacts with a carboxyl group of the block copolymer and an active energy ray-curable functional group. Manufacturing method.

[Wherein, R ¹ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ² is an alkyl group having 1 to ² carbon atoms or a nitrile group, and R ³ is — (CH ₂ ) _m — (m Is an integer of 0 to 2.), R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵ is an alkyl group having 1 to 4 carbon atoms independently of each other, and R ⁶ Are each independently an alkyl group having 1 to 4 carbon atoms, and R ⁷ is independently an alkyl group having 1 to 4 carbon atoms. ]   The method for producing a dispersant according to claim 6, wherein the functional group is an epoxy group. The method for producing a dispersant according to claim 6 or 7, wherein the monomer for introducing the carboxyl group into the block copolymer is a compound represented by the following general formula (2).

Wherein, ^{R 8} is a hydrogen atom or a methyl group, may or may not be ^{R 9} is a, if with ^{R 9} is, -C (O) -O -, - OC (O) -, - NH— or —C ₆ H ₄ —, R ¹⁰ is R ¹¹ —O— (R ¹¹ is an alkyl group having 2 to 4 carbon atoms), and R ¹² —C (O) —O— (R ¹² is carbon number) 1-8 alkyl ^{group), R 13 -O-C (} O) -R 14 - (R 13 represents an alkyl group having 1 to 8 carbon ^{atoms, R 14} is an alkyl group having 1 to 8 carbon atoms), - _{C 6} H ₄ — or —CH ₂ ═CH ₂ —, and n is 0 to 4. ]   The method for producing a dispersant according to any one of claims 6 to 8, wherein the active energy ray-curable functional group is at least one of an acryloyl group and a methacryloyl group.