JP5407415B2 - Dispersant, method for producing the same, and pigment composition using the same - Google Patents

Description

  The present invention relates to a dispersant, and more specifically, a dispersant capable of producing a dispersion excellent in dispersibility, fluidity, and stability, which is suitable for the fields of paints and colored resin compositions, and the production thereof. The present invention relates to a method and a pigment composition using the method.

  Generally, when manufacturing ink etc., it is known that it is difficult to disperse | distribute a pigment stably at high concentration, and it is known that it will cause various problems with respect to a manufacturing process or the product itself. For example, dispersions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from the disperser, and if bad, cause gelation during storage and use It can even be difficult. Furthermore, regarding the surface of the color-exposed product, a state defect such as a decrease in gloss and a leveling defect occurs. When different types of pigments are mixed and used, color unevenness due to aggregation or phenomena such as sedimentation may cause uneven color and a marked decrease in coloring power.

  Therefore, in general, a dispersant is used in order to maintain a good dispersion state. The dispersant has a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance between these two functional sites. Various dispersants are used in accordance with the surface state of the pigment to be dispersed, but a basic dispersant is generally used for pigments having an acid-biased surface. In this case, the basic functional group serves as a pigment adsorption site. As a dispersant having an amino group as a basic functional group, for example, a dispersant having polyallylamine or polyethyleneimine is described in Patent Document 1, Patent Document 2, Patent Document 3, and the like.

  However, in Patent Document 1, Patent Document 2, and Patent Document 3, the dispersion ability is maintained, but the side chain is limited, the solvent and binder resin that can be used are limited, and the coating film has poor resistance. Further, Patent Document 4, Patent Document 5, and Patent Document 6 have a certain degree of dispersion ability, but it was necessary to increase the amount of use in order to produce a stable dispersion with low viscosity. However, increasing the amount used is not preferable in view of development in inks, paints, etc., because the resistance of the coating film may be reduced.

Japanese Patent Laid-Open No. 9-169821 Japanese Patent Laid-Open No. 8-143813 JP-A-8-507960 JP-A-1-080434 Japanese Unexamined Patent Publication No. 1-164429 JP-A-10-339949

  An object of this invention is to provide the dispersing agent for obtaining the pigment dispersion which is excellent in the dispersibility, fluidity | liquidity, and storage stability with the low usage-amount, and excellent in the tolerance of a coating film. Furthermore, the present invention is suitable for offset inks, gravure inks, resist inks for color filters, ink jet inks, paints, and colored resin compositions, and the like. The object is to provide a method and a pigment composition using the method.

The problem is
A solvent having a hydroxyl group in one terminal region, which is obtained by radical polymerization of an ethylenically unsaturated monomer (a1) in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule. An affinity vinyl polymer (a), and
An ethylenically unsaturated monomer (b2) containing an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule ), A basic vinyl polymer having a hydroxyl group in one terminal region (b),
An isocyanate group of a polyisocyanate compound (c) having two or more isocyanate groups and a hydroxyl group of the compound (d) having a hydroxyl group containing
This is solved by a dispersing agent obtained by reacting.
In a preferred embodiment of the dispersant according to the present invention, the number average molecular weight of the solvophilic vinyl polymer (a) is 1,000 to 10,000.

In a preferred embodiment of the dispersant according to the present invention, the number average molecular weight of the basic vinyl polymer (b) is 1,000 to 8,000.
In a preferred embodiment of the dispersant according to the present invention, the amine value is 5 to 200 mgKOH / g.

  In a preferred embodiment of the dispersant according to the present invention, the compound (s) having one or two hydroxyl groups and one thiol group in the molecule has two hydroxyl groups and one thiol group in the molecule. It is a compound (s1).

  In a preferred embodiment of the dispersant according to the present invention, the ethylenically unsaturated monomer (a1) includes a monomer (a2) represented by the following general formula (1).

  General formula (1):

[In General Formula (1), R is a linear or branched alkyl group having 1 to 4 carbon atoms. ]
In a preferred embodiment of the dispersant according to the present invention, the amino group of the ethylenically unsaturated monomer (b1) having an amino group is a tertiary amino group.

  In a preferred embodiment of the dispersant according to the present invention, the number average molecular weight of the dispersant is 3,000 to 30,000.

  In a preferred embodiment of the polyester dispersant according to the present invention, the amine value of the dispersant is 5 to 200 mgKOH / g.

  Furthermore, this invention relates to the pigment composition formed by containing the said dispersing agent and a pigment.

  The present invention also relates to the pigment composition, wherein the pigment contains a halogenated zinc phthalocyanine pigment.

  Furthermore, a derivative having one or more kinds of acidic substituents selected from the group consisting of a dye derivative having an acidic substituent, an anthraquinone derivative having an acidic substituent, an acridone derivative having an acidic substituent, and a triazine derivative having an acidic substituent It relates to the pigment composition comprising

In addition, in the presence of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule, a hydroxyl group is formed in one terminal region, which is obtained by radical polymerization of the ethylenically unsaturated monomer (a1). A first step of producing a solvophilic vinyl polymer (a) having:
An ethylenically unsaturated monomer (b2) containing an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule A second step of producing a basic vinyl polymer (b) having a hydroxyl group in one terminal region, which is obtained by radical polymerization of
The hydroxyl group of the compound (d) having a hydroxyl group including the solvophilic vinyl polymer (a) and the basic vinyl polymer (b), and the isocyanate group of the polyisocyanate compound (c) having two or more isocyanate groups A third step of reacting;
The manufacturing method of the dispersing agent containing this.

By using the dispersant of the present invention, it was possible to provide a pigment composition having dispersibility, fluidity and storage stability, which was not obtained conventionally. Furthermore, it is suitable for offset inks, gravure inks, color filter resist inks, ink jet inks, paints, and colored resin compositions, and has excellent dispersibility and fluidity, and has high storage stability and high temporal stability. A dispersion could be provided.

<Dispersant>
In general, a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent as a dispersion medium, and the performance of the dispersant is determined by the balance between these two parts. . That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important.

  The dispersant of the present invention has a structure in which a solvophilic vinyl polymer (a) having a hydroxyl group in one terminal region and a basic vinyl polymer (b) having a hydroxyl group in one terminal region are connected with diisocyanate, That is, it has a structure having a solvent affinity block and a basic block. The basic block having an amino group is excellent in pigment adsorptivity to a pigment surface that is acidic and can be dispersed and stabilized.

Each component of the dispersant of the present invention will be described.
<< Solvent affinity vinyl polymer (a) >>
The precursor of the solvent affinity block in the dispersant of the present invention is a radical of an ethylenically unsaturated monomer in the presence of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule. It is a solvent-affinity vinyl polymer (a) having a hydroxyl group at one end formed by polymerization.

  The number average molecular weight of the solvophilic vinyl polymer (a) is preferably from 1,000 to 10,000, which makes it possible to obtain excellent dispersibility, fluidity, and storage stability with excellent steric repulsion effect. It is. The number average molecular weight of the vinyl polymer (a) is more preferably 2,000 to 8,000, and most preferably 3,000 to 7,000. If it is less than 1,000, the steric repulsion effect due to the solvent affinity block is reduced, which may be undesirable. On the other hand, if it exceeds 10,000, the viscosity of the dispersion may increase, which may be undesirable.

  In the solvophilic vinyl polymer (a), the thiol group of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule acts as a chain transfer agent, and the solvent affinity is obtained via the S atom. Since it is synthesized by introducing the vinyl polymer portion (A), the molecular weight of the vinyl polymer (a) depends on the amount of the compound (s) used relative to the ethylenically unsaturated monomer (a1). It is easy to adjust to the said range, As a result, the affinity to a solvent can also be adjusted suitably.

  The number average molecular weight of the solvophilic vinyl polymer (a) is theoretically calculated as [total weight of ethylenically unsaturated monomer (a1)] / [one or two hydroxyl groups and one thiol group in the molecule. The number of moles of the compound (s) having

[Ethylenically unsaturated monomer (a1)]
As the ethylenically unsaturated monomer (a1), for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as isomyristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol monomethyl Ether (meth) acrylate, polyethylene glycol monomethyl ether lauryl ether ) Acrylate, or polyethylene glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
Styrenes such as styrene or α-methylstyrene; or
As a monomer that can be used in combination with the acrylic monomer,
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
An ethylenically unsaturated monomer having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, or crotonic acid; or
Examples include ethylenically unsaturated monomers having a nitrogen atom that does not have an amino group, such as (meth) acrylamide or (meth) acrylonitrile, but are not limited to these and are used alone or in combination of two or more. can do.

  However, the dispersant of the present invention is characterized by a structure obtained by reacting the hydroxyl group of the solvent-affinity vinyl polymer (a) and the basic vinyl polymer (b) with the isocyanate group of the diisocyanate compound (c). It is not preferable to use an ethylenically unsaturated monomer having a hydroxyl group as the polymerizable unsaturated monomer (a1).

  Further, the dispersant of the present invention has a structure in which a solvent affinity block having a solvophilic vinyl polymer (a) as a precursor and a basic block having a basic vinyl polymer (b) as a precursor are unevenly distributed. As the ethylenically unsaturated monomer (a1) constituting the solvent affinity block, a basic ethylenically unsaturated monomer such as an ethylenically unsaturated monomer having an amino group It is not preferred to use

  In the present invention, among the ethylenically unsaturated monomers (a1) exemplified above, the ethylenically unsaturated monomer (a2) represented by the following general formula (1) is preferably used. The amount of the ethylenically unsaturated monomer (a2) represented by the following general formula (1) is preferably 20% by weight to 100% by weight with respect to the whole ethylenically unsaturated monomer (a1), -70 wt% is more preferred. When the monomer represented by the general formula (1) is used, the solvent affinity is improved and the pigment dispersibility is improved. If it is less than 20% by weight, the effect of improving the solvent affinity may be insufficient.

  General formula (1):

[In General Formula (1), R is a linear or branched alkyl group having 1 to 4 carbon atoms. ]

[Compound (s) having one to two hydroxyl groups and one thiol group in the molecule]
Examples of the compound (s) having one to two hydroxyl groups and one thiol group in the molecule include 1-mercaptoethanol, 2-mercaptoethanol, 1-mercapto-1,1-methanediol, and 1-mercapto. -1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2 -Mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl -1,3-propanediol and the like. In the present invention, since a larger number of pendant carboxylic acids can be formed by reaction with the acid anhydride (c), the compound (s1) having two hydroxyl groups and one thiol group in the molecule It is preferable that 3-mercapto-1,2-propanediol (thioglycerin) is more preferable.

(Amount of compound (s) used)
Using the compound (s) as a chain transfer agent, an ethylenically unsaturated monomer and, optionally, a polymerization initiator are mixed and heated in accordance with the molecular weight of the target vinyl polymer (a). A polymer (a) can be obtained. The compound (s) is preferably bulk polymerized or solution polymerized using 1 to 30 parts by weight with respect to 100 parts by weight of the ethylenically unsaturated monomer (a1), more preferably 1.5 to 15 parts. Parts by weight, more preferably 2 to 11 parts by weight, particularly preferably 5 to 9 parts by weight. If it is less than 1 part by weight, the molecular weight becomes large and the viscosity of the dispersion becomes high, which is not preferable. When it exceeds 30 parts by weight, the molecular weight is decreased, and the steric repulsion effect by the solvent affinity block is decreased, which may not be preferable.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. When the temperature is lower than 40 ° C., the polymerization does not proceed sufficiently.

(Polymerization initiator)
In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, an azo compound and an organic peroxide can be used.
Examples of the azo compounds include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) ), 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazoline-2- Yl) propane] and the like.

  Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

  These polymerization initiators can be used alone or in combination of two or more.

(Polymerization solvent)
In the case of solution polymerization, the polymerization solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used, but is not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more. After completion of the reaction, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

<< Basic vinyl polymer (b) >>
The basic block in the dispersant of the present invention is an ethylenically unsaturated monomer having an amino group in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule. It consists of a basic vinyl polymer (b) having a hydroxyl group in one terminal region, which is obtained by radical polymerization of an ethylenically unsaturated monomer (b2) containing (b1).

  The number average molecular weight of the basic vinyl polymer (b) is preferably 1,000 to 8,000, which makes it possible to obtain excellent dispersibility, fluidity, and storage stability with excellent pigment adsorption. is there. From this viewpoint, the number average molecular weight of the vinyl polymer (b) is more preferably 1,200 to 6,000, and most preferably 2,000 to 4,000. If it is less than 1,000, the pigment adsorbing effect by the basic block is reduced, which may not be preferable. On the other hand, if it exceeds 8000, the viscosity of the dispersion increases, which may be undesirable.

  In the basic vinyl polymer (b), the thiol group of the compound (s) having one or two hydroxyl groups and one thiol group in the molecule acts as a chain transfer agent, and the basic vinyl polymer is bonded via an S atom. The molecular weight of the basic vinyl polymer (b) depends on the amount of the compound (s) used relative to the ethylenically unsaturated monomer (b2). It is easy to adjust to the said range, and the adsorptivity to a pigment can also be adjusted suitably.

  The number average molecular weight of the basic vinyl polymer (b) is [total weight of ethylenically unsaturated monomer (b2)] / [compound having 1 to 2 hydroxyl groups and 1 thiol group in the molecule ( The number of moles of s)].

[Ethylenically unsaturated monomer having amino group (b1)]
As the ethylenically unsaturated monomer (b1) having an amino group contained at least in the ethylenically unsaturated monomer (b2),
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
N-substituted (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine It is done.
In the present invention, from the viewpoint of pigment adsorptivity, the amino group is preferably a tertiary amino group.

  As the ethylenically unsaturated monomer (b2), an ethylenically unsaturated monomer (b3) having no amino group can be used in addition to the ethylenic unsaturated (b1) having an amino group. . As the ethylenically unsaturated monomer (b3) having no amino group, the monomers mentioned as the ethylenically unsaturated monomer (a1) used for the synthesis of the solvent-affinity vinyl polymer (a) The same thing is mentioned. As the ethylenically unsaturated monomer (b3), the same monomer as the ethylenically unsaturated monomer (a1) or a different monomer may be used. Further, the ethylenically unsaturated monomer (a2) represented by the following general formula (1) may or may not be used as the ethylenically unsaturated monomer (b3).

  General formula (1):

[In General Formula (1), R is a linear or branched alkyl group having 1 to 4 carbon atoms. ]

  In the present invention, the amount of the ethylenically unsaturated monomer (b1) having an amino group is such that the ethylenically unsaturated monomer (b) constituting the basic vinyl polymer (b) having a hydroxyl group at one terminal region ( It is preferably 20% by weight to 100% by weight and more preferably 50% by weight to 100% by weight relative to b2). If it is less than 20% by weight, the pigment adsorbability of the basic block may be undesirably lowered.

  The basic vinyl polymer (b) comprises an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule. It can be obtained by radical polymerization of the ethylenically unsaturated monomer (b2). Examples of the compound (s) used for the synthesis of the basic vinyl polymer (b), the polymerization initiator and the polymerization solvent that can be used as necessary include the same as the solvent-affinity vinyl polymer (a). The reaction conditions such as the amount and the reaction temperature can be selected from the same range, but the compound (c) used in the basic vinyl polymer (b), the amount used, the polymerization initiator, the polymerization solvent, and the reaction temperature can be selected as solvent affinity. May be the same as the conductive vinyl polymer (a), and does not necessarily need to be matched.

<< Polyisocyanate Compound (c) >>
Since the dispersant of the present invention has a polyurethane chain as a main chain and a side chain having a solvophilic block and a basic block, it can be based on a linear polyurethane main chain generated by the reaction of a diol and a diisocyanate. preferable. Accordingly, as the basic polyisocyanate (c) used in the present invention, a diisocyanate compound (d0) having two isocyanates is basically used, and if necessary, for adjusting the molecular weight and the dispersant skeleton, the isocyanate is used. An isocyanate compound having three or more groups is used.

  As the diisocyanate compound (c0) serving as the basis of the polyisocyanate compound (c), conventionally known ones can be used. For example, diisocyanate (c1) having an aromatic group, diisocyanate (c2) having an aliphatic group, Examples thereof include diisocyanate (c3) having an aromatic group and an aliphatic group, or diisocyanate (c4) having an alicyclic group.

  Examples of the diisocyanate (c1) having an aromatic group include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- Examples include tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, or 1,3-bis (isocyanatomethyl) benzene.

  Examples of the diisocyanate (c2) having an aliphatic group include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. Examples thereof include diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the diisocyanate (c3) having an aromatic group and an aliphatic group include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate. Examples include -1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, or 1,3-tetramethylxylylene diisocyanate.

Examples of the diisocyanate (c4) having an alicyclic group include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Examples include cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, or methyl-2,6-cyclohexane diisocyanate.
As mentioned above, the listed diisocyanate compound (c0) is not necessarily limited to these, and two or more kinds can be used in combination.

  As the diisocyanate compound (c0) used in the present invention, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate, IPDI) is preferable because it is hardly yellow-modified.

  For the purpose of increasing the molecular weight of the dispersant, polyisocyanate (c5) having 3 or more isocyanate groups in one molecule may be used. Polyisocyanate having an aromatic group, polyisocyanate having an aliphatic group And polyisocyanates having an aromatic group and an aliphatic group, or polyisocyanates having an alicyclic group.

  As polyisocyanate (c5) having three or more isocyanate groups in one molecule, specifically, isocyanurate of diisocyanate, or diisocyanate trimer such as biuret of diisocyanate, polyol adduct of diisocyanate, Examples thereof include copolymers of two or more of the above diisocyanates, triisocyanates having an aromatic group, and isocyanate oligomers having a polymeric aromatic group.

As polyisocyanate (c5) having three or more isocyanate groups per molecule, for example,
Isocyanurate of tolylene diisocyanate (hereinafter sometimes abbreviated as TDI), isocyanurate of isophorone diisocyanate (hereinafter sometimes abbreviated as IPDI), 4,4′-diphenylmethane diisocyanate (hereinafter referred to as MDI) May be abbreviated) isocyanurate, hexamethylene diisocyanate (hereinafter abbreviated as HDI) isocyanurate, HDI biuret, HDI trimethylolpropane (hereinafter abbreviated as TMP). Diisocyanate modifieds such as adducts, TMP TMP adducts, or TDI / HDI copolymers;
An aromatic triisocyanate such as 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, or 4,4 ', 4 "-triphenylmethane triisocyanate;
And polymer type aromatic isocyanate oligomers such as polymethylene polyphenyl polyisocyanate (also known as MDI oligomer).

<Manufacture of dispersant>
The dispersant of the present invention is
A solvent having a hydroxyl group in one terminal region, which is obtained by radical polymerization of an ethylenically unsaturated monomer (a1) in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule. A first step of producing an affinity vinyl polymer (a);
An ethylenically unsaturated monomer (b2) containing an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule A second step of producing a basic vinyl polymer (b) having a hydroxyl group in one terminal region, which is obtained by radical polymerization of
A third step of reacting the hydroxyl group of the compound (d) having a hydroxyl group containing the solvophilic vinyl polymer (a) and the basic vinyl polymer (b) with the isocyanate group of the polyisocyanate (c);
It is manufactured in three steps.

<First step>
The first step comprises radical polymerization of an ethylenically unsaturated monomer (a1) in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule. This is a process for producing a solvophilic vinyl polymer (a) having a hydroxyl group in the region.
As shown in the following general formula (2), by radical polymerization of the ethylenic vinyl monomer (a1) in the presence of the compound (s1) having two hydroxyl groups and a thiol group in the molecule, the S atom is introduced. Thus, a solvent-affinity vinyl polymer (a) s1-A having a solvent-neophilic vinyl polymer site (A) and having two hydroxyl groups in one end region is produced.

  General formula (2):

  Further, as shown in the following general formula (3), by radical polymerization of the ethylenic vinyl monomer (a1) in the presence of the compound (s2) having one hydroxyl group and a thiol group in the molecule, S atom A solvent-affinity vinyl polymer (a ′) s2-A having a solvent-neophilic vinyl polymer site (A) and having one hydroxyl group at one terminal region is produced.

  General formula (3):

  The components of the first step, the polymerization initiator used as necessary, the polymerization solvent, the polymerization conditions, and the like are as described in detail in << Solvent Affinity Vinyl Heavy Compound (a) >>.

<Second step>
In the second step, an ethylenically unsaturated group containing an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule. This is a step for producing a basic vinyl polymer (b) having a hydroxyl group in one terminal region, which is obtained by radical polymerization of a saturated monomer (b2).
As shown in the following general formula (4), an ethylenically unsaturated compound containing an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s1) having two hydroxyl groups and a thiol group in the molecule. By radical polymerization of the monomer (b2), a basic vinyl polymer (b) s1- having a basic vinyl polymer portion (B) via an S atom and having two hydroxyl groups in one terminal region. B is manufactured.

  General formula (4):

  In addition, as shown in the following general formula (5), an ethylenic compound containing an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s2) having one hydroxyl group and a thiol group in the molecule. A solvent-affinity vinyl polymer (b ′) having a basic vinyl polymer moiety (B) via an S atom and having one hydroxyl group at one terminal region by radical polymerization of the unsaturated monomer (b2). ) S2-B is manufactured.

  General formula (5):

  The components of the first step, the polymerization initiator used as necessary, the polymerization solvent, the polymerization conditions, and the like are as described in detail in << Solvent Affinity Vinyl Heavy Compound (a) >>.

<Third step>
The third step will be described by taking as an example the case where the compound (d) having a hydroxyl group is only an essential component, ie, the solvent-affinity vinyl polymer (a) and the basic vinyl polymer (b). The compound (d1) having a hydroxyl group other than (a) and (b) will be described later. (The description will be made whenever necessary.) The polyisocyanate compound (d) will also be described by taking the case of the diisocyanate compound (c0), which is a basic component, as an example.

  In the third step, the hydroxyl group of the solvophilic vinyl polymer (a) and the hydroxyl group of the basic vinyl polymer (b) are reacted with the isocyanate group of the diisocyanate (c0) and linked to form a polyurethane structure. Useful as a pigment dispersant having a structure in which a solvophilic block comprising a solvophilic vinyl polymer moiety (A) and a basic block comprising a basic vinyl polymer moiety (B) are linked to a block having This is a process for producing polyurethane.

  A basic block having a plurality of tertiary aminos is effective as an adsorbing group for a pigment having an acidic surface, and a solvent affinity block having a plurality of solvent-affinity polymer chains is suitable for pigment carriers such as organic solvents and resins. It is effective as an affinity group.

  In the third step of the present invention, a solvophilic vinyl polymer (a) having two hydroxyl groups in one terminal region, a basic vinyl polymer (b) having two hydroxyl groups in one terminal region, and a diisocyanate compound ( The molar ratio of c0) can be arbitrarily determined, but the polymer (a) and (b) having a hydroxyl group in one terminal region is excessive with respect to the diisocyanate compound (c0), or the diisocyanate compound (c0) ) In excess, and a necessary amount of alcohol [compound (d0) having a hydroxyl group other than (a) and (b)] is often added to react with the remaining isocyanate. Depending on the amine value and molecular weight of the target dispersant, the solvent-affinity vinyl polymer (a), basic vinyl polymer (b), and diisocyanate compound (c) may be used in any proportion. It is easy in design to control the solvent affinity and basicity at the respective weight ratios. The weight ratio of the vinyl polymer (a) to the total amount of the vinyl polymer (a) and the vinyl polymer (b) is preferably 0.4 to 0.9, more preferably 0.6 to 0.00. 8. If it is outside this range, the balance between solvent affinity and pigment adsorptivity becomes poor, which may lead to deterioration in dispersion stability. Further, the equivalent ratio of the hydroxyl groups in the vinyl polymer (a) and the vinyl polymer (b) to the isocyanate groups of the diisocyanate compound (c) is not particularly limited, but preferably [hydroxyl group] / [isocyanate group] is 0.00. It is 5-2.0, More preferably, it is 0.8-1.5. If it is out of this range, a large amount of components other than the target structure of the present invention may be produced, resulting in poor dispersibility.

<< Compound having a hydroxyl group other than the solvophilic vinyl polymer (a) and the basic vinyl polymer (b) >>
In addition to the alcohol [compound (d0)] to be reacted with the residual isocyanate, a compound having a hydroxyl group other than the solvophilic vinyl polymer (a) and the basic vinyl polymer (b) may be used.

(Other polyol compound (d1))
As a component of the compound (d) having a hydroxyl group, other polyol compounds (d1) other than the polymers (a) and (b) may be used at an arbitrary ratio. By using the other polyol compound (d1), it becomes easy to adjust the molecular weight and the ratio of the basic block and the solvent affinity block.

  Examples of the polyol compound (d1) used in the present invention include polyhydric alcohols such as ethylene glycol and propylene glycol, polyether glycols such as polyoxyethylene glycol and polyoxypropylene glycol, and polyester polyols.

(Reaction catalyst)
In the third step of the present invention, a known catalyst can be used as the catalyst. For example, a tertiary amine compound, an organometallic compound, etc. can be mentioned.

As the tertiary amine compound, for example,
Examples include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like.

Examples of organometallic compounds include tin compounds and non-tin compounds.
Examples of tin compounds include:
Dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyl Examples thereof include tin ethoxide, dioctyl tin oxide, tributyltin chloride, tributyltin trichloroacetate, and 2-ethylhexanoic acid tin.

Examples of non-tin compounds include:
Titanium systems such as dibutyltitanium dichloride, tetrabutyltitanate, or butoxytitanium trichloride;
Lead systems such as lead oleate, lead 2-ethylhexanoate, lead benzoate or lead naphthenate;
Iron systems such as iron 2-ethylhexanoate or iron acetylacetonate;
Cobalt-based benzoate or cobalt 2-ethylhexanoate, etc .;
Zinc-based such as zinc naphthenate or zinc 2-ethylhexanoate; or
Zirconium-based compounds such as zirconium naphthenate can be mentioned.

  Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate or the like is preferable in terms of reactivity and hygiene.

(Reaction solvent)
The dispersant of the present invention can be produced using only the raw materials listed so far, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. As the solvent to be used, known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, methoxy pyrrole acetate, or the like can be given. The polymerization solvent used in the first step or the second step can be used as it is. Moreover, the solvent used for the reaction can be removed by an operation such as distillation after the completion of the reaction, or can be used as a part of the product as it is.

(Reaction temperature)
The reaction temperature is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. If it is 50 ° C. or lower, the reaction rate is slow, and if it is higher than 120 ° C., it becomes difficult to control the reaction rate, and a urethane prepolymer having a predetermined molecular weight and structure may not be obtained.

(Number average molecular weight)
The number average molecular weight of the obtained dispersant is preferably 3,000 to 30,000, more preferably 4,000 to 20,000, and still more preferably 8,000 to 15,000. If the number average molecular weight is less than 3,000, the stability of the pigment composition may be reduced, and if it exceeds 30,000, the interaction between the resins may become strong and the viscosity of the pigment composition may increase. .

(Amine number)
Furthermore, the amine value of the obtained dispersant is preferably 5 to 200 mgKOH / g. More preferably, it is 20-150 mgKOH / g, More preferably, it is 30-100 mgKOH / g. When the amine value is less than 5 mgKOH / g, the pigment adsorbing ability may be lowered and there may be a problem in pigment dispersibility. When the amine value exceeds 150 mgKOH / g, the interaction between resins becomes strong and the viscosity of the pigment dispersion composition increases. There is a case.

<Pigment>
For example, the pigment can be favorably dispersed by the dispersant of the present invention. Examples of the pigment that can be dispersed by the dispersant of the present invention include various pigments used in inks and the like. Organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ansan There are throne pigments, indanthrone pigments, flavanthrone pigments, pyranthrone pigments, diketopyrrolopyrrole pigments, etc.
More specific examples are indicated by the generic name of the color index: Pigment Black 7, Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, or 58, Alternatively, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 144, 146, 149, 166, 168, 177, 178, 179, 185, 206, 207, 209, 220, 221, 238, 242, 254, or 255, or Pigment Violet 19, 23, 29, 30, 37, 40, or 50, or Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 1 7, 148, 150, 151, 154, 155, 166, 168, 180, or 185, or Pigment Orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74, etc. Can be given.

  Further, the dispersant of the present invention is a metal oxide such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, silica, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, chrome lead, or carbon. It can also be used for inorganic pigments such as black.

  Furthermore, the dispersant of the present invention is used for dispersing fine particles other than pigments, for example, solid fine particles containing metal fine particles such as gold, silver, copper, platinum, iron, cobalt, nickel, titanium and / or alloys thereof. be able to.

  The dispersant of the present invention is not limited to the above-illustrated pigments, but may be applied to any fine powders. However, the dispersant of the present invention preferably has an acidic surface because it has a basic block and has a strong interaction with solid fine particles (particularly pigments) whose surface is acidic. The acidic index is preferably 50 to 700 μmol / g, more preferably 100 to 600 μmol / g, in terms of the amount of adsorbed amine. The amine adsorption amount referred to in the present invention is defined as a case where n-hexylamine is measured as an adsorbed amine substance in accordance with the method described in Coloring Materials, 67 [9], 547-554 (1994).

  Examples of the pigment having an acidic surface include C.I. I. Pigment Green 58 (200 to 700 μmol / g) and C.I. I. Pigment Green 150 (100 to 250 μmol / g) and the like.

  The pigment dispersion of the present invention refers to a paste or a chip that can be obtained by dispersing a pigment with the dispersant of the present invention. A pigment dispersion can be obtained only with the dispersant and the pigment of the present invention. Further, by using the dispersant of the present invention, a pigment dispersion can be obtained by dispersing the pigment in a pigment carrier (resin, precursor thereof, or mixture thereof) other than the dispersant, a solvent, varnish, or the like. it can.

  The blending amount of the dispersant is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 75 parts by weight, and most preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the pigment. If the dispersant is less than 0.1 parts by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and if it exceeds 100 parts by weight, the dispersibility may be deteriorated.

<< Dispersant such as pigment derivative >>
A dispersant having an acidic group selected from the group consisting of a pigment derivative having an acidic group, an anthraquinone derivative having an acidic group, an acridone derivative having an acidic group, and a triazine derivative having an acidic group is added to the pigment dispersion of the present invention. Thus, they can be adsorbed on the pigment surface and modified to be acidic to improve the effect of the dispersant of the present invention.

<Dispersant such as a pigment derivative having an acidic substituent>
The pigment dispersion of the present invention includes an acidic substituent selected from the group consisting of a dye derivative having an acidic substituent, an anthraquinone derivative having an acidic substituent, an acridone derivative having an acidic substituent, and a triazine derivative having an acidic substituent. At least one type of dispersant having the above can be used. The dispersant having an acidic substituent is adsorbed on the surface of the pigment, and even a non-acidic pigment can make the surface acidic. The pigment derivative having an acidic substituent is classified into a pigment derivative having no charge represented by the following general formula (20) or a pigment derivative having a charge represented by the following general formula (21) or (22). It is done.

Formula (20):
PZ ¹
In the general formula (20), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. And an organic dye residue selected from perinone, flavanthrone, pyranthrone, and anthrapyrimidine, and Z ¹ is a sulfonic acid group or a carboxyl group.

Formula (21):
(PZ ² ) [N ⁺ (R ² , R ³ , R ⁴ , R ⁵ )]
In general formula (21), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. R ² is an alkyl group having 5 to 20 carbon atoms, and R ³ , R ⁴ , and R ³ are organic dye residues selected from perinone, flavanthrone, pyranthrone, and anthrapyrimidine. ⁵ are each independently a hydrogen atom or an alkyl group having a carbon number 1 to 20, Z ² is SO ₃ ^- or COO ^- is.

Formula (22):
(P−Z ² ) M ⁺
In the general formula (22), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. , perinone, flavanthrone-based, an organic colorant residue of one member selected from the pyranthrone and anthrapyrimidine, M is Na or K atom, Z ² is SO ₃ ^- or COO ^- is.

  In the pigment dispersion of the present invention, the total amount of the dispersant such as a pigment derivative having an acidic substituent is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight with respect to 100 parts by weight of the pigment. Most preferably, it is 5 to 25 parts by weight. If the amount is less than 1 part by weight relative to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and if it exceeds 50 parts by weight, the heat resistance and / or light resistance may be deteriorated.

<Pigment dispersion>
The pigment dispersion of the present invention comprises a pigment, the dispersant of the present invention, and optionally a dispersant such as a pigment derivative having an acidic substituent, and, if necessary, an organic solvent, a resin, a varnish, and the like. Then, it can be obtained by dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, or attritor. All the components may be mixed and then dispersed, but initially only the pigment and a dispersant such as a pigment derivative having an acidic group, or a dispersant such as a pigment derivative having an acidic group and the dispersant of the present invention. Or only a dispersant such as a pigment and a pigment derivative having an acidic group and the dispersant of the present invention may be dispersed, and then another component may be added to perform dispersion again.

  Also, before dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, or attritor, etc., pre-dispersion using a kneader mixer such as a kneader, three roll mill, etc., solid dispersion with a two roll mill, or You may process the dispersing agent of the pigment derivative etc. which have an acidic substituent to a pigment, and / or the dispersing agent of this invention. In addition, any disperser or mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic disperser can be used to produce the dispersion of the present invention.

"solvent"
Examples of various solvents that can be used in the pigment dispersion of the present invention include organic solvents and water. As the organic solvent, the organic solvent used in the course of synthesizing the polyester dispersant of the present invention may be used as it is. In addition, the organic solvent used in the synthesis process may be removed after the reaction is completed by an operation such as distillation, and then the same organic solvent or a different solvent may be used. Two or more organic solvents may be used in combination according to the purpose.

  Examples of the organic solvent include hexane, isophorone, toluene, o-xylene, m-xylene, m-diethylbenzene, n-butylbenzene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, ethyl acetate. N-amyl acetate, n-butyl acetate, isoamyl acetate, n-butyl acetate, isobutyl acetate, propyl acetate, ethyl lactate, propyl lactate, butyl lactate, dibasic acid ester, n-propyl acetate, cyclohexanol acetate, 3- Ethyl ethoxypropionate, 3-methoxy-3-methylbutyl acetate, 3-methoxybutyl acetate, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, γ-butyrolactone, N-methyloxazolidino N-ethyloxazolidinone, acetonitrile, 1,2,3-trichloropropane, o-chlorotoluene, p-chlorotoluene, o-dichlorobenzene, m-dichlorobenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4 -Heptanone, diisobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, n-butyl alcohol, isobutyl alcohol, benzyl alcohol, cyclohexanol, 3-methoxy Butanol, methylcyclohexanol, 3-methoxy-3-methyl-1-butanol, diacetone alcohol, 1,3-butanediol, 2-methyl-1,3-propanediol, 3-methyl-1,3-butyl Diol, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl Ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether Ter, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , Dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether Acetate, dipropylene glycol monobutyl ether acetate, 1,3-butylene glycol diacetate, propylene glycol diacetate, ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, Butylene glycol diacetate, pentanediol diacetate, butylene glycol diacetate has 1,4-butylene glycol diacetate, 1,3-butylene glycol diacetate, pentanediol diacetate has 1,5-pentanediol diacetate Or triacetin and the like, but is not necessarily limited thereto.

Moreover, when using for an active energy ray hardening-type composition, you may use an active energy ray-curable liquid monomer and liquid oligomer as a medium instead of an organic solvent. When used in an active energy ray-curable composition, as an active energy ray-curable liquid monomer or liquid oligomer, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyester Glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
(Meth) acrylic acid, acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl Carboxyl groups such as hexahydrophthalate, 2- (meth) acryloyloxypropylhexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate (Meth) acrylates having;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl Phthalate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) Acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) Acrylate, poly (propylene glycol - tetramethylene glycol) mono (meth) acrylate, or having a hydroxyl group such as glycerol (meth) acrylate (meth) acrylates;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol- Tetramethylene glycol) di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, or 2-ethyl, 2-butyl-propanediol di ( (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate,
Dimethylol dicyclopentane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A Di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol F di (meth) acrylate, tetramethylene oxide modified bisphenol F di (meth) Acrylate, zinc diacrylate, ethylene oxide-modified phosphate triacrylate, or glycerol di (meth) acrylate Di (meth) acrylate and the like;
(Meth) acrylates having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, or diethylaminopropyl (meth) acrylate;
Glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate Trifunctional or higher polyfunctional (meth) acrylates such as
Glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct, 1,6-butanediol diglycidyl ether, Alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenyl glycidyl ether- (meth) acrylic acid adduct, styrene oxide- (meth) acrylic acid adduct, bisphenol A di Glycidyl ether- (meth) acrylic acid adduct, propylene oxide-modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic acid adduct, epichlorohydride -Modified phthalic acid- (meth) acrylic acid adduct, epichlorohydrin-modified hexahydrophthalic acid- (meth) acrylic acid adduct, ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, polyethylene glycol diglycidyl ether- (meta ) Acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolac type epoxy resin- (meth) acrylic acid adduct, cresol novolac Type epoxy resin- (meth) acrylic acid adducts or other epoxy resins- (meth) acrylic acid adducts and other epoxy (meth) acrylates;
(Meth) acryloyl-modified isocyanurate, (meth) acryloyl-modified polyurethane, (meth) acryloyl-modified polyester, (meth) acryloyl-modified melamine, (meth) acryloyl-modified silicone, (meth) acryloyl-modified polybutadiene, or (meth) acryloyl-modified rosin (Meth) acryloyl-modified resin oligomers such as;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, and allyl (meth) acrylate;
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;
Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-vinylformamide; or
Examples include acrylonitrile.
These can be used alone or in admixture of two or more. Moreover, it is not necessarily limited to these.

"resin"
The acrylic urethane dispersant of the present invention can also be used as a binder resin for a pigment dispersion.

  In addition to the acrylic urethane dispersant of the present invention, examples of resins that can be used in the pigment dispersion of the present invention include thermoplastic resins, thermosetting resins, and active energy ray curable resins.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl chloride-vinyl acetate copolymer, poly Vinyl acetate, polyurethane resin, polyester resin, acrylic resin, methacrylic resin, alkyd resin, polystyrene resin, silicone resin, fluororesin, polyamide resin, rubber resin, cyclized rubber resin, chlorinated rubber, oxidized rubber, hydrochloric acid Examples thereof include rubber, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, petroleum resin, casein, shellac, nitrocellulose, and cellulose acetate butyrate, but are not necessarily limited thereto.

  Examples of thermosetting resins include epoxy resins, benzoguanamine resins, melamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, rosin-modified maleic acid resins, rosin-modified phenol resins, urea resins, amino resins, phenol resins, Saturated polyester resins, drying oils, synthetic drying oils and the like can be mentioned, but are not necessarily limited thereto. They can also be used in combination as a thermal crosslinking agent for the thermoplastic resin.

  As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used. However, it is not necessarily limited to these.

《Other additives》
In the pigment dispersion of the present invention, as other additives, a photopolymerization initiator, a chain transfer agent, a plasticizer, a surface conditioner, an ultraviolet ray inhibitor, a light stabilizer, an antioxidant, an antistatic agent, an antiblocking agent Antifoaming agents, viscosity modifiers, waxes, surfactants, leveling agents and the like can be added.

<Application>
The pigment dispersion of the present invention can be used in non-aqueous, aqueous or solvent-free paints, gravure inks, offset inks, ink jet inks, color filter inks, digital paper inks, or plastic colorants.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

Example 1 <Production Example of Solvent Affinity Vinyl Polymer (a)>
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 250 parts of methyl methacrylate, 250 parts of n-butyl acrylate, and 130 parts of propylene glycol monomethyl ether acetate and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution in which 0.5 part of 2,2′-azobisisobutyronitrile was dissolved in 28 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. The solid content measurement confirmed that 95% had reacted, and the reaction was terminated to obtain a solvophilic vinyl polymer (a-1) having a number average molecular weight of 2000. Using propylene glycol monomethyl ether acetate, the solid content was adjusted to 50% to obtain a solvent-affinity vinyl polymer (a-1) solution.

(Examples 2 to 9) <Examples of Solvent Affinity Vinyl Polymer (a) and Basic Vinyl Polymer (b)>
Solvent-affinity vinyl polymers (a-2) to (a-6) and basic vinyl polymers (b-1) were prepared in the same manner as in Example 1 except that the raw materials and the amounts charged were listed in Table 1. ) To (b-3) were obtained. Each was adjusted to a solid content of 50% using propylene glycol monomethyl ether acetate to obtain a polymer solution.

(Example 10) <Production of dispersant>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 500 parts of the solvent-compatible vinyl polymer (a-1) solution, 55.6 parts of isophorone diisocyanate, and 0.05% of dibutyltin dilaurate as a catalyst. And heated at 100 ° C. for 3 hours. Further, 163 parts of the basic vinyl polymer (b-1) solution was added and reacted at 100 ° C. for 2 hours. Finally, 9.3 parts of n-butanol was added to obtain a dispersant (1) having a number average molecular weight of 6500 and an amine value of 67. Furthermore, using propylene glycol monomethyl ether acetate, the solid content was adjusted to 50% to obtain a dispersant (1) solution.

Examples 11 to 18 <Production Examples of Dispersant>
Dispersants (2) to (9) were obtained in the same manner as in Example 10 except that the raw materials and amounts charged in Table 2 were used. Further, using propylene glycol monomethyl ether acetate, the solid content was adjusted to 50% to obtain dispersant (2) to (9) solutions.

  In Tables 1 and 2, the abbreviations of the materials used are as follows.

<Polyisocyanate>
IPDI: Isophorone diisocyanate HDI: Hexamethylene diisocyanate

<Comparison dispersant (1)>
EFKA4300 (manufactured by Ciba Specialty Chemicals, amine value 52-60, solid content 80%) was diluted with propylene glycol monomethyl ether acetate to adjust the solid content to 50%, and a comparative dispersant (1) solution was obtained.

<Comparison dispersant (2)>
DISPERBYK2001 (by Big Chemie, amine value 29, acid value 19, solid content 46%) is concentrated to 50% or more of the solid content, diluted with propylene glycol monomethyl ether acetate, adjusted to a solid content of 50%, and comparative dispersion Agent (2) solution was obtained.

《Amine adsorption capacity of pigment》
C. used in Examples for glass containers that can be sealed. I. 1 g of Pigment Yellow 150 pigment was weighed, and 30 ml of a methoxypropyl acetate solution of 0.02 mol / l n-hexylamine (adsorbent) was added. The container was capped and adsorbed on the pigment surface for 1 hour in an ultrasonic cleaner. The pigment was settled through a centrifugal separator to obtain a supernatant. 15 ml of the supernatant was sampled, and the remaining n-hexylamine was back titrated with a potentiometric titrator using a 0.02 mol / l perchloric acid dioxane solution. When the blank was measured and quantified, the amine adsorption capacity was 130 μmol / g.

  Similarly, C.I. used in Examples of the present invention. I. Pigment Green 58 is also described in C.I. I. When confirmed in the same manner as Pigment Green 150, the amine adsorption capacity was 550 μmol / g.

  Similarly, other C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Green 36, and C.I. I. The amine adsorption capacity of Red 177 was measured and found to be 45, 42, and 27 μmol / g, respectively.

(Example 19)
14 g of Pigment Green 58 as a pigment, 12 g of the dispersant (1) solution obtained in Example 10 (6 g as a solid content), 74 g of propylene glycol monomethyl ether acetate, 60 g of glass beads (diameter 0.8 mm), Was placed in a 140 mL mayonnaise bottle and placed on a Scandex SO400 (hereinafter referred to as Scandex) manufactured by F & FM, and dispersed for 3 hours. The glass beads were removed from this dispersion to obtain a dispersion. The dispersion was allowed to stand at 25 ° C. for 24 hours, and then the viscosity at 25 ° C. at a rotational speed of 1 rad / sec (this was the initial viscosity) using a cone plate with a diameter of 60 mm and an angle of 0 ° 59 min. Measured) was 16 mPa · s, and the TI value ([viscosity at a rotational speed of 10 rad / sec] ÷ [viscosity at a rotational speed of 1 rad / sec]) was 1.08. Further, when the dispersion was stored in an oven at 40 ° C. for 1 week, the viscosity (this is called the viscosity with time) was measured in the same manner as described above, and it was 17 mPa · s, and the rate of change in viscosity (viscosity with time ÷ The initial viscosity was 106%.

(Examples 20 to 32)
In the same manner as in Example 19, using the vinyl dispersants (1) to (9) obtained in Examples 10 to 18 above, the blending amounts (g) shown in Tables 3 and 4 were prepared. A pigment dispersion was obtained for each. Evaluation was performed in the same manner as in Example 19, and the results are shown in Tables 3 and 4. However, the viscosity stability was evaluated as ○ when the rate of change in viscosity before and after storage at 40 ° C. for 1 week was within ± 10%, and × when exceeding ± 10%.

(Comparative Examples 1-4)
In the same manner as in Example 19, using the above comparative dispersants (1) to (2), the blending amounts (g) shown in Table 5 were prepared, and dispersions were obtained. Evaluation was performed in the same manner as in Example 19, and the results are shown in Table 5. However, when the initial viscosity exceeds 100, it is expressed as impossible to disperse. The viscosity stability is ○ if the rate of change in viscosity before and after storage at 40 ° C for 1 week is within ± 10%, and × if it exceeds ± 10%. did.

  In Tables 3 to 5, the abbreviations of the materials used are as follows.

<Pigment>
Pigment Green 58: Halogenated zinc phthalocyanine green pigment Pigment Blue 15: 3: Copper phthalocyanine blue pigment Pigment Green 36: Halogenated copper phthalocyanine green pigment Pigment Yellow 150: Pigment Red 177 pigment: Anthraquinone red pigment

《Derivative》
<Dye derivatives with acidic substituents, etc.>
Acidic derivative (1): Pigment derivative (1) having an acidic substituent represented by the following general formula (26)
General formula (26):
(PZ ² ) [N ⁺ (R ² , R ³ , R ⁴ , R ⁵ )] (26)
(Wherein P is copper phthalocyanine, Z ² is —SO ₃ ^— , R ² is a propyl group, R ³ is an ethyl group, R ⁴ is an ethyl group, R ⁵ is H.)

Acidic derivative (2): Dye derivative (2) having an acidic substituent represented by the following general formula (27)
Formula (27):
(PZ ² ) [N ⁺ (R ² , R ³ , R ⁴ , R ⁵ )] (27)
(Wherein P is quinacridone, Z ² is —SO ₃ ^— , R ² is a propyl group, R ³ is a butyl group, R ⁴ is a butyl group, R ⁵ Is H.)

"solvent"
PGMAc: Propylene glycol monomethyl ether acetate

  In the present invention, the use of a dispersant having a basic block suitable as a pigment adsorption site makes it possible to disperse at a low viscosity, and a dispersion having good storage stability can be obtained from the examples. did it.

  On the other hand, the comparative dispersant (1) was excellent in dispersibility, but the viscosity stability was not sufficient. In addition, the comparative comparative dispersant (2) was inferior in dispersibility with pigments whose surface was biased to acidity. As described above, the prior art dispersants have drawbacks.

Claims (12)

In the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule,
Ethylenically unsaturated monomer (excluding those having an amino group) (a1) A solvent-affinity vinyl polymer having a hydroxyl group at one end region (a) obtained by radical polymerization of (a1)
as well as,
An ethylenically unsaturated monomer (b2) containing an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule ), A basic vinyl polymer having a hydroxyl group in one terminal region (b),
In addition, in some cases, the compound (d) having a hydroxyl group-containing compound other than that,
The hydroxyl group of (a), the hydroxyl group of (b), and optionally the hydroxyl group of the other hydroxyl group-containing compound ;
An isocyanate group of the polyisocyanate compound (c) having two or more isocyanate groups;
A dispersant obtained by reacting The dispersing agent according to claim 1, wherein the number average molecular weight of the solvophilic vinyl polymer (a) is 1,000 to 10,000. The dispersant according to claim 1 or 2, wherein the number average molecular weight of the basic vinyl polymer (b) is 1,000 to 8,000. The dispersant according to any one of claims 1 to 3, wherein the amine value is 5 to 200 mgKOH / g. The compound (s) having one or two hydroxyl groups and one thiol group in the molecule is a compound (s1) having two hydroxyl groups and one thiol group in the molecule. The dispersing agent in any one of 1-4 . The dispersant according to any one of claims 1 to 5, wherein the ethylenically unsaturated monomer (a1) contains a monomer (a2) represented by the following general formula (1).
General formula (1):
[In General Formula (1), R is a linear or branched alkyl group having 1 to 4 carbon atoms. ] The dispersant according to any one of claims 1 to 6, wherein the amino group of the ethylenically unsaturated monomer (b1) having an amino group is a tertiary amino group. The dispersing agent according to any one of claims 1 to 7 , wherein the number average molecular weight is 3,000 to 30,000. A pigment composition comprising the dispersant according to claim 1 and a pigment. The pigment composition according to claim 9, wherein the pigment contains a halogenated zinc phthalocyanine pigment. Furthermore, a derivative having one or more kinds of acidic substituents selected from the group consisting of a dye derivative having an acidic substituent, an anthraquinone derivative having an acidic substituent, an acridone derivative having an acidic substituent, and a triazine derivative having an acidic substituent The pigment composition according to claim 9 or 10, comprising: Radical polymerization of ethylenically unsaturated monomer (excluding those having an amino group) (a1) in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule . A first step of producing a solvophilic vinyl polymer (a) having a hydroxyl group in one terminal region;
An ethylenically unsaturated monomer (b2) containing an ethylenically unsaturated monomer (b1) having an amino group in the presence of a compound (s) having one or two hydroxyl groups and one thiol group in the molecule A second step of producing a basic vinyl polymer (b) having a hydroxyl group in one terminal region, which is obtained by radical polymerization of
Of the solvent-affinity vinyl polymer (a) and the basic vinyl polymer (b), and optionally a compound (d) having a hydroxyl group-containing compound other than that,
The hydroxyl group of (a), the hydroxyl group of (b), and optionally the hydroxyl group of the other hydroxyl group-containing compound ;
A third step of reacting the isocyanate group of the polyisocyanate compound (c) having two or more isocyanate groups;
The manufacturing method of the dispersing agent containing this.