JP2577441B2 - Cationic aqueous pigment dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a cationic aqueous pigment dispersion using a novel dispersant and having excellent dispersibility and dispersion stability.

Conventionally, in water-based paints such as emulsion paints and water-soluble resin paints containing pigments, the coloring effect of the coated surface is reduced due to the difficulty in dispersing the pigments during production and the aggregation and sedimentation of the pigments during storage, flooding, It is well known that undesirable phenomena, such as floating (floating mottle) and loss of gloss, occur. For this reason, an aqueous pigment dispersion in which a pigment is dispersed in advance with a dispersant is prepared in advance, and this is mixed and dispersed in a water-based paint to be colored to prepare an aqueous paint.

In conventional aqueous pigment dispersions, low-molecular-weight compounds such as surfactants are mainly used as dispersants. However, the adverse effects of the dispersants, that is, the secondary adverse effect that the coating film performance or the coating state is reduced, are reduced. Inevitably, recently, the use of an oligomer or a polymer having a medium molecular weight as a dispersant has been used to suppress a decrease in coating film performance and the like.

However, when an oligomer or a polymer is used as a dispersant, the amount used is larger than that of a low molecular surfactant, and the use of the obtained aqueous pigment dispersion depends on the type of binder used in the aqueous paint. There are disadvantages such as being limited. This goes against the rationalization of paint production, and there is therefore a strong demand for the development of aqueous pigment dispersions that can be commonly used in various aqueous paints.

The present inventor has disclosed, as a dispersant for a cationic aqueous pigment dispersion capable of easily dispersing a pigment in a small amount, a copolymer composition as disclosed in JP-A-60-146164 and JP-A-60-217271. Proposed.

These copolymer compositions have a so-called comb-like structure in which the hydrophobic part and the hydrophilic part are well-balanced, contain a nitrogen component having excellent adsorption ability to the pigment, and have a very good interface in aqueous solution. It had a high activity and exhibited excellent pigment dispersibility with a smaller amount of compounding than conventional water-soluble resins.

However, the aqueous pigment dispersion obtained by using the above copolymer composition as a dispersant has excellent pigment dispersibility at the time of production, but in the long-term storage of the dispersion, the pigments are partially aggregated. It becomes a hard or caking state, and it is impossible to return it to the state before storage even if it is redispersed using a stirrer. Had the problem of bringing

Accordingly, the present inventors have made intensive efforts to solve the above problems, and as a result, a monomer having a fatty acid group as a monomer component; a macromonomer obtained by polymerization of a nitrogen-containing unsaturated monomer; (Meth) acrylate and / or aminoalkyl (meth) acrylamide and / or
Alternatively, the present inventors have found that the above problems can be solved by using a copolymer containing an unsaturated vinyl monomer containing a glycidyl group as an essential monomer component as a pigment dispersion stabilizer, and completed the present invention.

That is, the present invention, the pigment, dispersing agent and the aqueous pigment dispersion consisting of an aqueous medium, the dispersant, (A) modified vinyl having C ₈ or more fatty acid residues in the molecular terminal unsaturated monomer ( Hereinafter, this is referred to as “modified vinyl monomer”)
3 to 90 parts by weight (B) a nitrogen-containing macromonomer having at least one radical polymerizable functional group selected from acryloyloxy, methacryloyloxy, allyloxy and aromatic vinyl at one end (hereinafter referred to as "nitrogen-containing macromer") monomer"
2 to 90 parts by weight (C) at least one vinyl monomer selected from aminoalkyl (meth) acrylate, aminoalkyl (meth) acrylamide and glycidyl group-containing vinyl unsaturated monomer (hereinafter referred to as 1 to 50 parts by weight (D) 0 to 91 parts by weight of an unsaturated monomer having a nitrogen-containing heterocyclic ring; and (E) the above (A), (B), (C) ) And (D), a copolymer obtained by copolymerizing 0 to 91 parts by weight of an α, β-ethylenically unsaturated monomer other than (D), wherein the copolymer is a water-soluble or water-dispersed product. Is supplied.

According to the present invention, the above copolymer has a structure in which a long chain component having a strong hydrophobic property is bonded in a separated form to a main chain containing a specific nitrogen-containing monomer having a strong hydrophilicity derived from a macromonomer. When this is used as a dispersant and the pigment is dispersed in water in the presence thereof, the functional group of the copolymer is adsorbed or chemically bonded to the pigment particles, while the main component of the copolymer is The long-chain component separated from the chain is entangled with the long-chain component of the copolymer and envelops around the pigment particles to form a strong hydrophobic barrier layer, and becomes a form in which the hydrophilic component is dispersed in water. It is possible to obtain a stable aqueous pigment dispersion of the pigment in an aqueous medium. As described above, the hydrophobic pigment dispersion is surrounded by a barrier layer having a hydrophobic property between the pigment and water and itself having a component having excellent hydrolysis resistance. In addition, the barrier layer is composed of a component having a large steric hindrance, thereby preventing the pigments from approaching each other, and as a result, has excellent storage properties without sedimentation or aggregation. Further, since the copolymer has a surface activity that is excellent in the balance between the hydrophobicity derived from the long-chain component and the hydrophilicity derived from the macromonomer component, the pigment dispersibility and the property excellent in storage properties are improved. Show.

Further, the nitrogen-containing component in the copolymer can be easily and reliably introduced by using the macromonomer component used in the present invention. In addition, since the macromonomer component has a large nitrogen content obtained by copolymerizing or homopolymerizing a nitrogen-containing unsaturated monomer, it strongly adsorbs or binds to the pigment. As a result, the pigment dispersion of the present invention using the copolymer as a dispersant has pigment dispersibility,
Shows properties with excellent storage stability.

Hereinafter, the dispersant used in the aqueous pigment dispersion of the present invention will be described in more detail.

Modified vinyl-based monomer (A): modified vinyl-based monomer used in the dispersant of the present invention, monomers containing C ₈ or more fatty acid residues and an ethylenically unsaturated bond at a molecular terminal is included is, for example, monomers of C ₈ or more fats and oils containing ethylenically unsaturated bonds, fatty acids, fatty alcohols, monomers modified with modifier such as fatty acid glycidyl esters or fatty amines.

As the monomer containing an ethylenically unsaturated bond,
A monomer having a functional group such as a hydroxyl group, a carboxyl group, a glycidyl group, an isocyanate group, or an aziridine group in a molecule. Specifically, for example, a hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate, Hydroxyl group-containing monomers such as propyl (meth) acrylate; carboxyl group-containing unsaturated monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylic acid, (anhydride) maleic acid, and itaconic acid; glycidyl (meth) Acrylate, allyl glycidyl ether,
A glycidyl group-containing unsaturated monomer such as vinylphenyl glycidyl ether; a diisocyanate compound (eg, isophorone diisocyanate, toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, etc.) and a hydroxyalkyl (meth) acrylate having a molar ratio of 1: 1; Adduct, α, α-dimethyl-
Isocyanate group-containing unsaturated monomers such as m-isopropenylbenzyl isocyanate and isocyanatoethyl (meth) acrylate; and aziridine group-containing unsaturated monomers such as aziridinylethyl (meth) acrylate.

As the modifier, C ₈ or higher, preferably C ₁₀ -C ₂₄
Fats, fatty acids, fatty alcohols, fatty acid glycidyl esters, fatty amines, etc., specifically, saturated fatty acids such as lauric acid, 2-ethylhexanoic acid, and stearic acid; coconut oil, olive oil, castor oil, Safflower oil, linseed oil, soybean oil, sesame oil, knoll oil, cottonseed oil,
Fats and oils such as dehydrated castor oil and fatty acids thereof; aliphatic alcohols such as 2-ethylhexyl alcohol, lauryl alcohol, and stearyl alcohol; Cardura E (Gercidyl ester of versatile citrate, manufactured by Shell Chemical Company)
Glycidyl esters of fatty acids such as octylamine, dodecylamine and stearylamine.

The following are examples of the knitted vinyl monomer (A).

(I) an alkyl ester of (meth) acrylic acid; for example, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, stearyl (meth) acrylate and the like.

(Ii) Adducts of a glycidyl group-containing unsaturated monomer with a fatty acid (JP-A-59-227940); for example, adducts of glycidyl (meth) acrylate with a safflower oil fatty acid.

(Iii) isocyanate group-containing unsaturated monomer (JP-A-61
For example, a reaction product of an adduct of tolylene diisocyanate / 2-hydroxyethyl methacrylate (molar ratio 1/1) and oleyl alcohol.

(Iv) Esterified product of a hydroxyl group-containing unsaturated monomer and a fatty acid (JP-A-59-227940); for example, an esterified product of 2-hydroxyethyl methacrylate and linseed oil fatty acid.

(V) An adduct of an aziridine group-containing unsaturated monomer with a fatty acid (Japanese Patent Application Laid-Open No. 61-103537); for example, an adduct of aziridinylethyl methacrylate with linseed oil fatty acid.

Nitrogen-containing macromonomer (B): The macromonomer used in the dispersant of the present invention is a polymer obtained by polymerizing a nitrogen-containing unsaturated monomer as a molecular main chain, and acryloyl at one end of the main chain. It has a radically polymerizable unsaturated group such as oxy, methacryloyloxy, allyloxy, and aromatic vinyl (eg, styryl).

Examples of the nitrogen-containing unsaturated monomer component constituting the molecular chain include one or more of an unsaturated monomer having a nitrogen-containing heterocycle and a nitrogen-containing derivative of (meth) acrylic acid. Obtained by homopolymerization or copolymerization of the above monomers.

[1] As unsaturated monomers having a nitrogen-containing heterocyclic ring, 1 to
It includes monomers in which a monocyclic or polycyclic heterocyclic ring containing three, preferably one or two ring nitrogen atoms is bonded to a vinyl group, and particularly includes the following monomers.

(I) vinylpyrrolidones; for example, 1-vinyl-2-pyrrolidone, 1-vinyl-
3-pyrrolidone and the like.

(II) vinylpyridines; for example, 2-vinylpyridine, 4-vinylpyridine,
5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine and the like.

(III) vinylimidazoles; for example, 1-vinylimidazole, 1-vinyl-2-
Methyl imidazole and the like.

(IV) Vinyl carbazoles; for example, N-vinyl carbazole and the like.

(V) vinylquinolines; for example, 2-vinylquinoline and the like.

(VI) vinylpiperidines; for example, 3-vinylpiperidine, N-methyl-3-vinylpiperidine and the like.

(VII) Others; For example, (Where R ₁ represents a hydrogen atom or a methyl group), or N- (meth) acryloylmorpholine represented by the formula: (Where R ₁ has the above-mentioned meaning)
(Meth) acryloylpyridine and the like.

Among the unsaturated monomers having a nitrogen-containing heterocyclic ring described above, preferred are vinylpyrrolidones, vinylimidazoles and vinylcarbazoles, among which those having a tertiary ring nitrogen atom are preferred. is there.

[2] Nitrogen-containing derivatives of (meth) acrylic acid include those having a substituted or unsubstituted amino group in the ester portion of (meth) acrylic acid ester, amides of (meth) acrylic acid and those substituted in the amide portion. Those containing an amino group are included, and in particular, the following formulas (I) to (III) In the above formulas, R ₁ represents the meaning of the previous year, R ₂ and R ₃ each independently represent a hydrogen atom or a lower alkyl group, R ₄
Represents a hydrogen atom or lower alkyl, R ₅ is a hydrogen atom,
Represents a lower alkyl group, a di (lower alkyl) amino lower alkyl group, a hydroxy lower alkyl group or a lower alkoxy lower alkyl group, and n represents an integer of 2 to 8, aminoalkyl (meth) acrylate and (meth) Acrylamide is suitable. Where "low"
Means that the group to which it is attached has 6 or fewer carbon atoms,
It means that the number is preferably 4 or less.

As a specific example of such a nitrogen-containing (meth) acrylic monomer, aminoalkyl (meth) of the above formula (I)
Examples of the acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) ) Acrylate, N, N-dimethylaminobutyl (meth) acrylate, N-propylaminoethyl (meth) acrylate, N-butylaminoethyl (meth) acrylate, etc., and the aminoalkyl (meth) Examples of) acrylamide include N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like, and examples of (meth) acrylamide of the above formula (III) include: (Meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acryl Amide, N
-Butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, N
-Methylol (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylaminopropylacrylamide and the like. As these nitrogen-containing (meth) acrylic monomers, those having a tertiary nitrogen atom are most suitable, and those having a secondary tertiary atom are also suitably used. Among them, N, N-dimethylacrylamide and N, N-dimethylaminopropyl (meth) acrylamide which are excellent in hydrolysis resistance are preferable.

The α, β-ethylenically unsaturated nitrogen-containing monomers described above can be used alone or in combination of two or more.

Preparation of the macromonomer to be used in the present invention is carried out according to a conventionally known method. For example, the above-mentioned monomer can be used, for example, a chain transfer agent having a carboxyl group such as thioglycolic acid and, for example, azobisisobutyronitrile , A prepolymer having a carboxyl group at one end obtained by a polymerization reaction in the presence of a polymerization initiator such as benzoyl peroxide, or the above monomer, for example, azo-based having a carboxyl group such as azobiscyanovaleric acid A prepolymer having a carboxyl group at one end obtained by performing a polymerization reaction in the presence of a polymerization initiator and a tertiary amine is reacted with a vinyl monomer having a functional group capable of reacting with a carboxyl group of the prepolymer. It can be done by doing. As the above-mentioned vinyl monomer, typically, for example, glycidyl acrylate, glycidyl methacrylate,
Monomers containing acryloyloxy or methacryloyloxy groups such as -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; containing allyloxy groups such as allyl alcohol and allyl glycidyl ether Monomers and monomers having an aromatic vinyl group such as p-isopropenylphenyl glycidyl ether and p-vinylphenyl glycidyl ether are exemplified.

When the molecular weight of the macromonomer used in the present invention is too small, the storage stability of the aqueous pigment dispersion is inferior.On the other hand, when the molecular weight is too large, the balance between the molecular weight of the main chain and the side chain is lost, Since the pigment dispersibility and the storage stability of the aqueous pigment dispersion tend to be poor, the number average molecular weight is generally in the range of 500 to 15,000, preferably in the range of 700 to 10,000.

Vinyl monomer (C) selected from aminoalkyl (meth) acrylate, aminoalkyl (meth) acrylamide monomer and glycidyl group vinyl unsaturated monomer: In the dispersant of the present invention, a vinyl monomer Examples of the aminoalkyl (meth) acrylate and aminoalkyl (meth) acrylamide-based monomer that can be suitably used as the compound (C) include the monomers represented by the aforementioned general formulas (I) and (II). . Among them, aminoalkyl (meth) acrylamide of the above formula (I) is preferable from the viewpoint of water dispersibility and storage stability of the aqueous pigment dispersion (excellent in hydrolysis resistance), and especially, N, N-dimethylamino Propyl (meth) acrylamide is optimal.

In addition, a glycidyl group-containing vinyl unsaturated monomer can also be used as the vinyl monomer (C), and specific examples thereof include glycidyl (meth) acrylate, allyl glycidyl ether, and vinyl phenyl glycidyl ether. And the like.

Unsaturated monomer (D) having a nitrogen-containing heterocyclic ring: having a nitrogen-containing heterocyclic ring which can be used in combination with any of the monomers (A) to (C) used in the dispersant of the present invention. Examples of the unsaturated monomer include the unsaturated monomers having a nitrogen-containing heterocyclic ring described in the above [1] with respect to the nitrogen-containing macromonomer (B) component. Among them, vinylpyrrolidones, particularly N-vinyl-2-pyrrolidone, are preferred from the viewpoints of pigment dispersibility and hydrolysis resistance.

Other α-β-ethylenically unsaturated monomers (E): Furthermore, α-β-ethylenically unsaturated monomers (E) other than the above (A), (B), (C) and (D) ) Is not particularly limited, and can be selected widely according to the performance desired for the dispersant of the present invention. Representative examples of such unsaturated monomers are as follows.

(A) Ester of acrylic acid or methacrylic acid: For example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacryl acid isopropyl, butyl methacrylate, C ₁ ~ ₇ alkyl esters of acrylic acid or methacrylic acid such as hexyl methacrylate; methoxybutyl acrylate, methacrylic acid methoxybutyl, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, alkoxyalkyl esters of C ₂ ~ ₇ of acrylic acid or methacrylic acid such as methacrylic acid ethoxybutyl; allyl acrylate, C ₂ ~ ₇ a of acrylic acid or methacrylic acid and allyl methacrylate Luque sulfonyl ester; hydroxyethyl acrylate, hydroxyethyl El methacrylate, hydroxypropyl acrylate, C ₂ ~ ₇ acrylic acid or methacrylic acid such as hydroxyethyl methacrylate
Hydroxyalkyl esters; C ₃ ~ ₇ carboxyalkyl esters of acrylic acid or methacrylic acid such as 2-carboxyethyl acrylate; allyl oxyethyl acrylate, C ₃ ~ ₇ alkenyloxy alkyl esters of acrylic acid or methacrylic acid such as allyloxy methacrylate .

(B) Vinyl aromatic compounds: for example, styrene, α-methylstyrene, vinyltrain, p-chlorostyrene.

(C) polyolefin-based compound: for example, butadiene,
Isoprene, chloroprene.

(D) α, β-ethylenically unsaturated carboxylic acid: for example,
Acrylic acid, methacrylic acid, maleic acid, itaconic acid, etc.

(E) Others: acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, vinyl propionate, Praxel FM-3 (trade name, manufactured by Daicel Chemical Industries, ε-caprolactone-modified vinyl monomer), Praxel FM-5 ( Same as left).

This unsaturated monomer is appropriately selected depending on the physical properties desired for the aqueous pigment dispersion, may be used alone,
Alternatively, two or more kinds can be used in combination.

According to the present invention, the modified vinyl monomer (A) described above,
Nitrogen-containing macromonomer (B), vinyl monomer (C),
Unsaturated monomer (D) having a nitrogen-containing heterocycle and α, β-
The ethylenically unsaturated monomers (E) are copolymerized with one another. The copolymerization can be carried out according to a method known per se for producing a (meth) acrylic copolymer, for example, using a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or the like.

When performing the copolymerization, the mixing ratio of the above five components can be changed depending on the performance desired as a dispersant,
It is appropriate to mix the following components based on 100 parts by weight of the total of the five components (A) to (D) (the same in the description and the applied clams).

Modified vinyl monomer (A): 3 to 90 parts by weight, preferably 10 to 85 parts by weight, more preferably 15 to 70 parts by weight from the viewpoint of pigment dispersibility and storage stability, nitrogen-containing macromonomer (B): 2 to 90 parts by weight, preferably 3 to 70 parts by weight, more preferably 4 to 60 parts by weight, from the viewpoint of pigment dispersibility and storage stability, vinyl monomer (C): 1 to
50 parts by weight, preferably 2 to 40 from the viewpoint of water solubility and coating film performance
Parts by weight, more preferably 3 to 35 parts by weight, (D) 0 to 91 parts by weight of an unsaturated monomer having a nitrogen-containing heterocycle, preferably 5 to 80 parts by weight from the viewpoint of water solubility and coating performance. Preferably, it is 8 to 70 parts by weight, α, β-ethylenically unsaturated monomer (E) other than the above (A) to (D): 0 to 91 parts by weight, preferably 5 to 91 parts by weight in view of coating film performance. -85 parts by weight, more preferably 7-80 parts by weight.

The above-mentioned copolymerization reaction is preferably carried out advantageously according to a solution polymerization method. The above-mentioned five components are usually used in a suitable inert solvent in the presence of a polymerization catalyst, usually at about 0 to about 180 ° C., preferably at about 180 ° C. At a reaction temperature of 40 to about 170 ° C, about 1 to about 20
The reaction can be carried out for a period of time, preferably about 6 to about 10 hours.

As the solvent to be used, it is desirable to use a solvent that dissolves the produced copolymer and is miscible with water. Particularly, those which can be used as they are without being removed when obtaining a cationic aqueous pigment dispersion are preferred. Examples of such a solvent include cellosolve solvents of the formula HO—CH ₂ CH ₂ —OR ₆ , wherein R ₆ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, for example, ethylene glycol, butyl cellosolve, ethyl Cellosolve etc .; formula Wherein R ₆ has the same meaning as described above, for example, a propylene glycol-based solvent such as propylene glycol monomethyl ether; a compound of the formula HO—CH ₂ CH ₂ —OCH ₂ CH ₂ —OR _{6 wherein} R ₆ is the same as above Carbitol solvents such as diethylene glycol, methyl carbitol, butyl carbitol and the like; formula R ₇ O—CH ₂ CH ₂ —OR
_{8 wherein} R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms, such as ethylene glycol dimethyl ether; a compound of the formula R ₇ O—CH ₂ CH ₂ O
A diglyme-based solvent of CH ₂ —CH ₂ OR ₈ where R ₇ and R ₈ have the same meaning as above, such as diethylene glycol dimethyl ether; formula R ₉ O—CH ₂ CH ₂ OCO—CH
₃ [where R ₉ represents a hydrogen atom or CH ₃ or C ₂ H ₅ ] cellosolve acetate solvents such as ethylene glycol monoacetate, methyl cellosolve acetate, etc .; Formula R ₁₀ OH [where R ₁₀ is the number of carbon atoms Alcohols such as ethanol, propanol, butanol, etc .; and diacetone alcohol, dioxane, tetrahydrofuran, acetone, dimethylformamide, 3-methoxy-
3-methyl-butanol and the like can be used.

However, inert solvents that are immiscible with water can also be used, and such water-immiscible solvents have a boiling point of 250 ° C. or lower so that they can be easily removed by distillation under normal pressure or reduced pressure after the completion of the polymerization reaction. Is preferred. Such solvents include, for example, Wherein R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Wherein R ₁₂ and R ₁₃ each represent an alkyl group having 1 to 4 carbon atoms;
For example, toluene, xylene and the like; formula R ₁₄ —COO—R
_{15 wherein} R ₁₄ represents an alkyl group having 1 to 6 carbon atoms, and R ₁₅ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms or a cyclohexyl group; For example, acetic acid, ethyl formate,
Butyl acetate, cyclohexyl acetate, etc .; formula R ₁₆ R ₁₇ C = O
Wherein R ₁₆ and R ₁₇ each represent an alkyl group having 1 to 8 carbon atoms. Ketones represented by, for example, methyl ethyl ketone,
Cyclohexanone and the like; formula R ₁₆ —O—R ₁₇ [provided that R ₁₆
And R ₁₇ have the same meaning as described above], for example, ethyl ether, hexyl ether and the like; represented by the formula R ₁₈ OH, wherein R ₁₈ represents an alkyl group having 5 to 11 carbon atoms. Alcohols, for example, hexanol.

These solvents are used in an amount of 15 to 90% of the total weight of the five copolymerized components.
It can be used in the range of weight%.

Further, as the polymerization catalyst, for example, azo compounds, peroxide compounds, sulfides, sulfins,
Radical initiators that can be used for ordinary radical polymerization such as sulfinic acids, diazo compounds, nitroso compounds, redox systems and ionizing radiation are used.

In the present invention, a substantially satisfactory aqueous pigment dispersion can be obtained even if the molecular weight of the produced copolymer changes,
If the molecular weight is too low, the physical properties of the coating film of the water-based paint to be colored may be reduced. On the other hand, if the molecular weight is too high, the viscosity increases, and if the molecular weight is lowered, the concentration of the copolymer decreases and the dispersibility of the pigment decreases. Therefore, the copolymerization reaction generally has a number average molecular weight of about 700
Advantageously, it is in the range of from about 150,000 to about 150,000, preferably from about 1,000 to about 100,000.

Further, the copolymer thus obtained is generally at least
0.02 meq / g copolymer, preferably at least 0.2 meq / g copolymer, more preferably 0.2-3.0 meq / g
It can have the amino group equivalent of the copolymer.

The copolymer thus produced is made water-soluble or water-dispersed as it is or after distilling off the solvent.
This water-solubilization or water-dispersion can be performed, for example, by using (B) and (C) in the copolymer when an aminoalkyl (meth) acrylic monomer is used as a monomer component.
After neutralizing or quaternary ammonium-forming the amino group derived from the above monomer component with a conventionally known neutralizing agent, the amino group can be dissolved or dispersed in water. Examples of the neutralizing agent that can be used include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, hydroxyacetic acid, and lactic acid; boric acid,
Inorganic acids such as hydrochloric acid, phosphoric acid, and sulfuric acid; and the like can be used.
Particularly, formic acid and acetic acid are preferred.

The neutralization treatment can be easily carried out by a conventional method by adding the above-described neutralizing agent or an aqueous solution thereof to the copolymer or a solution thereof obtained as described above. The amount of the neutralizing agent to be used is generally 0.1 to 2.0 equivalents, preferably 0.3 to 1.0 equivalents, based on amino groups in the resin.

The quaternary ammonium conversion of the copolymer is carried out, for example, by reacting the copolymer with the following 1,2-epoxy compound in the presence of an acid and / or water to form a secondary or tertiary amino acid in the copolymer. This can be done by quaternizing the group.

1,2-- which can be used for quaternary ammoniumation of the copolymer
As the epoxy compound, for example, the following formula (IV) Wherein R ₁ has the previous meaning, R ₁₉ is a hydrogen atom, an alkyl group, a cycloalkyl group, —CH ₂ —O—R ₂₀ , Or a substituted or unsubstituted phenyl group, wherein R ₂₀ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or a substituted or unsubstituted phenyl group. The alkyl and cycloalkyl groups, which may be represented by R ₁₉ and / or R ₂₀ , may generally have from 1 to 18, preferably from 1 to 8, carbon atoms, and the alkenyl groups preferably have from 2 to It can have 6 carbon atoms. Further, examples of the substituent on the phenyl group include a lower alkyl group and a lower alkoxy group.

 Representative examples of such 1,2-epoxy compounds include ethylene.
Oxide, prolene oxide, 1,2-butylene oxide
Side, 1,2-pentylene oxide, 1,2-octylene
Oxide, styrene oxide, glycidol,
T) Glycidyl acrylate, glycidyl acetate, laurin
Glycidyl acid, CARDURA E (Grass of versatile acid
Sidyl ester, manufactured by Ciel Chemical Co., Ltd.), butyl glycidyl
Ether, octyl glycidyl ether, phenyl gly
Sidyl ether, p-tert-butylphenyl glycidyl
Ether, allyl glycidyl ether, etc.
You.

The amount of these 1,2-epoxy compounds used can vary depending on the type of amino group to be quaternized,
In general, it is convenient to use a 2- to 4-fold molar amount for a secondary amino group and a 1-2-fold molar amount for a tertiary amino group.

On the other hand, examples of the acid used for the quaternization reaction include organic acids such as formic acid, acetic acid, lactic acid, (meth) acrylic acid, propionic acid, butyric acid, and hydroxyacetic acid; boric acid, hydrochloric acid, phosphoric acid, and sulfuric acid. Inorganic acids. These acids are used in an amount of about 1 to 1 amino group to be quaternized ammonium.
It is expedient to use them in a proportion of about 2 mol.

The water is suitably used in a ratio of about 0.5 to about 20 mol per amino group to be quaternized.

One suitable method for quaternary ammonium conversion of the amino group derived from the aminoalkyl (meth) acrylic monomer (C) in the copolymer is to prepare a mixture of the copolymer and the acid as described above. , A 1,2-epoxy compound and water, and reacting at a temperature from room temperature to about 120 ° C. for about 1 to about 7 hours. When the amino group to be quaternary ammonium is a secondary amino group, the secondary amino group is first changed to a tertiary amino group by reaction with a 1,2-epoxy compound, and then the tertiary amino group is converted to a tertiary amino group. You may make it change into a quaternary ammonium group.

When a glycidyl group-containing vinyl unsaturated monomer is used as the monomer component (C) of the copolymer, for example, a glycidyl group in the copolymer and a secondary amine (eg, dimethylamine, diethylamine , Monoethanolamine,
Diethanolamine, diisopropanolamine, morpholine, etc.) to form a tertiary amino group newly formed by addition reaction with the tertiary amino group and an amino group derived from the monomer component (B) in the copolymer. Neutralizing treatment with a neutralizing agent, or the above-mentioned quaternary ammonium (1,2
-Reaction in the presence of an epoxy compound, an acid and / or water), and then dissolving or dispersing in water to make it water-soluble or water-dispersible. In addition to the above, a tertiary amine (eg, triethylamine, tributylamine, triethanolamine, benzyldimethylamine, etc.) is added to the copolymer in the presence of the same acid and / or water as used in the above quaternization. After the glycidyl group in the copolymer is converted to a quaternary ammonium, it can be dissolved or dispersed in water.

The quaternary ammonium-modified copolymer should contain a sufficient amount of quaternary ammonium groups to make the copolymer water-soluble, the amount of which depends on the type and molecular weight of the copolymer. Generally, it varies from 0.01 to 6 meq / g.
The range of the copolymer, preferably 0.1-5 meq / g copolymer, more preferably 0.1-3 meq / g copolymer is suitable.

The dispersant comprising the copolymer solubilized or dispersed in water as described above is generally used in an amount of about 1 to about 5 per 100 parts by weight of the pigment.
It can be used in an amount of about 00 parts by weight, preferably about 1 to about 300 parts by weight. When the use amount of the dispersant exceeds the upper limit of this range, the balance between the coloring power and the viscosity of the aqueous pigment dispersion tends to be unbalanced.On the other hand, when the amount is outside the lower limit, the dispersion stability of the pigment decreases. Cheap.

The aqueous medium that can be used in the cationic aqueous pigment dispersion of the present invention is substantially water, but if necessary,
For example, when the degree of hydrophilicity of the dispersant is low and sufficient pigment dispersion performance cannot be obtained, a hydrophilic organic solvent can be used in combination. As the hydrophilic organic solvent, the same ones used in the production of the polymer can be used alone or in combination. The pigments used in the cationic aqueous pigment dispersion of the present invention can be inorganic and organic pigments usually used in this kind of pigment dispersion. For example, the inorganic pigments include (1) oxidized pigments. (Zinc white, titanium dioxide, benkara, chromium oxide, cobalt blue, iron black, etc.); (2) hydroxide (alumina white, yellow iron oxide, etc.); (3) sulfide, selenide (sulfide) (4) Ferrocyanide (navy blue, etc.); (5) Chromate (graphite, zinc chromate, molybdenum red, etc.); (6) Sulfate (Precipitable barium sulfate etc.);
(7) Carbonates (precipitable calcium carbonate, etc.); (8) Silicates (hydrous silicates, clay, ultramarine blue, etc.); (9) Phosphates (manganese violet, etc.); (10) Carbon System (carbon black, etc.); (11) metal powder system (aluminum powder,
Bronze powder, zinc dust, etc.). Examples of the organic pigments include (1) nitroso pigments (such as naphthol green B); (2) nitro pigments (such as naphthol yellow S); and (3) azo pigments. (Resole Red, Lake Red C,
Fast yellow, naphthol red, red, etc.);
(4) Dyed lake pigments (alkali blue lake, rhodamine lake, etc.); (5) phthalocyanine pigments (phthalocyanine blue, fast sky blue, etc.); (6)
Condensed polycyclic pigments (perylene red, quinacridone red, dioxazine biored, isoindolinone yellow, etc.) and the like are included.

The content of the pigment in the cationic aqueous pigment dispersion of the present invention is not particularly limited, but is generally about 2 to about 90% by weight, preferably 5 to about 90% by weight based on the weight of the dispersion. 85% by weight.

The cationic aqueous pigment dispersion of the present invention can be prepared by mixing the above components together in a suitable dispersing apparatus. Examples of the dispersing apparatus that can be used include those generally used in the paint industry. Ball mill,
Roll mills, homomixers, sand grinders, shakers, attritors and the like are mentioned.

If necessary, conventionally known surfactants and protective colloids can be added to the cationic aqueous pigment dispersion of the present invention to improve the dispersion stability.

In the cationic aqueous pigment dispersion of the present invention thus obtained, the pigment is dispersed very uniformly and finely, and the pigment particles hardly aggregate or settle even when stored for a long time.

Thus, the cationic aqueous pigment dispersion of the present invention is an aqueous alkyd resin, an acrylic resin, an epoxy resin, a urethane resin, a conventionally known water-soluble resin such as a maleated polybutadiene resin used in aqueous paints and aqueous inks, Good miscibility with water-dispersible resin, emulsion, etc.
There is no limitation by these resins, and they can be widely used for coloring water-based paints made of any of these resins. In particular, it is effective for a cationic water-dispersible resin and a polymerizable emulsion, which themselves have poor pigment dispersibility.

The mixing ratio of the cationic aqueous pigment dispersion of the present invention to the aqueous paint can be changed in a wide range depending on the kind of the pigment in the dispersion, the degree of coloring required for the final paint, and the like. The pigment dispersion can be blended in an amount of about 2 to about 1000 parts by weight, preferably 3 to 800 parts by weight, based on 100 parts by weight of the resin component of the above-mentioned aqueous paint.

Next, the present invention will be described in more detail by way of examples. In the examples, parts and% indicate parts by weight and% by weight.

Reference Example (A-1) 236 parts of safflower oil fatty acid 119 parts of glycidyl methacrylate 0.4 part of hydroquinone 0.2 part of tetraethylammonium bromide 0.2 part was placed in a reaction vessel. 140-150 ℃ while stirring the reaction
, To obtain an addition reaction product of the modified acrylic monomer (A-1). The addition reaction between the epoxy group and the carboxyl group was followed while measuring the amount of the remaining carboxyl group. It took about 4 hours to complete the reaction.

Reference Example (A-2) Linseed oil fatty acid 364 parts Aziridinylethyl methacrylate 208 parts Hydroquinone 0.6 parts After the above components are placed in a reaction vessel, the reaction temperature is maintained at 140 to 150 ° C. while stirring the reaction solution. An addition reaction was performed. The addition reaction between the epoxy group and the carboxyl group was followed while measuring the amount of the remaining carboxyl group. The modified acrylic monomer (A-2) was obtained in a reaction time of about 4 hours.

Reference Example (A-3) 2-Hydroxyethyl methacrylate was placed in a reaction vessel.
278 parts, 208 parts of toluene diisocyanate and 0.1 part of hydroquinone were charged and reacted at 60 ° C. for 3 hours to obtain an unsaturated monomer having an isocyanate group. Then, 430 parts of oleyl alcohol was added to 486 parts of the unsaturated monomer having an isocyanate group obtained above, and the mixture was reacted at 80 ° C. for 3 hours to obtain an unsaturated monomer having a urethane bond (A-3). .

Reference Example (B-1) 250 parts of ethanol was charged into a reaction vessel, and the temperature was raised to 70 ° C. Next, 4,4'-azobisisobutyronitrile 12.5
Parts were separately added dropwise over 2 hours to a monomer solution in which 250 parts of N-vinyl-2-pyrrolidone was dissolved and a solution in which 17.5 parts of mercaptoacetic acid was dissolved in 80 parts of ethanol to carry out polymerization. After completion of the polymerization, the mixture was cooled to 20 ° C., poured into 10,000 parts of diethyl ether to cause coagulation and sedimentation, and the obtained powder was dried at 80 ° C. for 10 hours at 10 mmHg under reduced pressure. The acid value of the powder was 26.1.

Next, 213 parts of ethyl cellosolve and 200 parts of the above powder were added to another reaction vessel, and the temperature was raised to 70 ° C. to completely dissolve the powder. Once cooled to 20 ° C., 13.2 parts of glycidyl methacrylate, tetraethylammonium bromide 0.2
And 0.3 part of hydroquinone, and reacted at 120 ° C. for 5 hours to obtain a 49% macromonomer solution (B-1) of N-vinyl-2-pyrrolidone having an acid value of 0.5.

Reference Example (B-2) 200 parts of ethanol was charged into a reaction vessel, and the temperature was raised to 70 ° C. 100 parts of N-vinyl-2-pyrrolidone, ethanol 1
A solution prepared by mixing and dissolving 00 parts and 20 parts of 4,4'-azobis (4-cyano) valeric acid was added dropwise over 2 hours. 20 ° C after dropping
This was poured into 10,000 parts of diethyl ether to cause coagulation and sedimentation, and the resulting powder was dried at 80 ° C. for 10 hours at 10 mmHg under reduced pressure. The acid value of the powder was 34.2.

Next, 104 parts of ethyl cellosolve and 95 parts of the above powder were charged into another reaction vessel, and the temperature was raised to 70 ° C. and completely dissolved.
Glycidyl methacrylate 8.3 parts, tetraethylammonium bromide 0.2 parts, hydroquinone 0.2
And reacted at 115 ° C. for 5 hours. A 50% macromonomer solution of N-vinyl-2-pyrrolidone having an acid value of 1.0 (B-
2) was obtained.

Reference Example (B-3) Instead of N-vinyl-2-pyrrolidone of Reference Example 1,
Production was carried out in the same manner as in Reference Example using the same amount of N, N-dimethylaminoacrylamide. 51% macromonomer of N, N-dimethylaminoacrylamide having an acid value of 1.5 (B-
3) was obtained.

Example 1 300 parts of n-butyl cellosolve was placed in a reaction vessel and heated to 120C. Next, a mixture having the following ratio was separately added dropwise to the solution over about 2 hours. The reaction was performed while stirring the solution under nitrogen injection.

A mixture consisting of 113 parts of a modified acrylic monomer (A-1), 186 parts of a macromonomer (B-1) and 44 parts of N, N-dimethylaminoethyl methacrylate; 19 parts of azobisdimethylvaleronitrile and 50 parts of n-butyl cellosolve 1 hour after the completion of dropping of the mixture, 2.5 parts of azobisisobutyronitrile was added to the reaction vessel, and further 2 hours later,
Add azobisisobutyronitrile 2.5 parts to the reaction solution,
Thereafter, the reaction was carried out at 120 ° C. for 2 hours. After completion of the reaction, the unreacted monomer and n-butyl cellosolve were distilled under reduced pressure to obtain a copolymer solution having a heating residue of 70.5% and a Gardner viscosity (40% n-butyl cellosolve solution) E. Further, 180 parts of the copolymer solution was placed in a reaction vessel, and was heated to about 50 ° C.
Temperature, add 6.6 parts of 88% lactic acid aqueous solution
C. and heated for about 30 minutes. Thereafter, the mixture was cooled to 50 ° C., 4.7 parts of 1,2-butylene oxide and 3.5 parts of water were added, and the mixture was heated to 110 ° C. and reacted for about 2.5 hours to perform quaternary ammonium conversion. The quaternary ammonium group content of the obtained copolymer was about 0.25 meq / g copolymer. After cooling the obtained water-solubilized copolymer to room temperature, water was added to obtain a 40% dispersant (I).

Next, a mixture of 8.3 parts of this dispersant (I) and 200 parts of titanium white pigment (Titanium White R-5N manufactured by Sakai Chemical Co., Ltd.) was dispersed for 0.5 hour using a Red Devil disperser, and the aqueous pigment dispersion of the present invention was dispersed. Liquid (a) was obtained.

Similarly, pigments were dispersed at the ratios shown in Table 1 below to obtain aqueous pigment dispersions (b) and (c) of the present invention. The pigments other than titanium white were dispersed for one hour.

The properties of the resulting cationic aqueous pigment dispersion are summarized in Table 1 below.

Next, the formulations comprising the pigment dispersion and the aqueous resin shown in Table 2 below were sufficiently mixed to obtain aqueous paints (1) to (4). The coating performance of the obtained water-based paint is summarized in Table 2 below.
Shown in

Example 2 350 parts of n-butyl cellosolve was placed in a reaction vessel and heated to 120C. Next, a mixture having the following ratio was added dropwise to this solution over about 2 hours. The reaction was performed under nitrogen injection.

Modified acrylic monomer (A-2) 113 Macromonomer (B-2) 252 parts N, N-dimethylaminoethyl methacrylate 11 parts Azobisdimethylvaleronitrile 17 parts Keep the reaction temperature at 120 ° C, and stir the reaction solution. The above mixture was added dropwise, and polymerization was carried out in the same manner as in Example 1 to obtain a heating residue of 70.8% and a Gardner viscosity (40%).
% N-butyl cellosolve solution) H was obtained. Further, 211 parts of this copolymer solution was placed in a reaction vessel, the temperature was raised to about 50 ° C., 3.5 parts of an 88% lactic acid aqueous solution was added, and then the temperature was raised to 70 ° C., and 2.5 parts of 1,2-butylene oxide and 2.5 parts of 1,2-butylene oxide were added. 2 parts of water was added, the temperature was further raised to 110 ° C., and the reaction was carried out for about 3 hours to perform quaternary ammonium conversion. The quaternary ammonium group content of the obtained copolymer was about 0.2 meq / g copolymer. Water was added to the water-soluble copolymer to obtain a 40% dispersant (II).

Next, using the obtained dispersant (II), the pigments shown in Table 1 below were dispersed in the same manner as in Example 1 to obtain an aqueous pigment dispersion (d) of the present invention.

Further, this pigment dispersion (d) and an aqueous resin shown in Table 2 below were sufficiently mixed to prepare an aqueous paint (5).

The properties of the pigment dispersion (d) and the coating properties of the water-based paint (5) are shown in Tables 1 and 2 below.

Example 3 Unsaturated monomer (A-3) 113 parts Macromonomer (B-3) 230 parts N, N-dimethylaminoethyl methacrylate 44 parts and a mixture of azobisdimethylvaleronitrile 17 parts n-butyl cellosolve 50 parts The mixture was polymerized according to the method described in Example 1. A copolymer solution having a heating residue of 70.5% and a Gardner viscosity (40% n-butyl cellosolve solution) B was obtained. Further, 180 parts of this copolymer solution is placed in a reaction vessel, and is heated to about 50 ° C.
After adding 6.6 parts of an 88% lactic acid aqueous solution, the temperature was raised to 80 ° C., 4.7 parts of 1,2-butylene oxide and 35 parts of water were added, and the mixture was further reacted at 110 ° C. for about 2.5 hours to obtain a quaternary. Ammonification was performed. The quaternary ammonium group content of the obtained copolymer was about 0.3 meq / g copolymer. Water was added to the water-soluble copolymer to obtain a 40% dispersant (III).

Next, using the obtained dispersant (III),
Was dispersed in the same manner as in Example 1 to obtain an aqueous pigment dispersion (e) of the present invention.

Further, this pigment dispersion (e) and an aqueous resin shown in Table 2 below were sufficiently mixed to prepare an aqueous paint (6).

The properties of the pigment dispersion (e) and the coating properties of the water-based paint (6) are shown in Tables 1 and 2 below.

Example 4 Stearyl methacrylate 102 parts Reference example (B-1) 184 parts Acrylic acid 11 parts N, N-dimethylaminopropyl methacrylamide 44 parts and a mixture of azobisdimethylvaleronitrile 17 parts n-butyl cellosolve 50 parts The polymerization reaction was carried out according to the method described in Example 1. A copolymer solution having a heating residue of 70.5% and Gardner viscosity (40% n-butyl cellosolve solution) J was obtained. Further, 180 parts of this copolymer solution is placed in a reaction vessel, and is heated to about 50 ° C.
After adding 7.7 parts of acetic acid, the temperature was raised to 80 ° C.
Add 9.5 parts of butylene oxide and 10.0 parts of water, and add 1 part.
The temperature was raised to 10 ° C., and the reaction was carried out for about 3.5 hours to form quaternary ammonium. The quaternary ammonium group content of the obtained copolymer was about 0.5 meq / g copolymer. Water was added to the water-soluble polymer to obtain a 40% dispersion (IV).

Next, using the obtained dispersant (IV), the pigments shown in Table 1 below were dispersed in the same manner as in Example 1 to obtain an aqueous pigment dispersion (f) of the present invention.

The pigment dispersion (f) and the aqueous resin shown in Table 2 below were sufficiently mixed to prepare an aqueous paint (7). The properties of the pigment dispersion (f) and the coating properties of the water-based paint (7) are shown in Tables 1 and 2 below.

Example 5 Modified acrylic monomer (A-1) 93 parts Macromonomer (B-2) 100 parts N-vinylpyrrolidone 33 parts N, N-dimethylaminoethyl methacrylate 44 parts n-butyl methacrylate 30 parts A mixture of azobisdimethyl valeronitrile and 18 parts of n-butyl cellosolve was polymerized according to the method described in Example 1. A copolymer solution having a heating residue of 71.0% and Gardner viscosity (40% n-butyl cellosolve solution) H was obtained. Further, 180 parts of this copolymer solution is placed in a reaction vessel, and is heated to about 50 ° C.
After adding 13.2 parts of 88% lactic acid aqueous solution, the temperature was raised to about 90 ° C., 17.5 parts of butyl glycidyl ether and 8.0 parts of water were added, and the mixture was reacted at 120 ° C. for about 3 hours to perform quaternary ammonium conversion. Done. The quaternary ammonium group content of the obtained copolymer was about 0.45 meq / g copolymer. Water was added to the water-soluble copolymer to obtain a 40% dispersant (V).

Next, using the obtained dispersant (V), the pigments shown in Table 1 below were dispersed in the same manner as in Example 1 to obtain an aqueous pigment dispersion (g) of the present invention.

Further, this pigment dispersion (g) and an aqueous resin shown in Table 2 below were sufficiently mixed to prepare an aqueous paint (8).

The properties of the pigment dispersion (g) and the coating properties of the water-based paint (8) are shown in Tables 1 and 2 below, respectively.

Comparative Example 1 Instead of Reference Example (B-1) of Example 1, N-vinyl-
A polymerization reaction was carried out using 93 parts of 2-pyrrolidone to obtain a copolymer solution having a heating residue of 70.4% and Gardner viscosity (40% n-butyl cellosolve solution) F. As described above, the first embodiment
Water was added in the same manner as described above to obtain a 40% dispersant (VI).

Next, using the obtained dispersant (VI), the pigments shown in Table 1 below were dispersed in the same manner as in Example 1 to obtain an aqueous pigment dispersion (h).

Further, this pigment dispersion (h) and an aqueous resin shown in Table 2 below were sufficiently mixed to prepare an aqueous paint (9). The properties of the pigment dispersion (h) and the coating properties of the water-based paint (9) are shown in Tables 1 and 2 below.

[Coating film performance test] Aqueous drier (trade name "Dicnate", manufactured by Dainippon Ink Co., Ltd., cobalt metal content 3) was added to the aqueous paints (1) to (9).
%) Was added at a ratio of 1 part to 100 parts of the resin solid content, and was applied to a mild steel sheet. After drying at 20 ° C. and a relative humidity of 75% for 3 days, it was subjected to a test.

Adhesiveness of the Goban eyes: 100 pieces of Gobang eyes having a width of 1 mm were made, and a Serophane adhesive tape was stuck thereon, and the vigorously peeled off the tape, the test was performed.

Water resistance: The coated surface was immersed in tap water at 20 ° C. for 2 days and visually inspected for the state of the coated surface.

Claims (19)

(57) [Claims] 1. A pigment, the aqueous pigment dispersion comprising a dispersant and an aqueous medium, the dispersant, (A) modified vinyl unsaturated monomer 3 having a C ₈ or higher fatty acid residues in the molecular end 90 parts by weight (B) at least one selected from acryloyloxy, methacryloyloxy, allyloxy and aromatic vinyl
Nitrogen-containing macromonomer having one kind of radical polymerizable functional group at one end 2 to 90 parts by weight (C) From aminoalkyl (meth) acrylate, aminoalkyl (meth) acrylamide and glycidyl group-containing vinyl unsaturated monomer 1 to 50 parts by weight of at least one selected vinyl monomer (D) 0 to 91 parts by weight of an unsaturated monomer having a nitrogen-containing heterocyclic ring; and (E) the above (A), (B), (C) ) And (D), a copolymer obtained by copolymerizing 0 to 91 parts by weight of an α, β-ethylenically unsaturated monomer other than (D), wherein the copolymer is a water-soluble or water-dispersed product. Cationic aqueous pigment dispersion. 2. The modified vinyl unsaturated monomer (A) is an ethylenically unsaturated monomer having a functional group selected from a hydroxyl group, a carboxyl group, a glycidyl group, an isocyanate group and an aziridine group. _2. The dispersion according to claim 1, wherein the dispersion is modified with a modifier selected from _eight or more fats, fatty acids, fatty alcohols, fatty acid glycidyl esters, and aliphatic amines. 3. The homo- or copolymer of an unsaturated monomer having a nitrogen-containing heterocyclic ring and a nitrogen-containing unsaturated monomer selected from a nitrogen-containing derivative of (meth) acrylic acid as the nitrogen-containing macromonomer (B). Acryloyloxy at one end of the main chain,
2. The dispersion according to claim 1, wherein at least one radical polymerizable functional group selected from methacryloyloxy, allyloxy and aromatic vinyl is introduced. 4. The unsaturated monomer having a nitrogen-containing heterocyclic ring,
4. The dispersion according to claim 3, which is at least one monomer selected from vinylpyrrolidones, vinylimidazoles and vinylcarbazoles. 5. The nitrogen-containing derivative of (meth) acrylic acid is represented by the following formulas (I) to (III): In the above formulas, represents R ₁ hydrogen atom or a methyl group, R ₂ and R ₃ each independently represent a hydrogen atom or a lower alkyl group, R ₄ represents a hydrogen atom or a lower alkyl, R ₅
Represents a hydrogen atom, a lower alkyl group, a di (lower alkyl) amino lower alkyl group, a hydroxy lower alkyl group or a lower alkoxy lower alkyl group, and n represents an integer of 2 to 8, and an aminoalkyl (meth) acrylate represented by 4. The dispersion according to claim 3, wherein the dispersion is selected from the group consisting of and (meth) acrylamide. 6. The nitrogen-containing derivative of (meth) acrylic acid is N,
4. The dispersion according to claim 3, wherein the dispersion is N-dimethylacrylamide or N, N-dimethylaminopropyl (meth) acrylamide. 7. A dispersion according to claim 1, wherein the macromonomer has a number average molecular weight in the range of from 500 to 15,000. 8. An aminoalkyl (meth) acrylate and an aminoalkyl (meth) acrylamide represented by the following formula (I):
~ (III): In the above formulas, represents R ₁ hydrogen atom or a methyl group, R ₂ and R ₃ each independently represent a hydrogen atom or a lower alkyl group, R ₄ represents a hydrogen atom or a lower alkyl, R ₅
Represents a hydrogen atom, a lower alkyl group, a di (lower alkyl) amino lower alkyl group, a hydroxy lower alkyl group or a lower alkoxy lower alkyl group, and n represents an integer of 2 to 8. 2. The dispersion according to item 1, wherein 9. The dispersion according to claim 1, wherein the vinyl monomer (C) is an aminoalkyl (meth) acrylamide of the formula (I). 10. The dispersion according to claim 9, wherein the aminoalkyl (meth) acrylamide is N, N-dimethylaminopropyl (meth) acrylamide. 11. The dispersion according to claim 1, wherein the glycidyl group-containing vinyl unsaturated monomer (C) is selected from glycidyl (meth) acrylate, allyl glycidyl ether and vinyl phenyl glycidyl ether. liquid. 12. A patent wherein the unsaturated monomer (D) having a nitrogen-containing heterocycle is selected from vinylpyrrolidones, vinylpyridines, vinylimidazoles, vinylcarbazoles, vinylquinolines and vinylpiperidines. The dispersion according to claim 1. 13. The dispersion according to claim 12, wherein the unsaturated monomer (D) having a nitrogen-containing heterocycle is N-vinyl-2-pyrrolidone. 14. An α, β-ethylenically unsaturated monomer (E)
2. The dispersion according to claim 1, wherein the dispersion is at least one selected from esters of (meth) acrylic acid, vinyl aromatic compounds, polyolefin compounds, and α, β-ethylenically unsaturated carboxylic acids. 15. The dispersant is modified vinyl unsaturated monomer (A) 10 to 85 parts by weight Nitrogen-containing macromonomer (B) 3 to 70 parts by weight Vinyl monomer (C) 2 to 40 parts by weight A copolymer obtained by copolymerizing 5 to 80 parts by weight of an unsaturated monomer (D) having a nitrogen-containing heterocycle and 5 to 85 parts by weight of another α, β-ethylenically unsaturated monomer (E) The dispersion according to claim 1, which is a combined water-soluble compound or a water-dispersed product. 16. The dispersion of claim 1, wherein the copolymer has a number average molecular weight in the range of about 700 to about 150,000. 17. The dispersion of claim 1 wherein the copolymer has an amino group equivalent of at least 0.02 meq / g copolymer. 18. The method according to claim 1, wherein the dispersant is used in an amount of about 1 to about 500 per 100 parts by weight of the pigment.
The dispersion according to claim 1, which is contained in a range of parts by weight. 19. A water-based paint containing the dispersion according to claim 1.