JPH0576507B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an aqueous pigment dispersion that uses a novel dispersant and has excellent dispersibility and dispersion stability. Conventionally, in water-based paints such as emulsion paints and water-soluble resin paints containing pigments, there have been problems such as decreased color hardening, flattening (floating), and flow on the painted surface due to poor dispersion of pigments during manufacturing and pigment aggregation/sedimentation during storage. It is well known that undesirable phenomena such as staining (floating mottling) and reduction in gloss occur. For this reason, generally, an aqueous pigment dispersion is prepared by dispersing the pigment in advance with a dispersant, and this is mixed and dispersed in the aqueous paint to be colored to color the aqueous paint. Conventional aqueous pigment dispersions mainly use low-molecular weight compounds such as surfactants as dispersants, but these dispersants cause negative effects, such as secondary adverse effects such as deterioration of coating performance or coating condition. This is unavoidable, and recently oligomers or polymers having a medium molecular weight have been used as dispersants to suppress the deterioration of coating performance. However, when oligomers or polymers are used as dispersants, the amount used is larger than that of low-molecular surfactants, and the resulting aqueous pigment dispersion is limited to the types of binders used in water-based paints. There are disadvantages such as being limited by This goes against the rationalization of paint manufacturing, and there is therefore a strong demand for the development of a water-based pigment dispersion that is common to various water-based paints. Therefore, the present inventors have developed an ideal dispersion that allows pigments to be easily dispersed in small amounts, is compatible with various water-based resins, and is polymeric in itself and does not cause a decline in the coating performance of water-based paints. The present invention was completed as a result of intensive research aimed at developing a particularly difficult aqueous system. Thus, according to the present invention, in an aqueous pigment dispersion comprising a pigment, a dispersant, and an aqueous medium, the dispersant comprises (A) an oil/fat fatty acid modified (meth)acrylic monomer (hereinafter referred to as "fatty acid"). (referred to as "modified (meth)acrylic monomer") 3 to 98 parts by weight (B) α,β-ethylenically unsaturated nitrogen-containing monomer
2 to 97 parts by weight (C) 0.5 to 40 parts by weight of carboxyl group-containing (meth)acrylic ester and (D) α,β-ethylenically unsaturated monomer other than the above (A), (B), and (C) An aqueous pigment dispersion is provided, which is characterized in that it is a water-soluble product of a polymer obtained by copolymerizing 0 to 91 parts by weight of a pigment. The polymer used as a dispersant for the aqueous pigment dispersion of the present invention is a non-crystalline and lipophilic long side chain composed of a relatively hydrophilic α,β-ethylenically unsaturated nitrogen-containing monomer and Because it has a structure in which it is bonded in a separate form to the main chain containing the carboxyl group-containing acrylic ester, it has very high pigment dispersion ability.
Furthermore, since the polymer contains both basic components derived from α,β-ethylenically unsaturated nitrogen-containing monomer units and acidic components derived from carboxylic acids, it can disperse a wide range of pigments such as acidic pigments and basic pigments. It has the advantage of being possible. In addition to its excellent pigment dispersing ability, this dispersant also has a relatively low acid value, that is, a small absolute amount of carboxyl groups, so it has excellent properties such as corrosion resistance and can be used to produce good colored coatings. membrane can be obtained. Hereinafter, the dispersant used in the aqueous pigment dispersion of the present invention will be explained in more detail. Fatty acid modified (meth)acrylic monomer (A) Fatty acid modified (meth) used in the present invention
The acrylic monomer (A) can be obtained by introducing an oil fatty acid such as a drying oil fatty acid, a semi-drying oil fatty acid, a non-drying oil fatty acid, etc. into a (meth)acrylic monomer as described below by the method described below. It is a monomer produced. Typical fatty acids that can be used in the present invention include, for example, safflower oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, poppy oil fatty acid, eno oil fatty acid, hempseed oil fatty acid, grape kernel oil fatty acid, and corn oil fatty acid. , tall oil fatty acids,
Drying and semi-drying oil fatty acids such as sunflower oil fatty acids, cottonseed oil fatty acids, walnut oil fatty acids, rubber seed oil fatty acids, tung oil fatty acids, oiticica oil fatty acids, dehydrated castor oil fatty acids, hygienic fatty acids; and coconut oil fatty acids, olive oil fatty acids, castor oil fatty acids,
Examples include non-drying oil fatty acids such as hydrogenated castor oil fatty acids and palm oil fatty acids; each of these fatty acids can be used alone or in a mixture of two or more. The amount of the fatty acid used can vary widely depending on the drying properties and coating performance desired for the aqueous pigment dispersion provided by the present invention, but in general,
It is advantageous to use amounts ranging from 5 to 65% by weight, preferably from 10 to 60% by weight, based on the weight of the polymer obtained. In addition, in the present invention, among the above-mentioned fatty acids, drying oil fatty acids and semi-drying oil fatty acids having an iodine value of about 100 or more are preferred because they can impart crosslinking drying properties to the resulting dispersant at room temperature. The (meth)acrylic monomer into which such a fatty acid is introduced is an ester of acrylic acid or methacrylic acid containing a functional group capable of reacting with the carboxyl group of the fatty acid, such as an epoxy group or a hydroxyl group, in the ester residue portion. can be exemplified. Therefore, one type of (meth)acrylic monomer into which the fatty acid described above is introduced in order to obtain the fatty acid-modified (meth)acrylic monomer (A) is "acrylic ester having an epoxy group or methacrylic ester". esters" (hereinafter sometimes abbreviated as "epoxy-containing (meth)acrylic esters"), and examples of this type of ester include those containing a glycidyl group in the ester residue of acrylic acid or methacrylic acid, Particularly preferred are glycidyl acrylate and glycidyl methacrylate. Fatty acid modified acrylic monomer (A) using such epoxy-containing (meth)acrylic acid ester
can be prepared by reacting the aforementioned fatty acid with an epoxy-containing (meth)acrylic ester in the presence or absence of a suitable inert solvent, usually in the absence of a solvent, according to a conventional method. The reaction is generally carried out at a temperature of from about 60°C to about 220°C, preferably from about 120°C to about 220°C.
It can be carried out at a temperature of about 170°C, and the reaction time is generally about 0.5 to about 40 hours, preferably about 3
~ Approximately 10 hours. The epoxy-containing (meth)acrylic acid ester is usually 0.7 to 1.5 mol per mol of the fatty acid,
It is advantageous to use preferably a proportion of 0.8 to 1.2 mol. The inert solvent that may be used as necessary is preferably a water-immiscible organic solvent that can be refluxed at a temperature of 220°C or lower, such as aromatic hydrocarbons such as benzene, toluene, and xylene; heptane, Examples include aliphatic hydrocarbons such as hexane and octane. Furthermore, in the above reaction, a polymerization inhibitor, such as hydroquinone, methoxyphenol, tert-butyl catechole, benzoquinone, etc., is added to the reaction system as necessary, and the epoxy-containing (meth)acrylic ester and/or the resulting fatty acid modification are added. It is advantageous to suppress the polymerization of the (meth)acrylic ester. In the above reaction, esterification accompanied by cleavage of the oxirane ring occurs between the oxirane group (epoxy group) of the epoxy-containing (meth)acrylic acid ester and the carboxyl group of the fatty acid, resulting in the (meth)acrylic acid ester modified with the fatty acid. is obtained. In addition, the (meth)acrylic monomer that is reacted with the above fatty acid to produce another type of fatty acid-modified (meth)acrylic monomer (A) includes "acrylic ester or methacrylic ester containing a hydroxyl group" (hereinafter sometimes abbreviated as “hydroxyl group-containing (meth)acrylic acid ester”),
This type of ester includes one having one hydroxyl group in the ester residue of acrylic acid or methacrylic acid and containing 2 to 24, preferably 2 to 8 carbon atoms in the ester residue. Including, among others, the following formula () or ()

[ka]

[Chemical formula] In each of the above formulas, R ₁ represents a hydrogen atom or a methyl group, n is an integer of 2 to 8, p and q are each an integer of 0 to 8, provided that the sum of p and q is 1
-8, hydroxyl group-containing (meth)acrylic esters of the type shown below are suitable. Particularly suitable hydroxyl group-containing (meth) in the present invention
The acrylic esters are hydroxyalkyl acrylates and hydroxyalkyl methacrylates represented by the above formula (), especially 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate. The latter type of fatty acid-modified (meth)acrylic monomer (A) is usually prepared by mixing the fatty acid with the hydroxyl group-containing (meth)acrylic ester in an appropriate inert solvent in the presence of an esterification catalyst. This can be done by reacting with. The reaction is generally carried out under heating at a temperature of about 100 to about 180°C, preferably about 120 to about 160°C, and the reaction time is generally about
0.5 to about 9 hours, usually about 1 to about 6 hours. The hydroxyl group-containing (meth)acrylic ester is
Usually, it can be used in a proportion of 0.5 to 1.9 mol per mol of said fatty acid, preferably 1.0 to 1.5 mol per mol of said fatty acid. Examples of the esterification catalyst used in the above reaction include sulfuric acid, aluminum sulfate, potassium hydrogen sulfate, p-toluenesulfonic acid, hydrochloric acid, methyl sulfate, and phosphoric acid. Approximately 0.001 of the total amount of the above fatty acid and hydroxyl group-containing (meth)acrylic ester
~about 2.0% by weight, preferably from about 0.05 to about 1.0% by weight
used at a rate of In addition, as the inert solvent used as necessary, water-immiscible organic solvents that can be refluxed at a temperature of 180°C or lower are preferred, such as aromatic hydrocarbons such as benzene, toluene, and xylene; heptane, Examples include aliphatic hydrocarbons such as hexane and octane. Furthermore, in the above reaction, a polymerization inhibitor, such as hydroquinone, methoxyphenol, tert-butylcatechol, benzoquinone, etc., is added to the reaction system as necessary to produce a hydroxyl group-containing (meth)acrylic ester and/or a fatty acid to be produced. It is advantageous to suppress the polymerization of the modified (meth)acrylic ester. In the above reaction, esterification occurs between the hydroxyl group of the hydroxyl group-containing (meth)acrylic ester and the carboxyl group of the fatty acid, and a fatty acid-modified (meth)acrylic ester is obtained. As yet another method for preparing the fatty acid-modified (meth)acrylic monomer (A), in addition to the above-mentioned method, glycidyl esters of the fat and oil fatty acids (for example, "Blemmer DFA" manufactured by NOF Corporation) can be used. It is also possible to esterify acrylic acid or methacrylic acid as described above. α,β-ethylenically unsaturated nitrogen-containing monomer (B): Next, as the α,β-ethylenically unsaturated nitrogen-containing monomer (B) used in the present invention, one or a monomer having a plurality of (usually up to 4) basic nitrogen atoms and one ethylenically unsaturated bond; typical examples include unsaturated monomers having a nitrogen-containing heterocycle; Examples include nitrogen-containing derivatives of (meth)acrylic acid. These monomers will be explained in more detail below. [1] The unsaturated monomer having a nitrogen-containing heterocycle is a monomer in which a monocyclic or polycyclic heterocycle containing 1 to 3, preferably 1 or 2 ring nitrogen atoms is bonded to a vinyl group. In particular, the monomers shown below can be mentioned. () Vinylpyrrolidones; For example, 1-vinyl-2-pyrrolidone, 1
-vinyl-3-pyrrolidone, etc. () Vinylpyridines; For example, 2-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, etc. () Vinylimidazoles; For example, 1-vinylimidazole, 1-vinyl-2-methylimidazole, etc. () Vinylcarbazoles; For example, N-vinylcarbazole. () Vinylquinolines; For example, 2-vinylquinoline. () Vinylpiperidines; For example, 3-vinylpiperidine, N-methyl-3-vinylpiperidine, N-methyl-3-
vinylpiperidine etc. () Other; For example, expression

N-(meth)acryloylmorpholine represented by [Formula] (wherein R ₁ has the above meaning) or the formula

N-(meth)acryloylpyrrolidine represented by the formula: (wherein R ₁ has the above meaning), etc. Among the above-mentioned vinyl monomers having a nitrogen-containing heterocycle, vinyl pyrrolidones, vinyl imidazoles and vinyl carbazoles are preferable, and among them, those in which the ring nitrogen atom is tertiary are preferable. [2] Nitrogen-containing derivatives of (meth)acrylic acid include
Includes (meth)acrylic acid esters containing a substituted or unsubstituted amino group in the ester moiety and amides of (meth)acrylic acid, particularly those of the following formula () or ()

[ka]

[Chemical formula] In each of the above formulas, 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 group, and R ₅ represents a hydrogen atom, a lower alkyl group, or a di(lower alkyl group). alkyl) represents an amino lower alkyl group, a hydroxy lower alkyl group or a lower alkoxy lower alkyl group, and R ₁ and n have the above meanings. Aminoalkyl (meth)acrylates and (meth)acrylamides of the formula are suitable. The term "lower" herein means that the group to which this term is attached has no more than 6 carbon atoms, preferably no more than 4 carbon atoms. Therefore, as specific examples of such nitrogen-containing (meth)acrylic monomers, examples of the aminoalkyl (meth)acrylate of the above formula () include N,N-dimethylaminoethyl (meth)acrylate, N,
N-diethylaminoethyl (meth)acrylate, N-t-butylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminobutyl (meth)acrylate, N-propylaminoethyl (meth)acrylate, N-butylaminoethyl (meth)acrylate, etc. are included, and examples of (meth)acrylamide in the above formula () include (meth)acrylamide, N-methyl (meth)
Acrylamide, N-ethyl (meth)acrylamide, 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 etc. are included. As these nitrogen-containing (meth)acrylic monomers, those in which the existing nitrogen atoms are tertiary are optimal, and those in which the nitrogen atoms are secondary are also preferably used. The α,β-ethylenically unsaturated nitrogen-containing monomers described above can be used alone or in combination of two or more. Carboxyl group-containing (meth)acrylic acid ester
(C): Next, the carboxyl group-containing (meth)acrylic ester (C) used in the present invention has 1
carboxyl groups and 2 to 6, preferably 2 to 3 carbon atoms in the ester residue moiety, and the following formula ()

embedded image In the formula, R ₁ includes those shown as in the above formula (1), and m represents an integer from 2 to 6 and is a carboxyl group-containing (meth)acrylic ester. Examples of such carboxyl group-containing (meth)acrylic esters include 2-carboxyethyl (meth)acrylate and 2-carboxypropyl (meth)acrylate, each of which may be used alone or in combination of two or more. I can do it. Other α, β-ethylenically unsaturated monomers (D): Furthermore, α, β-ethylenically unsaturated monomers (D) other than the above (A), (B), and (C) include: There are no particular restrictions,
A wide range of choices can be made depending on the desired performance of the dispersant of the present invention. Representative examples of such unsaturated monomers are as follows. (a) Esters of acrylic acid or methacrylic acid, such as methyl acrylate, ethyl acrylate,
Propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate,
C1 _~ of acrylic acid or methacrylic acid such as octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, lauryl methacrylate, etc. ₁₈
Alkyl ester; glycidyl acrylate,
Glycidyl methacrylate; _C2-18 alkoxyalkyl ester of acrylic acid or methacrylic acid, such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate;
_C2-8 alkenyl esters of acrylic acid or methacrylic acid such as allyl acrylate, allyl methacrylate; hydroxyethyl acrylate,
C _2-8 hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate;
_C3-18 alkenyloxyalkyl ester. (b) Vinyl aromatic compounds: e.g. styrene, α
-Methylstyrene, vinyltoluene, p-chlorostyrene. (c) Polyolefin compounds: for example, butadiene, isoprene, chloroprene. (d) Others: acrylonitrile, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, beoba monomer (Siel Chemicals), vinyl propionate, vinyl pivalate, etc. The unsaturated monomers are appropriately selected depending on the physical properties desired for the aqueous pigment dispersion, and each may be used alone or in combination of two or more. According to the present invention, the fatty acid-modified (meth)acrylic monomer (A), the α,β-ethylenically unsaturated nitrogen-containing monomer (B), the carboxyl group-containing (meth)acrylic ester (C ) and the α,β-ethylenically unsaturated monomer (D) are copolymerized with each other. The copolymerization can be carried out according to methods known per se for producing (meth)acrylic copolymers, such as solution polymerization, emulsion polymerization, suspension polymerization, and the like. The blending ratio of the above four components when performing copolymerization can be changed depending on the desired performance as a dispersant, but it is generally appropriate to mix them in the following ratios. (1) Fatty acid modified (meth)acrylic monomer (A): 3
~98 parts by weight, preferably 10 to 85 parts by weight in terms of coating film drying properties and coating performance, (2) α,β-ethylenically unsaturated nitrogen-containing monomer (B):
2 to 97 parts by weight, preferably 3 to 90 parts by weight from the viewpoint of pigment dispersion, (3) Carboxyl group-containing (meth)acrylic acid ester (C): 0.5 to 40 parts by weight, preferably water-soluble,
2 to 18 parts by weight in terms of coating film performance, (4) Unsaturated monomers (D) other than the above (A), (B), and (C): 0 to
91 parts by weight, preferably 5 to 83 parts by weight in terms of coating performance
Weight part. The above copolymerization reaction is preferably carried out according to a solution polymerization method, in which the above four components are mixed in a suitable inert solvent in the presence of a polymerization catalyst, usually at about 0 to about 180°C, preferably. is at a reaction temperature of about 40 to about 170°C for about 1 to about 20 hours, preferably about 6 to about
This can be carried out by continuing the reaction for 10 hours. As the solvent used, it is desirable to use a solvent that can dissolve the produced copolymer and is miscible with water so that gelation does not occur during the copolymerization reaction. Particularly preferred is one that can be used as is without being removed when obtaining an aqueous pigment dispersion. Examples of such solvents 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] such as ethylene glycol, butyl cellosolve, and ethyl cellosolve. etc; expression

[Formula] [However, R ₆ has the same meaning as above] Propylene glycol solvent such as propylene glycol monomethyl ether; Formula CO-
Carbitol solvents of CH ₂ CH ₂ −OCH ₂ CH ₂ −OR ₆ [wherein R ₆ has the same meaning as above] such as diethylene glycol, methyl carbitol, butyl carbitol; formula R ₇ O−CH ₂ CH ₂
-OR ₈ [However, R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms] Glyme solvent such as ethylene glycol dimethyl ether; formula R ₇ O-CH ₂ CH ₂ OCH ₂ -CH ₂ OR ₈ [However,
R ₇ and R ₈ have the same meanings as above] Diglyme solvent such as diethylene glycol dimethyl ether; formula R ₉ O-CH ₂ CH ₂ OCO-CH ₃
[However, R ₉ is a hydrogen atom, CH ₃ or C ₂ H ₅
cellosolve acetate solvents with the formula R ₁₀ OH [however,
R ₁₀ represents an alkyl group having 1 to 4 carbon atoms], such as ethanol, propanol, etc.; and diacetone alcohol, dioxane, tetrahydrofuran, acetone, dimethylformamide, 3-methoxy-3-
Methyl-butanol etc. can be used. However, it is also possible to use inert solvents that are immiscible with water, and such water-immiscible solvents include those having a boiling point of 250°C or less so that they can be easily removed by distillation at normal or reduced pressure after the polymerization reaction is completed. Preferably. Such solvents include, for example,
formula

[Formula] [However, R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] or the formula

Aromatic hydrocarbons represented by the formula [wherein R ₁₂ and R ₁₃ each represent an alkyl group having 1 to 4 carbon atoms], such as toluene, xylene, etc.; formula R ₁₄ -COO-R ₁₅ [ however,
_R14 represents an alkyl group having 1 to 6 carbon atoms, and _R15 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclohexyl group]
Acids or esters such as acetic acid,
Ethyl formate, butyl acetate, cyclohexyl acetate, etc.; formula R ₁₆ R ₁₇ O [wherein R ₁₆ and R ₁₇ each represent an alkyl group having 1 to 8 carbon atoms]; and

Ketones represented by [Formula], such as methyl ethyl ketone, cyclohexanone, etc.;
Ethers represented by the formula R ₁₆ -O-R ₁₇ [wherein R ₁₆ and R ₁₇ have the same meanings as above], such as ethyl ether, hexyl ether, etc.;
Alcohols represented by R ₁₈ OH [wherein R ₁₈ represents an alkyl group having 5 to 11 carbon atoms],
Examples include hexanol. These solvents are based on the total weight of the four copolymer components.
It can be used in a range of 15-90% by weight. Examples of polymerization catalysts include azo compounds, peroxide compounds, sulfides, sulfin compounds, sulfinic acids, diazo compounds, nitroso compounds, redox compounds, and radical initiators that can be used in normal radical polymerization such as ionizing radiation. agent is used. In the present invention, a substantially satisfactory aqueous pigment dispersion can be obtained even if the molecular weight of the copolymer to be produced changes, but if the molecular weight is too low, there is a risk of deterioration of the physical properties of the water-based paint to be colored. There is. Also, if the molecular weight is too high, the viscosity will increase,
When the viscosity is lowered, the concentration of the copolymer becomes lower and the dispersibility of the pigment decreases. Therefore, the above copolymerization reaction is
Generally, the number average molecular weight of the copolymer produced is approximately
Advantageously, the range is from 500 to about 150,000, preferably from about 1,000 to about 100,000. The copolymer resin thus produced is made water-soluble as it is or after distilling off the solvent. This water solubility can be achieved by a conventional method, for example, by neutralizing the carboxyl groups present in the copolymer resin with a conventionally known neutralizing agent. Examples of neutralizing agents that can be used include ammonia, amines, alkali metal hydroxides, alkali metal hydroxides, alkali metal carbonates or bicarbonates, and the like. The amine is the first
primary, secondary or tertiary alkylamines;
and cycloalkylamines, etc. can be used. In addition, examples of alkali metal hydroxides include potassium hydroxide and sodium hydroxide; examples of alkali metal carbonates and bicarbonates include potassium carbonate, sodium carbonate, and sodium bicarbonate.
Among these neutralizing agents, potassium hydroxide and sodium hydroxide are particularly preferred. The neutralization treatment can be easily carried out by a conventional method by adding the neutralizing agent or an aqueous solution thereof to the copolymer resin or its solution obtained as described above. The amount of neutralizing agent used is generally 0.01 to 2.0 equivalents, preferably 0.3 to 2.0 equivalents based on the carboxyl group in the resin.
It is 1.0 equivalent. The water-solubilized polymer thus obtained is used as a dispersant in an aqueous pigment dispersion consisting of a pigment, a dispersant, and an aqueous medium. The amount of the dispersant made of the above water-soluble polymer to be used is:
The amount may generally be from about 1 to 500 parts by weight, preferably from about 1 to 300 parts by weight per 100 parts by weight of pigment. When the upper limit of this range is exceeded, the balance between coloring power and viscosity of the aqueous pigment dispersion tends to become imbalanced, while when it is outside the lower limit, the dispersion stability of the pigment tends to decrease. The aqueous medium used in the aqueous pigment dispersion of the present invention is essentially water, but if necessary,
For example, if 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, those used in the production of the polymer can be used alone or in combination. Furthermore, the pigments used in the aqueous pigment dispersion of the present invention can be inorganic and organic pigments commonly used in this type of pigment dispersion. (zinc white, titanium dioxide, red iron oxide, chromium oxide, cobalt blue, iron black, etc.); (2) hydroxide type (alumina white,
(yellow iron oxide, etc.); (3) sulfides, selenide-based (zinc sulfide, vermilion, cadmium yellow, cadmium red, etc.); (4) ferrocyanide-based (dark blue, etc.); (5) chromate-based (yellow (lead, zinc chromate, molybdenum lead, etc.); (6) Sulfate type (precipitated barium sulfate, etc.);
(7) Carbonate-based (precipitated calcium carbonate, etc.); (8) Silicate-based (hydrated silicates, clay, ultramarine, etc.); (9) Phosphate-based (manganese violet, etc.); (10) Carbon Examples of organic pigments include (1) nitroso pigments (naphthol green B, etc.); (2) metal powders (aluminum powder, bronze powder, zinc powder, etc.); ) Nitro pigments (Naphthol Yellow S, etc.); (3) Azo pigments (Resol Red,
Lake Red C, Fast Yellow, Naphthol Red, Red, etc.); (4) Dyeing Lake Pigment system (Alkali Blue Lake, Rhodamine Lake, etc.); (5) Phthalocyanine pigment system (Phthalocyanine Blue, Fast Sky Blue, etc.); (6) Condensed polycyclic pigments (perylene red, quinacridone red, dioxazine violet, isoindolinone yellow, etc.) are included. The content of the pigment in the aqueous pigment dispersion of the present invention is not particularly technically limited, but is generally about 2 to 90% by weight based on the weight of the dispersion. The aqueous pigment dispersion of the present invention can be prepared by mixing together the above-mentioned components in a suitable dispersion device, and the dispersion devices that can be used include those commonly used in the paint industry. Examples include ball mills, roll mills, homomixers, sand grinders, sheakers, and attritors. If necessary, conventionally known surfactants and protective colloids can also be added to the aqueous pigment dispersion of the present invention. In the thus obtained aqueous pigment dispersion of the present invention, the pigment is very uniformly and finely dispersed.
Pigment particles hardly aggregate or settle even after long-term storage. This is presumed to be because the lipophilic part of the acid splitter is adsorbed on the surface of the pigment, and the hydrophilic part dissolves in the aqueous medium, so that the pigment is stably dispersed in the aqueous medium. Therefore, the aqueous pigment dispersion of the present invention can contain alkyd resins used in water-based paints and inks,
It has good miscibility with conventionally known water-soluble resins, water-dispersible resins, emulsions, etc. such as acrylic resins, epoxy resins, urethane resins, and maleic polybutadiene resins, and there are no restrictions due to these resins, and it can be used with any of the following. It can also be widely used for coloring water-based paints made of resin. As specific examples of the above-mentioned water-based resins, for example, alkyd resins are synthesized from the same raw materials as conventional solvent-based alkyd resins, and include polybasic acids, polyhydric alcohols,
It is obtained by subjecting oil components to a condensation reaction using a conventional method. Acrylic resins include α,β-ethylenically unsaturated acids (e.g., acrylic acid, methacrylic acid, maleic acid, etc.), (meth)acrylic acid esters (e.g., ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, etc.). , ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc.) and vinyl aromatic compounds (for example, styrene, vinyltoluene, etc.). Epoxy resins can be produced by synthesizing epoxy esters by reacting the epoxy groups of epoxy resin with unsaturated fatty acids, and adding α,β-unsaturated acids to this unsaturated group, or by combining the hydroxyl groups of epoxy esters with phthalic acid. Examples include epoxy ester resins obtained by esterifying a polybasic acid such as trimellitic acid and a polybasic acid such as trimellitic acid. In addition, as the urethane resin, polyisocyanate compounds (for example, toluene diisocyanate, diphenylmethane diisocyanate, 1,6
-Hexane diisocyanate, isophorone diisocyanate, etc.) to introduce a urethane group into the resin skeleton, and a carboxyl group using dimethylolpropionic acid or the like. When using the above-mentioned aqueous resin as water-soluble, it is synthesized so that the resin has an acid value of about 35 to 200, and this is neutralized with an alkaline substance such as sodium hydroxide or amine to make it water-soluble. Subjected to color paint. On the other hand, when these resins are used in a self-dispersion type, the acid value of the resin is made into a low acid value resin of about 5 to 35, and this resin is neutralized and used as a water-dispersed paint. In addition, emulsions include emulsifier-dispersed emulsions obtained by dispersing alkyd resins, acrylic resins, epoxy resins, and urethane resins using anionic or nonionic low-molecular-weight surfactants; Emulsion polymerization emulsion obtained by emulsion polymerization of monomers such as acrylic ester, acrylonitrile, styrene, butadiene, vinyl acetate, vinyl chloride; maleated polybutadiene, maleated alkyd resin,
Obtained by emulsion polymerization and graft reaction of the monomers described above using water-soluble resins such as maleated fatty acid-modified vinyl resins, drying oil or semi-drying oil fatty acid-modified acrylic resins, and other water-soluble polymers as emulsion stabilizers. Examples include soap-free emulsions. The aqueous pigment dispersion of the present invention is particularly effective when blended into aqueous paints made of low acid value water-dispersible resins and emulsions that have poor pigment dispersibility. Among these, the effect is particularly remarkable for low acid value water-dispersible resins and emulsions that have oxidative curability. The blending ratio of the aqueous pigment dispersion of the present invention to the aqueous paint can be varied within a wide range depending on the type of pigment in the dispersion and the degree of coloring required for the final paint, but in general, The pigment dispersion can be blended in an amount of 2 to 1000 parts by weight per 100 parts by weight of the resin content of the aqueous paint. Next, the present invention will be further explained by examples.
In the examples, parts and % indicate parts by weight and % by weight. Example 1 (1-a) The following components: Safflower oil fatty acid 236 parts Glycidyl methacrylate 119 parts Hydroquinone 0.4 parts Tetraethylammonium bromide 0.2 parts were placed in a reaction vessel. The reaction is 140 while stirring.
The addition reaction product was obtained at a temperature of ~150°C.
The addition reaction between epoxy groups and carboxyl groups was monitored while measuring the amount of remaining carboxyl groups. The reaction took approximately 4 hours to complete. (1-b) 300 parts of n-butyl cellosolve was placed in a reaction vessel and heated to 120°C. Two mixtures in the proportions shown below were then added dropwise to this solution separately over a period of approximately 2 hours. The reaction was carried out under a nitrogen atmosphere. A mixture of 113 parts of the fatty acid-modified monomer obtained in (1-a) above, 126 parts of N-vinylpyrrolidone, and 22 parts of 2-carboxyethyl methacrylate. A mixture of 18 parts of azobisdimethylvaleronitrile and 50 parts of n-butyl cellosolve. The reaction temperature was maintained at 120° C., and the above mixture was added dropwise while stirring the reaction solution. One hour after the completion of the dropwise addition, 2.5 parts of azobisisobutyronitrile was added to the reaction solution, and after another 2 hours, 2.5 parts of azobisisobutyronitrile was added to the reaction solution, and the reaction was then continued while maintaining the temperature at 120°C for 2 hours. Summer. After the reaction was completed, unreacted monomers and n-butyl cellosolve were distilled under reduced pressure to obtain a copolymer solution with a heating residue of 70.8%, a resin acid value of 40.7, and a Gardner viscosity (40% n-butyl cellosolve solution) H. Further, this copolymer was neutralized with triethylamine (1.0 equivalent neutralization), and water was added to obtain a dispersant (1) consisting of an aqueous solution with a heating residue of 40%. Next, a mixture of 8.3 parts of this dispersant and 200 parts of titanium white pigment (Titanium White R-5N manufactured by Sakai Chemical Co., Ltd.) was added to Red
Dispersion was carried out for 0.5 hours using a Devil disperser to obtain an aqueous pigment dispersion (A) of the present invention. Pigments were similarly dispersed according to the formulations shown in Table 1 below to obtain aqueous pigment dispersions (B) to (D) of the present invention.
Incidentally, pigments other than titanium white were dispersed for 1 hour. The properties of the obtained aqueous pigment dispersion are summarized in Table 1 below. Next, 10 parts of aqueous pigment dispersion (A) and water-dispersed alkyd resin (linseed oil fatty acid/pentaerythritol/benzoic acid/isophthalic acid/maleic anhydride =
Yucho made from 903/705/1140/610/45 (parts)
40% solids solution obtained by neutralizing 1.0 equivalent of alkyd resin with triethylamine and acid value 16)
Water-based paint (1) by thoroughly mixing a formulation consisting of 23.4 parts
was prepared. In the same way, the pigment dispersion liquid and the water-based resin shown in Table 2 below were sufficiently mixed to form a water-based paint (2).
~(6) was obtained. The coating film performance of the obtained water-based paint is summarized in Table 2 below. Example 2 (2-a) The following ingredients: Safflower oil fatty acid 70.9 parts Hydroquinone 0.03 parts n-heptane 4.56 parts were placed in a reaction vessel and heated to 160°C while stirring. Next, a mixture of the following components: 41.2 parts of hydroxyethyl methacrylate, 0.03 parts of hydroquinone, 0.95 parts of dodecylbenzenesulfonic acid, and 3.7 parts of toluene was added dropwise into a reaction vessel at 160° C. over a period of 2 hours. When the generated condensation water is removed from the reaction system and the reaction product has an acid value of 5.5 and a Gardner viscosity of _A2 , the reaction vessel is reduced in pressure, toluene and n-heptane are removed under reduced pressure, and the acid value is 5.0 and the Gardner viscosity is A2. A fatty acid-modified acrylic monomer of _A1 was obtained. (2-b) 300 parts of n-butyl cellosolve was placed in a reaction vessel and heated to 120°C. Next, a mixture in the proportions shown below was added dropwise to this solution over about 2 hours. The reaction was carried out under nitrogen injection. Fatty acid modified monomer obtained in (2-a) above 75 parts n-butyl methacrylate 17 parts N,N-dimethylaminoethyl methacrylate
125 parts 2-carboxypropyl (meth)acrylate
24 parts Azobisdimethylvaleronitrile 18 parts The reaction temperature was maintained at 120°C, and the above mixture was added dropwise while stirring the reaction solution. One hour after the completion of the dropwise addition, 2.5 parts of azobisisobutyronitrile was added to the reaction solution, and after another 2 hours, 2.5 parts of azobisisobutyronitrile was added to the reaction solution, and the reaction was then continued while maintaining the temperature at 120°C for 2 hours. Summer. After the reaction, the unreacted monomer and n-butyl cellosolve were distilled under reduced pressure, and the heating residue was 71.0%, the resin acid value was 41.0, and the Gardner viscosity (40% n-butyl cellosolve solution) was K.
A copolymer solution was obtained. Furthermore, this copolymer was neutralized with triethylamine (1.0 equivalent neutralization,
Water was added to obtain a dispersant (2) consisting of an aqueous solution with a heating residue of 40%. Next, using the obtained dispersant (),
The pigment shown in Example 1 was dispersed in the same manner as in Example 1 to obtain an aqueous pigment dispersion (E) of the present invention. In addition, a water-based paint (7) was prepared by thoroughly mixing this pigment dispersion (E) and a water-based resin shown in Table 2 below. The properties of the pigment dispersion (E) and the coating performance of the water-based paint (7) are shown in Tables 1 and 2 below, respectively. Comparative Example 1 Commercially available pigment dispersant SAM1440H (ARCOC
titanium white K-
10 parts of a pigment dispersion (pigment content 70.0%) prepared by dispersing 5N (titanium oxide manufactured by Sakai Chemical Co., Ltd., trade name) in a solid weight ratio of titanium white/dispersant = 22/1 and the table below - A water-based paint for comparison was obtained by mixing 17.5 parts of emulsion (b) of No. 2. The coating film performance of this product is shown in Table 2 below.

【table】

【table】

【table】

[Coating film performance test]

Add a water-based dryer (trade name: "Deiknate", manufactured by Dainippon Ink Co., Ltd., containing 3% cobalt metal) to water-based paints (1) to (10) at a ratio of 1 part to 100 parts of resin solid content, and paint on a mild steel plate. did. 20℃, relative humidity 75%
After drying for 3 days, it was used for testing. String adhesion: A test was carried out by making 100 burls with a width of 1 mm, pasting cellophane adhesive tape thereon, and peeling it off vigorously. Water resistance: The condition of the coated surface was visually examined by immersing it in tap water at 20°C for 2 days.

Claims (1)

[Scope of Claims] 1. An aqueous pigment dispersion comprising a pigment, a dispersant, and an aqueous medium, wherein the dispersant is (A) an oil/fat fatty acid modified (meth)acrylic monomer.
3 to 98 parts by weight (B) α.β-ethylenically unsaturated nitrogen-containing monomer
2 to 97 parts by weight (C) 0.5 to 40 parts by weight of carboxyl group-containing (meth)acrylic ester and (D) α,β-ethylenically unsaturated monomer other than the above (A), (B), and (C) An aqueous pigment dispersion, characterized in that it is a water-soluble product of a polymer obtained by copolymerizing 0 to 91 parts by weight.