JPS61115962A - Aqueous dispersion of cationic pigment - Google Patents

Abstract

PURPOSE:To provide the titled dispersion which has excellent easy dispersibility and dispersion stability, consisting of a dispersant which is a neutralized copolymer of monomers contg. a modified (meth)acrylic monomer and a (meth)acrylic monomer, a pigment and an aq. medium. CONSTITUTION:An aq. pigment dispersion consists of a pigment, a dispersant and an aq. medium. The dispersant is a neutralized product or a quaternary ammonium compd. of a polymer obtd. by copolymerizing 3-98pts.wt. modified (meth)acrylic monomer (A) composed of a reaction product between a fatty acid or a hydroxy acid condensate and an aziridine group-contg. (meth)acrylate, 1-97pts.wt. at least one (meth)acrylic monomer (B) selected from among an aminoalkyl (meth)acrylate, an aminoalkyl-(meth)acrylamide and a quaternary ammonium salt-contg. (meth)acrylic monomer, 0-96pts.wt. alpha,beta-ethylenically unsaturated nitrogen-contg. monomer (C) other than component B and 0-91pts. wt. alpha,beta-ethylenically unsaturated monomer (D) other than components A, B and C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-cationic aqueous 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, the coloring effect on the painted surface decreases due to the difficulty of dispersing the pigments during manufacturing and the aggregation and sedimentation of the pigments during storage.
It is well known that undesirable phenomena such as 7-lapding, 70-ting, and reduction in gloss occur. To keep this in mind, generally an aqueous pigment dispersion is prepared by dispersing the pigment in advance with a dispersant, and this is mixed into 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 in coating performance.

However, when oligomers and polymers are used as dispersants, the amount used is larger than that of low-molecular surfactants. There are drawbacks such as restrictions depending on the type. This goes against the rationalization of paint manufacturing, and there is therefore a strong demand for the maintenance of aqueous pigment dispersions that are common to various water-based paints.

Therefore, the inventors of the present invention were able to easily disperse pigments in small amounts, and various water-based pigments were used. To develop an ideal dispersant that is compatible with lI fats, especially cationic aqueous Ist fats, and which is itself a polymer and does not cause a decline in the coating performance of water-based paints, especially in difficult aqueous systems. As a result of intensive research aimed at this purpose, the present invention was completed.

Thus, according to the present invention, in an aqueous pigment dispersion comprising a pigment, a dispersant, and an aqueous medium, the dispersant is a reaction product of an AFNI fatty acid or oxyacid condensate and a (meth)acrylate having an aziridine group. Modified (meth)acrylic monomer consisting of 3 to 98 parts by weight (up to) aminoalkyl (meth)acrylate, aminoalkyl (meth)acrylamide, quaternary ammonium oxide (meth)
One or more (meth)acrylic monomers that are common to acrylic (hereinafter, these may simply be referred to as "cationic (meth)acrylic monomers") 1 to 97 parts by weight (C) a,/-ethylenically unsaturated nitrogen-containing monomers other than the above ■ 0 to 96 parts by weight, and (B) σ,/- ethylenically unsaturated monomers other than the above (2), @, and (C) 0 A cationic aqueous pigment dispersion is provided, which is characterized in that it is a neutralized product or a quaternary ammonium compound of a polymer obtained by copolymerizing K to 91 parts by weight.

The polymer used as a dispersant for the cationic aqueous pigment dispersion of the present invention has a relatively lipophilic long side chain separated from a main chain containing a hydrophilic nitrogen-containing (meth)acrylic monomer. Because it has a structure in which it is bonded in the form of particles, it has very high pigment dispersion ability. Furthermore, this polymer has very good pigment adsorption ability derived from nitrogen-containing monomer units, so it strongly adsorbs pigments and has excellent storage stability of paints, and because it is basic, it has excellent properties such as corrosion resistance. It is also possible to obtain a very good colored smear.

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

Modified (meth)acrylic monomer (A) The fatty acid-modified (meth)acrylic monomer or oxyacid condensate-modified (meth)acrylic monomer used in the present invention has an aziridine group as described below. have (meta)
Acrylic monomer, drying oil fatty acid, semi-drying oil fatty acid,
Oil fatty acids such as non-drying oil fatty acids are monomers produced by introducing synthetic saturated fatty acids or oxyacid condensates as described below by methods as described below.

Typical fat and oil 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, dino oil fatty acid, hempseed oil fatty acid, pudoku selective oil fatty acid, and horse sorghum oil fatty acid. Drying oil and semi-drying oil fatty acids, such as mint oil fatty acid, tall oil fatty acid, castor oil fatty acid, cottonseed oil fatty acid, walnut oil fatty acid, rubber seed oil fatty acid, tung oil fatty acid, olive oil fatty acid, dehydrated and coconut oil fatty acid, high diene fatty acid; and non-drying oil fatty acids such as coconut oil fatty acids, olive oil fatty acids, castor oil fatty acids, 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 types. .

In addition, the synthetic saturated fatty acids used in the present invention can be obtained from natural fats, fatty acids, or petroleum raw materials by ozone oxidation method, paraffin liquid phase air oxidation method, oxo method, Koch method, etc.
It is a linear or branched saturated aliphatic carboxylic acid having 4 to 24 carbon atoms, preferably 5 to 18 carbon atoms, which is artificially induced by a method such as the method, and is a typical synthetic saturated fatty acid. are neopentanoic acid, 2-ethylhexadionic acid, heptanoic acid, 2-ethylhexadiate, isooctanoic acid, nonanoic acid, isononanoic acid, decanoic acid, isodecasic acid,
neodecanoic acid, indoridecanoic acid, impalmitic acid,
Examples include isostearic acid.

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, the weight of the resulting polymer is used as a standard setting. It falls within the range of 5 to 65% by weight, preferably 10 to 60% by weight.

Advantageously, it is used in quantities.

Nineth, in the present invention, among the above fatty acids, drying oil fatty acids and semi-drying oil fatty acids having an iodine value of about 100 or more,
This is preferred because it can impart crosslinking drying properties to the resulting dispersant at room temperature.

In addition, the oxyacid condensate is a condensate of aliphatic monocarposi acids (hydroxy fatty acids) having one hydroxyl group in the molecule, and examples of the hydroxy fatty acids include ring-opened products of the lactoshi compounds described above, ricinoleic acid, oxyacid Examples include stearic acid and lapalmitic acid. The condensates of these oxyacids are produced by a conventional method using a mixture of the above-mentioned hydroxy fatty acids, a refluxing solvent (xylene, toluene, heptane, etc.), and an esterification catalyst (methyl sulfuric acid, dodecylbenzenesulfonic acid, etc.) for about 140 min. This can be carried out by heating and condensing at ~250°C.

The oxyacid condensates may be used alone or in combination of two or more.

(Meth)acrylates having an aziridine group that react with fatty acids or oxyacid condensates include, for example, aziridinylmethyl (meth)acrylate, aziridinylethyl (meth)
These include acrylate, aziridinylethyl (meth)acrylate, and aziridinylbutyl (meth)acrylate.

The modified (meth)acrylic monomer (2) is prepared by converting the fatty acid or oxyacid condensate into an aziridine group in the presence or absence of a suitable inert solvent, usually in the absence of a solvent, according to a conventional method. This can be done by combining 515 with a (meth)acrylate having the following. The reaction generally takes about 40
It can be carried out at a temperature of up to about 200°C, preferably about 80 to about 170°C, and the reaction time is generally about 0.5 to about 170°C.
About 40 hours, preferably about 3 to about 10 hours.

The aziridine group-containing (meth)acrylate is usually 0.7 per mole of the fatty acid or the oxyacid condensate.
It is advantageous to use a proportion of ~1.5 mol, preferably 0.8-1.2 mol.

Next, as an inert solvent to be used as necessary, 2
Water-immiscible organic solvents that can be refluxed at temperatures below 00°C are preferred, and include aromatic hydrocarbons such as benzene, toluene and xylenedi; aliphatic hydrocarbons such as heptane, hexane and octane.

Furthermore, in the above reaction, if necessary, a polymerization inhibitor may be added to the reaction system, such as hydroquino, methoxyphenol, terin-Petit! Recatecol, beshizokinoshi, etc. are added to (meth)acrylate having an aziridine group and/or
Alternatively, it is advantageous to suppress the polymerization of the fatty acid-modified (meth)acrylic monomer or the oxyacid condensate-modified (meth)acrylic monomer that is produced.

In the above reaction, esterification accompanied by cleavage of the aziridine group occurs between the aziridine group of the (meth)acrylate having an aziridine group and the carboxyl group of the fatty acid or oxyacid condensate. A (meth)acrylic acid ester is obtained.

Kakioshi-type (meth)acrylic monomers (B K used in the present invention include those containing a substituted or unsubstituted amino group in the ester moiety of (meth)acrylic acid ester and those containing a substituted or unsubstituted amino group in the amide moiety of (meth)acrylic acid. Those containing substituted or unsubstituted amino groups are included, and in particular those containing the following formula (1
) or (1) In each of the above formulas, R1 represents a hydrogen atom or a methyl group, R2+ R3 and R4 each independently represent a hydrogen atom or a lower alkyl group, and n is an integer from 2 to 8. things are suitable. Here, the word "lower" means that the number of carbon atoms in the nine groups to which this word is attached is 6 or less, preferably 4 or less. .

As a specific example of such an aminoalkyl (meth)acrylic monomer, #-
1SN, 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 (meth2acrylate,
N-butylaminoethyl (meth)acrylate and the like are included. Further, in the example shown by the above formula (1), N, N
-dimethylaminoethyl (meth)acrylamide, N,
N-dimethylaminopropyl (meth)acrylamide and the like are included, and these can be used alone or in combination of two or more.

teA quaternary asimonicum salt-containing (meth)acrylic monomer used as a cationic (meth)acrylic monomer other than the above may contain one quaternary asimonicum salt group and one quaternary asimonicum salt group in one molecule. The monomer containing two (meth)acryloyl groups is included, and is typically represented by the following general formula (1), where R1 represents the above meaning, and Y is 10-0 g.
H2g-group (where g is a number from 2 to 8).

-0-CH2-CH-CH2- group or H-N-CgH2g- group (where R8 represents a hydrogen atom or a lower alkyl group, and g has the above meaning), and R5, R6 and 2 are , each independently represents a lower alkyl group, a hydroxy lower alkyl group, a hydroxy lower alkyl group, a lower alkoxy lower alkyl group, a cycloalkyl group, a substituted or unsubstituted phenyl group, an aralkyl group, and represents an anion. suitable. In the formula, the anion represented by X includes the ion or the anionic residue of an acid, and specifically KtiC1, Br.

1e, Fe, H8o4e≧8o; e, No3e, poi
e, HPO2e, R2,. , e, C6H55O3e,
0He41F2>E, preferably CI S
Br
2-hydroxy-3(meth)acryloxyprobyltriptylammonicum chloride, 2-hydroxy-3
(meth)acryloxyprobyl triethanolammonicum chloride, 2-hydroxy-3(meth)acryloxypropyldimethylpecidyl asimonicum chloride, 2-hydroxy-3(meth)acryl leoxyprobyl dimethylphenylammonium Examples include chloride, (meth)acryloxyethyltrimethylammonicum chloride, (meth)acrylamidopropyltrimethylammonicum chloride, and these can be used alone or in combination of two or more.

Furthermore, the aminoalkyl (meth)acrylates, aminoalkyl (meth)acrylamides, and quaternary asimonicum salt-containing (meth)acrylates used in the present invention can be used alone or in combination of two or more.

Next, α other than the above (9) used in the present invention,
As the β-ethylenically unsaturated nitrogen monomer (C), 1
The molecule includes a monomer containing one or more (usually up to 4) basic nitrogen atoms and one ethylenically unsaturated bond, and typically has a nitrogen-containing heterocycle. Examples include unsaturated monomers and 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 has 1 to 3, preferably 1 or 2 ring nitrogen atoms.

It includes monomers in which a monocyclic or polycyclic heterocycle containing a vinyl group is bonded to a vinyl group, and in particular, the following monomers can be mentioned.

(I) Vinylpyrrolidones: For example, l-vinifre-2-pyrrolidone, l-vinyl-
3-pyrrolidone etc.

(Vinyl pyridine; For example, 2-vinylpyridine, 4-vinylpyridine, 5-vinylpyridine,
-Methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, etc.

(1) Vinylimidazoles: For example, 1-vinylimidazole, 1-vinyl-2-methylimidazole, etc.

(2) Vinyl carbazoles; For example, N-vinylcarbazolate.

(v) Vinylquinolines; For example, 2-vinylquinoline.

(W) Vinylpiperidines; For example, 3-vinylpiperidine, N-methyl-3-vinylpiperidine, etc.

(to) Others; N-(meth)acryloylmorpholine represented by (has the above meaning), N-(meth)acryloylpyrrolidine represented by), etc.

Among the above-mentioned vinyl monomers having a nine-unit nitrogen heterocycle, vinyl pyrrolidones, vinyl imidazoles and vinyl carbazoles are preferred, and among them, those in which the ring nitrogen atom is tertiary are preferred. .

[2] Nitrogen-containing derivatives of (meth)acrylic acid include amides of (meth)acrylic acid, particularly in the following formula (ff) I R9 represents a hydrogen atom or lower alkyl, RIG represents a hydrogen atom or lower alkyl Suitable are (meth)acrylamides represented by a hydroxyl-lower alkyl group or a lower alkoxy-lower alkyl group, and R1 has the above meaning.

Here, the term "lower" 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, examples of the (meth)acrylamide of the above formula (IV) 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, and the like are included.

The above-mentioned J-ethylenically unsaturated nitrogen-containing monomers can be used alone or in combination of two or more.

α, β-ethylenically unsaturated monomer■ In addition, 1 above (A), @, (O other than α, /-
There are no particular restrictions on the ethylenically unsaturated monomer, and it can be selected from a wide range depending on the performance of the dispersant of the present invention. Representative examples of such unsaturated monomers are as follows.

(a) Esters of acrylic or methacrylic acid: for example, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, ucryl acrylate, methacrylic acid C1-18 alkyl esters of acrylic acid or methacrylic acid such as methyl, ethyl methacrylate, propyl methacrylate, inglovir methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, ucrylic methacrylate; glycidyl acrylate, glycidyl methacrylate; Methoxybutyl acrylate, methoxybutyl methacrylate,
02-18 of acrylic acid or methacrylic acid such as methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate, etc.
Alkoxyalkyl ester; acrylic acid or methacrylic acid such as allyl acrylate, allyl methacrylate, etc.
C2-8 alkenyl ester of acrylic acid or methacrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl acrylate; C2-8 hydroxyalkyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate, allyloxymethacrylate, or C3-18 alkenyloxyalkyl ester of methacrylic acid.

(υ Vinyl aromatic compounds: for example, ethyl>, α-methylstyrene, vinyltoluene, p-thalolstyrene.

(d Boriolephisi-based compounds: for example, butadiene 1
, isoprene, chlorogredi.

(d) a, β-ethylenically unsaturated carboxylic acid: for example,
Acrylic acid, methacrylic acid, maleic acid, itacosic acid, etc.

(d Others: acrylonitrile, methacrylaterile, methyl ingropenylgtone, vinyl acetate, peopamonomer (Shell Chemical In), vinyl propionate, vinyl bivalate.

The unsaturated monomers are appropriately selected depending on the physical properties desired for the aqueous test sample separation solution, and each may be used alone or in combination of two or more.

According to the present invention, the modified (meth)acrylic monomer (A), the cationic (meth)acrylic monomer (to),
a, the β-ethylenic unsaturated nitrogen-containing monomer (C) and the unsaturated monomer a) I/-i 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) Modified (meth)acrylic monomer (A): 3-98
Parts by weight, preferably from 5 to 5 in terms of drying properties and recoating performance of the coating film
90 parts by weight, more preferably 15 to 75 parts by weight, (2) Cationic (meth)acrylic monomer (B:
1 to 97 parts by weight, preferably 3 to 97 parts by weight from the viewpoint of pigment fraction
90 parts by weight, more preferably 5 to 80 parts by weight, (3) α, β-ethylenically unsaturated nitrogen-containing monomer (C
): 0 to 96 parts by weight, preferably 5 to 90 parts by weight in terms of water solubility and coating performance, more preferably 10 to 75 parts by weight, (A above (to), @, (Unsaturated monomers other than CJ groups) Weight: 0 to 91 parts by weight, preferably 2 to 83 parts by weight from the viewpoint of coating film performance, more preferably 5 to 75 parts by weight, The above copolymerization reaction is advantageously carried out according to a solution polymerization method. Preferably, the above four components are mixed in a suitable inert solvent in the presence of a polymerization catalyst at a reaction temperature of usually about θ to about 180°C, preferably about 40 to about 170°C, at a reaction temperature of about 1 to about 20°C. This can be carried out by continuing the reaction for a period of time, preferably about 6 to about 10 hours.

As the solvent used, it is desirable to use a solvent that can dissolve the copolymer to be produced and is miscible with water. In particular, when obtaining a cationic aqueous chain reagent separation solution, there is no need to remove it! ! It's good to have something that can be used. Such solvents include, for example, the formula: IO-CH2CH2-ORII (:
HOCH2-CH-OR11 (R11 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), for example, ethylene glycol, butyl cellosolve, or ethyl cellosol;
propylene glycol solvents with the formula CH3 having the same meaning as above], such as propylene glycol monomethyl ether; carpitol solvent ratios with the formula HO-CH2CH20CH2CH2-ORII [however, R11 has the same meaning as above], such as diethylene glycol, methyl Calpitol, butylcarpitol, etc.; Formula R12O-CH2CH
2-ORts (R12 and R13 each represent an alkyl group having 1 to 3 carbon atoms) Glyme-based solvent ratio, such as ethylene glycol dimethyl ether; formula Rt20-CH2CH20CH2-CH20R13
C, where R12 and R13 have the same meanings as above] diglyme solvent ratio, such as diethylene glycol dimethyl ether; formula R14O-CH2CH20CO
Cellosolve acetate solvents of the following formula: CHa C, and R14 represents CH3 or C2C5 as a hydrogen atom], such as ethylene glycol monoacetate, methyl seron lupacetate; formula R150H (however, R
Examples of alcoholic solvents (representing an alkyl group having 1 to 4 carbon atoms) include ethanol, propatool, butanol, etc.; Methoxy-3-methyl-pronol and the like can be used.

However, inert solvents that are immiscible with water can also be used. Preferably. Such solvents include, for example, aromatic hydrocarbons represented by the formula [representing an alkyl group having 1 to 4 molecules], such as toluene, xylene, etc.; formula Rag-COOR20 [
In the following formula, R19 represents an alkyl group having 1 to 6 carbon atoms, and R2O is a hydrogen atom'! ! 9 represents an alkyl group or a cyclohexyl group having 1 to 6 carbon atoms] The acids represented by esters in the order such as acetic acid, ethyl formate, butyl acetate, cyclohexyl acetate, etc.; formula R21R2
2C=0 (Tomodashi, R21 and R22 are each an alkyl group having 1 to 8 carbon atoms, such as methyl ethyl ketone, cyclohexanone, etc.; Formula R2l-0-R22
Ethers represented by (ft, stock, R21 and R22 have the same meanings as above), β-, such as ethyl ether, hexyl ether, etc.; (representing an alkyl group), such as hexanol.

This means that the solvent is 15 to 9 of the total weight of the four copolymer components.
It can be used in a range of 0% by weight.

(9) Examples of polymerization catalysts include radical initiators that can be used in normal radical polymerization, such as azo compounds, barocypoid compounds, sulfides, sulfines, sulfic acids, diazo compounds, nitroso compounds, redox compounds, and 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.

Moreover, if the molecular weight is too high, the viscosity will increase, and if the viscosity is lowered, the concentration of the copolymer will decrease and the dispersibility of the pigment will decrease. Therefore, in the above copolymerization reaction, the number average molecular weight of the copolymer produced is generally about 500 to 150,000. Advantageously, the range is preferably within the range of about 1,000 to about 100,000.

The copolymer thus produced can be made water-solubilized as it is or after distilling off the solvent by the method described below.

The copolymer is made of a cationic (meth)acrylic monomer (ElrB, condensate, quaternary acymonic base-containing (meth)acrylate as the main component, and the water solubility of the copolymer is simply water-soluble. can be easily made water-soluble by adding .

Ninth, the copolymer resin containing the cationic (meth)acrylic monomer @component raw material and aminoalkyl (meth)acrylate as a main component can be made water-soluble by a conventional method, for example, by adding water to the copolymer resin. This can be carried out by neutralizing the amino groups present in the compound using a conventionally known neutralizing agent. Examples of neutralizing agents that can be used include organic acids such as formic acid, acetic acid, propionic acid, butyric acid, hydroxyacetic acid, and lactic acid; and inorganic acids such as boric acid, hydrochloric acid, phosphoric acid, and sulfuric acid. Particularly suitable are formic acid and acetic acid.

The neutralization treatment can be easily carried out by a conventional method by adding the above-mentioned neutralizing agent or an aqueous solution thereof to the copolymer obtained as above or its solution.

The amount of neutralizing agent used is generally 0 to 7 mino groups in the resin.
．． O1 to 2.0 equivalents, preferably 0.3 to 1.0 equivalents.

The water-solubilized polymer thus obtained is used as a dispersant in a cationic aqueous pigment separation solution consisting of a pigment, a dispersant, and an aqueous medium. Dispersion of the pigment with the water-soluble polymer is usually carried out by neutralization and then with a resin.
If necessary, the pigment may be dispersed and then neutralized.

Next, the cationic (meth)acrylic monomer constituting the copolymer @component raw material, water solubility of the differential polymer resin whose main component is aminoalkyl (meth)acrylate or aminoalkyl (meth)acrylnamide. This can be achieved by converting the amino group into a quaternary asimonic compound. 4
For example, the copolymer may be subjected to the following 1.
This can be carried out by reacting a 2-epoxy compound in the presence of an acid and/or water to convert the secondary or tertiary amine 7 groups in the copolymer into quaternary asimonics.

1,2- which can be used for quaternary asimonic formation of the copolymer
Examples of epoxy compounds include the following formula (V)υ, where R1 has the above meaning, and R24 is a hydrogen atom, an alkyl group, a cycloalkyl group, -CH2-0-R25, -CM2-0-C- Rzsj or a substituted or unsubstituted phenyl group, where R25 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alknyl group, or a substituted or unsubstituted phenyl group is suitable. In the formula R24 and/or R
Alkyl and cycloalkyl groups which may be represented by 2H may generally have 1 to 18, preferably 1 to 8 carbon atoms, and alknyl groups preferably have 2 to 6 carbon atoms. I can do it. Furthermore, examples of substituents on the phenyl group include lower alkyl groups and lower alkoxy groups.

Representative examples of such 1,2-epoxy compounds include styrene oxide, propylene oxide, 1,2-7' tyrene oxide, 1,2-pentylene oxide F, 1.2
-Octylene oxide, styrene oxide, glycidol, glycidyl (meth)acrylate, glycidyl acetate, glycidyl lawalate, CARDURA E (glycidyl ester of barbic acid, manufactured by Shell Chemical Co., Ltd.), butyl glycidyl ether, octyl glycidyl ether, Phenylglycidyl ether, phenylglycidyl ether, p-t
Examples include ert-7' tylphenyl glycidyl ether, allyl glycidyl ether, and the like.

The amount of these 1,2-epoxy compounds to be used can be changed depending on the type of amide 7 group to be converted into quaternary asimonicum, etc.
Generally, in the case of a secondary amino group, #i2 to 4 times the molar amount, 3
In the case of class amino groups, it is convenient to use 1 to 2 times the molar amount.

On the other hand, examples of acids used in the quaternization reaction include formic acid, acetic acid, lactic acid, (meth)acrylic acid, propionic acid,
Examples include organic acids such as butyric acid and hydroxyacetic acid; inorganic acids such as boric acid, hydrochloric acid, phosphoric acid, and sulfuric acid. These acids are conveniently used in a proportion of about 1 to about 2 moles per ami7 group to be quaternized.

′! Next, water is suitably used in a proportion of about 0.5 to about 20 moles per amino group to be converted into quaternary asimonicum.

One suitable method for quaternary asimonication of the amino-7 group derived from the aminoalkyl (meth)acrylic monomer (BK) in the copolymer is to convert the copolymer into a mixture of the copolymer and the above acid. , a 1,2-epoxy compound and water are added, and the reaction is carried out in the dark for about 1 to about 7 hours at a temperature of room temperature to about 120°C.The amino group to be converted into a quaternary asimonic compound is
When the secondary amino group is a 1,2-
It may be converted into a tertiary amino group by reaction with an epoxy compound, and then the tertiary amino group may be converted into a quaternary acymonicum group.

The quaternary ammonium-containing copolymer should contain a sufficient amount of quaternary ammonium groups to make the copolymer water-soluble, and the amount depends on the type and molecular weight of the copolymer. Generally, 0.01 to 6 meq/f copolymer, preferably 0.1 to 5 meq/f copolymer, more preferably 0.1 to 3 meq/f copolymer, although it varies depending on the type of copolymer. A range of is appropriate.

The amount of the dispersant made of the water-soluble polymer used is 10% of the pigment.
0 parts by weight can generally be about 1 to 500 parts by weight, preferably about 1 to 300 parts by weight. When the upper limit of this range is exceeded, the coloring power and viscosity of the aqueous pigment dispersion tend to be unbalanced, while when the lower limit is exceeded, the dispersion stability of the pigment tends to decrease.

The aqueous medium used in the cationic aqueous pigment dispersion of the present invention is essentially water, but if necessary, for example, if the dispersant has a low degree of hydrophilicity and sufficient dispersion performance is obtained. In such cases, a hydrophilic organic solvent can be used in combination. As the hydrophilic organic solvent, nine kinds used in the production of the above polymer can be used alone or in combination.

Further, the pigments used in the cationic aqueous pigment dispersion of the present invention can be inorganic and organic pigments commonly used in this type of pigment dispersion. Materials (zinc white, titanium dioxide, red iron oxide, chromium oxide, cobalt blue, iron black '4F)
: (2) Hydroxide type (alumina white, yellow iron oxide, etc.); (3) Fit, compound, selenide type (Ti#, zinc oxide, untreated, cadmium yellow, cadmium red, etc.):
(A) 7 erocyanide type (prussian blue, etc.); (5) chromate type (yellow, zinc chromate, moriguteshi red, etc.)
:(6) Sulfate type (precipitated palicum sulfate etc.) :(7) Charcoal! ! ! Dibases (precipitated lucium carbonate, etc.): (8) Sulfate-based (hydrated silicates, clay, ultramarine, etc.); (9) Phosphate-based (manganese violet, etc.): (10) Carbon-based (carbon black, etc.) ) : (11) Metal powder-based pigments (aluminum powder, bronze powder, zinc powder, etc.) are listed, and organic pigments include (1) nitroso-pigment-based (naphthol green B, etc.): (2) nitro-pigment-based pigments. (Naphthol Yellow S, etc.): (3) Azo pigments (Lysol Revd, Lake Red C1 Fast Yellow, Naphthol Red, Red, etc.): (a) Dyeing lake pigments (Alkali Blue Lake, Roguemin Lake'ri: (5) 7 Talocyanine l1F
f-type (7 talocyanici blue, 7 asto sky blue, etc.): (6) Condensed polycyclic single-component systems (perylene red, quinacridone red, dioxazine bioleft, isoindolinone yellow, etc.) and the like are included.

Although there is no particular technical limit to the content of the pigment in the cationic aqueous repellent dispersion liquid of the present invention, it is generally about 2 to 90% by weight based on the 1X amount of the dispersion liquid. ``The preparation of the cationic aqueous pigment dispersion of the present invention can be carried out by mixing together the above-mentioned components in a suitable dispersion apparatus, and the fractional apparatus that can be used includes those commonly used in the paint industry. Examples include ball mills, roll mills, homomixers, sand grinders, shakers, and attritors.

The cationic aqueous pigment dispersion of the present invention further contains 6
Therefore, it is also possible to improve the dispersion stability by adding a conventionally known surfactant or protective colloid.

In the cationic aqueous pigment dispersion of the present invention thus obtained, the pigment is very uniformly and finely dispersed, and the pigment particles hardly aggregate and subsequently settle even when stored for a long time. This is presumed to be because the lipophilic part of the dispersant 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 cationic aqueous pigment dispersion of the present invention can be made from conventionally known water-soluble resins such as alkyd resins, acrylic resins, epoxy resins, Cretaceous resins, and β-lained polypucdiene resins used in water-based paints and inks. ,
It has good miscibility with water-dispersible resins, emulsions, etc., is not limited by these resins, and can be widely used for coloring water-based paints made of any resin. It is particularly effective for cationic moisture-absorbing resins and polymeric emulsions that have poor pigment dispersibility by themselves.

The blending ratio of the cationic aqueous pigment dispersion of the present invention to the aqueous paint can vary within a wide range depending on the type of pigment in the dispersion and the final paint (required degree of coloring, etc.), 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 resin in the aqueous paint.

The present invention will be explained in more detail with the following KW examples. In the examples, parts and % indicate parts by weight and % by weight. Example f7 Raw oil fatty acid 236 parts Aziridinylethyl methacrylate 128 parts Hydroquinone
Add 0.4 parts to the reaction container.

The reaction was carried out at a temperature of 120° C. with stirring to obtain an addition reaction product. The addition reaction between aziridine group and carboxyl group is
Next, monitor and measure the amount of remaining carboxyl groups. The reaction takes approximately 4 hours to complete.

133 parts of isononasilic acid 128 parts of aziridinylethyl methacrylate Hydroquinone
A fatty acid-modified methacrylic monomer (1) was obtained by carrying out an addition reaction of 0.3 parts of the above components under the same conditions as in the production example of the modified monomer (1).

! 12- and 2155 parts of droxystearic acid, 383 parts of toluene, and 4.3 parts of monomethylsulfonic acid were placed in a reaction vessel.
The reaction was continued at 145° C. for about 4 hours while removing the condensed water produced from the system. When the resin acid value reached 34.0, 202 parts of aziridinylethyl nucleate and 2 parts of hydroquinone were added, and the mixture was reacted at a reaction temperature of 110°C for about 6 hours.
Now the oxyacid condensation modified acrylic monomer (1).

Production example of copolymer solutions for dispersants (a) to (O) 320 parts of n-butylcellosorg was placed in a reaction vessel and heated to 120 parts.
It was set to ℃. Next, a mixture in the proportions shown below was added dropwise to this solution separately over a period of about 2 hours. Anti-Ff5 was carried out in a nitrogen atmosphere.90 Fatty acid modified methacrylic monomer (1) 113 parts N-vinylpyrrolidone 126 parts N,N-dimethylaminoethyl methacrylate 11 parts mixture and azobisdimethylvalonitrile 17 A mixture consisting of 50 parts of n-butyl cellosolve: 1 hour after the completion of dropping the above mixture, 2.5 parts of abpisisobutyronitrile 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 at 120° C. for 2 hours.

After completion of the reaction, unreacted monomer and n-butyl selon were distilled under reduced pressure, leaving a heating residue of 70.3% and amine (1.
A copolymer solution (a) with a Gardner viscosity (A0% n-butyl cellosolve solution) of C was obtained.

Similarly, the polymerization reaction and vacuum distillation were carried out with the formulation shown in Table 1 below under the same conditions as in the production example of the copolymer solution for dispersants (a), and the copolymer solutions for dispersants (b) to (f)
) got nine. The properties of the dispersant copolymer solution (ω to (f)) are summarized in Table 1 below.

The copolymer solution for dispersant (a) is neutralized with acetic acid and water is added to obtain an aqueous dispersant mixture consisting of an aqueous solution of the heating residue 409/). Similarly, the dispersant copolymer solution (8 to (
f) are respectively neutralized and water-solubilized to form an aqueous dispersant (B~
(B now next.

Further, after converting the copolymer solution for dispersion (a) and <bJ into a quaternary asimonicum salt as shown below, water was added to prepare the aqueous dispersant (C).

Put 80 parts of the copolymer solution for dispersion (ω) into a reaction container,
After raising the temperature to about 50°C and adding 7.8 parts of an 88% lactic acid aqueous solution, the temperature was further raised to 90°C and heating was performed for about 30 minutes. Thereafter, the mixture was cooled to 50° C., 5.0 parts of 1,2-butylene oxide and 3.6 parts of water were added, the temperature was raised to 100° C., and the mixture was reacted for about 4 hours to form a quaternary asimonycum salt. Further, the # polymer was cooled to room temperature, and then water was added to obtain a 40% dispersion of 0. Similarly, from the copolymer solution for dispersion (b), add 40% aqueous dividing agent (to).

Next, 350 parts of n-butyl cellosolve was added to the reaction container.
Next, heat to 120℃. Next, a mixture in the proportions shown below was added dropwise to this solution over a period of about 2 hours. The reaction was carried out under nitrogen injection.

Fatty acid modified acrylic monomer (1) 118 parts N
- Vinylpyrrolidone 126 parts 50% methacryloxyethyltrimethylammonicum chloride aqueous solution 6 parts (bottle 1
Monomer ff) 17.5 parts of azobisdimethylvaleronitrile While keeping the reaction temperature at 8071: and stirring the reaction solution, the above mixture was added dropwise. One hour after the completion of the dropwise addition, 2.5 parts of azobisisobutyronitrile was added to the reaction solution, and an additional 2.5 parts of azobisisobutyronitrile was added.
After an hour, 2.5 parts of azobisisobutyronitrile was added to the reaction solution, and then 11 reactions were carried out while keeping the temperature at WIJ80°C for 2 hours. After the reaction, the unreacted monomer and n-butyl cellosolve were distilled under reduced pressure to obtain a dispersant copolymer solution (g) with a heating residue of 70.2% and a Gardner viscosity (A0% n-butyl cellosolve solution) H. A friend. Similarly, the table below - IK
The polymerization reaction and vacuum distillation were carried out under the same conditions as in the production example of the above copolymer solution for dispersant (-) to prepare copolymer solutions (h) and (i) for dispersant with the formulation shown.

The properties of the dispersant copolymer solutions (g) to (i) are summarized in Table 1 below.

Add water to the above copolymer solution for dispersant (- and heat residue 4
Aqueous dispersant (I) consisting of a 0% aqueous solution is now used.

Similarly, the above-mentioned dispersant copolymer solutions (h) and (i)
were respectively made water-soluble to obtain an aqueous dispersant (J) and an aqueous dispersant (J).

Next, 8.3 parts of this aqueous dispersant (A) and 200 parts of titanium white pigment (Titanium White R-5N manufactured by Sakai Kagaku Co., Ltd.) were mixed together to disperse the pigment according to the formulation shown in Table 2 below. An aqueous aqueous preparation liquid of the invention ~0 was obtained.

In addition, pigments other than titanium white are dispersed for 1 hour and ft-
.

The properties of the nine pigment dispersion obtained are summarized in Table 2 below.

Examples 1 to 15 Water-based paints were prepared by sufficiently mixing the Kuhonsei picture preparation teaching liquids ■ to Φ obtained in the above production examples and a formulation consisting of water-dispersible cationic resins or cationic emulsions shown in Table 3. Then, the water-based paints of Examples 1 to 1 were applied. The coating properties of the obtained nine-pole paints are summarized in Table 3 below.

*1 Monomer (V): 50% 2-hydroxy-3-
Methacryloxyglopyltrimethylammonicum chloride aqueous solution Monomer ('W): 50% acrylamidepropyl trimethylammonicum chloride aqueous solution *240% n-butyl cellosolve solution *3 Titanium white R-5N: Titanium oxide carbon MA manufactured by Sakai Chemical Co., Ltd. : Mitsubishi Kasei Carbon Plaque 04 Measured according to ASTM D1201-64 *5
A cationic resin consisting of a blocked product of Epon 1002, polyamide resin, and diphenyl metasidi incyanate. Amine (milliequivalents/f resin) and resin viscosity (60%
Contains n-butyl cellosolve F[)Zon-butyl cellosolve 301i@%. Neutralize with 0.3 equivalents of acetic acid and add water to create a dispersed emulsion with a solid content of 40%.

*6 Product name: “Cemeshitecsu CJ (manufactured by Obanaya Sangyo)”
Cationic ethyreceive butadiene latex solid content = 3
0% Paint film curing conditions: (C) Created using the dispersion emulsion in 5), then dried the paint at 180°C for 30 minutes,
The paint prepared using the cationic styrene styrene latex of 6) was dried at 20° C. (75% relative humidity) for 7 days.

[Coating film performance test]

String adhesion: 100 goblets of 1s+s+width were made, and a cello 7A adhesive tape was kicked onto them and the tape was vigorously scratched to perform a test.

Water resistance: The condition of the painted surface was visually inspected by immersing it in tap water at 20°C for 2 days.

Claims (1)

[Scope of Claims] An aqueous pigment dispersion consisting of a pigment, a dispersant, and an aqueous medium, wherein the dispersion is modified to consist of a reaction product of (A) a fatty acid or oxyacid condensate and a (meth)acrylate having an aziridine group. (meth)acrylic monomer 3 to 98 parts by weight (B) One or more (meth)acrylics selected from aminoalkyl (meth)acrylate, aminoalkyl (meth)acrylamide, and (meth)acrylic containing quaternary ammonium salt 1 to 97 parts by weight of meth)acrylic monomer (C) 0 to 96 parts by weight of α,β-ethylenically unsaturated nitrogen-containing monomer other than the above (B), and (D) the above (A), (B) ), a neutralized product or a quaternary ammonium compound of a polymer obtained by copolymerizing 0 to 91 parts by weight of an α,β-ethylenically unsaturated monomer other than (C) Cationic aqueous pigment dispersion.