JPS60123563A - Aqueous pigment dispersion - Google Patents

Abstract

PURPOSE:The titled dispersion having improved dispersibility, dispersion stability, compatibility with water, providing a film with improved corrosion resistance, adhesivity, etc., obtained by using a specific water-soluble copolymer as a dispersant. CONSTITUTION:(A) 3-98pts.wt. lactone or oxy acid condensate-modified (meth) acrylic monomer {e.g., compound shown by the formula I [R1 is H, or methyl; R2 is group shown by the formula II (m is 2-8), group shown by the formula III(R4 is H, or methyl); R3 is group shown by the formula IV (n is 2-18)], etc.} is copolymerized with (B) 2-97pts.wt. alpha,beta-ethylenic unsaturated nitrogen-containing monomer (e.g., 1-vinyl-pyrrolidone, etc.), (C) 0-20pts.wt. ethylenic unsaturated carboxylic acid (e.g., acrylic acid, etc.), and (D) 0-91pts.wt. alpha.beta-ethylenic unsaturated monomer (e.g., methyl acrylate, etc.) except components A, B, and C, and solubilized to give a water-soluble copolymer. The water soluble copolymer is blended with pigment and an aqueous medium, to give the desired dispersion.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides an aqueous pigment dispersion with excellent dispersibility and dispersion stability using a λJ standard pre-dispersion method 15-1.

Conventionally, in water-based paints such as emulsions 67, pigments, and water-soluble resin coatings containing pigments, j+l (dispersibility of pigments during manufacture, i. Decline, flooding (??-ki).

It is well known that a myriad of problems such as floating (floating mottling) and reduction in gloss occur. For this/C, generally, a water-based pigment dispersion is prepared by dispersing the first phase with a dispersant in advance, and this is mixed and dispersed in the water-based paint to color the water-based paint. It is.

The conventional aqueous M material dispersion 2fM has an interface l'I',?i
Low molecular weight compounds such as Mll are used as dispersed Mll.

The negative effects caused by the dispersant, ie, secondary negative effects such as deterioration of wall film performance or coating condition, cannot be avoided.

In the vicinity of 1.1, the current situation is to use oligomers or medium-sized molecular weight polymers as dispersants to suppress deterioration in coating film performance, etc.

However, when oligomers or small aggregates are used as dispersants, the amount used is larger than that of low-molecular surfactants, and the use of the resulting aqueous pigment dispersion depends on the type of binder used in the aqueous paint. There are drawbacks such as restrictions. This goes against the rationalization of the production of the four materials, and for this reason, it is highly desirable to develop a water-based pigment dispersion solution common to all water-based paints.

Therefore, the present inventors have developed an ideal solution that can easily disperse pigments in small quantities, is compatible with various water-based resins, and does not cause any deterioration in the wall performance of water-based paints because the pigment is itself a molecule. The present invention was completed as a result of intensive research into the development of dispersed lighting, particularly for use in difficult water systems.

Thus, according to the invention, in an aqueous pigment dispersion comprising a pigment, a dispersant, and an aqueous medium, the dispersant comprises:

(A) Lactone or oxic acid M? (Meth)acrylic yarn monojunum modified with @Q 3-98 parts (B) α, β-ethylenically unsaturated nitrogen-containing monomer 2-9
7 coulometric parts (C) α,β-ethylenic non-1'! , :jl fu carboxylic acid 0-20 city hJ: part and (D) α other than the above (A)-CB)-(C).

An aqueous pigment dispersion is provided, which is a water-soluble product of a polymer obtained by copolymerizing 0 to 91 overlapping portions of a β-ethylenically unsaturated cleaning material.

The polymer used as a dispersant for the aqueous pigment dispersion of the present invention has a non-crystalline relatively linear long side button that is bonded in a separate form to a main chain containing a hydrophilic nitrogen-containing monomer. Due to its structure, it has very high pigment dispersion ability. Further, when the aqueous pigment dispersion of the present invention is used, it is possible to obtain a colored coating film which is extremely excellent in properties such as monolithic corrosion resistance and adhesion.

The dispersant used in the aqueous pigment dispersion of the present invention will be explained in more detail below.

A (meth)acrylic monomer modified with a lactone or an oxycondensate (hereinafter referred to as "modified (meth)acrylic monomer") used in the present invention (A) H (meth)
It is a monomer obtained by reacting an acrylic monomer with a lactone or an oxyacid A46 compound, and is typically represented by the following formula (1)% formula% (1) where -R is a hydrogen atom or Next to the amount of methyl, Noah 2 is a -CmH2m group (where 'n't is an integer from 2 to 8 and 11
,') or -C11pi1i-C1i2-)□(, (where it411 represents a hydrogen atom or the methyl amount i, and R8
represents a -CJi group (where n is an integer of 2 to 18), and p represents 1 to 7.

Includes those shown.

The lactone used as a modifying agent in the two modified (meth)acrylic yarn single caps shown by the above formula (1) is:
It is a cyclic ester compound containing an ester functional group -Co-Q- in j■, and typical lactones include r-lactone, δ-lactone, ε-lactone, γ-caprolactone, and δ-caprolactone.

Examples include methyl ε-caprolactone (including ¥44).

The oxyacid condensate is a condensate of aliphatic monocarboxylic acids (hydroxy fatty acids) having one hydroxyl group in one molecule, and the hydroxy fatty acids include ring-opened products of the lactone compounds mentioned above, ricinoleic acid, etc. , oxystearic acid, lanonolumitic acid, and the like. The production of condensates of these oxyacids is carried out using the above-mentioned hydroxy fatty acids and refluxing solvents (xylene, toluene, heptane, etc.) in accordance with conventional methods.
and an esterification catalyst (methyl acid, dodecylbenzenesulfonic acid%) at about 140-250°C.
This can be carried out by heating and condensing.

The lactone compound or oxyacid condensate mentioned above is as follows.
As if floating, it becomes a (meth)acrylic monomer. Each of these lactone compounds or oxyacid compounds may be used alone, or two or more may be used in combination.

Therefore, in order to obtain one lactone-modified (meth)acrylic single unit, the above-mentioned lactone compound is introduced into the (meth)acrylic single unit, and the ester residue moiety contains one unit.
A hydroxyl group-containing (meth)acrylic acid ester having a hydroxyl group of 17.1 and having 2 to 8 carbon atoms in the remaining ester portion is preferably used, and specifically, 2-hydroxyethyl Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2
-Hydroxypropyl methacrylate and the like.

The lactone-modified (meth)acrylic monomer (A) using such a hydroxyl group-containing (meth)acrylic acid ester component can be prepared by a method known per se, for example, lp\lj''1l.
rj 57-195714, and is usually carried out using the lactone and water alZ-',,! (meth)acrylic standard ester in the presence of a catalyst at about 20-220°C, preferably at about 5°C.
This can be carried out by stirring the reaction at 0 to 180°C. The reaction time is generally about 0.5 to 40 hours, preferably 5 to 20 hours. As a catalyst, 1-1 (Ling-Sin compound, 1, alkyl titanate, lead compound, 1-catalyst, etc.) are used in Europe.

The molecular weight of the lactone-modified (meth)acrylic system thus obtained is 200 to 1500. It is preferable to have a value of 400 to 1000, and Fn 41< of the molecule Yli can be easily determined by appropriately changing the blending ratio of the lactone and the hydroxyl group-containing (meth)acrylic ester. be able to.

In addition, in order to obtain the oxyenemy A4e4 combination I proboscis-modified (meth)acrylic single-use body, the previous fil-: Shita Ogishi! 1. (Meth)acrylic yarn in which Okinamono is introduced j) l j
; d as the i-form: (meth)acrylic esters containing a dalicidyl group in the ester residue moiety, particularly glycidyl acrylate and glycidyl methacrylate, preferably glycidyl acrylate;
I can stay.

Such oxyacid condensate-modified (meth)acrylic monomer (
A) is prepared by using the above-mentioned oxyacid-containing ester and (meth)
This can be carried out by reacting with a glycidyl group-containing ester of acrylic acid.

The reaction temperature is generally about 60-220°C, preferably about 120-220°C.
It can be carried out at a temperature of 170 DEG C. and the reaction time is generally about 0.5 to 40 hours, preferably about 3 to 10 hours.

The (meth)acrylic acid glycylate 4.1 (free esdel is 0 per mole of the oxyVAil&4)
．． It is advantageous to use it at a rate of 7 to 1.5 mol, preferably 0.8 to 1.2 mol, per month. Note that 1. Approximately 100-2,500-77 (approximately 2
Molecule ir of 00~2,000σ stage 1.1j, 1ji-1
It is advantageous to have an i-view.

α, β-Ethylenically unstable 1-order nitrogen-containing monoh (body (B):
Next, the α,β-ethylenic non-prefecture L1 mole containing ji-axis body (B) used in this research is 111·'1' in -1 molecule? It includes a single action containing a basic hydrogen atom of l or f5j number 1 (up to 1:1) and one ethylenically unsaturated bond, and typical examples include Examples include unsaturated monomers having an unsaturated structure and (meth)acrylic monomers. Below, we will explain more specifically about these Qffi 1
The situation becomes clear.

[1] Unsaturated monomers that satisfy the nitrogen-containing polychord J theory are 1 to 3 (i, l, 1. IF→, monomer or polynomial containing preferably 1 or 2 ring nitrogen atoms). This includes 141 monomers in which the excreta is bonded to a vinyl group, and in particular shown below)) 1
(1) Vinylpyrrolidones; For example, l-vinyl-2-pyrrolidone, ■-vinyl-3
- such as pyrrolidone.

(11) Vinylpyridines; For example, 2-vinylpyridine, 4-vinylpyridine, 5
-Methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, etc.

(iii) Vinylimidazoles; Example Ir,! '
, 1-vinylimidazole, 1-vinyl-2-methylimidazole, etc.

(1v) Vinylcarbazoles; Example i is N-vinylcarbazole.

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

(vl) Vinylquinolines; For example, -3-vinylpiperidine, N-) thyl-3-vinylpiperidine, etc.

(vii) Others; AI-(meth)acryloylpyrrolidine represented by N-(meth) (wherein R has the above meaning), etc.;

Among the above-mentioned vinyl monomers having a nitrogen-containing heterocycle, preferred are vinylpyrrolidones, vinylimidazoles, and vinylcarbazoles, and among them, those in which the ring nitrogen atom is tertiary are preferred. be.

[2] For elephant nitrogen derivatives of (meth)acrylic acid.

Those having a substituted or unsubstituted amine group in the ester moiety of (meth)acrylic esters and amides of (meth)acrylic acid are included, and in particular, the following formula 0 formula % ([) In each of the above formulas, R6 and R6 and f17 each independently represent a hydrogen atom and an alkyl thread, and I and a hydrogen atom or lower alkyl represent -R.

is a hydrogen atom, a lower alkyl atom, :5. Di(lower alkyl)amine lower alkyl group, hydroxy other alkyl group: or (, L!, 9 alkoxy+, 1. L-class alkyl group, q represents an integer from 2 to 8, l? , (has the above meaning, and aminoalkyl (meth)acrylate represented by
Meth) Acrylamide is greasy. Here, "lower"ii'Ft means that the number of carbon atoms in the group to which this candy is attached is 6.
', f[bl or less, preferably -λ, preferably 4 or less: Ze! Taste.

Therefore, as a specific example 1 of such a nitrogen-containing (meth)acrylic optical mer, examples of the aminoalkyl (meth)acrylate of the above formula (It) include N,N-dimethylaminoethyl (meth)acrylate, N.

N-diethylaminoethyl (meth)acrylate, N-
t-Butylaminoethyl (meth)acrylate, N, N
-dimethylaminopropyl (meth)acrylate, AI
,? V-dimethylaminobutyl (meth)acrylate,
N-propylaminoethyl (meth)acrylate, N-
Examples of the (meth)acrylamide of the above formula (Ill) include (meth)acrylamide, N-methyl (meth)acrylate, etc.
Acrylamide, N-ethyl (meth)acrylamide,
N-Butyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide 2N-methylol (meth)acrylamide, 8-ethoxymethyl ( Included are meth)acrylamide, N-butoxymethyl(meth)acrylamide, N,N-tumethylaminopropylacrylamide, and the like. Talented 1. The most suitable methacrylic monomers are those in which the existing nitrogen atoms are tertiary.
Next, those that have been secondaryized are also used for J.J.

The four α,β-ethylenic nitrogen-containing monomers described above can be used alone or in combination of 2'4rJi or more.

Ethylenically unsaturated carboxylic acid (C): Next, the ethylenically unsaturated carboxylic acid (G) included in J41 in the present invention has an addition polymerizable property between the carbon atom to be carboxylized and the carbon atom in contact with it. Suitable are unsaturated aliphatic mono- or polycarboxylic acids of the type having double bonds of the type containing 3 to 5 carbon atoms per 23 to 8 carbon atoms and having carboxyl or 2 carbon atoms, typically teeth.

The following general formula (IV'1) In the formula, R represents a hydrogen atom or a lower alkyl group.1
1 and o represent a hydrogen atom, lower alkyl represents a carboxyl group, and R and 1 represent a hydrogen atom.

Represents a lower alkyl group or a carboxy lower alkyl group.

and the following general formula (V) 1 1 (v) CB,=C COOC. In the formula H, COOH, R1 represents the above meaning, and r is an integer from 2 to 6, and those represented by these are included. In the above formula (■'), the lower alkyl group is preferably one having 4 or less carbon atoms, especially a methyl group.

An example of such an ethylenic dihydrogen carbone is as follows:
Acrylic acid, methacrylic acid, crotonic acid, itacon 71
, maleic acid, K1jl: water maleic Ii'? −． 7
2-carboxyethyl (meth)acrylate, 2-carboxypropyl (meth)acrylate, etc. can be used alone or in combination with two or more silks.

Other α,β-ethylenic deficiencies iffl 'M11'I
Moon, 1 body (D): Furthermore, the above (A), l? )-(C
) other than α.

The β-ethylenically unsaturated monomer (D) is not particularly limited and can be selected from a wide range depending on the desired performance of the dispersant of the present invention. Representative examples of such unsaturated old metals are as follows.

(α) Esters of acrylic acid or methacrylic acid; for example, methyl acrylic acid, ethyl acrylic acid.

Propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, furopyl methacrylate, isopropyl methacrylate, butyl methacrylate, methacrylic acid C1-CIB alkyl esters of acrylic or methacrylic acid such as hexyl, octyl methacrylate, lauryl methacrylate, glycidur acrylate, glycidur methacrylate; methoxybutyl acrylate, methoxybutyl methacrylate. C2~1m alkoxyalkyl ester of acrylic acid or methacrylic acid such as acrylic powder methoxyethyl, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate; C2 of acrylic acid or methacrylic acid such as allyl acrylate, allyl methacrylate, etc. ~G, alkenyl ester: hydroxyethyl acrylate, hydroxyethyl methacrylate-1.

C2 of acrylic acid or methacrylic acid in the form of hydroxypropyl acrylate or hydroxypropyl methacrylate
, 8-hydroxyargyl ester; C3-18 alkenyl oxydialkynyl ester of acrylic acid or methacrylic acid such as allyloxyethyl acrylate and allyloxymethacrylate.

(b) Vinyl aromatic compounds: for example, styrene-α-
Methylstyrene, vinyltoluene, p-ri.

Lustyrene.

(C) Polyolefin compounds: for example, butadiene, isoprene, chloroprene.

(d) Others: acrylonitrile-methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, Beopa monomer (Shell Chemical Products), vinyl propionate, vinyl pivalate, etc.

These unsaturated monomers are appropriately selected depending on the desired physical properties of Ri, and may be used alone or in combination of 2M8 or more.

According to the present invention, the above modified (meth)acrylic yarn mono% i
J body (A), α,β-ethylenically unsaturated nitrogen-containing single sleeve body (
B), the ethylenically unsaturated carboxylic acid 0 and the unsaturated monomer (D) are copolymerized with each other. The copolymerization is carried out according to a method known per se for producing acrylic copolymers, for example, using a bath liquid "0 method, emulsification method 26 method. mfa".
This can be done using the llK method or the like.

What is the blending ratio of the above four components when copolymerizing?

Although it can be changed depending on the performance desired as a dispersant, it is appropriate to mix it in the following proportions.

ill fi (meth)acrylic monomer (A) j3~
98 car weight parts, 10 to 85 car weight parts from the viewpoint of skillful coating film performance, (2) α,β-ethylenically unsaturated nitrogen-containing monomer (B)
; 2 to 97 parts (1i. parts, preferably 3 to 90 parts) from the viewpoint of pigment dispersion.

(3) Ethylenically unsaturated carvone #(G): o~20
Heavy areas, preferably water bath disintegration, coating film properties fj ratio from 2 to 2
18jufubu.

(4) Unsaturated monomers (D
): 0 to 9] 1F State capital, preferred 1 5 from the viewpoint of paint film performance
~83 pieces 4 parts.

The above-mentioned copolymerization reaction is preferably carried out according to the M-liquid market method, and is preferably carried out according to the above-mentioned No. 41 method. In an inert bath liquid suitable for molecules, in the presence of a polymerization catalyst, the temperature is usually about 0 to about 180°.
The reaction can be carried out by continuing the reaction for about 1 to about 20 hours, preferably about 6 to about 10 hours, at a reaction temperature of G, preferably about 40 to about 170 degrees Celsius.

As the solvent to be used, it is preferable to use a solvent that can completely dissolve the produced copolymer and be miscible with water so that no gel formation occurs in the copolymerization reaction 13. Particularly preferred is one that can be used even in its grooves without being removed when obtaining the aqueous pigment dispersion 2. Examples of such solvents include Formula 1 HO-C
1i, C1i, -OR, 2 [wherein R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms] cellosolve-based solvents such as ethylene glyconol, butyl cellosolve, ethyl ketone rub, etc.; Formula 110CIi
2-CH-01? , □ [Just C1i.

and RI2 has the same meaning as above], such as propylene glycol monomethyl ether; formula 110-C1i2C1i2-OCR
.

C1i, -01l,, [However, R12 has the same meaning as above] Carpitol solvent such as diethylene glycol, methylcarpitol, butylcarpitol, etc.; Formula R,, O-CM, C1i, -OR, [However, , R and R34 each represent an alkyl group having 1 to 3 carbon atoms] Glyme yarn bath medium such as ethylene glycol methyl ether etc. 1 formula R, α-CH2C
H1!0C11,! -CD20R, 4 [However, 17.
3 and R14 have the same meanings as above; for example, diethylene glycol dimethyl ether; formula R, 0-C11, C1i, 0CO-CB; [however, R1 is
, ] cellosolve acetate solvents such as ethylene glycol monoacetate, methyl cellosolve acetate; formula R3゜Oli [where IIl'+
6 represents an alkyl group having 1 to 4 carbon atoms] alcoholic solvents such as ethanol, propatool;
In addition, dia-7ton alcohol, nooxane, tetrahydrofuran, acetone, dimethylpolamide, 3-
Methoxy-3-methyl-butanol and the like can be used instead.

However, inert solvents that are immiscible with water can also be used, such water-immiscible solvents having a boiling point below 250°C so that they can be easily removed by distillation under normal or reduced pressure after the polymerization reaction is completed. Preferably. Examples of such solvents include aromatic hydrocarbons of the formula R2o, such as toluene and xylene; -Coo -112, [However -1
” 20 represents an alkyl group having 1 to 6 carbon atoms;
R2I is a hydrogen atom, an argyl group having 1 to 6 carbon atoms, or a cyclohexyl thread] or esters such as acetic acid and ethyl formate.

Gtylacetate, Azushima'cyclohegycyl, etc.; Formula R,! 2R
23C-O [tag ζ, R2□ and R23(r, j',
alkyl groups each having 1 to 8 carbon atoms] and ethyl ketone, cyclohexyl thread fl toi formula R
22-0-1 et al. [/Kotashi, Il, 2 and ln, 3
11.401-1 [wherein and 4 are carbon] Kyoko Sano 5~ Alcohols represented by 11 alkyl groups.

Examples include hexanol.

These solvents contain 15~
It can be used for a period of up to 90 yen.

However, as a combined catalyst, for example - azo compounds, peroxide compounds, sulfides, sulfines, sulfinic acids, diazo compounds, nitroso compounds, redox compounds and short-lived radiation, etc., can be used for normal radical polymerization. Any available lasocal initiator is used.

In the present invention, a substantially satisfactory aqueous pigment dispersion 144 can be obtained even if the molecular weight of the copolymer to be produced changes, but if the molecule U is too low, the physical properties of the water-based paint to be colored will deteriorate. There is a risk.

However, 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. Advantageously, the reaction is carried out until the molecular weight is within a range of from about 500 to about 150.00 (1, preferably from about 110,000 to about 100,000).

After the copolymer resin thus produced is frozen or the bath medium is distilled off, it is made hydrostatic. This water solubility can be achieved by a conventional method, for example, by neutralizing the carboxyl groups present in the co-Hf-attached resin with a conventionally known intermediate agent. Medium size 3"1"
Examples of the agent include ammonia, amines, alkaline woodblocks, and alkaline carbonates.

The amines include primary, secondary, C,,! , tertiary alkylamines; secondary or tertiary alkanolamines; and cycloalkylamines. Further, as the hydroxide of the alkali group, potassium hydroxide, sodium hydroxide, etc. can be used; as the carbonate and bicarbonate of the alkali group, potassium charcoal, sodium carbonate-sodium bicarbonate, etc. can be used. Among these neutralizing agents, potassium hydroxide and sodium hydroxide are suitable for poetry.

The treatments A and E can be easily carried out in a conventional manner by adding the above-mentioned neutralizing agent or its water bath 11 to the copolymer resin obtained as described above or its bath solution.

The amount of fl agent used is generally 0.01 to 2.0, preferably 0.01 to 2.0, per carboxyl group in the compound.
do, 3 to 1.0 common use.

The water-bathable offshore body thus obtained is used as a dispersant in an aqueous pigment dispersion consisting of a pigment 1 dispersant and an aqueous medium.

What is the usage amount of the dispersant made of the above-mentioned water bathable offshore body?

Generally about 1 to 500 parts per 100 parts of pigment,
Preferably, it can be about 1 to 300 canters. 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, when the degree of hydrophilicity of the dispersant is low and sufficient pigment dispersion performance cannot be obtained. (a) An aqueous organic solvent can be used in combination. As the residual water organic solvent, those used in the production of the above polymer can be used alone or in combination.

In addition, the pigment used in the aqueous pigment dispersion of the present invention can be of the inorganic and organic (77 & Th family) commonly used in this pigment dispersion (revised); for example, as an inorganic pigment, (1 ) !', iZ compound type (zinc white, titanium dioxide, red iron oxide, chromium nitride-cobalt glue,
iron black, etc.); t2+ hydroxide type (alumina white, yellow iron oxide, etc.); f31 value compounds, selenide type (sulfide I
IJ lead, vermilion, cadmium yellow, cadmium red, etc.)
; (4) Ferrocyanide thread (Navy-1'etc.); (
5) Chromium ul-salt system (yellow lead-sync chromate, molybdenum red, etc.) i (6) Sulfate system (precipitated barium sulfate, etc.) + (charcoal compact salt system (precipitated calcium carbonate, etc.);
8) Silicate yarn (hydrated silicate, clay, ultramarine, etc.) r (
91 Phosphate type (manganese violet, etc.); (Field carbon type (Carbon black, etc.); α1) Gold kite powder thread (aluminum powder, bronze powder, zinc powder, etc.) etc. are reduced and are in good condition. The pigments include (1) nitroso pigment yarn (naphthol green B, etc.); (31 azo pigment yarn (naphthol green B, etc.);
Lake Red C, Fast Yellow, Naphthol Red)
(4) Dyeing lake pigment system (alkali blue lake pigment system (phthalocyanine blue, fast sky blue, etc.); (6) Condensed polycyclic pigment thread (herylene red, quinacridone red, dioxazine iolet);

isoindolinone yellow, etc.).

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 times φ based on the weight of the dispersion.

The aqueous pigment dispersion of the present invention can be prepared using a suitable dispersion device imi.
The dispersion device b1 that can be used is as follows. ＞lVijo? Ball mills, roll mills, homogenizers, sand grinders, shakers, attritors, etc., which are used repeatedly in r-format j:,:g, are listed.

It is also possible to add conventionally known surfactants and color-retaining colloids to the aqueous pigment dispersion of the present invention, if necessary.

In the thus obtained aqueous pigment dispersion of the present invention, the pigment is very uniformly and finely dispersed, and the pigment particles hardly aggregate or 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 is aqueous (1 is also bath-decomposed in the body, so the pigment is stably dispersed in the aqueous medium.

Therefore, the aqueous pigment dispersion of the present invention is an alkyd resin used in aqueous paints and inks.

Acrylic resin, epoxy resin, urethane resin.

It has good miscibility with conventionally known water-soluble resins such as maleated polybutadiene resins, water-dispersible resins, emulsions, etc., and is not limited by these resins, and can be widely used for coloring water-based pigments made of any resin. can do.

As a specific example of the above-mentioned aqueous resin, for example, alkyd resin is synthesized from the same raw materials as conventional bath agent-type alkyd resins, and is a polybasic r-functional and polyalkylic alcohol.

It is obtained by subjecting oil components to a condensation reaction using a conventional method. Acrylic resin is α,β-ethylenically non-AiIIf1
Acrylic acids (e.g. acrylic acid, methacrylic acid, maleic acid, etc.), (meth)acrylic acid esters (e.g. ethyl acrylate, propyl acrylate-glutyl acrylate,
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate): Obtained by combining JR- and vinyl aromatic compounds (e.g. styrene, vinyl toluene, etc.). be. As epoxy 1,11 resin, epoxy resin F-F
An epoxy ester is synthesized by the reaction of 11 unsaturated 1/j t'i with oxy yarn, and α and β are added to this defective 111 group.
-No 1jc'! How to add fll P'z-, the hydroxyl group of epoxy ester, phthalic acid and trimellitic y
Epoxy ester produced by esterification of polyester fibers such as epoxy ester.

As the urethane-based IV4 fat, polyisocyanate compounds (for example, toluene diisocyanate) are used.

(duphenylmethane diisocyanate-1, 1,6-hexane diisocyanate, isophorone twinocyanate, etc.)
Using 19j urethane in the fat skeleton! This is a resin in which i← has been introduced and a carboxyl group f has been introduced using dimethylolpropionic acid or the like.

When using the above water-based resin as water-soluble, the resin is synthesized to have an acid value of approximately 35 to 200, and this is mixed with an alkaline substance such as sodium hydroxide, amine, etc. On the other hand, when these resins are used in a self-dispersing form, the acid value of the resin is a low acid value resin of about 5 to 35, and this is completely neutralized and water-dispersed. Served as mold paint.

i 7' (, 1?) Anionic type moji is an emulsifier-dispersed emulsion obtained by dispersing an alkyd resin, acrylic resin, epoxy resin, or urethane resin using a chiion type low-molecular-weight surfactant; Emulsion jF, combined emulsion obtained by emulsion polymerization of monomers such as (meth)acrylic ester, acrylonitrile, styrene, butadiene, vinyl acetate-vinyl chloride, etc.; IiW, maleated fatty acid modified vinyl wax (
! 1 fat, drying oil or semi-drying oil Water soluble such as fatty acid modified acrylic resin 4! :'! Whole fat emulsified cheap 'f11 and (~
A soap-free emulsion is produced by emulsion polymerization and kraft reaction of the four components described above.

The water-based dispersion of the present invention is effective for blending into water-based paints consisting of L'1jliT and emulsions, which have low acid value water dispersibility and poor pigment dispersibility.

Water/19) of the aqueous bowl dispersion of the present invention, the formulation 1'J" 4 for the ingredients is 4 for the council 1) + 1' for the pond/naka! eyebrow Z"
Although it is possible to vary widely by 14 degrees depending on the 1 Y/μ'' per groove required for LIy and ring road paints, in general, +13 il:ul\ water-based pigments are used. The resin content can be blended with a needle size of 100, and the pigment fraction can be blended with a surface of 2 to 1000 needles.

Next, the present invention will be further explained with reference to Examples.

In the examples, 1st part and 1st part indicate the vehicle volume part and the weight part, respectively.

Example 1 300 parts of n-butyl cellosolve was placed in a reaction vessel and heated to 120°C. θ(2+41 of the ratio shown below)
The known mixtures were added separately to this solution VC dropwise over a period of approximately 2 hours. The reaction was carried out under nitrogen injection.

N,N-dimethylacrylamide 91 parts acrylic acid
Part 33, 71)'Xi Takashi'1 Of course.

A mixture of 18 parts of azobisdimethylvaleronitrile and 50 parts of n-butyl cellosolve.

While keeping the reaction temperature at 120°C and stirring the bath solution, the above 7 compound 1 total i! l'; I got down. southward r
) 2.5 liters of azobisisobutyronitrile every 1 hour
Add 1 part to the entire reaction solution, and add 2.5 parts of 2 [1, 1, 1, 2, azobis isoptiloni] IJ to the reaction 1'6 grade υ (
Plus, 2 hours after that! After the completion of the C0 reaction, the unreacted mono[;; body and n
- Coercive distillation of butyl cellosolve, heating residue 705%
, 4q11i hydric acid 1 song 911, ) j-donor viscous 1f (
The communicable dissolution of 40% n-1 til cellosolve bath solution) P was conducted. Further, this copolymer was neutralized with triethylamine-C and 10% of 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 amount and 200 parts of Techno White Material (Titanium White 1i-5A' manufactured by Sakai Chemical Co., Ltd.) was dispersed for 0.5 hours using a Reti Devi1 dispersion method. At least one aqueous pigment dispersion of the present invention (A
) was obtained.

1M:I 45NK Aqueous Batteries (13) to (D) of the present invention without any pigment dispersion were obtained using the formulations shown in Table 1. In addition, for regular materials other than titanium white, dispersion is performed for 1 hour.

? The properties of the aqueous N filler fraction Yw are summarized in Section 1 below.

Next, 10 parts of aqueous pigment dispersion (A) and water-dispersed alkyd resin (linseed oil fatty acid/Pentaerys IJ Toll/
Rest 'pif tM / Isophthalic acid / Maleia anhydride
Acid = 903 / 705 / 1140 / 610
/ Oil made from 45 (parts) & 30 and acid value 16
An aqueous F-R preparation (1) was prepared by thoroughly mixing a formulation consisting of 23.4 parts of a solution with a solid content of 40% obtained by neutralizing 1.0 equivalent of alkyd resin with triethylamine.

In the same manner, the pigment dispersion liquid and the water-based resin composition shown in Coating-2 below were sufficiently mixed to obtain water-based paints (2) to (6). Summary of the coating film performance of the obtained water-based paint Example 2゜n~ Reaction volume of butyl cellosolve 350 t'tlI:
It was heated to 120'C. Next J:),
The whole mixture of split rocks shown below, about 21i, +1i in this bath
;Drop by I/lx/ζ. The reaction Vi nitrogen was under two people.

N-vinylpyrrolidone 126 parts Acrylic acid 11 parts Azobisisobutyronitrile 9 parts While maintaining the reaction temperature at a total of 120'C and stirring the reaction YG solution, the above mixture was poured down to 13 ml. One hour after the completion of the reaction, 2.5 parts of azobisinbutyronitrile was added to the reaction solution for another 2 hours. After the reaction was completed, unreacted monomer and n-butyl cellosolve were distilled under reduced pressure, and the heated residue was distilled to 70%
．． Section 3, resin acid value 34.8, guider viscosity (40%
A copolymer solution of π-butyl cellosolve solution) G was obtained. Furthermore, this copolymer was neutralized with triethylamine.1. A dispersant (■) consisting of a water bath liquid with a heating residue of 40% was obtained by adding water.

Next, using the obtained dispersant (n)ff, the pigment was dispersed in the same manner as in Pigment Example 1 shown in Clothing-1 below to obtain an aqueous pigment dispersion (E) of the present invention.

This pigment dispersion (E) was thoroughly mixed with the water-based resin shown in Coating-2 below to prepare a water-based paint (7).

The properties of the pigment dispersion (E) and the quasi-membrane performance of the water-based paint (7) are shown in Coating-1 and Table-2 below, respectively.

Example 3゜(3-α) 12-hydroxystearin (H2tss part tornidi
383 parts and 4.3 parts of monomethylsulfonic acid were placed in a reaction vessel, and the reaction was allowed to proceed at 145°C for about 4 hours while removing the produced condensation water from the system. Resin acid value is 3
When it reaches 4.0, 221 parts of glycidyl methacrylate,
2 parts of hydroquinone and 10 parts of tetraethylammonium fluoride, reaction temperature 145
The reaction was carried out at ℃ for about 6 hours, and the resin acid value was 5.8.

C3-b) Reactant obtained in (3-(Z)) 132 parts N-vinylpyrrolidone 126 parts 2-carpogyethyl acrylate (US 114A, 1colac company i) 11 parts Azobistumethylvaleronitrile 17°5 parts The monomer mixture was subjected to a polymerization reaction according to the method described in Example 1.〃1'' Thermal residue: 71.θ% - Cutting ratio: 26.5, Gardner viscosity (copolymerization of 40% n-butyl cellosolve solution) A combination solution was proposed. This solution was neutralized with triethylamine (1.0% neutralized).

A dispersant (III) consisting of an aqueous solution having a heating residue of 40% was obtained.

Next, using the obtained dispersant (III), the pigment shown in Clothing-1 described below was dispersed in the same manner as in Example 1 to obtain an aqueous pigment dispersion (F) of the present invention.

Further, this pigment dispersion (F) and the aqueous resin shown in Coating-2 below were sufficiently mixed to prepare an aqueous paint +8) -<11.

The properties of the pigment component F+''1.I' and the film performance of the water-based paint (8) are shown in Table 1 and Table 2, respectively.

Example 4 In Example 3, N-vinylpyrrolidone was replaced with N,
The polymerization reaction was carried out under the same conditions as in Example 3, except that N-trimethylaminoethyl methacrylate was used at t12, and the heating residue was 71.3%, and the fatty acid value was 39.5. A copolymer solution having a Gardner viscosity (40 coefficient n-butyl cellosolve bath solution) of E was obtained. Next, this product was neutralized with triethylamine to obtain a dispersant (■) consisting of 1.0 equivalents of 1/2 mol [J] and a water bath with a heating residue of 40 parts.

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

In addition, this Chestnut dispersion (G) and the aqueous a shown in Postscript Cloth-2
A water-based paint (9) was prepared by sufficiently mixing R fat.

The properties of the pigment dispersion (G) and the coating film performance of the water-based paint (9) are shown in Coating-1 and Table-2, respectively.

Example 5゜'X7Ai Example 1 except that 1-vinylimidazole was used instead of N-vinylpyrrolidone in Example 1.
The polymerization reaction was carried out under the same conditions as above, and the heating residue was 70.3% and the resin acid value was 86. A copolymer solution with a Gardner viscosity (40% n-butyl cellosolve solution) Q was obtained. Next, the mixture was neutralized with triethylamine (1.0% neutralization) to obtain a dispersant (V) consisting of an aqueous solution with a heating residue of 40%.

Next, using the obtained dispersant (v), the pigment to be described later was dispersed in Clothing-1 in the same manner as in Example 1 to obtain an aqueous pigment dispersion CH of the present invention.

Further, this pigment dispersion (H) and the aqueous resin shown in Coating-2 below were sufficiently mixed to prepare a water-based paint ([0)].

The properties of the pigment dispersion (H) and the coating film performance of the water-based paint (10) are shown in Table 1 below.

Comparative Example 1 Il commercially available pigment dispersant SMA 144011 CARC
Titanium white R-5N using sodium salt of styrene-maleic anhydride type combination (trade name) manufactured by OChgmica1.
10 parts of a pigment dispersion (pigment content: 70, 0%) prepared by dispersing (Titanium Sodium, trade name, manufactured by Sakai Chemical Co., Ltd.) at a solid content weight ratio of titanium white/dispersant = 2271, and the coating described below. -2 emulsion (b) 17.5 parts f was mixed to make a water-based paint for comparison. The biofilm performance of this product is shown in Section 2 below.

*1 Titanium White R-5N: Sakai Chemical Co., Ltd. Titanium Oxide Carbon MA: Mitsubishi Kasei Co., Ltd. Calf 1-7 Black Copper Phthalocyanine Green 6YK: Toyo Ink Manufacturing Co., Ltd. Yellow GKZR-8: Kikuchi Color Co., Ltd. *2 According to ASTM D1201-64 Performance I] Fixed *3
The acid value of the water-dispersed alkyd resin used in Example 1 was 60.
An emulsion obtained by polymerizing 70 parts of n-butyl acrylate using 30 parts of a neutralized resin as an emulsion stabilizer (solid content: 40 parts) *4 Sodium salt of dodecylbenzene Total styrene/methyl as an emulsion stabilizer Methacrylate/? An emulsion obtained by total polymerization of a monomer mixture consisting of h-butyl memetarylate = 35/15150 (solid content 50%)
) [Coating film performance test] Water-based paint (1) ~ α@ with a water-based dryer (trade name: 0 Daykunate, manufactured by Inu Nippon Ink Co., Ltd., Cobalt Metal Functional 3-chi)
- Added at a ratio of 1 part to 100 parts of tsukuza solid content and painted on a mild steel plate. After drying at 20° C. and 75% relative humidity for 3 days, it was used for testing.

Gopin adhesion: 100 gopins of 1 m+xllVi'+ were made, and a cellophane adhesive tape was applied thereon and the tape was peeled off vigorously for testing.

Water resistance: f? after soaking in tap water at 20℃ for 2 days. The condition of the painted surface was visually inspected.

Claims (1)

[Claims] In an aqueous pigment dispersion consisting of a material, a dispersant, and an aqueous medium, the dispersant is (A) a (meth)acrylic yarn extender modified with a lactone or an oxyacid condensate. Vehicle volume department (1) ) α, β-ethylenically unsaturated nitrogen-containing single substance 2
~97@Group (G) 0 to 20 parts by volume of ethylenically unsaturated carboxylic acid and (D) α other than the above (A) and (BL l;'). By copolymerizing 0 to 91 parts by weight of β-ethylenically unsaturated monomer, I, et al. 71. It is a water-soluble compound of a polymer that is free of water and is a water-soluble dispersion.