JPH03294334A - Fine powder of colored resin - Google Patents

Abstract

PURPOSE:To obtain fine powder of a colored resin having excellent weather resistance, colored to clear and deep color and suitable as pigment, etc., by using a colorant, a polymer composed of a reaction product of a polycarbonate diol and (meth)acrylic acid, etc., as essential components. CONSTITUTION:A colorant is dissolved or dispersed in (A) a reaction product produced by reacting preferably 0.5mol of a polycarbonate diol with preferably 1-5mol of (meth)acrylic acid and/or (B) a reaction product produced by reacting preferably 1.1-2.0 chemical equivalent (based on 1 chemical equivalent of OH of a polycarbonate diol) of the NCO group of an organic polyisocyanate with preferably 1.0-1.1 chemical equivalent (based on 1 chemical equivalent of the NCO group of the organic polyisocyanate) of a hydroxyl-containing (meth) acrylate compound or in a composition containing the above reaction products. The components are subjected to emulsion polymerization or suspension polymerization to obtain the objective fine powder of colorant.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a colored resin fine powder, particularly a colored resin fine powder which has excellent weather resistance and can be used as various pigments.

(Prior Art) A colored resin fine powder produced by coloring a resin with a dye and pulverizing the same is disclosed in, for example, US Pat. No. 2809.
No. 954, No. 2938873 and No. 311625
As described in No. 6, a composition is known in which a formaldehyde cocondensate of an aminotriazine compound and an aromatic monosulfamide compound is used as a basic resin, and this is colored with a colorable dye. With the above method, there are problems in that it is not possible to obtain a clear and highly concentrated colorant, and the light fastness is very poor.As an improvement to these problems,
As described in Japanese Patent Publication Nos. 52-29336 and 53-9623, colored resin fine powders consisting of copolymers of specific unsaturated monomers and colorants are known.

(Problem to be solved by the invention) The above-mentioned Japanese Patent Publications No. 52-296336 and No. 53-962
Is it true that the colored resin fine powder described in Specification No. 3 has improved light resistance?It has sufficient light resistance and weather resistance for long-term outdoor use, such as automotive paints and colorants. does not have.

(Means for Solving the Problems) In order to solve the above problems, the inventors of the present invention, as a result of intensive research, have developed a colored resin microorganism that has good light fastness, excellent weather resistance, and is brightly colored and highly concentrated. succeeded in providing powder.

That is, the present invention provides a polymer (A ) and a coloring agent (B).

The colored fine powder of the present invention is composed of polycarbonate diol and (
Reactant of meth)acrylic acid and/or polycarbonate diol, organic polyisocyanate and hydroxy-containing (
A coloring agent (B
) is dissolved or dispersed, and then this mixture is subjected to emulsion polymerization or suspension polymerization in an aqueous system by a conventional method, or
It can be obtained by polymerization methods that produce similar microparticles. Emulsion polymerization or suspension polymerization is carried out using a water-soluble dispersant, surfactant, suspension stabilizer, or the like.

In the present invention, a reaction product (a) of a polycarbonate diol and (meth)acrylic acid and/or a reaction product of a polycarbonate diol, an organic polyisocyanate, and a hydroxy-containing (meth)acrylate compound is used.

A reaction product of polycarbonate diol and (meth)acrylic acid is known and can be produced by reacting polycarbonate diol with acrylic acid or methacrylic acid at elevated temperature.

Specific examples of polycarbonate diol include diol components such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-bentanediol,
Neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, l,
4-dimethylolcyclohexane, 1,8-octanediol, etc. and diaryl carbonate or dialkyl carbonate, such as diphenyl carbonate, bis-
Polycarbonate diols obtained by transesterification with chlorophenyl carbonate, dinaphthyl carbonate, phenyl-chlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, etc., or ε obtained by transesterification between the above polycarbonate diols and polycaprolactone diols. -Caprolactone-modified polycarbonate diols and the like can be mentioned. These polycarbonate diols can be easily obtained from the market. For example, Niraporan 98 (made by Nippon Polyurethane ■, average molecular weight 2000. A polycarbonate diol whose unit is 1,6-hexanediol), Niraporan 981 (Japan Polyurethane side type, average molecular weight 1000. whose unit is 1,6-hexanediol) polycarbonate diol),
Niraporan 982 (made by Japan Polyurethane, average molecular weight 2000, ε-caprolactone modified polycarbonate diol), Niraporan 983 (Japan Polyurethane side type,
Examples include ε-caprolactone-modified polycarbonate diol with an average molecular weight of 1000.

A reaction product of polycarbonate diol and (meth)acrylic acid is produced by reacting polycarbonate diol with acrylic acid or methacrylic acid or a mixture thereof.

The preferred amount of acrylic acid or methacrylic acid used is about 1 to 5 moles thereof per 0.5 mole of charged polycarbonate diol. The reaction is preferably carried out in the presence of a polymerization inhibitor to minimize or retard the polymerization of (meth)acrylic double bonds. The above polymerization inhibitors are well known to those skilled in the art, and they
Used at a concentration of ~5% by weight. Examples of these polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,
Examples include 4-dimethyl-6-t-butylphenol, p-benzoquinone, phenothiazine, N-nitrosodiphenylamine, thiourea, copper salt, and the like. The reaction is carried out at a temperature of about 50° C. to 130° C., preferably 656° C. to 90° C.
The esterification of the polycarbonate diol with acrylic acid or methacrylic acid to form a (meth)acrylic ester is carried out at a temperature of This time will vary depending on the batch size, the respective feed compounds and catalysts and the reaction conditions employed. Also, the esterification catalyst is preferably 0.0% relative to the acrylic acid or methacrylic acid used.
It is present in a concentration of 1 to 15 mol %, particularly preferably 1 to 6 mol %. Any known esterification catalyst can be used, examples of which include p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, sulfuric acid, and the like. It may be desirable to have an inert solvent such as hexane, cyclohexane, benzene, or toluene present to aid in the removal of water formed during the esterification reaction.

A reaction product of a polycarbonate diol, an organic polyisocyanate, and a hydroxy-containing (meth)acrylate compound is known, and by reacting the polycarbonate diol and organic polyisocyanate, and then reacting a hydroxy-containing (meth)acrylate compound,
Alternatively, it can be produced by a conventional method by reacting an organic polyisocyanate with a hydroxy-containing (meth)acrylate compound and then reacting with a polycarbonate diol. Typical organic polyisocyanates include tolylene diisocyanate, 4,4゛-
diphenylmethane diisocyanate, isophorone diisocyanate, 4.4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,
Examples include 2°,4-trimethylhexamethylene diisocyanate. The ratio of use of polycarbonate diol and organic polyisocyanate in the urethanization reaction is as follows: 1 chemical equivalent of OH group of polycarbonate diol, organic polyisocyanate of
It is preferable to use the GO group in a range of 1.1 to 2.0 chemical equivalents, particularly preferably 1.5 to 2.0 chemical equivalents. This urethanization reaction can be carried out in procedures known to those skilled in the art.

The reaction temperature of this urethanization reaction is preferably room temperature to 1
00'C1 is particularly preferably 50 to 80°C. The reaction time is preferably 3 to 50 hours, particularly preferably 5 to 15 hours.
It's time. Then, in the (meth)acrylation reaction, a hydroxy-containing (meth)acrylate compound is added to the oxy-containing (meth)acrylate compound per chemical equivalent of the NGO group of the compound having a terminal isocyanate group obtained in the urethanization reaction.
It is preferable to use the H group in a range of 0.9 to 1.5 chemical equivalents, particularly preferably 1.0 to 1.1 chemical equivalents. The reaction temperature is room temperature ~
The temperature is preferably 100°C, particularly preferably 50 to 80°C. The reaction time is preferably 3 to 50 hours, particularly preferably 5 to 15 hours. A typical example of a hydroxy-containing (meth)acrylate compound is β-hydroxyethyl (
meth)acrylate, β-hydroxypropyl(meth)
Examples include acrylate, ε-caprolactone-β-hydroxyethyl (meth)acrylate, and 1,4-butanediol mono(meth)acrylate.

Also, organic polyisocyanate and hydroxy-containing (meth)
When reacting an acrylate compound and then a polycarbonate diol, hydroxy-containing (
The meth)acrylate compound has an OH group of 0.4 to 0.
It is preferable to use it within a range of 6 chemical equivalents, and particularly preferably within a range of 0.49 to 0.52 chemical equivalents. The reaction temperature is preferably room temperature to 100°C, particularly preferably 50 to 80°C. The reaction time is usually 3
~30 hours, preferably 5 to 15 hours. And then organic polyisocyanates and hydroxy-containing (meth)
The OH group of the polycarbonate diol is preferably 0.9 to 1.1 chemical equivalent, particularly preferably 0.95 to 1 chemical equivalent, per 1 chemical equivalent of NCO group of the reactant of the acrylate compound.
It is used and reacted within a range that gives a chemical equivalent of 1.05. The reaction temperature is usually room temperature to 100°C, preferably 5°C.
0-80°C. The reaction time is 3 to 50 hours, preferably 5 to 15 hours.

The proportion of the reactant (a) contained in the reactive monomer used to obtain the polymer (A) is preferably 20 to 100% by weight, particularly preferably 50 to 100% by weight.

As the reactive monomer other than the reactant (a) used to produce the polymer (A), an ethylenically unsaturated group-containing compound can be used. Typical examples of ethylenically unsaturated group-containing compounds other than reactant (a) include tetrahydrofurfuryl (meth)acrylate, calpitol (meth)acrylate, and phenoxyethyl (meth)acrylate.
Acrylate, isobornyl (meth)acrylate, 2
-Hydroxyethyl (meth)acrylate, 2-hydroxybrobyl (meth)acrylate, acrylamide,
Vinylpyridine, acid phosphooxyethyl (meth)
Acrylate, 2-acid phosphooxypropyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, ε-caprolactone adduct of 2-hydroxyethyl (meth)acrylate (manufactured by Daicel Chemical Industries, Ltd.) Praxel FA-1, FA-2, FM-1, etc.),
Hydrogenated dicyclopentadiene (meth)acrylate (manufactured by Hitachi Chemical, FA-513A, FA-513MA), 2
-Hydroxy-3-chloropropyl (meth)acrylate, methylene, vinyl acetate, methacrylonitrile, methyl (meth)acrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, hydroxypivalic acid neobenchi polyglycol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, bisphenol A polypropoxy di(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxypivalic acid neo Di(meth)acrylate of ε-caprolactone adduct of pentyl glycol (manufactured by Nippon Kayaku, KAYARA
D HX-200, HX-620), trimethylolpropane tri(meth)acrylate, epoxy(meth)acrylate (e.g. bisphenol A epoxy resin (meth)acrylate, bisphenol F epoxy resin (meth)acrylate, bisphenol A (meth)acrylates of urethane-modified epoxy resins, etc.), polyester (meth)acrylates (e.g. ethylene glycol, propylene glycol, diethylene glycol,
Dipropylene glycol, 1,5-bentanediol,
(meth)acrylate of a polyester diol consisting of a diol component such as l, 6-hexanediol and a dibasic acid such as succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, the diol component and a dibasic acid (meth)acrylate of a lactone-modified polyester diol consisting of Typical polyol compounds include ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, cyclohexane dimetatool, trisifurobucadimethylol, 1
．． 4-Butanediol! , 6-hexanediol, polyols such as trimethylolpropane, polyether polyols such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, propylene-modified polytetramethylene glycol, the above polyol or polyether polyol, or the above polyol with ε-
A compound to which caprolactone or valerolactone is added is used as the alcohol component, and one of the acid components is dicarboxylic acid such as adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic acid. Examples include polyester polyols obtained using basic acids or their anhydrides. Typical organic diisocyanates include trirediisocyanate, 4゜4゛-diphenylmethane diisocyanate, isophorone diisocyanate, 4.4°-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,2°, 4-trimethylhexamethylene. Diisocyanates and the like can be mentioned.

The usage ratio in the urethanization reaction between a polyol compound and an organic diisocyanate is determined by the O of the polyol compound.
It is preferable to use the organic diisocyanate in a range where the NGO group is 1.1 to 2.0 chemical equivalents per 1 chemical equivalent of the H group, particularly in a range where the NGO group is 1.5 to 2.0 chemical equivalents. It is preferable to use it in This urethanization reaction can be carried out in procedures known to those skilled in the art.

Next, in the (meth)acrylation reaction, a (meth)acrylic ester having a hydroxyl group is added to the OH group of the (meth)acrylic ester having a hydroxyl group per chemical equivalent of the NGO group of the compound having a terminal isocyanate group obtained in the urethanization reaction. is 0
．． It is preferably used within a range of 9 to 1.5 chemical equivalents, particularly preferably 1.0 to 1.1 chemical equivalents.

Representative examples of (meth)acrylic acid esters having a hydroxyl group include β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, and ε-caprolactone-β-hydroxyethyl (meth)acrylate.
Examples include acrylate, 1,4-butanediol mono(meth)acrylate, and the like. ), etc.

When obtaining the polymer (A), an ethylenically unsaturated group-containing compound other than the reactant (a) can be used, but the proportion used is 0 to 80% by weight based on the total amount of reactive monomers to be polymerized.
is preferred, and 0 to 50% by weight is particularly preferred. these,
The ethylenically unsaturated group-containing compound other than the reactant (a) is
Easily available from the market.

can. Preferred ones include tribropylene glycol di(meth)acrylate, neopenticle glycol di(meth)acrylate, l,6-hexanethiol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, and hydroxypivalin. Examples include di(meth)acrylate of ε-caprolactone adduct of acid neopentyl glycol, poly(meth)acrylate of ε-caprolactone adduct of dipentaerythritol, polyester (meth)acrylate, and polyurethane (meth)acrylate.

Various colorants can be used as the colorant (B) of the colored resin fine powder of the present invention. For example, triphenylmethane, diphenylmethane, xanthine, acridine, azine, thiazine, thiazole, oxazine, azo basic dyes, cationic dyes, etc., which have amino groups or derivatives thereof and exhibit cationic properties in dilute acidic solutions. is C,1,
(Color index) Ba5ic Yellow
1. C, 1, Ba5ic Yellow 13. C
,1,Ba5ic Orange 22. C,1,B
a5ic Redl, C, 1, Ba5ic Viole
t25. C,1,Ba5ic Violet 10
°C, 1, Ba5ic Blue 1. C,1,Ba
5ic Green 1. C.I.

Ba5ic Black 2, etc., azo-, anthraquinone-, triphenylmethane-, nitro-, nitroso-, xanthine-, azine-, and quinoline-based acid dyes that have a sulfone group or a carboxyl group and are soluble in water, specifically C, 1 , Acid Yellow 1.
C, 1, Ac1d Yellow 19. C,1,
Ac1d Or-ange 19. C,1,Ac1d
Red 9. C, 1, Ac1d Red 30°C
, 1, Ac1d Blue 71. C,1,Ac1d
Green 16. C, [.

Azo-, stilbene-, thiazole-, dioxazine-, disazo-, and trisazo-based direct dyes, such as Ac1d Black 48, which are soluble in water and are able to directly dye vegetable fibers such as cotton and viscose, specifically, C , 1, Direct Yel-1ow 85. C,
1, Direct Orange6, C, 1, Dire
ct Redl, C, 1, Direct Blue
22. C.

1. Direct 6. C, 1, D Direct B
water-soluble or insoluble fluorescent brighteners such as Lack 22, diaminostilbendisulfonic acid type, distyrylbenzene type, benzidine type, benzidine sulfone type, diaminofluorene type, imidazole type, imidasilone type, triazole type, Coumarin derivatives, oxazole derivatives, thiazole derivatives and naphthalic acid imide derivatives, specifically C,1,Fluoresc-ent Br
i-ghtening Agent 177, C,1
, Fluorescent Bright-eing
Agent 91. C,1,Fluorescent
BrighteningAgent 172. C,
1, Fluorescent Brightening
Agent 163. C,1,Fluorescen
t Brightening Agent135, C,
1, Fluore-scent Brightenin
g Agent 153, etc., dyes that are soluble in fats and oils and hydrocarbons, and dyes that are soluble in polar solvents; most belong to the azo family, but also belong to the anthraquinone family, nigrosine family, azine family, and others. Oil-soluble dyes, including C,1,5olven
t Red 49. C,1,5olvent Yel
-1ow 116. C,1,5olvent Yel
low 33. C, 1, Dispe-rse Yel
low 54. C,1,5olvent Yellow
w 151. C.I.

5olvent Yellow 82. C,1,5o
lvent Orange 81°C, 1,5olve
nt Orange 67, C, 1,5olvent
Red 70°C, 1, Vat Red 41. C
, 1,5olvent Red 132. C.I.

5olvent Blue 70. C,1,5olv
ent Blue 83. C.I.

5olvent Red 111, or inorganic or organic pigments.

The above coloring agent (B) can be used alone or in a mixture of two or more in any proportion as necessary. The amount of these colorants used is 0.1 to 60% by weight in the colored resin fine powder.
is preferred, and 1 to 50% by weight is particularly preferred.

The colored resin fine powder of the present invention can be produced according to a known method. For example, a hydrophobic complex is created by adding a substance with a different charge to a water-soluble dye, and this is combined with a reactant (
a) or a composition (C) containing an ethylenically unsaturated group-containing compound other than the reactant (a), or an emulsion of the reactant (a) or the composition (C). liquid,
The reactant (a) or composition (c) is added to the suspension, or conversely, the reactant (a) or composition (c) is added to the hydrophobic complex and emulsified and suspended. (C
) in which a hydrophobic complex is dissolved or dispersed and polymerized in an aqueous system. In this case, the hydrophobic complex can be prepared by first dissolving the water-soluble dye in water and then adding a substance with a different charge, or vice versa.

Substances with a different charge from this dye include basic dyes,
Acids or their salts are used for cationic dyes and cationic fluorescent whitening dyes, or bases or their salts are used for acidic dyes, anionic direct dyes, and anionic fluorescent whitening dyes.

Examples include p-) luenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, oxalic acid, tartaric acid, benzoic acid, polyoxyethylene alkyl sulfate sodium salt, polyoxyethylene alkyl phenyl sulfate sodium salt, naphthalene sulfonic acid, Foonic acid formalin condensate, alkylnaphthalenesulfonate sodium salt, dodecylbenzenesulfonate sodium salt, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, laurylpurinium chloride, poly Oxyethylene alkylamine, laurylamine acetate, dimethylamine, and other substances. It is preferable to use equivalent amounts of the dye and the true charge substance. In addition, oil-soluble dyes and the like can be added to the above-mentioned reactant (a) or composition (
C) or added to an emulsion, suspension of said reactant (a) or composition (c), or vice versa, said reactant (a) in an oil-soluble dye. or composition (C
) is added and emulsified and suspended to dissolve and disperse the oil-soluble dye in the reactant (a) or composition (C), which is then polymerized in an aqueous system.

Inorganic or organic pigments are mixed and dispersed in the reactant (a) or composition (C), and then polymerized in an aqueous system. In order to emulsify or suspend in an aqueous system, various surfactants, suspension stabilizers, inorganic substances, etc. are used.

As a polymerization initiator for polymerization, a normal polymerization initiator is used at a normal temperature (40 to 95°C). For example, benzoyl peroxide, lauryl peroxide, α・α′-azobisisobutyronitrile 2,2′-azobis(2,4
-dimethylvaleronitrile), orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, potassium persulfate, ammonium persulfate, and the like. As the polymerization method, a method under normal pressure or high pressure may be used.

The colored resin fine powder of the present invention preferably has a diameter of 50 μm or less, particularly preferably 30 μm or less.

In the present invention, antioxidants, ultraviolet absorbers, light stabilizers, etc. may be further added as necessary.

The colored resin fine powder of the present invention, like general colored pigments,
It can be used to color various products in the following various forms. For example, the colored resin fine powder of the present invention can be suspended or emulsified in water and added with a suitable fixing agent to be used as a pigment resin color or water-based paint for cloth.

Furthermore, the press cake obtained by filtering the colored resin fine powder aqueous dispersion is suitable as a raw material for pigment resin color water-based paints, and the colored resin fine powder aqueous dispersion can be dried after filtration or without filtration. The fine powder obtained can be applied to all fields where pigments are generally used.

(Example) Hereinafter, the present invention will be specifically explained using examples.

Note that parts in the examples are parts by weight.

[Synthesis Examples 1 to 3 of the reaction product of polycarbonate diol and (meth)acrylic acid] Synthesis Example 1 Polycarbonate diol (manufactured by Nippon Polyurethane ■, Niraporan 983.08 value 112.2 mg KoH/g, average molecular weight 1000) 700 parts, acrylic 121 parts of acid,
14 parts of p-toluenesulfonic acid, 1.0 parts of hydroquinone
1, 560 parts of benzene, and 140 parts of cyclohexane are charged and heated. The produced water is distilled and condensed together with the solvent, and only the water is removed from the system in a separator, and the solvent is returned to the reactor. 2 water
When 5.2 parts were produced, it was cooled. The reaction time was about 15 hours. The reaction temperature was 80-86°C. The reaction mixture was dissolved in 960 parts of benzene and 240 parts of cyclohexane and neutralized with a 20% aqueous solution of caustic soda.
Wash three times with 500 parts of saline.

The solvent was distilled off under reduced pressure to obtain the desired product, a pale yellow liquid 69.
I got 0 copies.

Synthesis Example 2 Polycarbonate diol (manufactured by Nippon Polyurethane ■, Niraporan 982, OH value 56 mgKoH/g, average molecular weight 2000) 700 parts, acrylic acid 61 parts, p-)luenesulfonic acid 6 parts, hydroquinone 0.4 part, benzene 560 140 parts of cyclohexane were added, and the reaction was carried out in the same manner as in Synthesis Example 1 until the amount of water produced was 12.6 parts. Reaction temperature is 81-86℃
Met. The reaction mixture was dissolved in 1200 parts of benzene and 30 parts of cyclohexane, and in the same manner as in Synthesis Example 1, neutralization and
After washing and removing solvent, the desired product, pale yellow liquid 6
Obtained 54 copies.

Synthesis Example 3 Polycarbonate diol (manufactured by Nippon Polyurethane ■, Nippon-y: /983.08 value 112.2mgKoH/
g, average molecular weight 1000) 700 parts, methacrylic acid 14
5 parts of sulfuric acid, 4.5 parts of sulfuric acid, 1.1 parts of hydroquinone, and 700 parts of toluene, and the reaction was carried out in the same manner as in Synthesis Example 1 until the amount of produced water became 25.2 parts. The reaction temperature is 105-11
The temperature was 6°C. The reaction mixture was dissolved in 1000 parts of toluene, and the solution was neutralized, washed, and desolventized in the same manner as in Synthesis Example 1 to obtain 723 parts of a pale yellow liquid, which is the desired product.

[Synthesis example 4 of a reaction product of polycarbonate diol, organic polyisocyanate, and hydroxy-containing (meth)acrylate compound] Synthesis example 4 Polycarbonate diol (manufactured by Nippon Polyurethane ■, Niraporan 981.08 value 112.2 mg KoH/g,
1,000 parts (average molecular weight 1,000) and 444.6 parts of isophorone diisocyanate were charged, heated to 80°C, and heated until the NCO group concentration of the reaction mixture reached 5.8% by weight.
The reaction was carried out for 0 hours, and then 0.8 parts of methoquinone and 244 parts of 2-hydroxyethyl acrylate were added.
C, the reaction was carried out for about 15 hours until the NCO group concentration in the reaction mixture became 0.3% by weight or less, and the target product, a pale yellow solid compound, was obtained.

Example 1: 100 parts of distilled water was charged into a 500-inch flask equipped with a stirrer and a reflux condenser, and the temperature was raised to 60°C.
Next, Gohsenol GM-17 (Nippon Gosei Chemical Industry ■
1 part of polyvinyl alcohol, partially saponified type) and 3 parts of polyoxytylene lauryl ether, and then
Add 5 parts of C, 1, No, 5olvent to 50 parts of the reaction product of polycarbonate diol and acrylic acid obtained in Synthesis Example 1.
Dissolve Red 49 and 0.5 part of benzoyl peroxide.
The dispersed material was placed in a flask, stirred, and polymerized for about 10 hours. After polymerization, 1 part of aluminum sulfate was added, heated, salted out, filtered, washed with water, dried, and sieved to obtain a red colored resin fine powder of 10 to 20 microns.

Example 2 200 parts of distilled water, 2 parts of polyvinyl alcohol, 1.8 parts of sodium alkylnaphthalene sulfonate, and 3 parts of polyoxyethylene lauryl ether were added to a 500° flask, and then the mixture obtained in Synthesis Example 2 was added. To 16 parts of the reaction product of polycarbonate diol and acrylic acid and 64 parts of the reaction product of polycarbonate diol and methacrylic acid obtained in Synthesis Example 3, organic pigment rbrightRedJ (manufactured by Toyo Ink ■) 32 was added.
Next, 1.5 parts of α·α'-azobisisobutyronitrile were added, the temperature was gradually raised to 80°C, and polymerization was carried out at that temperature for about 10 hours. Then,
Add 2 parts of aluminum sulfate, salt out, filter, wash with water,
It was dried and sieved to obtain a fine red colored resin powder of 10 to 29 microns.

Example 3 Into a 500° flask, 120 parts of distilled water, 1.2 parts of partially saponified polyvinyl alcohol, 3 parts of sodium alkylbenzene sulfonate, 2 parts of polyoxyethylene lauryl ether, and C, 1, No, 5olvent. Blue
5 parts of e70 were charged, the temperature was raised to 40°C, and the mixture was stirred for 1 hour. While stirring, a dissolved mixture of 50 parts of neopentyl glycol diacrylate hydroxypivalate and 50 parts of the reaction product of polycarbonate diol obtained in Synthesis Example 4, organic polyisocyanate, and hydroxy-containing (meth)acrylate compound was added, and the mixture was stirred for 30 minutes. Stirred. Next, 2 parts of potassium persulfate were added while stirring. Polymerization was continued for 5 to 6 hours while observing changes in polymerization temperature and dropping 20 parts of a 10% aqueous solution of sodium hydrogen sulfite as appropriate.

A blue polymerized emulsion was obtained. Further 50~60℃
While heating the mixture, 2 parts of aluminum sulfate was added for salting out. After filtering and washing with water, dry and sieve to a 10-20μ
A blue colored fine resin powder was obtained.

Example 4 A 500 yd flask was charged with 200 parts of distilled water, 1.2 parts of partially saponified polyvinyl alcohol, 3 parts of sodium alkylbenzenesulfonate, and 3 parts of polyoxyethylene nonylphenyl ether, and heated at 60°C. The temperature is raised to
Next, diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD
HX-220) 20 parts and c, r.

A solution of 5 parts of No. Disprese Yellow 54 and 1 part of benzoyl peroxide was placed in a flask, stirred, and polymerized for about 10 hours. After polymerization,
1.5 parts of aluminum sulfate was added, heated, salted out, filtered, washed with water, dried, and sieved to obtain a yellow colored resin fine powder of 10 to 20 μm in size.

Comparative Example 1 100 parts of distilled water, 1 part of partially saponified polyvinyl alcohol, and 3 parts of polyoxyethylene lauryl ether were added to a 500° flask, and then tetraethoxy diacrylate of bisphonol A (manufactured by Nippon Kayaku ■, KAY
ARAD R-551) 50 parts to 5 parts 0°1, No.
A solution of 5olvent Red 49 and 0.5 parts of benzoyl peroxide was placed in a flask, stirred, and polymerized for about 10 hours. After polymerization, add 1 part of aluminum sulfate, heat, salt out, filter, wash with water, dry,
A fine red colored resin powder of 10 to 20 microns was obtained by sieving.

(Application example 1) Colored resin fine powder 1 obtained in Examples 1 to 4 and Comparative example 1
7 parts of urethane paint made by Nippon Polyurethane ■, 100 parts of Niraporan 174, 7.6 parts of Coronate EH, 30 parts of butyl acetate, and 23 parts of toluene. The sample was dried and cured to obtain a test piece. A weather resistance test was conducted using this test piece. Sunshine Carbon Weatherometer (Suga Test Machine W) was used as an accelerated exposure tester in the test.
E-SUN-DC type) was used, and the test conditions were rainfall 1
2 min/l cycle 60 min, black panel temperature 63±3
°C for 2000 hours. Discoloration and fading after the test was measured using a color tester (manufactured by Suga Shikenki ■), and the degree of discoloration was expressed as △E. The smaller the value of △E, the less the discoloration caused by the weather resistance test.

(Effects of the Invention) The colored resin fine powder of the present invention has good light fastness, excellent weather resistance, and is highly colored, so it can be used in various fields where light fastness and weather resistance are particularly required. It is useful as a coloring agent in various fields such as pigment resin colors and water-based paints.

Claims (1)

[Claims] 1. Polymer (A) of a reaction product of polycarbonate diol and (meth)acrylic acid and/or a reaction product of polycarbonate diol, organic polyisocyanate, and hydroxy-containing (meth)acrylate compound, or a composition containing the same and coloring A colored resin fine powder comprising an agent (B).