JPH0436326A - Colored resin particle - Google Patents

Abstract

PURPOSE:To prepare a clearly and deeply colored resin particle excellent in color fastness and weatherability by compounding a compd., such as a reaction product of a hydroxylated fluorine compd. with (meth)acrylic acid, with a colorant. CONSTITUTION:The title particle contains a reaction product of a hydroxylated fluorine compd. with (meth)acrylic acid and/or a reaction product of the fluorine compd., an org. polyisocyanate, and a hydroxylated (meth)acrylate or a copolymer thereof with another ethylenically unsated. compd. and a colorant. An aq. dispersion of the particles with a binder added thereto is used as a pigment resin color for a fabric and as an aq. coating compsn. A press cake obtd. by filtering the dispersion is suitable as the raw material of the pigment resin color and the aq. coating compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) 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 colorants.

(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. According to this method, there are problems in that it is not possible to obtain a clear and highly concentrated coloring agent, and that the light fastness is very poor. As described in 2003, colored resin fine powders made of copolymers of specific unsaturated monomers and colorants are known.

(Problems to be Solved by the Invention) Although the colored resin fine powders described in the above-mentioned Japanese Patent Publication No. 52-29336 and Japanese Patent Publication No. 539623 do show improvement in light resistance, they are not suitable for long-term outdoor use. For example, it does not have sufficient light resistance or weather resistance as an automobile paint or coloring agent.

(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 relates to a reaction product of a fluorine compound having one or more hydroxyl groups in the molecule and (meth)acrylic acid, and/or a reaction product of a fluorine compound having one or more hydroxyl groups in the molecule, an organic polyisocyanate, and a hydroxy-containing (meth)acrylic acid. ) A reaction product with an acrylate compound, or a polymer of this and another ethylenically unsaturated group-containing compound (A) and a colorant (B)
The present invention relates to a colored resin fine powder comprising:

The colored resin fine powder of the present invention is, for example, a reaction product of a fluorine compound having one or more hydroxyl groups in the molecule and (meth)acrylic acid, and/or a reaction product of a fluorine compound having one or more hydroxyl groups in the molecule and an organic polyisocyanate. and hydroxy-containing (
If necessary, add other ethylenically unsaturated group-containing compounds to the reaction product with meth)acrylate (hereinafter referred to as (a)), dissolve or disperse the colorant (B) therein, and then add this mixture. can be obtained by emulsion polymerization or suspension polymerization in an aqueous system using conventional methods, or by polymerization methods that produce similar fine particles. 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 of a fluorine compound having one or more hydroxyl groups in the molecule and (meth)acrylic acid, and/or a reaction product of a fluorine compound having one or more hydroxyl groups in the molecule, an organic polyisocyanate, and a hydroxy-containing (meth)acrylate The reactant (a) with the compound is used.

A reaction product of a fluorine compound having one or more hydroxyl groups in the molecule and (meth)acrylic acid is known, and it is a reaction product of a fluorine compound having one or more hydroxyl groups in the molecule and acrylic acid or methacrylic acid at an elevated temperature. Can be manufactured.

A specific example of a reaction product of a fluorine compound having one or more hydroxyl groups in the molecule and (meth)acrylic acid is H-CCF2
CF2±2CH20CCH=CH2, H±CF2CFr
Completed thlJL: tFLlh, CH3 CH3 C@F+3CH2-CH-CH2-0-C-C=CH2
, Ii*=l;HU-υ-CH2CHreC)'x4CH2CH2-0-CCH"CH2,0-C-CH=
CH2 will be.

A reaction product of a fluorine compound having one or more hydroxyl groups in the molecule, an organic polyisocyanate, and a hydroxy-containing (meth)acrylate compound is known.
Fluorine compounds having more than
rhcH2-OH, H+cF2cFrhcH2-OH1
CJ l 2CH2CH2-Kano, (CF,)2CFCH
2- Kano, HO-CHrfCFrhCH2-OH1HO-
CH2CH云CFrhC1(2CH2-OH, cyanate (e.g. isophorone diisocyanate, 4,4'
Examples include -sydicouhexylmethane diisocyanate, hexamethylene diisocyanate, 2,2.4-trimethylhexamethylene diisocyanate, 2,4.4-)trimethylhexamethylene diisocyanate, and the like. ) and then a hydroxy-containing (meth)acrylate compound (e.g., β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, ε-caprolactone-β-hydroxyethyl (meth)acrylate, 1,4 -butanediol mono(meth)acrylate, etc.). Alternatively, it can be produced by reacting an organic polyisocyanate with a hydroxy-containing (meth)acrylate compound, and then reacting with a fluorine compound having one or more hydroxyl groups in the molecule. The usage ratio in the urethanization reaction between a fluorine compound having one or more hydroxyl groups in the molecule and an organic polyisocyanate is as follows:
For every chemical equivalent of the OH group of the fluorine compound having at least 1.1 to 1 chemical equivalent of the NGO group, the organic polyisocyanate is
It is preferable to use the chemical equivalent in a range of 2.0 chemical equivalents, and particularly preferably in a range of 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 100°C, particularly preferably 50 to 80°C. Reaction time is 3-50
The duration is preferably 5 to 15 hours, particularly preferably 5 to 15 hours.

Then, in the (meth)acrylation reaction,
For 1 chemical equivalent of the NGO group of the compound having a terminal isocyanate group obtained in the urethanization reaction, the hydroxy-containing (meth)acrylate compound is added to the OH group or 0
．． It is preferable to use it within a range of 9 to 1.5 chemical equivalents, and particularly preferably within a range of 1.0 to 1.1 chemical equivalents. The reaction temperature is preferably room temperature to
100°C, particularly preferably 50 to 80°C. The reaction time is preferably 3 to 50 hours, particularly preferably,
It is 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.

In the present invention, when obtaining the polymer (A), an ethylenically unsaturated group-containing compound other than the reactant (a) may be used. Typical examples of this ethylenically unsaturated group-containing compound include tetrahydrofurfuryl (meth)acrylate, carpitol (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. Acrylate, 2-hydroxypropyl (meth)acrylate, acrylamide, vinylpyridine, acid nasal phosphooxyethyl (meth)acrylate, 2-acid phosphooxypropyl (meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate ) acrylate, ε-caprolactone adduct of 2-hydroxyethyl (meth)acrylate (
Made by Daicel Chemical Industry ■, Plaxel FA-1, FA-2
, FM-1, etc.), hydrogenated dicyclopentadiene (meth)acrylate (manufactured by Hitachi Chemical, FA-513A, F
A-513MA), 2-hydroxy-3-chloropropyl (meth)acrylate, styrene, vinyl acetate metacyclonitrile, methyl (meth)acrylate, glycidyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, Hydroxypivalate neopentyl glycol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, polypropoxy di(meth)acrylate to bisphenol,
Polyethoxy di(meth)acrylate neopentyl glycol di(meth)acrylate of bisphenol A, di(meth)acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate (manufactured by Nippon Kayaku ■, KAYARAD HX-220, HX-620 )
Trimethylolpropane tri(meth)acrylate, epoxy(meth)acrylate (e.g. bisphenol A
(meth)acrylate of epoxy resin, (meth)acrylate of epoxy resin of bisphenol F, (meth)acrylate of urethane-modified epoxy resin to bisphenol), polyester (meth)acrylate (e.g. ethylene glycol, propylene glycol, diethylene glycol, Polyester diol ( meth)acrylate, (meth)acrylate of lactone-modified polyester diol consisting of the diol component, dibasic acid, and ε-caprolactone or valerolactone), polyurethane (meth)acrylate (e.g., containing a polyol compound, an organic diisocyanate, and a hydroxyl group) It is obtained by reacting with (meth)acrylic acid ester until it contains substantially no NOC group. Typical polyol compounds include ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl Glycol, cyclohexane dimetatool, tricyclodecanedimethylol, 1,4-butanediol, 1,6-hexanediol, polyols such as trimethylolpropane, polypropylene glycol, polyethylene glycol, polytetramethylene glycol propylene modified polytetramethylene glycol polyether polyols such as ε
- A compound with caprolactone or valerolactone added thereto is used as the alcohol component, and one acid component is dicarboxylic acid such as adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc. Examples include polynistyl polyols obtained using basic acids or their anhydrides. Typical organic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, and 4,4'
Examples include dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,2',4-)limethylhexamethylene diisocyanate, and the like. The usage ratio in the urethanization reaction between a polyol compound and an organic diisocyanate is
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 it 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 preferable to use it within a range of 9 to 1.5 chemical equivalents, and particularly preferably within a range of 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-βhydroxyethylene (meth)acrylate.
Examples include acrylate, 1°4-butanediol mono(meth)acrylate, and the like. ) etc.

It is contained in the reactive monomer used when obtaining the polymer (A). The proportion of the ethylenically unsaturated group-containing compound other than the reactant (a) is preferably 0 to 80% by weight, particularly preferably 0 to 50% by weight. Ethylenically unsaturated group-containing compounds other than these reactants (a) are easily available on the market. Preferred examples include tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, hydroxypivalic acid neobentyl glycol di(meth)acrylate, and hydroxypivalin. Di(meth)acrylate of ε-caprolactone adduct of acid neopentyl glycol, poly(meth)acrylate of ε-caprolactone adduct of dipentaerythritol, polyester(meth)acrylate, polyurethane (
Examples include 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, which has an amino group or its derivative group and exhibits cationic properties (soaked in dilute acidic solution),
Azo basic dyes, cationic dyes, specifically C,
1, (color index) Ba5ic Yellow
w 1. C, 1, Basic Yellow 13.
C,1,Ba5ic Orange 22. C,1,B
a5ic Redl, C,1,Ba5ic Viol
et 25. C,1,Ba5ic Violet 1
0°C, 1, Ba5ic Blue 1. C,1,B
a5ic 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, A:id Oran-ge 19.
C, I, Ac1d Red 9. C
, 1, Ac1d Red 80. C.Summer.

Ac1d Blue 71. C,1,Ac1d Gr
een 16. Azo, stilbene, thiazole, dioxazine, disazo, trisazo direct dyes, such as C, 1, Ac1dBlack 48, etc., which are soluble in water and dye well directly on vegetable fibers such as cotton and viscose, specifically is C, 1, Direct Yellow 8
5. C, 1, Direct Orange 6. C
, 1, DirectRed 1. C,1,Direc
t Blue 22. C, 1, Direct 6.
C.I.

Direct Black 22, etc., diaminostilbendisulfonic acid type, distyrylbenzene type, benzidine type, benzidine sulfone type, diaminofluorene type, imidazole type, imidasilone type, triazole type, which are water soluble or insoluble fluorescent brighteners. , coumarin derivatives, oxazole derivatives, thiazole derivatives and naphthalic acid imide derivatives, specifically C, l
FIUOreSCentBrightening A
gent 177, C, 1, Fluorescent
Brightening Agent 91.
C, 1, Fluorescent Brighte
-ning Agent 172. C,1,Fluo
recent BrighteningAgent
163. C,1,Fluorescent Brig
htening Agent135, C,1,Flu
orescent Brightening Agen
Dye that is soluble in fats and oils and hydrocarbons, such as T 153, and dyes that are soluble in polar solvents.Most of them belong to the azo family, but there are also those that belong to the anthraquinone family, nigrosine family, azine family, and others. The oil-soluble dyes contained, specifically, C,1,
5olvent Red 49. C,1,5olve
nt Yellow116, C, 1,5olvent
Yellow 33. C,1,DisperseY
yellow 54. C,1,5olvnntYel
low 151. C,[,,5oI-vent Ye
low 82. C,1,5olvent Oran
ge81. C.I.

5olvent Orange 67, C, 1, 5o
lvent Red 70. C.I.

Vat Red41. C,1,5olvent Re
d132. C, I, 5olventBlue 7
0. C,1,5olvent Blue 83. C
, 1,5olventRed 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 preferably 0.1 to 60% by weight, particularly preferably 1 to 50% by weight, based on the colored resin fine powder.

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 mixture (C) of this and an ethylenically unsaturated group-containing compound other than the reactant (a), or an emulsion or suspension of the reactant (a) or the mixture (C). The reactant (a) or the mixture (c) is added to the suspension, or vice versa, by adding the reactant (a) or the mixture (c) to the hydrophobic complex and emulsifying and suspending the reactant (a) or the mixture (c). In this method, a hydrophobic complex is dissolved or dispersed in a water system and then polymerized in an aqueous system. In this case, the hydrophobic complex can be made 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 acids or their salts for basic dyes, cationic dyes, and cationic fluorescent whitening dyes, as well as acidic dyes, anionic direct dyes, and anionic fluorescent whitening dyes. For dyes, bases or their salts are used.

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. Formalin condensate, alkylnaphthalene sulfuric acid sodium salt,
Dodecylbenzenesulfonate sodium salt, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, laurylpurinium chloride, polyoxyethylene alkylamine, laurylamine acetate, dimethyl Are there amines or other substances? It is preferable to use equivalent amounts of the dye and the above-mentioned true charge substance.

In addition, oil-soluble dyes and the like can be used as the reactant (a) or the mixture (C
) or added to an emulsion, suspension of said reactant (a) or mixture (c), or vice versa, said reactant (a) or mixture (c) in an oil-soluble dye. (C)
The oil-soluble dye is dissolved and dispersed in the reactant (a) or mixture (C) by adding and emulsifying and suspending it, and this is polymerized in an aqueous system. Inorganic or organic pigments are mixed and dispersed in the reactant (a) or mixture (C) and 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 is used.

The particle size of the colored resin fine powder of the present invention is preferably 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 has excellent light resistance, weather resistance, and heat resistance, and can be colored vividly and with high concentration.

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 filtered or dried without filtration. The fine powder obtained can be applied to all fields where pigments are generally used.

(Example) In the following, the present invention will be explained in detail with reference to Examples.

Note that parts in the examples are parts by weight.

[Synthesis of a reaction product of a fluorine compound having one or more hydroxyl groups in the molecule, an organic polyisocyanate, and a hydroxy-containing (meth)acrylate compound (Synthesis Examples 1 to 3)] Synthesis example.

Charge 290 parts of IH, IH, 2H, 2H, 7H, 7H, 8H, 8H-octafluorooctane-1,8-diol and 420 parts of trimethylhexamethylene diisocyanate and maintain the temperature at 75 to 80°C. The reaction was continued until the amount of free isocyanate groups in the reaction product reached 11.8% by weight. Next, 239 parts of 2-hydroxyethyl acrylate, and as a diluent, structural formula: CsF+tC
H2CH20CCH=CH2(') reactive monomer 237
part and 0.6 part of methoquinone, 75-80"C
The reaction was carried out at a temperature of The reaction was continued until the amount of free isocyanate in the reaction product was about 0.3% by weight or less.

The obtained product was a liquid with a viscosity (60°C) of 93P and a refractive index (25°C) of 1.425.

Synthesis Example 2 399.01 parts of a compound with the following structural formula, C@F+a CH2CHCH20H H trimethylhexamethylene diisocyanate 382,6
1 part was charged and the reaction was carried out while maintaining the temperature at 75-80°C. The amount of free isocyanate groups in the reactants9
．． The reaction was continued until the concentration was 79% by weight.

Then 2-hydroxyethyl acrylate 217.87
1 part and 0.5 part of methoquinone were added, and the reaction was carried out at a temperature of 75 to 80°C. The reaction was continued until the amount of free isocyanate groups in the reactant was about 0.3% by weight or less. A pale yellow liquid was obtained. This product has a viscosity (40°C) of 15
00P, and the refractive index (23°C) was 1.4480.

Synthesis Example 3゜523.86 parts of a compound with the following structural formula, CsF+□-C
H2CHCH20H H Trimethylhexamethylene diisocyanate 334,0
4 parts were charged, and the reaction was carried out in the same manner as in Synthesis Example 1 until the amount of free isocyanate groups reached 5.19%.

Then 2-hydroxyethyl methacrylate 142,1
0 parts and 0.5 parts of methoquinone were added, and the reaction was carried out in the same manner as in Synthesis Example 1. A pale yellow liquid was obtained. Viscosity (60℃')
200P, and the refractive index (23° C.) was 1.4480.

Example 1 100 parts of freshly distilled water was charged into a 500 ml flask equipped with a stirrer and a reflux condenser and the temperature was raised to 60°C. 1 part of partially saponified type) and 3 parts of polyoxyethylene lauryl ether were added, followed by 5 parts of C,1,5elvent Red 49 and 0.
A solution in which 5 parts of benzoyl peroxide was dissolved and dispersed was placed in a flask, stirred, and polymerized for about 10 hours. After polymerization, add 1 part of aluminum sulfate, heat, and after salting out,
The mixture was filtered, washed with water, dried, and sieved to obtain a fine red colored resin powder with a particle size of 10 to 20 μm.

Example 2 In a 500 yd flask, 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.
Next, 40 parts of the compound obtained in Synthesis Example 1 and 32 parts of the organic pigment rBright RedJ (manufactured by Toyo Ink ■) were kneaded into the mixture, and then α, α
1.5 parts of '-azobisisobutyronitrile was charged, the temperature was gradually raised to 80°C, and polymerization was carried out at that temperature for about 10 hours. Next, 2 parts of aluminum sulfate was added, and after salting out, it was filtered, washed with water, dried, and sieved to reduce the particle size to 10~20
A red colored resin fine powder of μ was obtained.

Example 3 In a 5001 nl flask, 120 parts of distilled water, 1.2 parts of partially saponified polyvinyl alcohol, 3 parts of sodium alkyl hense sulfonate, 2 parts of polyoxyethylene lauryl ether, and C,1,5olvent Blue7
0 parts were charged, the temperature was raised to 40°C, and the mixture was stirred for 1 hour. While stirring, add 50 parts of the compound obtained in Synthesis Example 2 and C, F.
1sCH2Cl-12-0-C-CHCH250 parts of the dissolved mixture was added and stirred for 30 minutes.

Next, 2 parts of potassium persulfate were added while stirring.

While observing changes in the polymerization temperature, 20 parts of a 10% aqueous solution of sodium bisulfite was added dropwise as appropriate, and the polymerization was continued for 5 to 6 hours. A blue polymer emulsion was obtained. While further heating to 50 to 60°C, 2 parts of aluminum sulfate was added for salting out. After filtering and washing with water, it was dried and sieved to obtain a blue colored resin fine powder with a particle size of 10 to 20 μm.

Example 4 A 500° flask was charged with 200 parts of distilled water, 1.2 parts of partially saponified polyvinyl alcohol, 3 parts of sodium alkylbenzene sulfonate, and 3 parts of polyoxyethylene nonylphenyl ether, and heated to 60°C. The temperature was raised, and then 30 parts of the compound obtained in Synthesis Example 3 and C,1,Disper
5 parts of se Yellow 54 and 1 part of benzoyl peroxide
The dissolved and dispersed portions were placed in a flask, stirred, and polymerized for about 10 hours. After polymerization, aluminum sulfate 1
．． Add 5 parts, heat, salt out, filter, wash with water, dry,
A fine yellow colored resin powder with a particle size of 10 to 20 μm was obtained by sieving.

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 5 parts of 1.6 hexanediyl diacrylate was added to 50 parts of 1.6 hexanediyl diacrylate. C,1,5olven
t Red 49 and 0.5 part of benzoyl peroxide were dissolved and dispersed in a flask, stirred, and dissolved for about 10 minutes.
Time polymerization was performed. 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 with a particle size of 10 to 20 μm.

Application Example 1 Colored resin fine powder 1 obtained in Examples 1 to 4 and Comparative Example 1
Part 7 and Nippon Polyurethane, which is a urethane paint vehicle■
100 copies of Nilaporan 174 and Colone) EH7,
6 parts, 30 parts of butyl acetate, and 23 parts of toluene,
It was coated on chin-free steel with a wire bar to a thickness of 10 μm and dried and cured at 40°C to obtain a test piece. Weather resistance test of test pieces [Sunshine Carbon Weatherometer (Suga Test Instruments WE-3UN-D) as an accelerated exposure tester
C type) was used, and the test conditions were a 60 minute cycle of 12 minutes/l of rain and a black panel temperature of 63±3°C for 2000 hours. ] The subsequent discoloration and fading was measured using a color tester (manufactured by Suga Shikenki ■), and the results are shown in Table 1. The degree of discoloration and fading is expressed as ΔE, and the smaller the value of ΔE, the less discoloration occurs during the weather resistance test.

Example 5 In Example 2, colored resin fine powder was obtained in the same manner as in Example 2 with 40 parts of the compound obtained in Synthesis Example 1, and the test was conducted in the same manner as in Application Example 1. The results obtained were similar to those obtained using the colored resin fine powder obtained in Example 2.

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

Claims (1)

[Claims] 1. Fluorine compounds having one or more hydroxyl groups in the molecule and (
A reaction product with meth)acrylic acid and/or a reaction product between a fluorine compound having one or more hydroxyl groups in the molecule, an organic polyisocyanate, and a hydroxy-containing (meth)acrylate compound, or this and other ethylenically unsaturated groups A colored resin fine powder comprising a polymer (A) with a containing compound and a colorant (B).