KR20020056026A - Acrylic resin composition and its usage - Google Patents

Abstract

PURPOSE: Provided are a thermosetting acryl resin composition modified by novel acryl monomer containing acid radical of metal salt excellent in pigment dispersion, storage and appearance characters, and a high concentration of colorant containing the same. CONSTITUTION: The thermosetting acryl resin composition for paint comprises 1-30 parts by weight of dispersing acryl monomer of formula 1; 60 parts by weight or less of vinyl monomer; 20-90 parts by weight of nonfunctional acryl monomer; 10-50 parts by weight of hydroxyl group containing acryl monomer; 10 parts by weight or less of carboxylic acid monomer; and 10 parts by weight or less of amine monomer, as monomers. In the formula 1, R1 represents hydrogen atom or methyl group, R2 represents hydrogen atom, COOH, OH, NH2, NH(CH2)mCH3, N((CH)2mCH3)2(wherein m is an integer of 1-7), M represents barium, magnesium, strontium, copper, cobalt, stannum or aluminum, n is an integer of 1-20.

Description

Thermosetting acrylic resin composition for paints and colorants containing same {Acrylic resin composition and its usage}

The present invention relates to a thermosetting acrylic resin composition for paints and to a colorant containing the same, and more particularly, to a thermosetting resin modified with a novel acrylic monomer containing a metal hydrochloric acid group having excellent pigment dispersibility, shelf life and appearance, in particular carbon black pigment dispersibility. It relates to an acrylic resin composition and a method for producing a high-concentration colorant for automotive topcoat using the same.

The car body is subjected to electrodeposition coating and middle coating process, and then top coat is applied to give a color on the middle coat, then transparent paint is applied, and top coat and transparent paint are coated by two coats one baking method.

Top coats are generally one-component thermosetting paints composed of acrylic resins, melamine resins, pigments, resins for dispersing, dispersing agents, flow control agents, ultraviolet absorbers, light stabilizers, acid catalysts and the like.

Conventional automotive topcoats, in particular carbon black paints, have a weaker dispersion and dispersion stability than other pigments. As a result, the topcoat is poor in storage stability, which implies many problems in use, and also the blackness of the final coating is insufficient, resulting in a poor appearance of the coating. In addition, since the dispersibility is insufficient, the viscosity of the colorant and the paint is increased after the dispersion of the pigment, so that the pigment content of the paint is decreased at the time of final coating, so that the coating film needs to be thickened to maintain the hiding power of the coating. Therefore, the cost of paint increases and the amount of organic solvent volatilized during coating increases environmental pollution.

Accordingly, the present invention is to overcome the problems of the conventional top coat, a novel functional acrylic monomer containing an acid group of a metal salt having excellent dispersibility into the acrylic resin composition for dispersing, when manufacturing a high-concentration colorant for automotive topcoat The present invention was completed by knowing that a small amount of a phthalocyanine blue pigment, which is generally used as a blue pigment, may be added as a dispersant to obtain excellent dispersibility.

Therefore, the object of the present invention is very excellent in dispersibility when manufacturing a carbon black top coat and prevents the aggregation of the pigment to improve the paint storage property, the blackness of the final coating film is increased, the appearance is excellent, viscosity than the conventional colorant Low and high pigment content, the hiding power of the final coating is improved, so it is possible to paint with thin film than the conventional coating of automobile base paint, which reduces the amount of paint required, and thus has the advantage of reducing cost and environmental pollution. However, the present invention provides a thermosetting acrylic resin composition capable of improving various physical properties such as chipping resistance, water resistance cold cycle resistance, adhesiveness, gasoline resistance, weather resistance, etc., because of excellent dispersibility.

In addition, an object of the present invention is to provide a colorant or a colored paint containing the above-mentioned thermosetting acrylic resin composition.

The thermosetting acrylic resin composition of the present invention for achieving the above object is 1 to 30 parts by weight of a dispersible acrylic monomer represented by the following formula (1) as a monomer, within 60 parts by weight of a vinyl monomer, 20 to 90 weight of a nonfunctional acrylic monomer It is characterized by including 10-50 weight part of hydroxyl group containing acrylic monomers, 10 weight part of carboxylic acid monomers, and 10 weight part of amine monomers.

Formula 1

Wherein R ₁ is a hydrogen atom or a methyl group,

R ₂ is a hydrogen atom, COOH, OH, NH ₂ , NH (CH ₂ ) _m CH ₃ , N [(CH ₂ ) _m CH ₃ ) ₂ (where m is an integer from 1 to 7),

M is barium, magnesium, strontium, copper, cobalt, tin or aluminum,

n is an integer of 1-20.

The present invention will be described in more detail as follows.

Looking at the monomer and other additives constituting the acrylic resin composition according to the present invention in more detail.

(1) a dispersible acrylic monomer represented by Chemical Formula 1

The production method and composition of the novel dispersible acrylic monomer added in order to improve pigment dispersibility, shelf life and appearance, in particular carbon black pigment dispersibility, are as follows; 5 to 50% by weight of metal sulfates such as barium sulfate, magnesium sulfate, strontium sulfate, copper sulfate, tin sulfate, and aluminum sulfate, 20 to 50 parts by weight of alkyl sodium represented by the following Chemical Formula 2, and the following Chemical Formula 3 When 15 to 55 parts by weight of sodium acrylate or sodium methacrylate is reacted at room temperature, a novel acrylic monomer of the metal salt represented by Chemical Formula 1 is formed. Then, 20 to 80 parts by weight of this monomer and 20 to 80 parts by weight of organic solvents such as aromatic hydrocarbons, saturated hydrocarbons, ketones, and esters are mixed, and then washed three times with ionized water, followed by filtration. It is possible to obtain a novel functional monomer of the metal salt represented by the formula (1) diluted. Or, if necessary, in order to use a high-purity new functional monomer containing no organic solvent, a new functional monomer diluted in an organic solvent is subjected to a process of recovering the organic solvent in a vacuum state. ) May also be prepared.

Wherein R ₂ is H, COOH, OH, NH _2, NH (CH ₂ ) _m CH ₃ , N [(CH ₂ ) _m CH ₃ ) ₂ , wherein m is a heavy water of 1-7,

n is an integer of 1-20.

Formula 3

R ₁ is a hydrogen atom or a methyl group.

The content of the dispersible acrylic monomer represented by Chemical Formula 1 is 1 to 30 parts by weight of the total acrylic resin composition. If the content is less than 1% by weight, the dispersibility is insufficient. If the content is more than 30 parts by weight, the weather resistance or the appearance of the coating film is Can be bad.

(2) non-functional monomer

Nonfunctional monomers include methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, normal butyl methacrylate, tertiary butyl methacrylate, normal hexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl Methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isobutyl acrylate, normal butyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, normal octyl acrylate, Isobonyl acrylate, cyclohexyl acrylate, and the like can be used.

The content is 20 to 90 parts by weight of the total acrylic resin composition. If the content is less than 20 parts by weight, the compatibility with other resins, organic solvents, and additives used in the manufacture of paints may be reduced. If the physical properties are lowered and the content of other functional monomers is more than 90 parts by weight, the crosslinking density of the coating film is lowered, so that physical properties such as durability are lowered, and pigment dispersibility is also lowered.

(3) vinyl monomers

Styrene, vinyltoluene, vinyl acetate, alpha -methylstyrene, etc. can be used as a vinylic monomer, The content is preferably 60 weight% or less. If the content is more than 60% by weight, weather resistance is not good.

(4) hydroxyl-containing acrylic monomers

As a hydroxyl-containing acrylic monomer, 2-hydroxyethyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, carduraacrylate, Carduramethacrylate, caprolactone acrylate, caprolactone methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, polypropylene modified acrylate, polypropylene modified methacrylate , 4-hydroxymethylcyclohexyl-methylacrylate, 4-hydroxymethylcyclo-methylmethacrylate, 2,2,4-trimethyl-1,3-pentanediol monoacrylate, 2,2, 4-trimethyl-1,3-pentanediol monomethacrylate, isobornyl acrylate, isobornyl methacrylate and the like can be used.

If the content is 10 to 50 parts by weight of the total acrylic resin composition, if the content is less than 10 parts by weight, the crosslinking degree of the coating film is reduced, the durability is poor, and if the content exceeds 50 parts by weight, coating appearance and storage properties are insufficient. Become.

(5) carboxylic acid monomer

As the carboxylic acid monomer, acrylic acid, methacrylic acid, maleic acid, itagonic acid, crotoninic acid and the like can be used within 10% by weight.

(6) amine monomer

Examples of the amine monomers include ene-diethylaminoethyl acrylate, ene-diethylaminoethyl methacrylate, ene-dimethylaminoethyl acrylate, ene-dimethylaminoethyl methacrylate and ene-diethylamino Propyl acrylate, en-diethylaminopropyl methacrylate, tertiary butylaminoethyl acrylate, tertiary butylaminoethyl methacrylate and the like can be used.

The content is preferably within 10% by weight.

(6) solvent

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, ethyl propyl ketone, methyl isobutyl ketone and methyl alkyl ketone; And ester solvents such as methyl acetate, ethyl acetate, normal propyl acetate, isopropyl acetate, isopropyl acetate, butyl acetate, methyl cellosolve acetate, cellosolve acetate, butyl cellosolve acetate, and carbitol acetate; Normal propanol, isopropanol, normal butanol, isobutanol, tertiary butanol and the like may be used as an alcohol solvent.

(7) initiator

As initiator, 2, 2- azobis (2-methylbutylonitrile), 2, 2- azobis isobutyl nitrile, dibenzoyl peroxide, tertiary butyl peroxy benzoate, dibutyl butyl peroxide, tertiary Butyl peroxy 2-ethylhexanoate, tertiary butyl peroxy acetate, cumyl hydroperoxide, dicumyl peroxide, tertiary hydroperoxide and the like can be used.

The acrylic resin composition of such a composition has a solid content of 30 to 80% by weight, a molecular weight of 2,000 to 70,000, a hydroxyl value of 20 to 180 mgKOH / g and an acid value of 0 to 30 mgKOH / under an aromatic hydrocarbon solvent, an ester solvent, and an alcohol solvent. g, glass transition temperature (Tg) between -30-60 ° C. And amine number is 0-30 mgKOH / g (relative to solid content). Preferably 5-20 mgKOH / g (compared to solids). Other acrylic monomers may be selected and prepared by solution polymerization by a free radical mechanism at a reaction temperature of 80-200 ° C. using a thermal decomposition initiator.

If the hydroxyl value of the acrylic resin is less than 20, the crosslinking density of the coating film is decreased, resulting in a decrease in the coating film properties. If it is 180 or more, the crosslinking density of the coating film is improved to improve the coating properties, but the surface tension is increased. It is lowered, and the appearance of the coating film is deteriorated due to the decrease in compatibility with the solvent, the resin, and the transparent coating layer beyond the required level, which is not preferable. When the acid value is more than 30 mgKOH / g, the curing reaction is accelerated, but the water resistance and weather resistance of the coating film are lowered, which is not preferable. If the amine value is more than 30 mgKOH / g, the curing rate is lowered, the appearance and cold resistance chipping may be weak.

Colorants or colored paints can be produced using the acrylic resin thus obtained, and when added to the colorants or colored paints, the content thereof is preferably 5 to 70% by weight. The specific composition preferably contains 5 to 70% by weight of the acrylic resin and 0.5 to 10% by weight of a dispersant selected from the group consisting of phthalocyanine blue pigments, extracts of phthalocyanine blue pigments and copper-phthalocyanates.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Example 1

48.8 parts by weight of xylene was added to a four-necked flask equipped with a thermometer and a cooler, and the temperature was raised to 138-142 ° C to reflux. Next, as a monomer, 20 parts by weight of styrene, 10 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, 12.4 parts by weight of butyl methacrylate, 10 parts by weight of ethylhexyl acrylate, and 5.8 parts of 2-hydroxyethyl methacrylate. Part, caplactone methacrylate (product name: PLACELL FM-2D manufactured by Daicel Japan), 5 parts by weight of ene-diethylaminoethyl methacrylate, 1.0 part by weight of methacrylic acid, the monomer component (Formula 1, R ₁ = H, R ₂ = COOH, Me = Cu, n = 10) A mixture consisting of 10 parts by weight and 2.5 parts by weight of dibenzoyl peroxide as an initiator was added dropwise over 3 hours.

Next, after keeping at reflux temperature for 2 hours, 0.2 weight part of dibenzoyl peroxide which is an initiator was melt | dissolved in 8.9 weight part of butyl acetate, and the dissolved liquid mixture was dripped for 10 minutes. Then, the mixture was further maintained for 1.5 hours, followed by dropwise addition of 0.2 parts by weight of dibenzoyl peroxide, followed by maintaining for 2 hours to obtain an acrylic resin.

The obtained acrylic resin solution had a weight average molecular weight of 31,700, a glass transition temperature of 30 ° C, a hydroxyl value of 50 mgKOH / g, an acid value of 7.0 mg KOH / g, a solid content of 60%, a viscosity (Gardner viscosity) Z1, and a Gardner color of 1 It is a transparent resin.

Example 2)

The production method was the same as in Example 1, 48.8 parts by weight of xylene was added to a four-necked flask equipped with a thermometer and a cooler, and heated to reflux at 138 to 142 ° C. Next, as a monomer, 20 parts by weight of styrene, 10 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, 12.4 parts by weight of butyl methacrylate, 10 parts by weight of ethylhexyl acrylate, and 5.8 parts of 2-hydroxyethyl methacrylate. Part, caplactone methacrylate (Japan Daicel Co., Ltd. product name: PLACELL FM-2D) 15.8 parts by weight, ethylene-diethylaminoethyl methacrylate 5 parts by weight, methacrylic acid 1.0 part by weight, monomer components (Formula 1, R ₁ = H, R ₂ = OH, Me = Cu, n = 6) A mixture consisting of 10 parts by weight and 2.5 parts by weight of dibenzoyl peroxide as an initiator was added dropwise over 3 hours.

Otherwise, the monomer mixed solution was reacted in the same manner as in Example 1 to obtain an acrylic polyol.

The obtained acrylic resin solution had a weight average molecular weight of 31,000, a glass transition temperature of 30 ° C., a hydroxyl value of 60 mgKOH / g, an acid value of 7.0 mg KOH / g, a solid content of 60%, a viscosity (Gardner viscosity) Z1, and a Gardner color of 1 It is a transparent resin.

Example 3

The production method was the same as in Example 1, 48.8 parts by weight of xylene was added to a four-necked flask equipped with a thermometer and a cooler, and heated to reflux at 138 to 142 ° C. Next, as a monomer, 20 parts by weight of styrene, 10 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, 17.4 parts by weight of butyl methacrylate, 5 parts by weight of ethylhexyl acrylate, 5 parts by weight of ethylhexyl methacrylate, 2- 5.8 parts by weight of hydroxyethyl methacrylate, caplactone methacrylate (product name: PLACELL FM-2D manufactured by Daicel Japan), 1 part by weight of methacrylic acid, monomer components (formula 1, R ₁ = H, R ₂₎ = NH ₂ , Me = Cu, n = 4) A mixture consisting of 10 parts by weight and 2.5 parts by weight of dibenzoyl peroxide as an initiator was added dropwise over 3 hours.

Otherwise, the monomer mixed solution was reacted in the same manner as in Example 1 to obtain an acrylic polyol.

The obtained acrylic resin solution had a weight average molecular weight of 32,000 glass transition temperature of 30 ° C., a hydroxyl value of 50 mgKOH / g, an acid value of 7.0 mg KOH / g, a solid content of 60%, a viscosity (Gardner viscosity) Z1, and a Gardner color of 1 It is a transparent resin.

Example 4

The production method was the same as in Example 1, 25 parts by weight of xylene was added to a four-necked flask equipped with a thermometer and a cooler, and heated to reflux at 138 to 142 ° C. Next, 20 parts by weight of styrene, 5 parts by weight of butyl acrylate, 10.2 parts by weight of butyl methacrylate, 5 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of 2-ethylhexyl methacrylate, 2-hydroxyethyl 10.4 parts by weight of methacrylate, caplactone methacrylate (product name: PLACELL FM-2D manufactured by Daicel Japan), 5 parts by weight of ene-diethylaminoethyl methacrylate, 1.0 part by weight of methacrylic acid, and a monomer component (Formula 1, R ₁ = H, R ₂ = COOH, Me = Cu, n = 10) A mixture consisting of 10 parts by weight and 5 parts by weight of dibenzoylperoxide as an initiator was added dropwise over 3 hours. Otherwise, the monomer mixed solution was reacted in the same manner as in Example 1 to obtain an acrylic polyol.

The obtained acrylic resin solution had a weight average molecular weight of 17,000, a glass transition temperature of 20 ° C, a hydroxyl value of 90 mgKOH / g, an acid value of 7.0 mgKOH / g, a solid content of 70%, and a viscosity (Gardner viscosity) Z2-Z3, Gardner color Is a 1+ transparent resin.

Example 5

The production method was the same as in Example 1, 25 parts by weight of xylene was added to a four-necked flask equipped with a thermometer and a cooler, and heated to reflux at 138 to 142 ° C. Next, 20 parts by weight of styrene, 5 parts by weight of butyl acrylate, 10.2 parts by weight of butyl methacrylate, 5 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of 2-ethylhexyl methacrylate, 2-hydroxyethyl 10.4 parts by weight of methacrylate, caprolactone methacrylate (product name: PLACELL FM-2D manufactured by Daicel Japan), 5 parts by weight of ene-dimethylaminoethyl methacrylate, 1.0 part by weight of methacrylic acid, monomer component A (Formula 1, R1 = H, R2 = COOH, Me = Cu, n = 10) A mixture consisting of 10 parts by weight and 5 parts by weight of dibenzoyl peroxide as an initiator was added dropwise over 3 hours.

Otherwise, the monomer mixed solution was reacted in the same manner as in Example 1 to obtain an acrylic polyol.

The obtained acrylic resin solution had a weight average molecular weight of 14,500, a glass transition temperature of 20 ° C, a hydroxyl value of 100 mgKOH / g, an acid value of 7.0 mg KOH / g, a solid content of 70%, a viscosity (Gardner viscosity) Z2 +, and a Gardner color of 1 It is a transparent resin which is +.

Example 6

The preparation method was the same as in Example 1, 25 parts by weight of xylene was added to a four-necked flask equipped with a thermometer and a cooler, and heated to 138-142 ° C. to reflux. Next, 20 parts by weight of styrene, 5 parts by weight of butyl acrylate, 10.2 parts by weight of butyl methacrylate, 5 parts by weight of 2-ethylhexyl acrylate, 10.0 parts by weight of 2-ethylhexyl methacrylate, 2-hydroxyethyl 10.4 parts by weight of methacrylate, caprolactone methacrylate (product name: PLACELL FM-2D manufactured by Daicel Japan), 1.0 part by weight of methacrylic acid, monomer components (Formula 1, R ₁ = H, R ₂ = NH ₂ , Me = Cu, n = 4) A mixture consisting of 10 parts by weight and 2.5 parts by weight of dibenzoyl peroxide as an initiator was added dropwise over 3 hours. Otherwise, the monomer mixed solution was reacted in the same manner as in Example 1 to obtain an acrylic polyol.

The obtained acrylic resin solution had a weight average molecular weight of 15,000, a glass transition temperature of 20 ° C, a hydroxyl value of 90 mgKOH / g, an acid value of 7.0 mg KOH / g, a solid content of 70%, a viscosity (Gardner viscosity) Z2 +, and a Gardner color. 1+ is a transparent resin.

Comparative Example 1)

The production method was the same as in Example 1, 48.8 parts by weight of xylene was added to a four-necked flask equipped with a thermometer and a cooler, and heated to reflux at 138-142 ° C. Next, as a monomer, 20 parts by weight of styrene, 10 parts by weight of methyl methacrylate, 11.3 parts by weight of butyl acrylate, 20.0 parts by weight of butyl methacrylate, 5.0 parts by weight of ethylhexyl acrylate, and 2-hydroxyethyl methacrylate. .8 parts by weight, 15.8 parts by weight of caprolactone methacrylate (trade name: PLACELL FM-2D manufactured by Daicel Japan), 5 parts by weight of ene-diethylaminoethyl methacrylate, 2.1 parts by weight of methacrylic acid and dibenzoyl as an initiator A mixture consisting of 2.5 parts by weight of peroxide was added dropwise over 3 hours. Otherwise, the monomer mixed solution was reacted in the same manner as in Example 1 to obtain an acrylic polyol.

The obtained acrylic resin solution had a weight average molecular weight of 39,000, a glass transition temperature of 30 ° C, a hydroxyl value of 50 mgKOH / g, an acid value of 15.0 mg KOH / g, a solid content of 60%, a viscosity (Gardner viscosity) Z5, and a Gardner color of 1 It is transparent resin which is the following.

Comparative example 2)

The production method was the same as in Example 1, 25 parts by weight of xylene was added to a four-necked flask equipped with a thermometer and a cooler, and heated to reflux at 138 to 142 ° C. Next, 20 parts by weight of styrene, 11.3 parts by weight of butyl acrylate, 20.0 parts by weight of butyl methacrylate, 5.0 parts by weight of 2-ethylhexyl acrylate, 5.0 parts by weight of 2-ethylhexyl methacrylate, 2-hydroxyethyl 10.4 parts by weight of methacrylate, 28.4 parts by weight of caprolactone methacrylate (trade name: Daicel Co., Ltd. product name: PLACELL FM-2D), 5.0 parts by weight of ene-dimethylaminoethyl methacrylate, 1.0 part by weight of methacrylic acid and an initiator A mixture consisting of 5.0 parts by weight of benzoyl peroxide was added dropwise over 3 hours. Otherwise, the monomer mixed solution was reacted in the same manner as in Example 4 to obtain an acrylic polyol.

The obtained acrylic resin solution had a weight average molecular weight of 17,000, a glass transition temperature of 30 ° C., a hydroxyl value of 50 mgKOH / g, an acid value of 15.0 mg KOH / g, a solid content of 60%, a viscosity (Gardner viscosity) Z5, and a Gardner color of 1 It is transparent resin which is the following.

Specific compositions of the acrylic resins prepared according to Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 1 below.

Example Comparative example One 2 3 4 5 6 One 2 Zyren 48.8 48.8 48.8 25 25 25 48.8 25 SM 20 20 20 20 20 20 20 20 MMA 10 10 10 - - - 10 - BA 10 10 10 5 5 5 11.3 11.3 BMA 12.4 12.4 17.4 10.2 10.2 10.2 20.0 20.0 EHA 10 10 5 5 5 5 5.0 5.0 EHMA - - 5 5 5 10.0 - 5.0 HEMA 5.8 5.8 5.8 10.4 10.4 10.4 5.8 10.4 FM-2 15.8 15.8 15.8 28.4 28.4 28.4 15.8 28.4 DEAEMA 5.0 5.0 - - - - 5.0 - DMAEMA - - - 5.0 5.0 - - 5.0 MAA 1.0 1.0 1.0 1.0 1.0 1.0 2.1 2.1 Formula 1 R ₁ = H, R ₂ = COOH, n = 10 10 - - 10 - - - - R ₁ = H, R ₂ = OH, n = 6 - 10 - - 10 - - - R ₁ = H, R ₂ = NH ₂ , n = 4 - - 10 - - 10 - - BPO 2.5 2.5 2.5 5.0 5.0 5.0 1.5 5.0 BPO 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Butyl acetate 8.9 8.9 8.9 8.9 8.9 8.9 8.9 8.9 BPO 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Butyl acetate 8.9 8.9 8.9 8.9 8.9 8.9 8.9 8.9 Solid content (%) 60 60 60 70 70 70 55 70 Viscosity Z1 Z Y Z2 Z2-Z3 Z2 + Z3 W Acid 7 7 7 7 7 7 15 15 Hydroxyl value 50 60 50 90 100 90 50 90 Glass transition temperature (℃) 30 30 30 20 20 20 30 20 Molecular Weight 31,700 31,000 32,000 17,000 14,500 15,000 39,000 17,000 SM: styrene monomer, MMA: methyl methacrylate, BA: butyl acrylate, BMA: butyl methacrylate, EHA: 2-ethylhexyl acrylate, EHMA: 2-ethylhexyl methacrylate, FM-2 : Caprolactone methacrylate, DEAEMA: n, n-diethylaminoethyl methacrylate, DMAEMA: n, n-dimethylaminoethyl methacrylate, MAA: methacrylic acid, BPO: dibenzoyl peroxide

Experimental Example) Preparation of Colorant

In order to compare the coating properties with the respective acrylic resins prepared according to Examples 1 to 6 and Comparative Examples 1 to 2, the resin for dispersing obtained from Examples 1 to 6 prepared a colorant with the same composition as in Preparation Example 1 below. And the resin for dispersion obtained by the said Comparative Examples 1-2 was manufactured with the same composition as the following manufacture comparative example 1.

The physical properties and final coating film properties of the respective colorants obtained were compared, and the results are shown in Table 2 below.

<Manufacture example 1>

Dispersion Acrylic Resin (Examples 1 to 6) 420

Xylene 270

Carbon Black 62

Phthalocyanine Blue Pigment 8

Cocosol # 100 292

Total 1000

<Production Comparative Example 1>

Dispersion Acrylic Resin (Comparative Examples 1 and 2) 420 (Comparative Examples 1 and 2 Resin)

Xylene 270

BYK161 25

Carbon Black 62

Cocosol # 100 292

Total 1000

Example Comparative example One 2 3 4 5 6 One 2 Colorant properties Solid content (%) 28.2 28.2 28.2 32.9 32.9 32.9 25.9 32.9 Viscosity (SEC) 35 37 33 42 44 39 162 194 Pigment Content (%) 6.2 6.2 6.2 6.2 6.2 6.2 6.2 6.2 Final Coating Properties Appearance (PGD-IV) 0.7 0.7 0.7-0.8 0.7 0.7 0.7-0.8 0.7 0.7 Black degree 25.9 26.1 26.1 26.0 26.1 25.9 24.9 25.1 Storability (SEC) + D +3 +2 +5 +2 +3 +18 +20 Concealed Coating Thickness (㎛) 8 8 8 8 8 8 13 13 Solvent resistance (minutes) 17 15 18 20 22 23 15 19 Water resistance Good Good Good Good Good Good Good Good Chipping resistance 7+ 7+ 7 7+ 7 7 7 7 Crack resistance Good Good Good Good Good Good Good Good Adhesion Good Good Good Good Good Good Good Good

1) Solid content: 150 ℃ * 15 minutes baking

2) Viscosity: FORD CUP Viscometer # 4

3) Appearance (PGD): Measured by PGD Ⅳ of Tokyo Koden Corporation.

4) Blackness: L value measurement

5) Shelf life: viscosity increase measurement after 60 ℃ * 3 days

6) Solvent resistance: SPOT is sprayed at room temperature and left for 20 minutes to evaluate coating state.

7) Chipping resistance: Measured after maintaining at -40 ℃ for 3 hours

8) Adhesion: Cross Cut 100/100 (2mm)

9) Water resistance: Check for abnormality of coating after 10 days storage at 40 ℃

10) Crack resistance: 30 cycles test with top coat and clear coat up to 4 times each (1cycle: -40 ℃ * 2 hours + 110 ℃ * 2 hours + -40 ℃ * 2 hours + 110 ℃ * 2 hours) + -40 ℃ hot water * 14 hours test)

As described in detail above, when the acrylic resin composition containing the novel dispersible acrylic monomer is applied to a colorant or a colored paint according to the present invention, dispersibility is very excellent, and paint storage properties are improved by preventing aggregation of pigments. As the blackness of the final coating film is increased, the appearance is excellent. Since the viscosity is lower and the pigment content is higher than that of the conventional colorant, the hiding power of the final coating film is improved. As a result, cost and environmental pollution can be reduced.

Claims (5)

As a monomer, 1-30 weight part of dispersible acrylic monomers represented by following General formula (1), 60 weight part of vinylic monomers, 20-90 weight part of non-functional acrylic monomers, 10-50 weight part of hydroxyl-containing acrylic monomers, carboxylic acid monomer The thermosetting acrylic resin composition for paints containing less than 10 weight part and less than 10 weight part of amine monomers. Formula 1 Wherein R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom, COOH, OH, NH ₂ , NH (CH ₂ ) _m CH ₃ , N [(CH ₂ ) _m CH ₃ ) ₂ (where m is an integer from 1 to 7), M is barium, magnesium, strontium, copper, cobalt, tin or aluminum, n is an integer of 1-20. The resin composition according to claim 1, wherein the resin composition has a hydroxyl value of 20 to 180 mgKOH / g, an acid value of 0 to 30 mgKOH / g, a molecular weight of 2,000 to 70,000, a solid content of 30 to 80% by weight, and a glass transition temperature of 40 to It is 70 degreeC, The amine titer is 0-40 mgKOH / g, The thermosetting acrylic resin composition for paints characterized by the above-mentioned. The coloring agent or colored paint containing the acrylic resin composition of Claim 1. The coloring agent or colored paint of Claim 3 containing 5 to 70 weight% of the acrylic resin composition of Claim 1. The acrylic resin composition of claim 1, wherein the acrylic resin composition of claim 1 comprises 0.5 to 10% by weight of at least one dispersant selected from the group consisting of phthalocyanine blue pigment, extract of phthalocyanine blue pigment and copper-phthalocyanate. Colorants or colored paints.