JP2000256410A - Non-aqueous dispersion resin composition, and coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous dispersion resin composition having a good dispersion stability and a long pot-life which is suitable for coatings, and a coating composition having an excellent dispersion stability and a long pot-life which yields a coated film having a high transparency, weather resistance and curability. SOLUTION: The non-aqueous dispersion resin composition comprises a vinylic polymer particle (C) which is insoluble in an organic solvent (A) and is obtained by polymerizing a vinylic monomer in an organic solvent (A), mainly comprising an aliphatic hydrocarbon, in the presence of a vinylic polymer (B) which is soluble to the above-mentioned organic solvent (A) and is obtained by polymerizing an ethylenically unsaturated monomer (b1) of the formula (wherein R1 is H or methyl group; R2 and R3 are each independently H or an alkyl group; and m is an integer of from 1 to 10) and a carboxyl group-containing ethylenically unsaturated monomer (b2). A coating composition is prepared by mixing a polyisocyanate compound as a hardener to this non-aqueous dispersion resin composition at a hydroxyl group/isocyanate group equivalent ratio of from 0.5 to 2.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-aqueous dispersion type resin composition and a coating composition using the same.

[0002]

2. Description of the Related Art Paints used for building exteriors, anti-corrosion top coats and the like are required to have high durability, that is, weather resistance, water resistance, moisture resistance, acid resistance, alkali resistance and the like. For this reason,
In order to satisfy these requirements, acrylic urethane-based resin compositions in which an acrylic polyol and a polyisocyanate are combined are often used. However, these resin compositions use a solvent containing xylene, toluene, or the like as a main component, which poses a problem of harm to the human body and the environment. In addition, since the solvent has a strong dissolving power, it is difficult to coat the base material. There are problems such as causing a lifting phenomenon that damages the film.

In order to solve this problem, a solvent containing an aliphatic hydrocarbon as a main component such as a mineral terpene is used.
Attempts have been made to use a so-called weak solvent-soluble acrylic urethane resin as a coating resin. However, a weak solvent-soluble acrylic urethane resin generally has a drawback that drying properties are poor due to low volatility of the solvent. In addition, since the weak solvent has low solubility of the resin, there is a disadvantage that the kind of acrylic monomer that can be used for dissolving the resin is limited. In order to cover these disadvantages, a non-aqueous dispersion type resin having a form in which polymer particles are dispersed in a weak solvent has been proposed. The non-aqueous dispersion type resin has the advantages of not only solving the above-mentioned problem but also improving the sagging property and mechanical properties of the paint.
No. 8518 describes a coating material in which a non-aqueous dispersion type acrylic polyol resin using an aliphatic hydrocarbon-based solvent and a polyisocyanate compound are combined therewith.

However, these methods are effective in improving sagging properties and mechanical properties, but when a monomer having a carboxyl group is copolymerized in order to further improve curability, an isocyanate-based curing agent is used. When used and cured at room temperature, there is a problem that the pot life of the coating material is shortened and coating workability is extremely reduced.

[0005]

The object of the present invention is to provide a non-aqueous dispersion type resin composition which is excellent in dispersion stability, has a long pot life and is suitable for coating. The invention according to claim 2 provides a non-aqueous dispersion type resin composition which is excellent in weather resistance and curability and is suitable for a coating material, in addition to the effects of the invention described in claim 1. The third aspect of the present invention is to provide a coating composition which is excellent in dispersion stability, transparency of a coating film, weather resistance and curability, and has a long pot life.

[0006]

Means for Solving the Problems The present invention provides the following (1) to
(3). (1) In an organic solvent (A) mainly containing an aliphatic hydrocarbon, a compound represented by the general formula (I)

Embedded image (Wherein, R ¹ represents hydrogen or a methyl group, and R ² and R ³
Each independently represents hydrogen or an alkyl group, and m represents 1 to 1
0 is an integer of 0) and the organic solvent of the above (A) obtained by polymerizing the ethylenically unsaturated monomer (b1) and the carboxyl group-containing ethylenically unsaturated monomer (b2). Non-aqueous solution containing vinyl polymer particles (C) insoluble in the organic solvent of (A) obtained by polymerizing vinyl monomers in the presence of soluble vinyl polymer (B) Dispersion type resin composition.

(2) The non-aqueous dispersion type resin composition according to the above (1), wherein the vinyl polymer (B) and / or the vinyl polymer particles (C) have a hydroxyl group. (3) A polyisocyanate compound as a curing agent is blended with the non-aqueous dispersion type resin composition described in the above (1) or (2) so as to have a hydroxyl / isocyanate group equivalent ratio of 0.5 to 2.0. Paint composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of the aliphatic hydrocarbon of the organic solvent (A) (hereinafter abbreviated as the component (A)) containing an aliphatic hydrocarbon as a main component include, for example, a linear aliphatic hydrocarbon. Hydrogen, cycloaliphatic hydrocarbons and the like, and examples of the linear aliphatic hydrocarbon include, for example, pentane, hexane,
Heptane, octane, decane and the like can be mentioned, and as the cycloaliphatic hydrocarbon, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane and the like can be mentioned. The amount of these aliphatic hydrocarbons is preferably 50 parts by weight or more, more preferably 60 parts by weight or more, based on 100 parts by weight of the total organic solvent. If the amount is less than 50 parts by weight, the safety to the human body and the environment is inferior, and the lifting phenomenon tends to occur during repair workability.

As the component (A), mineral spirits, mineral thinners, petroleum spirits, white spirits, mineral terpenes and the like, which are mixed solvents of aliphatic hydrocarbons, can also be used. Furthermore, as long as the compounding amount of the aliphatic hydrocarbon is within the above range and does not inhibit the curing reaction between the hydroxyl group and the isocyanate group described below, an organic solvent component other than the aliphatic hydrocarbon can be used. . Examples of the component other than the aliphatic hydrocarbon include, for example, aromatic hydrocarbons, esters, ketones, and the like.Examples of the aromatic hydrocarbon include toluene, xylene, and the like. Ethyl acetate, butyl acetate and the like can be mentioned, and as ketones, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like can be mentioned.
In addition, alcohols can be used as components other than the aliphatic hydrocarbons, but they may inhibit a curing reaction between a hydroxyl group and an isocyanate group, and are used without departing from the object of the present invention. It is necessary to. These aliphatic hydrocarbons and components other than the aliphatic hydrocarbons can be used alone or in combination of two or more.

In the present invention, the vinyl polymer (B) soluble in the component (A) comprises, in the component (A), an ethylenically unsaturated monomer (b1) represented by the general formula (I): The following (b1)
Component), an ethylenically unsaturated monomer (b2) having a carboxyl group (hereinafter abbreviated as component (b2)) and another ethylenically unsaturated monomer (b3) (hereinafter abbreviated as component (b3)) Can be produced by polymerizing

The component (b1) has the general formula (I)

Embedded image (Wherein, R ¹ represents hydrogen or a methyl group, and R ² and R ³
Each independently represents hydrogen or an alkyl group, and m is 1 to
Which is an integer of 10).

In the formula (I), the alkyl groups of R ² and R ³ are preferably, for example, alkyl groups having 1 to 8 carbon atoms. Among them, the effect of extending the pot life is preferred. In view of the large value, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an n-butyl group is more preferable.

As a specific example of the component (b1), for example,
Aminoethyl acrylate, N-methylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate,
N-methylethylaminoethyl acrylate, N, N-
Dipropylaminoethyl acrylate, aminopropyl acrylate, N-methylaminopropyl acrylate, N, N-dimethylaminopropyl acrylate,
N, N-diethylaminopropyl acrylate, N, N
-Methylethylaminopropyl acrylate, N, N-
Dipropylaminopropyl acrylate, aminohexyl acrylate, N-methylaminohexylamino acrylate, N, N-dimethylaminohexyl acrylate, N, N-diethylaminohexyl acrylate,
N, N-methylethylaminohexyl acrylate,
N, N-dipropylaminohexyl acrylate, aminohexyl acrylate, N-methylaminohexyl acrylate, N, N-dimethylaminohexyl acrylate, N, N-diethylaminohexyl acrylate,
N, N-methylethylaminohexyl acrylate,
N, N-dipropylaminohexyl acrylate, aminoethyl methacrylate, N-methylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-methylethylaminoethyl methacrylate, N , N-dipropylaminoethyl methacrylate,
N, N-dimethylaminopropyl methacrylate, N,
N-diethylaminopropyl methacrylate, N, N-
Methylethylaminopropyl methacrylate, n-
Dipropylaminopropyl methacrylate, aminohexyl methacrylate, N-methylaminohexyl methacrylate, N, N-dimethylaminohexyl methacrylate, N, N-diethylaminohexyl methacrylate, N, N-methylethylaminohexyl methacrylate, N, N-dipropyl Aminohexyl methacrylate, aminohexyl methacrylate, N-methylaminohexyl methacrylate, N, N-dimethylaminohexyl methacrylate, N, N-diethylaminohexyl methacrylate, N, N-methylethylaminohexyl methacrylate, N, N-dipropylaminohexyl Methacrylate and the like.

These components (b1) may be used alone or
Used in combination of more than one type. These (b1)
Among the components, N, N-dimethylaminoethyl acrylate and N, N-dimethylaminoethyl methacrylate are preferred because they have a large pot life extending effect.

The component (b2) is an ethylenically unsaturated monomer having a carboxyl group, for example, α, β
—Unsaturated carboxylic acids and the like, and specific examples thereof include acrylic acid, methacrylic acid, and monoalkyl maleate. These components (b2)
Used alone or in combination of two or more.

The component (b3) is an ethylenically unsaturated monomer other than the above, such as an acrylate derivative, a methacrylate derivative, a styrene derivative, and other compounds having a polymerizable double bond. Is mentioned. Examples of the acrylic acid derivative and the methacrylic acid derivative include an alkyl acrylate, an alkyl methacrylate, a hydroxyl alkyl acrylate, a hydroxyl alkyl methacrylate, an acrylamide and its derivatives, an acrylate having an oxirane group, and an oxirane group. Methacrylate having a hindered amino group, methacrylate having a hindered amino group, acrylate having a benzotriazole group, methacrylate having a benzotriazole group, and the like.

Examples of the alkyl acrylate and alkyl methacrylate include n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, and 2-ethylhexyl. Methacrylate, lauryl acrylate, lauryl methacrylate,
Hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, octyl acrylate, octyl methacrylate,
Acrylic esters and methacrylic esters having 4 or more alkyl groups such as isobornyl acrylate, isobornyl methacrylate, eicosyl acrylate, eicosyl methacrylate, dicyclopentanyl acrylate, and dicyclopentanyl methacrylate are exemplified.

Examples of the alkylhydroxylalkyl acrylate and alkylhydroxylalkyl methacrylate include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate. (Poly) alkylene glycol monoacrylates and (poly) alkylene glycol monomethacrylates such as alkyl esters and hydroxyalkyl esters of methacrylic acid, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, etc. , Hydroxyalkyl vinyl ethers such as mud carboxymethyl butyronitrile vinyl ether, allyl alcohol, allyl alcohols such as methallyl alcohol, or those described above and, for example, ε- caprolactone, adduct of lactones such as γ- valerolactone.

Examples of the acrylamide derivative include N-methylol acrylamide and its alkyl ether compound. Examples of the acrylate having an oxirane group and the methacrylate having an oxirane group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, and 3, 4-epoxycyclohexyl methacrylate and the like. Examples of the styrene derivative include vinylpyrrolidone, α-methylstyrene, chlorostyrene and the like.

Other compounds having a polymerizable double bond include, for example, vinyl chloride, vinyl acetate, dialkyl maleate and the like. Also obtained (B)
As long as the vinyl polymer of the component is soluble in the component (A), a polymerizable unsaturated compound other than the polymerizable unsaturated compound can be used. Such polymerizable unsaturated compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n
Acrylates and methacrylates having an alkyl group carbon number of 3 or less, such as -propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, and iso-propyl methacrylate.

The mixing ratio of the component (b1) is determined from the viewpoint of the balance between the pot life and the water resistance of the obtained composition.
The content is preferably 0.01 to 10% by weight, more preferably 0.1 to 8% by weight, and even more preferably 0.1 to 5% by weight, based on 100 parts by weight of the total amount of the components. If the compounding ratio is less than 0.01% by weight, the effect of extending the pot life tends to be hardly expected, and if it exceeds 10% by weight, the water resistance of the obtained composition tends to decrease.

The proportion of the component (b2) is preferably 0.01 to 10% by weight based on 100 parts by weight of the total amount of the component (B) from the viewpoint of pot life and curability of the obtained composition. More preferably, 0.1 to 5% by weight,
More preferably, the content is 0.1 to 3% by weight. If the blending ratio is less than 0.01% by weight, the curability tends to decrease, and if it exceeds 10% by weight, the pot life of the obtained composition tends to be short and coating tends to be difficult.

The use of a hydroxylalkyl acrylate monomer or a hydroxylalkyl methacrylate monomer among the component (b3) is preferable because the coating properties such as weather resistance are improved. At this time, the mixing ratio of the hydroxylalkyl acrylate monomer and the hydroxylalkyl methacrylate monomer is preferably such that the vinyl value of the vinyl polymer (B) is 0 to 150 mgKOH / g. -100 mgKOH / g is more preferable, and 20-70 mgKOH is more preferable. If the hydroxyl group exceeds 150 mgKOH / g, the water resistance of the coating film tends to be poor.

The compounding ratio of the other component (b3) may be within a range in which the vinyl polymer (B) is soluble in the organic solvent (A), but usually the alkyl group has 4 or more carbon atoms. The mixing ratio of the (meth) acrylic acid ester is preferably at least 40 parts by weight, more preferably at least 50 parts by weight, based on 100 parts by weight of the total amount of the component (B). If the compounding ratio of the (meth) acrylate having 4 or more carbon atoms in the alkyl group is less than 40 parts by weight, the dispersion stability of the non-aqueous dispersion type resin tends to decrease.

Examples of the polymerization initiator used for synthesizing the vinyl polymer (B) include organic peroxides and azo compounds. As organic peroxides, isobutyl peroxide, lauroyl peroxide, 3,
5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (T-butylperoxy) -3,3,5-trimethylcyclohexane, 3,
3,5-trimethylcyclohexanone peroxide,
Methylcyclohexanone peroxide, diisobutylperoxydicarbonate, 2-diethylhexylperoxydicarbonate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane,
1,1-bis (t-hexylperoxy) -3,3,5
-Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-
Butylperoxy) cyclohexane, 2,2-bis (t
-Butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, t-butylperoxy-2-ethylhexanoate, 1,1, 3,3-tetramethylbutylperoxy-
2-ethylhexanoate, t-hexylperoxy-
2-ethylhexanoate, t-butyl peroxyisobutyrate, and the like.

As the azo compound, 2,2'-
Azobis-isobutyronitrile, dimethylazodiisobutyrate, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis ( 4-methoxy 2,4-
Dimethylvaleronitrile), (1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2 2,4
-Trimethylpentane), 2-phenylazo-2,4-
Dimethyl-4-methoxyvaleronitrile, 2,2'azobis (2-methylpropane) and the like can be mentioned. These polymerization initiators can be used alone or in combination of two or more.

The amount of the polymerization initiator used is determined according to the desired molecular weight of the component (B).
It is preferable that the content is 0.1 to 10.0% by weight based on 100 parts by weight of the total amount of the polymerizable unsaturated monomer used for the synthesis of the component (B). Further, if necessary, the molecular weight may be adjusted using a chain transfer agent. Examples of the chain transfer agent include n-dodecyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, and the like.

(A) Vinyl polymer soluble in component (B)
Various known polymerization methods can be used to synthesize the compound (A), but it is simple and can be directly used in the following synthesis step of the vinyl polymer particles (C) insoluble in the component (A). Solution polymerization is preferred from the viewpoint that it is possible. The solution polymerization method is
Add a polymerizable unsaturated compound and a polymerization initiator to the organic solvent,
This is a method of causing a polymerization reaction. As the organic solvent, the component (A) can be used.

In the synthesis of the component (B), the compounding amount of this organic solvent is 100% of the total amount of the polymerizable unsaturated monomer of the component (B).
The amount is preferably from 25 to 400 parts by weight, more preferably from 40 to 250 parts by weight, based on parts by weight. If it is less than 25 parts by weight, the viscosity during polymerization tends to be high, the synthesis tends to be difficult, and the viscosity of the varnish obtained tends to be high. On the other hand, when the amount exceeds 400 parts by weight, the resin content concentration of the obtained varnish is low, so that it may not be possible to adjust to a desired solid content concentration at the time of coating. The reaction temperature during the polymerization is usually preferably from 60 to 160 ° C, and the reaction time is preferably from 1 to 12 hours.

The weight average molecular weight of the component (B) in the present invention (gel permeation; a value measured by GPC and converted by a calibration curve prepared using standard polystyrene, the same applies hereinafter) is 10,000 to 400,000. And more preferably 30,000 to 200,000. If the weight average molecular weight is less than 10,000, the dispersion stability of the non-aqueous dispersion tends to decrease, and
When it exceeds 000, the viscosity of the resin becomes high, and it tends to be practically difficult to prepare a paint.

In the synthesis of the vinyl polymer particles (C) which are insoluble in the component (A) according to the present invention, the vinyl polymer particles (C) are composed of the vinyl polymer particles soluble in the components (A) and (A). It is obtained by polymerizing vinyl polymer particles (C) in the presence of polymer (B). The vinyl monomer used can be appropriately selected so that the monomer used in polymerizing the above-mentioned vinyl polymer (B) is insoluble in the component (A). For example, the ethylenically unsaturated monomer (b1) represented by the above general formula (I), the ethylenically unsaturated monomer having a carboxyl group (b2), hydroxylalkyl acrylate, hydroxylalkyl methacrylate And acrylates having an alkyl group having 3 or less carbon atoms, methacrylates having an alkyl group having 3 or less carbon atoms, styrene-based derivatives, acrylonitrile derivatives, and acrylamide derivatives.

As the polymerization initiator used for the polymerization of the component (C), the same polymerization initiator as exemplified in the description of the component (B) is used. The amount used is determined by the target molecular weight of the obtained non-aqueous dispersion resin, and is usually preferably 0.1 to 10.0% by weight. The reaction temperature during the polymerization is usually preferably from 60 to 160 ° C, and the reaction time is preferably from 1 to 12 hours.

In the present invention, the blending ratio of the component (B) and the component (C) is such that the total amount of the components (B) and (C) is 100 parts by weight, and the blending amount of the vinyl polymer (B) is 5 to 5. 70
Parts by weight, the blending amount of the vinyl polymer particles (C) is 30 to 9
5 parts by weight, preferably vinyl polymer (B)
Is more preferably 15 to 60 parts by weight and the blending ratio of the vinyl polymer particles (C) is 40 to 85 parts by weight. If the blending amount of the vinyl polymer particles (C) is less than 30 parts by weight, the drying property tends to be poor and the sagging property tends to be poor. If the blending amount is more than 95 parts by weight, the dispersion stability of the vinyl polymer particles (C) is poor. It tends to be inferior. For the purpose of improving dispersion stability, it is also possible to graft the vinyl polymer (B) and the vinyl polymer particles (C).

The average particle size of the vinyl polymer particles (C) (for example, a value obtained by measuring with an N4 type submicron particle analyzer manufactured by Coulter Co., Ltd. in an INTENSITY mode at a temperature of 20 ° C., the same applies hereinafter) is about 100-150
Preferably it is 0 nm, more preferably about 300-1000 nm. If it is too small, the viscosity of the resin solution tends to be high, and if it is too large, the particles swell or aggregate during storage, the appearance of the coating film deteriorates, and the sagging property immediately after coating tends to deteriorate. The average particle size is determined by the molecular weight of the organic solvent (A), the vinyl polymer (B), the mixing ratio of the vinyl polymer (B) and the vinyl polymer particles (C), and the solubility parameter (SP value). Adjusted by selection.

The weight average molecular weight of the whole resin in the non-aqueous dispersion type resin composition thus obtained is 10,000.
~ 400,000, preferably 30,000 ~
More preferably, it is 200,000. If the weight average molecular weight is less than 10,000, the weather resistance tends to be inferior, and if it exceeds 400,000, the viscosity of the resin becomes high, and it becomes difficult to make a coating material practically.

The non-aqueous dispersion type resin composition of the present invention can be used as a coating composition by adding a polyisocyanate compound as a curing agent. The polyisocyanate compound is a compound containing two or more isocyanate groups in the molecule, for example, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, methylcyclohexane diisocyanate, isopropyl Aliphatic or alicyclic isocyanates such as redenebis (4-cyclohexyl isocyanate), trimers and the like, and these isocyanates and propanediol, butanediol, hexanediol, decanediol, dodecanediol, 12-hydroxystearyl alcohol , Polyethylene glycol, trimethylolpropane, pentaerythritol,
Examples thereof include a polyhydric alcohol compound such as dimer diol and a compound formed by a reaction with water.

The compounding amount of the polyisocyanate compound is 0.5 in the equivalent ratio of hydroxyl group / isocyanate group of the non-aqueous dispersion type resin.
~ 2.0, preferably 0.8 ~ 1.
More preferably, it is set to 2. If it is less than 0.5, the unreacted polyisocyanate compound remains in the coating film, so that the properties of the coating film tend to decrease. If it exceeds 2.0, the water resistance and weather resistance of the coating film tend to decrease. In addition,
It is preferable that the non-aqueous dispersion type resin composition of the present invention and the polyisocyanate compound are blended and mixed immediately before coating.

The curable composition of the present invention can be made into an enamel coating by a conventional method by adding pigments such as titanium white, carbon black and phthalocyanine blue, extenders such as calcium carbonate and barium sulfate, and a solvent. These are usually added to the base. It is also possible to make a clear paint without adding the pigment. As a method for forming an enamel coating, for example, a known method such as a roll, a sand mill, and a disperser can be used. In addition, when enamel coating with a non-aqueous dispersion resin, high shear force is applied, the resin may cause agglomeration, so a seed pen having good compatibility with the curable composition obtained by the present invention. It can also be used to create an enamel paint. Further, in order to improve the performance as a paint, a pigment dispersant, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer and the like can be added at the time of forming the paint or after the paint is formed.

[0039]

Next, the present invention will be described with reference to examples and comparative examples. “Parts” and “%” indicate “parts by weight”.

Synthesis Examples 1 to 3 [Production of vinyl polymer (B)] In a flask equipped with a stirrer, a reflux condenser and a thermometer, a mineral turpentine 5 was added.
0 parts were charged, the temperature was raised to 120 ° C. under a nitrogen stream, and a mixture indicated by the composition shown in Table 1 was added dropwise over 2 hours. Subsequently, 10 parts of t-butylperoxy-2-ethylhexanoate was added, and the mixture was further kept warm for 2 hours. Then cool down,
Mineral turpen was added so that the heating residue was about 50%. A vinyl polymer solution (A-1 to A-3) was obtained.
Table 1 shows the heating residue, acid value, hydroxyl value, and weight average molecular weight of the obtained polymer solution.

[0041]

[Table 1]

Examples 1 to 4 and Comparative Examples 1 to 3 [Synthesis of Non-Aqueous Dispersion Type Resin Solutions (N-1 to N-7)] A resin solution of the component (B) obtained in Synthesis Examples 1 to 3 and 5 parts of Solvesso 100 (manufactured by Exxon, trade name: aromatic hydrocarbon solvent) were charged, and the temperature was raised to 120 ° C. under a nitrogen stream. did.
Thereafter, while maintaining the temperature at 120 ° C., a mixed solution of the vinyl monomer and the polymerization initiator having the composition shown in Table 2 was dropped uniformly over 2 hours. After completion of the dropwise addition, t-butylperoxy-2
-Ethyl hexanoate (10 parts) was added, the mixture was further kept warm for 2 hours, cooled, and diluted with a mineral turpentine so that the heating residue was about 50%. In any of the synthesis examples, as the polymerization progresses, the resin solution gradually becomes cloudy, and finally a milky white non-aqueous dispersion type resin solution (N
-1 to N-7) were obtained. Table 2 shows the heating residue of the obtained non-aqueous dispersion type resin solution, the acid value of the resin solution, the hydroxyl value of the resin, the weight average molecular weight of the resin, and the average particle size.

120 parts of the vinyl polymer solution (A-1) prepared in Synthesis Example 1 and titanium white (Typek CR-9)
5, Ishihara Sangyo Co., Ltd.) 400 parts, mineral turpentine 10
0 parts were kneaded to produce a white seed pen. The obtained white seed pen and a non-aqueous dispersion type resin solution (N-1 to N-7) 1080
Parts, 100 parts of mineral terpene and duranate TSA-100 as a polyisocyanate compound (Asahi Kasei Corporation)
And trade name) were blended such that the hydroxyl value and the isocyanate group of the resin were equimolar, and using a bar coater # 60,
Bonderite # 144 treated steel sheet (Japan Test Panel Co., Ltd.)
Co., Ltd.) so as to have a thickness of 30 μm.
It was left to dry for a week and a test plate was prepared.

[Evaluation] Non-aqueous dispersion type resin solution (N-1)
(N-4) and a test plate prepared therefrom,
According to the following method, the dispersion stability of the resin solution, the transparency, the gloss of the coating film, the accelerated weather resistance, the water resistance, the curability, and the pot life of the paint were evaluated. The evaluation results are shown in Table 3.

(1) Evaluation of dispersion stability Each of the non-aqueous dispersion type resin solutions (N-1) to (N-4) was diluted 15 times (weight) with a mineral turpentine, and then diluted.
The solution was allowed to stand for 4 days, and the appearance of the solution was examined. In Table 3, in the evaluation criteria of dispersion stability, ○ indicates a state in which the dispersed state is maintained, △ indicates a state in which the dispersed particles are slightly settled, and X indicates a state in which the dispersed particles are settled and separated. .

(2) Evaluation of Transparency of Coating Film Non-aqueous dispersion type resin solutions (N-1) to (N-4) were mixed with polyisocyanate compound duranate TSA-100 (trade name, manufactured by Asahi Kasei Corporation). Is blended so that the equivalent ratio of hydroxyl group / isocyanate group of the non-aqueous dispersion type resin becomes 1.0, applied to a glass plate with an applicator 300 μm under the conditions of 5 ° C. and 25 ° C., and dried at the same temperature for 3 days. Then, the transparency of the coating film was visually observed. In the evaluation criteria for transparency in Table 3,
○ indicates transparent, Δ indicates slightly turbid or fluorescent color, and × indicates turbid.

(3) Gloss The specular reflectance (%) of the prepared test plate was measured with a gloss meter (manufactured by Nippon Denshoku Co., Ltd.). (4) Accelerated weathering resistance Sunshine Wezao Meter (Suga Test Instruments Co., Ltd.)
After the test plate prepared was tested for 800, 1500 hours under the conditions of JIS K5400, the gloss was measured, and the gloss retention was calculated by the following equation (1).

(Equation 1)

(5) Water resistance After the prepared test plate was immersed in tap water for one month, the appearance of the coating film was visually judged. (6) Curability After applying the paint used for preparing the test plate with a bar coater # 60, the coating was dried at room temperature and the time until no trace of the masking tape remained was measured. (7) Pot life 15 g of the paint used for preparing the test plate was sealed in a 30 ml glass bottle, and the time until the paint did not flow at room temperature was measured.

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

The non-aqueous dispersion type resin composition according to the first aspect has excellent dispersion stability, has a long pot life, and is suitable for use in paints. The non-aqueous dispersion type resin composition according to claim 2 has excellent weather resistance and curability in addition to the effects of the invention according to claim 1, and is suitable for use as a coating material. The paint according to claim 3 is excellent in dispersion stability, transparency of a coating film, weather resistance, curability, and has a long pot life.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI theme coat ゛ (Reference) C09D 175/04 C09D 175/04 (72) Inventor ▲ Kuzu ▼ Toru Hara, Oaza-machi, Hasaki-cho, Kashima-gun, Ibaraki Prefecture Banichi Hitachi Chemical Co., Ltd. Kashima Plant F-term (reference) 4J011 AA05 HA03 PA23 PA69 PB08 PB30 PC02 PC08 4J026 AA45 BA05 BA25 BA27 BA29 BA30 BA31 BA32 BA36 BB01 DA02 DA13 DB02 DB13 FA04 GA01 4J038 CC021 CC022 CH121 CG141 CH142 CH202 CJ131 CJ132 DG262 GA03 GA06 GA09 JA02 KA03 KA06 MA07 NA03 NA04 PB05

Claims (3)

[Claims] In an organic solvent (A) containing an aliphatic hydrocarbon as a main component, a compound represented by the general formula (I): (Wherein, R ¹ represents hydrogen or a methyl group, and R ² and R ³
Each independently represents hydrogen or an alkyl group, and m is 1 to
An integer of 10), and the organic solvent (A) obtained by polymerizing the ethylenically unsaturated monomer (b1) represented by the formula (I) and the ethylenically unsaturated monomer (b2) having a carboxyl group. Non-aqueous solution containing vinyl polymer particles (C) insoluble in the organic solvent of (A) obtained by polymerizing vinyl monomers in the presence of soluble vinyl polymer (B) Dispersion type resin composition. 2. The non-aqueous dispersion type resin composition according to claim 1, wherein the vinyl polymer (B) and / or the vinyl polymer particles (C) have a hydroxyl group. 3. A coating composition comprising the non-aqueous dispersion type resin composition according to claim 1 or 2 and a polyisocyanate compound as a curing agent in a hydroxyl / isocyanate equivalent ratio of 0.5 to 2.0. Composition.