JP2001261715A - Nonaqueous polymer dispersing liquid and coating composition containing the same polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonaqueous polymer dispersing liquid which does not cause both of the deterioration of the gloss and finished appearance of a coating film and the deterioration of a room temperature drying property and a coating film performance, can impart structural viscosity to a coating material and is excellent in dispersion stability. SOLUTION: This nonaqueous polymer dispersing liquid is a (co)polymer from at least one of ethylenically unsaturated monomers containing an ethylenically unsaturated monomer having a 10-20C cyclic saturated hydrocarbon group as a component and is obtained by polymerizing at least one of the above polymerizable unsaturated monomers in an organic liquid dissolving the polymerizable unsaturated monomers but virtually not dissolving any polymer formed from at least one of the polymerizable unsaturated monomers in the presence of a dispersion stabilizer having a solubility parameter (an SP value) of 7.5-9.3. A coating composition comprises the above nonaqueous polymer dispersing liquid and a basic resin as resinous components, and a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous polymer dispersion capable of imparting sagging resistance to a coating without deteriorating the gloss, finish appearance and drying property of a coating film, and a coating composition containing the polymer. About.

[0002]

2. Description of the Related Art
Non-aqueous polymer dispersions are used to improve physical properties such as high solids differentiation, weather resistance, and mechanical properties of paints, and to improve the orientation and sagging resistance of metallic pigments by imparting structural viscosity to paints. Have been.

As non-aqueous polymer dispersions, those using polyester such as 12-hydroxystearic acid self-condensate, cellulose acetate butyrate, acrylic resin and the like as a dispersion stabilizer (skin component) are known. .

However, the non-aqueous polymer dispersion containing the self-condensate of 12-hydroxystearic acid or cellulose acetate butyrate as a dispersion stabilizer is hardly compatible with the base resin, and has an effect of imparting structural viscosity to the paint. However, there is a problem that the glossiness of the coating film is reduced particularly in the case of an ordinary dry type application. Further, in the case of a non-aqueous polymer dispersion using a self-condensate of 12-hydroxystearic acid as a dispersion stabilizer, the resulting coating film has reduced drying properties. On the other hand, in order to hardly reduce the gloss of the coating film, it is preferable to obtain a non-aqueous polymer dispersion of small particles as much as an acrylic resin as a dispersion stabilizer, but the dispersion stabilization ability of the dispersion stabilizer is not sufficient. In addition, a fine design of the dispersion stabilizer, the dispersion medium, and the composition of the polymer particles was required, and the design range was extremely small. Moreover, in the non-aqueous polymer dispersion using such an acrylic resin as a dispersion stabilizer, sagging resistance was not sufficiently imparted to the paint.

[0005] In order to improve the stabilizing ability of an acrylic resin-based dispersion stabilizer, it is necessary to improve the solubility of the dispersion stabilizer in a dispersion medium system of a poor solvent such as heptane. It is a common practice to copolymerize a large amount of a monomer having a long-chain alkyl group, such as 2-ethylhexyl acrylate or lauryl methacrylate, which is a monomer capable of lowering the polarity of the monomer. The resulting polymer had a low glass transition temperature (Tg), and had problems in the hardness of the resulting coating film, dryness at room temperature, gasoline resistance and the like.

An object of the present invention is to improve the orientation and sagging resistance of a metallic pigment by imparting structural viscosity to a coating without causing a decrease in gloss of a coating film or a reduction in finished appearance. It is an object of the present invention to obtain a non-aqueous polymer dispersion having good hardness, dryness at room temperature, gasoline resistance and the like of the resulting coating film.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have developed a copolymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer having a specific cyclic saturated hydrocarbon group as one monomer component. The present inventors have found that a non-aqueous polymer dispersion obtained by polymerizing a monomer in the presence of a dispersion stabilizer as described above can achieve the above object, thereby completing the present invention.

[0008] That is, the present invention relates to a method for preparing a compound having 10 to 20 carbon atoms.
Is a (co) polymer of an ethylenically unsaturated monomer containing the ethylenically unsaturated monomer having a cyclic saturated hydrocarbon group as one component, and has a solubility parameter (SP value) of 7.
In the presence of a dispersion stabilizer of from 5 to 9.3, the polymerizable unsaturated monomer is dissolved, but the polymer formed from the polymerizable unsaturated monomer is substantially insoluble in an organic liquid. It is intended to provide a non-aqueous polymer dispersion obtained by polymerizing an unsaturated monomer.

The present invention also provides a coating composition containing, as a resin component, the nonaqueous polymer dispersion, a base resin other than the nonaqueous polymer dispersion, and a curing agent.

Hereinafter, the non-aqueous polymer dispersion of the present invention and the coating composition of the present invention will be described in detail.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the non-aqueous polymer dispersion of the present invention will be described in detail.

In the non-aqueous polymer dispersion of the present invention, a polymerizable unsaturated monomer is dissolved but a polymer formed from the polymerizable unsaturated monomer is not substantially dissolved in the presence of the following dispersion stabilizer. It is obtained by polymerizing the polymerizable unsaturated monomer in an organic liquid.

Dispersion Stabilizer The dispersion stabilizer used in the production of the non-aqueous polymer dispersion of the present invention is an ethylenically unsaturated monomer having a cyclic saturated hydrocarbon group having 10 to 20 carbon atoms (hereinafter, referred to as "a"). (Sometimes abbreviated as “cyclic saturated group-containing monomer”) as a component or a polymer or copolymer of an ethylenically unsaturated monomer.

Examples of the cyclic saturated hydrocarbon group having 10 to 20 carbon atoms in the cyclic saturated group-containing monomer include an isobornyl group, a tricyclodecanyl group, and an adamantyl group. A decanyl group is preferred. Representative examples of the cyclic saturated group-containing monomer include, for example, isobornyl acrylate, isobornyl methacrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, adamantyl acrylate, adamantyl methacrylate, and the like. The above-mentioned cyclic saturated group-containing monomers can be used alone or in combination of two or more.

In the present invention, the dispersion stabilizer contains a monomer having a cyclic saturated group as a constituent monomer component, and the content thereof is not particularly limited. Preferably 30 to 70
Preferably it is in the range of weight%.

Other ethylenically unsaturated monomers (hereinafter abbreviated as "other monomers") which can constitute a dispersion stabilizer together with the above-mentioned cyclic saturated group-containing monomer.
Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (Meth) acrylate, stearyl (meth) acrylate,
Esters of acrylic acid or methacrylic acid such as isostearyl acrylate (trade name, manufactured by Osaka Organic Chemical Co., Ltd., alkyl acrylate in which the alkyl group is a branched alkyl group having 18 carbon atoms), cyclohexyl (meth) acrylate, and benzyl methacrylate Fluorine-containing vinyl monomers such as Biscoat 3F, 3MF, 8F, and 8MF (all of which are manufactured by Osaka Organic Chemical Co., Ltd., trade names), perfluorocyclohexyl (meth) acrylate, and vinyl fluoride; N-dimethylaminoethyl (meth)
Acrylate, N, N-diethylaminoethyl (meth)
Nitrogen-containing vinyl monomers such as acrylate and N, N-diethyl methacrylamide; vinyl ether monomers such as vinyl ethyl ether and vinyl butyl ether; aromatic vinyl monomers such as styrene, α-methylstyrene and vinyl toluene Acrylonitrile, methacrylonitrile, divinylbenzene, ethylene glycol di (meth)
Acrylates; carboxyl group-containing polymerizable unsaturated monomers such as acrylic acid and methacrylic acid; epoxy group-containing polymerizable unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate; isocyanatoethyl methacrylate; m-isopropenyl-α, α-dimethylbenzyl Isocyanato group-containing polymerizable unsaturated monomers such as isocyanate; 2-hydroxyethyl acrylate, 2
And hydroxy-containing polymerizable unsaturated monomers such as -hydroxyethyl methacrylate, hydroxypropyl acrylate and 2-hydroxypropyl methacrylate. In the present invention, the suffix “(meth) acrylate” means acrylate or methacrylate.

The content of the other monomer in the ethylenically unsaturated monomer constituting the dispersion stabilizer is usually 0.
Suitably, it is in the range of -80% by weight, preferably 30-70% by weight.

The dispersion stabilizer (B) is required to be soluble in a relatively low-polarity solvent such as an aliphatic hydrocarbon. Therefore, the dispersion stabilizer (B) has a solubility parameter (SP value).
Is in the range of 7.5 to 9.3. For this reason, as other monomers, the alkyl portion of the ester has 3 carbon atoms (propyl).
As described above, those containing mainly 6 (hexyl) or more esters of acrylic acid or methacrylic acid are suitable.

The (co) polymerization of the above ethylenically unsaturated monomer to obtain a dispersion stabilizer can be carried out by a polymerization method known per se, for example, in the presence of a radical polymerization catalyst in an organic solvent. It can be suitably obtained by a solution polymerization method performed below.

The dispersion stabilizer is a (co) polymer of an ethylenically unsaturated monomer comprising the above-mentioned cyclic saturated group-containing monomer and, if necessary, other monomers, and the (co) polymer is a (co) polymer. The polymer may have a polymerizable unsaturated group introduced into the polymer.

The method for introducing a polymerizable unsaturated group into the (co) polymer includes the following method (1) or (2). (1) As a part of other monomers in the ethylenically unsaturated monomer, a polymerizable unsaturated monomer containing a first chemically reactive group such as a carboxyl group, an epoxy group, an isocyanato group or a hydroxyl group is used. A method in which polymerization is carried out, and then a polymerizable unsaturated monomer having a second chemically reactive group capable of reacting with the first chemically reactive group in the polymer is reacted to introduce a polymerizable unsaturated group. In the (co) polymerization of an ethylenically unsaturated monomer, a carboxyl group, a hydroxyl group,
By conducting the polymerization in the presence of a chain transfer agent containing a first chemically reactive group such as an amino group, the first chemically reactive group is introduced at the polymer chain end, and then the first chemically reactive group in the polymer is removed. A method in which a polymerizable unsaturated monomer having a second chemically reactive group capable of reacting with a chemically reactive group is reacted to introduce a polymerizable unsaturated group. Furthermore, the catalytic chain transfer method (C
atlytic Chain Transfer Po
lymerization, CCTP method) to introduce a polymerizable unsaturated group.
No. 209, Japanese Patent Publication No. 7-35411, Japanese Patent Publication No. 9
JP-501457, JP-A-176256,
Macromolecules 1996, 29, 80
83-8089).

In the above method (1), typical examples of the polymerizable unsaturated monomer containing a first chemically reactive group include carboxyl group-containing polymerizable unsaturated monomers such as acrylic acid and methacrylic acid. An epoxy group-containing polymerizable unsaturated monomer such as glycidyl acrylate and glycidyl methacrylate; an isocyanato group-containing polymerizable unsaturated monomer such as isocyanatoethyl methacrylate and m-isopropenyl-α, α-dimethylbenzyl isocyanate; 2-hydroxyethyl acrylate ,
Examples thereof include hydroxyl group-containing polymerizable unsaturated monomers such as 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

As the second monomer for introducing a polymerizable unsaturated group by reacting with the first chemically reactive group in the above copolymer, for example, the first chemically reactive group is a carboxy group. In some cases, when the first chemically reactive group is an epoxy group, the carboxyl group-containing polymerizable unsaturated monomer; when the first chemically reactive group is an epoxy group, the first chemically reactive group is an isocyanate. When the first chemically reactive group is a hydroxyl group, the above-described polymerizable unsaturated monomer containing an isocyanato group can be suitably used.

In the above method (2), the chain transfer agent containing a first chemically reactive group such as a carboxyl group, a hydroxyl group or an amino group may be mercaptoacetic acid, 2-mercaptopropionic acid, or 3-mercaptopropionic acid. 2, 2-mercaptoethanol, 2-aminoethanethiol and the like can be suitably used.

Examples of the second monomer for introducing a polymerizable unsaturated group by reacting with the first chemically reactive group in the above-mentioned copolymer include, for example, a case where the first chemically reactive group is a carboxy group. Wherein the epoxy group-containing polymerizable unsaturated monomer; wherein the first chemically reactive group is a hydroxyl group, and wherein the isocyanate group-containing polymerizable unsaturated monomer; When it is a group, the above-mentioned epoxy group-containing polymerizable unsaturated monomer can be suitably used.

In the present invention, the dispersion stabilizer contains polymerizable unsaturated double bonds on average from 0.1 to about 1.
Eight, preferably 0.1 to 1.2, more preferably 0.2 to 1.0, having a solubility parameter (SP value) of 7.5 to 9.3, preferably 8.0 to 8.0. 9.0, a weight average molecular weight of 1,000 to 50,000, preferably 3,000 to 20,000, and a hydroxyl value of 0 to 180 mgKOH / g, preferably 20 to 150 m
Suitably in the range of gKOH / g.

The solubility parameter represents a measure of the intermolecular interaction of liquid molecules. The SP value of a homopolymer of a polymerizable monomer can be obtained from J. Paint Tecnology, vo
l. 42, 176 (1970). The SP value of the copolymer of the mixture of the polymerizable monomers can be calculated by the following equation.

SP value = SP ₁ × f _w1 + SP ₂ × f _w2 +...
.. + SP _n × f _{wn In the} above formula, SP ₁ , SP ₂ ,..., SP _n represents the SP value of a homopolymer of each polymerizable monomer, and _{fw 1} , _{fw 2} ,
... F _wn represents a weight fraction of each monomer with respect to the total amount of the monomers.

The non-aqueous polymer dispersion of the present invention can be obtained by polymerizing a polymerizable unsaturated monomer in the following organic liquid in the presence of the above-mentioned dispersion stabilizer.

The organic liquid dissolves the polymerizable unsaturated monomer to be polymerized, but does not substantially dissolve a polymer formed from the polymerizable unsaturated monomer;
Those having a small polarity are preferable. For example, aliphatic or aromatic hydrocarbons having relatively low solubility such as VM & P naphtha, mineral spirit, solvent kerosene, aromatic naphtha and solvent naphtha; n-butane, n-hexane And aliphatic hydrocarbons such as n-heptane, n-octane, isononane, n-decane and n-dodecane; and alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclobutane. If necessary, a small amount of a polar solvent such as an ester solvent, an ether solvent, a ketone solvent, or an alcohol solvent can be used. As the polymerizable unsaturated monomer polymerized in the presence of the organic liquid or the dispersion stabilizer mixture, the same monomer as described above as the ethylenically unsaturated monomer forming the dispersion stabilizer may be used. Can be. Above all, it is necessary that the formed polymer does not substantially dissolve in the organic liquid, and therefore, styrene, acrylonitrile and esters of methacrylic acid in which the alkyl portion of the ester has 4 or less carbon atoms (butyl) (Especially, methyl methacrylate) is preferred. As a part of the polymerizable unsaturated monomer, for example, a monomer having two mutually reactive chemically reactive groups is used, and the chemically reactive groups are reacted with each other to form a chemical bond (for example,
Reaction using acrylic acid having a carboxyl group and glycidyl methacrylate having an epoxy group)
The resulting polymer can be internally crosslinked by doing so or by using a polyvinyl compound such as divinylbenzene.

When the above polymerizable unsaturated monomer is polymerized into polymer particles, a polymerization initiator is blended to adjust the polymerization temperature to 30 to 150 ° C., preferably 50 to 110 ° C. It is preferable to set it to about 10 hours.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t
Organic peroxides such as -butyl peroctoate and diacetyl peroxide; azo initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl α, α'-azoisobutyrate; diisopropyl peroxydicarbonate And redox initiators. The concentration of the polymerization initiator is preferably in the range of 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the polymerizable unsaturated monomer.

The polymer particles have a glass transition temperature of -20 to 10 in view of performance and stability in the polymerization reaction.
It is preferably in the range of 0 ° C, more preferably in the range of 0 to 80 ° C, and the average particle size is preferably in the range of 50 nm to 500 nm. The inside of the polymer particles may be internally crosslinked.

Coating Composition The coating composition of the present invention contains the non-aqueous polymer dispersion of the present invention, a base resin other than the non-aqueous polymer dispersion, and a curing agent as essential components. The coating composition of the present invention is usually an organic solvent type coating.

The base resin may be any resin capable of forming a good coating film by reacting with a curing agent, such as a resin having a reactive group such as an epoxy group, a hydroxyl group or a carboxyl group. Examples of the resin having a reactive group include a bisphenol-type epoxy resin, a novolak-type epoxy resin, an acrylic resin, a polyester (including an alkyd resin), and a fluororesin.

The curing agent may be any as long as it can react with the base resin to form a cured coating film.
Amino resins such as melamine resins and urea resins; polyisocyanate compounds in which isocyanato groups may be blocked; and low molecular weight, high acid value carboxyl group-containing compounds.

When the coating composition of the present invention is used as a top coating, the base resin is a hydroxyl group-containing acrylic resin, and the curing agent is selected from an amino resin and a polyisocyanate compound which may be blocked. At least one kind of paint can be suitably used. In particular, the hydroxyl group-containing acrylic resin as the base resin has a weight average molecular weight of 1,000 to 80,000, a hydroxyl value of 30 to 180 mg KOH / g, and a solubility parameter (SP value) of 7.5 to 9.5. Can be suitably used.

The amount of the non-aqueous polymer dispersion of the present invention to be incorporated into the coating composition of the present invention is 100% of the total resin solid content (including the resin solid content of the non-aqueous polymer dispersion) of the coating composition. The amount of the solid content is usually in the range of 1 to 20 parts by weight, more preferably 3 to 10 parts by weight. It is suitable in terms of finished appearance and the like.

The mixing ratio of the base resin and the curing agent in the coating composition of the present invention is not particularly limited as long as a good cured coating film can be obtained. It is preferable that the base resin and the curing agent are in the ranges of 50 to 90% by weight and 10 to 50% by weight, respectively, based on the total solid content of the above.

The coating composition of the present invention contains the above-mentioned non-aqueous polymer dispersion, the above-mentioned base resin, the above-mentioned curing agent, and an organic solvent, and further comprises a curing catalyst, a pigment, a defoaming agent, It may contain paint additives known per se, such as a surface conditioner, a flow conditioner and a surface slip agent.

The coating composition of the present invention can be applied to an object to be coated as a one-coat coating, an undercoat, an intermediate coating, a top coating coloring coating, a top coating clear coating, or the like.

The object to be coated is iron, aluminum,
Brass, copper plate, stainless steel plate, tin plate, galvanized steel plate, alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe
Metals such as plated steel sheets; surface-treated metal sheets obtained by subjecting these metal surfaces to chemical conversion treatment such as phosphate treatment and chromate treatment; non-metallic materials such as plastic, wood, concrete, and mortar; Examples thereof include a film-forming coated object obtained by applying a primer and / or a middle coat and / or a top coat base to a metal plate or a non-metallic material. The coating film thickness of the coating composition of the present invention is not particularly limited, but is usually in the range of 5 to 100 μm in dry film thickness, and particularly in the range of 20 to 60 μm to prevent the sagging. It can be remarkably exhibited.

[0043]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Hereinafter, “parts” and “%” are based on weight unless otherwise specified.

Synthesis of Acrylic Resin Solution (Base Resin Solution) Synthesis Example 1 A reaction vessel was charged with 80 parts of xylene and heated to 125 ° C., and a mixture of the following monomer and polymerization initiator was added thereto.
The mixture was dropped at a uniform rate over a period of time, and aged at the same temperature for 2 hours to obtain an acrylic resin (A-1) solution having a solid content of 55%.

Styrene 20 parts t-butyl methacrylate 20 parts cyclohexyl methacrylate 20 parts 2-ethylhexyl acrylate 21.7 parts acrylic acid 0.5 part 2-hydroxyethyl acrylate 17.8 parts 2,2′-azobisisobutyronitrile 3.3 parts The resin solid content of the obtained acrylic resin (A-1) solution is:
It had an SP value of 8.84, a hydroxyl value of 86 mg KOH / g resin, and a weight average molecular weight of about 11,000.

Synthesis Example 2 A reaction vessel was charged with 80 parts of xylene and heated to 125 ° C., and a mixture of the following monomer and polymerization initiator was added to the reaction vessel.
The mixture was dropped at a uniform rate over time, and aged at the same temperature for 2 hours to obtain an acrylic resin (A-2) solution having a solid content of 55%.

Styrene 30 parts Methyl methacrylate 30 parts n-butyl methacrylate 5 parts Methyl acrylate 14 parts Methacrylic acid 2 parts 2-hydroxyethyl acrylate 19 parts 2,2′-azobisisobutyronitrile 4 parts The obtained acrylic resin ( A-2) The resin solid content of the solution is:
It had an SP value of 9.58, a hydroxyl value of 92 mg KOH / g resin, and a weight average molecular weight of about 9,000.

Production Example 1 of Dispersion Stabilizer 80 parts of toluene were mixed in a reaction vessel, and a mixture of the following monomers and a polymerization initiator was refluxed at a uniform rate over 3 hours under reflux. After dropping, the mixture was aged at the same temperature for 2 hours to obtain an acrylic resin varnish.

Isobornyl acrylate 30 parts Styrene 10 parts n-butyl acrylate 20 parts 2-ethylhexyl methacrylate 13 parts Acrylic acid 2 parts 2-hydroxyethyl methacrylate 25 parts tert-butyl peroxyoctoate 6 parts To 180 parts of the resin varnish, 2.4 parts of glycidyl methacrylate, 0.02 part of 4-tert-butylpyrocatechol and 0.1 part of N, N-dimethylaminoethanol were added, and the mixture was stirred at 110 ° C. for 5 hours. A 55% dispersion stabilizer (B-1) solution was obtained. The dispersion stabilizer resin has an average of about 1.0 polymerizable double bonds per molecule, an SP value of 8.81, a weight average molecular weight of about 6,000, and a hydroxyl value of about 108 mg KOH / g resin. Met.

Production Example 2 In a reaction vessel, 80 parts of toluene was blended, and a mixture of the following monomers and a polymerization initiator was dropped therein at reflux at a uniform rate over 3 hours under reflux. After aging at the same temperature for 2 hours, an acrylic resin varnish was obtained.

Tricyclodecanyl methacrylate 50 parts Styrene 10 parts n-butyl acrylate 20 parts Methacrylic acid 1 part 2-hydroxyethyl methacrylate 19 parts 2,2′-azobisisobutyronitrile 2 parts Next, the obtained acrylic resin To 180 parts of varnish, 0.6 part of glycidyl methacrylate, 0.02 part of 4-tert-butylpyrocatechol and 0.1 part of N, N-dimethylaminoethanol were added, and the mixture was stirred at 110 ° C. for 5 hours. % Dispersion stabilizer (B-2) solution was obtained. The dispersion stabilizer resin has an average of about 0.8 polymerizable double bonds per molecule, an SP value of 8.67, a weight average molecular weight of about 19,000, and a hydroxyl value of about 82 mg KOH / g resin. Met.

Production Example 3 82 parts of toluene was charged into a reaction vessel, and heated to 80 to 85 ° C. while blowing nitrogen gas into 100 parts of isobornyl acrylate, 1.6 parts of mercaptoacetic acid and 2,2 parts of mercaptoacetic acid.
A mixed solution of 2 parts of 2'-azobisisobutyronitrile
The polymerization was carried out dropwise over a period of time at a uniform rate. Then, after aging at the same temperature for 2 hours, it was heated at 95 ° C. for 1 hour and 55%
A prepolymer solution was obtained. The acid value of the obtained prepolymer solution was 4.7 mgKOH / g. Then, 2.7 parts of glycidyl methacrylate, 1.2 parts of tetrabutylammonium bromide as a catalyst and 0.1 part of hydroquinone monomethyl ether as a polymerization inhibitor were added thereto.
After adding 04 parts, the mixture was reacted at 95 ° C. for 8 hours to obtain a dispersion stabilizer (B-3) solution having a nonvolatile content of about 55%. The conversion of glycidyl methacrylate in this reaction was 99% or more. The dispersion stabilizer resin has an average of about 1.0 polymerizable double bonds per molecule, is mainly composed of a terminal methacrylate type isobornyl acrylate macromonomer, and has a number average molecular weight of about 3,800. And the weight average molecular weight was about 8,700.

Production Example 4 (Production of comparative dispersion stabilizer) In a reaction vessel, 80 parts of toluene was mixed, and under reflux, a mixture of the following monomer and polymerization initiator was added for 3 hours. The mixture was dropped at a uniform rate, and after dropping, aging was performed at the same temperature for 2 hours to obtain an acrylic resin varnish.

Styrene 10 parts Isobutyl methacrylate 30 parts tert-butyl methacrylate 10 parts cyclohexyl methacrylate 10 parts 2-ethylhexyl methacrylate 13 parts acrylic acid 2 parts 2-hydroxyethyl methacrylate 25 parts tert-butyl peroxyoctoate 6 parts To 180 parts of the resulting acrylic resin varnish, 2.4 parts of glycidyl methacrylate, 0.02 part of 4-tert-butylpyrocatechol and 0.1 part of N, N-dimethylaminoethanol were added, and the mixture was stirred at 110 ° C. for 5 hours, and nonvolatile. About 55% of the dispersion stabilizer (C-1) solution was obtained. The dispersion stabilizer resin has an average of about 1.0 polymerizable double bonds per molecule, an SP value of 8.79, a weight average molecular weight of about 6,000, and a hydroxyl value of about 108 mg KOH / g resin. Met.

Production Example 5 (Production of a comparative dispersion stabilizer) In a reaction vessel, 80 parts of toluene was blended, and a mixture of the following monomers and a polymerization initiator was added thereto under reflux for 3 hours. The mixture was dropped at a uniform rate, and after dropping, aging was performed at the same temperature for 2 hours to obtain an acrylic resin varnish.

Styrene 20 parts Methyl methacrylate 40 parts 2-Ethylhexyl methacrylate 18 parts Methacrylic acid 2 parts 2-hydroxyethyl acrylate 20 parts 2,2′-azobisisobutyronitrile 4.5 parts Next, the obtained acrylic resin varnish To 180 parts, 2.1 parts of glycidyl methacrylate, 0.02 part of 4-tert-butylpyrocatechol and 0.1 part of N, N-dimethylaminoethanol were added, and the mixture was stirred at 110 ° C. for 5 hours. To obtain a dispersion stabilizer (C-2) solution. The dispersion stabilizer resin has an average of about 1.2 polymerizable double bonds per molecule, an SP value of 9.36, a weight average molecular weight of about 8,000, and a hydroxyl value of about 97 mg KOH / g resin. Met.

Production of Nonaqueous Polymer Dispersion Example 1 In a reaction vessel, 164.5 parts of heptane and about 5 nonvolatile components were added.
45.5 parts of a 5% dispersion stabilizer (B-1) solution is blended,
The temperature was raised to 95 ° C. A mixture of the following monomer and polymerization initiator was added dropwise thereto at a uniform rate over 3 hours, and the mixture was aged at the same temperature for 2 hours to obtain a non-aqueous polymer dispersion liquid (I).

Styrene 5 parts Methyl methacrylate 25 parts Methyl acrylate 19 parts Acrylonitrile 25 parts Acrylic acid 1 part 2-hydroxyethyl acrylate 25 parts t-butyl peroxyoctoate 3 parts The obtained non-aqueous polymer dispersion (I) is Milky white, having a nonvolatile content of about 40% by weight, and having a polymer particle size of about 200
nm. This non-aqueous polymer dispersion liquid (I) had good storage stability even when left closed for 3 months at room temperature (20 ° C.).

Examples 2 to 3 and Comparative Examples 1 and 2 In Example 1, a mixture having the composition shown in Table 1 below was used as a mixture of a dispersion stabilizer, an organic solvent, and a monomer and a polymerization initiator. Except for the above, the same procedure was performed as in Example 1,
A milky white non-aqueous polymer dispersion having a nonvolatile content of about 40% by weight was obtained. The properties, storage stability, and the ratio of polymer particle-forming monomer / dispersion stabilizer of each of the obtained non-aqueous polymer dispersions are shown in Table 1 below.

The storage stability in Table 1 was determined by placing the non-aqueous polymer dispersions obtained in the respective examples in a closed container at room temperature (20 ° C.).
It is the result of evaluating the liquid state of the non-aqueous polymer dispersion liquid after being left for a month. A case where there was no change in the liquid state was defined as good, and a case where the dispersion liquid was gelled or the resin settled and was not redispersible was indicated as poor.

[0061]

[Table 1]

Production of coating composition Example 4 163.6 parts of an acrylic resin (A) solution having a solid content of 55% obtained in Synthesis Example 1 and Sumidur N-3500 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.) A coating composition was obtained by mixing 30.9 parts of the polyisocyanate compound and 25 parts of the nonaqueous polymer dispersion (I) having a solid content of about 40% obtained in Example 1.

Examples 5 to 7 and Comparative Examples 3 to 5 A coating composition was obtained in the same manner as in Example 4, except that the components used were as shown in Table 2 below.

(Note) in Table 2 has the following meanings. (Note 1) Cymel 303: manufactured by Mitsui Cytec Co., Ltd., trade name, methylated melamine resin. (Note 2) Nacure 5225: manufactured by King Industries, USA, trade name, amine salt solution of dodecylbenzenesulfonic acid, curing catalyst.

Preparation of Test Plate Each coating composition obtained in Examples 4 to 7 and Comparative Examples 3 to 5 was applied to a thinner having a composition of xylene / butyl acetate = 50/50 (weight ratio) with a viscosity of 11 seconds ( Ford Cup # 4, 2
(5 ° C.), and spray-coated on a tin plate that was placed almost vertically so that the dry film thickness was about 40 μm. Examples 4 to 6 and Comparative Examples 3 to 5 were allowed to stand at room temperature (20 ° C.) for one week and dried to obtain test plates. In Example 7, after standing at room temperature for 5 minutes, the sample was placed at approximately 140 ° C.
A test plate was obtained by baking for 0 minutes. The resulting test plate was tested for finished appearance and vertical gloss based on the following test method. Further, the sagging limit film thickness was also tested based on the following test method. The test results are shown in Table 2 below.

Test method Finish appearance: The glossiness, smoothness and transparency of the coating film of the test plate were visually determined and evaluated according to the following criteria. A: Very good B: Good B: Somewhat bad X: Bad.

Vertical gloss: JIS K5400 7.6
In accordance with the 20 ° specular gloss specified in (1990), the degree of gloss of the coating film and the reflectance when the incident angle and the light receiving angle were each 20 ° were measured, and the reference surface of the specular gloss was set to 100. It was expressed as a percentage (20 ° gloss).

Sagging limit film thickness: A tin plate is set up almost vertically, and each coating composition is applied with the film thickness inclined so as to gradually increase the film thickness. The coated plate after standing at (20 ° C.) was observed, and a film thickness at which sagging starts to occur (dry film thickness) was defined as a sagging limit film thickness.

[0069]

[Table 2]

[0070]

The non-aqueous polymer dispersion of the present invention is an ethylenically unsaturated monomer containing as one component an ethylenically unsaturated monomer having a cyclic saturated hydrocarbon group having 10 to 20 carbon atoms. A non-aqueous polymer dispersion obtained by polymerizing in the presence of a dispersion stabilizer which is a (co) polymer of the above, wherein the use of the above dispersion stabilizer lowers the gloss of the coating film and lowers the finished appearance. The effect of imparting structural viscosity to the coating material is large, without lowering the drying property at room temperature and the coating film performance, and the orientation and sagging resistance of the metallic pigment can be improved. Further, the non-aqueous polymer dispersion of the present invention has excellent drying properties and can be applied to a room temperature-curable coating.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 AA05 AA07 BA03 BA04 DA04 HA03 HB28 PC02 4J038 CG141 CG142 CH072 FA132 GA03 GA06 GA07 GA09 GA11 GA12 JA02 JA06 JA17 JA25 JA56 KA06 KA09 MA07 NA01 NA23 NA24 PA18 PA19 PC02 PC04 PC06 PC06 PC06 PC04 PC06

Claims (6)

[Claims] 1. A (co) polymer of an ethylenically unsaturated monomer containing, as one component, an ethylenically unsaturated monomer having a cyclic saturated hydrocarbon group having 10 to 20 carbon atoms and a solubility parameter. In the presence of a dispersion stabilizer having an (SP value) of 7.5 to 9.3, an organic solvent in which a polymerizable unsaturated monomer is dissolved but a polymer formed from the polymerizable unsaturated monomer is not substantially dissolved. A non-aqueous polymer dispersion obtained by polymerizing the polymerizable unsaturated monomer in a liquid. 2. The method according to claim 1, wherein the cyclic saturated hydrocarbon group of the ethylenically unsaturated monomer having a cyclic saturated hydrocarbon group having 10 to 20 carbon atoms is an isobornyl group or a tricyclodecanyl group. Non-aqueous polymer dispersion. 3. An ethylenically unsaturated monomer having a cyclic saturated hydrocarbon group having 10 to 20 carbon atoms in which at least 20% by weight of a monomer component constituting a (co) polymer as a dispersion stabilizer is present. The non-aqueous polymer dispersion according to claim 1 or 2, wherein 4. The dispersion stabilizer according to claim 1, wherein said dispersion stabilizer has an average molecular weight of 0.1.
The non-aqueous polymer dispersion according to any one of claims 1 to 3, having a polymerizable unsaturated double bond in the range of 1 to 1.8. 5. The dispersion stabilizer has a weight average molecular weight of 1,000.
0-50,000 and hydroxyl value 0-150 mgKOH /
The non-aqueous polymer dispersion according to any one of claims 1 to 4, wherein the dispersion has a weight of 5 g. 6. A coating composition comprising, as a resin component, the non-aqueous polymer dispersion according to any one of claims 1 to 5, a base resin other than the non-aqueous polymer dispersion, and a curing agent.