JPH0952905A - Nonaqueous dispersion type resin composition and resin composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new composition keeping characteristics of nonaqueous dispersion resin itself and excellent in performances of coating such as weather resistance. SOLUTION: This stable nonaqueous dispersion type resin composition is obtained by copolymerizing vinylic monomers in an organic solvent which dissolves vinylic monomers, but does not dissolve vinylic polymers (A) obtained from the monomers in the presence of a polymer (B) modified with a silicone compound, containing the silicone compound in an amount of about 1-60wt.% and capable of dissolving into the above organis solvent. The silicone compound is preferably expressed by an organopolysiloxane, etc., having a functional group of the formula [R is OH group, etc., binding to C-Si bond; R' is H, an alkyl, etc.; (n) is 0.5-2.0; (m) is 0.0-2.5]. Furthermore, the component A is preferably obtained by using, as essential components, a vinyl ester of α, β-unsaturated (di)carboxylic acid and vinyl acetate as monomers having copolymerizable unsaturated double bonds forming the component A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful non-aqueous dispersion type resin composition and a non-aqueous dispersion type resin composition containing the non-aqueous dispersion type resin composition as an essential film-forming component. The present invention relates to a resin composition for paint which is useful as

More specifically, the present invention is particularly modified with a silicone compound and is excellent in weather resistance and the like, and is particularly useful as a coating material for building exteriors, which is of a conventional type. The present invention relates to a highly practical non-aqueous dispersion type resin composition and a resin composition for paints, which has little influence on an old paint film (existing paint film) unlike a form using organic solvents.

[0003] In addition, the present invention is a highly practical non-coating material, which has coating film properties comparable to those of conventional systems using organic solvents. The present invention relates to a water dispersion type resin composition, and a resin composition for a coating, which is of a form containing the non-aqueous dispersion type resin composition and has extremely high practicality.

[0004]

2. Description of the Related Art Non-aqueous dispersion (NAD) type resins are used as binders for interior / exterior buildings, metals, automobiles, etc., but can form dispersed particles stably in a solvent. In order to
Vinyl monomers such as vinyl acetate and lower alkyl esters of (meth) acrylic acid such as (meth) acrylic acid methyl ester and (meth) acrylic acid ethyl ester, which are not so good in weather resistance, Even from the fact that a relatively large amount has to be used, the degree of freedom in resin design is naturally limited, and as a result, there is no need for dispersed particles, that is, there is no design freedom in the form of containing dispersed particles at all. Compared with a high solvent-soluble resin, it tends to be inferior particularly in terms of weather resistance.

Further, in recent years, there is a tendency that complaints about odors caused by organic solvents and unreacted monomers increase with the increase of awareness of environmental problems and revision of the Odor Control Law. However, although there is an urgent need to deal with them, the present inventors have already disclosed as one of means for solving such a problem in Japanese Patent Laid-Open No. 6-184490.
We are proposing the technology disclosed in the publication.

[0006]

As described above, in the conventional technique, the non-aqueous dispersion type resin (that is, the non-aqueous dispersion of the resin), in particular, the weather resistance, is significantly improved. It is the actual situation that the ones in the shape of T have not been developed yet.

[0007] Therefore, the problem to be solved by the present invention is to solve the above problems and to improve the weather resistance of the non-aqueous dispersion type resin (composition). Among other things, obtained using the non-aqueous dispersion resin composition thus prepared,
In particular, it has excellent weather resistance, has little effect on the old paint film (existing paint film), and the performance of the paint film is the same as that of the conventional type using organic solvents. That is, it is to provide a resin composition for paint having extremely high practicality.

[0008]

Means for Solving the Problems Accordingly, the present inventors have:
As described above, as a result of intensive and intensive studies, focusing on the problem to be solved by the invention, as a polymer (B) soluble in an organic solvent, this polymer (B) is a silicone compound. The present invention has been completed by finding that the non-aqueous dispersion type resin, in particular, the weather resistance and the like can be improved by using the modified form.

That is, according to the present invention, basically, a vinyl type monomer is dissolved, but a copolymer (A) of this monomer is not dissolved in a specific organic solvent. In the stable non-aqueous dispersion obtained by copolymerizing the vinyl-based monomers in the presence of the polymer (B) soluble in an organic solvent, the polymer (B)
As an essential component, a silicone compound is contained in about 1
To about 60% by weight, and a novel non-aqueous dispersion type resin composition in which the polymer (B) is modified with a silicone compound. To try to provide things,

Further, the silicone compound has the general formula [I]

[0011]

Embedded image

(Wherein R is at least one functional group 1 selected from the group consisting of a hydroxyl group bonded to a carbon-silicon bond, a carboxyl group, an epoxy group and an alkoxy group.
A valent organic group or a copolymerizable unsaturated double bond, R'represents a hydrogen atom or an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group, and n is 0. 0.5 to 2.0, and m is 0.0 to 2.5.
, And m + n is 0.
It is assumed that the number is within the range of 5 to 3.0. )

Has at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an alkoxy group, an aryloxy group and an acyloxy group represented by or at least one in one molecule.
It is an object of the present invention to provide a novel non-aqueous dispersion type resin composition such as an organopolysiloxane having individual copolymerizable unsaturated double bonds.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Specifically, when exemplifying the non-aqueous dispersion resin composition provided by the present invention, the silicone compound is an organopolysiloxane represented by the general formula [I]. A non-aqueous reaction product of a polysiloxane and a compound having both a specific functional group having reactivity with a functional group contained in the organopolysiloxane and a copolymerizable unsaturated double bond. Dispersion type resin composition;

The polymer (B) soluble in the organic solvent is
About 1 to about 60% by weight of the silicone compound that modifies the polymer (B) and about 40 to about 99% by weight of the monomers containing a copolymerizable unsaturated double bond forming the polymer. And a non-aqueous dispersion type resin composition containing 100% by weight of each of these monomers.

The polymer (B) soluble in the organic solvent is
Vinyl-based monomers containing at least 20 wt% of (meth) acrylic acid ester having an alkyl side chain and / or styrene-based monomers having an alkyl side chain, each having at least 3 carbon atoms A non-aqueous dispersion type resin composition in the form of:

The polymer (B) soluble in the organic solvent is
2 of (meth) acrylic acid ester (b-1) having an alkyl side chain having at least 3 carbon atoms and / or styrene-based monomers (b-2) having an alkyl group side chain
0 to 98% by weight of a resin containing a copolymerizable unsaturated double bond (b
Other vinyl monomers (b) copolymerizable with 0 to 80% by weight of (3) and the above (b-1) and (b-2).
-4) from about 2 to 80% by weight, and about 30 to about 99% by weight of the vinyl-based monomer mixture selected such that the total amount of each of these monomers is 100% by weight. A non-aqueous dispersion type resin composition in the form of about 1 to about 60% by weight of the silicone compound represented by the above-mentioned general formula [I].

The polymer (B) soluble in the organic solvent is
An oil-modified alkyd resin having an oil length of at least 50% and modified with a silicone compound represented by the above general formula [I]. Resin / silicone compound = 40
A specific non-aqueous dispersion type resin composition, such as ~ 99/1 to 60;

The main component of the vinyl-based monomers forming the polymer (A) which is insoluble in the organic solvent is a (meth) acrylic acid ester or (meth) acrylate having an alkyl group side chain with 1 to 2 carbon atoms. A specific non-aqueous dispersion type resin composition such as esters of α, β-unsaturated (poly) carboxylic acid or vinyl acetate excluding acrylic acid;

Composition of polymer (B) soluble in the organic solvent with respect to vinyl polymer (A) which is composed of monomers soluble in the organic solvent and is insoluble in the organic solvent. The ratio is 10 to 90 / in terms of solid content weight ratio.
A non-aqueous dispersion type resin composition having a content of 90 to 10;

For the non-aqueous dispersion resin in which the unreacted monomers contained in the resin composition are 3% by weight or more in the solvent, the unreacted monomers are added in an amount of 3% by weight in the solvent. A non-aqueous dispersion type resin composition which has been distilled off until the amount becomes less than

To the obtained non-aqueous dispersion type resin,
A resin composition for a coating composition, in which a dryer is added as a curing accelerator in an amount of 0.01 to 10% by weight based on the resin solid content;

The resulting non-aqueous dispersion type resin is
As the curing agent, at least one selected from the group consisting of metal alkoxides, metal acylates and metal chelates is used in an amount of about 0.001 to about 20% by weight based on the resin solid content. , A compounded resin composition for paints;

To the obtained non-aqueous dispersion type resin,
As the curing agent, a polyisocyanate compound is used in which the equivalent ratio of the hydroxyl group in the non-aqueous dispersion type resin to the isocyanate group in the polyisocyanate compound is 1.
A resin composition for a coating composition, which is blended so as to be in the range of 0 / (0.2 to 1.5);

To the obtained non-aqueous dispersion type resin,
As a curing agent, a non-aqueous dispersion resin / amino resin, in a resin solid content ratio, within a range of 50 to 90/10 to 50, a resin composition for paint in a form in which amino resins are blended;

It is intended to provide

Here, the organopolysiloxane represented by the general formula (I) which can be used in the present invention has a chain structure or a cyclic structure, and has a hydroxyl group and a carboxyl group, respectively. Group, an epoxy group, an alkoxy group, an aryloxy group and an acyloxy group, at least one or more functional groups selected from the group consisting of at least one in one molecule,

[0028] If only the typical market products of such a form are listed, "SH
-6018 or BX16-190 "(above, examples of hydroxyl group-containing substances) or" BX16-191 "(examples of epoxy group-containing substances) [all are trade names of Toray Dow Corning Silicone Co., Ltd.]; "TSR-160" (example of hydroxyl group-containing substance), "TSR-165" (example of methoxy group-containing substance) or "YR-3168" (example of hydroxyl group-containing substance) [All are products manufactured by Toshiba Silicone Co., Ltd. Name];

"KR-211, KR-212 or K
R-213 "(above, examples of hydroxyl group-containing substances)," KR-2
16, KR-217 or KR-9218 "(above,
Examples of methoxy group-containing products), "X-22-173A, X-
22-343, KF-101 or KF-102 "
(The above are examples of epoxy group-containing products) or "X-22-3
715 "(example of carboxyl group-containing product) [trade name of Shin-Etsu Chemical Co., Ltd.];

Alternatively, "SY-231" (example of methoxy group-containing product) or "SY-409 or SY-43"
0 "(above, an example of a hydroxyl group-containing substance) and the like, and further," SY-550 or VP-201 (above, an example of a methoxy group-containing substance) [trade name manufactured by Wacker Chemie GmbH in Germany] and the like. There

In addition to the above, when only typical ones having a copolymerizable unsaturated double bond are exemplified, "X-22-164B, X-22-16"
4C or X-22-5002 "or" KR-21
5 ”[trade name of Shin-Etsu Chemical Co., Ltd.]; or“ Silaplane TM0701 or FM07 series ”[trade name of Chisso Co., Ltd.].

If the amount of these silicone compounds used is less than 1% by weight, the use effect cannot be obtained, and if the amount of these silicone compounds exceeds 60% by weight, the formed film becomes soft depending on the silicone compound used. However, the hardness, solvent resistance, anti-adhesion resistance, and the like are reduced, and on the contrary, the film formed is hard and brittle, and mechanical properties are deteriorated, which is not preferable. Therefore, the usage amount is about 1 to about 60.
The weight range is preferably in the range of 3 to 50% by weight.

Next, the vinyl-based monomers used in the present invention are soluble, but the copolymers of the monomers are not, which means that they can be dissolved in specific organic solvents having low solubility. Examples of the polymer (B) include acrylic copolymers (including vinyl copolymers) having a specific composition, and
It is desirable to use oil-modified alkyd resins.

First, when the polymer (B) is an acrylic copolymer, an alkyl acrylate or an alkyl methacrylate having an alkyl group having 3 or more carbon atoms in its side chain, which is used as an essential component thereof. As a typical example of the class (b-1), general formula [II]

[0035]

Embedded image

[Wherein R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents -C _n H _{2n + 1} (where n is an integer of 3 to 18).] Represents an alkyl group, a cycloalkyl group or a side chain alkyl group-containing cycloalkyl group represented by. ]

And the like.

If only typical examples of such alkyl acrylates or alkyl methacrylates (b-1) are exemplified, propyl (meth) will be mentioned.
Acrylate, isopropyl (meth) acrylate [i
-Propyl (meth) acrylate], n-butyl (meth) acrylate, i-butyl (meth) acrylate,
tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,

The lauryl (meth) acrylate, "acrylic ester SL" [manufactured by Mitsubishi Rayon (Co.), C ₁₂ - /
Trade name of C ₁₃ -methacrylate mixture], stearyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate or adamantyl (meth) acrylate.

Further, only the typical examples of the styrene-based monomers (b-2) having an alkyl group in the side chain described above will be exemplified.

[0041]

[Chemical 6]

[0042] [However, R in the formula "is, -C _n H _{2n + 1}
(However, n is an integer of 1 to 4). ]

Various compounds such as those represented by

Specific examples of such styrenic monomers (b-2) include vinyltoluene, p-methylstyrene, ethylstyrene, propylstyrene, isopropylstyrene and p-. te
For example, rt-butylstyrene.

As described above, each of the various alkyl acrylates or alkyl methacrylates (b-1) and / or the styrene-based monomers (b-2) has a solubility as described below. It is intended to be used for the purpose of imparting a weak function of dissolving at least one kind of a specific solvent to the obtained copolymers themselves, and monomers of such a form. The total amount of monomers used is about 20 to about 98% by weight.
The range is suitably, and preferably 30 to 80% by weight.

If the amount used is less than about 20% by weight, the solubility in solvents will inevitably decrease and it will become cloudy. Also, in the case of a system in which white turbidity is likely to occur at low temperatures or where the amount of the copolymerizable unsaturated bond-containing resins (b-3) used as described above is large, at room temperature Whether it is

Even if it is transparent, when it is vinylated, that is, when it is copolymerized, it may be difficult to obtain a desired copolymer having desired performance.
In the case of exceeding the above, although the solubility is good, it is inevitable to use a so-called functional group-containing component which should impart dispersibility, adhesion to a substrate, or a crosslinking function. In any case, it is not preferable because it easily disappears.

Next, the above-mentioned copolymerizable unsaturated bond-containing resins (b-3) make the pigment dispersibility of the obtained vinyl copolymer (B) more excellent. The main purpose is to increase the nonvolatile content at the time of coating, or to improve the solubility in non-polar organic solvents.

Specific examples of such resins (b-3) include only polyester resins, vinyl copolymers, petroleum resins, rosin esters or polyether polyols. Among others, the use of polyester resins (including oil-modified types) or acrylic copolymers is particularly desirable.

However, most of the polyester resins, which are so-called oil-free alkyd resins, which are not oil-modified, themselves have poor solubility in solvents. The amount of the alkyd resin used should be kept at a level such that the target copolymer (B) can be obtained without turbidity.

Such polyester resins (including oil-modified types) or vinyl copolymers (among others, acrylic copolymers) are disclosed in Japanese Examined Patent Publication No. 45-2201.
1, gazette 44-7134 gazette or gazette 46-20.
No. 502, or Japanese Unexamined Patent Publication No. 48-78233 or No. 50-58123, etc., a raw material component having a copolymerizable unsaturated bond is essential, and further The resin skeleton obtained by reacting with the raw material components has a form in which this copolymerizable unsaturated bond is retained,

Alternatively, as disclosed in JP-B-49-47916 or JP-A-50-6223, first, a saturated polyester having no copolymerizable unsaturated bond is obtained, and then the saturated polyester is obtained. A functional group such as a hydroxyl group or a carboxyl group present therein, or an epoxy group or the like introduced by reacting a diepoxy compound is used, and a functional group reactive with these functional groups and a vinyl group. Compounds having both of the following: for example, various compounds having both an acid chloride group and a vinyl group, such as (meth) acrylic acid chloride;

Such as glycidyl (meth) acrylate,
Various compounds having both an epoxy group and a vinyl group; various compounds having both an alkoxysilanol group and a vinyl group, such as vinylmethoxysilane or (meth) acryloxyethyltrimethoxysilane;
Various compounds having an acid anhydride group and a vinyl group such as maleic anhydride or tetrahydrophthalic anhydride; various compounds having a carboxyl group and a vinyl group such as fumaric acid or (meth) acrylic acid Compounds;

Alternatively, vinyl-based monomers having both an isocyanate group and a vinyl group, such as 2-hydroxypropyl (meth) acrylate-hexamethylene diisocyanate equimolar adducts or isocyanate ethyl methacrylate, are added to the saturated polyester. Various compounds having both a hydroxyl group and a copolymerizable unsaturated bond obtained by

Copolymerization is carried out in advance by using vinyl monomers having a functional group such as a hydroxyl group, a carboxyl group or an epoxy group as an essential component, and an acrylic copolymer having these functional groups is copolymerized. Compounds having a functional group having reactivity with a functional group contained in the acrylic copolymer, and a vinyl group, as in the case of introducing a polymerizable unsaturated bond. Among other things, for example,
Compounds having both an acid chloride group and a vinyl group, such as (meth) acrylic acid chloride;

Such as glycidyl (meth) acrylate,
Various compounds having both epoxy group and vinyl group; Various compounds having both alkoxysilanol group and vinyl group, such as vinylmethoxysilane or (meth) acryloxyethyltrimethoxysilane;

Various compounds having a combination of an acid anhydride group and a vinyl group such as maleic anhydride or tetrahydrophthalic anhydride; a combination of a carboxyl group and a vinyl group such as fumaric acid or (meth) acrylic acid. Or various vinyl compounds such as 2-hydroxypropyl (meth) acrylate-hexamethylene diisocyanate equimolar adducts or isocyanatoethylmethacrylate, which have both an isocyanate group and a vinyl group. Various compounds and the like having both a hydroxyl group and a copolymerizable unsaturated bond, which are obtained by subjecting the acrylic copolymer to an addition reaction with the acrylic copolymer, and the like.

Such polyester resins include various saturated fatty acids such as octylic acid, lauric acid, stearic acid or "versatidic acid" (trade name of synthetic fatty acid manufactured by Shell Co., Netherlands); Various unsaturated fatty acids such as oleic acid, linoleic acid, linoleic acid, eleostearic acid or ricinoleic acid;

"Pamorin 200 or 300" (trade name of synthetic drying oil fatty acid, manufactured by Hercules, USA),
Chinese laurel oil (fatty acid), flaxseed oil (fatty acid), dehydrated castor oil (fatty acid), tall oil (fatty acid), cottonseed oil (fatty acid), soybean oil (fatty acid), olive oil (fatty acid), safflower oil (fatty acid), castor oil (fatty acid) ) Or various (semi) drying oils (fatty acids) such as rice bran oil (fatty acids);

Alternatively, at least one compound selected from various oils or fatty acids such as various non-drying oils (fatty acids) such as hydrogenated coconut oil fatty acid, coconut oil fatty acid or palm oil fatty acid. With or without

Various polyvalent compounds such as ethylene glycol, propylene glycol, glycerin, trimethylolethane, trimethylolpropane, neopentyl glycol, 1,6-hexanediol, 1,2,6-hexanetriol, pentaerythritol or sorbitol. One or more alcohols,

Benzoic acid, p-tert-butylbenzoic acid, (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid, tetrahydro (anhydrous) phthalic acid, tetrachloro (anhydrous) phthalic acid, hexachloro (anhydrous) phthalic acid, tetrabromo (Anhydrous) phthalic acid, trimellitic acid, "hymic acid" [trade name of Hitachi Chemical Co., Ltd.], (anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, adipic acid , One or more of various carboxylic acids such as sebacic acid or oxalic acid,

It can be obtained by reacting by a conventional method. In that case, if necessary, depending on the respective purposes, such as adhesion, chemical resistance, and further improvement of weather resistance, etc. ,
Various monoepoxy compounds represented by various fatty acid glycidyl esters such as branched synthetic fatty acid glycidyl esters);

"Epiclon 200 or 400"
[Product name of polyepoxy resin manufactured by Dainippon Ink and Chemicals, Inc.] or “Epicoat 828 or 100
Various polyepoxy resins, such as "1" (trade name of polyepoxy resin manufactured by Shell, The Netherlands);

Alternatively, various diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-methylenebis (cyclohexyl isocyanate); these diisocyanates and polyhydric alcohols and water as listed above. Various polyisocyanates such as are obtained by addition reactions with;

Or various isocyanuric ring-containing polyisocyanates obtained by (co) polymerization of diisocyanates, or one or more of various reactive silicone compounds as described above, Examples thereof include those obtained by substituting a part of polyhydric alcohols, carboxylic acids and the like as described above and reacting them by a conventional method.

In the case of the copolymerizable unsaturated bond-containing acrylic copolymer used as the above (b-3), each vinyl-based monomer as described above or as described below is used. Among them, those obtained by appropriately selecting a desired monomer and copolymerizing it with a desired monomer composition by a conventional method are suitable.

The polyester resins or vinyl copolymers may be used alone or in combination of two or more kinds, or by using one kind or two or more kinds of these types of resins with each other. Of course, it is possible.

The amount of these two types of resins used is appropriately in the range of 0 to about 80% by weight, and about 80% by weight.
If it is used in an excessively large amount in excess of weight%, the viscosity of the obtained copolymer will inevitably increase, or gelation will occur during the reaction, which is not preferable.

Further, in the case where so-called dryer curing in a form in which dryers are mixed as a curing accelerator is carried out, polyester resins are
Needless to say, it is essential to carry out modification with (semi) drying oil (fatty acid).

In such a case, in order to obtain a cured coating film having desired coating film properties by curing with a dryer, the amount of the polyester resin used is at least about 20. Wt% is required. Therefore, in such a case, about 20 to about 8
It is suitable to be in the range of 0% by weight.

As the curing agent, for example, at least one selected from the group consisting of the above-mentioned metal alkoxides, metal acylates and metal chelates, or a polyisocyanate compound or amino resins is used. In this case, if the physical properties of the cured coating film are taken into consideration, it is more preferable that the resin structure of the polyester resin has a hydroxyl group in addition to the unsaturated bond as much as possible. , Favorable results are obtained.

Next, the above-mentioned vinyl monomers (b-
4) That is, the above-mentioned alkyl acrylates or alkyl methacrylates (b-1) and / or styrene-based monomers (b-2) and the above-mentioned copolymerizable unsaturated bond-containing resins (b-3). Other vinyl-based monomers having a copolymerizability with) correspond to the monomers (b-1) and / or (b-2) and the resins (b-3). Various compounds ranging from the group (a) to the group (g) as described below are particularly representative examples.

That is, (a) styrene; methyl (meth) acrylate or ethyl (meth) acrylate, benzyl (meth) acrylate or cyclohexyl (meth) acrylate as described above (b-
Alkyl (meth) acrylates other than 1); dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate or methoxyethyl (meth) acrylate
Various alkoxyalkyl (meth) acrylates such as acrylates; represented by maleic acid, fumaric acid or itaconic acid such as dimethyl maleate, diethyl malate, diethyl fumarate, dibutyl fumarate or dibutyl itaconate Such diesters of various dicarboxylic acids and monohydric alcohols;

Various vinyl esters such as vinyl acetate, vinyl benzoate or "Veoba" (vinyl ester of branched aliphatic monocarboxylic acids manufactured by Shell, Netherlands); "Biscoat 3F, 3FM, 8F, 8FM.
Or 17FM ”[trade name of fluorine-containing acrylic monomers manufactured by Osaka Organic Chemical Co., Ltd.], perfluorocyclohexyl (meth) acrylate, di-perfluorocyclohexyl fumarate or Ni-propyl perfluorooctane. Various fluorine-containing polymerizable compounds such as various (per) fluoroalkyl group-containing vinyl esters such as sulfonamide ethyl (meth) acrylate, -vinyl ethers,-(meth) acrylates or -unsaturated polycarboxylic acid esters Compounds;

Alternatively, various nitrogen-containing vinyl monomers such as (meth) acrylonitrile, and various functional group-free halogens typified by vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride. Olefins and the like.

(B) (meth) acrylamide, dimethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, diacetone acrylamide, dimethylaminopropyl acrylamide or alkoxylated N-methylol Amide bond-containing vinyl monomers such as (meth) acrylamides;

(C) dialkyl [(meth) acryloyloxyalkyl] phosphates, (meth) acryloyloxyalkyl acid phosphates, dialkyl [(meth) acryloyloxyalkyl] phosphite or (meth) acryloyloxyalkyl acid phosphite And so on,

Further, various epoxy group-containing vinyl compounds such as alkylene oxide adducts of the above (meth) acryloyloxyalkyl acid phosphates or -acid phosphites, glycidyl (meth) acrylate and methylglycidyl (meth) acrylate. Various phosphorus atom-containing vinyl monomers such as ester compounds of monomers and phosphoric acid or phosphorous acid or their acidic esters, or 3-chloro-2-acid phosphoxypropyl (meth) acrylate;

(D) Dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate.

Any of the amide bond-containing vinyl monomers, phosphorus atom-containing vinyl monomers, dialkylaminoalkyl (meth) acrylates, etc., described above,
Vinyl-, especially, among acrylic copolymers,
Each of them is used to impart an internal catalytic function, or to improve the adhesion to the material or substrate, the compatibility with other resins, the pigment dispersibility, etc. Two or more types may be used in combination,

From the viewpoint of use effect, the amount of each of these monomers used is within the range of 0.05 to 5% by weight in the case of phosphorus atom-containing vinyl-based monomers. In the case of containing vinyl-based monomers or dialkylaminoalkyl (meth) acrylates, the range of 0.05 to 10% by weight is suitable.

Further, other vinyl monomers (b-4) include (e) glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate or (meth) allyl glycidyl ether. , Α, β-ethylenically unsaturated carboxylic acids and mono-
For various carboxylic acids such as equimolar additions of various hydroxyl group-containing vinyl monomers such as 2- (meth) acryloyloxymonoethyl phthalate with polycarboxylic anhydrides as described above. , "Epiclon 200,
400, 441, 850 or 1050 "[trade name of polyepoxy resin manufactured by Dainippon Ink and Chemicals, Inc.]," Epicoat 828, 1001 or 100 "
4 "(trade name of polyepoxy resin manufactured by Shell in the Netherlands),

"Araldite 6071 or 608
4 "(polyepoxy resin manufactured by Ciba-Geigy, Switzerland)," Chissonox 221 "[epoxy compound manufactured by Chisso Corporation] or" Denacol EX-611 ".
Epoxy group-containing polymerization obtained by addition reaction of various polyepoxy resins having at least two epoxy groups in one molecule such as [Epoxy compound manufactured by Nagase & Co., Ltd.] at an equimolar ratio. Like compounds,

(F) Various silicon-based monomers such as vinylethoxysilane, α-methacryloxypropyltrimethoxysilane or trimethylsiloxyethyl (meth) acrylate.

For the purpose of further improving weather resistance, for example, "NORBLOC 7966" as disclosed in US Pat. No. 4,528,311.
Benzotriazole-based acrylic monomers such as [trade name of NORAMCO, USA];

Alternatively, various polymerizable ultraviolet absorbers and polymerizable light stabilizers such as "Adeka Stab T-37 or LA-82" [trade name of Asahi Denka Co., Ltd.] may be copolymerized. You can

(G) Further, JP-A-63-1280
Nos. "AA-6, AS-6, AN-6" as disclosed in Japanese Patent Application Laid-Open No.
Alternatively, various high molecular weight monomers (macromonomers or macromers) having a functional group end capable of copolymerization, such as AB-6 "[all are trade names of Toagosei Kagaku Kogyo Co., Ltd.] Can also be used,

(H) 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate or mono -2-hydroxyethyl-
Starting with monobutyl fumarate,

Polyethylene glycol or polypropylene glycol mono (meth) acrylate or an adduct of these with ε-caprolactone, "Plaxel"
FM or FA series ”[trade name of caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.], various hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acid; (meth) acrylic acid, Crotonic acid,
Various α, β such as various unsaturated mono- or dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid or citraconic acid, and monoesters of these dicarboxylic acids and monohydric alcohols. -Ethylenically unsaturated carboxylic acids,

Addition products of the α, β-ethylenically unsaturated carboxylic acids and ε-caprolactone, or various α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters as described above, succinic acid and maleic acid. , Phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid,
"Hymic acid" [trade name of Hitachi Chemical Co., Ltd.],
Adducts of various polycarboxylic acids with anhydrides, such as tetrachlorophthalic acid or dodecynylsuccinic acid,
"Curdra E", monoglycidyl esters of various monovalent carboxylic acids such as coconut oil fatty acid glycidyl ester or octyl acid glycidyl ester, or various monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide Adducts; or various hydroxyl group-containing vinyl monomers such as hydroxyethyl vinyl ethers,

(I) Various unsaturated mono-types as described above
Or various α, β-ethylenically unsaturated carboxylic acids such as dicarboxylic acids, monoesters of these dicarboxylic acids and monohydric alcohols; or various α, β-ethylenic compounds as described above. It is possible to copolymerize various carboxyl group-containing vinyl monomers such as an adduct of unsaturated carboxylic acid hydroxyalkyl ester with an anhydride of various polycarboxylic acids as described above.

At this time, when the hydroxyl group-containing vinyl type monomers are used for the purpose of improving adhesion, the amount of the monomers used is 0 to about 5% by weight. When used within the range for the purpose of introducing cross-linking points of the cross-linking agent component, the amount of the monomers to be used includes the solubility of the intended vinyl copolymer (B), non-aqueous dispersant From the viewpoint of the amount of hydroxyl groups in the John resin, the range of 0 to about 30% by weight is suitable, and the range of 0 to 15% by weight is suitable.

When it is used in the dispersoid (polymer particles) described later, the range of about 1 to about 45% by weight is, among others,
The range of 3 to 30% by weight is suitable. When the amount is less than about 1% by weight, the remarkable crosslinking effect is hard to appear. On the other hand, when the amount is more than about 45% by weight and the amount is too large, the crosslinking effect is inevitable and the coating composition is almost full. Both are not preferable because the price becomes high.

The carboxyl group-containing vinyl monomers are
In many cases, it exhibits an internal catalytic action or an internal catalytic effect, and therefore it may impair the storage stability of the paint. Or, in consideration of compatibility with other resins, etc., when expecting only such an internal catalytic effect or internal catalytic effect, the range of 0 to about 5% by weight is preferably 0.2 Is suitable within the range of up to 3% by weight,

When used as a cross-linking point of metal alkoxides, metal acylates or metal chelates, in the case of the intended vinyl copolymer (B),
From the viewpoint of solubility of the copolymer (B), the range of about 1 to about 20% by weight, and the range of 3 to 15% by weight are suitable.

When it is used for the dispersoid (polymer particles) described later, it is within the range of about 1 to about 30% by weight,
Especially, the range of 3 to 20% by weight is suitable. If the amount is less than about 1% by weight, no significant crosslinking effect can be manifested, and if the amount exceeds about 30% by weight, the solubility tends to decrease. Neither is preferable.

As the vinyl-based monomers (b-4), various monomers as listed above are the above-mentioned monomers (b-1) and / or (b-2). ) And the above-mentioned resins (b-3) and copolymerizability, particularly, coating workability, gloss, hardness, flexibility, weather resistance, drying property, solvent resistance, compatibility, dilution. From various aspects such as solubility, solubility or pot life, the amount of each monomer component used and its combination are appropriately selected and determined within the range of about 20 to about 80% by weight. You can do so.

To prepare the above-mentioned polymer (B) which is an essential base resin component used in the present invention,
As described above, (b-1) and (b
-2), (b-3) and (b-4) by using the respective raw material components, by making full use of various known and commonly used copolymerization reaction method or grafting reaction method (graft copolymerization reaction method) Is that you can carry out,

At that time, azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), t
ert-butyl perbenzoate (TBPB), ter
t-Butyl hydroperoxide (TBHPO), di-
tert-butyl peroxide (DTBPO), cumene hydroperoxide (CHP) or o, o-ter
Single use of various radical generators (radical generating polymerization catalysts or radical polymerization initiators) such as to-o (1,2,2,6,6-pentamethyl-4-piperidinyl) monoperoxycarbonate , Or two or more types are used in combination.

Incidentally, also in the preparation of the non-aqueous dispersion resin composition, various radical generators such as those mentioned above are used, and various known non-aqueous dispersion polymerization methods are used, whereby It goes without saying that this non-aqueous dispersion polymerization method for obtaining such a non-aqueous dispersion resin or a non-aqueous dispersion resin composition can be carried out.

When an oil-modified alkyd resin is used as the polymer (B) instead of the above acrylic copolymer, various reactive silicone compounds such as those mentioned above are used. It is essential that it is modified with such a modification amount, and
In order to have a dissolving power for organic solvents, it is absolutely necessary that the oil length in that case is about 50% or more, preferably 55% or more.

Further, as the oil component, non-drying oils and / or
Or when using semi-drying oils, or when using these various fatty acids, there are no grafting points, or else, in that case, it tends to run short, and in such a case, For example, the above-mentioned Japanese Patent Publication No. 49-479.
It goes without saying that there is no problem even if the grafting point is introduced according to various methods as disclosed in Japanese Patent Publication No. 16 or No. 50-6223.

In addition, there are no special restrictions on polyhydric alcohols and polycarboxylic acids.
Therefore, it goes without saying that there is no problem even if a desired one is used according to the desired performance of the coating film (various).

These various compounds are used as so-called dispersion stabilizers in order to stabilize the dispersion of polymer particles, and the amount or proportion of the compound used is different from that of the non-aqueous dispersion resin. From the viewpoint of exhibiting unique characteristics or characteristics, or from the viewpoint of dispersion stability,

In terms of the solid content weight ratio of the polymer (B) which is a dispersion stabilizer / the vinyl polymer (A) which is a dispersoid,
A range of about 10 to about 90 / about 90 to about 10 is preferable, and above all, the solid content weight ratio ratio of the dispersion stabilizers / dispersoids is 20 to 80/80 to 20. Within the range is appropriate.

When the amount of the dispersion stabilizers is less than about 10% by weight, it becomes difficult to obtain a stable dispersion. On the other hand, when it exceeds about 90% by weight, the nonaqueous dispersion resin is inevitable. In this case, it is not preferable in any case, because the characteristics as described above hardly appear.

Next, as the so-called dispersoid vinyl-based monomers, (meth) acrylic acid esters having an alkyl side chain having 1 or 2 carbon atoms; α, β other than (meth) acrylic acid -Unsaturated (di) carboxylic acid esters; vinyl acetate and the like as main components, but more specifically, various compounds from the group (a) to the group (to) as described above. However, it is used with the above-mentioned usage ratio.

If desired, for the purpose of obtaining a non-aqueous dispersion resin having a so-called special function such as a water / oil repellency function or a weather resistance function,
For example, the following various substances can be copolymerized, or the following various substances can be added and mixed before the copolymerization reaction.

That is, "Defencer" series or "Megafuck 170" series [all are trade names of Dainippon Ink and Chemicals, Inc.], "Aron G"
F-150 or GF-300 "[trade name of Toagosei Chemical Industry Co., Ltd.] or" FA series, FM series or FS series "[trade name of Mitsubishi Yuka Co., Ltd.] Type copolymer type surfactants, fluorine type block copolymers,

"Fluonate K-700" series [trade name of Dainippon Ink and Chemicals, Inc.], "Lumiflon" series [trade name of Asahi Glass Co., Ltd.] or "Kainer ADS or SL" (US pen Various fluororesins such as those manufactured by Walt) or various reactive silicone resins described above; or benzophenone-based, benzotriazole-based, cyanoacrylate-based, anilide oxalate-based, or salicylate esters. Such as various non-polymerizable ultraviolet absorbers except for the polymerizable ultraviolet absorbers and the polymerizable light stabilizers belonging to the above (f) group,

"Tinuvin 144, 292, 700 or 765" (all are trade names manufactured by Ciba Geigy, Switzerland) or "Adeka Stab LA-52 or LA-87" [all manufactured by Asahi Denka Co., Ltd. Such as various non-polymerizable light stabilizers other than the polymerizable light stabilizers belonging to the above (f) group, represented by hindered amine compounds such as After the high weather resistance raw materials are added and mixed with the vinyl-based monomers prior to polymerization, the group (a) to the group (g) are reached,
It is also possible to include such high weather resistance raw materials in the particles by copolymerizing various vinyl monomers as described above.

Further, although the vinyl-based monomer used in preparing the polymer (B) and the non-aqueous dispersion resin composition is dissolved, the vinyl-based copolymer (A) obtained from the monomer is dissolved. Examples of organic solvents that do not dissolve) include only "Marcazole R or E" or "Swazol 310" [trade name of Maruzen Petroleum Co., Ltd.], "LA".
WS ”or“ HAWS ”or“ Shellzol 7
0 or 71 "(trade name of Shell company in the Netherlands),
"Diana Solvent No. 0 or No. 1"
[Product name of Idemitsu Kosan Co., Ltd.],

"IP Solvent 1016, 1020 or 1620" (same as above), "Shellsol D-4
0 "(trade name of Shell Co.)," A solvent, K solvent or AF solvent "[trade name of Nippon Oil Co., Ltd.]," Exxon naphtha No. 3, No. 5 or No. 6 ", Exol D-30, D-40, D
-60 or D-70 "," Isopar C, E, G or H "[trade name of Exxon Chemical Co., Ltd.], and further, aliphatic carbonization such as n-hexane or n-heptane Examples of the solvent include hydrogen as a main component. These hydrocarbon solvents may be used alone or in combination of two or more.

Further, in order to adjust the viscosity, volatility, dispersion and agglomeration, dripping property or electrostatic coating property of the composition, toluene, xylene, "Solvesso 100" [trade name of Exxon Chemical Co., Ltd.] ] Various aromatic hydrocarbon solvents, such as alcohol solvents, acetic acid esters, propylene glycol ether solvents,
Various polar solvents such as propylene glycol ether ester-based solvents or ethoxyethyl propionate are also within a range not departing from the gist of the present invention or within a range not impairing the effects of the present invention. Can be used together.

Further, in the case where a trace amount of unreacted monomers is present, the unreacted monomers can be removed by a known and appropriate means such as distillation under reduced pressure. By performing the removal, it is possible to reduce so-called odor, which is one of the environmental problems related to the paint.

In particular, when the main component of the dispersoid is vinyl acetate and / or (meth) acrylic acid ester, etc., the copolymerizability is inferior, and therefore, within a predetermined time, About 90% by weight of monomers
Above all, to bring more than 95% by weight,
It becomes difficult and difficult.

Therefore, after confirming that the monomer addition rate has reached about 90% by weight or more, the remaining amount is about 10% by weight. Strictly speaking, it is about 3% by weight or more and about 1%.
By measuring the amount of unreacted monomers of less than 0% by weight using gas chromatography (GC), a vacuum distillation method or nitrogen is used until the amount of unreacted monomers is less than about 3% by weight in the solvents. Alternatively, by removing unreacted monomers from the system by a suitable method such as blowing a large amount of so-called inert gas into the system, such as carbon dioxide, The odor caused by such unreacted monomers is remarkably reduced.

Next, the above-mentioned dryer used as the curing accelerator is, for example, all so-called metal dryers which have been used so far, such as cobalt-based, lead-based, zirconium-based or calcium-based. These may be used alone or in combination of two or more kinds, and are about 0.01 to
It can be used within a range of about 10% by weight.

When the amount used is less than about 0.01% by weight, it becomes difficult to sufficiently achieve the effect of curing promotion, while when the amount used exceeds about 10% by weight, an excessive amount is used. However, since there is a tendency that storage stability and colorability are inevitably deteriorated in any case, it is not preferable in any case. Therefore, the amount of the dryer used is usually about 0.01 to about A range of 10% by weight, preferably a range of 0.1 to 5% by weight is suitable.

Further, used as the above-mentioned curing agent,
As the metal alkoxides, metal acylates or metal chelates, various examples are listed, and among others, aluminum-based, zirconium-based or titanium-based ones are considered to be industrially easily available. From the above, it can be mentioned as a preferable one.

Of the preferred ones, only typical ones will be exemplified. "Acetop" [trade name of Hope Pharmaceutical Co., Ltd.], "Titacoat"
[Product name of Nippon Soda Co., Ltd.], "Plenact" [Product name of Ajinomoto Co., Ltd.], "Organics TA series, TC series, ZA series, ZB series, Z"
C series or AL series "[trade name of Matsumoto Pharmaceutical Co., Ltd.]," AIPD, AMD, ASBD or A
LCH series ”or“ Aluminum chelate A, D or M ”[trade name of Kawaken Fine Chemicals Co., Ltd.]

[Tencalate TP series]
Various compounds that are marketed under the trade names such as [Tenka Polymer Co., Ltd.] and widely used and used in the industry are available. These may be used alone or in combination of two or more kinds, and can be used within a range of about 0.001 to about 20% by weight based on the resin solid content.

At that time, alcohols, acetylacetone, acetoacetic acid esters or lactic acid are used in order to improve the storage stability within a range not departing from the object of the present invention or within a range not impairing the effects of the present invention. There is no problem even if various stabilizers such as esters are added.

The metal alkoxides as listed above,
When the amount of the metal acylate or metal chelate used is less than about 0.001% by weight, it becomes difficult to sufficiently achieve the effect of promoting the curing, while about 20
When it is used in an excessively large amount in excess of weight%, storage stability, colorability and solubility tend to be inevitably deteriorated, which is not preferable in any case. The amount is usually about 0.001 to about 20% by weight, preferably 0.05 to 10% by weight.

Further, the polyisocyanate compound used as the above-mentioned curing agent may be any compound, but it seems that the polyisocyanate compound is not sufficiently soluble in the above-mentioned solvents, that is, specific hydrocarbon solvents. In the case of using such a hydrocarbon, it is inevitable that when it is blended in the obtained resin composition for coating, the problem of separation easily occurs, and therefore the hydrocarbon itself has poor solubility. It is desirable to use a compound having sufficient solubility in the system solvents.

If only representative examples of such polyisocyanate compounds are given, only Japanese Patent Laid-Open Nos. 61-72013, 4-130124, 4-130171, and 4-132720 are given. As disclosed in Japanese Patent Publication No. 4-132782 or the like, and if only representative examples of market products of such a form are given as examples,

[Bernock DN-990, DN-99
1, DN-991S, DN-992 or BO-35
7 "[trade name of Dainippon Ink and Chemicals, Inc.], [Desmodur Z-4370] [trade name of Sumitomo Bayer Urethane Co., Ltd.], or" Duranate THA-1 "
00 ”[Asahi Kasei Co., Ltd.] and the like.

The amount of the above-mentioned polyisocyanate compound used is in the range of about 0.2 to about 1.5 equivalents of isocyanate groups per equivalent of hydroxyl groups in the resin composition. It is suitable that the inside thereof, that is, the equivalent ratio of OH / NCO is 1 / about 0.2 to about 1.5.

When the use ratio of isocyanate group to 1 equivalent of hydroxyl group is less than about 0.2 equivalent, it is difficult to achieve the effect of use. On the other hand, when the use ratio exceeds about 1.5. If it is used in an excessively large amount, it becomes inevitable because of problems such as foaming when coated on the surface having a high water content and the cost of the coating. Therefore, it is usually appropriate that the equivalent ratio is 1 / about 0.2 to about 1.5, and preferably 1 / about.
The range of the equivalent ratio of 0.5 to 1.2 is suitable.

Further, to exemplify only the particularly representative amino resins mentioned above used as curing agents, alkylated melamine resins, alkylurea resins, alkylurea / melamine resins or Alkyl benzoguanamine resins and the like, but from the viewpoint of weather resistance, among others, mineral spirit tolerance is at least about 300%, preferably 500%.
It is desirable to use the above alkylated melamine resins.

All of these can be prepared by a conventional method. For example,
"Super Beckamine L-161, L-117-60
Alternatively, "L-118-60" [all are trade names of Dainippon Ink and Chemicals, Inc.] and the like are already on the market.

The usage ratio of such amino resins is as follows:
The solid content weight ratio of the non-aqueous dispersion resin / amino resin is within the range of about 50 to about 90 / about 10 to about 50, which is particularly suitable in view of coating film physical properties and dispersion stability. It can be said that there is.

The amount of the amino resin used is about 10% by weight.
If it is less than 50% by weight, the physical properties of the coating tend to be difficult to appear. On the other hand, if it is used in an excessively large amount exceeding about 50% by weight, the coating tends to become brittle and the acid resistance is inevitable. It is not preferable in any case since the above will decrease.

The thus obtained non-aqueous dispersion resin for paint according to the present invention, that is, the non-aqueous dispersion resin composition and the resin composition for paint are particularly suitable for automobile repairs, roofs or building exteriors. , When applying a coating film that is easily attacked by so-called polar organic solvents on a material that has already been formed, or when repairing this type of material, reduce the amount of polar organic solvents used, or eliminate it altogether. Then,

[0136] It gives a good coating film which is smooth and has high commercial value, without causing lifting (chrinking) which is observed when a coating material containing the polar solvent is applied, and is resistant to the polar solvent. Even in the case of a plastic material having poor solvent resistance such as polycarbonate, which is apt to be damaged, troubles such as generation of solvent cracks are less likely to occur.

In addition, as compared with the soluble type, it is very difficult to sag, and in metallic coating for automobiles or automobile repairs, unevenness of metal return is less likely to occur and a metallic feeling is easily obtained. .

Also, in two-tone finishing or repair of automobiles or motorcycles, the repainting interval is very short, and as nonpolar organic solvents to be used,
If you use a photochemically inert and low toxic substance,
Compared with the case where a polar organic solvent having strong toxicity is used as in the past, the working environment is remarkably improved, the pollution is reduced, and the performances are remarkably improved.

Further, in the present invention, room temperature drying, forced drying, and heat drying (baking) are performed, and in the case of urethane type, a method of curing in an amine stream, that is, a vapor cure system or a VIC system is used. , Applicable to any curing means or curing conditions,

Such as pigment dispersants, leveling agents, UV absorbers, light stabilizers or curing accelerators, etc.,
It goes without saying that various kinds of additives for coatings, which are commonly known in the art, can be usually used in conventional amounts.

As long as it is soluble in the solvent used by being compatible with the resin composition for coating composition of the present invention, plasticizers, other plasticizers and other materials are used for the purpose of improving various performances. Resins such as acrylic copolymers, fibrin compounds, acrylated alkyd resins, alkyd resins,
Silicone resins, fluororesins, epoxy resins and the like can be appropriately used in combination,

Also in this case, it is possible to use the above-mentioned plasticizers and other resins within a range not deviating from the object of the present invention or within a range not impairing the effect of the present invention. Needless to say, it is essential.

The non-aqueous dispersion resin composition for paints and the resin composition for paints according to the present invention are mixed with pigments and kneaded, or dispersed pigments and processed pigments are mixed, It can be used as a so-called enamel paint, or can be used as a so-called clear paint without using pigments.

In the coating at that time, it is needless to say that various known means such as spray, brush or roller can be applied.

The thus-obtained non-aqueous dispersion resin composition for paints and the resin composition for paints according to the present invention are particularly excellent in weather resistance as compared with conventional non-aqueous dispersion compositions. It is excellent and has little effect on the old paint film, and the performance of the paint film is not very different from that of the conventional type using solvents, and is extremely useful. Out.

In this way, particularly representative uses of the non-aqueous dispersion resin composition for paints and the resin composition for paints according to the present invention will be summarized.

First, regarding the use as a building material, a building material, an anticorrosive top coat, etc., a so-called inorganic base material for building materials such as cement, mortar, silica plate, ALC or gypsum board is used. Of course, those that can be painted include those that target polar or non-polar substrates, but on old and new organic coatings (new or existing organic coatings) that target these various substrates. In addition, it means that coating can be performed without causing coating film defects such as so-called lifting.

Secondly, regarding the use as plastics, it is a coating for so-called general-purpose plastics such as ABS, polystyrene or vinyl chloride (polyvinyl chloride), and further nylon, polyurethane or unsaturated. It can be applied to various plastics such as polyester, of course, such as polycarbonate and the like, which are intended for plastic materials having inferior solvent resistance. However, it is possible to coat these various base materials without causing coating defects such as so-called solvent cracks.

Thirdly, for use as an automobile, by using a curing agent (crosslinking agent) such as polyisocyanate compound and melamine resin together,
Examples include treated and untreated metal substrates, and those intended for electrodeposition coatings or intermediate coatings. And the like, and the coating film properties required for such applications are also improved.

Fourthly, with regard to applications for automobile repair, industrial machinery, motorcycles, etc., mainly those intended for metal base materials such as iron plates, etc. can be mentioned. , Curing agent (crosslinking agent)
It is up to you whether or not to use it together, and even if you do not use this curing agent (crosslinking agent), you can use it for various substrates such as iron plates, primer or medium It means that, in particular, the adhesion, etc. to the coating will be good, and the coating film properties required for such applications will also be good.

[0151]

EXAMPLES Next, the present invention will be explained more specifically with reference to Reference Examples, Examples and Comparative Examples. In the following, all parts and percentages are by weight unless otherwise specified. It shall be the standard.

Reference Example 1 [Preparation Example of Copolymerizable Unsaturated Bond-Containing Resins (b-3)] In a four-necked flask equipped with a stirrer, a thermometer, a reaction product water remover, and a nitrogen gas inlet tube, Soybean oil fatty acid 57
7 parts, 55 parts of phthalic anhydride, 8 parts of maleic anhydride,
300 parts of "SH-6018" (hydroxyl group-containing silicone compound), 20 parts of pentaerythritol and 105 parts of glycerin were charged, and the temperature was raised to 180 ° C.

After holding at the same temperature for 2 hours,
After raising the temperature to 220 ° C. over 3 hours and maintaining it at the same temperature in a nitrogen gas atmosphere until the acid value becomes 9 or less, the “LAWS” [Exxon] is adjusted so that the nonvolatile content becomes 70%. Trade name of an aliphatic-aromatic hydrocarbon mixed solvent manufactured by Kagaku Co., Ltd.], the nonvolatile content is 70%, and the Gardner viscosity at 25 ° C. (hereinafter abbreviated as viscosity) is X. And an acid value of 5.0, and
A solution of the target resin having a hydroxyl value (solid content) of 30 was obtained.
Hereinafter, this is abbreviated as resin (b-3-1).

Reference Example 2 (same as above) In a flask similar to that of Reference Example 1, 5 pieces of "CURDULA E" was added.
78 parts, 103 parts of trimethylolpropane, 228 parts of phthalic anhydride and 89 parts of fumaric acid were charged to prepare 2
The temperature was raised to 00 ° C.

By keeping the same temperature until the acid value becomes 6 or less and then diluting it with "Swazol 310", the nonvolatile content is 70%, the viscosity is Z, and the acid value is 3.0.
A solution of the target resin having a hydroxyl value of 91 was obtained.
Hereinafter, this is abbreviated as resin (b-3-2).

Reference Example 3 (same as above) A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introducing tube was placed in a "LAW".
667 parts of "S" were charged and the temperature was raised to 120 ° C.
At this temperature, i-butylmethacrylate 4
16 parts, 100 parts of lauryl methacrylate, 250 parts of 2-ethylhexyl methacrylate, 200 parts of tert-butyl styrene, 20 parts of β-hydroxyethyl acrylate and 8 parts of monobutyl maleate, te
20 parts of rt-butyl peroctoate and tert
A mixture of 10 parts butyl perbenzoate was added dropwise over 4 hours.

After the dropping, the temperature was kept at 120 ° C. for 8 hours, and when the nonvolatile content reached 59%,
The temperature was lowered to 100 ° C., and 6 parts of glycidyl methacrylate and 0.1 parts of hydroquinone monomethyl ether were added.
3 parts, 166 parts of "Exol D-40", 2-
Add 0.1 parts of methyl imidazole,

By keeping this at 100 ° C. until the acid value becomes 1 or less, the nonvolatile content is 60%, the viscosity is Z ₁ , the acid value is 0.5, and the hydroxyl value is 7 .2
A solution of the desired resin was obtained. Hereinafter, this is referred to as resin (b-3).
Abbreviated as -3).

Reference Example 4 [Preparation Example of Modified Silicone Compound (1)] In a 4-necked flask similar to Reference Example 3, 280 xylene was added.
Parts, 600 parts of “SH-6018” and 5 parts of hydroquinone monomethyl ether were charged, and the temperature was raised to 100 ° C. to uniformly dissolve them.

At this temperature, and further when the solution state became uniform, 60 parts of γ-methacryloxypropyltrimethoxysilane was added, and then 0.1 part of tetraisopropyl titanate was added. , As it is, 10
By holding at 0 ° C. for 2 hours, a solution of the modified silicone compound (1) having a copolymerizable unsaturated double bond and having a nonvolatile content of 70% was obtained.

Reference Example 5 [Preparation Example of Modified Silicone Compound (2)] In a four-necked flask similar to Reference Example 3, 225 xylene was added.
Parts, 340 parts of “TSR-165” (a methoxy group-containing silicone compound) and 5 parts of hydroquinone monomethyl ether were charged, and the temperature was raised to 100 ° C. to uniformly dissolve them.

At this temperature, and when the solution state became uniform, 4-hydroxybutyl acrylate 1
85 parts was added, and then 0.1 part of tetraisopropyl titanate was also added.
By holding for 2 hours, the nonvolatile content becomes 70%.
A solution of the modified silicone compound (2) having a copolymerizable unsaturated double bond was obtained.

Reference Example 6 [Preparation Example of Modified Silicone Compound (3)] In a four-necked flask similar to Reference Example 3, 97 parts of ethoxyethyl propionate and “X-22-173A” (containing epoxy group) were prepared. 370 parts of silicone compound) and 5 parts of hydroquinone monomethyl ether were added to prepare 1
The temperature was raised to 00 ° C. to dissolve it uniformly.

At this temperature, and further, when the solution state became uniform, 18 parts of acrylic acid was gradually added over 30 minutes, and after this addition was completed,
By holding at 100 ° C. for 2 hours, a solution of the modified silicone compound (3) having a copolymerizable unsaturated double bond and having a nonvolatile content of 80% was obtained.

Reference Example 7 [Preparation Example of Vinyl Polymer (B)] In a four-necked flask similar to Reference Example 3, 5 pieces of "LAWS" was added.
00 parts and 166 parts of “IP Solvent 1620” were charged, and the temperature was raised to 120 ° C. At this temperature, 150 parts of tert-butylstyrene, tert
-220 parts of butyl methacrylate, 300 parts of i-butyl methacrylate, 100 parts of cyclohexyl methacrylate, 100 parts of 2-ethylhexyl methacrylate.
Department,

100 parts of "SH-6018" (hydroxyl group-containing silicone compound), 10 parts of acrylic acid, 10 parts of "ADEKA STAB LA-82" and 10 parts of methacryloxyethyltrimethoxysilane, and tert-butyl perocto A mixture of 40 parts of ate and 10 parts of tert-butyl perbenzoate was added dropwise over 4 hours.

After the completion of dropping, the solution was kept at 120 ° C. for 8 hours to obtain a solution of a vinyl polymer (B) having a nonvolatile content of 59.0% and a viscosity of Y.
Next, this resin solution was gradually depressurized to 500 mg to obtain a mixture of monomers and solvents,
A quantity of 50 parts was distilled, so here, "LAW
By adding 35 parts of "S", a desired solution of the vinyl polymer (B) having a nonvolatile content of 59.5%, a viscosity of Z and an acid value of 4.8 was obtained. Hereinafter, this is referred to as a polymer (B
-1) is abbreviated.

Reference Example 8 (same as above) In the same four-necked flask as in Reference Example 3, 571 parts of the resin (b-3-1) obtained in Reference Example 1 and 16 of "LAWS" were added.
Charge 2 parts and 333 parts of "A Solvent"
The temperature was raised to 20 ° C.

At the same temperature, 90 parts of i-propyl methacrylate, 150 parts of tert-butyl methacrylate,
200 parts of i-butyl methacrylate, 150 parts of 2-ethylhexyl acrylate and 10 parts of monobutyl maleate and 35 parts of tert-butyl peroctoate.
Part and 10 parts of tert-butyl perbenzoate were added dropwise over 4 hours.

Even after the completion of dropping, the vinyl copolymer (B) having a nonvolatile content of 60%, a viscosity of T and an acid value of 2.2 is maintained at 120 ° C. for 8 hours.
A solution of Hereinafter, this is abbreviated as copolymer (B-2).

Reference Example 9 (Same as above) A 4-necked flask similar to Reference Example 3 was charged with 1,000 parts of the resin (b-3-1) obtained in Reference Example 1 and "Exol D-40". After charging with 366 copies,
As the monomers, 200 parts of tert-butyl methacrylate and 100 parts of n-butyl acrylate,

The radical generators are te
20 parts of rt-butyl peroctoate and tert
In the same manner as in Reference Example 8 except that 10 parts of -butyl perbenzoate was used, the nonvolatile content was 60%.
Thus, a solution of the vinyl polymer (B) having a viscosity of U and an acid value of 2.0 was obtained. Hereinafter, this is a polymer (B-3)
Abbreviated.

Reference Example 10 (same as above) In a four-necked flask similar to Reference Example 3, 142 parts of the resin (b-3-2) obtained in Reference Example 1 and 4 of "LAWS" were added.
After charging 100 parts, as the monomers, 100 parts of methyl methacrylate,

142 parts of the modified silicone compound obtained in Reference Example 4 and 250 parts of tert-butyl methacrylate
Parts, 200 parts of i-butyl methacrylate, 50 parts of n-butyl methacrylate, 150 parts of “Acryester SL”, 50 parts of β-hydroxyethyl acrylate,

As an additional solvent, 1 of "LAWS" is used.
In the same manner as in Reference Example 8 except that 84 parts were used and, as radical generators, 30 parts of tert-butyl peroctoate and 10 parts of tert-butyl perbenzoate were used. The nonvolatile content is 60%, the viscosity is Z ₁ , the acid value is 0.9, and
A solution of the vinyl polymer (B) having a hydroxyl value of 22 was obtained. Hereinafter, this is abbreviated as polymer (B-4).

Reference Example 11 (Same as above) [0176]
After charging 170 parts of "E" and 581 parts of "A solvent", 100 parts of tert-butylstyrene and 286 parts of the modified silicone compound obtained in Reference Example 5 were used as the monomers. ,further,

130 of tert-butyl methacrylate
Parts, i-butylmethacrylate 100 parts, 2-ethylhexylmethacrylate 94 parts, "acryester
50 parts of "SL", 50 parts of i-propyl acrylate,
Using a mixture of 56 parts of β-hydroxyethylmethacrylate and 50 parts of acrylic acid,

One hour after the completion of dropping, the reaction temperature was set to 1
Reference Example 8 except that the temperature was raised to 30 ° C. and the temperature was kept at the same value until the acid value became 5 or less.
In the same manner as above, a solution of the vinyl polymer (B) having a nonvolatile content of 60%, a viscosity of X, an acid value of 3.5, and a hydroxyl value of 38 was obtained. Hereinafter, this is a polymer (B-5)
Abbreviated.

Reference Example 12 (same as above) In a four-necked flask similar to Reference Example 3, 83 parts of the resin (b-3-3) obtained in Reference Example 3 and 55 of "LAWS" were used.
After charging with 8 parts, as monomers,
100 parts of tert-butyl styrene, 375 parts of the modified silicone compound obtained in Reference Example 6, 150 parts of isobornyl methacrylate, 250 parts of i-butyl methacrylate, 100 parts of lauryl methacrylate, of β-hydroxyethyl acrylate Modified to use a mixture consisting of 40 parts and 10 parts of monobutylmalate,

The radical generators are te
40 parts of rt-butyl peroctoate and tert
In the same manner as in Reference Example 8 except that 10 parts of -butyl perbenzoate was used, the nonvolatile content was 60%.
, The viscosity is W, the acid value is 2.2, and the hydroxyl value is 1.
A solution of vinyl polymer (B) 2 was obtained. Hereinafter, this is abbreviated as polymer (B-6).

Reference Example 13 (same as above) In a four-necked flask similar to Reference Example 3, resin (b-3-1) and resin (b) obtained in Reference Examples 1 and 2 were obtained.
-3-2) and 143 copies each, and "WAWS" 49
After charging 4 parts, as monomers,
100 parts of tert-butylstyrene, 286 parts of the modified silicone compound obtained in Reference Example 4,

220 parts of isobornyl acrylate, 4
-Tert-butylcyclohexyl methacrylate 1
Modified to use a mixture consisting of 50 parts, 100 parts of “Acryester SL”, 40 parts of β-hydroxyethyl acrylate, 20 parts of 1,4-butanediol monoacrylate and 10 parts of monobutylmalate,

The radical generator is ter
A nonvolatile content of 60% was obtained in the same manner as in Reference Example 8 except that 40 parts of t-butyl peroctoate and 10 parts of tert-butyl perbenzoate were used.
Thus, a solution of the vinyl polymer (B) having a viscosity of X, an acid value of 2.3 and a hydroxyl value of 27 was obtained.
Hereinafter, this is abbreviated as polymer (B-7).

Reference Example 14 (same as above) 525 parts of dehydrated castor oil fatty acid, 19 of isophthalic acid
Parts, 8 parts of maleic anhydride, 5 parts of pentaerythritol
9 parts and 92 parts of 1,6 hexanediol were charged and the temperature was raised to 220 ° C.

Reaction is carried out in a nitrogen gas atmosphere until the acid value becomes 15 or less, and when the acid value reaches the target value,
Decrease the temperature to 130 ° C, and change to "TSR-165"
00 parts and 0.2 parts of tetraisopropyl titanate were charged, and the nonvolatile content was 70% and the viscosity was the same as in Reference Example 1 except that the reaction was carried out until the acid value became 7 or less. Was Z, the acid value was 3.5, and the oil length was 55% to obtain a solution of a medium oil alkyd resin as a target polymer. Hereinafter, this is abbreviated as polymer (B-8).

Reference Example 15 (same as above) 400 parts of safflower oil fatty acid, 269 parts of dehydrated castor oil fatty acid, 62 parts of phthalic acid, 128 parts of trimethylolpropane, 200 parts of "KR-216" and 3 parts of pentaerythritol. I changed to use the section, and moreover,
As the solvent, except that the "Shellzol D-40" was changed to be the same as in Reference Example 14, the nonvolatile content was 70%, the viscosity was Y, and the acid value was 3.5. In addition, a solution of a long oil alkyd resin as an objective polymer having an oil length of 70% was obtained. Hereinafter, this is abbreviated as polymer (B-9).

Example 1

The method of producing the non-aqueous dispersion resin composition according to the present invention will be specifically described with reference to this example.

In a four-necked flask equipped with a reflux condenser, a thermometer, an inert gas inlet and a stirrer, 333 parts of the polymer (B-1) obtained in Reference Example 7 and "LAWS" 534 parts were charged and the temperature was raised to 90 ° C.

After reaching this temperature, 200 parts of methyl methacrylate, 300 parts of vinyl acetate, 292 parts of ethyl acrylate and 8 parts of acrylic acid, te
20 parts of rt-butyl peroctoate and tert
-A mixture of 5 parts of butyl perbenzoate,
It was added dropwise over 4 hours.

After completion of dropping, the temperature was maintained at 90 ° C. until the monomer conversion reached 99%, and then about 500 m.
Unreacted monomers were removed by vacuum distillation at mHg.

Then, by "WAWS", the non-volatile content was diluted to 60%, and the non-volatile content was 60%.
A target non-aqueous dispersion resin composition having a Brookfield viscosity at 5 ° C. (hereinafter also abbreviated as viscosity) of 4,100 cps and an acid value of 3.5 was obtained. Hereinafter, this is abbreviated as (Bu-1).

Examples 2 to 10 The target non-aqueous dispersion resin composition was prepared in the same manner as in Example 1 except that the raw materials were used in the proportions shown in Table 1. (Bu-2)
~ (Bu-10) were obtained.

However, in the case of Examples 2 to 4, the unreacted monomers were removed by blowing nitrogen gas, not by distillation under reduced pressure. In the case of 10 to 10, unreacted monomers were not removed at all.

The property values (characteristic values) of the various non-aqueous dispersion resin compositions obtained here are summarized in the second
It is shown in the table.

[0196]

[0197]

[0198]

[Table 3]

<< Footnotes in Table 1 >> Each numerical value in the table is the number of copies.

In the table, the terminology (item) of "monomers" is provided to avoid the term "vinyl-based monomers" for the purpose of notation. It should be understood that the terms “monomers” are synonymous with “vinyl-based monomers” and are merely abbreviations, without any special meaning.

"Tert-butyl perocto" ...
Abbreviation for "tert-butyl peroctoate"

"Tert-butylperbenzo" ...
Abbreviation for "tert-butyl perbenzoate"

"1,1-bis (tert-bub)" ...
Abbreviation of "1,1-bis (tert-butylperoxy) hexanone"

[0204]

[Table 4]

[0205]

[Table 5]

[0206]

[Table 6]

<< Footnote in Table 1 >>"[beta]-HEA" ...
………………… Abbreviation for β-hydroxyethyl acrylate

"Perfluorocyclohexyla" ...
Abbreviation of "perfluorocyclohexyl acrylate"

[LA-82] ………………………………
Abbreviation of "ADK STAB LA-82"

[0210]

[Table 7]

[0211]

[Table 8]

<< Footnote in Table 1 >> Abbreviation of "1,4-butanediol monoacrylate" ... "1,4-butanediol monoacrylate"

[Chemisorb 74] is a product of Chemipro Corporation.
It is the trade name of the ultraviolet absorber made by.

[0214]

[Table 9]

Examples 11 to 26 and Comparative Examples 1 to 3

This example was obtained in the previous Examples 1-10.
Using each non-aqueous dispersion resin composition,
This is to prepare the resin composition for coating material of the present invention.

That is, obtained in Examples 1 to 10,
Each of the non-aqueous dispersion resin compositions (Bu-1) to (Bu-10) was used, and the non-aqueous dispersion resin composition was made to be kneaded by a conventional method according to the kneaded meat composition shown in Table 3. Yes,

Then, a cross-linking agent component was also compounded according to the composition of the kneaded meat as shown in Table 4 to obtain the intended resin composition for coating.

Each of the paints thus obtained was diluted with "LAWS" as a thinner, and the paint viscosity was determined by Ford Cup No. After being diluted with No. 4 for 30 seconds, it was spray-coated on a Bonde # 144-treated dull steel plate so that the dry film thickness was 50 microns (μm).

Then, in each of Examples 11 to 23, each Example was left to stand at room temperature for 2 weeks to be dried and cured.
In the case of No. 4, by carrying out forced drying at 80 ° C. for 30 minutes, Examples 25 and 26 are further obtained, and 140 ° C. in each case.
In the above, baking and drying were carried out for 30 minutes, and thereafter, the film was allowed to stand at room temperature for 1 week to obtain various cured coating films.

Then, with respect to each of the thus obtained cured coating films, various performances were evaluated and examined. In addition, in each case of Comparative Examples 1 to 3, three types of commercially available products were used.

The outline of various physical properties and performance evaluation tests of various coating materials is as follows.

(1) Odor test: Based on the overall judgment of the sensory test by 5 persons. ◎ ………… No odor ○ ……… There is a slight odor

(2) Hikarizawa ………… 60 degree specular reflectance (%)

(3) Hardness ......... Hardness with scratches by pencil

(4) Adhesiveness: Based on a cross-cut adhesion test.

(5) Acid resistance: The coated surface state was visually evaluated after performing a spot test for 24 hours with a 5% sulfuric acid aqueous solution.

(6) Alkali resistance: The coated surface state was visually evaluated after a spot test was conducted for 24 hours with a 5% aqueous sodium hydroxide solution.

(7) "Recoatability" for old paint film
Of the old coating film (existing coating film) after the natural exposure for 2 years, each coating was individually coated and the state of the coated surface was visually determined.

[0230] ◎ ... No abnormalities ○ ......... Lifting phenomenon is recognized, although it is very slight. △ ......... Lifting phenomenon is observed to a considerable extent. X ......... Remarkable lifting phenomenon is recognized.

(8) The coating composition and the suitability test in the "overcoating suitability" are as follows.

Coating composition: [Coating (a)-(1) / Coating (a)-(2) / Coating (b) / Substrate slate plate]

Procedure: Coating film (a) for the first coat-
After coating (2), it is left at 30 ° C. for about 6 seconds, and then the same paint is applied on the coating film (a)-(1). The coating film (a)-(2), which is the top coat of the eyes, causes lifting.

The above-mentioned coating film (b) is a mastic paint layer, and the mastic paint therefor has the following composition.

“Taipaque R-550” [trade name of titanium oxide manufactured by Ishihara Sangyo Co., Ltd. 100 parts] “Demol EP” [dispersant manufactured by Kao Corporation] 3 parts “Neugen EA-120” [ Daiichi Kogyo Seiyaku Co., Ltd. 1.5 parts, trade name of emulsifier] Ethylene glycol 3 parts "SN Deformer 154" [San Nop 1.5 parts, trade name of blowing agent, Co., Ltd.] 28% Ammonia water 1 part Water 24 parts 2% "Hydro-Metroses 90SH-100" 18.6 parts [Shin-Etsu Chemical Co., Ltd. product name of thickener] "Boncoat 3650" [Dainippon Ink and Chemicals 104 6 parts Acrylic emulsion product name manufactured by Gaku Kogyo Co., Ltd.] “Self-top HP-103” [trade name of thickener manufactured by 1.1 part Kojin Co., Ltd.]

(9) Regarding the influence of the solvent used on the material (that is, the influence of the solvent on the plastic material), the degree of occurrence of solvent cracks was visually judged.

∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙

[0238]

[Table 10]

<< Footnotes in Table 3 >> Each numerical value in the table is the number of "copies".

Note 1) Abbreviation of “CR-95” ………… “Taipec CR-95” [trade name of rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.]

Note 2) “LAWS” was used.

Note 3) "Skinner TM" [trade name of Toagosei Chemical Industry Co., Ltd.] was used.

Note 4) "KP-324" [trade name of Shin-Etsu Chemical Co., Ltd.] was used.

[0244]

[Table 11]

[0245]

[Table 12]

[0246]

[Table 13]

<< Footnotes in Table 4 >> Each numerical value in the table is the number of copies. The amounts of the cross-linking agent components other than cobalt naphthenate and lead octylate are all expressed in terms of solid content.

The term "6% cobalt naphthenate" means that the metal cobalt content (that is, the active ingredient content) is 6%.

The term "24% lead octylate" means that the content of metallic lead (that is, the content of active ingredient) is 24%.

[0250]

[Table 14]

<< Footnote in Table 4 >>"Long oil alkyd coating",
"Vinegar-acrylic coating", "NAD acrylic coating",
Both "acrylic lacquer coating film" and "overcoating property" are data for showing "recoating property".

The "vinyl acetate-acrylic coating" is a coating of vinyl acetate-acrylic copolymer resin.

[0253]

[Table 15]

<< Footnote in Table 4 >> Both "PPO resin" and "polycarbonate" are data for showing "influence on plastic material".

[0255]

[Table 16]

<< Footnote in Table 4 >>"Aluminum chelate A" ... An aluminum chelate manufactured by Kawaken Fine Chemical Co., Ltd., which was used in the form of a 40% acetylacetone solution.

“AIPD” ……………… Aluminum alcoholate manufactured by Kawaken Fine Chemicals Co., Ltd., which has a nonvolatile content (NV) of 100%, but is in the form of a 40% i-propanol solution. I used it.

[0258]

[Table 17]

[0259]

[Table 18]

[0260]

[Table 19]

<< Footnotes in Table 4 >>"TP-110" ... "Tencalate TP-11"
0 ”(Titanium chelate manufactured by the above-mentioned company; NV = 33%, effective titanium chelate content = 60%)

"ZC-540" ... Abbreviation of "Organics ZC-540" (zirconium chelate manufactured by the above-mentioned company; NV = 60%).

"DN991S" ......... "Barnock D
N-991S "(Terpen-soluble polyisocyanate compound manufactured by the above-mentioned company; NV = 100%, NCO content = 13.
%) Abbreviation

[0264]

[Table 20]

[0265]

[Table 21]

[0266]

[Table 22]

<< Footnote in Table 4 >>"L-161" ......... "Super Beckamine L"
-161 ", butylated melamine resin; N
V = 98%

[0268]

[Table 23]

[0269]

[Table 24]

[0270]

[Table 25]

[0271]

[Table 26]

[0272]

[Table 27]

[0273]

[Table 28]

<< Footnotes in Table 5 >> 1) Natural Bakuro …………………… Miyazaki City Suburbs 2nd Year Bakuro

2) Accelerated weathering test ......... Sunshine weather test; 2,000 hours (JIS method)

As described above, the non-aqueous dispersion resin composition according to the present invention has little effect on the old coating film (existing coating film), and moreover, especially, various coating film performances such as weather resistance. Compared with the conventional type using organic solvents, it is not less inferior than that of the conventional type, and is extremely highly practical. Therefore, such a non-aqueous dispersion resin composition for paint is an essential component. Contained as,
The coating resin composition of the present invention is also an old coating film (existing coating film).
The effect on the coating film is small, and in particular, it is also excellent in various coating film properties such as weather resistance.

[0277]

INDUSTRIAL APPLICABILITY As described above, the non-aqueous dispersion resin composition according to the present invention has a low viscosity, is less likely to sag during coating work, and does not attack the old coating film (existing coating film). (NAD) Resin retains its original characteristics, and in particular, various coating film performances such as weather resistance are better than those of conventional organic solvents.
It is extremely practical, being as good as winning.

Therefore, this non-aqueous dispersion resin composition for paint is contained as an essential component,
The coating resin composition of the present invention is also an old coating film (existing coating film).
The effect on the coating film is small, and in particular, various coating film properties such as weather resistance are excellent.

Claims (14)

[Claims] 1. A polymer soluble in the above organic solvent in an organic solvent in which vinyl monomers are soluble but the vinyl polymer (A) obtained from these monomers is insoluble. B)
In the stable non-aqueous dispersion type resin composition obtained by copolymerizing the above vinyl-based monomers in the presence of, a polymer (B) soluble in the organic solvent is a silicone compound. Has been modified,
Moreover, about 1 to about 60% by weight of this silicone compound
A non-aqueous dispersion type resin composition characterized by being contained within the following range. 2. The vinyl polymer (A) is an alkyl side chain having 1 or 2 carbon atoms as a monomer having a copolymerizable unsaturated double bond forming the polymer (A). A vinyl ester of α, β-unsaturated (di) carboxylic acid excluding (meth) acrylic acid ester and (meth) acrylic acid having a vinyl ester and vinyl acetate as essential components, The non-aqueous dispersion type resin composition according to claim 1. 3. The composition ratio of the above polymer (B) to the above vinyl polymer (A) is in the range of about 10 to about 90 / about 90 to about 10 in terms of solid content weight ratio. The non-aqueous dispersion type resin composition according to claim 1, wherein 4. The above-mentioned silicone compound is represented by the general formula [I]: (However, R is at least one functional group monovalent organic group or copolymerizable unsaturated double bond selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which are bonded to a carbon-silicon bond. R '
Is a hydrogen atom or an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group, and n is a number in the range of 0.5 to 2.0, and m is It is assumed that the number is within the range of 0.0 to 2.5, and m + n is 0.5 to 3.0.
Shall be a number within the range. ) Is an organopolysiloxane having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, an alkoxy group, an aryloxy group and an acyloxy group, or in one molecule, At least 1
The non-aqueous dispersion type resin composition according to claim 1, which is an organopolysiloxane having one copolymerizable unsaturated double bond. 5. The above-mentioned silicone compound is represented by the general formula [I]: (However, R represents at least one functional group monovalent organic group or copolymerizable unsaturated double bond selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which are bonded to a carbon-silicon bond. R '
Is a hydrogen atom or an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group, and n is a number in the range of 0.5 to 2.0, and m is It is assumed that the number is within the range of 0.0 to 2.5, and m + n is 0.5 to 3.0.
Shall be a number within the range. ), A reaction product of a compound having both a functional group having reactivity with a functional group possessed by the organopolysiloxane and a compound having a copolymerizable unsaturated double bond. Item 2. The non-aqueous dispersion type resin composition according to Item 1. 6. The above-mentioned polymer (B) soluble in an organic solvent comprises about 1 to about 60% by weight of a silicone compound for modifying the polymer (B), and the polymer (B). It is composed of about 40 to about 99% by weight of monomers having a copolymerizable unsaturated double bond for forming, and the total amount of each of these components is 100% by weight.
It is what is obtained by using so that it becomes.
The non-aqueous dispersion type resin composition according to. 7. The above-mentioned polymer (B) soluble in an organic solvent has a carbon number as a monomer having a copolymerizable unsaturated double bond for forming the polymer (B). Three
At least 20% by weight of the above-mentioned (meth) acrylic acid ester (b-1) having an alkyl side chain and / or styrene-based monomers (b-2) having an alkyl side chain having 3 or more carbon atoms. The non-aqueous dispersion type resin composition according to any one of claims 1 to 4, which is obtained by being used as described above. 8. The above-mentioned polymer (B) soluble in an organic solvent has a carbon number as a monomer having a copolymerizable unsaturated double bond for forming the polymer (B). Three
20 to 20 of the above-mentioned (meth) acrylic acid esters (b-1) having an alkyl side chain and / or a styrene-based monomer (b-2) having an alkyl group side chain having 3 or more carbon atoms
98% by weight and a copolymerizable unsaturated double bond-containing resin (b-
0 to 80% by weight of 3) and the above-mentioned monomers (b-1)
And 2 to 80% by weight of the other vinyl-based monomers (b-4) copolymerizable with (b-2), and each of these monomers Is 10
The non-aqueous dispersion type resin composition according to any one of claims 1 to 5, which is obtained by using so as to be 0% by weight. 9. The above-mentioned polymer (B) soluble in an organic solvent is an oil-modified alkyd resin having an oil length of at least 50% and has the general formula [I]: (However, R is at least one functional group monovalent organic group or copolymerizable unsaturated double bond selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which are bonded to a carbon-silicon bond. R '
Is a hydrogen atom or an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group, and n is a number in the range of 0.5 to 2.0, and m is It is assumed that the number is within the range of 0.0 to 2.5, and m + n is 0.5 to 3.0.
Shall be a number within the range. ) Is modified with a silicone compound represented by the formula (1), and comprises about 40 to about 99% by weight of the oil-modified alkyd resin and about 1 to about 60% by weight of the silicone compound. The non-aqueous dispersion type resin composition according to claim 1, which is obtained by using the oil-modified alkyd resin and the silicone compound in a total amount of 100% by weight. 10. When the unreacted monomers remaining in the obtained non-aqueous dispersion type resin composition are contained in an amount of about 3% by weight or more based on the solvent for the non-aqueous dispersion type resin. 2. The non-aqueous dispersion type resin composition according to claim 1, which is obtained by distilling off these unreacted monomers until the amount becomes less than about 3% by weight in the solvent. 11. A resin composition for paints, characterized in that a dryer is added as a curing accelerator to the non-aqueous dispersion type resin composition according to any one of claims 1 to 10. 12. The non-aqueous dispersion type resin composition according to claim 1, wherein the curing agent is at least one selected from the group consisting of metal alkoxides, metal acylates and metal chelates. A resin composition for paints, characterized in that the compound of (1) is added. 13. A resin composition for paint, comprising the polyisocyanate compound as a curing agent in the non-aqueous dispersion type resin composition according to any one of claims 1 to 10. 14. A resin composition for paints, characterized in that the non-aqueous dispersion type resin composition according to any one of claims 1 to 10 is blended with amino resins as curing agents.