JPH09169807A - Nonaqueous dispersion type resin and coating resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonaqueous dispersion type resin which is lowly viscous, scarcely sags when it is applied, does not attack the old coating film and is excellent in weather resistance, etc., by copolymerizing a vinyl monomer in an organic solvent which does not dissolve vinyl polymer A comprising a vinyl monomer in the presence of polymer B soluble in the solvent and modifying the obtained copolymer with a silicone compound. SOLUTION: The polymer B/polymer A ratio should be (10/90) to 90/10 (in terms of a ratio by weight of solid content). The silicone compound is an organopolysiloxane (e.g. SH-6018) represented by formula I (wherein R is a functional group bonded to a C-Si bond and is carboxyl, epoxy, an alkoxyl, a monovalent organic group or a copolymerizable double bond; R' is H, an alkyl, an aryl, an acyl, an aryloxy or an acyloxy; (n) is 0.5-2.0; (m) is 0.0-2.5; and (m+n)=0.5-3.0). The amount of the silicone compound contained in polymers A and B is 1-60wt.%. The organic solvent is, for example, LAWS.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful method for producing a non-aqueous dispersion type resin, and a novel and useful coating material containing the resin as an essential film-forming component. It relates to a resin composition.

More specifically, the present invention comprises a specific non-aqueous dispersion type resin in which both the dispersed particles and the dispersion stabilizer are modified with a silicone compound, and the resin is used. Regarding the resin composition for paint, these resins and the resin composition for paint are both
Above all, from the point that it is excellent in weather resistance of the coating film,

In particular, it is also useful as a paint for building exteriors, and also as a paint for automobile repairs or a paint for baking, which is different from the conventional ones using organic solvents. The present invention relates to a highly practical non-dispersion type resin and a resin composition for coating material using the resin, each of which has very little effect on the coating film (existing coating film).

Moreover, the non-aqueous dispersion type resin for paints and the non-aqueous dispersion type resin having various coating film properties which are not inferior to those of the conventional type using organic solvents. The present invention relates to a resin composition for coating material, which comprises a resin.

[0005]

2. Description of the Related Art Non-aqueous dispersion type resins are used as binders for interiors and exteriors of buildings, metals, automobiles, etc. However, in order to stably form dispersed particles in a solvent, , Vinyl compounds such as vinyl acetate, which are not particularly good in weather resistance, and lower alkyl esters of (meth) acrylic acid such as (meth) acrylic acid methyl ester and (meth) acrylic acid ethyl ester However, since there is no choice but to use a relatively large amount, the degree of freedom in resin design is naturally limited, and there is no need for dispersed particles. In particular, it tends to be inferior in terms of weather resistance and the like.

[0006] In recent years, with the increasing awareness of environmental issues and the revision of the Odor Control Law, complaints about odors caused by organic solvents, unreacted monomers and the like have been increasing. However, it is urgently necessary to respond to the problem, but as one of the solutions to this problem, the present inventors have already disclosed in
One technique is disclosed as disclosed in Japanese Patent No. 184490.

[0007]

As described above, in the conventional technology, the non-aqueous dispersion type resin is
In fact, it has not been developed yet that it can provide sufficient weather resistance and the like.

[0008] Therefore, the problem to be solved by the present invention is, in part, a non-aqueous dispersion type resin.
In particular, it is an improvement in weather resistance and the like, which is obtained by using the obtained resin, in particular, is also excellent in weather resistance, in addition, has little influence on the old coating film, and further Also provided are a non-aqueous dispersion type resin having extremely high practicability and a resin composition for a coating obtained by using the resin, in which various performances of the membrane are not different from those of a conventional solvent type. Especially.

[0009]

Means for Solving the Problems Accordingly, the present inventors have:
Focusing on the problems to be solved by the invention as described above, as a result of intensive and thorough studies, a polymer (A) that does not dissolve in an organic solvent, and a polymer (B) that dissolves in an organic solvent It has been found that, by modifying (comprising) a silicone compound as an essential component for both of them, the weather resistance and the like of the non-aqueous dispersion type resin can be improved. Thus, the present invention has been completed here.

That is, in the present invention, basically, vinyl monomers (vinyl monomers) are dissolved,
By copolymerizing the vinyl-based monomers in the presence of the polymer (B) soluble in the organic solvent in a specific organic solvent in which the copolymer (A) of the monomers is insoluble, A stable non-aqueous dispersion comprising the polymer (A) and the polymer (B) containing a silicone compound as an essential component thereof,

More specifically, the above silicone compound is contained in the above-mentioned polymer (A) and polymer (B) at a specific ratio of about 1 to about 60% by weight. It is intended to provide a non-aqueous dispersion type resin that consists of containing

More specifically, for example, each of the above-mentioned silicone compounds has the following general formula [I]

[0013]

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One molecule of at least one functional group or copolymerizable unsaturated double bond 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 The present invention also aims to provide a non-aqueous dispersion type resin, which is a specific organopolysiloxane containing at least one or more therein.

Alternatively, in more detail, the above-mentioned silicone compound is a hydroxyl group, a carboxyl group, an epoxy group, an alkoxy group, an aryloxy group or an acyloxy group represented by the above-mentioned general formula [I]. A specific organopolysiloxane containing at least one functional group or copolymerizable unsaturated double bond selected from the group consisting of at least one in one molecule, and It is also an object of the present invention to provide a non-aqueous dispersion type resin comprising a silicone compound in an amount of about 1 to about 60% by weight.

Further, in the present invention, specifically, for example, a vinyl-based monomer can be dissolved, but a vinyl-based polymer (A) composed of the monomer can not be dissolved. For a coating material using a stable non-aqueous dispersion type resin obtained by copolymerizing vinyl monomers in the presence of a polymer (B) soluble in the organic solvent In the resin composition, the polymer (A) of the vinyl monomer and the polymer (B) described above are both modified with a silicone compound, which is novel. It is also intended to provide a resin composition for paints,

Alternatively, each of the above-mentioned polymers (A) and (B) may contain the above-mentioned silicone compound in a specific ratio of about 1 to about 60% by weight. The present invention also aims to provide a resin composition for paints,

In addition, in the present invention, specifically, the ratio of the above-mentioned polymer (B) to the above-mentioned polymer (A) is, for example, polymer (B) / polymer (A). In terms of solids parts by weight, about 10 to about 90 / about 90 to about 1
The present invention is also intended to provide a specific coating resin composition that is within the range of 0,

In addition, the content of unreacted monomers (monomers) remaining in the coating resin composition with respect to the organic solvent is 3% by weight or more based on the organic solvent. In certain special cases, such unreacted monomers may be distilled off to less than 3% by weight to provide a particular coating resin composition which is also reduced. It is what

Further, for various types of non-aqueous dispersion resins as described above,
As a curing accelerator, for example, it is intended to provide a specific coating resin composition in the form of blending a dryer,

The present invention is also intended to provide a specific coating resin composition in the form of being mixed with, for example, a metal alkoxide, a metal acylate or a metal chelate as a curing accelerator.

Further, further, a specific resin composition for coating composition in which a polyisocyanate compound as a curing agent is added to each of the various types of non-aqueous dispersion type resins as described above. The present invention also aims to provide a resin composition for a specific coating material in the form of a compound or an amino resin as a curing agent.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, first of all, a specific organic compound in which vinyl-based monomers are dissolved but a vinyl-based polymer (A) composed of the monomers is not dissolved is described. A stable non-aqueous dispersion type resin, which is stable by copolymerizing vinyl monomers in a solvent in the presence of a polymer (B) soluble in the organic solvent, Monomer polymer (A)
And the above-mentioned polymer (B) are both modified with a silicone compound to claim a novel non-aqueous dispersion type resin,

Next, in a specific organic solvent in which the vinyl-based monomers are dissolved but the vinyl-based polymer (A) composed of the monomers is not dissolved, a heavy solvent which can be dissolved in the organic solvent is used. A non-aqueous dispersion type resin which is stable by copolymerizing vinyl-based monomers in the presence of the polymer (B), which is the above-mentioned polymer (A) of vinyl-based monomer and And the polymer (B) prepared above are both modified with a silicone compound, and the silicone compound is contained in an amount of about 1 to about 60% by weight. It also claims a non-aqueous dispersion type resin,

The silicone compound is at least 1 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 the above-mentioned general formula [I]. A particular non-aqueous dispersion type resin consisting of a particular organopolysiloxane having at least one functional group or copolymerizable unsaturated double bond in one molecule,

Alternatively, this silicone compound is copolymerized with a specific organopolysiloxane represented by the above-mentioned general formula [I] and a functional group reactive with a functional group contained in the organopolysiloxane. And a specific non-aqueous dispersion type resin in the form of being a reaction product of a compound having both an unsaturated unsaturated bond and a compound,

The above-mentioned vinyl polymer (A) which is composed of monomers soluble in an organic solvent and is insoluble in the organic solvent is a silicone compound which modifies the polymer (A). About 1 to about 60% by weight of the polymer (A)
Of about 40 to about 99% by weight of the monomers having a copolymerizable unsaturated double bond, which form the above-mentioned monomer, and the total amount of each of these monomers is 100% by weight. It also claims a specific non-aqueous dispersion type resin in the form that it is used.

Polymer (B) soluble in the above-mentioned organic solvent
Of the silicone compound that modifies the polymer (B).
To about 60% by weight and about 40 to about 99% by weight of the monomers having a copolymerizable unsaturated double bond forming the polymer (B), and It also claims a specific non-aqueous dispersion type resin in such a form that the total amount of each of these monomers is 100% by weight.

The above-mentioned vinyl-based polymer (A), which is composed of monomers soluble in an organic solvent and is insoluble in the organic solvent, forms the polymer (A). (Meth) acrylic acid esters having an alkyl group side chain having 1 or 2 carbon atoms as monomers having a double bond, α, β-ethylenically unsaturated (poly) except for (meth) acrylic acid Carboxylic acid esters and /
Alternatively, a specific non-aqueous dispersion type resin having a shape obtained by using vinyl acetate as a main component;

That is, the polymer (A) which does not dissolve in the organic solvent has an alkyl group side chain having 1 to 2 carbon atoms as a main component of the vinyl-based monomers forming the polymer (A). (Meth) acrylic acid esters, (meth) acrylic acid-excluding (meth) acrylic acid esters and / or vinyl acetate in the form of being obtained using vinyl acetate , A specific non-aqueous dispersion type resin is also claimed,

The above-mentioned polymer (B) soluble in an organic solvent is an alkyl group having 3 or more carbon atoms as monomers having a copolymerizable unsaturated double bond forming the polymer (B). A form obtained by using vinyl-based monomers containing at least about 20% by weight or more of styrene-based monomers having a (meth) acrylic acid ester having a side chain and / or an alkyl side chain. , A specific non-aqueous dispersion type resin is also claimed,

The above-mentioned polymer (B) soluble in an organic solvent forms the polymer (B) and has (meth) acrylic acid ester (b-1) having an alkyl side chain having 3 or more carbon atoms. And / or about 20 to about 98% by weight of the styrenic monomer (b-2) having an alkyl group side chain.
And 0 to 0 of the copolymerizable unsaturated double bond-containing resin (b-3).
About 80% by weight, and (b-1) and (b-
2) and 2 to 80% by weight of other vinyl-based monomers (b-4) copolymerizable with each of
Moreover, about 30% of the vinyl-based monomer mixture selected such that the total of these monomers is 100% by weight.
To about 99% by weight and about 1 to about 70% by weight of the silicone compound of the general formula [I] as described above, a specific non-aqueous dispersion type. I am also claiming resin,

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 the silicone compound represented by the general formula [I] as described above. Has been denatured with
Moreover, about 40 to about 90% by weight of the oil-modified alkyd
And a specific non-aqueous dispersion type resin in the form of comprising from about 1 to about 40% by weight of the silicone compound.

That is, 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 is represented by the above-mentioned general formula [I]. It has been modified with a silicone compound, and its modification amount is, in terms of parts by weight, oil-modified alkyd resin / silicone compound = about 40 to about 99 / about 1.
To a particular non-aqueous dispersion type resin, such as in the range of about 60 to about 60,

In contrast to the above-mentioned vinyl polymer (A) which is composed of monomers soluble in an organic solvent and is insoluble in the organic solvent, a polymer (B) which is soluble in the organic solvent.
The composition ratio of the polymer (B) / polymer (A) is in the range of about 10 to about 90 / about 90 to about 10 in terms of the solids weight ratio of polymer (B) / polymer (A). It also claims a water dispersion type resin,

In the present invention, first, in a specific organic solvent in which vinyl monomers are dissolved, but vinyl polymer (A) composed of the monomers is not dissolved, In the coating resin composition using a stable non-aqueous dispersion type resin by copolymerizing vinyl monomers in the presence of the polymer (B) which is soluble in the organic solvent, the above-mentioned vinyl is used. Claiming a novel resin composition for coatings, in which the polymer (A) of the base monomer and the above-mentioned polymer (B) are both modified with a silicone compound And

Then, in a specific organic solvent in which the vinyl-based monomers are dissolved but the vinyl-based polymer (A) composed of the monomers is not dissolved, a heavy solvent which can be dissolved in the organic solvent is used. A resin composition for a coating composition, which uses a stable non-aqueous dispersion type resin by copolymerizing vinyl monomers in the presence of the polymer (B),
Both the above-mentioned vinyl monomer polymer (A) and the above-mentioned polymer (B) are modified with a silicone compound, and the silicone compound is added in an amount of about 1 to about 60. It also claims a novel resin composition for coatings, which is composed of the content in the range of% by weight,

The above-mentioned silicone compound is at least one 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 the above-mentioned general formula [I]. Claiming a particular coating resin composition in the form of an organopolysiloxane having at least one functional group or copolymerizable unsaturated double bond in one molecule. And

The above-mentioned silicone compound is at least one 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 the above-mentioned general formula [I]. A kind of organopolysiloxane having at least one functional group or copolymerizable unsaturated double bond in one molecule, and a functional group having reactivity with a functional group present in the organopolysiloxane, It also claims a specific coating resin composition in the form of a reaction product with a compound having a copolymerizable unsaturated double bond,

The vinyl polymer (A) which is composed of the above-mentioned monomers which are soluble in an organic solvent and which is insoluble in the organic solvent is about 1% of the silicone compound which modifies the polymer (A). To about 60% by weight, and about 40% of the monomers having a copolymerizable unsaturated double bond forming the polymer (A).
To about 99% by weight of the particular coating resin composition in the form of,

The above-mentioned vinyl polymer (B) soluble in an organic solvent forms the polymer (B) with about 1 to about 60% by weight of the silicone compound which modifies the polymer (B). About 40 of monomers having a copolymerizable unsaturated double bond
To about 99% by weight of the particular coating resin composition in the form of,

The above-mentioned vinyl polymer (A) composed of monomers soluble in an organic solvent and insoluble in the organic solvent is a copolymer other than the silicone compound forming the polymer (A). (Meth) acrylic acid ester and / or (meth) having an alkyl group side chain having 1 or 2 carbon atoms as the monomer having a polyunsaturated double bond
Α, β-ethylenically unsaturated (poly), excluding acrylic acid
Carboxylic acid esters and / or vinyl acetate,
It also claims a specific coating resin composition in the form of being obtained by using it as a main component,

The above-mentioned polymer (B) soluble in an organic solvent has 3 carbon atoms as monomers having a copolymerizable unsaturated double bond other than the silicone compound forming the polymer (B). For a specific coating material in the form of containing at least 30% by weight or more of the above-mentioned (meth) acrylic acid ester having an alkyl side chain and / or styrene monomer having an alkyl side chain. It also claims a resin composition,

The above-mentioned polymer (B) soluble in an organic solvent has 3 or more carbon atoms as monomers having a copolymerizable unsaturated double bond forming the polymer (B). About 20 to about 98 of (meth) acrylic acid esters (b-1) having an alkyl side chain and / or a styrene-based monomer (b-2) having an alkyl side chain.
% By weight and copolymerizable unsaturated double bond-containing resin (b-3)
0 to about 80% by weight and 2 to 80% by weight of the other vinyl-based monomers (b-4) copolymerizable with the monomers (b-1) and (b-2) described above. %, And the sum of each of these monomers is 10
It also claims a specific coating resin composition in a form such that it is obtained by using it so as to be 0% by weight,

The above-mentioned polymer (B) soluble in an organic solvent is an oil-modified alkyd having an oil length of at least 50%, and has the general formula [I] as described above.
It is modified with a silicone compound represented by the formula (1) and is composed of about 40 to about 99% by weight of the oil-modified alkyd and about 1 to about 60% by weight of the silicone compound. It also claims a specific resin composition for paint in the form of

With respect to the above-mentioned vinyl polymer (A),
The use ratio of the above-mentioned polymer (B) is about 10 to about 90 in terms of the solid part weight ratio of polymer (B) / polymer (A).
/ About 90 to about 10, which is also claimed as a specific coating resin composition,

The unreacted monomers for the non-aqueous dispersion type resin remaining and contained in the coating resin composition according to the present invention are 3% by weight or more based on the above-mentioned organic solvent. In some cases, the unreacted monomers are reduced by distilling to less than 3% by weight, such as
It also claims a specific coating resin composition,

The non-aqueous dispersion type resin obtained as described above is mixed with a dryer as a curing accelerator, and a specific coating resin composition is also described in more detail. It also claims a specific resin composition for coating composition which is compounded in the range of about 0.01 to about 10% by weight,

A specific coating resin composition prepared by blending the non-aqueous dispersion type resin obtained as described above with a metal alkoxide, a metal acylate or a metal chelate as a curing agent, respectively. More specifically, it also claims a specific resin composition for coating composition which is blended in the range of about 0.001 to about 20% by weight based on the resin solid content. ,

A specific coating resin composition prepared by blending the non-aqueous dispersion type resin obtained as described above with a polyisocyanate compound as a curing agent is also described in more detail. And the equivalent ratio of the isocyanate group in the above compound is about 1 /
It also claims a specific coating resin composition that has been compounded within a range of (about 0.2 to about 1.5).

A specific coating resin composition prepared by blending the non-aqueous dispersion type resin obtained as described above with amino resins as curing agents, more specifically, the above resin / the above A specific coating composition in which the amino resins are blended within a range of about 50 to about 90 / about 10 to about 50 in terms of resin solid content ratio. A resin composition for use is also claimed.

<< Structure >>

Here, first, the above-mentioned organopolysiloxane represented by the above-mentioned general formula [I] is, for example, one having a chain structure or a cyclic structure, and a hydroxyl group, It refers to a compound having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an alkoxy group, an aryloxy group and an acyloxy group in one molecule. ,

Of these, particularly representative organopolysiloxanes, particularly, commercially available products of the organopolysiloxane are exemplified by "SH-6018 or BX16-190" (both containing a hydroxyl group. Compound) or "BX16-191" (compound containing epoxy group) [above, product of Toray Dow Corning Silicone Co., Ltd.];

"TSR-160" or "YR-31"
68 "(both are hydroxyl group-containing compounds) or" TSR-1
65 (a methoxy group-containing compound) [product of Toshiba Silicone Co., Ltd.]; "KR-211, KR-212 or KR-213" (above, a hydroxyl group-containing compound), "KR-
216, KR-217 or KR-9218 "(above, a compound containing a methoxy group)," X-22-173A,
X-22-343, KF-101 or KF-10
2 "(above, an epoxy group-containing compound) or" X-22
-3715 "(carboxyl group-containing compound) [Shin-Etsu Chemical Co., Ltd. product];

"SY-231" (methoxy group-containing compound), "SY-409 or SY-430" (both are
Hydroxyl-containing compound) or “SY-550 or VP
-201 "(both are methoxy group-containing compounds) (product of Wacker Chemie, Germany), and more,
Vinylethoxysilane, α-methacryloxypropyltrimethoxysilane or trimethylsiloxyethyl (meth) acrylate or “KR-215 or X
-22-5002 "[produced by Shin-Etsu Chemical Co., Ltd.], and various silicon-based monomers.

By using these silicone compounds, it is possible to modify the vinyl polymer (A) and the vinyl polymer (B), respectively, as described above, by various known and conventional methods.

That is, the copolymerizable unsaturated double bond-containing silicone compound may be copolymerized during the preparation of these vinyl-based polymers, or in these vinyl-based polymers. Alternatively, the functional groups contained in the silicone compound may be reacted with the functional groups contained in the silicone compound and grafted to modify.

A compound having both a functional group of the silicone compound and a group reactive with the functional group;
The reaction product with the silicone compound may be modified according to the type of functional group remaining in the reaction product by a method using various known and commonly used reaction formats.

When the amount of each of these silicone compounds used is less than about 1% by weight, the use effect tends to be difficult to expect, mainly the effect of improving the film, especially the weather resistance. On the other hand, in the case of more than about 60% by weight, the coating film obtained therefrom is inevitably softened depending on the silicone compound used, that is, the coating film formed therefrom is softened, and, in particular, the hardness is increased. , Solvent resistance and anti-adhesion resistance may decrease,

On the contrary, since the formed film becomes hard and brittle, and causes deterioration of mechanical properties,
Either case is not preferred. Therefore, the amount of the silicone compound used is appropriately within the range of about 1 to about 60% by weight, and particularly within the range of 3 to 50% by weight.

In the non-aqueous dispersion type resin according to the present invention, the above-mentioned polymer (B) which is a so-called dispersion stabilizer and should be used for preparing the resin, which is soluble in an organic solvent, is described. Then, when the polymer (B) is an acrylic copolymer, it is used as an essential raw material component thereof, as described above.
Alkyl acrylates (alkyl acrylates) or methacryls having alkyl groups having 3 or more carbon atoms in the side chains, particularly having an alkyl group in the range of C _{3 to} C ₁₈ in the side chains. If only typical examples of the acid alkyl esters (alkyl methacrylates) (b-1) are given, the following general formula [II] may be used.

[0063]

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

Examples thereof include compounds represented by

As only specific examples of the alkyl acrylates or alkyl methacrylates (b-1), propyl (meth) acrylate, iso (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 or lauryl (meth). Acrylate,

[0067] "ACRYESTER SL" [manufactured by Mitsubishi Rayon (Co.), C ₁₂ - trade name / C ₁₃ methacrylate mixture, stearyl (meth) acrylate, 4-tert
-Butylcyclohexyl (meth) acrylate or isobornyl (meth) acrylate or adamantyl (meth) acrylate.

The styrenic monomers (b-2) having an alkyl group on the side chain are usually C ₁ -C
₄ refers to a compound having an alkyl group in the side chain in the range of _{4, and the} monomer (b-
If only typical examples are exemplified as 2), the general formula [III]

[0069]

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[In the formula, R represents an alkyl group represented by -C _n H _{2n + 1} (where n is an integer of 1 to 4). ]

Examples thereof include compounds represented by

Specific examples of such styrenic monomers (b-2) are not particularly limited, and vinyltoluene, p-methylstyrene, ethylstyrene,
Propylstyrene, isopropylstyrene or pt
tert-butylstyrene and the like.

As described above, various alkyl acrylates or alkyl methacrylates (b-
1) and / or styrenic monomers (b-2)
Are used for the purpose of imparting to the obtained copolymers at least one kind of solvent having a weak dissolving power, which is to be dissolved in a specific solvent as described later. Therefore, the amount of the monomers to be used is appropriately within the range of about 20 to about 98% by weight, and preferably within the range of 30 to 80% by weight, in the total monomer mixture.

When the amount used is less than about 20% by weight, the solubility in solvents is inevitably reduced to cause cloudiness, or even if it is transparent at room temperature, cloudiness occurs at low temperature. In a system in which the amount of the polymerizable unsaturated bond-containing resins (b-3) used is large, regardless of whether it is at room temperature or at low temperature, even if it is transparent, it is desired when vinylated. When it is difficult to give the objective copolymer having the performance of 1. On the other hand, when it exceeds about 98% by weight and is too much, the solubility is good but the dispersibility and the substrate are inevitable. In any case, it is not possible to use a functional group-containing component that imparts adhesiveness to and a cross-linking function.

Next, the above-mentioned copolymerizable unsaturated bond-containing resins (b-3) make the obtained vinyl-based copolymer (B) more excellent in pigment dispersibility, Its main purpose is to increase the nonvolatile content during coating or to improve the solubility in non-polar organic solvents, and it is particularly representative as such resins (b-3). Examples of the polyester resins are vinyl resins, vinyl copolymers, petroleum resins, rosin esters, and polyether polyols. It is also suitable to use acrylic copolymers.

However, most of the polyester resins, which are so-called oil-free alkyd resins that are not oil-modified, have poor solubility in solvents, so the amount of such oil-free alkyd resins used is It is better to keep the target copolymer (B) at such a level that it can be obtained without turbidity.

Only typical examples of such polyester resins (including oil-modified types) or vinyl-based copolymers (among others, acrylic-based copolymers) will be exemplified. , Japanese Patent Publication No. 45-2201
No. 1, No. 46-20502 or No. 44-
No. 7134 or Japanese Patent Laid-Open No. 48-78233 or 50-58123 discloses a raw material component having a copolymerizable unsaturated bond as an essential component, together with other raw material components, A resin skeleton having this copolymerizable unsaturated bond in the form of being obtained by reacting,

Alternatively, as disclosed in Japanese Patent Publication No. 49-47916 or No. 50-6223, first, saturated polyesters having no copolymerizable unsaturated bond are obtained, and then the saturated polyesters are obtained. These functional groups, which are present in the various functional groups such as a hydroxyl group or a carboxyl group, or the epoxy groups introduced by reacting a diepoxy compound Compounds having both a functional group having reactivity with and a vinyl group, 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 an epoxy group and a vinyl group;
Various compounds having both an alkoxysilanol group and a vinyl group, such as vinylmethoxysilane or (meth) acryloxyethyltrimethoxysilane; and an acid anhydride group and a vinyl group, such as maleic anhydride or tetrahydrophthalic anhydride. Various compounds having both a carboxyl group and a vinyl group, such as fumaric acid or (meth) acrylic acid; or 2-
In a form obtained by adding vinyl monomers having both isocyanate groups and vinyl groups, such as hydroxypropyl (meth) acrylate-hexamethylene diisocyanate equimolar adducts or isocyanate ethyl methacrylate, to a saturated polyester. Various compounds having both a hydroxyl group and a copolymerizable unsaturated bond;

A vinyl-based monomer having various functional groups such as a hydroxyl group, a carboxyl group or an epoxy group is previously used as an essential raw material component to carry out a copolymerization reaction,
In the acrylic copolymer having these functional groups, a functional group having reactivity with the functional group contained in the acrylic copolymer, as in the case of introducing a copolymerizable unsaturated bond. Compounds having a vinyl group, for example, compounds having an acid chloride group and a vinyl group, such as (meth) acrylic acid chloride; epoxy group and a vinyl group, such as glycidyl (meth) acrylate Various compounds having both; and various compounds having both an alkoxysilanol group and a vinyl group, such as vinylmethoxysilane or (meth) acryloxyethyltrimethoxysilane;

Alternatively, various compounds having an acid anhydride group and a vinyl group, such as maleic anhydride or tetrahydrophthalic anhydride; having a carboxyl group and a vinyl group, such as fumaric acid or (meth) acrylic acid. Various compounds; or vinyl monomers having both an isocyanate group and a vinyl group, such as 2-hydroxypropyl (meth) acrylate-hexamethylene diisocyanate equimolar adducts or isocyanate ethylmethacrylate, etc. Examples thereof include various compounds having both a hydroxyl group and a copolymerizable unsaturated bond, which are obtained by addition reaction with a polymer.

Such polyester resins are available in various types such as octylic acid, lauric acid, stearic acid or "versatic acid" [synthetic branched (branched) fatty acid manufactured by Shell Co., Netherlands]. Saturated fatty acids; various unsaturated fatty acids such as oleic acid, linoleic acid, linoleic acid, eleostearic acid or ricinoleic acid; "Pamoline 200 or 300" (synthetic drying oil fatty acid manufactured by Hercules, USA) (Fatty acid), linseed 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); hydrogenated coconut oil fatty acids, coconut oil fats With or without at least one compound selected from various oils or fatty acids, such as various non-drying oils (fatty acids), such as acids or palm oil fatty acids;

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, (phthalic anhydride), hexahydro (phthalic anhydride) phthalic acid, tetrahydro (phthalic anhydride) phthalic acid, tetrachlorophthalic anhydride, hexachlorophthalic anhydride, tetrabromophthalic anhydride, trimellit Acid, "Hymic acid" [product of Hitachi Chemical Co., Ltd .; "Hymic acid" is a registered trademark of the company. ],
(Anhydrous) succinic acid, (anhydrous) maleic acid, fumaric acid,
It can be obtained by reacting one or more of various carboxylic acids such as (anhydride) itaconic acid, adipic acid, sebacic acid or oxalic acid by a conventional method.

In such a case, if necessary, for various purposes such as improvement of film performance such as adhesion, chemical resistance, weather resistance, etc.
Various monoepoxy compounds, such as "Kajura E" (trade name of glycidyl ester of fatty acid, manufactured by Shell, The Netherlands);

"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);

Or various diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 4,4'-methylenebis (cyclohexyl isocyanate);
Various polyisocyanates in the form of being obtained by an addition reaction of each of these diisocyanates with various polyhydric alcohols or water as described above;

Or an isocyanuric ring-containing polyisocyanate in the form of being obtained by a (co) polymerization reaction of diisocyanates; or one or more of various reactive silicone compounds as described above. Various polyhydric alcohols, carboxylic acids and the like are partially replaced, and various compounds in the form of being obtained by reacting by a conventional method.

When the copolymerizable unsaturated bond-containing acrylic copolymer is used as one of the copolymerizable unsaturated bond-containing resins (b-3), as described above, It is appropriate to use a vinyl monomer having a form such that it can be obtained by a copolymerization reaction by a conventional method by appropriately selecting from the vinyl-based monomers as described below to obtain a desired monomer composition. is there.

The polyester resins or vinyl-based copolymers may be used alone or in combination of two or more kinds, or one of these two types of resins may be used.
Needless to say, it is possible to use two or more species.

It is appropriate that the amount of these two types of resins used is in the range of 0 to about 80% by weight. The viscosity of the coalesced tends to be high,
In any case, it is not preferable because it easily gels during the reaction.

When a so-called drier curing in which a drier is blended as a curing accelerator is carried out, the polyester resin is
Needless to say, it is essential to perform modification with (semi) drying oils (fatty acids).

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% by weight. %is required.
Therefore, in such a case, it is appropriate that the amount is in the range of about 20 to about 80% by weight.

Further, as the curing agent, for example, at least one selected from the group consisting of metal alkoxides, metal acylates and metal chelates is used, or as such a curing agent, for example, poly In the case of using an isocyanate compound or an amino resin, in consideration of various physical properties of the cured coating film, in addition to the copolymerizable unsaturated bond, as much as possible in the resin structure of the polyester resin, The one having a hydroxyl group is more preferable than the one having a hydroxyl group.

Then, the above vinyl-based monomers (b
-4), that is, the aforementioned alkyl acrylates or alkyl methacrylates (b-1) and / or
Alternatively, the other vinyl monomers having copolymerizability with the styrene monomer (b-2) and the copolymerizable unsaturated bond-containing resin (b-3) described above include monomers (b- 1) and / or (b-2) also include resins (b)
The compounds which do not fall under -3) and which belong to the class from the group (a) to the group (g) as shown below are particularly typical examples.

That is, (a) styrene; methyl (meth) acrylate or ethyl (meth) acrylate as well as 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 acrylate; various types represented by maleic acid, fumaric acid or itaconic acid, such as dimethyl malate, diethyl malate, diethyl fumarate, dibutyl fumarate or dibutyl itaconate Diesters of dicarboxylic acids and monohydric alcohols;

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

Alternatively, various nitrogen-containing vinyl monomers such as (meth) acrylonitrile,
Further, various halogenated olefins containing no functional group, such as represented by vinyl chloride, vinylidene chloride, vinyl fluoride or vinylidene fluoride, are also included.

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

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

Further, various epoxy groups such as alkylene oxide adducts of the above-mentioned (meth) acryloyloxyalkyl acid phosphates or -acid phosphites, glycidyl (meth) acrylate, and methylglycidyl (meth) acrylate. Ester compound of vinyl-containing monomers and phosphoric acid or phosphorous acid or their acid esters, or 3-chloro-2
-Various phosphorus atom-containing vinylic monomers such as acid phosphoroxypropyl (meth) acrylate;

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

The amide bond-containing vinyl monomers, phosphorus atom-containing vinyl monomers, dialkylaminoalkyl (meth) acrylates and the like are all vinyl-based copolymers, especially acrylic-based copolymers. Mainly to give an internal catalytic function to the class, or to adhere to the material or substrate,
In the case of trying to improve the compatibility with other resins as well as the pigment dispersibility, it is to be used,

These may be used alone or in combination of two or more kinds. The amount of each of these monomers used is about 0.05 in the case of phosphorus atom-containing vinyl monomers, from the viewpoint of use effect. It is suitable to be in the range of about 5 to about 5% by weight, and particularly about 0.05 to about 10% by weight in the case of amide bond-containing vinyl monomers or dialkylaminoalkyl (meth) acrylates. Within the range is appropriate.

Further, the above-mentioned other vinyl type monomers (b-4) which are copolymerizable with the monomers (b-1) and / or (b-2), respectively, are particularly typical. To give just one example,

(E) Starting with glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate or (meth) allyl glycidyl ether,
α, β-ethylenically unsaturated carboxylic acids and mono-2-
Such as (meth) acryloyloxy monoethyl phthalate, various hydroxyl group-containing vinyl monomers and the like, and the above-mentioned equimolar adducts with polycarboxylic anhydrides;
Various carboxylic acids include "Epiclon 200, 40"
0, 441, 850 or 1050 "[made by former company,
Trade name of polyepoxy resin], “Epicoat 828,
1001 or 1004 "(trade name of polyepoxy resin manufactured by former company),

"Araldite 6071 or 608
4 "(trade name of a polyepoxy resin manufactured by Ciba Geigy, Switzerland)," Chissonox 221 "[trade name of an epoxy compound manufactured by Chisso Corporation] or" Denacol EX-611 "[Nagase Sangyo ( Co., Ltd., trade name of epoxy compound], which is obtained by subjecting various polyepoxy resins having at least two epoxy groups in one molecule to an addition reaction at an equimolar ratio. Such as various epoxy group-containing polymerizable compounds,

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

Further, among the film performances, in particular, the weather resistance and the like are further improved,
For example, such as "NORBLOC 7966" (a product of NORAMCO, USA) as disclosed in U.S. Pat. No. 4,528,311.
Copolymerization of various polymerizable UV absorbers and polymerizable light stabilizers such as benzotriazole-based acrylic monomers; or “ADEKA STAB T-37 or LA-82” [Asahi Denka Co., Ltd.] You can also make it react,

(G) Furthermore, 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 (macromones or macromers) having a functional group terminal capable of copolymerization, such as AB-6 "[all manufactured by Toa Gosei Chemical Industry Co., Ltd.], are also used. I can do it,

(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-
Including monobutyl fumarate,

Polyethylene glycol or polypropylene glycol mono (meth) acrylate or an adduct of these with ε-caprolactone, "Plaxel F
M or FA monomer] [manufactured by Daicel Chemical Industries, Ltd.
Hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids, such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid or citraconic acid. , Including various unsaturated mono- or dicarboxylic acids,

Various α, β-ethylenically unsaturated carboxylic acids such as monoesters of these dicarboxylic acids and monohydric alcohols, and the α, β
-Adducts of ethylenically unsaturated carboxylic acids with ε-caprolactone, or various α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters as described above, and succinic acid, maleic acid, phthalic acid, hexa Hydrophthalic acid, tetrahydrophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, "hymic acid",
Adducts of various polycarboxylic acids with anhydrides, such as tetrachlorophthalic acid or dodecynylsuccinic acid,

"Cardura E", monoglycidyl esters of various monovalent carboxylic acids such as coconut oil fatty acid glycidyl ester or octyl acid glycidyl ester, or various monoepoxys such as butyl glycidyl ether, ethylene oxide or propylene oxide. Adducts with compounds; or various hydroxyl group-containing vinyl monomers such as hydroxyethyl vinyl ethers,

(B) Various α, β-ethylenic monomers such as various unsaturated mono- or dicarboxylic acids as described above, and monoesters of these dicarboxylic acids and monohydric alcohols. Saturated carboxylic acids;
Alternatively, various carboxyl group-containing vinyls such as adducts of various α, β-ethylenically unsaturated carboxylic acid hydroxyalkyl esters as described above with anhydrides of various polycarboxylic acids as described above. It can be said that the copolymerization reaction of the system monomers is performed.

At this time, when the hydroxyl group-containing vinyl type monomer is used for the purpose of improving the adhesion, the amount of the monomer used is within the range of 0 to about 5% by weight. Is suitable, and when the monomer is used for the purpose of introducing a cross-linking point of the cross-linking agent component, the amount of the monomers to be used is the solubility of the target vinyl-based copolymer (B). From the viewpoint of the amount of hydroxyl groups in the non-aqueous dispersion type 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 as dispersed particles (polymer particles) described later, the range of about 1 to about 45% by weight is suitable, and the range of 3 to 30% by weight is particularly suitable. Is. If the amount is less than about 1% by weight, a significant crosslinking effect is difficult to appear, while about 4% by weight.
If it is used in excess of 5% by weight, it is inevitable that the price of the coating material will be high.

[0117] Carboxyl group-containing vinyl monomers often exhibit an internal catalytic action or an internal catalytic effect, and therefore, there is a tendency to impair the storage stability, etc. of the coating composition. In the case of using such compounds, in particular, in consideration of improving the adhesiveness or compatibility with other resins, etc., in the case of expecting such internal catalytic action or only internal catalytic effect, 0 to about The range of 5% by weight is suitable, and the range of 0.2 to 3% by weight is suitable, and

Further, when it is used as a cross-linking point of metal alkoxides, metal acylates or metal chelates, in the case of the intended vinyl copolymer (B), the polymer (B ), Especially from the viewpoint of solubility and the like, the range of about 1 to about 20% by weight is suitable, and the range of 3 to 15% by weight is particularly suitable.

In the case of being used for dispersed particles (polymer particles) described later, about 1 to about 30% by weight.
The range of 3 to 20% by weight is suitable. If the amount is less than about 1% by weight, it is unavoidable that the remarkable crosslinking effect cannot be exhibited. On the other hand, if the amount exceeds about 30% by weight, the amount becomes too large.
In any case, the solubility is liable to decrease, which is not preferable in any case.

The various monomers as listed above as the vinyl-based monomers (b-4) are listed above.
The 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, From various aspects such as dilutability, solubility and pot life, the amount of each monomer component used and its combination may be appropriately selected and determined. It may be selected and determined within the range of 20 to about 80% by weight.

The above-mentioned vinyl polymer (B), which is one of the essential base resin components used in the present invention.
Is prepared by preparing various raw materials (b-1), (b-2), (b-3) and (b-4) as listed above.
By using the components, it can be carried out by making full use of various known and commonly used copolymerization reaction methods or grafting reaction methods (graft copolymerization reaction method).

Azobisisobutyronitrile (AIB
N), benzoyl peroxide (BPO), tert-
Butyl perbenzoate (TBPB), tert-butyl hydroperoxide (TBHPO), di-tert
-Butyl peroxide (DTBPO), cumene hydroperoxide (CHP) or o, o-tert-o-
Various radical generators (radical generating polymerization catalysts or radical polymerization initiators) such as (1,2,2,6,6-pentamethyl-4-piperidinyl) monoperoxycarbonate, More than one species can be used together.

When preparing the non-aqueous dispersion type resin, various radical generators such as those mentioned above may be used and the known non-aqueous dispersion polymerization method may be used to carry out this. Of course, you can do that.

When an oil-modified alkyd resin is used as the polymer (B) instead of the above-mentioned acrylic copolymer, the amount of modification as described above is obtained by using the various reactive silicone compounds described above. Therefore, it is essential that the oil length is about 50% or more, and preferably 55% or more so as to have a dissolving power for organic solvents. By all means, it is necessary.

Further, as the oil component, non-drying oils and / or
In the case of using semi-drying oils or these various fatty acids, there will be no grafting points, or else there is a tendency for shortages. , Japanese Patent Publication No. 49-47916
It goes without saying that there is no problem even if the grafting points are introduced according to various methods as disclosed in Japanese Patent Publication No. 50-6223 or Japanese Patent Publication No. 50-6223.

In addition, polyhydric alcohols, polycarboxylic acids and the like are not particularly limited, and of course, even if desired ones are used depending on the desired performance of the coating film (various), There is no problem.

These various compounds are used as so-called dispersion stabilizers for stabilizing the dispersion of the polymer particles, and the amount or ratio of their use is unique to the non-aqueous dispersion type resin. The polymer (B), which is a dispersion stabilizer, from the viewpoint of exhibiting the characteristics or characteristics of the above, or from the viewpoint of dispersion stability.
It is appropriate that the ratio by weight of the solid content of vinyl monomers as dispersed particles is in the range of about 10 to about 90 / about 90 to about 10, and in particular, dispersion stabilizers / dispersed particles. It is appropriate that the solid content weight ratio is within the range of 20 to 80/80 to 20.

When the amount of the dispersion stabilizers is less than about 10% by weight, it is difficult to obtain a stable dispersion, while it is more than about 90% by weight and too much. In such a case, the characteristics as a non-aqueous dispersion type resin are hard to appear by any means, which is not preferable in any case.

Then, the vinyl polymer (A) which is composed of the specific monomers soluble in an organic solvent as described above and is insoluble in the organic solvent, that is, the non-aqueous dispersion resin The vinyl-based monomers forming the dispersed particles include (meth) acrylic acid esters having an alkyl side chain having 1 or 2 carbon atoms, α, β-ethylenically unsaturated (poly (meth) acrylic acid) other than (meth) acrylic acid. ) Carboxylic acid esters, vinyl acetate and the like are the main components, but more specifically, various compounds from the group (a) to the group (g) as described above are It is a typical representative example, and is used in the proportions shown above.

For the purpose of obtaining a non-aqueous dispersion type resin having a so-called special function such as a water- and oil-repellent function or a weather resistance function, if desired, for example, the following will be mentioned. Such various substances can be subjected to a copolymerization reaction, or the following various substances can be added and mixed, and then the copolymerization reaction can be performed.

That is, "Defencer" series or "Megafuck 170" series [all are products of Dainippon Ink and Chemicals, Inc.], "Aron GF-1"
50 or GF-300] [Toa Gosei Chemical Industry Co., Ltd.
Product] or “FA Series, FM Series or F
S series ”(product of Mitsubishi Petrochemical Co., Ltd.), various fluorine-based copolymer type surfactants, fluorine-based block copolymers;

"Fluoronate K-700" series [Product of Dainippon Ink and Chemicals, Inc.], "Lumiflon"
Series [Asahi Glass Co., Ltd. product] or "Kainer AD
Such as various fluororesins such as "S or SL" or various reactive silicone resins such as those mentioned above,
Alternatively, various benzophenone-based, benzotriazole-based, cyanoacrylate-based, anilide oxalate-based or salicylic acid esters except various polymerizable ultraviolet absorbers and polymerizable light stabilizers belonging to the above-mentioned (f) group can be used. Such as non-polymerizable UV absorbers,

"Tinuvin 144, 292, 700 or 765" (all are manufactured by Ciba-Geigy, Switzerland) or "Adeka Stab LA-52 or LA-"
87 ”[all are products manufactured by Asahi Denka Co., Ltd.], except for various types of non-polymerizable light stabilizers belonging to the above (f) group, which are represented by hindered amine compounds. So-called highly weather-resistant raw materials such as polymerizable light stabilizers are added to and mixed with vinyl monomers for the polymerization reaction prior to the polymerization reaction, and then from (a) group to (g) group. It is also possible to incorporate and incorporate the above-mentioned various vinyl monomers into the particles by subjecting them to a copolymerization reaction.

Further, although the vinyl-based monomer used in preparing the vinyl-based polymer (B) and the non-aqueous dispersion type resin is dissolved, the vinyl-based copolymer (A ) Is not dissolved, but only specific representative examples of specific organic solvents that do not dissolve

"Marcazole R or E" or "Swazol 310" [both are products of Maruzen Oil Co., Ltd.],
"LAWS", "HAWS" or "Shersol 7"
0 or 71 "(both products of Shell, Netherlands),
"Diana Solvent No. 0 or No. 1"
[Products of Idemitsu Kosan Co., Ltd.], “IP Solvent 101
6, 1020 or 1620 "(same as above)," Shellsol D-40 "(product of Shell Company in the Netherlands)," A solvent "," K solvent "or" AF solvent "[both are products of Nippon Oil Co., Ltd.],

Alternatively, “Exon naphtha No. 3, N
o. 5 or No. 6 "," Exol D-30,
D-40, D-60 or D-70 "or" Isopar C, E, G or H "[Exxon Chemical Co., Ltd. product] and the like, and further n-hexane or n-
It is various solvents containing aliphatic hydrocarbons as a main component, such as heptane. These hydrocarbon solvents are
They may be used alone or in combination of two or more.

Furthermore, the viscosity, volatility, dispersion agglomeration, sag property, electrostatic coating property, etc. of the non-aqueous dispersion type resin according to the present invention and the resin composition for coating material using the resin are adjusted. To this end, aromatic hydrocarbon solvents such as toluene, xylene, "Solvesso 100" [product of Exxon Chemical Co., Ltd.], or alcohol solvents; acetate ester solvents; propylene glycol ether solvents , A propylene glycol ether ester-based solvent or ethoxyethyl propionate, a so-called polar solvent is also included, within a range that does not deviate from the gist of the present invention, and a range that does not impair the effects of the present invention. It can be used in combination.

Furthermore, when a trace amount of unreacted monomers is present, the unreacted monomers are removed by an appropriate means such as distillation under reduced pressure, and thus the paint is concerned. It is possible to reduce odor, which is one of the environmental problems.

Particularly when the main component of the dispersed particles is a compound such as vinyl acetate and / or (meth) acrylic acid ester, the copolymerizability is inferior in all cases. It is extremely difficult to bring the addition rate of the monomers to about 90% by weight or more, especially 95% by weight or more within a predetermined time.

Therefore, such a monomer addition rate is approximately 9%.
For the time being, after confirming that the amount of unreacted monomers was 0% or more, the remaining amount of about 10% by weight, strictly speaking, 3% or more and less than 10% by weight of unreacted monomers was analyzed by gas chromatography ( GC) to measure less than 3% by weight in organic solvents, such as vacuum distillation; or a large amount of inert gas such as nitrogen or carbon dioxide in the system. By removing such unreacted monomers from the system by a suitable method such as blowing, the odor caused by the unreacted monomers is significantly reduced.

Next, the above-mentioned dryer used as the curing accelerator means all the so-called metals such as cobalt-based, lead-based, zirconium-based or calcium-based materials that have been used so far. This refers to a dryer, and these may be used alone or in combination of two or more, and can be used within a range of about 0.01 to about 10% by weight based on the resin solid content. .

If the amount used is less than about 0.01% by weight, the effect of accelerating the curing cannot be sufficiently achieved, and if it exceeds about 10% by weight, the amount is too large. When used for, the storage stability and the coloring property tend to be deteriorated by any means.

Therefore, the amount of the dryer used is usually within the range of about 0.01 to about 10% by weight, and preferably within the range of 0.1 to 5% by weight. is there.

Further, used as the above-mentioned curing agent,
Examples of the metal alkoxides, metal acylates or metal chelates include various compounds. Among them, aluminum-based, zirconium-based, and titanium-based compounds are industrially easily available. , As preferred ones.

Of the preferable examples, only typical ones are exemplified, and "acetope" is given.
[Hope Pharmaceuticals Co., Ltd. products], "Citacoat" [Nippon Soda Co., Ltd. products], "Planeact" [Ajinomoto Co., Inc. products], "Organics TA series, TC series, ZA series, ZB series, ZC series or AL series ”[Matsumoto Pharmaceutical Co., Ltd. product],“ AIP
D, AMD, ASBD or ALCH series "or" Aluminum chelate A, D or M "[Kawaken Fine Chemicals Co., Ltd.] or" Tencalate TP "
Various compounds and the like, which are put on the market under the trade name of "series" (product of Tenka Polymer Co., Ltd.) and widely used in the industry.

Each of these compounds, even when used alone,
It is needless to say that one or more kinds may be used in combination, and it may be used within a range of about 0.001 to about 20% by weight based on the resin solid content.

At that time, the non-aqueous dispersion type resin according to the present invention and the resin composition for coating material using the resin,
In particular, in order to improve the storage stability, for example, alcohols, acetylacetone, acetoacetic acid ester, etc. within a range that does not deviate from the object of the present invention or within a range that does not impair the effects of the present invention. However, there is no problem even if various stabilizers such as lactic acid compounds or lactic acid esters are added.

When the amount of metal alkoxide, metal acylate or metal chelate used as described above is less than about 0.001% by weight, it is inevitable that
The effect of accelerating curing becomes difficult to be achieved sufficiently,
On the other hand, when it is used in an excessively large amount exceeding about 20% by weight, there is a tendency that storage stability, coloring property, solubility, etc. are inevitably deteriorated.

Therefore, the amount of these substances to be used is usually 0.001 to 20% by weight, preferably 0.05 to 10% by weight.

Furthermore, the polyisocyanate compound used as one of the above-mentioned curing agents may be any compound, but the above-mentioned organic solvents, that is,
In the case where a solvent having insufficient solubility in a specific hydrocarbon solvent is used, a problem of separation occurs when the resin composition is blended in the obtained coating resin composition. Therefore, it is desirable to use a compound which has sufficient solubility in hydrocarbon solvents, which itself has poor solubility.

If only typical examples of such polyisocyanate compounds are given, the following are disclosed in JP-A-61-22013 and JP-A-4-130124.
-130171, -132720 or 132782 and the like, and
If only the representative products on the market are given as examples, "Bernock DN-990, DN-991, D
N-991S, DN-992 or BO-357 "
Examples include [Dainippon Ink and Chemicals, Inc. product], [Desmodur Z-4370] [Sumitomo Bayer Urethane Co., Ltd. product], or “Duranate THA-100” [Asahi Kasei Co., Ltd.].

As described above, the amount of the polyisocyanate compound to be used is an isocyanate group based on 1 equivalent of the hydroxyl group in the non-aqueous dispersion type resin according to the present invention and the coating resin composition using the resin. Is about 0.
2 to about 1.5 equivalents, that is, OH /
It is suitable that the equivalent ratio of NCO is in the range of about 1 / 0.2 to about 1 / 1.5.

When the ratio of the isocyanate group used to 1 equivalent of the 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 will be undesirably in view of problems such as foaming when coating a skin-coated surface having a high water content and the cost of the coating.

Therefore, usually, about 1 / 0.2 to about 1
The range of the equivalent ratio of /1.5 is suitable, and the range of the equivalent ratio of 1 / 0.5 to 1.2 is preferable.

Also used as one of the curing agents,
If only typical examples of the above-mentioned amino resins are exemplified, alkylated melamine resins, alkyl urea resins, alkyl urea / melamine resins or alkyl benzoguanamine resins, among others,
From the viewpoint of weather resistance and the like, the mineral spirit tolerance is at least 300% or more, preferably 50% or more.
It is desirable to use 0% or more of alkylated melamine resins.

All of these can be obtained by a conventional method, for example, "Super Beckamine L
-161, L-117-60 or L-118-6
0 "(both products of Dainippon Ink and Chemicals, Inc.) and the like are on the market.

The ratio of the amino resins used is as follows.
It is appropriate that the solid content weight ratio of the non-aqueous dispersion type resin / amino resin is in the range of about 50 to about 90 / about 10 to about 50, and in particular, aspects such as coating film physical properties and dispersion stability. Therefore, it can be said that such a range is appropriate.

The amount of the amino resin used is about 10% by weight.
If it is less than 100% by weight, the physical properties of the coating film tend to be difficult to appear. On the other hand, if it is used in an excessively large amount of more than about 50% by weight, the coating film tends to become brittle, and in particular, it has an acid resistance. In any case, it is not preferable because the sex and the like will be deteriorated.

The thus obtained non-aqueous dispersion resin for paints and the resin composition for paints according to the present invention are
Mainly when coating materials already formed with a film susceptible to so-called polar organic solvents, such as automobile repair, roof or building exterior, etc., or when repairing these types of materials In addition, if the amount of such polar organic solvents used is reduced or eliminated,

When a paint containing the polar solvent is applied,
So-called lifting (chumi) often seen
Does not occur, gives a good coating film that is smooth and has high commercial value, and even if it is a plastic material with poor so called solvent resistance such as polycarbonate that is easily attacked by the polar solvents, solvent cracking occurs. This brings about the advantage that troubles such as the above 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, metal return unevenness hardly occurs and a metallic feeling is easily obtained. That's what it means.

Also, in two-tone finishing of automobiles or motorcycles, repairing, etc., 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 conventional use of highly toxic polar organic solvents, the working environment is remarkably improved, the pollution is reduced, and the performance is significantly improved. .

Further, in the present invention, room temperature drying, forced drying and heat drying (baking), or urethane type curing in an amine stream, that is, vapor cure system, VIC system, etc.
It can be applied 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 coating additives, which are commonly known in the art, can be used in conventional amounts.

For the purpose of improving performance, plasticizers and other plasticizers may be used as long as they are soluble in the organic solvents used in compatibility with the coating resin composition of the present invention. Other resins, for example, acrylic copolymers, fibrin compounds, acrylated alkyd resins, alkyd resins, silicone resins, fluororesins or epoxy resins may be used in combination as appropriate. However, even in that case, it is important to use various ones such as those mentioned above within a range that does not deviate from the object of the present invention or within a range that does not impair the effects of the present invention. Needless to say,

The non-aqueous dispersion type resin for paints and the resin composition for paints according to the present invention may be mixed with pigments for kneading, or may be mixed with dispersed pigments or processed pigments. Thus, it can be used as a so-called enamel paint, or can be used as a so-called clear paint without using such pigments.

The non-aqueous dispersion type resin and the resin composition for coating material according to the present invention obtained as described above are formed into a coating material by a conventional method and are mainly used for coating the following objects. It is painted on (base materials).

That is, if only representative examples of the above-mentioned base materials are given as examples, aluminum,
Various metallic materials or products, such as stainless steel, chrome-plated, galvanized or tinplate;
Or roof tiles; glass; or various inorganic building materials,

Concretely, such as an automobile body or automobile (for) parts, a motorcycle or a motorcycle (for) parts, and various building materials such as gates or fences; aluminum sashes, etc. , Various building interior and exterior materials; or various materials or products of various ferrous or non-ferrous metals such as aluminum foil.

In the coating at that time, various known and commonly used means such as a spray, a brush or a roller can be used and applied.

The non-aqueous dispersion type resin for paints and the resin composition for paints according to the present invention thus obtained are, as compared with conventional non-aqueous dispersion compositions,
In particular, it is excellent in weather resistance and the like, has little influence on the old coating film, and has various coating film performances which are very useful as those using conventional solvents.

[0172]

EXAMPLES Next, the present invention will be explained more specifically by reference examples, examples and comparative examples, but the present invention is never limited to these examples. Not a thing. In the following, all parts and percentages are by weight unless otherwise specified.

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,
Charge 300 parts of "SH-6018", 20 parts of pentaerythritol, and 105 parts of glycerin to prepare 1
The temperature was raised to 80 ° C., kept at the same temperature for 2 hours, and then raised to 220 ° C. over 3 hours.

After maintaining the same temperature in an atmosphere of nitrogen gas until the acid value becomes 9 or less, it is diluted with "AWS" so that the nonvolatile content becomes 70%, and the nonvolatile content becomes 70%.
And the Gardner viscosity at 25 ° C (same below) is X
Thus, a solution of the target resin having an acid value (solid content) of 5.0 and 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 "Curdra E" was added.
78 parts, 13 parts of neopentyl glycol, 73 parts of trimethylolpropane, 200 of "SH-6018"
Part, 279 parts of phthalic anhydride and 20 parts of fumaric acid were charged, heated to 200 ° C. and kept at the same temperature until the acid value was 6 or less,

Diluted with "Swazol 310" [trade name of aromatic hydrocarbon solvent manufactured by Maruzen Petrochemical Co., Ltd.] to have a nonvolatile content of 70%, a viscosity of Z and an acid value of 3.0.
A solution of the target resin having a hydroxyl value of 77 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 inlet tube was charged with "LAW".
667 parts of "S" were charged and the temperature was raised to 120 ° C. At this temperature, 30% of i-butylmethacrylate was obtained.
0 part, 100 parts of lauryl methacrylate, "KR-2
15 "(trade name of a silicone compound containing a hydroxyl group / copolymerizable double bond manufactured by the above-mentioned company), 116 parts,

25 of 2-ethylhexyl methacrylate
0 parts, 200 parts of tert-butylstyrene, 20 parts of β-hydroxyethyl acrylate and 8 parts of monobutylmalate, 20 parts of tert-butylperoctoate and 10 parts of tert-butylperbenzoate.
And the mixture was added dropwise over 4 hours.

After the completion of 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 hydroquinone monomethyl ether were added. 0.3 parts,
Add 166 parts of "Exol D-40" and 0.1 part of 2-methylimidazole,

By keeping at 100 ° C. until the acid value becomes 1 or less, the nonvolatile content is 60% and the viscosity is Z.
A solution of the target resin having an acid value of ₁ , an acid value of 0.5, and a hydroxyl value of 7.2 was obtained. Hereinafter, this is a resin (b-3-3)
Abbreviated.

Reference Example 4 [Preparation Example of Modified Silicone Compound (1)] In a four-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 dissolved by heating to 100C.

At this temperature and when the solution state became uniform, 80 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 target modified silicone compound (1) having a nonvolatile content of 70% and having a copolymerizable unsaturated double bond was obtained.

Reference Example 5 [Preparation Example of Modified Silicone Compound (2)] In a four-necked flask similar to Reference Example 3, 225 of xylene was added.
Parts, 340 parts of "TSR-165" (a methoxy group-containing silicone compound manufactured by the above-mentioned company) and 5 parts of hydroquinone monomethyl ether were charged and dissolved by heating to 100C.

At this temperature, and when the solution state became uniform, 4-hydroxybutyl acrylate 1
85 parts, and then 0.1 part of tetraisopropyl titanate is added.
A solution of the target modified silicone compound (2) having a copolymerizable unsaturated double bond, which has a nonvolatile content of 70% and is retained for a period of time, is 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" (manufactured by the above-mentioned company) were used. 370 parts of (epoxy group-containing silicone compound) and 5 parts of hydroquinone monomethyl ether were charged and the temperature was raised to 100 ° C. to dissolve them.

At this temperature, and further, when the solution state became uniform, 18 parts of acrylic acid was gradually added over 30 minutes, and after the addition was completed, 100 ° C. was kept as it was.
In addition, holding for 2 hours, the nonvolatile content becomes 80%,
A desired solution of the modified silicone compound (3) having a copolymerizable unsaturated double bond 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", 10 parts of acrylic acid, 10 parts of "ADEKA STAB LA-82" and 10 parts of methacryloxyethyltrimethoxysilane.
And 40 parts of tert-butyl peroctoate and 10 parts of tert-butyl perbenzoate were added dropwise over 4 hours.

Even after the completion of dropping, the temperature is kept at 120 ° C. for 8 hours, the nonvolatile content is 59.0%, and the viscosity is Y.
A solution of the target vinyl polymer (B) was obtained.

Then, this resin solution was gradually added to 500
When the pressure was reduced to mg, 50 parts of a mixture of the monomers and the solvent was distilled out. Therefore, 35 parts of "LAWS" was supplemented to obtain a nonvolatile content of 5 parts.
A solution of the objective vinyl polymer (B) having a viscosity of Z and an acid value of 4.8 was obtained at 9.5%. Hereinafter, this is abbreviated as polymer (B-1).

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 is raised to 20 ° C., and at this temperature, 90 parts of i-propyl methacrylate, 150 parts of tert-butyl methacrylate, 200 parts of i-butyl methacrylate, 2-
A mixture of 150 parts of ethylhexyl acrylate and 10 parts of monobutyl malate, 35 parts of tert-butyl peroctoate and 10 parts of tert-butyl perbenzoate was added dropwise over 4 hours.

After completion of the dropping, the temperature was kept at 120 ° C. for 8 hours, the nonvolatile content was 60%, the viscosity was T, and
Objective vinyl-based copolymer (B) having an acid value of 2.2
Was obtained. 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 monomers, 200 parts of tert-butyl methacrylate and 100 parts of n-butyl acrylate were used.

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 desired solution of the vinyl polymer (B) having a viscosity of U and an acid value of 2.0 was obtained. Hereinafter, this is abbreviated as a polymer (B-3).

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.
Then, 100 parts of methyl methacrylate, 142 parts of the modified silicone compound obtained in Reference Example 4, and tert-
250 parts of butyl methacrylate, 200 parts of i-butyl methacrylate, 50 parts of n-butyl methacrylate
Parts, 150 parts of “Acryester SL” and 50 parts of β-hydroxyethyl acrylate,

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

Reference Example 11 (Same as above) [0197]
After charging 170 parts of "E" and 581 parts of "A solvent", tert
-100 parts of butyl styrene, 286 parts of the modified silicone compound obtained in Reference Example 5, 130 parts of tert-butyl methacrylate,

100 parts of i-butyl methacrylate, 2
-Using a mixture consisting of 94 parts of ethylhexyl methacrylate, 50 parts of "Acryester SL", 50 parts of i-propyl acrylate, 56 parts of β-hydroxyethyl methacrylate and 50 parts of acrylic acid, and hand,

One hour after the completion of dropping, the reaction temperature was adjusted to
The nonvolatile content was 60% and the viscosity was X in the same manner as in Reference Example 8 except that the temperature was raised to 130 ° C. and the same value was maintained until the acid value became 5 or less. A target vinyl polymer (B) solution having an acid value of 3.5 and a hydroxyl value of 38 was obtained. Hereinafter, this is abbreviated as polymer (B-5).

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, 100 parts of tert-butylstyrene, 375 parts of the modified silicone compound obtained in Reference Example 6, 150 parts of isobornyl methacrylate, respectively, as monomers.

250 parts of i-butyl methacrylate, 100 parts of lauryl methacrylate, 40 parts of β-hydroxyethyl acrylate and 1 part of monobutyl maleate.
Using a mixture consisting of 0 parts,

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 was W, the acid value was 2.2, and the hydroxyl value was A target solution of vinyl polymer (B) 12 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, Reference Examples 1 and 2 were used.
And 143 parts of each of the resin (b-3-1) and the resin (b-3-2), which were obtained in 1.
After preparing 94 copies,

Each of the monomers is tert.
-Butylstyrene 100 parts, 286 parts of the modified silicone compound obtained in Reference Example 4, 220 parts of isobornyl acrylate, 150 parts of 4-tert-butylcyclohexyl methacrylate, 100 parts of "Acryester SL", β -Hydroxyethyl acrylate 40
Parts, 20 parts of 1,4-butanediol monoacrylate and 10 parts of monobutylmalate are used, and so on.

The radical generator is ter
40 parts of t-butyl peroctoate and tert-
The same procedure as in Reference Example 8 was carried out except that 10 parts of butyl perbenzoate was used.
A solution of the objective vinyl polymer (B) having 0%, 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
Charge 9 parts and 92 parts of 1,6 hexanediol,
The temperature is raised to 220 ° C., the reaction is performed in a nitrogen gas atmosphere until the acid value becomes 15 or less, and when the acid value reaches the target value, the temperature is lowered to 130 ° C., and “TSR- 1
65 "(a methoxy group-containing silicone compound manufactured by the above-mentioned company)
400 parts of tetraisopropyl titanate
Part and prepare,

Further, in the same manner as in Reference Example 1, except that the reaction was carried out until the acid value was 7 or less, the nonvolatile content was 70%, the Gardner viscosity at 25 ° C. was Z, and the acid value was 25%. Is 3.5 and the oil length is 55%,
A medium oil alkyd resin as a target polymer was obtained. 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. Like using parts, and
As the solvent, except that "Shellzol D-40" is used,

In the same manner as in Reference Example 14, the nonvolatile content was 70
%, The viscosity is Y, the acid value is 3.5, and the oil length is 70.
% Of a long oil alkyd resin as a target polymer was obtained. Hereinafter, this is abbreviated as polymer (B-9).

Example 1 This example is for describing the non-aqueous dispersion type resin according to the present invention, particularly for specifically explaining the preparation method thereof.

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.

When the temperature reached 90 ° C., 200 parts of methyl methacrylate, 300 parts of vinyl acetate, 192 parts of ethyl acrylate, 100 parts of “KR-215” and 8 parts of acrylic acid, and tert-butyl were used. A mixture of 20 parts of peroctoate and 5 parts of tert-butyl perbenzoate 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.
Unreacted monomers were removed by vacuum distillation at mmHg.

Then, with "LAWS", the nonvolatile content was diluted to 60%, and the nonvolatile content was 60%.
The Brookfield viscosity at 25 ° C (the same applies below) is 4,100 cps, and the acid value is 3.5.
The target non-aqueous dispersion type resin was obtained. Less than,
This is abbreviated as (Bu-1).

Examples 2 to 10 In the same manner as in Example 1 except that the raw materials were used in the proportions shown in Table 1, various desired non-aqueous dispersions were prepared. Mold resin (Bu-
2) to (Bu-10) were obtained.

However, in each case of Examples 2 to 4, the unreacted monomers were removed not by distillation under reduced pressure but exclusively by blowing nitrogen gas.
In each case of 0, no unreacted monomers were removed.

The property values (characteristic values) of each non-aqueous dispersion type resin thus obtained are shown in Table 2 together.

[0218]

[Table 1]

[0219]

[Table 2]

[0220]

[Table 3]

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

In the table, the heading (item) “monomers” is provided to indicate “vinyl-based monomers”.
The terminology is not used exclusively for convenience of notation, and there is no special meaning. Of course, this "monomer" is "vinyl-based monomer". It is intended as a synonym for "kind" and should be understood as an abbreviation.

"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"

[0226]

[Table 4]

[0227]

[Table 5]

[0228]

[Table 6]

<< Footnote in Table 1 >>"β-HEA" .... Abbreviation for β-hydroxyethyl acrylate.

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

"LA-82" ... "Adeka Stab L
Abbreviation of "A-82"

[0232]

[Table 7]

[0233]

[Table 8]

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

[0235]

[Table 9]

<< Footnote in Table 1 >>"Chemisorb74"
Is a trade name of an ultraviolet absorber manufactured by Chemipro Corporation.

[0237]

[Table 10]

Examples 11 to 26 and Comparative Examples 1 to 3 In this example, the resin composition for coating material of the present invention is prepared using the non-aqueous dispersion type resin obtained according to the method of the present invention. is there.

(Bu-1) obtained in Examples 1 to 10
To (Bu-10) each non-aqueous dispersion type resin, according to the composition of the kneaded meat as shown in Table 3,
The meat was kneaded by a conventional method.

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

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

Then, in each of Examples 11 to 23, each of them was left to stand at room temperature for 2 weeks to be dried and cured, and in the case of Example 24, at 80 ° C. for 30 minutes. About the cured coating film obtained by performing forced drying during

Further, in each case of Examples 25 and 26, it was obtained by baking and drying at 140 ° C. for 30 minutes, and then leaving at room temperature for 1 week. The cured coating film was examined for evaluation and judgment of various performances.

In each of Comparative Examples 1 to 3, three types of commercially available products were used. The test procedure for evaluation and judgment of various physical properties and performances of each paint is as follows.

(1) Odor test ………… Comprehensive judgment of sensory test by 5 persons ◎ ………… No odor ○ ……… Although there is a slight odor

(2) Mitsuzawa ............ 60 degree specular reflectance (%)

(3) Hardness ............ Measurement of scratch hardness with a pencil

(4) Adhesion property ………… cross-cut adhesion test

(5) Acid resistance: The coating surface condition after visually conducting a spot test for 24 hours with a 5% sulfuric acid aqueous solution was visually evaluated and judged.

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

(7) "Recoatability" for old paint film
Is to visually evaluate the condition of the painted surface after applying each paint separately on the old paint film (existing paint film) after two years of natural exposure.

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

(8) The coating film constitution and suitability test in "suitability for repeated coating" are as follows.

Coating structure: [Coating film (a)-(1) / coating film (a)-(2) / coating film (b) / base material slate plate] film

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 (1)-(2), which is the top coat of the first coat, 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 100 parts of Ishihara Sangyo Co., Ltd.] “Demol EP” [trade name of 3 parts dispersant manufactured by Kao Corporation] “Neugen EA” -120 "[trade name of emulsifying agent manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 1.5 parts] Ethylene glycol 3 parts" SN Deformer 154 "[San Nopco 1.5 parts manufactured by Foaming Agent] Trade name of agent] 28% ammonia water 1 part Water 24 parts 2% "Hydro-Metroses 90SH-100" 18.6 parts [trade name of thickener manufactured by Shin-Etsu Chemical Co., Ltd.] "Boncoat 3650" [ Dainippon Ink and Chemicals 104.6 parts Gaku Kogyo Co., Ltd.'s acrylic emulsion product name] "Self-top HP-103" [Kojin Co., Ltd. 1.1 part thickener product name]

(9) The influence of the solvent used on the material (that is, the influence of the solvent on the plastic material) is visually evaluated by the presence or absence of solvent cracks and the degree of their occurrence.

∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙ When the occurrence of solvent cracks

[0260]

[Table 11]

<< Footnotes in Table 3 >> All the numerical values in the table are "copies".

Note 1) Abbreviation of "CR-95" ... "Taipec CR-95" [rutile titanium oxide manufactured by Ishihara Sangyo Co., Ltd.]

Note 2) “LAWS” was used.

Note 3) "Skinner TM" [product of Toa Gosei Chemical Industry Co., Ltd.] was used.

Note 4) "KP-324" [produced by Shin-Etsu Chemical Co., Ltd.] was used.

In the table, the heading word (item) "name of paint base" is provided and the heading word (item) "name of base resin component for paint" is not used. , It is merely for convenience of notation, and there is no special meaning to it. Of course, this "name of paint base" is synonymous with "name of base resin component for paint", and is an abbreviation. Be understood to be.

[0267]

[Table 12]

[0268]

[Table 13]

[0269]

[Table 14]

<< Footnote 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 were all
It is expressed by the weight of solid content.

The term "6% cobalt naphthenate" refers to a material having a metal cobalt content (that is, active ingredient content) of 6%.

The term "24% lead octylate" refers to one having a metallic lead content (that is, active ingredient content) of 24%.

It should be understood that the "main component" in the table is synonymous with the above-mentioned "base resin component for paint".

[0274]

[Table 15]

[0275]

[Table 16]

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

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

Both "PPO resin" and "polycarbonate" are data for showing "effect on plastic material".

[0279]

[Table 17]

<< Footnote in Table 4 >>"Aluminum chelate A" ... A trade name of aluminum chelate manufactured by Kawaken Fine Chemicals Co., Ltd., which is used in the form of 40% acetylacetone solution. .

"AIPD" ............ The product name of aluminum alcoholate manufactured by the above-mentioned company. The nonvolatile content (NV) is 100%, but 40% i-
It is used in the form of a propanol solution.

[0282]

[Table 18]

[0283]

[Table 19]

[0284]

[Table 20]

<< Footnote of Table 4 >>"TP-110" ......... "Tencalate TP-11"
0 ”(trade name of titanium chelate manufactured by former company; NV =
33%, effective titanium / chelate content = 60%)

Abbreviation of "ZC-540" --- "Organics ZC-540" (trade name of zirconium chelate manufactured by the aforementioned company; NV = 60%)

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

[0288]

[Table 21]

[0289]

[Table 22]

[0290]

[Table 23]

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

[0292]

[Table 24]

[0293]

[Table 25]

[0294]

[Table 26]

[0295]

[Table 27]

[0296]

[Table 28]

[0297]

[Table 29]

<< Footnotes in Table 5 >> 1) Natural Bakuro ... …… Bakuro for two years in the suburbs of Miyazaki City

2) Accelerated weather resistance test ... Accelerated weather resistance test for 2,000 hours by the sunshine weatherometer (JIS method)

As described above, the non-aqueous dispersion type resin according to the present invention has little influence on the old paint film (existing paint film), and moreover, the paint film performance including weather resistance and the like. Compared to the conventional type using organic solvents, it is extremely practical and is not inferior.

Therefore, the resin composition for paint according to the present invention, which contains the thus obtained non-aqueous dispersion type resin for paints, is also particularly effective for the old coating film. However, it is easy to know that it is also excellent in various coating film properties such as weather resistance.

[0302]

INDUSTRIAL APPLICABILITY As described above, the non-aqueous dispersion type resin according to the present invention has little influence on the old coating film (existing coating film), and more particularly, the coating film including weather resistance. It also has a lot of performance, and it is extremely practical as compared to the one using conventional organic solvents, and it is extremely practical.

Therefore, the resin composition for paints according to the present invention in the form of containing such a non-aqueous dispersion type resin for paints, thus obtained, also has little influence on the old coating film, and , Among others,
It is also excellent in various coating properties such as weather resistance.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 22, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0080

[Correction method] Change

[Correction contents]

A vinyl-based monomer having various functional groups such as a hydroxyl group, a carboxyl group or an epoxy group is previously used as an essential raw material component to carry out a copolymerization reaction,
Vinyl-based copolymers having these functional groups (among others,
As described above, the vinyl-based copolymers (among others, the acrylic-based copolymers) are introduced in the same manner as in the case where the copolymerizable unsaturated bond is introduced into the saturated polyesters. Various compounds having both a functional group having reactivity with a functional group contained in (composites) and a vinyl group, for example, so-called, represented by (meth) acrylic acid chloride and the like, Various compounds having both an acid chloride group and a vinyl group; various compounds having a so-called epoxy group and a vinyl group, represented by glycidyl (meth) acrylate and the like; vinylmethoxysilane or (meth ) As represented by acryloxyethyltrimethoxysilane, so-called,
Various compounds having both an alkoxysilanol group and a vinyl group;

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08G 77/04 NUA C08G 77/04 NUA C08L 101/02 LSY C08L 101/02 LSY 101/08 101 / 08 101/10 101/10 C09D 5/00 C09D 5/00 175/04 PHR 175/04 PHR 183/04 PMS 183/04 PMS 201/02 PDC 201/02 PDC 201/08 201/08 201/10 201 / Ten

Claims (26)

[Claims] 1. A polymer (B) which is soluble in an organic solvent in an organic solvent in which a vinyl-based monomer is dissolved but a vinyl-based polymer (A) comprising the monomer is insoluble. )
By copolymerizing vinyl monomers in the presence of the above, a stable non-aqueous dispersion type resin, which is a polymer (A) of the vinyl monomer described above and a polymer (A) described above ( A non-aqueous dispersion type resin characterized in that both B and B are modified with a silicone compound. 2. A polymer (B) soluble in an organic solvent in an organic solvent which does not dissolve the vinyl polymer (A) comprising the monomer but dissolves the vinyl monomer. )
By copolymerizing vinyl monomers in the presence of the above, a stable non-aqueous dispersion type resin, which is a polymer (A) of the vinyl monomer described above and a polymer (A) described above ( B) and (B) are both modified with a silicone compound, and the silicone compound is contained in an amount of about 1 to about 60% by weight. Mold resin. 3. The silicone compound described above is represented by the following general formula [I]: (However, R in the formula is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which is bonded to a carbon-silicon bond, 1
A valent organic group or a copolymerizable unsaturated double bond,
R'represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group. Furthermore, n is a number of 0.5 to 2.0, m is a number of 0.0 to 2.5, and m + n is a number of 0.5 to 3.0. And ), At least one 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,
An organopolysiloxane having at least one functional group or copolymerizable unsaturated double bond in one molecule,
The resin according to claim 1. 4. The above-mentioned silicone compound is represented by the following general formula [I]: (However, R in the formula is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which is bonded to a carbon-silicon bond, 1
A valent organic group or a copolymerizable unsaturated double bond,
R'represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group. Furthermore, n is a number of 0.5 to 2.0, m is a number of 0.0 to 2.5, and m + n is a number of 0.5 to 3.0. And ), At least one 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,
Organopolysiloxane having at least one functional group or copolymerizable unsaturated double bond in one molecule, and a functional group having reactivity with the functional group present in the organopolysiloxane, copolymerizable The resin according to claim 1, which is a reaction product of a compound having an unsaturated double bond together. 5. The above-mentioned vinyl polymer (A) which is composed of monomers soluble in an organic solvent and is insoluble in the organic solvent is a silicone compound which modifies the polymer (A). About 1 to about 60% by weight, and about 4% of the monomers having a copolymerizable unsaturated double bond forming the polymer (A).
0 to about 99% by weight.
The resin according to any one of 1. 6. The above-mentioned vinyl polymer (B) soluble in an organic solvent comprises about 1 to about 60% by weight of a silicone compound which modifies the polymer (B), and the polymer (B). About 4 of the monomers having a copolymerizable unsaturated double bond to form
0 to about 99% by weight.
The resin described in. 7. The vinyl polymer (A), which is composed of the above-mentioned monomers soluble in an organic solvent and is insoluble in the organic solvent, is other than a silicone compound forming the polymer (A). As the monomers having a copolymerizable unsaturated double bond, (meth) acrylic acid esters having an alkyl group side chain having 1 or 2 carbon atoms, α, β-ethylenic non-ethylenic monomers other than (meth) acrylic acid The resin according to claim 1, which is obtained by using esters of saturated (poly) carboxylic acid and / or vinyl acetate as a main component. 8. The number of carbon atoms of the above-mentioned polymer (B) soluble in an organic solvent as monomers having a copolymerizable unsaturated double bond other than the silicone compound forming the polymer (B). The resin according to claim 1, which contains at least 30% by weight or more of (meth) acrylic acid esters having an alkyl group side chain of 3 or more and / or styrene-based monomers having an alkyl side chain. . 9. The above-mentioned polymer (B) soluble in an organic solvent has a carbon number of 3 as monomers having a copolymerizable unsaturated double bond forming the polymer (B). About 20 to about 98 of the (meth) acrylic acid esters (b-1) having an alkyl side chain and / or the styrene-based monomer (b-2) having an alkyl group side chain as described above.
% By weight and copolymerizable unsaturated double bond-containing resin (b-3)
0 to about 80% by weight and 2 to 80% by weight of the other vinyl-based monomers (b-4) copolymerizable with the monomers (b-1) and (b-2) described above. %, And the sum of each of these monomers is 10
Resin obtained in any one of Claims 1-8 obtained by using so that it may be 0 weight%. 10. The above-mentioned polymer (B) soluble in an organic solvent is an oil-modified alkyd having an oil length of at least 50%, and further has the following general formula [I]: (However, R in the formula is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which is bonded to a carbon-silicon bond, 1
A valent organic group or a copolymerizable unsaturated double bond,
R'represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group. Furthermore, n is a number of 0.5 to 2.0, m is a number of 0.0 to 2.5, and m + n is a number of 0.5 to 3.0. And ) Is modified with a silicone compound represented by the formula (1), and is composed of about 40 to about 99% by weight of the oil-modified alkyd and about 1 to about 60% by weight of the silicone compound. The resin according to claim 1. 11. The vinyl monomer is dissolved,
The vinyl-based polymer (A) composed of the monomers is copolymerized with the vinyl-based monomers in an organic solvent in which the vinyl-based polymer is insoluble and in the presence of the polymer (B) soluble in the organic solvent. In the resin composition for coating material, which is obtained by using the stable non-aqueous dispersion type resin, the above-mentioned vinyl monomer polymer (A) and the above-mentioned polymer (B) are both silicone. A resin composition for paint, which is modified with a compound. 12. The vinyl-based monomer is dissolved,
The vinyl-based polymer (A) composed of the monomers is copolymerized with the vinyl-based monomers in an organic solvent in which the vinyl-based polymer is insoluble and in the presence of the polymer (B) soluble in the organic solvent. In the resin composition for coating material, which is obtained by using the stable non-aqueous dispersion type resin, the above-mentioned vinyl monomer polymer (A) and the above-mentioned polymer (B) are both silicone. The silicone compound is modified with a compound,
A resin composition for coatings, characterized in that it is contained within a range of weight%. 13. The silicone compound of the following general formula [I]: (However, R in the formula is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which is bonded to a carbon-silicon bond, 1
A valent organic group or a copolymerizable unsaturated double bond,
R'represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group. Furthermore, n is a number of 0.5 to 2.0, m is a number of 0.0 to 2.5, and m + n is a number of 0.5 to 3.0. And ), At least one 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,
An organopolysiloxane having at least one functional group or copolymerizable unsaturated double bond in one molecule,
A composition according to claim 11. 14. The above-mentioned silicone compound is represented by the following general formula [I]: (However, R in the formula is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which is bonded to a carbon-silicon bond, 1
A valent organic group or a copolymerizable unsaturated double bond,
R'represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group. Furthermore, n is a number of 0.5 to 2.0, m is a number of 0.0 to 2.5, and m + n is a number of 0.5 to 3.0. And ), At least one 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,
Organopolysiloxane having at least one functional group or copolymerizable unsaturated double bond in one molecule, and a functional group having reactivity with the functional group present in the organopolysiloxane, copolymerizable with The composition according to claim 11, which is a reaction product with a compound having an unsaturated double bond. 15. The above-mentioned vinyl polymer (A) which is composed of monomers soluble in an organic solvent and is insoluble in the organic solvent is a silicone compound which modifies the polymer (A). 12. It comprises about 1 to about 60% by weight and about 40 to about 99% by weight of monomers having a copolymerizable unsaturated double bond forming the polymer (A).
15. The composition according to any one of items 14 to 14. 16. The above-mentioned vinyl polymer (B) soluble in an organic solvent comprises about 1 to about 60% by weight of a silicone compound which modifies the polymer (B), and the polymer (B). 12. It comprises about 40 to about 99% by weight of the monomers having a copolymerizable unsaturated double bond formed.
A composition according to any one of claims 1 to 14. 17. The above-mentioned vinyl polymer (A) which is composed of monomers soluble in an organic solvent and which is insoluble in the organic solvent is other than the silicone compound forming the polymer (A). As the monomers having a copolymerizable unsaturated double bond, (meth) acrylic acid esters having an alkyl group side chain having 1 or 2 carbon atoms, α, β-ethylenic non-ethylenic monomers other than (meth) acrylic acid The composition according to claim 11, which is obtained by using esters of saturated (poly) carboxylic acid and / or vinyl acetate as a main component. 18. The number of carbon atoms of the above-mentioned polymer (B) soluble in an organic solvent as a monomer having a copolymerizable unsaturated double bond other than the silicone compound forming the polymer (B). The composition according to claim 1, which comprises at least 30% by weight or more of (meth) acrylic acid esters having an alkyl side chain of 3 or more and / or styrene-based monomers having an alkyl side chain. Stuff. 19. The above-mentioned polymer (B) which is soluble in an organic solvent has a carbon number of 3 as monomers having a copolymerizable unsaturated double bond forming the polymer (B). About 20 to about 98 of the (meth) acrylic acid esters (b-1) having an alkyl side chain and / or the styrene-based monomer (b-2) having an alkyl group side chain as described above.
% By weight and copolymerizable unsaturated double bond-containing resin (b-3)
0 to about 80% by weight and 2 to 80% by weight of the other vinyl-based monomers (b-4) copolymerizable with the monomers (b-1) and (b-2) described above. %, And the sum of each of these monomers is 10
The composition according to any one of claims 11 to 18, which is obtained by using so as to be 0% by weight. 20. The above-mentioned polymer (B) soluble in an organic solvent is an oil-modified alkyd having an oil length of at least 50%, and further has the following general formula [I]: (However, R in the formula is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group and an alkoxy group, which is bonded to a carbon-silicon bond, 1
A valent organic group or a copolymerizable unsaturated double bond,
R'represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group. Furthermore, n is a number of 0.5 to 2.0, m is a number of 0.0 to 2.5, and m + n is a number of 0.5 to 3.0. And ) Is modified with a silicone compound represented by the formula (1), and is composed of about 40 to about 99% by weight of the oil-modified alkyd and about 1 to about 60% by weight of the silicone compound. The composition according to claim 11. 21. The ratio of the polymer (B) used to the polymer (A) of the vinyl-based monomer is
The composition according to any one of claims 11 to 22, wherein the ratio by weight of the solid content of polymer (B) / polymer (A) is within the range of about 10 to about 90 / about 90 to about 10. Stuff. 22. The content of unreacted monomers remaining in the coating resin composition with respect to the organic solvent,
When it is 3% by weight or more based on the above-mentioned organic solvent, it is reduced by distilling off the above-mentioned unreacted monomers to less than 3% by weight. 23. The composition according to any of 22. 23. The composition according to claim 11, wherein the resin according to any one of claims 1 to 11 is blended with a dryer as a curing accelerator. 24. The resin according to any one of claims 1 to 11, wherein a curing agent is mixed with a metal alkoxide, a metal acylate or a metal chelate, respectively. 23. The composition according to any of 22. 25. The composition according to any one of claims 11 to 22, wherein the resin according to any one of claims 1 to 11 is blended with a polyisocyanate compound as a curing agent. 26. The composition according to claim 11, wherein the resin according to any one of claims 1 to 11 is mixed with amino resins as curing agents.