JPH10158311A - Non-aqueous dispersion type resin and resin composition for coating material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-aqueous dispersion type resin that has low viscosity and can form a cured coating layer that resists to sagging on application without corroding an old coating layer by modifying a specific vinyl polymer with a silicone compound. SOLUTION: In an organic solvent that dissolves a vinyl monomer but does not dissolve the vinyl polymer A from this monomer, this non-aqueous dispersion type polymer is prepared by copolymerization of vinyl monomers, in the presence of a (meth)acrylic ester dissolving in this organic solvent and having a 3 or more C alkyl side chain and/or a polymer B composed of a polymer containing >=30wt.% of a styrene monomer bearing an alkyl side chain. In this case, the polymer A from the vinyl monomer is modified with a silicone compound of the formula (R is a monovalent organic group; R' is H, an alkyl; (n) is 0.5-2.0; (m) is 0.0-2.5; m+n is 0.5-3.0) such as polyorganosiloxane, preferably in an amount of 1-60wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous dispersion type resin itself, and a novel and useful resin composition for coatings comprising the resin as an essential film-forming component.

More specifically, the present invention relates to a non-aqueous dispersion-type resin based on specific dispersed particles in a form modified with a silicone compound, and a resin composition for coatings comprising the use of the resin. However, both of these resins and the resin composition for coatings are particularly excellent in weather resistance and the like of the coating film.

[0003] The non-aqueous dispersion type resin and the resin composition for paints according to the present invention are particularly useful as paints for building exteriors and the like, and also as paints for repairing automobiles or paints for baking. It is useful, and unlike conventional organic solvents, it has little effect on old coatings (existing coatings).
It is extremely practical.

[0004] In addition, the present invention provides a coating film having performance not inferior to conventional coating systems using organic solvents. The present invention relates to a well-balanced, highly practical non-aqueous dispersion type resin for coatings and a resin composition for coatings containing the non-aqueous dispersion type resin.

[0005]

2. Description of the Related Art Non-aqueous dispersion type resins have been used as binders for building interiors and exteriors, for metals, or for automobiles. However, dispersed particles are stably formed in a solvent. In order to achieve this, in particular, vinyl-based monomers such as vinyl acetate, whose weather resistance itself is not very good, and (meth) acrylates such as methyl (meth) acrylate and ethyl (meth) acrylate, etc. ) Because lower alkyl esters of acrylic acid must be used in relatively large amounts, the degree of freedom in resin design is naturally limited, and there is no need for dispersed particles. Compared to high solvent-soluble resins, especially in terms of weather resistance,
They tend to be inferior.

[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 has been proposed as disclosed in Japanese Patent Publication 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 means that the improvement of weather resistance and the like is realized, and when the obtained resin is used, it is particularly excellent in weather resistance and the like, and in addition, the influence on the old coating film is small, and The coating film properties are also the same as those using conventional solvents, such as a highly practical non-aqueous dispersion type resin and a coating resin composition obtained using the resin. It is to provide.

[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 studies, a polymer (A) that does not dissolve in an organic solvent is obtained using a silicone compound,
The present inventors have completed the present invention by finding that the modification (conversion) can improve the non-aqueous dispersion type resin, especially the weather resistance and the like.

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

[0011] More specifically, the non-aqueous dispersion type is characterized in that the silicone compound is contained in the polymer (A) at a specific ratio of 1 to 60% by weight. To offer resin,

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

[0013]

Embedded image

And 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. It is intended to provide a specific non-aqueous dispersion type resin comprising a specific organopolysiloxane containing at least one or more in a molecule, and

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

Further, the present invention specifically relates to a specific method such as dissolving vinyl monomers, but not dissolving the vinyl polymer (A) composed of the monomers. A coating resin using a stable non-aqueous dispersion type resin obtained by copolymerizing a vinyl monomer in the presence of a polymer (B) soluble in the organic solvent in the organic solvent. It is another object of the present invention to provide a novel coating resin composition, wherein the polymer (A) obtained from the above-mentioned vinyl monomer has been modified with a silicone compound. Is the thing,

Alternatively, 1 to 60% by weight of the silicone compound is added to the polymer (A).
It is intended to also provide a resin composition for coatings, which consists of being contained at a specific ratio within a certain range,

In addition, in the present invention, specifically, for example, the ratio of the polymer (B) used to the polymer (A) is polymer (B) / polymer (A). It is also intended to provide a specific coating resin composition such that the solid content is in the range of 10 to 90/90 to 10 by weight.

In addition, the content of the unreacted monomers (monomers) remaining in the resin composition for coating with respect to the organic solvent is 3% by weight or more based on the organic solvent. In certain special cases, such as those described above, the unreacted monomers are reduced by distilling them down to less than 3% by weight.
It is intended to provide a specific resin composition for coatings.

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,

It is another object of the present invention to provide a specific resin composition for a coating material in which a metal alkoxide, a metal acylate or a metal chelate is blended as a curing accelerator.

[0022] Furthermore, specific non-aqueous dispersion type resins as described above are mixed with a polyisocyanate compound as a curing agent, respectively, in a specific coating resin. An object of the present invention is to provide a specific coating resin composition in a form containing the composition or an amino resin as a curing agent.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a specific organic solvent in which a vinyl monomer is dissolved but a vinyl polymer (A) comprising the monomer is not dissolved. A stable non-aqueous dispersion resin obtained by copolymerizing a vinyl monomer in the presence of the polymer (B) soluble in the organic solvent. Polymer (A)
Is a novel non-aqueous dispersion-type resin consisting of being modified with a silicone compound,

Next, in a specific organic solvent in which the vinyl monomer can be dissolved but the vinyl polymer (A) composed of the monomer cannot be dissolved, a polymer which can be dissolved in the organic solvent is used. By copolymerizing vinyl monomers in the presence of the union (B), a stable non-aqueous dispersion type resin is obtained, wherein the polymer (A) of the vinyl monomer is a silicone resin. Modified with a compound, and the silicone compound is added in an amount of 1 to 60% by weight.
It is also claiming a novel non-aqueous dispersion type resin consisting of being contained within a certain range,

The silicone compound may be 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 particular non-aqueous dispersion type resin comprising a particular organopolysiloxane having at least one kind of functional group or copolymerizable unsaturated double bond per molecule;

Alternatively, the silicone compound comprises a specific organopolysiloxane represented by the aforementioned general formula [I], a functional group reactive with a functional group contained in the organopolysiloxane, and a copolymerizable Claiming a specific non-aqueous dispersion-type resin, such as a reaction product with a compound having an unsaturated double bond,

The above-mentioned vinyl polymer (A) composed of monomers soluble in an organic solvent and not soluble in the organic solvent is a silicone compound that modifies the polymer (A). 1 to 60% by weight, and 40 to 99% by weight of monomers having a copolymerizable unsaturated double bond forming the polymer (A). Claim a specific non-aqueous dispersion-type resin, such as one that is used so that the total of the classes is 100% by weight;

The above-mentioned vinyl polymer (A) consisting of monomers soluble in an organic solvent and not soluble in the organic solvent forms the copolymerizable unsaturated polymer (A). As a monomer having a double bond, one having 1 carbon atom
Or (meth) acrylic acid esters having two alkyl group side chains, esters of α, β-ethylenically unsaturated (poly) carboxylic acid and / or vinyl acetate, excluding (meth) acrylic acid, Specific non-aqueous dispersion-type resins, such as those obtained using

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 a vinyl monomer forming the polymer (A). (Meth) acrylates, (meth)
Α, β-ethylenically unsaturated (poly), excluding acrylic acid
It also claims certain non-aqueous dispersion-type resins, such as those obtained with carboxylic acid esters and / or vinyl acetate,

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

The above-mentioned polymer (B) soluble in an organic solvent is the above-mentioned (meth) acrylic ester (b-1) having an alkyl side chain having 3 or more carbon atoms, which forms this polymer (B). And / or 20 to 98% by weight of a styrenic monomer (b-2) having an alkyl group side chain;
0 to 80 of copolymerizable unsaturated double bond-containing resin (b-3)
% By weight, and 2 to 80% by weight of the other vinyl monomers (b-4) copolymerizable with the monomers (b-1) and (b-2) described above, Moreover,
Claiming a particular non-aqueous dispersion type resin, such as one comprising a vinyl-based monomer mixture selected such that the sum of each of these monomers is 100% by weight. And

The above-mentioned specific non-aqueous dispersion resin is also an oil-modified alkyd resin in which the polymer (B) soluble in an organic solvent has an oil length of at least 50%. ,

The composition ratio of the polymer (B) soluble in the organic solvent to the vinyl polymer (A) comprising the monomers soluble in the organic solvent and not soluble in the organic solvent is as follows. A specific non-aqueous dispersion type resin having a ratio of 10 to 90/90 to 10 in terms of a solid content part ratio of polymer (B) / polymer (A) is also claimed. Is what you do

In the present invention, a vinyl-based monomer is first dissolved, but the vinyl-based polymer (A) composed of the monomer is not dissolved in a specific organic solvent. In the presence of the polymer (B) which is soluble in an organic solvent, a vinyl-based monomer is copolymerized, whereby the above-mentioned vinyl-based resin composition is obtained in a coating resin composition using a stable non-aqueous dispersion-type resin. Claims are a novel resin composition for a paint, wherein the monomer polymer (A) is modified with a silicone compound.

Next, in a specific organic solvent in which the vinyl-based monomer is dissolved but the vinyl-based polymer (A) comprising the monomer is not dissolved, a polymer which can be dissolved in the organic solvent is used. A resin composition for coating using a stable non-aqueous dispersion type resin by copolymerizing a vinyl monomer in the presence of the union (B). A novel resin composition for coatings, wherein the union (A) is modified with a silicone compound and the silicone compound is contained in the range of 1 to 60% by weight. What you're asking for,

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]. Claims are also directed to certain coating resin compositions in the form of organopolysiloxanes having at least one functional group or copolymerizable unsaturated double bond per 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 aforementioned general formula [I]. An 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; Claiming a specific coating resin composition, such as a reaction product with a compound having a copolymerizable unsaturated double bond,

The above-mentioned vinyl polymer (A), which is composed of monomers soluble in an organic solvent and is not soluble in this organic solvent, is a silicone compound which modifies the polymer (A). % By weight of a monomer having a copolymerizable unsaturated double bond forming the polymer (A).
And a specific resin composition for coatings in the form of a composition comprising

The above-mentioned vinyl polymer (A) consisting of monomers soluble in an organic solvent and not soluble in the organic solvent is a copolymer other than the silicone compound forming the polymer (A). As monomers having an unsaturated double bond, α, β-ethylenically unsaturated monomers other than (meth) acrylates and / or (meth) acrylic acid esters having an alkyl group side chain having 1 or 2 carbon atoms are exemplified. It also claims a specific coating resin composition in the form of an ester of a saturated (poly) carboxylic acid and / or vinyl acetate as a main component,

The above-mentioned polymer (B) soluble in an organic solvent may be a monomer having a copolymerizable unsaturated double bond forming the polymer (B) may be an alkyl group having 3 or more carbon atoms. A specific coating resin composition having a content of at least 30% by weight or more of a (meth) acrylate having a chain and / or a styrenic monomer having an alkyl side chain is also provided. What you're asking for,

The polymer (B) soluble in an organic solvent is a monomer having a copolymerizable unsaturated double bond forming the polymer (B).
20 to 98% by weight of the (meth) acrylates (b-1) having an alkyl side chain and / or the styrene monomer (b-2) having an alkyl side chain.
And 0 to 0 of the copolymerizable unsaturated double bond-containing resin (b-3).
(B-1) and (b-2)
From 2 to 80% by weight of other vinyl monomers (b-4) copolymerizable with each of the following monomers:
Moreover, the present invention also claims a specific coating resin composition in a form such that the total amount of these monomers is 100% by weight.

[0042] The present invention also claims a specific coating resin composition in which the polymer (B) soluble in an organic solvent is an oil-modified alkyd having an oil length of at least 50%.

With respect to the above-mentioned vinyl polymer (A),
The use ratio of the above-mentioned polymer (B) is 10 to 90/9 based on the weight ratio of solid content of polymer (B) / polymer (A).
Claiming a specific coating resin composition, such as in the range of 0-10,

The unreacted monomers contained in the non-aqueous dispersion type resin contained in the resin composition for coatings according to the present invention are present in an amount of 3% by weight or more based on the above-mentioned organic solvent. In some cases, such unreacted monomers have been reduced by distilling off to less than 3% by weight,
It is also claiming a specific coating resin composition,

The non-aqueous dispersion type resin obtained as described above is mixed with a specific paint resin composition in which a drier as a curing accelerator is blended. And 0.01 to 10% by weight
It is also claiming a specific coating resin composition that was blended within a certain range,

A non-aqueous dispersion type resin obtained as described above is mixed with a metal alkoxide, a metal acylate or a metal chelate as a curing agent, respectively. More specifically, 0.001 to 20 with respect to the resin solid content.
It is also claiming a specific coating resin composition that is blended within the range of weight%,

A specific coating resin composition in which a polyisocyanate compound as a curing agent is blended with the non-aqueous dispersion type resin obtained as described above is also used in more detail. And the equivalent ratio of the isocyanate group in the compound described above to 1 /
Within the range of (0.2 to 1.5), the present invention also claims a specific coating resin composition that has been blended.

A specific coating resin composition obtained by mixing an amino resin as a curing agent with the non-aqueous dispersion type resin obtained as described above is also used in more detail. A specific coating resin composition in which the amino resin is blended with the amino resin within a range of 50 to 90/10 to 50 in terms of resin solid content ratio. Has also been claimed.

Hereinafter, the present invention will be described in more detail.

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

Among these, particularly representative organopolysiloxanes, especially marketed products of the organopolysiloxanes, are exemplified by "SH-6018 or BX16-190" (both are hydroxyl-containing). Compound) or "BX16-191" (epoxy group-containing compound) [all products of Toray Dow Corning Silicone Co., Ltd.];

"TSR-160" or "YR-31"
68 (both are hydroxyl-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" (compound containing a methoxy group), "SY-409 or SY-430" (both
Hydroxyl-containing compound) or “SY-550 or VP
-201 "(both are methoxy group-containing compounds) (both products of Wacker Chemie, Germany), and further, vinylethoxysilane, α-methacryloxypropyltrimethoxysilane or trimethylsiloxyethyl (meth) acrylate or "KR-215 or X-22-5002" [Shin-Etsu Chemical Co., Ltd.
Products], various silicon-based monomers.

By using these silicone compounds, the vinyl polymer (A) as described above can be modified by various known and commonly used methods.

That is, the copolymerizable unsaturated double bond-containing silicone compound may be copolymerized when preparing these vinyl polymers, or the functional groups contained in these vinyl polymers may be used. The groups may be reacted with a functional group of the silicone compound, and modified by grafting.

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.

The amount of each of these silicone compounds used is 1
When the amount is less than 10% by weight, the effect of use is likely to be hardly expected to be mainly the effect of improving the coating, particularly, the weather resistance and the like. On the other hand, when the amount exceeds 60% by weight, Inevitably, the coating film obtained therefrom depends on the silicone compound used, that is, the coating film formed therefrom becomes soft, and, in particular, the hardness, solvent resistance and anti-adhesion resistance are reduced,

On the other hand, from the viewpoint that the formed film becomes hard and brittle, which causes a decrease in mechanical properties,
Either case is not preferred. Therefore, the amount of the silicone compound to be used is appropriately in the range of 1 to 60% by weight, and particularly, in 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 is soluble in an organic solvent, to be used for preparing the resin will be described. Then, when the polymer (B) is an acrylic copolymer, it is used as an essential raw material component thereof,
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.

[0060]

Embedded image

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. ]

And the like.

As the alkyl acrylates or alkyl methacrylates (b-1), only typical ones are exemplified, and 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,

[0064] "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 in the side chain usually include 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]

[0066]

Embedded image

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

And the like.

As typical examples of such styrene-based monomers (b-2), vinyl toluene, p-methylstyrene, ethylstyrene,
Propylstyrene, isopropylstyrene or pt
tert-butylstyrene and the like.

Various alkyl acrylates or alkyl methacrylates (b-1) as described above
And / or the styrene-based monomers (b-2) have at least one of the following:
Species, the function of dissolving in a specific solvent, is to be used for the purpose of imparting to the obtained copolymers, the amount of the monomers used in the total monomer mixture, A range of 20 to 98% by weight is suitable, and a range of 30 to 80% by weight is suitable.

When this amount is less than 20% by weight,
Inevitably, the solubility in solvents decreases and it becomes cloudy,
Even if it is transparent at normal temperature, it may become cloudy at low temperature, or in a system where the amount of the copolymerizable unsaturated bond-containing resin (b-3) used is large, at room temperature, Regardless of whether it is transparent or not, even if it is transparent, it becomes difficult to give a target copolymer having desired performance when vinylated, and on the other hand, it exceeds 98% by weight and becomes too much. In this case, although the solubility is good, it is difficult to use a functional group-containing component that imparts dispersibility, adhesion to a substrate and a cross-linking function. Absent.

Next, the above-mentioned copolymerizable unsaturated bond-containing resin (b-3) makes the obtained vinyl copolymer (B) more excellent in pigment dispersibility, The main purpose is to increase the non-volatile content at the time of coating or to improve the solubility in non-polar organic solvents, and is particularly typical of such resins (b-3). Examples are polyester resins, vinyl copolymers, petroleum resins, rosin esters or polyether polyols, but polyester resins (oil-modified types) ) Or acrylic copolymers are suitable.

However, polyester resins which are not oil-modified, so-called oil-free alkyd resins, are mostly poorly soluble in solvents. It is better to keep the amount used so that the target copolymer (B) can be obtained without becoming cloudy.

As typical examples of such polyester resins (including oil-modified types) and vinyl copolymers (among others, acrylic copolymers), only typical ones are exemplified. , Respectively,
No. 1, No. 46-20502 or No. 44-
No. 7134 or JP-A-48-78233 or JP-A-50-58123, a raw material component having a copolymerizable unsaturated bond is essential, together with other raw material components, In a resin skeleton obtained by reacting, a form holding this copolymerizable unsaturated bond,

Alternatively, as disclosed in JP-B-49-47916 or JP-B-50-6223, first, a saturated polyester having no copolymerizable unsaturated bond is obtained, and then the saturated polyester is obtained. It reacts with these functional groups using various functional groups such as a hydroxyl group or a carboxyl group present therein, or further using an epoxy group introduced by reacting a diepoxy compound. Compounds having both a functional group having a property 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 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 to carry out a copolymerization reaction, and an acrylic copolymer having these functional groups is obtained. In union,
In the same manner as described above, in which a copolymerizable unsaturated bond is introduced into a saturated polyester resin, a functional group having a reactivity with a functional group contained in the acrylic copolymer and a vinyl group are combined. Compounds, for example, compounds having both an acid chloride group and a vinyl group, such as (meth) acrylic acid chloride; various compounds having both an epoxy group and a vinyl group, such as glycidyl (meth) acrylate; Or various compounds having both an alkoxysilanol group and a vinyl group, such as vinylmethoxysilane or (meth) acryloxyethyltrimethoxysilane;

Or various compounds having both an acid anhydride group and a vinyl group, such as maleic anhydride or tetrahydrophthalic anhydride; and having both a carboxyl group and a vinyl group, such as fumaric acid or (meth) acrylic acid. Various compounds; or vinyl monomers having both isocyanate groups and vinyl groups, such as 2-hydroxypropyl (meth) acrylate-hexamethylene diisocyanate equimolar adducts or isocyanate ethyl methacrylate. Various compounds having both a hydroxyl group and a copolymerizable unsaturated bond in the form of being obtained by an addition reaction to a polymer.

Such polyester resins include various kinds of resins such as octylic acid, lauric acid, stearic acid or “versatic acid” (synthetic branched (branched) fatty acids manufactured by Shell, The 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" (a synthetic dry oil fatty acid manufactured by Hercules, USA) (Fatty acids), linseed oil (fatty acids), dehydrated castor oil (fatty acids), tall oil (fatty acids), cottonseed oil (fatty acids), soybean oil (fatty acids), olive oil (fatty acids), safflower oil (fatty acids), castor oil (fatty acids) or Various (semi) drying oils (fatty acids), such as rice bran oil (fatty acids); or 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 polyvalents 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 and 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);

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 obtained by a (co) polymerization reaction of diisocyanates; or one or more of various reactive silicone compounds as described above. Various compounds such as those obtained by substituting a part of such various polyhydric alcohols and carboxylic acids and reacting them by a conventional method are obtained.

In the case where an acrylic copolymer containing a copolymerizable unsaturated bond is used as one of the copolymerizable unsaturated bond-containing resins (b-3), the above-mentioned resin or It is appropriate to use one having a desired monomer composition by appropriately selecting from vinyl-based monomers as described below and being obtained by a copolymerization reaction in a conventional manner. is there.

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

It is appropriate that the amount of these two types of resins be used in the range of 0 to 80% by weight, and when the amount is more than 80% by weight,
Either case is not preferable because the viscosity of the obtained copolymer tends to increase and the copolymer tends to gel during the reaction.

In the case where so-called dryer curing is performed in a form in which dryers are blended as a curing accelerator, polyester resins include
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 20% by weight. is required. Therefore, in such a case, it is appropriate to be within the range of 20 to 80% by weight.

The curing agent may be, for example, a case in which at least one selected from the group consisting of metal alkoxides, metal acylates and metal chelates is used, or such curing agents may be used. As, for example, in the case of using a polyisocyanate compound or an amino resin, if various physical properties of the cured coating film are taken into consideration, a copolymerizable unsaturated bond is contained in the resin structure of the polyester resin. In addition, those having a hydroxyl group as much as possible can provide more favorable results.

Next, the vinyl 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;
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 a branched (branched) aliphatic monocarboxylic acid manufactured by Shell Co., The 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;

Or various nitrogen-containing vinyl monomers such as (meth) acrylonitrile;
Further, vinyl chloride, vinylidene chloride, as represented by vinyl fluoride or vinylidene fluoride, functional group-free, various halogenated olefins and the like,

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

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

Further, various epoxy groups such as the above-mentioned (meth) acryloyloxyalkyl acid phosphates or alkylene oxide adducts of -acid phosphites, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate and the like. Compounds of vinyl-containing monomers and phosphoric acid or phosphorous acid or acidic esters thereof or 3-chloro-2
-Various phosphorus atom-containing vinyl monomers such as acid phosphoxypropyl (meth) acrylate;

(D) Various dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate,

The above-mentioned amide bond-containing vinyl monomers, phosphorus atom-containing vinyl monomers or dialkylaminoalkyl (meth) acrylates are all vinyl copolymers, especially acrylic copolymers. For the kind, mainly to give the internal catalytic function, respectively, 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 monomers may be used alone or in combination of two or more kinds. The amount of each of these monomers may be 0.05% in the case of phosphorus atom-containing vinyl monomers from the viewpoint of the effect of use. It is appropriate to be within the range of ~ 5% by weight,
Particularly, in the case of amide bond-containing vinyl monomers or dialkylaminoalkyl (meth) acrylates, the range of 0.05 to 10% by weight is appropriate.

Further, only the above-mentioned other vinyl monomers (b-4) which can be copolymerized with the monomers (b-1) and / or (b-2), respectively, are particularly representative. Just to illustrate

(E) 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 properties, in particular, for the purpose of further improving the weather resistance, etc.,
For example, such as "NORBLOC 7966" (a product of NORAMCO, USA) as disclosed in U.S. Pat. No. 4,528,311.
Benzotriazole-based acrylic monomers; or various polymerizable ultraviolet absorbers such as "ADK STAB T-37" (product of Asahi Denka Co., Ltd.); or "ADK STAB LA-82" [manufactured by Asahi Denka Co., Ltd.] , Hindered amine-based acrylic monomers], and various polymerizable light stabilizers can be copolymerized.

(G) Further, JP-A-63-1280
Nos. "AA-6, AS-6, AN-6" as disclosed in Japanese Patent Application Laid-Open No.
Alternatively, various high molecular weight monomers (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 thereof with ε-caprolactone, “Placcel 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 like,
-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,

Various types of monoglycidyl esters of monohydric carboxylic acids, such as "Kajura E", glycidyl ester of coconut oil fatty acid or glycidyl octylate, or various monoepoxys, such as butyl glycidyl ether, ethylene oxide or propylene oxide Adducts with compounds; or various hydroxyl-containing vinyl monomers such as hydroxyethyl vinyl ethers;

(I) Various α, β-ethylenically unsaturated monomers such as the above-mentioned various unsaturated mono- or dicarboxylic acids 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.

In this case, when the hydroxyl group-containing vinyl monomer is used for the purpose of improving adhesion, the amount of the monomer used is in the range of 0 to 5% by weight. When it is appropriate and used for the purpose of introducing a crosslinking point of a crosslinking agent component,
The amount of the monomers to be used is appropriately in the range of 0 to 30% by weight in view of the solubility of the target vinyl copolymer (B) and the amount of hydroxyl groups in the non-aqueous dispersion type resin. In particular, the range of 0 to 15% by weight is appropriate,

In the case where it is used for dispersion particles (polymer particles) described later, the amount is suitably in the range of 1 to 45% by weight, and particularly preferably in the range of 3 to 30% by weight. . If the amount is less than 1% by weight, a remarkable cross-linking effect hardly appears. On the other hand, if the amount is more than 45% by weight and the amount is excessively high, the price of the paint is inevitably increased. Either case is not preferred.

Carboxyl group-containing vinyl monomers often exhibit an internal catalytic action or an internal catalytic effect, and are therefore impaired in paints, particularly, storage stability and the like. In the case of using such a compound, especially when such internal catalysis or only the internal catalysis effect is expected while considering the improvement of adhesion or compatibility with other resins, 0 to 5 % Is appropriate, especially, 0.2 to 3% is appropriate,

In the case of using as a cross-linking point of a metal alkoxide, a metal acylate or a metal chelate, in the case of the target vinyl copolymer (B), the polymer (B) In particular, from the viewpoint of solubility and the like, the range of 1 to 20% by weight is appropriate.
In particular, a range of 3 to 15% by weight is appropriate,

In the case where it is used for dispersion particles (polymer particles) described later, the amount is suitably in the range of 1 to 30% by weight, and particularly preferably in the range of 3 to 20% by weight. is there. If less than 1% by weight,
A remarkable crosslinking effect cannot easily be exhibited, and
If the amount exceeds 0% by weight and becomes too large, the solubility is liable to be reduced, so that either case is not preferable.

The various monomers described above as the vinyl monomers (b-4) are as described above.
The monomers (b-1) and / or (b-
2) and the above-mentioned resins (b-3) and copolymerization properties, especially, coating workability, gloss, hardness, flexibility, weather resistance, drying properties, solvent resistance, compatibility, From various aspects such as dilutability, solubility, pot life, etc., the amount of each monomer component and the combination thereof may be appropriately selected and determined. What is necessary is just to select and determine within the range of ８０80% by weight.

The 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.

In preparing the non-aqueous dispersion resin according to the present invention, various radical generators as described above are used, and various known non-aqueous dispersion polymerization methods are used. Of course, this can be accomplished.

When an oil-modified alkyd resin is used as the polymer (B) instead of the above-mentioned acrylic copolymer, the above-mentioned various reactive silicone compounds are used to modify the above-mentioned amount of modification. It is essential that the oil-modified alkyd resin has an oil length of about 50% or more so as to have a dissolving power for organic solvents. Necessary, preferably 55% or more is appropriate.

In the case where non-drying oils and / or semi-drying oils or various fatty acids are used as the oil component for preparing the oil-modified alkyd resin. , If there is no graft point,
Otherwise, shortage tends to occur. In such a case, for example, according to various methods disclosed in Japanese Patent Publication No. 49-47916 or Japanese Patent Publication No. 50-6223 described above, this method is used. It goes without saying that there is no problem if the graft point is introduced.

In addition, polyhydric alcohols and polycarboxylic acids are not particularly limited.
Of course, there is no problem even if a desired one is used according to the desired coating film (various) performance.

These compounds are used as so-called dispersion stabilizers to stabilize the dispersion of the polymer particles themselves. The amount or ratio of the compounds used is not limited to the non-aqueous dispersion type resin. From the viewpoint of exhibiting characteristics or characteristics inherent to the polymer or from the viewpoint of dispersion stability, the ratio of the polymer (B) as a dispersion stabilizer to the vinyl monomer as a dispersion particle is defined by the solid content part ratio. Therefore, the range of 10 to 90/90 to 10 is appropriate, and particularly, the range of the solid content ratio of dispersion stabilizers / dispersed particles to 20 to 80/80 to 20 is appropriate. is there.

If the amount of the dispersion stabilizers is less than 10% by weight, it is difficult to obtain a stable dispersion, while if the amount exceeds 90% by weight, the amount becomes too large. Inevitably, it becomes difficult to show the characteristics as a non-aqueous dispersion type resin,
Either case is not preferred.

Next, the vinyl polymer (A) composed of the specific monomers soluble in the organic solvent as described above and not soluble in the organic solvent, that is, the non-aqueous dispersion resin Examples of the vinyl monomers forming the dispersed particles include (meth) acrylic esters having an alkyl side chain having 1 or 2 carbon atoms,

Further, α, other than (meth) acrylic acid,
Various monomers such as esters of β-ethylenically unsaturated (poly) carboxylic acid and vinyl acetate are the main components, and even more specifically, as described above. Various compounds ranging from group (a) to group (g) are particularly typical examples, and these vinyl monomers are used in the proportions as described above.

Further, if desired, for the purpose of obtaining a non-aqueous dispersion type resin having a so-called special function such as a water-repellent or oil-repellent function or a weather resistance function, for example, the following: These various substances can be copolymerized, or the copolymerization reaction can be carried out after adding and mixing the following various substances.

That is, the “Defensa” series or the “MegaFax 170” series (both manufactured by 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 ”[Mitsubishi Yuka Co., Ltd. products], such as various fluorine-based copolymer surfactants, and fluorine-based block copolymers,

Further, “Fluonate K-700”
Various fluoroplastics, such as the series [products of Dainippon Ink and Chemicals, Inc.], the "Lumiflon" series [products of Asahi Glass Co., Ltd.] or "Kyner ADS or SL" (product of Penn Walt, USA) Or various reactive silicone resins as mentioned above,

Alternatively, polymerizable ultraviolet absorbers and polymerizable light stabilizers belonging to the above-mentioned (f) group, such as benzophenone-based, benzotriazole-based, cyanoacrylate-based, oxalic anilide-based or salicylate esters, etc. Excluding various non-polymerizable UV absorbers,

[0132] "Tinuvin 144, 292, 700 or 765" (all products of Ciba Geigy, Switzerland) or "Adecastab LA-52 or LA-52"
87 "[all manufactured by Asahi Denka Co., Ltd.], except for the polymerizable light stabilizers belonging to the above-mentioned (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.
Various vinyl monomers ranging from the group (g) to the group (g) can be introduced and contained in the particles by copolymerization reaction.

Further, the vinyl-based monomer used for preparing the vinyl-based polymer (B) itself and for preparing the non-aqueous dispersion type resin according to the present invention can be dissolved, As a specific organic solvent which does not dissolve the vinyl copolymer (A) consisting of a polymer, only typical ones are exemplified.

“Marcazole R or E” or “Swazol 310” [both manufactured by Maruzen Petroleum 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 ”(product of the same company),“ Shellsol D-40 ”(product of Shell, Netherlands),
"A Solvent", "K Solvent" or "AF Solvent" [both manufactured by Nippon Oil Co., Ltd.]

Alternatively, “Exxon Naphtha No. 3, N
o. 5 or No. 6 ”,“ Exole D-30,
D-40, D-60 or D-70 "or" Isopar C, E, G or H "[both are products of Exxon Chemical Co., Ltd.], and further, n-hexane or n-heptane. Examples thereof include various so-called mixed solvents mainly containing aliphatic hydrocarbons. These hydrocarbon solvents may be used alone or in combination of two or more.

Furthermore, the non-aqueous dispersion type resin and the coating resin composition using the resin according to the present invention are particularly suitable for viscosity, volatility, dispersion aggregation, sagging or electrostatic coating. To adjust sex etc.
Aromatic hydrocarbon solvents such as toluene, xylene, “Solvesso 100” (manufactured by Exxon Chemical Co., Ltd.), or alcohol solvents;

So-called polar solvents such as acetic acid ester solvents; propylene glycol ether solvents; propylene glycol ether ester solvents; or ethoxyethyl propionate also do not depart from the spirit of the present invention. It goes without saying that they can be used together within such a range as not to impair the effects of the present invention.

Further, when a small amount of unreacted monomer is present, the unreacted monomer is removed by an appropriate means such as distillation under reduced pressure. It can be said that odor, which is one of the environmental problems related to paint, can be reduced.

In particular, when the main component of the dispersed particles is a compound represented by vinyl acetate and / or (meth) acrylic acid ester, etc. From the above, within a predetermined time, the rate of addition of the monomers was increased to about 90% by weight or more, especially 9% by weight.
It is very difficult to bring it to more than 5% by weight.

Therefore, when the monomer addition rate is about 9
After confirming that the amount of the unreacted monomer has reached 0% by weight or more, the remaining unreacted monomer of about 10% by weight, more specifically, 3% by weight or more and less than 10% by weight, is subjected to gas chromatography ( By measuring using GC), it is possible to use a vacuum distillation method until the amount becomes less than 3% by weight in the organic solvent,

Alternatively, the unreacted monomers are removed from the system by an appropriate method such as blowing a large amount of a so-called inert gas such as nitrogen or carbon dioxide into the system. Thus, the odor due to the unreacted monomers is significantly reduced.

Next, the dryer used as the above-mentioned hardening accelerator includes all so-called metals such as cobalt-based, lead-based, zirconium-based or calcium-based, which have been used so far. It is intended to refer to a dryer, these may be used alone or in combination of two or more, based on the resin solid content,
It can be used within the range of 0.01 to 10% by weight.

If the amount used is less than 0.01% by weight, the effect of accelerating hardening is hardly sufficiently achieved, and on the other hand, exceeding 10% by weight is used in an excessively large amount. In such a case, the storage stability and the coloring property tend to decrease,
Either case is not preferred.

Therefore, the use amount of the dryer is usually in the range of 0.01 to 10% by weight, and preferably in the range of 0.1 to 5% by weight.

The metal alkoxides, metal acylates or metal chelates used as the above-mentioned curing agents include various ones. Among them, aluminum-based, zirconium-based or titanium-based ones are particularly preferable. However, it is preferred because it is easily available industrially.

[0146] Among these preferable ones, particularly representative ones are exemplified only.
[Hope Pharmaceutical Co., Ltd. product], “Citacoat” [Nippon Soda Co., Ltd. product], “Plenact” [Ajinomoto Co., Ltd. product], “Orgatics TA series, TC series, ZA series, ZB series, ZC series or AL Series ”[both are products of Matsumoto Pharmaceutical Co., Ltd.],“ A
IPD, AMD, ASBD or ALCH series "
Or "Aluminum chelate A, D or M"
Various compounds which are marketed under trade names such as "Kawaken Fine Chemical Co., Ltd." or "Tencalate TP Series" [Tenka Polymer Co., Ltd.] and are widely used in the industry.

These various compounds can be used alone or
Needless to say, a combination of two or more kinds may be used, and it can be used within a range of 0.001 to 20% by weight based on the solid content of the resin.

At that time, the object of the present invention is not deviated in order to improve the storage stability of the non-aqueous dispersion type resin according to the present invention and the resin composition for coatings using the resin. Within such a range or within a range that does not impair the effects of the present invention, for example, various stabilizers such as alcohols, acetylacetone, acetoacetates or lactates are added. Even so, there is no problem at all.

When the amount of each of the metal alkoxides, metal acylates and metal chelates as described above is less than 0.001% by weight, the effect of accelerating the curing is indispensable. On the other hand, when it is used in a large amount exceeding 20% by weight,
Inevitably, especially, there is a tendency that storage stability, coloring property, solubility and the like are reduced,
Either case is not preferred.

Therefore, the use amount of these substances is usually in the range of 0.001 to 20% by weight, and preferably in the range of 0.05 to 10% by weight.

Further, any of the polyisocyanate compounds used as one of the above-mentioned curing agents can be used.
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.

Examples of only such typical polyisocyanate compounds are described in JP-A-61-72013 or JP-A-4-13012.
4, -130171, -132720 or 1327
No. 82, etc., and if only a typical product is exemplified as a marketed product, "Barnock DN-990, DN-
991, DN-991S, DN-992 or BO-
357 "[both products of Dainippon Ink and Chemicals, Inc.],
[Desmodur Z-4370] [product of Sumitomo Bayer Urethane Co., Ltd.] or [Duranate THA-10]
0 "[Asahi Kasei Corporation].

As described above, the amount of the polyisocyanate compound to be used is such that the isocyanate compound is used with respect to 1 equivalent of the hydroxyl group in the nonaqueous dispersion type resin according to the present invention and the resin composition for coating using the resin. Group is
0.2 to 1.5 equivalents, that is, OH
It is appropriate that the equivalent ratio of / NCO be in the range of 1 / 0.2 to 1 / 1.5.

When the use ratio of the isocyanate group to one equivalent of the hydroxyl group is less than 0.2 equivalent,
The effect of use becomes difficult to achieve, and on the other hand, if the use ratio exceeds 1.5 and is used in an excessively large amount, the problem of foaming when applied to the substrate surface having a high moisture content is inevitable. And it becomes less desirable in terms of paint prices.

Therefore, usually, 1 / 0.2 to 1 /
An equivalent ratio in the range of 1.5 is appropriate, and preferably an equivalent ratio in the range of 1 / 0.5 to 1.2.

Further, it is used as one of 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 use ratio of such amino resins is as follows:
The weight ratio of the solid content of the non-aqueous dispersion type resin / amino resin in the range of 50 to 90/10 to 50 is appropriate, and in particular, in view of the physical properties of the coating film and the dispersion stability. The range can be said to be appropriate.

When the amount of the amino resin used is less than 10% by weight, the physical properties of the coating film tend to hardly appear, and when the amount exceeds 50% by weight, the amount is too large. In any case, the coating is apt to become brittle, and in particular, the acid resistance also decreases.

The thus obtained non-aqueous dispersion type resin for paint according to the present invention and the resin composition for paint containing the resin are mainly used for so-called automotive repair, roof or architectural exterior. When recoating a material (substrate substrate) already formed with a film that is easily attacked by polar organic solvents, or when repairing this type of material (substrate substrate), If the amount of such polar organic solvents is reduced or further advanced, and it is completely eliminated,

When a coating containing the polar solvent was applied,
So-called lifting (chumi) often seen
Without producing, a smooth and high commercial value, gives a good coating film, and is susceptible to the polar solvents, for example, such as a plastic material having poor solvent resistance, such as polycarbonate. Also, troubles such as generation of so-called solvent cracks are less likely to occur,
The advantage is brought.

In addition, as compared with the soluble (soluble) type, it is very difficult to sag, and so-called metal return unevenness is less likely to occur during metallic coating for automobiles or automobile repairs. Is easy to obtain.

In the case of two-tone finishing and repair of automobiles or motorcycles, the repainting interval can be made very short, and the nonpolar organic solvents used are photochemically inert and If low-toxic ones are used, remarkably, compared to the conventional case of using highly toxic polar organic solvents,
The working environment is improved, pollution is reduced, and significant improvements in performance are also possible.

Further, when the non-aqueous dispersion type resin for paint and the resin composition for paint containing the resin according to the present invention are used, drying at room temperature, forced drying and drying by heating (baking), In the case of urethane, the method of curing in an amine stream, that is, using and applying to any curing means or curing conditions such as a vapor cure system or a VIC system Can do it,

Such as pigment dispersants, leveling agents, ultraviolet absorbers, light stabilizers or curing accelerators;
In general, it goes without saying that various paint additives can be used in conventional amounts, which are known and commonly used in the art.

As long as it is soluble in organic solvents used in the resin composition for coatings according to the present invention, plasticizers and the like are used for the purpose of improving performance. , Other resins, for example, acrylic copolymers, cellulose compounds, acrylated alkyd resins, alkyd resins, silicone resins, fluororesins or epoxy resins, as appropriate, You can do it,
At that time, as long as the purpose of the present invention is not deviated,
Alternatively, within a range that does not impair the effects of the present invention, these, various, as described above, plasticizers, compounds,
Needless to say, it is important to use (co) polymers or resins.

Further, the non-aqueous dispersion type resin for paint and the resin composition for paint containing the resin according to the present invention are mixed with pigments and kneaded,
It can also be used as a so-called enamel paint by mixing dispersed pigments or processed pigments, etc.
Alternatively, without using such pigments, they can also be used as so-called clear coatings.

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

That is, if only typical 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,

[0170] More specifically, various construction materials such as gates or fences, such as automobile bodies or automobile (parts) parts, motorcycles or motorcycle (parts) parts, and the like; aluminum sashes and the like. And various materials for building interior and exterior; and various materials or products of various iron or non-ferrous metals such as aluminum foil.

[0171] The coating at that time can be applied by using various known and commonly used means such as a spray, a brush or a roller.

The non-aqueous dispersion type resin for paint and the resin composition for paint according to the present invention thus obtained are different from the conventional non-aqueous dispersion composition.
In particular, it is excellent in weather resistance and the like, and has little effect on the old coating film, and also has various practical properties of the coating film, which are not so different from those using conventional solvents and have extremely high practicality.

[0173]

EXAMPLES Next, the present invention will be described in more detail by reference examples, examples and comparative examples, but the present invention is in no way limited to these examples. Not something. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation example of copolymerizable unsaturated bond-containing resin (b-3)] A four-necked flask equipped with a stirrer, a thermometer, a device for removing reaction water, and a nitrogen gas inlet tube was prepared. 57 of soybean oil fatty acids
7 parts, 286 parts of phthalic anhydride, 8 parts of maleic anhydride
, 13 parts of pentaerythritol and 191 parts of glycerin were added, the temperature was raised to 180 ° C, the temperature was maintained for 2 hours, and then 22 hours.
The temperature was raised to 0 ° C.

After maintaining the same temperature in an atmosphere of nitrogen gas until the acid value becomes 9 or less, the solution is diluted with “LAWS” so that the nonvolatile content becomes 70%, so that the nonvolatile content becomes 70%. Thus, a solution of the target resin having a Gardner viscosity at 25 ° C. (the same applies hereinafter) of X, 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 the same flask as in Reference Example 1, 5
78 parts, 157 parts of neopentyl glycol, 20 parts of trimethylolpropane, 422 parts of phthalic anhydride and 20 parts of fumaric acid are charged and heated to 200 ° C. until the acid value becomes 6 or less. , Hold at the same temperature,

By diluting with “Swazol 310” (trade name of aromatic hydrocarbon solvent manufactured by Maruzen Petrochemical Co., Ltd.), the nonvolatile content is 70%, the viscosity is Z, the acid value is 3 0.0 and a solution of the target resin having a hydroxyl value of 77 was obtained. Hereinafter, this is referred to as resin (b-3-2).
Abbreviated.

REFERENCE EXAMPLE 3 (Same as above) "LAW" was placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube.
667 parts of "S" were charged, and the temperature was raised to 120 ° C. At this temperature, i-butyl methacrylate 41
6 parts, 150 parts of lauryl methacrylate,

20-ethylhexyl methacrylate 20
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 completion of the dropwise addition, the temperature was maintained at 120 ° C. for 8 hours. When the nonvolatile content became 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 maintaining the temperature at 100 ° C. until the acid value becomes 1 or less, the nonvolatile content is 60%, the viscosity is Z, the acid value is 0.5, and the hydroxyl value is 7.2.
A solution of the desired resin was obtained. Hereinafter, this is referred to as resin (b-3).
Abbreviated as -3).

Reference Example 4 [Preparation Example of Modified Silicone Compound (1)] In the same four-necked flask as in Reference Example 3, 280 of xylene was added.
Parts, 600 parts of "SH-6018", and 5 parts of hydroquinone monomethyl ether were charged and dissolved by heating to 100C.

When the temperature reached this temperature and 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 target solution of the modified silicone compound (1) having a copolymerizable unsaturated double bond and having a nonvolatile content of 70% was obtained.

Reference Example 5 [Preparation Example of Modified Silicone Compound (2)] In the same four-necked flask as in 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.

When the temperature reached this temperature and the solution state became uniform, 4-hydroxybutyl acrylate 1
85 parts, and then 0.1 part of tetraisopropyl titanate is added.
By holding for a certain period of time, the intended solution of the modified silicone compound (2) having a copolymerizable unsaturated double bond and having a nonvolatile content of 70% was obtained.

Reference Example 6 [Preparation Example of Modified Silicone Compound (3)] In the same four-necked flask as in Reference Example 3, 97 parts of ethoxyethyl propionate and "X-22-173A" (manufactured by Idemitsu) were added. 370 parts of an epoxy group-containing silicone compound) and 5 parts of hydroquinone monomethyl ether were charged and dissolved by heating to 100 ° C.

When the temperature reached this level and the solution state became uniform, 18 parts of acrylic acid was gradually added thereto over 30 minutes, and after the addition was completed, the mixture was kept at 100 ° C. Then, by holding for 2 hours, the intended solution of the modified silicone compound (3) having a copolymerizable unsaturated double bond having a nonvolatile content of 80% was obtained.

Reference Example 7 [Preparation Example of Vinyl Polymer (B)] In the same four-necked flask as in Reference Example 3, 5
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, 400 parts of i-butyl methacrylate, 100 parts of cyclohexyl methacrylate, 110 parts of 2-ethylhexyl methacrylate
Department and

10 parts of acrylic acid and "Adeka stub"
A mixture of 10 parts of "LA-82", 40 parts of tert-butyl peroctoate and 10 parts of tert-butyl perbenzoate was added dropwise over 4 hours.

By maintaining the temperature at 120 ° C. for 8 hours after the completion of the dropping, the nonvolatile content was reduced to 59.0%.
And a solution of the target vinyl polymer (B) having a viscosity of X was obtained.

Next, this resin solution was gradually added to 500 parts
When the pressure was reduced to mg, 50 parts of a mixture of the monomers and the solvent was distilled out, so that 35 parts of "LOWS" was supplemented here, whereby the non-volatile content was reduced. 59.8%, the viscosity is Y, and
A solution of the target vinyl polymer (B) having an acid value of 4.8 was obtained. Hereinafter, this is abbreviated as polymer (B-1).

Reference Example 8 (same as above) In a four-necked flask similar to Reference Example 3, 571 parts of the resin (b-3-1) obtained in Reference Example 1 and 16 parts of “LAWS” were added.
Charge 2 parts and 333 parts of "A Solvent"
The temperature was raised to 20 ° C., and at this temperature, 90 parts of i-propyl methacrylate, 100 parts of tert-butyl methacrylate, 250 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.

By maintaining the temperature at 120 ° C. for 8 hours after the completion of the dropping, the nonvolatile content is 60%.
A solution of the target vinyl copolymer (B) having a viscosity of U and an acid value of 2.0 was obtained. Hereinafter, this is abbreviated as copolymer (B-2).

REFERENCE EXAMPLE 9 (Same as above) In a four-necked flask similar to that of Reference Example 3, 1,000 parts of the resin (b-3-1) obtained in Reference Example 1 and “Exol D-40” were prepared. After charging 366 parts,
As monomers, 200 parts of tert-butyl methacrylate and 100 parts of n-butyl acrylate were used.

The radical generators include 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 objective was to have a nonvolatile content of 60%, a viscosity of V, and an acid value of 2.2. A solution of the vinyl polymer (B) was obtained. Hereinafter, this is abbreviated as polymer (B-3).

Reference Example 10 (same as above) In a four-necked flask similar to that of Reference Example 3, 142 parts of the resin (b-3-2) obtained in Reference Example 1 and 4 parts of “LAWS” were added.
And then 100 parts of methyl methacrylate, 250 parts of tert-butyl methacrylate, 300 parts of i-butyl methacrylate, and 100 parts of n-butyl methacrylate, respectively.
Parts, 50 parts of n-butyl acrylate and 50 parts of β-hydroxyethyl acrylate.

Examples of the additional solvent include “LOWS” 1
84 parts, and as radical generators, ter
30 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 target solution of the vinyl polymer (B) having 0%, a viscosity of Z 2, an acid value of 0.8, and a hydroxyl value of 22 was obtained. Hereinafter, this is abbreviated as polymer (B-4).

Reference Example 11 (same as above) In the same four-necked flask as in Reference Example 3,
E ", 170 parts of xylene, 86 parts of xylene, and 581 parts of" A solvent "were charged. As monomers, 100 parts of tert-butylstyrene,
130 parts of tert-butyl methacrylate,

300 parts of i-butyl methacrylate, 2
A mixture consisting of 94 parts of ethylhexyl methacrylate, 50 parts of “acrylester SL”, 50 parts of 2-ethylhexyl acrylate, 56 parts of β-hydroxyethyl methacrylate and 50 parts of acrylic acid, hand,

One hour after the completion of the dropwise addition, the reaction temperature was raised to
The same procedure as in Reference Example 8 was carried out except that the temperature was raised to 130 ° C. and the temperature was maintained until the acid value became 5 or less. A target solution of the vinyl polymer (B) having an acid value of 3.3 and a hydroxyl value of 38 was obtained. Hereinafter, this is abbreviated as polymer (B-5).

Reference Example 12 (same as above) In the same four-necked flask as in Reference Example 3, 83 parts of the resin (b-3-3) obtained in Reference Example 3 and 63 parts of “LAWS” were added.
After charging 3 parts, the monomers were respectively 100 parts of tert-butylstyrene, 150 parts of isobornyl methacrylate, and 100 parts of cyclohexyl acrylate.

450 parts of i-butyl methacrylate, 2
-Using a mixture consisting of 100 parts of ethylhexyl methacrylate, 40 parts of β-hydroxyethyl acrylate and 10 parts of monobutyl maleate,

In addition, as radical generators, 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 V, the acid value was 2.0, and the hydroxyl value was 12 were obtained, which were the intended solutions of the vinyl polymer (B). Hereinafter, this is abbreviated as polymer (B-6).

Reference Example 13 (same as above) Resin (b-3-1) and resin (b-3-2) obtained in Reference Examples 1 and 2 were placed in the same four-necked flask as in Reference Example 3, respectively. 143 copies and 49
After charging 4 parts,

Each of the monomers is tert.
100 parts of butyl styrene, 200 parts of i-butyl methacrylate, 220 parts of isobornyl acrylate,
Consisting of 150 parts of 4-tert-butylcyclohexyl methacrylate, 100 parts of “acrylester SL”, 40 parts of β-hydroxyethyl acrylate, 20 parts of 1,4-butanediol monoacrylate and 10 parts of monobutyl maleate Change to using a mixture,

In addition, as a radical generator, 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 target vinyl polymer (B) having 0%, a viscosity of W, an acid value of 2.1, 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 and 400 parts of isophthalic acid
Parts, 8 parts of maleic anhydride, 3 parts of pentaerythritol
Reference Example except that 6 parts and 155 parts of 1,6 hexanediol were charged, the temperature was raised to 220 ° C., and the reaction was performed in a nitrogen gas atmosphere until the acid value became 7 or less. 70% non-volatile content as in 1.
The Gardner viscosity at 25 ° C. is Y and the acid value is 3.
3, and a medium oil alkyd resin as a target polymer having an oil length of 55% was obtained. Hereinafter, this is abbreviated as polymer (B-8).

Reference Example 15 (same as above) 400 parts of safflower oil fatty acid and 269 parts of dehydrated castor oil fatty acid, 242 parts of isophthalic acid, 141 parts of trimethylolpropane and 43 parts of pentaerythritol were used. As for, except that it was changed to use "Shellsol D-40",

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., 292 parts of methyl methacrylate, 300 parts of vinyl acetate, 100 parts of ethyl acrylate, 100 parts of “KR-215” and 8 parts of acrylic acid, and tert-butyl A mixture of 20 parts of peroctoate and 5 parts of tert-butyl perbenzoate was added dropwise over 4 hours.

After the completion of the dropwise addition, the mixture was kept at 90 ° C. until the conversion of the monomer became 99%.
Unreacted monomers were removed by vacuum distillation at 00 mmHg.

Next, by using "LOWS" to dilute the nonvolatile matter to 60%,
The intended non-aqueous dispersion type resin having a nonvolatile content of 60%, a Brookfield viscosity at 25 ° C. (the same applies hereinafter) of 4,100 cps, and an acid value of 3.5 was obtained. Hereinafter, this is abbreviated as (Bu-1).

Examples 2 to 10 These examples are also for explaining the non-aqueous dispersion type resin according to the present invention, particularly for specifically explaining the preparation method thereof.

[0216] The same procedures as in Example 1 were carried out except that the proportions of the raw materials used were changed as shown in Table 1.
Various non-aqueous dispersion type resins (Bu-2) to (Bu-10) were obtained.

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

The properties (characteristics) of each of the non-aqueous dispersion-type resins thus obtained are summarized in Table 2.

[0219]

[Table 1]

[0220]

[Table 2]

[0221]

[Table 3]

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

It should be noted that in the table, the provision of a heading (item) of “monomer” means that the terminology of “vinyl monomer” is not used. It is only for the purpose and there is no special purpose. Of course, this "monomer"
Is synonymous with "vinyl monomers".
It should be understood as an abbreviation.

"Tert-Butyl peroct" ......
Abbreviation for "tert-butyl peroctoate"

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

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

[0227]

[Table 4]

[0228]

[Table 5]

[0229]

[Table 6]

<< Footnotes in Table 1 >>"β-HEA": Abbreviation of β-hydroxyethyl acrylate

"Perfluorocyclohexylurea" ..........
Abbreviation of "perfluorocyclohexyl acrylate"

“LA-82”... ..................
Abbreviation of "ADK STAB LA-82"

[0233]

[Table 7]

[0234]

[Table 8]

<< Footnotes to Table 1 >> Abbreviation of "1,4-butanediol monoacrylate"... "1,4-butanediol monoacrylate"

[0236]

[Table 9]

<< Footnote to Table 1 >>"Cemisorb74"
Is a trade name of an ultraviolet absorber manufactured by Chemipro Corporation.

[0238]

[Table 10]

Examples 11 to 26 and Comparative Examples 1 to 3 In these examples, the resin composition for coating according to the present invention was prepared using the non-aqueous dispersion type resin according to the present invention as described above. To explain, in particular, its preparation method,
This is for specific explanation.

(Bu-1) obtained in Examples 1 to 10
Using each of the non-aqueous dispersion-type resins No. to (Bu-10), the mixture was kneaded in a conventional manner according to the kneading composition shown in Table 3.

Then, a crosslinking resin component was blended in accordance with the composition of the meat mixture as shown in Table 4 to obtain a desired resin composition for coating.

Thereafter, each of the paints thus obtained was coated with “LAWS” for diluent thinner, and the paint viscosity was changed to Ford Cup No. With 4,
The solution diluted to 30 seconds was spray-coated on a dull steel plate treated with Bonde # 144 so as to have a dry film thickness of 50 microns or micrometers (μm).

Then, in each case of Examples 11 to 23, the sample was left at room temperature for 2 weeks,
Regarding the cured coating film obtained by drying and curing, and in the case of Example 24, 80 ° C.
In, about the cured coating film obtained by performing forced drying for 30 minutes,

Further, in each case of Examples 25 and 26, baking and drying were performed at 140 ° C. for 30 minutes, and then allowed to stand at room temperature for one week. The cured coating film thus obtained was examined (tested) for evaluation and evaluation of various performances.

In the cases of Comparative Examples 1 to 3,
Three commercial products were used. For each paint, evaluation (judgment) of evaluation and judgment of various performances was performed.

At this time, the points of examination (test) for evaluating and judging various physical properties and various performances are as follows.

(1) Odor test: comprehensive evaluation of sensory test by five persons

◎: No odor ○: Very slight, but odor

(2) Hikarizawa: 60-degree specular reflectance (%)

(3) Hardness: Measurement of scratch hardness using a pencil

(4) Attachment property: Cross-cut adhesion test

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

(6) Alkali resistance ……………………………………………………………………………………………………………………………………………………………………………………………………………………… Evaluation

(7) “Recoating property” for old coating 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.

◎: No abnormalities…: Lifting phenomenon is observed, although it is extremely slight.…: A considerable degree of lifting phenomenon is observed. X: Extremely significant lifting phenomenon is observed.

(8) The coating film composition and the suitability test in “overcoat suitability” are as follows.

Coating film composition: [Coating film (a)-(1) / coating (a)-(2) / coating (b) / substrate slate plate] film

Procedure: First coating film (a)-
After coating (2), leave it at 30 ° C. for about 6 seconds, then apply the same paint to the coating film (a)-(1).
I paint on the top, but by doing this,
Lifting occurs in the coating film (a)-(2), which is the top coat of the first coat.

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

100 parts of "Taipec R-550" [trade name of titanium oxide manufactured by Ishihara Sangyo Co., Ltd.] "Demol EP" [trade name of 3 parts dispersion agent manufactured by Kao Corporation] "Neugen EA" −120 ”[Daiichi Kogyo Seiyaku 1.5 parts Co., Ltd., a brand name of an emulsifying agent] Ethylene glycol 3 parts“ SN Deformer 154 ”[San Nop 1.5 parts Co., Ltd.) [Brand name of foaming agent] 28% ammonia water 1 part Water 24 parts 2% "Hydro Metrolose 90SH-100" 18.6 parts [Product name of thickener manufactured by Shin-Etsu Chemical Co., Ltd.] "Boncoat 3650" [104.6 parts of Dai Nippon Ink Chemical Co., Ltd. The name of acrylic emulsion manufactured by Gaku Kogyo Co., Ltd.] "Self-top HP-103" [The name of thickener manufactured by 1.1 parts of Kojin Co., Ltd.] ]

(9) The influence of the solvent used on the material (that is, the effect of solvents on the plastic material) is evaluated by visually observing whether or not a solvent crack has occurred and the degree of the occurrence.

◎: No abnormality. 場合: Solvent cracks were observed, although very slight. △: A considerable amount of solvent cracks were observed. X: Solvent cracks were observed. If

[0263]

[Table 11]

<< Footnotes in Table 3 >> Each numerical value in the table is a "copy" number.

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

Note 2) Use "LOWS"

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

Note 4) Using “KP-324” [product of Shin-Etsu Chemical Co., Ltd.]

It is to be noted that in the table, the heading (item) of “name of paint base” is provided and the heading (item) of “name of base resin component for paint” is not used. However, this is merely for the convenience of notation, and there is no special purpose. Of course, the term “paint base name” is synonymous with the term “paint base resin component name”, and is an abbreviation. Should be understood.

[0270]

[Table 12]

[0271]

[Table 13]

[0272]

[Table 14]

<< Footnotes in Table 4 >> Each numerical value in the table is a "copy" number. The amounts of the respective crosslinker components other than cobalt naphthenate and lead octylate are also all expressed in terms of solid content weight.

“6% cobalt naphthenate” refers to a compound having a content of metallic cobalt of 6% (that is, the content of the active ingredient).

The term “24% lead octylate” refers to a compound having a metallic lead content (that is, an active ingredient content) of 24%.

Further, the “main ingredient” in the table means:
It should be understood that it is a synonym for the above-mentioned “base resin component for paint”.

[0277]

[Table 15]

[0278]

[Table 16]

<< Footnote to Table 4 >>"Long oil alkyd coating film",
"Vinegar-acrylic coating", "NAD acrylic coating",
“Acrylic lacquer coating film” and “overcoating property” are both data for indicating “recoating property”.

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

[0281] "PPO resin" and "polycarbonate" are both data for indicating "effect on plastic material".

[0282]

[Table 17]

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

"AIPD" is a trade name of aluminum alcoholate manufactured by the former company, which has a nonvolatile content (NV) of 100%, but 40% i-
It is used in the form of a propanol solution.

[0285]

[Table 18]

[0286]

[Table 19]

[0287]

[Table 20]

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

"ZC-540": Abbreviation of "Orgatics ZC-540" (trade name of zirconium chelate; 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%)

[0291]

[Table 21]

[0292]

[Table 22]

[0293]

[Table 23]

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

[0295]

[Table 24]

[0296]

[Table 25]

[0297]

[Table 26]

[0298]

[Table 27]

[0299]

[Table 28]

[0300]

[Table 29]

<< Footnotes to Table 5 >> 1) Natural Exposure: Exposure for two years in the suburbs of Miyazaki City

2) Accelerated weathering test: Accelerated weathering test for 2,000 hours using a sunshine weatherometer (JIS method)

As described above, the non-aqueous dispersion type resin according to the present invention has a small influence on the old coating film (existing coating film), and particularly has various coating properties such as weather resistance. In addition, compared to the conventional type using organic solvents, it is extremely practical, such as not less than superior,

Accordingly, the resin composition for a coating according to the present invention, which contains the non-aqueous dispersion type resin for a coating thus obtained, also has a particularly small effect on an old coating film. In addition, it is easy to know that the coating film is excellent in various properties such as weather resistance and the like.

[0305]

As described above, the non-aqueous dispersion type resin according to the present invention has a small influence on the old coating film (existing coating film), and in addition, particularly has a good coating property such as weather resistance. The performance of the membrane is also extremely high in practicality as it is not inferior to that of the conventional type using organic solvents,

Therefore, the thus-obtained coating resin composition according to the present invention in the form of containing such a non-aqueous dispersion type resin also has a particularly small influence on the old coating film, and And, above all,
It is also excellent in various coating properties such as weather resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/02 C08L 101/02 101/10 101/10 C09D 201/02 C09D 201/02 // C08F 283/12 C08F 283/12

Claims (23)

[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. )
Is a stable non-aqueous dispersion type resin obtained by copolymerizing a vinyl monomer in the presence of a vinyl monomer, and the polymer (A) of the vinyl monomer is a silicone compound A non-aqueous dispersion-type resin characterized by being modified by 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. )
Is a stable non-aqueous dispersion type resin obtained by copolymerizing a vinyl monomer in the presence of a vinyl monomer, and the polymer (A) of the vinyl monomer is a silicone compound In addition, this silicone compound is
A non-aqueous dispersion-type resin, which is contained in an amount of not more than 10% by weight. 3. The above silicone compound is represented by the following general formula [I]: Wherein R 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 binds to a carbon-silicon bond;
A valent organic group or a copolymerizable unsaturated double bond,
R ′ represents a hydrogen atom or an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group, n is a number from 0.5 to 2.0, and m is from 0.0 to 2.0. Assuming that the number is 2.5
In addition, m + n is a number from 0.5 to 3.0. 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 The resin according to claim 1, which is an organopolysiloxane having at least one of the following. 4. The above-mentioned silicone compound is represented by the following general formula [I]: Wherein R 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 binds to a carbon-silicon bond;
A valent organic group or a copolymerizable unsaturated double bond,
R ′ represents a hydrogen atom or an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group, n is a number from 0.5 to 2.0, and m is from 0.0 to 2.0. Assuming that the number is 2.5
In addition, m + n is a number from 0.5 to 3.0. 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 A reaction product of an organopolysiloxane having at least one, a functional group having reactivity with a functional group present in the organopolysiloxane, and a compound having a copolymerizable unsaturated double bond. The resin according to claim 1, which is present. 5. The above-mentioned vinyl polymer (A) comprising monomers soluble in an organic solvent and not being soluble in the organic solvent is a silicone compound which modifies the polymer (A). 1 to 60% by weight, and 40 to 40% by weight of monomers having a copolymerizable unsaturated double bond forming the polymer (A).
The resin according to claim 1, comprising 99% by weight. 6. The above-mentioned vinyl polymer (A) comprising monomers soluble in an organic solvent and not soluble in the organic solvent is a compound other than the silicone compound forming the polymer (A). Examples of monomers having a copolymerizable unsaturated double bond include α, β-ethylenically unsaturated monomers, excluding (meth) acrylates and (meth) acrylic esters having an alkyl group side chain having 1 or 2 carbon atoms. The resin according to claim 1, which is obtained by using an ester of a saturated (poly) carboxylic acid and / or vinyl acetate as a main component. 7. The polymer (B) soluble in an organic solvent is a (meth) acrylic acid ester having an alkyl side chain having 3 or more carbon atoms and / or a styrene monomer having an alkyl side chain. At least 30
The resin according to claim 1, wherein the resin is contained in an amount of not less than wt%. 8. The polymer (B) which is soluble in an organic solvent is the above-mentioned monomer having a copolymerizable unsaturated double bond forming the polymer (B). 20 to 98% by weight of (meth) acrylates (b-1) having a side chain and / or styrene monomer (b-2) having an alkyl group side chain and containing a copolymerizable unsaturated double bond Other vinyl monomers (b-4) copolymerizable with 0 to 80% by weight of the resin (b-3) and the monomers (b-1) and (b-2) described above. From 2 to 80% by weight of
The resin according to any one of claims 1 to 7, which is obtained by using the monomers so that the total of these monomers is 100% by weight. 9. The resin according to claim 1, wherein the polymer (B) soluble in an organic solvent is an oil-modified alkyd having an oil length of at least 50%. 10. The vinyl monomer is dissolved,
The vinyl-based polymer (A) composed of the monomer is copolymerized with the vinyl-based monomer in the presence of the polymer (B) that is soluble in the organic solvent in an organic solvent that cannot be dissolved. A resin composition for coating using a stable non-aqueous dispersion type resin, wherein the polymer (A) of the vinyl monomer is modified with a silicone compound. Characterized in that there is
Resin composition for paint. 11. The vinyl monomer is dissolved,
The vinyl-based polymer (A) composed of the monomer is copolymerized with the vinyl-based monomer in the presence of the polymer (B) that is soluble in the organic solvent in an organic solvent that cannot be dissolved. A resin composition for a coating composition using a stable non-aqueous dispersion type resin, wherein the polymer (A) of the vinyl monomer is modified with a silicone compound, and A resin composition for a coating, comprising the silicone compound in an amount of 1 to 60% by weight. 12. The above-mentioned silicone compound is represented by the following general formula [I]: Wherein R 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 binds to a carbon-silicon bond;
A valent organic group or a copolymerizable unsaturated double bond,
R ′ represents a hydrogen atom or an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group, n is a number from 0.5 to 2.0, and m is from 0.0 to 2.0. Assuming that the number is 2.5
In addition, m + n is a number from 0.5 to 3.0. 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 11. The composition of claim 10, wherein the composition is an organopolysiloxane having at least one. 13. The silicone compound of the following general formula [I]: Wherein R 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 binds to a carbon-silicon bond;
A valent organic group or a copolymerizable unsaturated double bond,
R ′ represents a hydrogen atom or an alkyl group, an aryl group, an acyl group, an aryloxy group or an acyloxy group, n is a number from 0.5 to 2.0, and m is from 0.0 to 2.0. Assuming that the number is 2.5
In addition, m + n is a number from 0.5 to 3.0. 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 A reaction product of an organopolysiloxane having at least one, a functional group having reactivity with a functional group present in the organopolysiloxane, and a compound having a copolymerizable unsaturated double bond. The composition of claim 10, wherein the composition is 14. 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). 1 to 60% by weight, and 40% of monomers having a copolymerizable unsaturated double bond forming the polymer (A).
14 to 99% by weight.
A composition according to claim 1. 15. The vinyl polymer (A) comprising the above-mentioned monomers soluble in an organic solvent and not being soluble in the organic solvent is a non-silicone compound other than the silicone compound forming the polymer (A). Examples of monomers having a copolymerizable unsaturated double bond include α, β-ethylenically unsaturated monomers, excluding (meth) acrylates and (meth) acrylic esters having an alkyl group side chain having 1 or 2 carbon atoms. The composition according to claim 10, which is obtained by using esters of saturated (poly) carboxylic acid and / or vinyl acetate as main components. 16. The above-mentioned polymer (B) soluble in an organic solvent has a carbon number of 3 each as a monomer having a copolymerizable unsaturated double bond forming the polymer (B). 20 to 98% by weight of the (meth) acrylic acid ester (b-1) having an alkyl side chain and / or the styrene monomer (b-2) having an alkyl group side chain, and a copolymerizable unsaturated diester 0 to 80% by weight of the heavy bond-containing resin (b-3) and (b-1) and (b-
2) and from 2 to 80% by weight of other copolymerizable vinyl monomers (b-4), and the total of these monomers is 100% by weight. 11. The method according to claim 10, wherein
16. The composition according to any one of claims 15 to 15. 17. The composition according to claim 10, wherein the polymer (B) soluble in an organic solvent is an oil-modified alkyd having an oil length of at least 50%. 18. The use ratio of the polymer (B) to the polymer (A) of the vinyl monomer is as follows:
The composition according to claim 10, wherein the composition is in a range of 10 to 90/90 to 10 in terms of a solid content part ratio of the polymer (B) / the polymer (A). 19. The content of the unreacted monomers remaining in the coating resin composition with respect to the organic solvent is as follows:
When the amount is 3% by weight or more based on the organic solvent, the amount is reduced by distilling off the unreacted monomers until the amount is less than 3% by weight. 18. The composition according to 17. 20. A resin composition for a coating, comprising a resin according to claim 1 and a dryer as a curing accelerator. 21. A coating material comprising a resin according to claim 1 mixed with a metal alkoxide, a metal acylate or a metal chelate as a curing agent. Resin composition. 22. A resin composition for a coating, comprising the resin according to claim 1 and a polyisocyanate compound as a curing agent. 23. A resin composition for a coating, comprising the resin according to claim 1 mixed with an amino resin as a curing agent.