JPS59179548A - High solid content non-aqueous dispersion resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a high solid content non-aqueous dispersion resin composition.

More specifically, the present invention relates to a thermosetting, high-solids, non-aqueous dispersion resin composition comprising a mixture of a non-aqueous solvent dispersion of a polyester-modified vinyl polymer and a crosslinkable copolymer resin.

In recent years, there has been an increasing demand for resource saving and pollution-free technology in the paint field as well.

In particular, high-solid paints, which are resource-saving paints with low solvent content and high solid content, are preferred because they can be used with conventional paint manufacturing methods or painting equipment. It seems that it has been done.

Furthermore, considering the recent efforts to regulate the use of solvents due to air pollution issues, it seems that conventional high-solid paints that use large amounts of aromatic and ester solvents are not industrially desirable. .

Furthermore, from the viewpoints of regulations on the use of solvents that have been tightened in recent years, non-pollution in a broad sense, and resource conservation, non-aqueous dispersion paints that use aliphatic hydrocarbon solvents as the main solvent have been proposed.
There is.

However, conventionally known non-aqueous dispersion compositions of this type include dispersion stabilizer/dispersion particle combinations such as decomposed natural rubber/acrylic resin, acrylic resin/acrylic resin, oil-modified alkyd resin/acrylic resin, Coating films obtained from thermosetting non-aqueous dispersion paints using polybutadiene/acrylic resin as a color vehicle generally do not have sufficient physical properties. For example, a flexible coating film may have insufficient hardness, and conversely, a hard coating Di may have insufficient hardness.
I couldn't find anything that had both properties at the same time, such as insufficient flexibility. In addition, sufficient performance was not always achieved in salt spray resistance, water resistance, water resistance, and secondary physical properties after each test.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to eliminate or improve the various drawbacks mentioned above.

That is, the present invention provides (c) unsaturated polyester and each intermediater (i) to (i)
5 to 50% by weight of the unsaturated polyester in an aliphatic hydrocarbon solvent that dissolves the intermediate (i) described later and does not dissolve the copolymer obtained from the intermediate (i). (i) In the presence of 30 to 80% by weight of a soluble polyester-modified vinyl resin dispersion stabilizer obtained by graft polymerization of 50 to 95% by weight of an α,β-monoethylenically unsaturated intermediate (:) α, β-%/hydroxyalkyl ester of ethylenically unsaturated carboxylic acid fl'1. ! (i) A non-aqueous dispersion obtained by copolymerizing 70 to 20% by weight of a small mixture consisting of one α,β-monoethyl unsaturated substance other than the above (i). , as solid content
...10 to 90% by weight, (B) (A) α,
N-alkoxymethylated intermediate of β-monoethylenically unsaturated carboxylic acid amide;
- A crosslinkable copolymer resin solution obtained from a monoethylenically unsaturated monomer, as a solid content...90
A11IiI type non-aqueous dispersion resin composition containing ~10jft amount %.

(1) (C) Description of Components The unsaturated polyester used in the present invention is produced by a normal condensation reaction from a multiuniform group # (even if it contains a monobasic acid if necessary, it is L) and a polyhydric alcohol. Any compound can be used as long as it is obtained by the method and is IjJ soluble or semi-soluble in an aliphatic hydrocarbon solvent. Therefore, methyl-substituted hydrogenation (
Particular preference is given to using phthalic anhydride. Also,
By using this component, it is possible to lower the viscosity and achieve 101 solid fractionation compared to using only ordinary aromatic polybasic acids such as phthalic anhydride and isophthalic acid #.
In addition, we have further improved the performance of the coating film, such as weather resistance and UV resistance.
jJ can be raised.

Moreover, compared to the case where hydrogenated (anhydrous) phthalic acid is used for the coating, various performances such as Erichsen resistance, salt spray resistance, and alkali resistance of the coating film can be improved.

Further, the use of this component is preferable since it also has the advantage of making the polished unsaturated polyester soluble or semi-soluble in the aliphatic hydrocarbon solvent.

The methyl-substituted hydrogenated (anhydrous) phthalic acid is preferably reacted in a proportion of 10 to 50% by weight in the unsaturated polyester.

In the above range, if the amount used is less than the lo weight, it is not preferable because it becomes difficult to lower the viscosity and increase the solidity of the composition. Furthermore, the Erichsen, salt spray resistance, and alkali resistance of the coating film also tend to decrease somewhat. In addition, the obtained unsaturated polyester itself is also undesirable because it has poor solubility in non-aqueous solvents made of aliphatic hydrocarbons.

On the other hand, when the amount of the above component used is 50% by weight or more,
Coating film performance such as initial adhesion, impact resistance, and alkali resistance deteriorates.

Specific examples of this component include methyltetrahydrophthalic anhydride, methyltetrahydrofucric acid, methylhexahydrophthalic anhydride, and methylhekidivitrophthalic acid, which may be used singly or as a mixture of two or more. be able to.

The polyester-modified vinyl resin used as a dispersion stabilizer in the present invention contains unsaturated polyester, (i) α,
By graft polymerizing the β-monoethylenically unsaturated Hit product, the excellent flexibility and appearance of polyester resins can be imparted to residential coating films.

Further, an α,β-unsaturated dicarboxylic acid is used as a raw material for the unsaturated polyester used in the present invention. This component comprises 91-10% by weight of unsaturated polyester, preferably 2
It is used in a proportion of ~7% by weight.

In the above range, if the content of this component is 1% by weight or less, there will not be sufficient heat for the α,β-monoethylenically unsaturated intermediate mixture during preparation of the polyester-modified vinyl resin, and therefore the polyester-modified vinyl resin will not be heated sufficiently. As a result, the product has a blended composition of unsaturated polyester and a mixture of α, β-monoethylenically unsaturated phase compound, resulting in significant whitening of the coating film and poor crosslinking properties. Paint film performance 1. In particular, adhesion tends to decrease.

If the content of the component is 10% by weight or more, 1. The reaction between the unsaturated polyester and the α,β-monoethylenically unsaturated polyester mixture tends to cause gelation, which is not preferred.

Specific examples of this component include fumaric acid, (anhydrous) maleic acid, itaconic acid, glutaconic acid, (anhydrous) citraconic acid, and the like. These can be used alone or as a mixture of two or more.

As a raw material for the unsaturated polyester used in the present invention, acid components other than those mentioned above may be used in a proportion of 0 to 40% by market weight, if necessary. Specific examples of such ingredients include (anhydrous) phthalic acid, isophthalic acid (anhydrous) trimellitic acid, (anhydrous) pyronolitho) acid, tetrahydro (anhydrous) phthalic acid, hexahydro (anhydrous) phthalic acid. , (anhydrous) succinic acid, adipic acid, sepatic acid, azelaic acid, benzoic acid, para-t-butylbenzoic acid, isononanoic acid, herzatisocic acid (C1o), and the like. These can be used alone or in combination with two or more of them.

Furthermore, as the polyalcohol used as a raw material for the unsaturated polyester of the present invention, those commonly used in this field can be used without any problem. In particular, when the glycidyl ester of class J (class synthesized saturated fatty acid) is used as a component of a polyhydric alcohol, the unsaturated polyester ()1 tends to become soluble or semi-soluble in aliphatic hydrocarbon solvents. This component is preferably used in an amount of 10 to 45% by weight in the unsaturated polyester.

In the above, the component is JO weight % or more [in this case,
The disadvantage is that the resulting unsaturated polyester itself has less solubility in non-aqueous solvents composed of aliphatic hydrocarbons. Furthermore, the chemical resistance, weather resistance, discoloration resistance against overbaking, etc. of the coating film tend to decrease.

On the other hand, if the content of this component is 45% by weight or more, this is not preferable since there is a drawback that the coating properties such as impact resistance and water resistance are slightly lowered. As a specific example of such ingredients,
So 1. Cardular E (manufactured by Shell Chemical Company, trade name) is mentioned.

In the present invention, a polyhydric alcohol component other than the glycidyl ester of the tertiary synthetic saturated fatty acid is added to the raw material of the unsaturated polyester used in the present invention, preferably in an amount of 10 to 5
It is used in a proportion of 0% by weight.

Specific examples of such ingredients include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythryl, dipentaerythryl, butanediol, and bentane. diol, hexanediol, 1
．． 4-Cyclohexane dimetatool, (hydrogenated) bisphenol A, 2-ethyl, 1,3-hexanediol,
Examples include lauryl alcohol and stearyl alcohol. These may be used alone or as a mixture of two or more.

In the present invention, if necessary, animal and vegetable oils, their fatty acids, petroleum resins, phenol resins, epoxy resins, etc. can also be used as modified raw materials for unsaturated polyesters.

The unsaturated polyester having the composition as described above,
By known methods, such as single-stage anti-Li51 or multi-stage reactions!
! be crushed. In the present invention, the polymerization solvent described below can also be used as a diluent, if necessary.

The acid value of the unsaturated polyester of the present invention is 50 or less (
Resin solid content: The acid of the present invention (the indications for all songs are the same), the hydroxyl value is 50 to 250 (resin solid content: below,
All hydroxyl values in the present invention are expressed in the same way), molecular weights are weight average molecular weights, and 2. (to.

~30.00f) is preferred. In addition, the weight average molecular weight is determined by δl by Gel Permeator 9 chromatography (HLCI type 2A manufactured by Toyo Soda Co., Ltd.) (TSF, the weight average molecular weight of the present invention is the same ).

i: In the range of acid values listed in ■, if the acid value is 50 or more, the alkali resistance etc. of the final coating film performance after graft polymerization of α,β-monoethylenically unsaturated monopolymers will deteriorate. There is a tendency to decrease.

In addition, if the hydroxyl value is lower than 50, the crosslinkability between the polyester-modified vinyl resin and the crosslinkable copolymer resin obtained by raft polymerization of the α,β-monoethylenically unsaturated monomer tends to be insufficient, and vice versa. If it is less than 250, the water resistance of the resulting coating film tends to decrease due to the increase in polar groups.

Furthermore, if the weight average molecular weight is lower than the Shimoda 2,000, the various properties of the polyester resin cannot be fully exhibited. On the other hand, if it exceeds 30,000, the molecular weight of the polyester resin is too high, and when it is modified with an α,β-monoethylenically unsaturated polymer, the viscosity becomes too high, resulting in high solidification and low viscosity. It becomes difficult to do so.

Generally speaking, the polyester-modified vinyl resin used as the dispersion stabilizer of the present invention consists of the unsaturated polyester and (1) α,β-monoethylenic intermediate in an aliphatic hydrocarbon solvent. It is obtained by raft polymerization.

The aliphatic hydrocarbon solvent has the following characteristics. That is, unsaturated polynisder, α described later
, β-monoethylenic intermediate), (i) and (i)
is soluble, but the above-mentioned 1' Imer (i) and the copolymer formed from (i) (1) are such that they are not soluble.

Specifically, for example, hexane, heptane, octane, cyclohexane, cyclohebutane, methylcyclohexane,
Examples include mixtures containing aliphatic hydrocarbons such as ethylcyclohexane and dimedylcyclohexane, mineral spirits, aliphatic naphtha, and the like as main components.

Graft polymerization onto the unsaturated polyester (i)
As the α,β-monoethylenically unsaturated intermediate, any intermediate can be used as long as it makes the polyester-modified vinyl resin as a dispersion stabilizer 0J soluble or semi-soluble in the aliphatic hydrocarbon solvent. It can be used even if there is.

In addition, it is particularly preferable to use a part of the α,β-monoethylenic scientumer represented by the general formula %:: [wherein R is H or CH3, and n represents an integer of 6 to 18] . This monomer is particularly preferred because it renders the dispersion stabilizer tlIJ soluble or semi-soluble in the solvent.

An intermediate having such a specific general formula includes (i) α,
It is used at a polymerization ratio of 5 to 60% by weight in β, β-monoethylene saturated monomers. In the above range, if it is less than the lower limit of 5% by weight, the effect of improving the solubility of the dispersion stabilizer in the solvent tends to decrease, which is not preferable.

If the content exceeds the upper limit of 60% by weight, it is similarly undesirable because coating properties such as hardness and impact resistance tend to deteriorate. Specific examples include 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate,
Examples include esters such as lauryl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. These can be used alone or as a mixture of two or more.

In addition, as the above-mentioned α,β-monoethylenically inert saturated monomer), other monomers other than the intermediate shown by the above-mentioned general formula -' can be added to the cough intermediate mer ( i) 40-95% market weight in
Can be used within the range. Specific examples of such monomers include:
Acrylic acid, methacrylic acid, itaconic acid, maleic acid,
α, β-monoethylenically unsaturated carboxylic acids such as fumaric acid; methyl (meth)acrylate, ethyl (meth)acrylate-I, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl ( meth)acrylate, 5ec-butyl(meth)acrylate, t
-Butyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3
-Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxybutyl (meth)acrylate, 6-hydro-1xyhexyl (meth)acrylate, neopentyl glycol nanano (meth)acrylate, 3-butoxy-2-hydroxypropyl (meth)
Acrylate, 2-hydroxy-1-phenylethyl (
meth)acrylate, polypropylene glycol mono
(meth)acrylate, glycerin mono(meth)acrylate, other N,,N'-dimethyl 7minoethyl (
Dialkyl esters of fumaric acid such as meth)acrylate, glycidyl(meth)acrylate, cyclohexyl(meth)acrylate, phenyl methacrylate, hensyl methacrylate di-butyl fumarate, styrene,
Examples include mff1 bodies such as vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate. These may be used alone or as a mixture of one or more.

In the present invention, the polyester-modified vinyl resin contains 5 to 50% by weight of the aforementioned unsaturated polyester and the aforementioned α and β.
- Monoethylenically unsaturated intermediate (i) 50-95% by weight
It consists of a graft polymerization reaction product with. As mentioned above, the amount of modification of the unsaturated polyester is.

It ranges from 5 to 50% by market weight, preferably from 10 to 40% by car weight. In the above, if it is lower than 5% by weight,
The advantages of polyester resin such as flexibility, pigment dispersibility, and excellent coating appearance cannot be fully utilized. vice versa,
If it exceeds 50% by weight, the hardness, stain resistance, etc., which are the characteristics of vinyl resin, will be impaired, which is also not preferable.

The polyester-modified vinyl resin used as the dispersion stabilizer of the present invention is produced by a fl solution polymerization method. for example,
A method of mixing an unsaturated polyester, a part of the medium (mixture) and a polymerization solvent, and dropping the remaining medium (mixture) and a polymerization initiator into the mixture to polymerize, or into the polymerization solvent,
A method in which an unsaturated polyester, a monomer (mixture), and a polymerization initiator are dropped and polymerized is applicable. In any case, the present invention does not intend to open its eyes to any particular solution polymerization method.

The solvent used in this solution polymerization method is the aliphatic hydrocarbon solvent described above. Further, as a polymerization initiator, for example, benzoyl peroxy 1ζ, t-butyl perbenzoate, t-butyl peroxybenzoate, t-bunalbaroxyoctoate.

1 peroxide such as lauroyl peroxide or azobisisobutyroni!・Use an azo compound such as ril. In addition, these polymerization initiators may be used alone or in an appropriate mixture of two or more.

In the present invention, if necessary, a chain transfer agent such as 1'decylmercaptan, 2-ethylhexyl thioglycolate, carbon tetrachloride, etc. may be used to adjust the molecular weight.

In the present invention, α, β, β-monoethylene saturated carboxylic acid hydroxyalkyl ester tuff form (i) and other α,
A polyester-modified vinyl non-aqueous dispersion (component A) obtained by copolymerizing with β-monoethylenic saturated monomer)
It includes the step of obtaining.

The nonaqueous solvent dispersion of the polyester-modified vinyl polymer needs to contain a hydroxyl group in the molecule in order to undergo a crosslinking reaction with the crosslinkable copolymer resin described below. Therefore, the above t¥1. α, β− as one component in the polymer mixture
A hydroxyalkyl ester intermediate (i) of a monoethylenically unsaturated carboxylic acid is used.

By the way, the monomer (i) has strong polarity. Therefore, a copolymer containing this intermediate as one component is difficult to dissolve in an aliphatic hydrocarbon solvent, and is therefore suitable for forming dispersed particles.

In addition, such an intermediate is added to the α,β-monoconidylenically unsaturated monomer mixture so that the hydroxyl value of the nonaqueous solvent dispersion of the polyester-modified vinyl polymer is approximately 20 to 180. It is used in a range of 5 to 30% by weight.

Needless to say, the monohydroxyl group 1i1i-1 of the nonaqueous solvent dispersion of the polyester-modified vinyl polymer refers to the monohydroxyl group 1i1i-1 of the dispersion particle [i.e. It refers to the total of the hydroxyl value in the heavy content and the hydroxyl value of the dispersion stabilizer component.

In the above range, if the monomer is 5% by weight or less, the crosslinking density becomes low in the reaction process with the crosslinkable copolymer resin, which is not preferable because the coating film's melt resistance decreases. . On the other hand, if it is used in an amount exceeding 30% by weight, the crosslinking density becomes too high during the reaction process with the crosslinkable copolymer resin, and the flexibility and water resistance of the coating film tend to decrease. do not have.

Specific examples of this type of monomer (i) include 2-hydroxypropyl(meth)acrylate-I, 2-hydroxypropyl(meth)acrylate, and 3-hydroxypropyl(meth)acrylate.
meth)acrylate, 2-hydroxybutyl(meth)acrylate, 3-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 5-
Hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, neopentyl glycol mono (meth)acrylate, 3-butoxy-2
-Hydroxypropyl (meth)acrylate, 2-hydroxy-I-phenylethyl (meth)acrylate, polypropylene glycol mono (meth)acrylate l/-1
-, glycerin mono(meth)acrylate, etc., these are one type or:.

It may be used as a mixture of more than one species.

Furthermore, in the presence of a dispersion stabilizer, the monomer (i) other than the hydroxyalkyl ester of the α,β-monoethylenically unsaturated carboxylic acid used for copolymerization is It is used in a range of 70 to 95% by weight.

Specific examples of the monomer (i) include α and β such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.
- Monoethylene unsaturated carboxylic acid; methyl (meth)
Acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec,
, (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 1-1n-octyl (meth)acrylate , lauryl (meth)acrylate, tridecyl (meth)acrylate, su-allyl (meth)acrylate, and other alkyl esters of acrylic acid or methacrylic acid; ) acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, dialkyl esters of fumaric acid such as dibutyl fumarate, and small molecules such as styrene, vinyltoluene, α-notylstyrene, (meth)acrylonitrile, and vinyl acetate. The above-mentioned monomers may be used in combination of 1f! or two or more, depending on the purpose and use of the coating composition.

The non-aqueous solvent dispersion of the polyester-modified vinyl polymer has a polyester-modified vinyl resin 3 as a dispersion stabilizer.
With a presence F of 0 to 80% by weight, said intermediates (i) and (i)
It is obtained by copolymerizing 70 to 20% by weight of a monomer mixture of. In the above, if the content of the polyester-modified vinyl resin as a dispersion stabilizer is less than 30% by weight, it becomes difficult to obtain a stable non-aqueous solvent dispersion. On the other hand, if it exceeds 80% by weight, it becomes difficult to obtain a non-aqueous solvent dispersion, which is also not preferred.

The above copolymerization temperature is determined by the type of polymerization initiator and polymerization solvent used. It is usually carried out at a temperature between 50°C and 200°C, with a range of 60°C and 150°C being particularly suitable.

As the polymerization initiator, the above-mentioned autogenous peroxide or azo compound is preferably used. Incidentally, in order to adjust the molecular weight, it is also possible to use the above-mentioned chain transfer method.

(ll'1 Description of component (B) First, as one of the components (B) of the composition of the present invention, α, β
The N-alkoxymethylated monomer (a) of -monoethylenically unsaturated carboxylic acid amide- is used.

Component (a) is an essential component for the crosslinking reaction with the non-aqueous solvent dispersion of the polyester-modified vinyl thread polymer.

The component (a) is 5 to 30% by weight, preferably 10 to 25% by weight in the crosslinkable copolymer resin, which will be explained in more detail later.
It is preferable to include it by weight of .

In the above 1. If the content of component (a) is 5% by weight or less, the crosslinking reaction with the polyester-modified vinyl polymer will be insufficient, resulting in a decrease in solvent resistance. On the other hand, 30 weight scale Vo
If it is above l; J, it is not preferable because gelation occurs during the production of the crosslinkable copolymer resin. Specific examples of such component (a) include N-1-oxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-
n-propoxymethyl (meth)acrylamide, N-isopropoxymethyl (meth)acrylamide, N-n-
Butoxymethyl (meth)acrylamide, N-5ec-
α, β-monoethylene saturated carboxylic acid amide-alkoxymethylated products such as butoxymethyl (ivy) acrylamide, N-t-butoxymethyl (meth)acrylamide, N-isobutoxymethyl (meth)acrylamide; or these Examples include N-methylolated products of. These may be used alone or as a mixture of one or more.

As one component of the crosslinkable copolymer resin used in the present invention, α,β-monoethylenically unsaturated carboxylic acid (2)
It is particularly preferred to use 0.5 to 10% by weight. Such a bulking body improves the total solubility of the crosslinkable copolymer resin and the nonaqueous solvent dispersion of the polyester-modified vinyl polymer, and has the effect of promoting the crosslinking reaction (In). If the amount is less than 0.5% by weight, the effect will be weakened.On the other hand, if it exceeds 10% by weight, the performance of the cured coating will deteriorate.
Not good.

Specific examples of such components include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. These may be used alone or as a mixture of two or more.

In addition to the above, the raw material 1 of the crosslinkable copolymer resin used in the present invention includes a copolymerizable α,β-monoethylenically unsaturated intermediate (3) in a proportion of 60 to 90% by weight of Wl1. It is preferable to react. Specific examples of such component (3) include 1. Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate,
Isopropyl (meth)acrylate, n-butyl (meth)acrylate, set, -butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl
Acrylic acids such as meth)acrylate, n-hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, 0-octyl(meth)acrylate lauryl(meth)acrylate, dodecyl(meth)acrylate, and stearyl(meth)acryle-1 or alkyl esters of methacrylic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (ivy) acrylate, 3-hydroxypropyl (meth)acrylate, 2
-115 xybutyl (meth)acrylate-1, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (ivy)acrylate, Neovent glycol mono(meth)acrylate, 3-butoxy-2-hydroxypropyl(meth)acrylate, 2-ht'roxy-1-phenylethyl(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerin mono(
meth)acrylate, and other di-fumaric acids such as N,,N'-dimethylamitsuyutyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, and dibutyl fumarate. Alkyl esters, styrene, vinyltoluene, α-methylstyrene,
(Ivy) Monomers such as acrylonitrile and vinyl acetate are mentioned. The l-type compound may be used alone or in combination of two or more depending on the purpose and use of the coating composition.

In addition, when it is necessary to solubilize the crosslinkable copolymer resin described in 0:J only in an aliphatic hydrocarbon solvent, i; ), it is preferable that the specific monomer represented by the above general formula accounts for 10 to 70% by weight.

The crosslinkable copolymer resin of the present invention is produced by a continuous solution polymerization method. The polymerization solvent used in the solution polymerization method is mainly the aliphatic hydrocarbon solvent mentioned above, and if necessary, alcohol solvents such as propyl alcohol and butyl alcohol, ester solvents such as ethyl acetate and butyl acetate, and acetone. , ketone yarn solvents such as methyl ethyl ketone,
In addition, solvents such as alcohol ester solvents and alcohol ether solvents may be used in combination.

In particular, it is preferable to use strongly polar solvents such as ester-based and ketone-based solvents to the extent that they do not impair the stability of the non-aqueous dispersion, which is component (iii) of the present invention.

Further, as the polymerization initiator used for polymerizing the crosslinkable copolymer resin, the above-mentioned organic peroxide or azo compound is used.

Furthermore, in order to adjust the molecular weight, the chain transfer agent described above can also be used.

The weight average molecular weight of the crosslinkable co-polymer resin of the present invention is about 1.
0.000 to 70,000, preferably 20,000
It is desirable that it be within the range of ~60.000. In the above range, if the weight average molecular weight is 10,000 or less, the coating performance will be insufficient;
If it is 0.0110 or more, the smoothness of the coated surface will be impaired. In addition, the resin solution of 70,000 or more is
If the solid content concentration is increased, the viscosity tends to decrease, which is not preferable.

In the present invention, a non-aqueous solvent dispersion of a polyester-modified vinyl polymer (component B) and a crosslinkable copolymer resin (component B) are used.
is used in a solid content weight ratio of 10/90 to 90/10. In the above usage ratio, the crosslinkable copolymer resin is
If it is less than 10%, the crosslinking properties of the coating film will be insufficient,
114 Solvent properties, smoothness of the coated surface, hardness of the coated film, etc. tend to decrease.

On the other hand, when the crosslinkable copolymer resin is more than 90% by weight,
Characteristics of polyester resin disappear.

That is, the tIJ flexibility and the appearance of the coating film are impaired. Further, unfavorable results are also brought about in terms of high solid fractionation, which is another feature of the present invention.

In addition, for the purpose of the present invention, the solid content type non-aqueous dispersion resin composition may contain, if necessary, in order to promote the crosslinking reaction between the polyester-modified vinyl polymer (component A) and the crosslinkable copolymer resin (component B). It is also possible to use one or more of the known acid catalysts and film-forming resins such as epoxy resins, cellulose resins, polyester resins, alkyd resins, amino resins, and blocked isocyanate compounds.

Moreover, in addition to the organic solvent contained in each component, the composition of the present invention may further contain an organic solvent, if necessary, to an extent that does not impair the stability of the composition.

Such an organic solvent may be the same as or different from the organic solvent contained in each component. The content of the self-solvent is such that the total solid content of the composition is 50%.
As mentioned above, it is preferable to set the amount to 55 to 80% by weight. Further, as the organic solvent, the solvent used in the solution polymerization method of the crosslinkable copolymer resin described above can also be suitably used.

In addition, the non-aqueous dispersion type resin composition of the present invention may contain, if necessary, inorganic or organic coloring pigments, metal powder pigments such as penium flakes, extender pigments, and additives commonly used in paints. etc. can be added and used.

Methods for coating the resin composition on the solid content non-water 11 of the present invention include brush coating, spray coating, electrostatic coating,
Various well-known coating methods can be used, such as curtain flow foot, shower coat, and roll coat.

In addition, heat the paint using hot spray (30 to 6
It is also possible to apply the coating at a temperature of 0°C.

In this case, it becomes possible to obtain a higher solid content, so that the characteristics of the present invention become more concentrated and more effective.

In addition, the conditions for overheating the composition of the present invention after coating vary depending on the content of crosslinkable functional disorder in the composition, film thickness, etc., but generally at an appropriate temperature in the range of 120 to 200°C. 1
A cured coating film can be obtained by heating for 0 to 40 minutes.

The cured coating film obtained in this way combines the excellent appearance of the polyester resin with the excellent hardness and stain resistance of the vinyl copolymer resin. The coating film has excellent secondary physical properties after testing such as salt spray resistance, moisture resistance, and water resistance.

The present invention will be explained below using specific examples.

In addition, [part 1 or [%1, 1-part by weight] or 1-weight%
”.

[Method for producing unsaturated polyester]

(1) Unsaturated polyester positive 1 (hereinafter abbreviated as MP-1) In a reaction vessel equipped with a stirrer, a thermometer, a partial condenser, and a nitrogen gas introduction tube, 15.0 parts of methylhexahydrophthalic anhydride and 15 parts of adipic acid were added. .6 parts, fumaric acid 2.7 parts, lauryl], 9.4.14
1<, 7.8 parts of trimethylolpropane and 39.5 parts of Cardular E (trade name manufactured by Shell Chemical) were charged, and the temperature was raised to 240°C under a nitrogen gas atmosphere, and then reacted at the same reaction temperature for about 10 hours. I let it happen. Thus, an unsaturated polyester having a hydroxyl value of 4.7, a hydroxyl value of 110, and a weight average molecular weight Jft of 5,200 was obtained. When this was diluted with mineral spirit to a nonvolatile content of 70%, the viscosity was 2.0 Stoke poise (20° C.).

(2) Unsaturated polyester 2 (hereinafter abbreviated as MP-2) Methylhexahydrophthalic anhydride '23. Part O, cepatic acid 13.
(1 part, isononanoic acid 10.0 parts, fumar 83.0 parts, 2-ethyl 1.3-hexanediol 11.0 parts, Cardurer E (trade name manufactured by Shell Chemical) 30.0 parts 1.
7.0 parts of trimethylolpropane and 3.0 parts of patterned erythritol were charged, and the temperature was raised to 240°C under a nitrogen gas atmosphere.

Next, the reaction was carried out at the same reaction temperature for 4 hours, and when the acid value reached about 20, the pressure inside the system was reduced, and the reaction was continued for about 4 hours.

As a result, an unsaturated polyester having an acid value of 7.9, a hydroxyl value of 81, and a weight average molecular weight of 119,800 was obtained. When this was diluted with mineral spirit to a non-volatile content of 70%, the viscosity was 9.3 Stokes Boise (20°C).

(:3) Unsaturated polyester N[L3 (hereafter MP-
3) Into a reaction vessel similar to that in which M i)-1 was synthesized, 10.0 parts of methyltetrahydrophthalic anhydride, 0 parts of Azelain M] B, and versatic acid (carbon number 10; manufactured by Shell Chemical) were added. name) 10.0 parts, fumaric acid 5.0 parts, neopentyl glycol 3.0 parts, Cardular E (trade name manufactured by Shell Chemical) 25.0 parts, trimethylolethane 3.0 parts, 2-ethyl 1,3 -hexanediol 26
．． Prepare 0 copies.

The temperature was then raised to 240° C. under a nitrogen gas atmosphere. Next, the reaction was carried out at the same reaction temperature for 3 hours, and when the acid value reached about 20, the pressure in the system was reduced and the reaction was continued for about 7 hours. As a result, the #I value was 5.6, the hydroxyl value was 91, and the weight was An unsaturated polyester having an average molecular weight of 6,000 was obtained. When this was diluted with mineral spirit/xylene 9/1 (weight ratio) to a non-volatile content of 70%, the viscosity was 5.1 Stokes Bois (20°C).

(4) Unsaturated polyester Sono 4 (hereinafter referred to as DoM)) -
(abbreviated as 4) In a reaction vessel similar to that in which MP-1 was synthesized, 21.0 parts of methylhexahydrophthalanhydride and 10 parts of cepatic acid were added.
．． 0 parts, isononanoic acid 17.0 parts, fumaric acid 4.0 parts, Cardular E (trade name manufactured by Shell Chemical) 37.0 parts
1 part, 4.0 parts of trimethylolpropane, and 7.0 parts of pentaerythritol, and heated to 240 parts in a nitrogen gas atmosphere.
The temperature was raised to ℃. Then, at the same reaction temperature, it was incubated for about 9 hours.
Let me stab you.

An unsaturated polyester having an acid 1i11i of 7.2, a hydroxyl value of 75, and a weight average molecular weight of 12.100 was obtained.

When this was diluted with mineral spirit to a non-volatile content of 70%, the viscosity was 7.7 Stokes Boids (20°C).

[Production method of polyester modified vinyl resin dispersion stabilizer]

(10σ parts of mineral spirit was added to a reaction vessel equipped with a stirrer, temperature needle, dropping funnel, and cooling tube, and the temperature was raised to 90°C.) The following intermediates, unsaturated polyesters, and initiators were added. The mixture was added dropwise over 3 hours.

45 parts of isobutyl methacrylate, 20 parts of styrene, 2
-35 parts of ethylhexyl acrylate, 85.7 parts of the unsaturated polyester (MP-1), and 0.8 parts of benzoyl peroxide.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same reaction temperature for 4 hours. Thus, acid value 2.5, hydroxyl value 41 weight + i average molecular weight + t, 3o
A resin solution with a non-volatile content of 6 (1.1%) was prepared, and the viscosity was 8.7 stroke poise/20° C. This was designated as MA-1.

(2) Put 73.8 parts of mineral spirit into a reaction vessel similar to that in which MA-1 was synthesized, and lower the temperature to 85.
After raising the temperature to .degree. C., a mixture of the intermediate, unsaturated polyester and initiator described in ) was added dropwise over a period of 3 hours.

35 parts of methyl methacrylate, 1.15 parts of 2-ethylhexyl allyrylate, 15 parts of 2-ethylhexyl methacrylate, 15 parts of styrene, 19.5 parts of ethyl acrylate
parts, 0.5 parts of acrylic acid, the unsaturated polyester (M
P-2) 42.9ft+ (2.5 parts of azobisisobutyronitrile.

After the dropwise addition was completed, 1 or 2 parts of azobisisobutyronitrile was added, and the reaction temperature was raised to 90°C.

The reaction was then carried out for a further 4 hours, thus making the acid 4.9
A resin solution with a hydroxyl value of 20, a weight average molecular weight of 78.300, and a nonvolatile content of 60.3% was obtained.

The clay had a temperature of 13.2 stix voids/20°C. This was designated as MA-2.

(3) Put 78.6 parts of mineral spirit into the same reaction vessel as that used to synthesize MA-1, raise the temperature to 90°C, and then add the following monomer, unsaturated polyester, and initiator mixture. was added dropwise over 3 hours.

10 parts of methyl methacrylate, 15 parts of isobutyl methacrylate, 50 parts of 2-ethylhexyl methacrylate,
25 parts of styrene, the unsaturated polyester (MP-3)
71.4 parts, -.0.8 parts of nzoyl peroxide.

After the dropwise addition, 1.2 parts of benzoyl peroxide was added and the reaction was further carried out for 4 hours at the same temperature, resulting in an acid value of 3.0, a hydroxyl value of 31, a weight average molecular weight of 58.600, and a non-volatile content of 59.8%. A resin solution was obtained. Clay is 11.2
The temperature was 1xpoise/20°C. This is MA-3
And so.

(4) Put 85.7 parts of mineral spirit into a reaction vessel similar to that in which MA-1 was synthesized, and raise the temperature to 85°C.
After heating, the mixture of tP, polymer, unsaturated polyester and initiator described in F was added dropwise over 3 hours.

18 parts of methyl methacrylate, 20 parts of 2-ethylhexyl acrylate, 35 parts of styrene, 5 parts of lauryl acrylate, 2 parts of 2-hydroxyethyl methacrylate, 20 parts of butyl acrylate, the unsaturated polyester (M
P-4) 114.3 parts, azobisisobutyronitrile 2
, 5 parts.

After the dropping was completed, 1.2 parts of abbisisobutyronitrile was added, and the reaction temperature was raised to 90°C.

Next, the reaction was carried out for an additional 4 hours, and the resin temperature reached an acid value of 2.5, a hydroxyl group of 111139, a weight average molecular weight of 75,000, and a non-volatile content of 59.7%. lk was (11). The viscosity was 12.5 stocks/20°C.

This was designated as MA-4.

(5) In the production of MA-3, the reaction was carried out in the same manner except for unsaturated polynisder (MP-3>) and 78.6 parts of mineral spirit was replaced with 66.7 parts, and the acid value was 1. 0, a weight average molecular weight of 48,000, and a non-volatile content of 60.1%.The viscosity was 20.
．． The temperature was 5 strokes/20°C. MA-
I gave it a 5.

[Method for producing a non-aqueous dispersion of polyester-modified vinyl polymer]

(1) Into a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a cooling tube, 104.5 parts of mineral spirate and 250 parts of a dispersion stabilizer (MA-1) were added, and the temperature was raised to 90°C. , the following monomers and methyl methacrylate 4
4 parts, 25 parts of styrene, 10 parts of butyl acrylate, 2
-20 parts of hydroxyethyl methacrylate, 1 part of acrylic acid, 4.0 parts of benzoyl peroxide.

After the dropping was completed, 1.2 parts of penzoyl peroxite was added, and the reaction was further carried out at the same reaction temperature for 4 hours. The reaction product was a milky white dispersion with an acid value of 5.2, a hydroxyl value of 60, and a non-volatile content of 55.4%.

The solvent was distilled off under reduced pressure, and the content of the four non-tidy compounds was reduced to 60.1%. This was designated as MD-1.

(2) In a reaction vessel similar to that in which MD-1 was synthesized, 97.6 parts of mineral spirit and a dispersion stabilizer (MA-2) were added.
After adding 166 parts and raising the temperature to 90° C., the following monomer and initiator mixture was added dropwise over 3 hours.

35 parts of methyl methacrylate, 24 parts of styrene, 20 parts of ethyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 1 part of acrylic acid, 1.2 parts of benzoyl peroxide.

After the dropwise addition was completed, 1.2 parts of benzoyl peroxide was added, and the reaction was further carried out at the same temperature for 4 hours.

The reaction product was a milky white dispersion with an acid (itli of 7.6, hydroxyl value of 55, and non-volatile content of 55.3%).

The solvent was distilled off under reduced pressure, and the nonvolatile content was reduced to 1.0%.
Ta. This was designated as MD-2.

(:() In the production of Mll-2, 332 parts of dispersion stabilizer (MA-2) and 1 part of mineral spirit were added.
The reaction was carried out in the same manner except that 13.5 parts were used. The reaction product was a milky white dispersion with an acid value of 7.2, a hydroxyl value of 44, and a non-volatile content of 55.1%. 1. Distill the solvent under reduced pressure. The nonvolatile content was 60°2%. This was designated as MD-3.

(4) Into a reaction vessel similar to that in which MD-1 was synthesized, mineral subiriso (・103.5 parts) and dispersion stabilizer (MA-
3) After adding 251 parts and raising the temperature to 85° C., the following intermediate and initiator mixture was added dropwise over 3 hours.

Methyl methacrylate 21.5 s, isobutymethacrylate 25.0 parts, styrene 15.0 parts, ethyl acrylate 26.5 parts, 2-hydroxypropyl methacrylate 10.0 parts, methacrylic acid 2.0 parts, azobisisobutyro 0.8 parts of nitrile.

After the dropwise addition was completed, 1.2 parts of azobisisobutyronitrile was added, and the reaction was further carried out at the same reaction temperature for 4 hours. The reaction product was a milky white dispersion with an acid+i+1i'/I, hydroxyl value of 36, and non-volatile content of 54.9%. The solvent was distilled off under reduced pressure, resulting in a nonvolatile content of 60.1%. This was designated as MD-4.

(5) In a reaction vessel similar to that in which MD-1 was synthesized, 93.3 parts of mineral spirit and a dispersion stabilizer (MA-4) were added.
After adding 134.0 parts and raising the temperature to 90°C, the following monomer and initiator mixture was added dropwise over 3 hours.

Methyl methacrylate 1/-22.0 parts 0 styrene 29,
Ofl<, 5.0 parts of butyl acrylate, 20.0 parts of ethyl acrylate, 22.0 parts of 2-hydroxyethyl methacrylate, 2.0 parts of methacrylic acid, 1.0 part of benzoyl peroxide After completion of dropping , 1.2 parts of penzoyl peroxite was added, and the reaction was further carried out for 4 hours at the same layer Lid temperature. The reaction product was a milky white dispersion with an acid value of 9.0, a hydroxyl value of 71 ions, and a nonvolatile content of 54.7%. The solvent was distilled off under reduced pressure to reduce the nonvolatile content to 60.0%. M1. )
-5.

(6) In the production method (2), a dispersion stabilizer (M
The reaction was carried out in the same manner except that A-2) was replaced with (MA-5). The reaction product was a milky white dispersion with an acid value of 5.1, a hydroxyl value of 44, and a nonvolatile content of 55.2%. The solvent was distilled off under reduced pressure, and the nonvolatile content was 6 (1,0
%. This is called MD-6).

(7) In the production method (4), minutes + l & stabilizer (M
A=3) with acid (itfill, hydroxyl group (illilol)
The reaction was carried out in the same manner except that the solution was replaced with a large oil-modified alkyd resin solution having an oil length of 30% and a non-volatile content [i of 0%]. The reaction product is a milky white dispersion of acid 1i1
1i L 1.6, hydroxyl value 7 and non-volatile content 54
．． '/%Met. The solvent was distilled off under reduced pressure F, and the nonvolatile content was 6
It was set to 0.0%. This was designated as MD-7.

[Production performance of crosslinkable copolymer resin solution]

(Pour 66.7 parts of mineral spirit into a reaction vessel equipped with a stirrer, temperature needle, dropping funnel and cooling tube,
After raising the temperature to 90°C, the following monomer and initiator mixture was added dropwise over 3 hours.

20 parts of methyl methacrylate, 33 parts of styrene, 25 parts of 2-ethylhexyl acrylate, 20 parts of N-n-butoxymethyl acrylate, 2 parts of acrylic acid, 1.5 parts of dodecylmercaptan, 2.
Part 5.

After the dropwise addition, 1.2 parts of azobisisobutyronitrile was added and the reaction was carried out for 4 hours at the same temperature, resulting in a tree I with an acid value of 18.2, a weight average molecular weight of 51.200, and a non-volatile content of 59.9%.
An IN solution was obtained. The viscosity is 10.1 stxvoids/2
It was 0°C. This was designated as NH-1.

(2) Put 66.7 parts of mineral spirit into the same reaction vessel as that used to synthesize NH-1, raise the temperature to 85°C, and then add the following monomer and initiator mixture dropwise over 3 hours. I did it.

12.5 parts of methyl methacrylate, 25 parts of styrene, 2
-Ethylhexyl methacrylate-1.35i41S.

10 parts of ethyl acrylate, 15 parts of N-n-butoxymethylacrylamide, 2.5 parts of methacrylic acid, 0.2 parts of dodecylmercaptan, 2 parts of azobisisobutyronitrile
．． Part 8.

After the dropwise addition, 1.2 parts of azobisisobutyronitrile was added, the reaction temperature was raised to 90"C, and the reaction was carried out for 4 hours.
．． A resin solution with a non-volatile content of 60.2% was obtained.The viscosity was 8.4 St. voids/20°C.

This was designated as NH-2.

Example 1 To 6 parts and 7 parts of resin solution (NH-1), 81 parts of titanium oxide was added.
．． 81B, Mineral Spirito (・10 parts, xylene 10
After kneading and dispersing to a particle size of 1 micron or less (measured with a grind gauge; the same applies hereinafter) using a di-ndo mill, 50 parts of the resin solution (NH-1) and a non-aqueous dispersion (MD-1) were added.
), 5 parts of mineral spirit, and 2 parts of xylene were added and mixed with stirring to obtain a uniform pigment dispersion.

Two parts of para-toluenesulfone M (30% ethylene glyfur monobutyl ether solution) were added to the slurry and mixed uniformly with a stirrer.

The obtained high solid content type non-aqueous dispersion resin composition of the present invention was polished to a film thickness of 35 to 4
Viscosity when painting to be 0 micron with Air Spray L No painting; Rock I] cup for 20 to 25 seconds/Adjust with mineral spirit/xylene-7/3 to bring it to room temperature; Solid content when painting 64%), After being left at room temperature for 20 minutes, each sample was heated and dried at a predetermined temperature to obtain a test piece.

Table 2 shows the heating drying conditions and performance test results for the coating film.

Examples 2 to 5 and Comparative Examples 1 to 2 A non-aqueous dispersion type composition was prepared in the same manner as in Example 1 using the formulations shown in Table 1, and was coated on a test plate in the same manner as in Example 1. It was subjected to a comparative test.

The results are shown in Table-2.

, $-1 formulation (medium formulation: parts) Table 2: Heating conditions and pharynx function 1 (Note 1) Using an E Rhibhi pencil Uni, apply it to the paint film at an angle of 45°, and then insert the front blade as it is. The hardness of the pencil does not leave traces of the pencil on the paint film.

(Note 2) Tape peeling test.

(Note 3) Based on Erichsen testing machine.

(Note 4) , +[5-u-5400,6,13,3B
By law.・(Note 5) Sacrificial resistance test (50°C 197%R
1+<) After 120 hours, goban tape hatari test.

◎ 100/100~95/100 0 94/100~B! 5 / 1.00Δ 84
/100~60/100X 59/100~
O/1.00 (Note 6) Salt water spray resistance; A test piece with a cross cut that reaches the substrate was tested using a salt water spray tester (JIS-Z-2371). After testing for 100 hours, the cross cut part was covered with cellophane. I removed the tape.

◎ (Peeling medium 2 pieces) 0 to 1.0 0 (〃 〃 ) 1.1 to 2.0 fi (Haku 912
middle) 2゜1~3, Q w,,.

× (〃 〃) 3.1 fl I-hi (
Note 7) Water resistance: After immersing in tap water at 20°C for 5 days, the tape was removed.

◎ 100 /100~95/1000 94 /
100~85 / 1.008 84/100~6
0 / I (10 It has the characteristics that it has excellent secondary adhesion after impact resistance, moisture resistance, water resistance, and salt spray resistance, and can also have a high coating solid content when adjusted to the viscosity at the time of coating.

Mr. Kazuo Wakasugi, Special Wrer Agency Ranking Officer 1.41 Indications 1982 Patent Application No. 54395 2 Title of Invention High Solids Non-aqueous Dispersion Resin Composition 3
, Relationship with the supplementary case Applicant Name (332) Large 11 coats, 1 Stock Co., Ltd. 14
, Agent 5, Date of amendment order, Issue 2, Box 20, Line 17, Add the following sentence between L1 and 1) (line 11) of the specification.

[Incidentally, the iM of the above-mentioned intermediates is 1 to 111! It is preferable to limit the amount of the intermediate containing a hydroxyl group to 5% by weight or less in (i) the α,β-monoethylenically unsaturated monomer. 1 3. Point F in the specification is corrected as follows.

Claims (1) (c) Unsaturated polyester and each intermediater (i) -
(i) dissolves, but the copolymer formed from intermediate P form (i) and intermediate form (i) does not dissolve in an aliphatic hydrocarbon solvent. i) In the presence of 30 to 80% by weight of a soluble polyester-modified vinyl resin dispersion stabilizer obtained by graft polymerizing 50 to 95% by weight of an α,β-monoethylenically unsaturated monomer, (i) 70-20% by weight of a monomer mixture consisting of a hydroxyalkyl ester monomer of an α,β-monoethylenically unsaturated carboxylic acid and (i) an α,β-monoethylenically unsaturated monomer other than the above (i) The solid content of the non-aqueous dispersion obtained by copolymerizing with 10 to 9
0% by weight, 0) (a) N-alkoxymethylated monomer of α, β to monoethylenically unsaturated carboxylic acid amide F, and υ) α, β-monoethylated monomer other than the above (a) 1. A high solids non-water fat silk composition comprising a crosslinkable copolymer resin solution prepared from a sexually unsaturated intermediate, with a solid content of 90 to 10% by weight.

(2) The unsaturated polyester is (al methyl substituted hydrogenated (anhydride) phthalic acid...JO~5
0 double purchase%, (blα, β-unsaturated dicarboxylic acid...about 1 to 10 flt%, (0) Acid components other than the above (81 and fb)...0 to 4
0%, (d) Glycidyl ester of tertiary synthetic saturated fatty acid...
・10 to 45% by weight, and (e) other than the above +di (itti 7 JL/,
1-/l/...10 to 50% by weight.

(:3) The methyl-substituted hydrogenated (anhydride) phthalic acid is methyltetrahy-1-''I'J anhydride) phthalic acid and/or Medjiru Kizahito'r+ (anhydride) phthalic acid, Claim (2) ) 10-Solid content type non-aqueous dispersion resin compact.

+41 1iij (i) α, β-monoethylenically unsaturated rli imperial is (1) −Meanary formula 1 % formula % [In the formula, R4 and 11 or CH, +, and n are integers from 6 to I11. The amount of α, β-monoethylenically unsaturated flJ, represented by J
...5 to 60% by weight and (2) the above (
α, β-monoethylene 4j unsaturated monomers other than 1)
...40 to 95% by weight of the high solid content non-aqueous dispersion resin composition according to claim o1rn.

(511jiJ general formula〇 H2= J]-COOCn
II, n+, T: α,β-monoethylenically unsaturated? li mer is 2-ethylhexyl (meth)
acrylate, 11-octyl (ivy) acrylate,
Claim No. 4, which is at least one compound selected from lauryl (meth)acrylate, L-decyl (meth)acrylate-1-, l:; and stearyl (meth)acrylate. Item: IN O) Solid content type non-moisture 1) (! +!+ Fat composition.

(6) Said (i) hydroxyalkyl ester of α,β-monoethylenese monounsaturated carboxylic acid monogf (i)
i) The amount of α, β-monoethyl unsaturated 1'1' other than the above (i) is 5 to 30% by weight of the former (i) and 70 to 95% by weight of the latter (i). The high solid content type non-aqueous dispersion resin composition according to claim (1), which is a monomer mixture in a proportion of .

(7) The crosslinkable copolymer resin is: (1) N-al:1-xymethylated monomer of α,β-monoethylenically unsaturated carboxylic acid amide...5 to 30
city p%, (2) α, β-monoethylenically unsaturated carboxylic acid.
・・0.5~10% heavy weight

Claims (1)

[Claims] (1) (c) Unsaturated polyester and each intermediater (1) -
(i) is dissolved, but intermediate (i) and the copolymer obtained from intermediate (i) are not dissolved. (i) In the presence of 30 to 80% by weight of an iiJ-soluble polyester-modified vinyl resin dispersion stabilizer obtained by graft polymerization with 50 to 95% by weight of an α,β-monoethylenically unsaturated intermediate, (i) Intermediate mixture 70 consisting of a hydroxyalkyl ester monomer of an α,β-monoethylenically unsaturated carboxylic acid and (i) an α,β-monoethylenically unsaturated saturated monomer other than the above (i) The solid content of the non-aqueous dispersion obtained by copolymerizing 20% by weight of 1O~90
City%, 0) (a) N-alkoxymethylated intermediate of α,β-monoethylenically unsaturated carboxylic acid amide, and (b) α,β-monoethylenically unsaturated other than the above (a) A high solid content type non-aqueous dispersion resin composition comprising a crosslinkable copolymer resin solution obtained from a monomer and a solid content of 90 to 10% by market weight. (2) The unsaturated polyester includes +al methyl substituted hydrogenated (anhydrous) phthalic acid...10 to 50% by weight, (blα, β-unsaturated dicarboxylic acid...1 to 10% by weight) , (C) Acid components other than the above (a) and (b)...
0-40% by weight, glycidyl ester of ldl tertiary synthetic saturated fatty acid...
10 to 45% by weight, and polyhydric alcohol other than al above +d+, -...
. . . 10 to 50% by weight of the high solid content type non-aqueous dispersion resin composition according to claim 11. ) phthalic acid is methyltetrahydrophthalic acid and/or methylhexahydrophthalic acid (
10-Solid content type non-aqueous dispersion resin composition as described in item 2). (4) The (i) α, β-monoethylenically unsaturated tPmer is represented by the general formula % [wherein R represents H or an integer of 6 to 18 if CHXn] α,β-Monoethylenically unsaturated monomer
... 5-60% market weight and (2) 0)
α,β-monoethylenically unsaturated scientists other than
. . . The high solid content type non-aqueous dispersion resin composition according to claim (1), which is mixed with 40 to 95% by market weight. (5) The general formula CH2=C-C00CnH,2,
α,β-monoethylenically unsaturated tt′4 denoted by +1
．． mer is 2-ethylhexyl (meth)acrylate,
n-octyl (meth)acrylate, lauryl (meth)
The high solid content type non-aqueous dispersion resin composition according to claim (4), which is at least one compound selected from acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate. +61 Above (i) Hydroxyalkyl ester of α,β,β-monoethylene saturated carboxylic acid
) The former (i) is 5 to 30% by weight of the α,β-monoethylenically inert saturated monomer other than the above (i), and the latter (i) is 7% by weight.
The high solids non-aqueous dispersion resin composition according to claim O), which is a monomer mixture in a proportion of 0 to 95% by weight. (7) The crosslinkable copolymer resin is: (1) α, β-monoethylenically unsaturated saturated carboxylic acid amide-alkoxymethylated intermediate 5 to
30% by weight, (2) α, β, β-monoethylene saturated carboxylic acid.
0.5 to 10% by weight, and (3) α1β-monoethylenically unsaturated intermediate other than f11 and (2) above...60 to 90% by weight. , a high solid content type non-aqueous dispersion resin composition according to claim (1).