JPS6198771A - Resin composition for coating - Google Patents

Abstract

PURPOSE:To obtain the titled composition for the coating of electrical appliance and exterior board for automobile, etc., free from cissing and depression and having excellent clarity and smoothness, by compounding a polyester with a vinyl-modified polyester resin at a specific ratio. CONSTITUTION:The objective composition can be prepared by mixing (A) 50-90 (wt)% polyester with (B) a copolymer produced by the copolymerization of (i) 50-99.9% unsaturated polyester containing 1-10% alpha, beta-ethylenic unsaturated dicarboxylic acid (anhydride) and (ii) 0.1-50% vinyl monomer composed of a (meth) macrylica cid ester of an alcohol containing fluorinated alkyl group and if necessary a vinyl monomer copolymerizable therewith, and preferably adding (C) <=50% crosslinking agent (e.g. aminoplast resin to the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a solvent-soluble polyester resin-based coating resin composition. More specifically, the present invention relates to a coating resin composition containing a solvent-soluble vinyl-modified polyester resin containing a fluorine-containing vinyl monomer as one component.

(Prior art) In recent years, coating films obtained from polyester resin coating compositions have superior weather resistance, chemical resistance, stain resistance, etc. compared to alkyd resin coating compositions. It has come to be widely used in electrical appliances, automobile exterior panels, etc.

However, coating films obtained from coating compositions using conventionally known polyester resins have problems in that they are prone to cissing, dents, etc., and lack smoothness.

As a method to improve these problems, for example, a coating composition using a combination of a short-oil or medium-oil alkyd resin and a polyester resin, or the use of silicone additives, etc., have been used.

However, when combined with short oil or medium oil alkyd resin,
There is a problem that the excellent weather resistance, which is a feature of polyester resin, is reduced, and when silicone additives are used, they have poor compatibility with polyester resin, resulting in uneven distribution within the paint and coating film, which may cause problems in painting work. Problems such as deterioration of properties and coating performance arise.

On the other hand, a method of modifying the polyester resin itself has also been proposed. For example, Japanese Patent Publication No. 58-44431 proposes modifying a polyester resin with a very small amount of a diisocyanate compound.

However, in either case, it was insufficient to eliminate the drawbacks of repelling and denting of the coating film.

Due to the above-mentioned drawbacks, polyester resin paints have hindered the expansion of their uses and fields of application, despite their excellent coating performance, and efforts are being made in this industry to improve or eliminate these problems. Currently, there is a strong demand for this.

(Problems to be Solved by the Invention) The present invention provides a polyester resin-based coating composition that takes advantage of the excellent coating performance of polyester resin and has excellent image clarity and smoothness without defects such as repelling or denting. The purpose is to provide the following.

That is, an acrylic ester or methacrylic ester (hereinafter simply referred to as "included") of an alcohol having a fluorinated alkyl group is added to an unsaturated polyester containing α,β-ethylenically unsaturated dicarboxylic acid or its anhydride as an essential component.
・The above objective is achieved by adding and mixing with polyester a vinyl-modified polyester resin obtained by copolymerizing a vinyl monomer) and other copolymerizable vinyl monomers if necessary. This is what I am trying to do.

(Means for Solving the Problems) The polyester (component (■)) used in the present invention is a saturated or unsaturated polyester.

The saturated polyester is a saturated basic acid, a saturated polybasic acid, or an acid anhydride thereof, which is usually used for paints.
About 0-70% by weight and polyhydric alcohol 30-70% by weight
It is a resin obtained by reacting with
15 weight 1 acid value (resin solid content: same below) 50 or less, preferably 20 or less, weight average molecular weight 2,000 to 100,
000, preferably about 4,000 to 80,000.

Further, the unsaturated polyester may be an unsaturated carboxylic acid or an acid anhydride thereof, which is usually used for paints.
It is a resin obtained by reacting about 10% by weight, 30-60% by weight of saturated basic acids, saturated polybasic acids or their anhydrides, and about 30-60% by weight of polyhydric alcohol, and has a hydroxyl value of 15-60% by weight. 200, preferably 40 to 150, acid value 50 or less, preferably 20 or less, weight average molecular weight 2.
000-100,000, preferably 4.000-8
0,000.

Specific examples of the saturated basic acids, saturated polybasic acids, or acid anhydrides thereof include phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, tetraphthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, and methyl. Examples include hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, benzoic acid, para-t-butylbenzoic acid, succinic acid, malonic acid, crotonic acid, adipic acid, sebacic acid, azelaic acid, etc. It can be used as a mixture of more than one species.

Further, specific examples of the unsaturated carboxylic acid or its anhydride include fumaric acid, maleic acid (anhydride), itaconic acid, citraconic acid (anhydride), etc., and these can be used singly or as a mixture of two or more. be able to.

Furthermore, specific examples of the polyhydric alcohol include dipentaerythritol, pentaerythritol, glycerin, trimethylolpropane, trimethylolethane, ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1. 6-hexanediol, 1.3-7'tanediol, hydrogenated bisphenol A; glycidyl esters such as Jura-E (trade name of Shell Chemical Company), glycidyl ethers such as 2-ethylhexyl glycidyl ether, etc. These can be used singly or as a mixture of two or more.

2 as a modified raw material for polyester as required
, animal and vegetable oils and their fatty acids, epoxy resins,
Petroleum resins, rosins, phenolic resins, etc. can be used in small amounts.

The saturated or unsaturated polyester in the present invention is produced by a single-stage reaction or a two-stage reaction by a known method such as a bulk polymerization method, a solvent reflux method, or a combination of the two, and there are no particular limitations on the production method. . Furthermore, an organic solvent, which will be described later, can be used as a diluent if necessary.

Next, the vinyl-modified polyester resin (Component (■)) used in the present invention will be explained.

The unsaturated polyester used in the present invention as component n (A) contains α,β-ethylenically unsaturated dicarboxylic acid or its anhydride as an essential component. As the component, the same components as those used in the production of the unsaturated polyester of component (1) can be used.

The components must be reacted in a proportion of 91 to 10% by weight of the unsaturated polyester. In other words, if this component is less than 1% by weight, the unsaturated polyester will not be sufficiently modified with the fluorine-containing vinyl monomer, which will be described later, and the unsaturated polyester and the fluorine-containing vinyl monomer will become unsaturated. There is a tendency that the resin solution is simply mixed with the copolymer resin, and the resin solution becomes cloudy or the coating performance deteriorates. On the other hand, if the component is used in an amount exceeding 10 weight,
This is not preferred because gelation occurs during the vinyl modification reaction.

In addition to the above α,β-ethylenically unsaturated carboxylic acid or its acid anhydride, the above-mentioned saturated basic acids, saturated polybasic acids, or their Acid anhydride preferably 3
The reaction is carried out in a proportion of 0 to 60% by weight.

Furthermore, the unsaturated polyester which is the If (A) component reacts with the polyhydric alcohol component preferably in a proportion of 30 to 60% by weight.

The unsaturated polyester which is the n (A) component is produced by a one-step or two-step reaction by the above-mentioned known method, and those having the same OH value, acid value, or weight average molecular weight as above can be used. .

Next, in the fluorine-containing vinyl monomer used in the present invention, all or part of the hydrogen atoms in the alkyl group are substituted with fluorine, and the total number of carbon atoms in the alkyl group in one molecule is 1 to 1.
20 is an acrylic ester or methacrylic ester of alcohol.

More specifically, it is a compound that CH2=CHC00CHzCh 1 CHz=CHCOOCH2CFZCFZH.

(lJIz =CHC00CH!(CF2CF2)2H
.

CIl□= CHCOOCHz (CF ICP
3H.

3H7 CHz = CHCOO(j(zC)IzOso□C1
1F+7.

CHz = CHC00CH2C7FIS.

CHz =CHC00CH2CH2CIFl?
.

CHz ”CHCOOCH2CH2RFCRFiC6F
I: mixture of l to c, □F2S) and the like. These can be used alone or as a mixture of two or more.

Furthermore, in the present invention, copolymerizable vinyl monomers other than fluorine-containing vinyl monomers that are used as necessary include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. α,β-monoethylenically unsaturated carboxylic acids; diethyl maleate, dibutyl maleate, dioctyl maleate, methyl maleate, ethyl maleate, propyl maleate, hexyl maleate, isobutyl maleate, pentyl maleate, diethyl fumarate, dibutyl Diesters or monoesters of α, β-monoethylenically unsaturated dicarboxylic acids such as fumarate, dioctyl fumarate, butyloctyl fumarate; 2-
Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Acrylate, 5-hydroxypentyl (meth)acrylate, 6-
Hydroxyhexyl (meth)acrylate, neopentyl glycol mono (meth)acrylate, 3-butoxy-2-hydroxypropyl (meth)acrylate, 2
-Hydroxyalkyl esters of α,β-monoethylenically unsaturated carboxylic acids such as hydroxy-1-phenylethyl (meth)acrylate, polypropylene glycol mono (meth)acrylate, glycerin heptano (meth)acrylate monohalf fumarate; Methyl (meth)
Acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 5ec-
Butyl (meth)acrylate, t-butyl (meth)acrylate.

Isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, lauryl (
Alkyl esters of acrylic acid or methacrylic acid such as meth)acrylate, tridecyl(meth)acrylate, stearyl(meth)acrylate; N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, Nn-probogysimethyl(meth)acrylate; )
Acrylamide, N-isopropoxymethyl (meth)acrylamide, N-n-butoxymethyl (meth)acrylamide, N-5ec-butoxymethyl (meth)acrylamide, N-t-butoxymethyl (meth)acrylamide, N-isobutoxymethyl N- of α,β-ethylenically unsaturated carboxylic acid amide such as (meth)acrylamide
Alkoxymethylated products or their N-methylolated products; other N,N'-dimethylaminoethyl (meth)
Examples include vinyl monomers such as acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl methacrylate, benzyl methacrylate, styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, and vinyl acetate.

The above-mentioned resin composition can be used alone or as a mixture of two or more depending on the purpose and use of the coating resin composition.

The other copolymerizable vinyl monomers can be used in an amount of 0 to 99.9% by weight in the monomer component, that is, component (B).

The vinyl-modified polyester resin of the present invention comprises a mixture of the unsaturated polyester (component A), a fluorine-containing vinyl monomer, and other vinyl monomers used as necessary (B).
component) and the former (component A) in an amount of 50 to 99.9% by weight, preferably 60 to 99.85% by weight, more preferably 80 to 99.85% by weight.
99.8% by weight and the latter (component B) 0.1-50% by weight
, preferably 0.15 to 40% by weight, more preferably 0
．． It is obtained by reacting at a ratio of 2 to 15% by weight.

If the amount of component (B) is less than 0.1% by weight within the above range, the desired effect of the present invention cannot be obtained;
When the component exceeds 50% by weight, the resin solution becomes extremely cloudy,
Not only does it produce a precipitate, but it is also economically unfavorable.

The vinyl-modified polyester resin of the present invention can be prepared by combining the above-mentioned A component and B component in a solvent in the presence of a polymerization initiator to produce a vinyl-modified polyester resin of about 80 to 15
It is obtained by solution polymerization at 0°C for about 2 to 10 hours.

The solvent used in the solution polymerization method includes xylene,
Aromatic hydrocarbons such as toluene; Esters such as ethyl acetate and butyl acetate; Ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; methanol, ethanol, n-propanol, impropanol,
Alcohol such as n-butanol, isobutanol;
Examples include ethylene glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and ethylene glycol monoethyl ether acetate; and diethylene glycol derivatives such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. These organic solvents can be used alone or as a mixture of two or more.

Furthermore, examples of the polymerization initiator used in the solution polymerization method include benzoyl peroxide, t-butyl perbenzoate, t-butyl peroxide, hydroperoxide, cumene hydroperoxide, di-t-
Butyl peroxide: Examples include organic peroxides such as t-butyl peroctoate, and azo compounds such as azobisisobutyronitrile and azoisobutyric acid nitrile. These polymerization initiators may be used alone or in an appropriate mixture of two or more.

The vinyl-modified polyester resin (solid content: 2 or less) thus obtained as component (n) of the present invention has an acid value of 20 or less, a hydroxyl value of 15 to 200, and a molecular weight (weight average molecular weight) of about 2,000 to 100,000. Preferably, it is within a certain range. If the acid value exceeds 20, coating performance such as water resistance tends to deteriorate, and if the hydroxyl value is less than 15, the crosslinking density tends to be insufficient when using a crosslinking agent, resulting in poor coating film performance. The chemical resistance and solvent resistance of On the other hand, when the hydroxyl value exceeds 200, the crosslinking density becomes too high, and the coating film tends to have poor flexibility and water resistance. Furthermore, if the weight average molecular weight is less than 2,000, it will be difficult to fully demonstrate the excellent flexibility and pigment dispersion stability of polyester resin, while if it exceeds ioo or ooo, the viscosity of the resin solution will increase.
This is not very desirable as it may impede painting workability.

The coating resin composition of the present invention comprises 50 to 99% by weight (solid content) of the polyester as the component (1) and the component (II).
1 to 50% by weight of vinyl-modified polyester resin (
solid content).

In the above range, if component (II) is less than 1% by weight, the effect of preventing repellency and denting of the coating film cannot be obtained, and if it exceeds 50% by weight, it becomes difficult to fully demonstrate the excellent performance of polyester. Neither is preferable.

In addition, when obtaining the resin composition for paint of the present invention, the composition (
Solid content) fluorine atoms are approximately 0.05 to 13fffffi
% of component (1), (n) (A
It is preferable to determine the amount of each component to be used, the type of fluorine-containing vinyl monomer, etc. within the usage range of component (II) and component (B).

The resin composition for coatings obtained as described above can be dissolved in the above-mentioned organic solvent and dried to form a coating film, but after mixing the crosslinking agent component commonly used for coatings, it can be heated at room temperature. It is preferable to form a film by curing or heating.

Examples of the crosslinking agent component include aminoplast resin,
Examples include isocyanate compounds (including blocked isocyanate compounds).

The aminoplast resin, which is one of the crosslinking agent components, reacts with the hydroxyl groups and carboxyl groups in the polyester and polyester-modified vinyl resin when heated to form a strong film.

The usage ratio of the aminoplast resin is (polyester +
It is preferable that vinyl modified polyester resin)/(aminoplast resin)=95-5015-50 (solid content weight ratio).

A coating film obtained from a composition in which the aminoplast resin is added in less than the above-mentioned proportion tends to have insufficient crosslinking density, resulting in a decrease in solvent resistance and chemical resistance of the coating film.On the other hand, A coating film obtained from a composition in which more aminoplast resin is added than the above ratio is not very preferable because the crosslinking density becomes too high and flexibility becomes poor.

Specific examples of aminoplast resins include urea-formaldehyde resins, melamine-formaldehyde resins, benzoguanamine-formaldehyde resins, resinous condensates produced by reacting various triazine derivatives with formaldehyde, and etherified products thereof. In addition, in the production of etherified products, alcohols used as etherification agents include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, 2-
Examples include ethylbutanol, 2-ethylhexanol, benzyl alcohol, lauryl alcohol, and alcohols having 1 to 4 carbon atoms are preferred.

In a composition using an aminoplast resin as a crosslinking agent, a curing accelerator such as phosphoric acid,
Conventional acid curing accelerators such as formic acid and aromatic sulfonic acids may also be used.

Further, the isocyanate compound, which is one of the crosslinking agent components used in the present invention, is an isocyanate compound having two or more isocyanate groups in the molecule, or a compound in which these isocyanate groups are blocked with a blocking agent.

The isocyanate compound is 50% by weight or less in the total composition,
Preferably, it is used in a ratio of (polyester + OH group in vinyl-modified polyester resin)/(NCO group in isocyanate compound) = 1/1.3 to 110.3 (equivalent ratio).

Total O of polyester and vinyl modified polyester resin
If the equivalent ratio of the NCO group in the isocyanate compound to the equivalent of H group is less than 0.3, the crosslinking density tends to be insufficient, and the solvent resistance and chemical resistance of the coating film tend to decrease. On the other hand, when the equivalent ratio of NGO groups exceeds 1.3, properties such as water resistance of the coating film tend to deteriorate due to unreacted isocyanate compounds.

Examples of the isocyanate compound include ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, decamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2.4-1-lylene diisocyanate, 2.6-
Drylene diisocyanate, 1.5-naphthylene diisocyanate, 4.4',4'-1-rephenylmethane triisocyanate, 4.4'-diphenylmethane-diisocyanate, 3,3'-dimethyl-4°4'-diphenylene - polyisocyanates such as diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, lysine isocyanate; 2,2.4-)tumethyl 1,3-pentadiol,
Hexamethylene glycol°, cyclohexane dimetatool, trimethylolpropane, hexanetriol,
Blocking of bifunctional or higher functional polyisocyanates obtained by addition reaction with low-molecular polyols such as glycerin and pentaerythritol, polyisocyanates with a biuret structure, polyisocyanates with allophanate bonds, or these isocyanate compounds with a blocking agent. isocyanate compound.

Examples of the blocking agent include phenols such as phenol and cresol, alcohols such as methanol, benzyl alcohol, and ethylene glycol monoethyl ether;
Active methylene series such as methyl acetoacetate and dimethyl malonate, acid amide series such as acetanilide and acetate amide, other imide series, amine series, imidazole series, urea series, carbamate series, imine series, oxime series, mercaptan series, There are sulfite-based, lactam-based, etc.

The coating resin composition of the present invention may contain other solvent-based resins such as phenol resins, polybutadiene resins, alkyd resins, epoxy ester resins, silicone resins, etc. in an amount of less than 50% by weight depending on the use and purpose. be able to.

Furthermore, in the composition of the present invention, pigments such as anticorrosion pigments, coloring pigments, extender pigments, and various additives such as anti-sag agents, color separation inhibitors, and surface conditioners may be added in desired amounts. A coating composition can be obtained by mixing and kneading using a known kneading method such as a sand mill, ball mill, roll mill, etc. The composition of the invention thus obtained can be applied by conventional coating methods such as roll coating, spray coating,
Coating metals such as cold-rolled steel, aluminum, brass, chemically treated materials, and other substrates such as glass, asbestos, cement roofing, leather, wood, paper, and textiles using electrostatic coating. can.

In addition, the resin composition for paint of the present invention can be dried at room temperature or
A coating film can be obtained by baking and drying at 00° C. to 200° C. for about 10 minutes to 40 minutes.

Thus, in the resin composition for paint of this invention, we believe that by introducing fluorine atoms into the resin composition, it is possible to reduce the surface tension of the paint film, which is one of the causes of repellency and denting of the paint film. Therefore, it is possible to form a coating film free of the above-mentioned defects.

The details of the present invention will be explained below with reference to Examples and Comparative Examples.

"Part" or "%" indicates "part by weight" or "% by weight". Incidentally, prior to the Examples, a polyester resin was manufactured as follows.

[Production method of polyester resin]

Production Example 1 Unsaturated polyester solution 1 (hereinafter referred to as PE-
35.7 parts of isophthalic acid, 18.7 parts of adipic acid, 2.0 parts of fumaric acid, and 34 parts of neopentyl glycol were placed in a reaction vessel equipped with a stirrer, a thermometer, a partial condenser, and a nitrogen introduction tube. .9 parts of hydrimethylolpropane and 8.7 parts of hydrimethylolpropane were charged, and the reaction temperature was 230°C for about 10 minutes in a nitrogen stream.
A time reaction was performed.

The obtained unsaturated polyester had an acid value of 9.5, a hydroxyl value of 103, and a weight average molecular weight of 12.000.

When this is dissolved and diluted with ethylene glycol monobutyl ether and xylene to a non-volatile content of 60%, the viscosity (20℃)
A solution of 4.9 Stokes was obtained.

In a reaction vessel similar to PE-1, isophthalic acid 35.7
9.8 parts of adipic acid, 10.0 parts of fumaric acid, 35.8 parts of neopentyl glycol, and 8.7 parts of trimethylolpropane were charged, and the reaction was carried out in the same manner.

The obtained unsaturated polyester had an acid value of 9.8, a hydroxyl value of 105, and a weight average molecular weight of 12,800.

When this is dissolved and diluted with ethylene glycol monobutyl ether and xylene to a non-volatile content of 60%, the viscosity (20℃)
A 7.0 Stokes solution was obtained.

In a reaction vessel similar to PE-1, 35.7 parts of isophthalic acid, 20.8 parts of adipic acid, neobenzyl 1) 1-) L
34.8 parts of t and 8.7 parts of trimethylolpropane were charged, and the reaction was carried out in the same manner.

The obtained saturated polyester resin had an acid value of 9.9, a hydroxyl value of 106, and a weight average molecular weight of 9,000.

When this is dissolved and diluted with ethylene glycol monobutyl ether and xylene to a non-volatile content of 60%, the viscosity (20℃)
A solution of 3.1 sq. was obtained.

[Method for producing vinyl-modified polyester resin solution] Production Example 1 1,45 parts of the above PE-1 was charged into a reaction vessel equipped with a stirrer, a thermometer, a cooler, and a dropping device, and the temperature was raised to 90°C. , fluorine-containing vinyl monomer (CHI = CH
C00CHzCh: Hereinafter abbreviated as FM-1]0.
A mixture consisting of 24 parts of benzoyl peroxide, 0.8 parts of benzoyl peroxide, and 13.4 parts of xylene was added dropwise over 1 hour.

After the dropwise addition was completed, the same temperature was maintained for 1 hour, then heated to 110° C., maintained at the same temperature for 2 hours, and finally cooled.

The obtained vinyl-modified polyester resin had a fluorine atom content of 0.1%, an acid value of 9.6, a hydroxyl value of 102, a weight average molecular weight of 14,000, and a viscosity of 3.3 Stokes (solution viscosity, hereinafter the same). there were.

The obtained vinyl modified polyester resin solution was converted into VPE-1.
It is abbreviated as

Production Example 2 145 parts of the PE-1 was prepared in the same manner as in Production Example 1,
A similar reaction was carried out using 1.5 parts of fluorine-containing vinyl monomer FM-1, 0.8 parts of benzoyl peroxide, and 1769 parts of xylene to obtain a fluorine atom content of 2.0%, an acid value of 9.8,
Hydroxyl value 98, weight average molecule ff1l 4. OOO
A vinyl modified polyester resin of 11 parts and 3.2 Stokes was obtained.

The obtained resin solution is abbreviated as VPE-2.

Production Example 3 In the same manner as Production Example 1, 145 parts of the above PE-1, 10 parts of fluorine-containing vinyl monomer (CH2=CHC00ClhCFzCFzH: hereinafter abbreviated as FM-2), and 0.8 parts of benzoyl peroxide. A similar reaction was carried out using 22.0 parts of xylene to obtain a vinyl-modified polyester having a fluorine atom f content of 4.2%, an acid value of 10.0, a hydroxyl value of 93, a weight average molecular weight of 14,300, and a viscosity of 2.8 Stokes. A resin was obtained.The obtained solution was subjected to VPE.
It is abbreviated as -3.

Production Example 4 In the same manner as in Production Example 1, 145 parts of the PE-1, fluorine-containing vinyl monomer (C1h = CHC00CHz (
CF2CFZ) zH: Hereinafter abbreviated as FM-3]15
part, 0.8 part of hensilver oxide and 2 parts of xylene
6.1 parts and reacted in the same manner to reduce the fluorine atom content to 7.
．． 7%, acid value 9.9, hydroxyl value 89, weight average molecular weight 1
4,600 and a viscosity of 2.5 Stokes was obtained. The obtained resin solution is abbreviated as VPE-4.

Production Example 5 In the same manner as in Production Example 1, 145 parts of the PE-1, fluorine-containing vinyl monomer (CHz = CHC00C1h (
CFICF 3H: hereinafter abbreviated as FM-4] 20 parts, benzoyl peroxide 0.8 part and xylene 30
．． 2 parts were reacted in the same manner, and the fluorine atom content was 11
．． 0%, acid value 9.5, hydroxyl value 85, weight average molecular weight 1
4,400 and a viscosity of 2.5 Stokes was obtained. The obtained resin solution is abbreviated as VPE-5.

Production Example 6 In the same manner as Production Example 1, 145 parts of the above PE-1, 25 parts of fluorine-containing vinyl monomer], and 0.8 parts of benzoyl peroxide were added.
34.3 parts of xylene and 111.6% fluorine atom content, acid value 9.1, hydroxyl value 81.
, weight average molecular weight 14,200, viscosity 2.37! , 1-
- A vinyl-modified polyester resin was obtained. The obtained resin solution is abbreviated as VPE-6.

Production Example 7 In the same manner as Production Example 1, 145 parts of the PE-1, 30 parts of fluorine-containing vinyl monomer], and 0.8 parts of benzoyl peroxide were added.
A similar reaction was carried out using 38.4 parts of xylene and 38.4 parts of xylene to obtain a fluorine atom content of 13.1%, an acid value of 9.1, and a hydroxyl value of 78.
A vinyl-modified polyester resin having a weight average molecular weight of 14,500 and a viscosity of 2.2 Stokes was obtained. The obtained resin solution is abbreviated as VPE-'7.

Production Example 8 In the same manner as in Production Example 1, 145 parts of the PE-1, fluorine-containing vinyl monomer (CHi = CHCOOCHzc
7F + s: Hereinafter abbreviated as FM-7, 340 parts, 0.8 parts of benzoyl peroxide and 46.6 parts of xylene were reacted in the same manner, and the fluorine atom content was 19.7%.
, acid value 8.8, hydroxyl value 72, weight average molecular weight 14.5
00, a vinyl modified polyester resin having a viscosity of 2.0 Stokes was obtained. The obtained resin solution is abbreviated as VPE-8.

Production Example 9 In the same manner as in Production Example 1, 145 parts of the PE-1, fluorine-containing vinyl monomer (CH,=CHC00CHZ(l(zcaF+t: hereinafter referred to as FM-8)
] 50 parts, benzoyl peroxide 0.8
A similar reaction was carried out using 54.7 parts of xylene and 54.7 parts of xylene to obtain a hydrogen atom content of 22.6%, an acid value of 8.5, and a hydroxyl value of 6.
8. A vinyl modified polyester resin having a weight average molecular weight of 14,400 and a viscosity of 1.7 Stokes was obtained. The obtained resin solution is abbreviated as VPE-9.

Production Example 10 In the same manner as Production Example 1, 145 parts of the PE-1, fluorine-containing vinyl monomer (CH2=CHC00CHzC'HzRF(RF:ChF+3~C
IZF! ! mixture of i) abbreviated as FM-9 under the two sides
60 parts of benzoyl peroxide and 62.9 parts of xylene were reacted in the same manner to obtain a fluorine atom content of 25.8%, an acid value of 8.3, a hydroxyl value of 63, a weight average molecular weight of 14,200, A vinyl-modified polyester resin having a viscosity of 1.4 Stokes was obtained. The obtained resin solution was subjected to VPE-
) is abbreviated as 0.

Production Example 11 In the same manner as Production Example 1, 150 parts of the above PE-1, 5 parts of fluorine-containing vinyl monomer (FM-2), 20 parts of methyl methacrylate, 12 parts of n-butyl methacrylate, 8 parts of lauryl methacrylate part, benzoyl peroxide 0
．． 8 parts and 51.1 parts of xylene were reacted in the same manner to obtain a product with a fluorine atom content of 1.6%, an acid value of 8.3, a hydroxyl value of 70, a weight average molecular weight of 14,500, and a viscosity of 2.8 Stokes. A vinyl modified polyester resin was obtained. The obtained lubricant solution is abbreviated as VPE-11.

Production Example 12 In the same manner as Production Example 1, 150 parts of the above PE-1, 10 parts of fluorine-containing vinyl monomer (FM-2), 18 parts of methyl methacrylate, 5 parts of n-butyl methacrylate, 5 parts of lauryl methacrylate parts, 7 parts of n-butyl acrylate, 28 parts of benzoyl peroxide, and 51 parts of xylene.
．． 1 part was reacted in the same manner to obtain a vinyl modified polyester resin having a fluorine atom content of 3.1%, an acid value of 8.1, a hydroxyl value of 70, a weight average molecular weight of 14,600, and a viscosity of 2.6 Stokes. Ta. The obtained resin solution was mixed with VPE-12.
It is abbreviated as

Production Example 13 In the same manner as in Production Example 1, 150 parts of the above PE-1, 15 parts of fluorine-containing vinyl monomer (FM-2), 16 parts of methyl methacrylate, 7 parts of lauryl methacrylate, and 7 parts of n-butyl acrylate were added. parts, benzoyl peroxide 0.
8 parts and 51.1 parts of xylene were reacted in the same manner to produce a product with a fluorine atom content of 4.7%, an acid value of 8.0, a hydroxyl value of 70, a weight average molecular weight of f14.500, and a viscosity of 2.6 Stokes. A vinyl modified polyester resin was obtained. The obtained resin solution is abbreviated as VPE-13.

Production Example 14 In the same manner as in Production Example 1, 120 parts of the above PE-1, 5 parts of fluorine-containing vinyl monomer (FM-4), 20 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 9 parts of lauryl methacrylate were added. 1 part of 2-hydroxyethyl methacrylate, 0.8 parts of benzoyl peroxide, and 48 parts of xylene were reacted in the same manner to obtain a fluorine atom content of 2.5%, an acid value of 7.3, a hydroxyl value of 68, A vinyl modified polyester resin having a weight average molecular weight of 114.600 and a viscosity of 2.4 Stokes was obtained. The obtained resin solution is VP
It is abbreviated as E-14.

Production Example 15 In the same manner as Production Example 1, 120 parts of the PE-1, 10 parts of fluorine-containing vinyl monomer (FM'-4), 18 parts of methyl methacrylate, 5 parts of n-butyl methacrylate, and lauryl methacrylate were added. 5 parts, n-butyl acrylate 5
1 part, 2 parts of 2-hydroxyethyl methacrylate, 0.8 parts of benzoyl peroxide, and 48 parts of xylene were reacted in the same manner to obtain 5.0% of fluorine atoms, an acid value of 7.0, and a hydroxyl value of 72. , weight average molecular weight 14,400
A vinyl-modified polyester resin having a viscosity of 2.6 Stokes was obtained. The obtained resin solution is abbreviated as VPE-15.

Production Example 16 In the same manner as in Production Example 1, 120 parts of the above PE-1, 15 parts of fluorine-containing vinyl monomer (FM-4), 16 parts of methyl methacrylate, 5 parts of lauryl methacrylate, and 6 parts of n-butyl acrylate were added. 1 part, 3 parts of 2-hydroxyethyl methacrylate, 0.8 part of benzoyl peroxide and 48 parts of xylene were reacted in the same manner to obtain a fluorine atom content of 7.5%, an acid value of 7.4, a hydroxyl value of 76, Weight average molecular weight 14.200. A vinyl-modified polyester resin having a viscosity of 2.8 Stokes was obtained. The obtained resin solution was subjected to VPE
It is abbreviated as -16.

Production Example 17 In the same manner as Production Example 1, 80 parts of the above PE-1, 5 parts of fluorine-containing vinyl monomer (FM-8), 20.8 parts of methyl methacrylate, 0.2 part of acrylic acid, n -butyl methacrylate) 10 parts, lauri/14 methacrylate 9 parts,
A similar reaction was carried out using 0.8 parts of benzoyl peroxide and 44 parts of xylene, and the fluorine atom content was 3.3.
%, acid value 10.5, hydroxyl value 56, weight average molecular weight 14
, 400 and a viscosity of 2.1 Stokes was obtained. The obtained resin solution is abbreviated as VPE-17.

Production Example 18 In the same manner as Production Example 1, 80 parts of the above PE-1, 10 parts of fluorine-containing vinyl monomer (FM-8), 19.4 parts of methyl methacrylate, 5 parts of n-butyl methacrylate, and lauryl were added. 5 parts of methacrylate, 5 parts of n-butyl acrylate
parts, 0.6 parts of acrylic acid, 0 parts of benzoyl peroxide
．． 8 parts of xylene and 44 parts of xylene were reacted in the same manner to produce a vinyl-modified product with a fluorine atom content of 6.7%, an acid value of 13.3, a hydroxyl value of 56, a weight average molecular fi of 14,300, and a viscosity of 2.0 Stokes. A polyester resin was obtained. The obtained resin solution is abbreviated as VPE-18.

Production Example 19 In the same manner as Production Example 1, 80 parts of the above PE-1, 15 parts of fluorine-containing vinyl monomer (FM-8), 17 parts of methyl methacrylate, 5 parts of lauryl methacrylate, and 7 parts of n-butyl acrylate were added. 1 part of acrylic acid, 0.8 parts of benzoyl peroxide, and 44 parts of xylene were reacted in the same manner to obtain a hydrogen atom atom content of 10.0% and an acid value of 1.
6.6, hydroxyl value 56, weight average molecular weight 14,300
A vinyl-modified polyester resin having a viscosity of 2.0 Stokes was obtained.

The obtained resin solution is abbreviated as VPE-19.

Examples 1 to 19 The components and blending amounts shown in Table 1 were mixed to obtain a resin composition for paint of the present invention.

Comparative Examples 1 to 6 The components and blending amounts shown in Table 2 were mixed to obtain paint resin compositions of comparative examples.

Comparative Experiment 1 part of xylene was added to 100 parts of the resin solution obtained in Examples 1 to 19 shown in Table 1 and Comparative Examples 1 to 6 shown in Table 2.
0 parts was added and stirred well to prepare a clear resin solution.

Similarly, a methylated melamine resin solution [manufactured by Monsanto Company, product name RESIMENE 717: Nibutyl alcohol solution with a solid content of 84%] was added to the resin solution at a solid content weight ratio of 7.
10% of xylene was further added and stirred well to prepare a melamine resin mixed solution.

Furthermore, in the same manner as above, a blocked isocyanate compound solution [Takenate Pharmaceutical Co., Ltd., product name Takenate B-82ONSU: solid content 60%: effective NGO content 4-3 PETZ 100 mixed solution] was added to the resin solution. The OH group in the block isocyanate compound and the NCO group in the blocked isocyanate compound are OH/NC0=1
10.8 (equivalent ratio), and further added 10% xylene and stirred well to prepare a blocked isocyanate compound mixed solution.

The clear resin solution, melamine resin mixed solution, and blocked isocyanate compound mixed solution obtained as described above were applied onto a glass plate (2×100×100wn=) using a 6 mm applicator to prepare a test piece. Three test pieces were prepared for each sample of the same type.

After leaving it at room temperature for 10 minutes, in the case of clear resin solution,
Forcibly dry at 50°C for 20 minutes, in the case of a melamine resin mixed solution, bake harden and dry at 150"C for 20 minutes, and in the case of a blocked isocyanate compound mixed solution, dry at 160°C for 20 minutes.
Bake harden and dry for minutes.

Table 3 shows the results of visually inspecting the test pieces obtained for the presence or absence of cissing and dents.

The data shown is the average value of three test pieces.

In the table, ○ marks indicate cissing and dents of 2 or less per 1QcJ.
Δ indicates more than 2 and 15 or less, × indicates more than 15 and 30 or less, and XX indicates more than 30.

It is clear from the comparative test results table that the coating film obtained from the coating resin composition of the present invention had an excellent appearance with no repelling or denting before or after drying.

On the other hand, in the coating films obtained from conventional unsaturated polyester or saturated polyester resin coating compositions (Comparative Examples 4 to 6), no repelling was observed before drying, but significant repelling and denting occurred after drying. did.

Furthermore, coating films obtained from coating compositions using vinyl-modified polyester resins outside the scope of the present invention (Comparative Examples 1 to 3)
The results were inferior to conventional coatings both before and after drying.

Claims (4)

[Claims] (1) (I) Polyester...50 to 99% by weight, (
II) (A) unsaturated polyester containing 1 to 10% by weight of α,β-ethylenically unsaturated dicarboxylic acid or its acid anhydride…50 to 99.9% by weight; (B) (i) fluorination A vinyl monomer consisting of an acrylic ester or methacrylic ester of an alcohol having an alkyl group, and (ii) optionally a copolymerizable vinyl monomer other than the above (i)...0.1 to 50% by weight , a vinyl-modified polyester resin obtained by copolymerizing . . . 1 to 50% by weight, and a resin composition for paint. (2) Acrylic esters or methacrylic esters of alcohols having a fluorinated alkyl group have the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [However, in the formula, R represents H or CH_3, and X is as shown below. The substituents are shown below. X: -CH_2CF_3 -CH_2CF_2CF_2H -CH_2(CF_2CF_2)_2H -CH_2(CF_2CF_2)_3H -CH_2C_7F_1_5 -CH_2CH_2C_8F_1_7 -CH_2CH_2RF(RF:C_6F_1_3~C
_1_2F_2_5 mixture)] The resin composition for paint according to claim (1), which is a compound represented by the following. (3) The resin composition for paint according to claim (1), wherein the resin composition for paint contains 50% by weight or less of a crosslinking agent component. (4) The resin composition for paint according to claim (3), wherein the crosslinking agent component is an aminoplast resin and/or an isocyanate compound.