JPH0517651A - Resin composition - Google Patents

Abstract

(57) [Summary] [Object] To obtain a resin composition having excellent weather resistance and acid resistance by combining a fluorine-containing copolymer having both a hydroxyl group and an epoxy group with a curing agent. [Structure] A fluorine-containing vinyl monomer (a-1), a hydroxyl group-containing vinyl monomer (a-2) and an epoxy group-containing vinyl monomer (a-3) are used as essential constituent units, and if necessary, ,
A resin composition containing, as a main component, a fluorine-containing vinyl copolymer (A) which also has other copolymerizable monomer (a-4) as a constituent unit. EFFECTS OF THE INVENTION By using a specific fluorine-containing copolymer and a curing agent as essential components, it is possible to obtain a resin composition having excellent weather resistance and forming a coating film having excellent acid resistance. it can.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a new and useful resin composition. More specifically, a fluorine-containing vinyl copolymer having a fluorine-containing vinyl monomer, a hydroxyl group-containing vinyl monomer and an epoxy group-containing vinyl monomer as an essential constituent unit, and a curing agent thereof are essential components. As comprising,
In particular, the present invention relates to a fluororesin composition which is excellent in long-term weather resistance and acid resistance and is suitable for automotive top coatings and the like.

[0002]

2. Description of the Related Art Heretofore, as a topcoating method for automobile bodies and the like, a topcoating paint using a melamine alkyd resin and a melamine acrylic resin has been used. However, the coating film obtained by coating these top-coat paints, when used for a long period of time, has reduced gloss and discoloration.

As a solution to such problems,
A method of using a fluororesin as the top coating material has also been proposed. (JP-A-61-197074 or 63-2
According to this method, although a coating film excellent in weather resistance for an extremely long period of time can be obtained, it cannot be said that the acid resistance is still sufficient.

In recent years, there has been a problem of coating film damage due to acid rain, which is considered to be caused by sulfur oxides and nitrogen oxides released into the atmosphere, and it is now time to improve acid resistance. , Strong, there is no demand for it.

[0005]

As described above, as long as the prior art is followed, a resin having extremely high practicability which can satisfy both weather resistance and acid resistance at the same time, that is, which meets current requirements. It can be said that it is impossible to find a composition.

[0006] However, the present inventors have earnestly started research in search of a novel resin composition which has excellent weather resistance and is capable of forming a film having excellent acid resistance.

Therefore, the problem to be solved by the present invention is just that the weather resistance and the acid resistance can be satisfied at the same time, that is, the current requirements are met.
It is to provide a resin composition having extremely high practicality.

[0008]

Accordingly, the inventors of the present invention have made extensive studies mainly in accordance with the problems to be solved by the invention as described above, and as a result, have found that the fluorine-containing vinyl monomer (a-1 ), A hydroxyl group-containing vinyl monomer (a-2) and an epoxy group-containing vinyl monomer (a-3) as an essential constituent unit, and other copolymerizable vinyl monomer (a If a resin composition containing the novel fluorine-containing vinyl copolymer (A) containing -4) also in a specific proportion and a specific curing agent (B) as main components is used, It was found that a coating film excellent in weather resistance and acid resistance can be obtained, and the present invention has been completed here.

That is, in the present invention, the fluorine-containing vinyl monomer (a-1), the hydroxyl group-containing vinyl monomer (a-2) and the epoxy group-containing vinyl monomer (a-3) are essential components, If necessary, a fluorine-containing vinyl copolymer (A) containing another copolymerizable vinyl monomer (a-4) and a specific curing agent (B) as main components. It is intended to provide a resin composition.

The present invention will be described in detail below.
As the fluorine-containing vinyl copolymer (A) in the present invention, first, the fluorine-containing vinyl copolymer (A) contains 20 to 70% by weight of the fluorine-containing vinyl monomer (a-1) and a hydroxyl group, respectively. 1 to 20% by weight of the contained vinyl monomer (a-2) and 5 to 4 of the epoxy group-containing vinyl monomer (a-3).
0% by weight and 0 to 50% by weight of other copolymerizable monomer (a-4) are obtained by copolymerization,
It is typically illustrated.

Here, the fluorine-containing vinyl monomer (a
When the amount used in -1) is less than the above range,
The weather resistance of the coating film is deteriorated, and on the other hand, when it exceeds the above range, the coating workability is deteriorated.

Further, a hydroxyl group-containing vinyl monomer (a-2)
If the amount used is less than the above range, the scratch resistance and solvent resistance of the coating film will decrease, while if it exceeds the above range, the flexibility of the coating film And so on, it is not preferable in any case.

When the amount of the epoxy group-containing vinyl monomer (a-3) used is less than the above range, the weather resistance of the coating film is deteriorated, while the above range is used. If it exceeds the above range, the flexibility of the coating film will be deteriorated, and in any case, it is not preferable.

The above-mentioned fluorine-containing vinyl monomer (a-1)
As just a typical example,
Such as vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene,
Fluorine-containing-α-olefins;

Alternatively, perfluoroalkyl perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether or heptafluoropropyl trifluorovinyl ether and (per) fluoroalkyl vinyl ethers (provided that the alkyl group has 1 carbon atom). ~ 1
Assume that it is 8. ) And other compounds,

Above all, the use of vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene or hexafluoropropylene is preferred. As the above-mentioned hydroxyl group-containing vinyl monomer (a-2), only typical ones are exemplified, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether and 4-hydroxybutyl. Vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether or 6
-Various hydroxyl group-containing vinyl ethers such as hydroxyhexyl vinyl ether;

Addition reaction products of these various vinyl ethers with ε-caprolactone; 2-hydroxyethyl (meth) allyl ether, 3-hydroxypropyl (meth) allyl ether, 2-hydroxypropyl (meth) allyl ether, 4-hydroxybutyl (meth) allyl ether, 3-hydroxybutyl (meth) allyl ether, 2-hydroxy-2-methylpropyl (meth)
Various hydroxyl group-containing allyl ethers such as allyl ether, 5-hydroxypentyl (meth) allyl ether or 6-hydroxyhexyl (meth) allyl ether;

These various allyl ethers and ε-
Addition reaction product with caprolactone; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth ) Various hydroxyl group-containing (meth) acrylates such as acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate or polypropylene glycol mono (meth) acrylate;

Alternatively, among the above-mentioned various (meth) acrylates and ε-caprolactone, which are the main components of the addition reaction, etc., it is preferable to use hydroxyl group-containing vinyl ethers or hydroxyl group-containing allyl ethers.

If only representative examples of the epoxy group-containing monomer (a-3) are given,
Various epoxy group-containing allyl ethers such as (meth) allyl glycidyl ether or 3,4-epoxycyclohexylmethyl allyl ether;

Glycidyl vinyl ether or 3,4
-Various epoxy group-containing vinyl ethers such as epoxycyclohexylmethyl vinyl ether; vinyl-
Various epoxy group-containing vinyl carboxylates such as 3,4-epoxycyclohexanecarboxylate; or glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate , Various epoxy group-containing (meth) acrylates and the like, among which the use of epoxy group-containing vinyl ethers, epoxy group-containing allyl ethers or epoxy group-containing vinyl carboxylates is preferred.

The other copolymerizable monomer (a-
As only 4), only typical ones will be exemplified. Methyl vinyl ether, ethyl vinyl ether, n
-Propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl butynyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl Various alkyl vinyl ethers or substituted alkyl vinyl ethers such as vinyl ether or phenylethyl vinyl ether;

Cyclopentyl vinyl ether, cyclohexyl
Xyl vinyl ether or methyl cyclohexyl bi
Various cycloalkyl vinyl ethers such as nyl ether
Teres; Vinyl-2,2-dimethylpropanoate, Bi
Nyl-2,2-dimethylbutanoate, vinyl-2,2
-Dimethylpentanoate, vinyl-2,2-dimethyl
Hexanoate, vinyl-2-ethyl-2-methylbutane
Noate, vinyl-2-ethyl-2-methylpentanoe
Vinyl, 3-chloro-2,2-dimethylpropano
Ate, vinyl acetate, vinyl propionate, vinyl butyrate
, Vinyl isobutyrate, vinyl caproate, vinyl caprylate
Nyl, vinyl caprate, vinyl laurate, C₉ Become
Aliphatic vinyl carboxylate, C_TenBranched aliphatic carvone
Vinyl acetate, C ₁₁Or branched aliphatic vinyl carboxylate
Is a variety of aliphatic carboxylic acids such as vinyl stearate
Vinyls;

Vinyl esters of various cyclic structure-containing carboxylic acids such as vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate or vinyl p-tert-butylbenzoate; methyl acrylate, ethyl acrylate, butyl acrylate or Acrylic acid esters such as cyclohexyl acrylate; various methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate or benzyl methacrylate;

Ethylene, propylene or butene-1
Various α-olefins such as styrene, various aromatic vinyl compounds such as styrene, α-methylstyrene or vinyltoluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldiethoxysilane, Vinyltris (β-methoxyethoxy) silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, methyldiethoxysilylpropyl vinyl ether ,
Monomers containing various hydrolyzable silyl groups, such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane or γ- (meth) acryloyloxypropylmethyldimethoxysilane. body;

Various amino group-containing amide systems such as N-dimethylaminoethyl (meth) acrylamide, N-diethylaminoethyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide or N-diethylaminopropyl (meth) acrylamide. Unsaturated monomers; various dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate or diethylaminoethyl (meth) acrylate;

Tert-Butylaminoethyl (meth) acrylate, tert-bitylaminopropyl (meth)
Various amino group-containing monomers such as acrylate, aziridinylethyl (meth) acrylate, pyrrolidinylethyl (meth) acrylate or piperidinylethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, itacone Acid, maleic acid or fumaric acid,
Monoesters of various carboxyl group-containing monomers or polyvalent carboxyl group-containing monomers such as itaconic acid, maleic acid or fumaric acid, and monoalkyl alcohols having 1 to 18 carbon atoms, carboxyl group-containing vinyl Such as monomers.

From the viewpoint of increasing the polymerization yield of the fluorine-containing vinyl copolymer (A) itself, it is desirable to use alkyl vinyl ethers, cycloalkyl vinyl ethers and / or carboxylic acid vinyl esters. From the viewpoints of coating workability and various coating film performances such as weather resistance, the type and amount of the monomer may be appropriately determined.

To prepare the fluorine-containing vinyl copolymer (A) component, a radical polymerization initiator is used and emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or other known and commonly used techniques are used. The above-mentioned radical polymerization initiator may be any of various diacyl peroxides such as acetyl peroxide or benzoyl peroxide; various ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide. Kind;

Such as hydrogen peroxide, t-butyl hydroperoxide or cumene hydroperoxide,
Various hydroperoxides; various dialkyl peroxides such as di-t-butylperoxide or dicumyl peroxide; various alkylperoxides such as t-butylperoxyacetate or t-butylperoxypivalate Oxyesters; various azo compounds such as azobisisobutyronitrile or azobisisovaleronitrile; or various persulfates such as potassium persulfate or ammonium persulfate are particularly representative. is there.

As the polymerization reaction method, there are various known methods as mentioned above. Among them, it is preferable to use the bulk polymerization or the solution polymerization, and further, the obtained copolymer in the form as it is, for example, From the viewpoint of being able to be used as a resin composition for a solution type coating, the solution polymerization method is particularly preferable.

As the solvent used in preparing the fluorine-containing vinyl copolymer (A) according to the solution polymerization method, particularly typical solvents are various aromatic hydrocarbons such as benzene, toluene or xylene. Various aliphatic hydrocarbons such as n-pentane, n-hexane or n-octane;

Such as cyclopentane, cyclohexane, methylcyclohexane or ethylcyclohexane,
Various alicyclic hydrocarbons; such as mineral spirits,
Various mixed hydrocarbons; methanol, ethanol, n-
Propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, n-hexanol, n-octanol, 2-ethylhexanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether. , Various alcohols such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether;

Dimethoxyethane, tetrahydrofuran,
Dioxane, diisopropyl ether or di-n-
Various ethers such as butyl ether; acetone,
Various ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone or isophorone;

Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene. Various esters such as glycol monobutyl ether acetate; N-methylpyrrolidone, dimethylformamide, dimethylacetamide, ethylene carbonate and the like can be mentioned.

These organic solvents may be used alone or in combination of two or more. From the various monomer components listed above,
In order to prepare the fluorine-containing vinyl copolymer (A) by a solution polymerization method, all the monomers, a polymerization initiator and a solvent are charged into a reactor at once and polymerized, or fluorine-containing vinyl monomers are used. And a reactor charged with a solvent, monomers other than the fluorine-containing vinyl monomers and a polymerization initiator, respectively, or continuously, or by adding in a divided manner to polymerize, further, only the solvent In the reactor that was charged with
A method in which all the monomers and the polymerization initiator are added continuously or in a divided manner to perform polymerization can be applied.

In the above description, the solvent-soluble fluorine-containing vinyl copolymer was mainly described, but of course, the copolymer (A) is in the form of a so-called non-aqueous dispersion dispersed in a solvent. Alternatively, it may contain particles partially gelled.

Fluorine-containing copolymer (A) thus obtained
Has a weight average molecular weight of 3,000 to 300,000.
Within the range of 0, in particular 5,000 to 250,000
It is desirable to manage it so that it falls within the range of 0.

When it is less than 3,000,
The weather resistance of the coating tends to decrease, while 30
This is because if it exceeds 50,000, it will be difficult to form a uniform film.

In the present invention, the fluorine-containing vinyl copolymer (A) is used in combination with a curing agent (B) as a so-called curable resin composition. The curing agent (B) is a compound having at least two functional groups (reactive polar groups) capable of reacting with the hydroxyl group and the epoxy group of the fluorine-containing vinyl copolymer (A) in one molecule. Use of is preferred.

As typical examples of the curing agent (B), various amino resins such as alkyl etherified melamine resin or alkyl etherified benzoguanamine resin; various kinds such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate. Aliphatic diisocyanates; various cyclic aliphatic diisocyanates (alicyclic diisocyanates) such as xylylene diisocyanate or isophorone diisocyanate; or tolylene diisocyanate or
Such as 4,4′-diphenylmethane diisocyanate,
Including organic diisocyanate compounds such as various aromatic diisocyanates,

Addition products of these organic diisocyanate compounds with polyhydric alcohols, low molecular weight polyester resins (polyester polyols) or water, or polymers of the organic diisocyanate compounds mentioned above (isocyanurate type polyisocyanate compounds) And an isocyanate biuret body, and further, an isocyanate compound obtained by blocking the various polyisocyanate compounds described above with a known and commonly used blocking agent;

Carboxylic anhydride-containing polyester, carboxylic acid anhydride-containing acrylic resin, carboxyl group-containing polyester or carboxyl group-containing acrylic resin; adipic acid, phthalic acid, isophthalic acid or dimer acid, or p-oxy There are carboxyl group-containing low molecular weight compounds such as oxycarboxylic acids such as benzoic acid (parahydroxybenzoic acid).

These curing agents may be used alone or in combination of two or more kinds. To prepare such a resin composition using the fluorine-containing vinyl copolymer (A) and the curing agent (B) thus obtained, which are essential constituents of the resin composition of the present invention, these are prepared by a conventional method. Both components may be simply mixed.

The compounding ratio of these curing agents to the fluorine-containing vinyl copolymer (A) is 3 to 1 parts by weight of the curing agent (B) with respect to 100 parts by weight of the fluorine-containing vinyl copolymer (A).
The range of 100 parts by weight is preferable from the viewpoint of the performance of the coating film.

That is, the fluorine-containing vinyl copolymer (A)
When the amount of the curing agent is less than 3 parts by weight per 100 parts by weight, it is difficult to obtain sufficient coating performance.
If the amount exceeds 100 parts by weight, the coating film tends to become brittle, and in any case, it is not preferable.

Incidentally, in preparing the intended resin composition using the above-mentioned fluorine-containing vinyl copolymer (A) and the curing agent (B), if necessary, a known and commonly used curing method may be used. A catalyst can be used.

As only such typical curing catalysts will be exemplified, first, as the curing agent (B),
When an isocyanate compound is used, it may be various organometallic compounds such as dibutyltin dilaurate, dibutyltin diacetate, tin dioctylate or cobalt naphthenate, or 1,4-diazabicyclo- (2.2.
2) -octane or 1,8-diazabicyclo-
(54.0) -Various amine compounds such as undecene-7.

When an amino resin is used as the curing agent (B), para-toluenesulfonic acid, phosphoric acid or mono- or dialkyl esters of this phosphoric acid; or "Nature 155, 2500X, X-49-1.
Examples include dinonylnaphthalene sulfonic acid, dodecyl benzene sulfonic acid, and organic amine block compounds thereof represented by "10, 3525 or 5225" (manufactured by King, USA).

Next, when a carboxyl group-containing compound is used as the curing agent (B), it is most preferable to use a commonly used basic catalyst. Among them, tetramethylammonium bromide and trimethylbenzylammonium hydro Oxide, 2-hydroxypyridine, trimethylbenzylammonium methoxide, phenyltrimethylammonium chloride, phenyltrimethylammonium bromide, phenyltrimethylammonium hydroxide, phenyltrimethylammonium iodide, phenyltrimethylammonium tribromide, phosphocholine chloride sodium salt, stearyl ammonium bromide. , Tetra-n
-Amyl ammonium iodide, tetra-n-butyl ammonium bromide, tetra-n-butyl ammonium hydroxide, tetra-n-butyl ammonium phosphate, tetra-n-decyl ammonium trichloride, tetraethyl ammonium hydroxide, tetraethyl ammonium tetrafluoroborate , Acetylcholine bromide, alkyldimethylbenzylammonium chloride, benzylcholine bromide, benzyl-n-butylammonium bromide,
It is various quaternary ammonium salts such as betaine, butyryl chloride, bis (tetra-n-butylammonium) dichromate or trimethylvinylammonium bromide.

The resin composition of the present invention can be used as it is as a clear paint, or a color pigment and / or a metal powder can be used. Furthermore, if necessary, various resins and solvents, flow regulators,
It goes without saying that various known and commonly used additives such as a color separation inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer or a silane coupling agent can be added.

As the above-mentioned various resins, only representative ones will be exemplified. In addition to various fibrous resins such as nitrocellulose or cellulose acetate butyrate, ketone resins, petroleum resins and acrylic resins. It is a polymer, an oil-free alkyd resin, an alkyd resin, an epoxy resin, or the like, and an acrylic resin is particularly suitable from the viewpoint of compatibility.

As the above-mentioned solvents, various solvents and mixtures thereof similar to those used in preparing the above-mentioned fluorine-containing vinyl copolymer (A) are used.

The coating of the paint using the resin composition of the present invention is carried out in the same manner as in the past, using a clear paint or a paint colored and toned with a coloring pigment and / or a metal powder.

That is, the surface treatment is applied, or
If necessary, the coating material is preliminarily coated with a primer, a surfacer, an undercoat coating material or the like, and the coating material is adjusted to a desired viscosity and coated so that the dry film thickness is 5 to 100 μm (μm).

The paint may be applied by a usual method such as roll coater, air spray, airless spray or electrostatic coating. After coating, a cured coating film can be obtained by drying at room temperature for 3 days or at a temperature of 60 to 300 ° C. for several seconds to 60 minutes.

[0057]

EXAMPLES Next, the present invention will be described in more detail with reference to Reference Examples, Examples, Comparative Examples, Application Examples and Comparative Application Examples, but unless otherwise specified, parts and% are as follows:
All are based on weight.

Reference Example 1 [Preparation Example of Fluorine-Containing Vinyl Copolymer (A)] 25 parts of ethyl vinyl ether and 25 parts of 4-hydroxybutyl vinyl ether were placed in a 1-liter stainless steel autoclave which was sufficiently replaced with nitrogen gas. parts, 150 parts of allyl glycidyl ether, "VeoVa 9" 50 parts (manufactured by the Netherlands shell, vinyl esters of branched fatty acids having C ₈ comprising alkyl group), 210 parts of xylene, tert- butylperoxy octoate 5 parts of azobisisovaleronitrile and 1,2,2,6,6-pentamethylpiperidine of 1.
Prepared 5 copies.

Next, 250 parts of liquefied and collected chlorotrifluoroethylene was injected under pressure and stirred at 60 ° C.
Then, after reacting for 15 hours, 28 of xylene
0 part was added, and the mixture was further reacted for 2 hours to give a nonvolatile content
A solution of the target copolymer (A) in which V) was 50% was obtained.
Hereinafter, this is referred to as A-1.

Reference Example 2 (Same as above) In a 1 liter stainless steel autoclave sufficiently replaced with nitrogen gas,
75 parts of ethyl vinyl ether, 50 parts of 4-hydroxybutyl vinyl ether, 125 parts of vinyl-3,4-epoxycyclohexanecarboxylate, 210 parts of xylene, 5 parts of tert-butylperoxyoctoate, azobisisovaleronitrile. 5 parts and 1,
1.5 parts of 2,2,6,6-pentamethylpiperidine were charged.

Next, 250 parts of hexafluoropropylene liquefied and sampled was pressed in and stirred at 60 ° C.,
After reacting for 15 hours, 280 parts of xylene was added, and further reacted for 2 hours to obtain a nonvolatile content (NV).
To obtain a solution of the target copolymer (A) having a content of 50%. Less than,
This is called A-2.

Reference Example 3 (Same as above) In a 1 liter stainless steel autoclave sufficiently replaced with nitrogen gas,
30 parts of 2-hydroxyethyl allyl ether, 150 parts of glycidyl vinyl ether, "VeoVa 9" 75 parts of (ibid Co., vinyl esters of branched fatty acids having C ₈ comprising alkyl group), 210 parts of xylene, tert-
5 parts of butyl peroxyoctoate, 5 parts of azobisisovaleronitrile and 1.5 parts of 1,2,2,6,6-pentamethylpiperidine are charged.

Next, 250 parts of liquefied and collected chlorotrifluoroethylene was injected under pressure and at 60 ° C. with stirring.
After reacting for 15 hours, 280 parts of xylene was added, and further reacted for 2 hours to obtain a nonvolatile content (NV).
To obtain a solution of the target copolymer (A) having a content of 50%. Less than,
This is called A-3.

Reference Example 4 (Preparation Example of Control Fluorine-Containing Copolymer Containing Hydroxyl Group) 1 sufficiently substituted with nitrogen gas
In a liter stainless steel autoclave, 90 parts of 4-hydroxybutyl vinyl ether, 65 parts of cyclohexyl vinyl ether, 65 parts of ethyl vinyl ether.
Parts, 210 parts of xylene, 5 parts of tert-butyl peroxyoctoate, 5 parts of azobisisovaleronitrile and 1.5 parts of 1,2,2,6,6-pentamethylpiperidine.

Then, 260 parts of liquefied and collected chlorotrifluoroethylene was introduced under pressure, and the mixture was stirred at 60 ° C.
Then, after reacting for 10 hours, 28 of xylene
0 part and 1 part of succinic anhydride were added and further reacted for 10 hours to obtain a solution of a fluorine-containing copolymer having a hydroxyl group and having a nonvolatile content (NV) of 50%. Hereafter, this is A '
-1.

Reference Example 5 [Preparation Example of Curing Agent (B) Having Carboxyl Group in Molecule] After charging 100 parts of xylene and 50 parts of butyl acetate, “Plaxel
308 "(caprolactone polymerized polyol manufactured by Daicel Chemical Industries, Ltd.) and 500 parts of hexahydrophthalic anhydride are reacted at 120 ° C for 2 hours to give a nonvolatile content of 80.4%. A solution of polyester resin was obtained. Hereinafter, it will be referred to as a curing agent (B-1).

Reference Example 6 (same as above) A four-necked flask equipped with a thermometer, a stirrer, a cooling tube and a nitrogen gas introducing tube was charged with 500 parts of xylene and 300 parts of n-butanol and heated to 120 ° C. To a warm place, as a monomer mixture, 300 parts of acrylic acid, 1 part of methyl methacrylate
Using 00 parts and 600 parts of n-butyl methacrylate, 15 parts of azobisisobutyronitrile (AIBN) and 70 parts of tert-butylperoxy 2-ethylhexanoate, respectively, were used as initiators. The mixture was added dropwise at the same temperature over 5 hours, and the reaction was continued by maintaining the same temperature for 7 hours even after the completion of the addition, and the non-volatile content was 50.2%. A solution of vinyl copolymer was obtained. Hereinafter, the curing agent (B-
2).

Reference Example 7 [Preparation Example of Curing Agent (B) Having Carboxylic Anhydride Group in Molecule] 500 xylene was placed in a four-necked flask equipped with a thermometer, a stirrer, a cooling tube and a nitrogen gas introducing tube. Parts and 300 parts of butyl acetate were charged and heated to 120 ° C. to obtain 300 parts of itaconic anhydride and 10 parts of methyl methacrylate as a monomer mixture.
0 parts and 600 parts of n-butyl methacrylate were used, with 15 parts of AIBN, respectively, as initiator,
A mixture with 70 parts of tert-butylperoxy 2-ethylhexanoate was added dropwise at the same temperature over 5 hours,
After completion of the dropping, the reaction was continued at the same temperature for 7 hours to obtain a solution of a target curing agent having a nonvolatile content of 50.3%, that is, a vinyl copolymer having a carboxylic acid anhydride group. Hereinafter, it will be referred to as a curing agent (B-3).

Reference Example 8 (Preparation Example of Undercoat Paint) Ford cup No. 1 was prepared by adding a solvent for dilution into a mixture prepared by a conventional paint manufacturing method so as to have the following ratio. 1 in 4
The viscosity was adjusted to 1 to 12 seconds to prepare an undercoat paint.

[0070] "Beckolite 57-1054" 72 parts [Manufactured by Dainippon Ink and Chemicals, Inc.   Hydroxyl-containing polyester resin of   Nonvolatile content = 70%] "Super Beckamine L-117-60" 42 parts (N-butylated melamine resin manufactured by the same company;   Nonvolatile content = 60%) "CAB-381-0.5" 25 parts (Cell manufactured by Eastman Kodak Company, USA   Loose acetate butyrate) "EPOLEN N-10" 15 copies (Wax produced by the same company) "Alpaste 1860YL" 23 parts [Aluminum manufactured by Toyo Aluminum Co., Ltd.   Nium paste; non-volatile   = 65%] ───────────────────────────────────                                                       177 copies Hereinafter, this is referred to as BC-1.

Reference Example 9 (Same as above) Ford cup No. 1 was mixed with a solvent for dilution into a mixture prepared by an ordinary coating material manufacturing method so that the following ratio was obtained. The viscosity was adjusted to 4 to 13 to 14 seconds to prepare an undercoat paint.

[0072] "Acridic 47-712" 160 copies [Made by Dainippon Ink and Chemicals, Inc.   Hydroxyl group-containing acrylic resin; non-volatile   Min = 50%] 33 parts of "Super Beckamine L-117-60" "Alpaste 1860YL" 23 parts "First Gen Blue NK" Part 2 [Manufactured by Dainippon Ink and Chemicals, Inc.   Cyanine blue) ──────────────────────────────────                                                      218 copies   Hereinafter, this is referred to as BC-2.

Examples 1 to 3 and Comparative Example 1 Various fluorine-containing vinyl copolymers obtained in Reference Examples 1 to 3, various curing agents obtained in Reference Examples 4 to 7, and commercially available amino. A resin and a commercially available isocyanate compound were blended as shown in Table 1 to separately prepare a topcoat paint, and xylene / “Solvesso 100” (petroleum-based solvent manufactured by Exxon USA) / butyl acetate = 40/40/20
Ford cup No. Four
And diluted for 23 seconds to prepare various topcoat paints.

For comparison, a conventional topcoat using a hydroxyl group-containing fluorocopolymer was prepared in the same manner.

[0075] * 1) Butylated melamine resin manufactured by Dainippon Ink and Chemicals, Inc .; nonvolatile content = 60% by weight * 2) Isocyanate compound manufactured by the same company * 3) "Tinuvin-900" (product of Ciba-Geigy, Switzerland) * 4 ) "LO-50" (product of Hoechst, Germany)

Application Examples 1 to 3 and Comparative Application Example 1 A mild steel sheet was coated with a cationic electrodeposition coating film and a polyester melamine-based surfacer, and an undercoat paint as shown in Table 2 was dried by air spray. It was coated so that the film thickness would be 20 μm.

Then, after setting for 5 minutes, the top coating material is dried by air spraying to a dry film thickness of 35 μm.
It was painted repeatedly. After leaving it at room temperature for 20 minutes, it was baked and dried at 150 ° C. for 30 minutes.

Each of the test pieces thus obtained was used to test the coating film performance. The results are shown together in the same table.

[0079] * 1) Visually judge the state of the coated surface after being immersed in a 5% aqueous solution of sulfuric acid at 70 ° C for 24 hours. * 2) 4,000 with a sunshine weather meter.
Perform 0 hour exposure and 60 ° before and after such exposure test
Displayed as gloss retention rate (%) according to gloss value

[0080]

The resin composition of the present invention comprises a specific fluorine-containing copolymer and a curing agent as essential components,
In particular, it has excellent weather resistance and has excellent acid resistance.

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[Procedure amendment]

[Submission date] January 8, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction content]

Reference Example 3 (Same as above) In a 1 liter stainless steel autoclave sufficiently replaced with nitrogen gas,
30 parts of 2-hydroxyethyl allyl ether, 150 parts of glycidyl vinyl ether, "VeoVa 9" 70 parts (ibid Co., vinyl esters of branched fatty acids having C ₈ comprising alkyl group), 210 parts of xylene, tert-
5 parts of butyl peroxyoctoate, 5 parts of azobisisovaleronitrile and 1.5 parts of 1,2,2,6,6-pentamethylpiperidine are charged.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

Reference Example 6 (same as above) A four-necked flask equipped with a thermometer, a stirrer, a cooling tube and a nitrogen gas introducing tube was charged with 500 parts of xylene and 300 parts of n-butanol and heated to 120 ° C. As a monomer mixture, 300 parts of acrylic acid and 1 part of methyl methacrylate were added.
Using 00 parts and 600 parts of n-butyl methacrylate, 15 parts of azobisisobutyronitrile (AIBN) and 70 parts of tert-butylperoxy 2-ethylhexanoate, respectively, were used as initiators. The mixture was added dropwise at the same temperature over 5 hours, and the reaction was continued by maintaining the same temperature for 7 hours after the completion of the addition, so that the nonvolatile content was 62.2%. A solution of the contained vinyl copolymer was obtained. Below, the curing agent (B
-2).

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0068

[Correction method] Change

[Correction content]

Reference Example 7 [Preparation Example of Curing Agent (B) Having Carboxylic Anhydride Group in Molecule] 500 parts of xylene was placed in a four-necked flask equipped with a thermometer, a stirrer, a cooling tube and a nitrogen gas introducing tube. Then, 300 parts of butyl acetate and 300 parts of itaconic anhydride and 10 parts of methylmethacrylate were added as a monomer mixture to a place where the temperature was raised to 120 ° C.
0 parts and 600 parts of n-butyl methacrylate were used, with 15 parts of AIBN, respectively, as initiator,
A mixture with 70 parts of tert-butylperoxy 2-ethylhexanoate was added dropwise at the same temperature over 5 hours, and after the addition was completed, the reaction was continued at the same temperature for 7 hours, Non-volatile content of 62.3% target curing agent,
That is, a solution of a carboxylic acid anhydride group-containing vinyl copolymer was obtained. Hereinafter, it will be referred to as a curing agent (B-3).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

[0075]

[Table 1] << Footnote in Table 1 >>"Super Beckamine L-117-60" ... Butylated melamine resin manufactured by Dainippon Ink and Chemicals, Inc .; nonvolatile content = 60% by weight "Bernock B7-887-60" ... As the isocyanate compound UV absorber manufactured by the same company, "Tinuvin-900" (product of Ciba-Geigy, Switzerland) was used. "LO-50" (product of Hoechst, Germany) was used as the silicon compound.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

[0079]

[Table 2] << Footnote in Table 2 >> Acid resistance ......... in a 5% sulfuric acid aqueous solution at 70 ° C for 24 hours,
Visually judge the state of the coated surface after immersion. Weather resistance:… By using a sunshine weather meter
Displayed as gloss retention (%) by 60 degree gloss value before and after such exposure test after exposure for 4,000 hours

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 61/20 LNM 8215-4J // (C08L 27/12 79:02)

Claims (7)

[Claims] 1. A fluorine-containing vinyl monomer (a-1), a hydroxyl group-containing vinyl monomer (a-2) and an epoxy group-containing vinyl monomer (a-3) as constituent units. A resin composition comprising a vinyl copolymer (A) and a curing agent (B). 2. A fluorine-containing vinyl monomer (a-1), a hydroxyl group-containing vinyl monomer (a-2), an epoxy group-containing vinyl monomer (a-3), and other copolymerizable monomers. A resin composition comprising a fluorine-containing vinyl copolymer (A) containing a vinyl monomer (a-4) as a constituent unit and a curing agent (B). 3. The above-mentioned fluorine-containing vinyl copolymer (A)
Is 20 to 70% by weight of the fluorine-containing vinyl monomer (a-1), 1 to 20% by weight of the hydroxyl group-containing vinyl monomer (a-2), and the epoxy group-containing vinyl monomer (a- 5) of 3)
40% by weight and other copolymerizable monomer (a-
The resin composition according to claim 1 or 2, which is obtained by copolymerizing 4) with 0 to 50% by weight. 4. The above-mentioned fluorine-containing vinyl monomer (a-1)
Is a compound of at least one kind selected from the group consisting of chlorotrifluoroethylene, hexafluoropropylene, vinyl fluoride and vinylidene fluoride, The resin composition according to claim 1. 5. The hydroxyl group-containing vinyl monomer (a-
The resin composition according to any one of claims 1 to 3, wherein 2) is a hydroxyl group-containing vinyl ether and / or a hydroxyl group-containing allyl ether. 6. The epoxy group-containing vinyl monomer (a)
-3) is at least one selected from the group consisting of an epoxy group-containing vinyl ether, an epoxy group-containing allyl ether, and an epoxy group-containing vinyl carboxylate, The resin composition according to any one of claims 1 to 3. . 7. The curing agent (B) is at least one compound selected from the group consisting of amino resins, isocyanate compounds and carboxylic acid compounds.
Or the resin composition according to 2.