JPH03244604A - Nonaqueous fluorovinyl polymer dispersion composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in film properties such as weathering resistance without detriment to the workability in coating by mixing a nonaqueous fluorovinyl polymer dispersion with a curing agent as the principal components. CONSTITUTION:A nonaqueous polymer dispersion composition mainly consisting of a nonaqueous fluorovinyl polymer dispersion, obtained by polymerizing a vinyl monomer in the presence of a fluorocopolymer and dispersing the product by phase inversion, and a curing agent. Examples of the fluorovinyl monomers which can be desirably used include vinyl fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoro propylene and perfluoroalkyl trifluorovinyl ether in which the alkyl has 1-18 C atoms. From the viewpoint of curing effect and weathering resistance, an isocyanate compound and/or an aminoplast is desirable as the curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful fluorine-containing vinyl nonaqueous polymer dispersion composition.

The fluorine-containing vinyl non-aqueous polymer dispersion composition of the present invention can be used, among other things, for paints, adhesives, and sealants. It is particularly desirable to use it as a

[Conventional technology]

In recent years, a fluorine-containing copolymer MIIi, which is solvent-based and can be cured at room temperature and provides a coating film with high weather resistance, has been developed and is mainly used for paints.

However, the solvents used in such solvent-based fluorine-containing copolymer compositions are mainly those with high solubility, such as aromatic hydrocarbons, esters, and/or ketones. .

However, when paints containing highly soluble organic solvents are applied over an existing paint film (hereinafter also referred to as "old paint film") or an undercoat film, By all means, the old paint film and undercoat film will swell and dissolve,
Furthermore, it has the fatal drawback of easily causing problems such as "shrinking" and swelling, and furthermore,
The solvent-based fluorine-containing copolymer used in this type of composition is a treatment that, like ordinary solvent-based resins, has the natural viscosity characteristic of increasing viscosity as the molecular weight increases. Therefore, in order to improve the physical properties of the paint film, when painting with a paint that uses a high molecular weight type fluorine-containing copolymer composition, a large amount of solvent is used to achieve a paintable viscosity. dilution becomes inevitable, and as a result,
The actual situation is that the concentration of nonvolatile matter (nonvolatile matter content) during painting is also low, resulting in problems such as poor painting workability.

In order to solve this problem, the use of non-aqueous dispersions of fluorine-containing copolymers has been proposed in Japanese Patent Application Laid-open Nos. 62-25130 and 64-66273, but none of them are exclusive. , a fluorine-containing copolymer is used as a dispersion stabilizer (
It is used as a dispersion liquid).

By the way, a non-aqueous polymer dispersion generally contains a polymer that is insoluble in an organic solvent (hereinafter also referred to as a dispersion portion) and a polymer that is soluble in an organic solvent and that is used to stably disperse the dispersion portion. It is composed of a so-called dispersion stabilizer.

As a matter of fact, as the proportion of the dispersion stabilizer increases, the stability of the non-aqueous polymer dispersion improves, but on the other hand, the viscosity of the non-aqueous dispersion increases significantly.

Therefore, when the dispersion portion does not contain a fluorine-containing copolymer and a fluorine-containing copolymer is used exclusively as a dispersion stabilizer, it is necessary to ensure the durability of the coating film. If you try to increase the fluorine content in a non-aqueous polymer dispersion, you will have to increase the proportion of dispersion stabilizer used, and as a result, the viscosity of the non-aqueous dispersion will increase. In the end, the high non-volatile content (solid content concentration) during coating, which is an important feature of compositions using this type of non-aqueous polymer dispersion, was not achieved at all. The new problem of not being able to do so will remain unresolved.

[Problem to be solved by the invention]

However, the present inventors have developed an extremely useful non-aqueous heavy duty solution backed by a novel technology in order to promptly eliminate or solve the various drawbacks or problems (unresolved issues) in the prior art as described above. In search of a combined dispersion liquid m-acid, we earnestly embarked on research. Therefore, the problem to be solved by the present invention is to solve the following problems: It is an object of the present invention to provide an extremely useful non-aqueous polymer dispersion composition which is free from the major disadvantage of a decrease in water resistance, etc., and further improves film performance such as weather resistance.

[Means to solve the problem]

Therefore, the inventors of the present invention focused on the problems to be solved by the invention as described above, and as a result of repeated studies,
It was discovered that a fluorine-containing non-aqueous vinyl polymer dispersion could be obtained by making full use of a special method called phase inversion dispersion method, and for the first time, it was discovered that the dispersion portion was made of a fluorine-containing copolymer, and in particular, it had excellent weather resistance. The fluorine-containing non-aqueous vinyl polymer dispersion is extremely useful because it not only has excellent coating workability but also does not swell or dissolve old paint films or undercoat paint films. By discovering the liquid, the present invention was completed.

That is, the present invention mainly consists of a fluorine-containing non-aqueous vinyl polymer dispersion obtained by polymerizing vinyl monomers and phase inversion dispersion in the presence of a fluorine-containing copolymer, and a curing agent. Fluorine-containing vinyl non-aqueous polymer dispersion liquid IJl as a component
It is an attempt to provide something.

In the present invention, the term "phase inversion dispersion method" mentioned above is
Solvent used during polymerization reaction (polymerization solvent)
It refers to the operation or means of partially or completely replacing the solvent with a solvent for the non-aqueous polymer dispersion (a non-aqueous dispersion solvent) when the polymerization reaction is completed. By taking operations and measures, the viscosity of the dispersion can be appropriately suppressed even though it is a non-aqueous polymer dispersion with a high solid content concentration, and therefore,
It is possible to ensure painting workability, and it also has the advantage of being free from the harmful effects of swelling or dissolving the old paint film, undercoat film, etc.

At this time, as the above-mentioned polymerization solvent, an organic solvent that can dissolve the fluorine-containing copolymer itself is used, and on the other hand, as the above-mentioned dispersion solvent, an organic solvent that can dissolve the vinyl copolymer itself is used. Although a solvent is used, an organic solvent that does not dissolve the fluorine-containing copolymer is used.

In this sense, the "phase inversion dispersion method" can ensure painting workability and also achieve freedom from the lifting phenomenon. It's a given.

By the way, the above-mentioned fluorine-containing copolymers are, respectively,
It refers to those obtained by the polymerization reaction of fluorine-containing vinyl monomers and other monomers that can be copolymerized with the fluorine-containing vinyl monomers listed below. It is preferable to use those containing

As such fluorine-containing vinyl monomers, any known and commonly used monomers can be used, but among them, only representative ones are exemplified, such as vinyl fluoride, vinylidene fluoride, Fluorine-containing compounds such as trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, promotrifluoroethylene, pentafluoropropylene or hexafluoropropylene
There are compounds containing a fluorine atom, such as α-olefins; or perfluoroalkyl perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether, or heptafluoroprobyl trifluorovinyl ether. Among them, it is preferable to use fluorinated vinyl, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, or perfluoroalkyl trifluorovinyl ether in which the alkyl group is 01 to C4.

Even if these fluorine-containing vinyl monomers listed above are used alone,
Of course, two or more types may be used in combination.

Further, as the monomers copolymerizable with such fluorine-containing vinyl monomers, it is preferable to use a hydroxyl group-containing vinyl monomer since the fluorine-containing copolymer is made to contain a hydroxyl group.

Typical examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, and 2-hydroxypropyl vinyl ether.
-Hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-
Vinyl ether M having a hydroxyl group such as hydroxyhexyl vinyl ether or polyalkylene glycol monovinyl ether, or polycaprolactone-modified vinyl ether.

Such copolymerizable monomers include vinyl monomers as long as they are copolymerizable with the fluorine-containing vinyl monomers and hydroxyl group-containing vinyl monomers listed above. Any of them can be used, but the most representative examples are methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, ter
t-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether,
Alkyl vinyl ethers or substituted alkyl vinyl ethers such as benzyl vinyl ether or phenylethyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; vinyl-2,2-dimethylpropanoate, vinyl-2, 2-dimethylbutanoate, vinyl-
2,2-dimethylpentanoate, vinyl-2,2-dimethylhexanoate, vinyl-2-ethyl-2-methylbutanoate, vinyl-2-ethyl-2-methylpentanoate, vinyl-3- Chloro-2,2-dimethylpropanoate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, C9
branched aliphatic vinyl carboxylate, C1° branched aliphatic vinyl carboxylate, C0 branched aliphatic vinyl carboxylate or aliphatic vinyl carboxylate such as vinyl stearate; vinyl cyclohexane carboxylate, vinyl methylcyclohexane carboxylate, benzoic acid. Vinyl acid or p-
Vinyl esters of carboxylic acids having a cyclic structure such as vinyl tert-butylbenzoate; α-olefins such as ethylene, propylene or butene-1; various halogenated olefins other than fluoroolefins such as vinyl chloride or vinylidene chloride Class; styrene, α
- aliphatic vinyl compounds such as methylstyrene or vinyltoluene; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate or cyclohexyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Methacrylic acid esters such as cyclohexyl methacrylate or benzyl methacrylate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyljethoxysilane, vinyltris(β-methoxyethoxy)silane, allyltrimethoxysilane, trimethoxysilyl Ethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, methyljethoxysilylpropyl vinyl ether, T-(meth)acryloyloxypropyltrimethoxysilane, r- (meth)acryloyloxypropyltriethoxysilane or r-(
Monomer containing a hydrolyzable silyl group such as meth)acryloyloxypropylmethyldimethoxysilane: N-
Dimethylaminoethyl (meth)acrylamide, N-diethyl agodiethyl (meth)acrylamide, N-dimethylaminopropyl (meth)acrylamide or N
-Amino group-containing amide unsaturated monomers such as diethylaminopropyl (meth)acrylamide; dialkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate or diethylaminoethyl (meth)acrylate; tert-butylaminoethyl An amino group-containing monomer such as (meth)acrylate, tert-bitylaminopropyl (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl (meth)acrylate or hyheridinylethyl (meth)acrylate or carboxyl group-containing monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid.

From the viewpoint of increasing the polymerization yield of the fluorine-containing copolymer itself, it is desirable to use alkyl vinyl ethers, cycloalkyl vinyl ethers, hydroxyl group-containing vinyl ethers, and/or carboxylic acid vinyl esters, and in particular, C2 -C2 alkyl group-containing vinyl ethers; -Hebutane tolerance) is particularly desirable in order to make it 200 or less.

Here, the n-hebutane tolerance mentioned above refers to n-hebutane being added dropwise to the solid content of the produced copolymer for which the tolerance is to be determined, until the copolymer becomes cloudy. It is defined as the amount of n-heptane required (in milliliters) divided by the solid content (duram) of the copolymer sampled for this measurement, multiplied by 100.

In the present invention, from the viewpoint of dispersion stability of the target fluorine-containing vinyl non-aqueous polymer dispersion itself, the n-hebutane tolerance of the fluorine-containing copolymer is controlled to be 200 or less. It is particularly desirable that

In order to prepare the fluorine-containing copolymer using the fluorine-containing vinyl monomers and other copolymerizable vinyl monomers as listed above, the fluorine atom content must be 5 to 6.
It should be controlled within a range of 0% by weight, preferably 10-40% by weight.

If it is less than 5% by weight, the weather resistance etc. of the film obtained tends to deteriorate, while if it exceeds 60% by weight, it tends to be difficult to form a film uniformly, and as a result, the gloss becomes poor. This is not preferable in either case, as it also causes a decrease in the temperature.

Furthermore, the amount of hydroxyl group-containing vinyl monomers used is 5 to 40
It is preferably within the range of % by weight.

Furthermore, an α,β-ethylenically unsaturated double bond (hereinafter also referred to as an unsaturated group) is introduced into the fluorine-containing copolymer, whereby in the presence of the fluorine-containing copolymer,
In polymerizing vinyl monomers, it is particularly desirable to carry out grafting in advance from the viewpoint of dispersion stability of the desired fluorine-containing vinyl non-hydroxyl group polymer dispersion composition.

As a method for introducing such an unsaturated group, for example, vinyl monomers having a reactive polar group (hereinafter referred to as functional group f) into the fluorine-containing copolymer may be used. is used as one of the monomers for copolymerization (comonomer), and then a reactive polar group (hereinafter referred to as functional group "2") having reactivity with this functional group f is copolymerized. Examples include a method of reacting an unsaturated group-containing compound having the following.

Here, particularly typical combinations of functional groups f and f2 are listed: hydroxyl group-isocyanate group, isocyanate group-hydroxyl group, epoxy group-rupoxyl group, carboxyl group-epoxy group, hydroxyl group-acid anhydride group. group, acid anhydride group-hydroxyl group, amino group-epoxy group, or epoxy group-agono group, etc., but the selection and design of such re-reactive polar groups are as follows:
It will be carried out as appropriate depending on the reaction conditions and the intended use of the non-aqueous polymer dispersion.

Therefore, in order to prepare the fluorine-containing copolymer, various monomers as listed above are added to an organic polymer capable of dissolving the various monomers in the presence of a radical polymerization initiator. Solution (pressure) polymerization in a solvent (organic solvent for polymerization) is said to be the simplest method, but other known and commonly used polymerization methods such as bulk polymerization, suspension polymerization, or emulsion polymerization can also be used. Of course, this is also possible, and in that case, the solid content may be separated and taken out after the polymerization is completed, and then dissolved in an organic solvent (an organic solvent for non-aqueous dispersion).

Such organic solvents for polymerization may be used, of course, for polymerizing vinyl monomers in the presence of a fluorine-containing copolymer when preparing a fluorine-containing copolymer and a fluorine-containing vinyl nonaqueous polymer. A copolymer of the vinyl monomers coexisting in a mixed state with a fluorine-containing copolymer or in a grafted state (hereinafter referred to as a vinyl copolymer) obtained by Any material can be used as long as it can dissolve Hydrocarbon solvents such as petroleum solvents manufactured by Exxon (USA); esters such as ethyl acetate, n-butyl acetate or ethylene glycol 7-methyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl isobutyl ketone, methyl amyl ketone or cyclohexanone Ketones such as dimethylformamide, dimethylacetamide or N
- Amides such as methylpyrrolidone; or methanol, ethanol, n-propanol, isopropanol,
Alcohols such as n-butanol, isobutanol, 5ee-butanol, tert-butanol or ethylene glycol monoalkyl ether are typical.

The weight average molecular weight of the fluorine-containing copolymer thus obtained is desirably controlled to be within the range of 3,000 to 300.000, particularly within the range of s, ooo to 250.000. .

If it is less than 3.000, the weather resistance of the film tends to deteriorate, while if it exceeds 300,000, it tends to be difficult to form a uniform film.

Next, the vinyl monomers to be polymerized in the presence of the fluorine-containing copolymer in the organic solvent for polymerization include the above-mentioned fluorine-containing vinyl monomers and/or hydroxyl group-containing vinyl monomers. Any other copolymerizable monomers can be used, but of course, these fluorine-containing vinyl monomers and/or water M group-containing vinyl monomers can also be used. Because it is a member of the fluorine-containing copolymer, it can be used in the same way, and in order to make the fluorine-containing vinyl non-aqueous polymer dispersion contain a hydroxyl group, as in the preparation of the fluorine-containing copolymer described above, hydroxyl group-containing vinyl Preference is given to using monomers.

By the way, a vinyl copolymer obtained by polymerizing only using such vinyl monomers in the absence of the above-mentioned fluorine-containing copolymer is a dispersion of a fluorine-containing vinyl non-aqueous polymer. From the point of view of dispersion stability, n-
It is desirable that the hebutane tolerance is controlled to be 3000 or more.

Considering such n-hebutane tolerance, such vinyl monomers include fluorine-containing vinyl monomers and hydroxyl group-containing vinyl monomers, as well as aliphatic monocarbons having an alkyl group of C4 to C4. Vinyl esters of acids, vinyl of cyclohexanecarboxylic acid, C3~
Alkyl vinyl ethers having an alkyl group of C4, cycloalkyl vinyl ethers having an alkyl group of 01 to CI4, as well as n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, ) The main component is at least one compound selected from the group consisting of (meth)acrylates of C4 or higher alkyl alcohols such as acrylate and stearyl (meth)acrylate.

Polymerization of such vinyl monomers is carried out by a known and commonly used method in the same manner as in the preparation of the fluorine-containing copolymer described above. As for the abundance ratio, the solid content weight ratio is 9
It is desirable that it be within the range of 0/10 to 40/60.

If the amount of the fluorine-containing copolymer is too large beyond this range, the dispersion stability of the target fluorine-containing vinyl non-aqueous polymer dispersion composition will tend to deteriorate; If the amount is too small, the viscosity of the obtained non-aqueous polymer dispersion (m-acid) tends to become high, and as a result, the coating workability becomes poor, which is not preferable in either case.

In addition, used in the target polymer dispersion composition of the present invention,
In the organic solvent used to prepare the fluorine-containing vinyl non-aqueous polymer dispersion, that is, as a non-aqueous dispersion solvent, the vinyl copolymer dissolves, but the fluorine-containing copolymer dissolves. Of course, any material can be used as long as it does not dissolve, but in consideration of ease of preparation of the resulting polymer dispersion or dispersion stability, we recommend using hexane, heptane, or octane. Aliphatic hydrocarbons;
Hydrocarbon mixtures with boiling points ranging from 30 to 300°C, such as petroleum benzine, petroleum ether, ligroin, mineral spirits, petroleum naphtha or kerosene; or alicyclic hydrocarbons, such as cyclohexane, methylcyclohexane or ethylcyclohexane. Of course, it is desirable to use these, and these may be used alone or in combination of two or more.

Thus, in order to produce the fluorine-containing non-aqueous vinyl polymer dispersion used in the objective fluorine-containing vinyl non-aqueous polymer dispersion composition of the present invention, for example, an organic solvent solution of the fluorine-containing copolymer, i.e. , the vinyl monomers forming the vinyl copolymer and the radical polymerization initiator are respectively added continuously or in portions to a reaction vessel containing a polymerization solvent solution, or A part of the vinyl monomers and/or the fluorine-containing copolymer polymerization solvent solution
Alternatively, the remaining monomers and the initiator may be added continuously or in portions to a reaction vessel containing a portion of the polymerization initiator, in a solvent. After polymerizing the vinyl monomers in the presence of a polymer, a new organic solvent, i.e., a non-aqueous dispersing solvent such as those mentioned above, is added and, with stirring, a portion of the previous polymerization solvent is added. Or just distill it all off.

Furthermore, in order to improve the dispersion stability, if necessary, a polymer having an n-hebutane tolerance of 300 or more is coexisted with a fluorine-containing copolymer in an organic solvent for polymerization, and then vinyl A method of polymerizing monomers may also be employed.

Typical examples of such polymers include acrylic resins, alkyd resins, alkyl etherified melamine resins, and self-condensing polyester resins of hydroxyl group-containing saturated fatty acids such as 12-hydroxystearic acid. be.

As the radical polymerization initiator used in this case, of course, known and commonly used ones can be mentioned, but among them, to exemplify only the most representative ones, abbisisobutyronitrile and azobisisovaleronitrile are mentioned. azo compounds such as nitriles; or tert-butylperoxypyhalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, benzoyl peroxide, lyloyl peroxide, acetyl peroxide, gter t-
These include peroxides such as butyl peroxide, dicumyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide or diisopropyl peroxycarbonate.

The amount of the radical polymerization initiator to be used depends on the type of polymerization initiator, polymerization temperature, molecular weight of the copolymer, etc.
However, it is generally determined that the total amount of monomers to be copolymerized is 0.
It may be about 0.01 to 10% by weight.

In addition, during such polymerization, the molecular weight can be adjusted using a chain transfer agent such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol, α-methylstyrene, or dimer.

Next, the curing agent, which is another essential component of the present invention, will be explained.

As the curing agent in the present invention, isocyanate compounds and/or aminoplasts are preferred from the viewpoints of curability and weather resistance.

First, to exemplify only particularly representative polyisocyanate compounds, aliphatic diisocyanates such as hexamethylene diisocyanate or trimethylhexamethylene diisocyanate; cycloaliphatic diisocyanates such as xylylene diisocyanate or isophorone diisocyanate: or organic diisocyanates such as aromatic diisocyanates such as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, or adducts of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins (polyester polyols), or water, etc. Furthermore, there are polymers of organic diisocyanates as listed above (including isocyanurate type polyisocyanate compounds6) and isocyanate biuret compounds, and examples of typical commercially available polyisocyanate compounds include To name a few, “Burnock D-750,
D-800, DN-950, DN-970゜DN-98
0, DN-981, DN-990 or DN-992
JC Dainippon Ink & Chemicals Co., Ltd. products], ``Desmodule L, N, HL or LL (products of Bayer AG, West Germany), ``Takenate D-102, D-202, D
-11ON or D-123NJ (Narita Pharmaceutical Co., Ltd. product), “Colo-O” L, HL, EH or 203” [Nippon Polyurethane Industries Co., Ltd. product], or “Deslane” 24A-90EX, (Asahi Kasei Co., Ltd.) ) products] etc.

In addition, typical examples of blocked polyisocyanate compounds refer to those obtained by blocking the various polyisocyanate compounds listed above with known and commonly used blocking agents, and particularly representative examples of such blocked polyisocyanate compounds include Examples of commercially available products include Parnock D-550J or Parnock B7-887-6.
0 or 89-282J (product of Dainippon Ink & Chemicals Co., Ltd.), "Takenate D-815-NJ (product of Narita Pharmaceutical Co., Ltd.)", "Azoitol (ADDITO)"
L) VXL-80J (Hoechst Go IIi, Co., Ltd. product) or "Coronate 2507. [Nippon Polyurethane Industries Co., Ltd. product]. These (blocks)
Among the polyisocyanate compounds, "Parnock DN990 or DN 992J" or "Parnock DN-980 or DN-981J" is particularly preferred from the viewpoint of compatibility with the above-mentioned fluorine vinyl non-aqueous polymer dispersion component.
It is particularly desirable to use compounds having an isocyanurate ring in the molecule, such as.

Furthermore, typical aminoplasts include melamine, urea, acetoguanamine, benzog, anamine,
A condensate obtained by reacting an amino group-containing compound such as steroguanamine or spiroguanine with an aldehyde compound component such as formaldehyde, paraformaldehyde, acetaldehyde or glyoxal, or each of these condensates. Examples include those obtained by etherification with alcohols, but it goes without saying that any of those commonly used for paints can be used.

Among these, those partially or completely etherified with C3 to C4 alcohols are preferred.
Specific examples of such aminoplasts include hexamethyl etherified methylol melamine, hexabutyl etherified methylol melamine, methylbutyl mixed etherified methylol melamine, methyl etherified methylol melagon, pure etherified methylol melamine or isobutyl etherified methylol melamine, or , their condensates, etc.

The thus obtained fluorine-containing vinyl non-aqueous polymer dispersion composition can be used as it is, but depending on the purpose of use, it can also be used with a colorant mixed therein.

Specific examples of such colorants include titanium oxide, zinc white,
Carbon black, iron black, copper chrome black, copper/iron/
Manganese black, yellow lead, cadmium yellow, ocher, titanium yellow, synchromate, Bengara, zinc/iron brown, cadmium red, chrome vermilion, manganese violet, dark blue, ultramarine, cobalt blue, chrome green, chromium oxide green, titanium・Cobalt, nickel, zinc green, vilician, emerald green, cobalt green, kaolin, bentonite,
Silica white, aluminum white, gypsum, chalk, precipitated calcium carbonate, inorganic pigments such as pallite, β-naphthol type, β-oxynaphthoic acid type, naphthol AS
acetoacetic acid anilide series, phthalocyanine series, anthraquinone series, isodigo series, perylene series, perinone series, dioxazine series, quinacridone series, isoindolinone series,
Examples include organic pigments such as metal complex salts, fluorobin, and quinophthalone, metal powders such as gold powder, silver powder, brass powder, aluminum powder or copper powder, and scaly sea urchin treated with titanium oxide. .

The present invention & [l paraboloids may further include various resins, solvents, curing accelerators, fluidity regulators, color separation inhibitors, antioxidants, ultraviolet absorbers, light stabilizers, or It is a matter of heat theory that various known and commonly used additives such as silane coupling agents and the like can be added.

The above resins include acrylic resin, fluorine-containing vinyl resin, cellulose resin such as nitrocellulose or cellulose acetate butyrate, vinyl chloride/vinyl acetate copolymer resin, petroleum resin, ketone resin, oil-free alkyd resin, or epoxy resin. Examples include resin.

[Effects of the Invention] The fluorine-containing vinyl non-aqueous polymer dispersion composition acid of the present invention obtained in this way not only provides a film with excellent weather resistance, but also completely removes the old paint film and undercoat film. It does not swell or dissolve, and has a high coating nonvolatile content, so it has excellent coating workability.

In particular, the release from swelling and dissolution of old paint films and undercoat paint films, high paint non-volatile content and improvement of painting workability are achieved through the innovative method of phase inversion dispersion or phase inversion dispersion method in the method of the present invention. Moreover, it is the effect that can be brought about by making full use of effective means, and the great results that can be brought about by making full use of such means.

〔Example〕

Next, the present invention will be specifically explained using reference examples, examples, comparative examples, applied examples, and comparative applied examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 (Preparation example of fluorine-containing copolymer) 100 parts of ethyl vinyl ether and "Beoba 9" were placed in a 1 liter stainless steel autoclave that was sufficiently purged with nitrogen gas.
(100 parts of branched fatty acid vinyl ester having an alkyl group called C8, manufactured by Shell, Netherlands), 50 parts of 4-hydroxybutyl vinyl ether, 200 parts of methyl ethyl ketone, 5 parts of ter L-butyl peroxyoctoate, 5 parts of abbisisovaleronitrile and 1 part of 1,2,2,6.6-pentamethylpiperidine
．． I prepared 5 parts.

Then, 2 of the liquefied and collected chlorotrifluoroethylene
00 parts and 50 parts of hexafluoropropylene were introduced under pressure and reacted at 60°C for 15 hours without stirring, then 2 parts of methacrylic anhydride and 300 parts of methyl ethyl ketone were added and the mixture was reacted for another 2 hours. The reaction was carried out to obtain a solution of the desired copolymer. The weight average molecular weight of this product was 50,000, the fluorine atom content was 22%, and the n-hebutane tolerance was 50.

Reference Example 2 (same as above) In a 1 liter stainless steel autoclave that was sufficiently purged with nitrogen gas, 50 parts of ethyl vinyl ether,
50 parts of vinyl acetate, 75 parts of 4-hydroxybutyl vinyl ether, 175 parts of cyclohexyl vinyl ether
parts, 10 parts of crotonic acid, 200 parts of ethyl acetate, te
5 parts of r t-butyl peroxyoctoate, 5 parts of abbisisovaleronitrile and 1,2,2,6.6
- 1.5 parts of pentamethylpiperidine was charged.

Then, 2 of the liquefied and collected chlorotrifluoroethylene
00 parts of ethyl acetate was introduced under pressure and reacted at 60°C with stirring for 5 hours.
0 parts of allyl glycidyl ether, 3 parts of allyl glycidyl ether, and 0.5 parts of triphenylphosphine were added, the temperature was raised to 115°C, and the temperature was maintained for 3 hours to carry out the addition reaction of this allyl glycidyl ether. A solution of the desired copolymer was obtained. The weight average molecular weight of this product is so, oo
o, the fluorine atom content was 19%, and the n-hebutane tolerance was 70.

Reference Example 3 (Example of Preparation of Vinyl Copolymer) 200 parts of methyl ethyl ketone was charged into a four-eye flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet.
The temperature was raised to 5°C, and at this temperature, 90 parts of n-butyl methacrylate and 1 part of 2-ethylhexyl methacrylate were added.
00 parts, 10 of β-hydroxypropyl methacrylate
A mixture of 0.8 parts of tert-butyl peroctoate and 0.8 parts of azobisisobutyronitrile was added dropwise over 4 hours, and the mixture was kept at the same temperature for about 15 hours to react. This was continued to obtain a solution of the desired copolymer with a nonvolatile content of 50%. The hebutane tolerance for this was 1,000. Hereinafter, it will be abbreviated as vinyl copolymer (A).

Reference Example 4 (same as above) In a 1 liter stainless steel autoclave that was sufficiently purged with nitrogen, 100 parts of ethyl vinyl ether was added.
200 parts of Beoba 9, 50 parts of 4-hydroxybutyl vinyl ether, 200 parts of ethyl acetate, 1,2.2.
1.5 parts of 6.6-pentamethylpiperidine, tert
- 5 parts of butyl peroctoate and 5 parts of azobisisovaleronitrile were charged.

Next, 1 of the liquefied and collected chlorotrifluoroethylene
50 parts of the copolymer was press-fitted and reacted at 60°C for 15 hours without stirring to obtain a solution of the desired copolymer. The n-hebutane tolerance of this product was 900. Hereinafter, it will be abbreviated as vinyl copolymer (B).

Reference Example 5 (Example of Preparation of Pigment Dispersing Resin) In a 1 liter stainless steel autoclave that was sufficiently purged with nitrogen, 100 parts of ethyl vinyl ether and
200 parts of ``Beoba 9'', 50 parts of 4-hydroxybutyl vinyl ether, 200 parts of ``Isopar EJ (petroleum solvent manufactured by Eson Corporation, USA), tert-
Charged 5 parts of butyl peroctoate and 5 parts of azobisisovaleronitrile.

Next, 1 of the liquefied and collected chlorotrifluoroethylene
50 parts of the resin was press-fitted and reacted at 60°C for 15 hours without stirring, and then 300 parts of "Isopar E" was added to obtain a solution of the desired resin. The n-hebutane tolerance of this product was 900.

Reference Example 6 (Example of Preparation of Fluorine-Containing Vinyl Non-aqueous Polymer Dispersion) In a reaction vessel similar to Reference Example 3, 600 parts of the fluorine-containing copolymer solution obtained in Reference Example 1 and 2 parts of methyl ethyl ketone were added.
00 parts and heated to 75°C, the vinyl copolymer (B
) with the vinyl monomers and polymerization initiator used in their preparation, respectively, i.e.
A mixture of the same composition, i.e. n-butyl methacrylate 90 parts 2
-Ethylhexyl methacrylate 100 β-hydroxypropyl methacrylate 10 parts ter
A mixture consisting of t-butylperoxyoctoate 0.8〃 and azobisisobutylnitrile 0.8〃 was added dropwise over 4 hours, and even after the dropwise addition was completed, the reaction was continued by maintaining the same temperature for 15 hours. I let it happen.

Next, the temperature was raised to 80°C, and while stirring, 300 parts of methyl ethyl ketone was distilled off under reduced pressure.

Thereafter, 330 parts of Isopar El (a petroleum solvent manufactured by Exxon, USA) was charged, and 200 parts of methyl ethyl ketone was distilled off under reduced pressure at 80"C while stirring.

The thus obtained fluorine-containing non-aqueous vinyl polymer dispersion, hereinafter abbreviated as NAD-1, has a non-volatile content of 60% and a Gardner viscosity at 25°C (the same applies hereinafter). was D, indicating that no blocks were generated and the dispersibility was good.

Reference Example 7 (same as above) 730 parts of the fluorine-containing copolymer solution obtained in Reference Example 2 was charged into a 2-liter stainless steel autoclave that was sufficiently purged with nitrogen gas, and further, in Reference Example 4, Fluorine-containing vinyl monomers and vinyl monomers, respectively, similar to those used in the preparation of the vinyl copolymer (B), which has already been confirmed to have an n-hebutane tolerance of 300 or more. 30 parts of ethyl vinyl ether 30 parts of ethyl vinyl ether 15 parts of ethyl acetate
A mixture consisting of 1.5 parts of 60 tert-butyl peroxyoctoate and 1.5 parts of azobisisovaleronitrile was charged.

Then, 4 of the liquefied and collected chlorotrifluoroethylene
5 parts were injected under pressure and the temperature was raised to 60°C to initiate a polymerization reaction, and this temperature was maintained for 15 hours with stirring to continue the reaction.

Then, while stirring continuously, 200 parts of ethyl acetate was distilled off, and 300 parts of LAWS J (a petroleum solvent manufactured by Shell in the Netherlands) was added.
While stirring, 170 parts of a solvent mainly composed of ethyl acetate was distilled off at 60°C under reduced pressure, producing a block with a nonvolatile content of 60% and a viscosity of C. A fluorine-containing non-aqueous vinyl polymer dispersion with good dispersibility was obtained, in which no dispersibility was observed. Hereinafter, this will be abbreviated as NAD-2.

Reference Example 8 In a reaction vessel similar to Reference Example 3, “Lumiflon LF-20
216 parts of 0J (fluorine-containing copolymer manufactured by Asahi Glass Co., Ltd.; fluorine atom content = 25%), 204 parts of n-hebutane, and 16 parts of n-butyl acetate were charged, and the temperature was raised to 80 °C. 80 parts of methyl methacrylate, 90 parts of methyl acrylate, 3 parts of β-hydroethyl methacrylate
A mixture consisting of 0 parts and 3 parts of tert-butylperoxy-2-ethylhexanoate was added dropwise over 3 hours, and even after the dropwise addition was completed, it was kept at the same temperature for 2 hours to ripen. of ethyl acetate was added.

The non-aqueous polymerized rest dispersion obtained for control had a non-volatile content of 50
% and the viscosity was D. Below, this is NAD-
It is abbreviated as 3.

Example 1 100 parts of NAD-1 obtained in Reference Example 6, 12.5 parts of "Parnock DN-990J (isocyanate compound manufactured by Dainippon Ink and Chemicals Co., Ltd.)" and "Tinuvin 90
A mixture of 2 parts of 0J (ultraviolet absorber manufactured by Ciba Geigy, Switzerland) was mixed with a diluting solvent;
LAWS) J/Cellosolve Acetate = 90/10
(ratio by weight) with a mixed solvent (hereinafter abbreviated as diluting solvent A) to obtain the desired fluorine-containing vinyl non-aqueous polymer dispersion composition.

Example 2 A mixture consisting of 100 parts of the resin for pigment dispersion obtained in Reference Example 5 and 100 parts of "Tie Bake CR-93JC titanium oxide manufactured by Ishihara Sangyo Co., Ltd." was kneaded in a sand mill, and further mixed in Reference Example 165 parts of NAD-2 obtained in ``
67 of Super Beckamine L-127-75J (butylated melamine resin manufactured by Dainippon Ink and Chemicals Co., Ltd.)
A portion of the dispersion was diluted with the diluting solvent A to obtain the desired fluorine-containing vinyl nonaqueous polymer dispersion composition.

Comparative Example 1 In Example 1, when the same amount of NAD-3 obtained in Reference Example 8 was used instead of NAD-1 and diluting solvent A was added, the mixture separated and could not be diluted.

Therefore, we diluted with a mixed solvent of xylene/n-butyl acetate/cellosolve acetate = 40/30/30 (weight ratio) (hereinafter abbreviated as diluent solvent B) for comparison to obtain a coating with a non-volatile content of 40%. A fluorine vinyl non-aqueous polymer dispersion-containing acid product was obtained.

Comparative Example 2 100 parts of Fluonate K-700J (solvent-type gold-fluorine copolymer manufactured by Dainippon Ink and Chemicals Co., Ltd.) and 12 parts of Burnock DN-980J were combined with Tinuvin.
900'' was diluted with diluting solvent B to obtain a comparative solvent-type gold-fluorine copolymer composition having a coating nonvolatile content of 27%.

Application Examples and Comparative Application Examples Amino alkyd white paints (hereinafter referred to as (abbreviated as undercoat A) or an alkyd resin-based white paint prepared from medium oil alkyd resin and rutile-type titanium oxide (hereinafter abbreviated as undercoat B) was applied, dried and cured in advance. Each composition was applied separately by air spray onto a zinc phosphate-treated steel sheet having a thickness of 0.811 parts m, and heated at 140'C for 30 minutes.
Various cured coating films were obtained by drying by heating for 1 minute or by leaving to dry at room temperature for 7 days.

Next, for each coating film, the so-called condition of the coating surface, such as "shrinking or blistering," was visually evaluated, and coatings with no abnormalities in the appearance of the coating surface were further treated with sunshine coating. Exposure was performed for 3,000 hours using a zaometer, and changes in gloss, that is, gloss retention, were also compared and examined.

The results are summarized in Table 1.

/ / As is clear from Table 1, the fluorine-containing non-aqueous vinyl polymer dispersion composition acid of the present invention not only provides a film with excellent weather resistance, but also replaces old paint films and undercoat films. It is also known that it does not swell or dissolve and also has excellent coating workability because it has a high coating nonvolatile content.

Claims (1)

[Claims] 1. A fluorine-containing non-aqueous vinyl polymer dispersion obtained by polymerizing vinyl monomers in the presence of a fluorine-containing copolymer and phase inversion dispersion, and a curing agent. A fluorine-containing vinyl non-aqueous polymer dispersion composition containing as a main component. 2. The above-mentioned fluorine-containing vinyl non-aqueous polymer dispersion is prepared by first polymerizing vinyl monomers in an organic solvent for polymerization in the presence of a fluorine-containing copolymer, and then adding the above-mentioned fluorine-containing copolymer. Adding a new organic solvent that dissolves the vinyl copolymer obtained by using only the vinyl monomers without using a polymer, but does not dissolve the fluorine-containing copolymer,
The fluorine-containing non-aqueous vinyl polymer dispersion composition according to claim 1, which is obtained by removing part or all of the organic solvent for polymerization. 3. The fluorine-containing copolymer described above has a fluorine atom content of 5 to 60% by weight, and 3,000 to 300% by weight.
The fluorine-containing vinyl nonaqueous polymer dispersion composition according to claim 1 or 2, which has a polymerization average molecular weight of ,000. 4. The fluorine-containing copolymer described above is vinylidene fluoride,
A copolymer of at least one fluorine-containing vinyl monomer selected from the group consisting of chlorotrifluoroethylene, tetrafluoroethylene, and hexafluoropropylene and other copolymerizable vinyl monomers, The fluorine-containing vinyl nonaqueous polymer dispersion composition according to claim 1, 2, or 3. 5. The fluorine-containing vinyl non-aqueous polymer dispersion composition according to claim 1, wherein the fluorine-containing non-aqueous vinyl polymer dispersion contains a hydroxyl group. 6. The fluorine-containing vinyl non-aqueous polymer dispersion composition according to claim 1, wherein the curing agent is at least one selected from the group consisting of isocyanate compounds and aminoplasts.