JPH03182539A - Fluororesin composition - Google Patents

Abstract

PURPOSE:To prepare a fluororesin compsn. improved in the water-repellent and oil-repellent properties and useful for a coating material, sealant, film, etc., by compounding a fluorocopolymer having reactive polar groups, a polysiloxane compd. having groups reactive with the polar groups, and an org. solvent. CONSTITUTION:15-70wt.% fluorovinyl monomer, 2-40wt.% vinyl monomer having a reactive polar group, and 0-83wt.% copolymerizable monomer are copolymerized in the presence of a radical polymn. initiator in a solvent at 0-140 deg.C to give a fluorocopolymer contg. 0.1-6.0 equivalents of the reactive polar group based on 1000g of the copolymer and having a number-average mol.wt. of 1000-100000. 100 pts.wt. compsn. comprising 50-99 pts.wt. of the copolymer and 50-1 pts.wt. polysiloxane compd. having groups reactive with the reactive polar groups is compounded with 5-1000 pts.wt. org. solvent and, if necessary, 1-50 pts.wt. curing agent reactive with the reactive polar groups.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a new and useful fluororesin composition. More specifically, the present invention uses, as essential components, a fluorine-containing copolymer having a reactive polar group (hereinafter also referred to as a functional group), and a polysiloxane having a group reactive with the functional group. The present invention relates to a fluorine-containing resin composition that contains a compound and an organic solvent, and further contains a curing agent that is reactive with the above-mentioned functional group, and has particularly excellent water and oil repellency. .

The crude fluorine-containing resin of the present invention can be used in a wide range of applications, including paints, sealants, and molded products such as films.

[Conventional technology]

In recent years, fluoroolefin copolymers that are soluble in organic solvents, can form coating films with extremely high weather resistance, and can be dried and cured at room temperature have been developed, hereinafter also referred to as fluororesins. ) has been developed and has come to be used mainly for paints.

However, such fluoroolefin copolymers
In order to impart solvent solubility to the copolymer, a fluoroolefin is copolymerized with other monomers that can be copolymerized with the fluoroolefin, such as vinyl ethers and vinyl esters. The reality is that the water and oil repellency inherent to fluororesin is impaired.

For this reason, paint films made from so-called fluororesin paints obtained using this type of fluoroolefin copolymer may be exposed to water during or after drying. In addition to being water and oil repellent, water and oil repellency may cause so-called water stains to remain, or even after being in contact with oil for a long period of time, oil stains may remain even after wiping off the oil. Well, there was a problem.

[Problem to be solved by the invention]

However, in view of the various negative effects caused by the lack of water and oil repellency in fluororesin paints, and based on the technical background described above, the present inventors have been working on developing water and oil repellents over a long period of time. As a result of extensive research to provide a practical fluorine-containing resin composition that provides a coating film with excellent oiliness, we have developed a functional group-containing fluorine-containing copolymer and a specific polysiloxane compound. The present inventors have discovered that a resin composition containing an essential part of an organic solvent has extremely excellent water and oil repellency, and has thus completed the present invention. .

Therefore, the problem to be solved by the present invention is to provide an extremely useful fluorine-containing resin composition that is excellent in water repellency, tΩ oil resistance, etc.

[Means to solve the problem]

Therefore, the inventors of the present invention focused exclusively on the problems to be solved by the invention as described above, and as a result of intensive studies, the inventors of the present invention have developed a novel method that can provide the desired fluororesin composition. A technological system has been established.

That is, the present invention uses, as essential components, a functional group-containing fluorine-containing copolymer (A) and a polysiloxane compound having a group reactive with such a functional group (hereinafter also referred to as a reactive group). (B) and an organic solvent (C), or a functional group-containing fluorine copolymer (A), a reactive group-containing polysiloxane compound (B), and an organic solvent (C); A curing agent (D
> or the functional group-containing fluorine-containing copolymer (A) and the reactive group-containing polysiloxane compound (B
) (hereinafter also referred to as modified polymer (A-B)). ] and an organic solvent (C), or a modified polymer (A-B), an organic solvent (C), and a curing agent (D) that is reactive with such a functional group.
The object of the present invention is to provide a new and useful fluorine-containing resin composition that is particularly excellent in water and oil repellency.

Here, first, the functional group-containing fluorine-containing copolymer (A), which is an essential bottom valve of the fluorine-containing resin composition of the present invention, refers to a fluorine-containing vinyl monomer and a vinyl monomer having a functional group. This term refers to a copolymer obtained by copolymerizing a group of monomers as an essential monomer component.

Such fluorine-containing vinyl monomers (a-1) include vinyl butylene, vinylidene butylene, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, promotrifluoroethylene, pentafluoropropylene, hexafluoropropylene, Typical examples include (per)fluoroalkyl vinyl ether in which the per)fluoroalkyl group has 1 to 18 carbon atoms.

Furthermore, the vinyl monomers (a-2) having a functional group include, for example, the lowest of various reactive polar groups such as a hydroxyl group, an amino group, a glycidyl group or an epoxy group, or a carboxyl group. Vinyl monomers having any one of them fall under this category.

Therefore, of course, any functional group having one or two of the above-mentioned functional groups can be used, but to exemplify particularly representative ones, two - Hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyethyl vinyl ether, β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, β-hydroxybutyl (meth)acrylate or allyl alcohol. Monomers containing hydroxyl groups such as: 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether, allylamine, N-methylaminoethyl vinyl ether, N-methylaminopropyl vinyl ether, N-methylallylamine, N,N-dimethylaminoethyl vinyl Ete/L
/, N, N-dimethylagonobrobyl vinyl ether,
Dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, N.

Monomers containing agono groups such as N-dimethylaminoethyl (meth)acrylamide or N,N-dimethylagonobrovir (meth)acrylamide; glycidyl (meth)acrylate, β-methylglycidyl (meth)
Monomers containing glycidyl groups such as acrylates or allyl glycidyl ethers: or half of (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, or α,β-monoethylenically unsaturated dicarboxylic acids. These include monomers containing carboxyl groups such as esters.

The fluorine-containing vinyl monomers (a-1) and the functional group-containing vinyl monomers (a-2) listed above, respectively.
In addition to the essential raw material components, other monomers (a-3) that can be copolymerized with these monomers include, of course, any monomers that are copolymerizable. Although they can be used, only the most representative ones are exemplified: methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n -pentyl vinyl ether, nhexyl vinyl ether, n
- Alkyl vinyl ethers such as octyl vinyl ether or 2-ethylhexyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; aralkyl vinyl ethers such as hensyl vinyl ether or phenethyl vinyl ether; 2゜2.3.3 -tetrafluoropropyl vinyl ether, 2.2, 3, 3.4, 4.
5.5-octafluoropentyl vinyl ether, 2,
2.3.3, 4.4.5, 5, 6, 6.7, 7, 8.8
,9.9-hexadecafluorononyl vinyl ether,
(Per)fluoroalkyl vinyl ethers such as perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorooctyl vinyl ether or perfluorohexyl vinyl ether; or vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, pivalin Representative examples include vinyl ethyl carboxylates such as vinyl acid, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl salicylate, or vinyl cyclohexanecarboxylate. Typical examples include ethylene, vinyl chloride, vinylidene chloride, (meth)acrylonitrile, and various (meth)acrylic esters. Among the other copolymerizable monomers [(a-3), it is desirable to use alkyl vinyl ethers and/or cycloalkyl vinyl ethers from the viewpoint of sufficiently increasing the polymerization rate; When using the copolymer as a base resin component for paint, from the viewpoint of coating hardness, vinyl esters of fatty acid monocarboxylic acids having branched alkyl groups having 4 to 17 carbon atoms, benzoic acid Particularly preferred is the use of at least one monomer selected from the group consisting of vinyl, vinyl pt-butylbenzoate and vinyl cyclohexanecarboxylate.

In order to prepare the fluorine copolymer (A) from each of the monomer components listed above, the yield of the copolymer, the weather resistance of the resulting coating film, and the From the viewpoint of water and oil repellency imparted by the reaction between the functional group and the polysiloxane compound (B), the usage ratio of each monomer component is determined by the ratio of the fluorine-containing vinyl monomers (a-1). 15
~70% by weight vinyl monomer containing functional groups! (a-
2 to 40% by weight of 2), and other copolymerizable monomers [0 to 83% by weight of (a-3), preferably (a-1
), 20 to 60% by weight of (a-2), 5 to 30% by weight of (a-2),
and (a-3), and the content of the functional group is within the range of 0 to 75% by weight of the copolymer, and the solid content of the copolymer is 1.0%.
0.1 to 6.0 equivalents, preferably 0.00 g.
The amount should be controlled to 3 to 4.5 equivalents, respectively.

To prepare the fluorine-containing copolymer (A) using the various monomer components listed above, a radical polymerization initiator is used to carry out emulsion polymerization, suspension polymerization, bulk polymerization, or solution polymerization. The polymerization reaction may be carried out by making full use of known techniques, and examples of such radical polymerization initiators include diacyl peroxides such as acetyl peroxide or benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide. Hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide or cumene hydroperoxide; Dialkyl peroxides such as di-t-butyl peroxide or dicumyl peroxide; t-butyl peroxyacetate or t-butyl peroxide; Typical examples include alkyl peroxy esters such as butyl peroxybivalate; azo initiators such as azobisisobutyronitrile or azobisisovaleronitrile; or persulfates such as ammonium persulfate or potassium persulfate. It is something.

The amount of the radical polymerization initiator to be used depends on the type of the initiator, the polymerization temperature, and the resulting fluorine-containing copolymer (A).
Although it is determined as appropriate depending on the molecular weight of
About 10 parts by weight is good.

As a copolymerization reaction method, there are various known methods as described above, but among these, bulk polymerization, solution polymerization, etc. are preferable.Furthermore, it is preferable to use the obtained copolymer as it is to form a solution-type paint. The solution polymerization method is particularly desirable from the standpoint of being usable as a resin composition for.

Typical solvents used in preparing the fluorine copolymer (A) by the solution polymerization method include:
Aromatic hydrocarbons such as benzene, triene or xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-octane or mineral spirits; alicyclics such as cyclopentane, cyclohexane, methylcyclohexane or ethylcyclohexane. Hydrocarbons; methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, n-
Alcohols such as hexanol, n-octatool, 2-ethylhexanol, cyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether; dimethoxyethane, tetrahydrofuran , dioxane, diisopropyl ether or di-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone or isophorone; methyl acetate, ethyl acetate, n-propyl acetate,
Esters such as 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 glycol monobutyl ether acetate: or chloroform, methylene Chloride, carbon tetrachloride, chlorinated hydrocarbons such as trichloroethane or tetrachloroethane, and furthermore, N-methylpyrrolidone, dimethylformamide,
Also included are dimethylacetamide or ethylene carbonate. Such solvents may be used alone or
Although it can be used as a mixture of two or more types, it is preferable to appropriately select one that can dissolve or disperse the copolymer to be produced. The amount used is 5 to 1,000 parts per 100 parts by weight of the total amount of monomers used.
000 parts by weight may be sufficient.

Among the various organic solvents listed above, fluorine-containing copolymers (
When using a polyisocyanate compound as described below as the curing agent (D) which is reactive with the functional group of A), the use of alcohol-based solvents should be avoided.

A fluorine-containing copolymer (A) from the monomer components listed above
In order to prepare by solution polymerization method, ① all the monomers, a polymerization initiator and a solvent are charged in a reactor at once and polymerized, or ② a fluorine-containing vinyl monomer and a solvent are charged in a reactor. , a monomer other than this fluorine-containing vinyl monomer, and a polymerization initiator may be added continuously or in portions for polymerization, or monomer and polymerization initiator,
Methods such as adding each component continuously or in portions and polymerizing them can be applied.

In such polymerization, the reaction temperature and reaction pressure are appropriately selected depending on the type of polymerization initiator, polymerization solvent, etc., and the molecular weight of the desired copolymer. ℃, preferably in the range of 40 to 100℃, and the reaction pressure is usually 100 kg1
A pressure of 0.02 or less is used.

The number average molecular weight of the fluorine-containing copolymer (A) containing functional groups obtained in this way is 1.000 to 10
A range of 0.000 is desirable.

Next, a polysiloxane compound having a group (reactive group) that is reactive with the reactive polar group present in the fluorine-containing copolymer (A) having a reactive polar group (functional group) prepared in this way. (B) each has a reactive group such as an amino group, a carboxyl group, or an epoxy group, and preferably the same reactive group is attached to at least one of the terminal ends of the molecule. It is desirable to use one that has at both ends.

Particularly typical examples of the reactive group-containing polysiloxane compound (B) include - formula % formula % (1) In particular, the formula [however, e in the formula is 1 to 50] Assume that there is.

] Formula [However, m in the formula shall be 1 to 150. ] or the formula [however, n in the formula shall be 1 to 150.

It is desirable to use compounds as shown in .

Furthermore, the above-mentioned organic solvent (C) may of course contain the fluorine-containing copolymer (A) or the fluorine-containing copolymer (A).
) and the polysiloxane compound (B), each of which is capable of dissolving or dispersing the modified polymer (A-B). Of these, particularly representative ones include various organic solvents that can be used when preparing the fluorine-containing copolymer (A) by solution polymerization as described above. It will be done. However, among the organic solvents (C), when using a polyisocyanate compound as listed below as a curing agent (D) that is reactive with the functional group of the fluorine-containing copolymer (A), an alcohol-based Only the use of solvents should be avoided.

Furthermore, the curing agent (D) has a group that is reactive with the functional group in the functional group-containing fluorine copolymer (A).
Tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate, methylcyclohexane
2.4-(or 2.6-) diisocyanate, 4.
4'-methylenebis(cyclohexyl isocyanate)
or diisocyanates such as 1,3-di(isocyanatomethyl)cyclohexane; triisocyanates such as 4-isocyanatomethyloctamethylene diisocyanate; the above diisocyanates and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or Polyisocyanate resins obtained by reacting a polyhydroxy compound such as a hydroxyl group-containing polyester; polyisocyanate resins having a billet bond obtained by reacting the diisocyanates with water; or polyisocyanate resins obtained by cyclopolymerizing the diisocyanates. Polyisocyanate resins having an isocyanurate ring obtained by Blocked isocyanates obtained by blocking with a compound having active hydrogen such as , phenol, methyl ethyl ketoxime or ε-caprolactam; polyvalent metal alkoxides such as tetrabutoxytitanium, tributoxyaluminum or tetrabutoxyzirconium; or the aforementioned polyvalent metal alkoxides. There are polyvalent metal chelate compounds obtained by reacting with a chelating agent such as acetylacetone or ethyl acetoacetate, and when the functional group of the fluorine-containing copolymer is a hydroxyl group, trimellitic anhydride or pyromellitic anhydride is used. Polycarboxylic acid anhydrides such as Polyepoxy compounds such as glycidyl esters of polycarboxylic acids can also be used.

To prepare the fluorine-containing resin composition of the present invention from the components (A), (B) tc, (C) and (D) listed above, (A) tc, (B) 1 minutes and (C)
1 minute, and if necessary, component (D) may also be blended at the same time, or the component (B) which has a functional group of component (A) and a group that is reactive with such functional group. are reacted in advance to form an adduct of components (A) and (B), and then (C) tc component is blended, and if necessary, curing agent (D)! There is also a method of combining the ingredients. The blending ratio is 50 to 99 parts by weight of component (A) to 50 to 1 part by weight of component (B).
Parts by weight of components (A) and (B) are blended or reacted so that the total amount is 100 parts by weight, and based on 100 parts by weight of this blend or modified polymer, the amount of component (C) About 5 to 1,000 parts by weight may be blended. Furthermore, if necessary, when blending component (D), (A)
(D) per 100 parts by weight of the total amount of component and (B) component.
It is desirable to blend 1 to 50 parts by weight of the ingredients.

The fluorine-containing resin composition of the present invention can be used as it is, or if necessary, can be added with various known and commonly used additives such as colorants, antioxidants, ultraviolet absorbers, or fillers. First, it can be used as a sealant or in various molded products such as films and sheets.

In addition, the above-mentioned modified polymers (A-B) are, respectively,
A functional group-containing fluorine-containing copolymer (A) as described above,
It is obtained by reacting the reactive group-containing polysiloxane compound (B) in the presence or absence of a known and commonly used catalyst, but of course, the modified polymer (A -B) should be prepared in advance before adding various ingredients such as the curing agent (D).

〔Effect of the invention〕

A fluorine-containing copolymer (A) having a functional group and a polysiloxane compound I containing a group reactive with such a functional group
The fluorine-containing resin composition of the present invention, which comprises FI (B), an organic solvent (C), and, if necessary, a curing agent (C) that is reactive with such a functional group, is a polysiloxane compound. By using (B), a film with extremely excellent water and oil repellency can be formed. Further, by using the fluorine-containing resin composition of the present invention, it is possible to provide a film that not only has ultra-high weather resistance but also has excellent 8-water (Ω) oil resistance and stain resistance.

Therefore, the present invention provides a fluorine-containing resin composition that has excellent performance and can be used in various applications such as paints, sealants, and films.

〔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. shall be taken as a thing.

Reference Examples 1 to 5 [Preparation example of functional group-containing fluorine-containing copolymer (A)] 11! sufficiently substituted with nitrogen! In a stainless steel autoclave, a portion of the solvent and an amount of bis(1, 2, 2, 2, 6,6-bentamethyl-4-piperidinyl) sebacate was charged, the temperature was raised to 60°C while stirring, and then a mixture of fluorine-containing vinyl monomers, other monomers, a polymerization initiator, and the remaining solvent was added. were added dropwise over a period of 3 hours. (However, among the fluorine-containing vinyl monomers, hexafluoropropylene and chlorotrifluoroethylene were liquefied and collected before being press-injected, while tetrafluoroethylene was directly injected without being liquefied and collected.) After the dropwise addition was completed, the reaction was carried out at the same temperature for 10 hours, and the temperature was further raised to 85°C, and the reaction was carried out for 4 hours to form a fluorine-containing copolymer (A
-1) to (A-5) were obtained. Each of the obtained basic fluorine copolymers was diluted with xylene so that the nonvolatile content was 50%. The number average molecular weight and Gardner color of each copolymer solution are also summarized in the same table.

Reference Examples 6 to 8 (Example of Preparation of Comparative Fluorine Copolymer) The same reactions and operations as in Reference Examples 1 to 5 were carried out, respectively.
The fluorine-containing copolymer (A'-
1) to (A'-3) were obtained.

Examples 1 to 5 A fluorine-containing copolymer, a polysiloxane compound, and a solvent of the types and amounts shown in Table 2, and a curing agent if necessary, were added to form a solution-type metal fluoride. Resin clear paints (CR-1) to (CR-5) were prepared. However, in Examples 3 and 5, the functional groups of the fluorine-containing copolymer solution and the polysiloxane compound were reacted in advance and used for blending.

Next, it was applied to a tin plate (150x80 square) using a 6 mil applicator, dried at 25°C for 7 days, and further functionalized at 100°C for 2 hours to form a fluorine-containing resin coating. I got a panel that was Water droplets and oil droplets (
soybean oil) was dropped on the surface of the coating, and the contact angle formed between the water droplet or oil droplet and the coating surface was measured. The contact angle was measured using Elma Optics (
A goniometer type contact angle measuring device rG-1 manufactured by Co., Ltd. was used. The results are summarized in the same table.

Comparative Examples 1 to 3 A control solution was prepared by adding a fluorine-containing copolymer, a polysiloxane compound, and a solvent as shown in Table 2 and a curing agent as required. Mold fluororesin clear paint (CR'-1) ~ (C
R'-3) was prepared.

Next, a coating film was formed and the contact angle was measured in the same manner as in Examples 1 to 5 described above. The results are also shown in Table 2.

From Table 2, solution-type fluororesin clear paints (CR-1) to (C
R-5) is known to have particularly excellent water and oil repellency compared to control paints (CR'-1) to (CR'-3) obtained using conventional resin compositions.

Application Examples 1 to 5 With the contents shown in Table 3, a fluorine-containing copolymer, a polysiloxane compound, a coloring material, an antioxidant, and an ultraviolet absorber,
Furthermore, if necessary, a curing agent is also added, and toluene/xylene/butyl acetate/cellosolve acetate = 3
Solution type gold fluororesin paints (SL-1) to (SL-5) were prepared by diluting with a mixed solvent of 0/30/30/10 (weight ratio) to a viscosity that allowed air spraying.

Next, as an undercoat, the base polymer was a copolymer having the following composition (methyl methacrylate/ethyl acrylate)/n-butyl methacrylate/β-hydroxyethyl methacrylate/acrylic acid = 30/20/3B/11/1 (weight ratio). On the other hand, the curing agent is "Parknock DN-950J (a polyisocyanate compound manufactured by Dainippon Ink and Chemicals Co., Ltd.)", and the pigment is "
Tybake CR-93J [rutile type titanium oxide manufactured by Ishiya Sangyo Co., Ltd.] is coated with an acrylic-urethane white paint with a PWC of 35% and has a thickness of 0.
．． Each of the fluorine-containing resin paints (SL-1) to (SL-5) obtained in Application Examples 1 to 5 was applied by air spray to a zinc phosphate-treated steel plate with an 8 V opening and a size of 150 x 70 W. It was coated and dried at 25° C. for 10 days to obtain a panel on which a fluorine-containing resin coating was formed.

At that time, only for paints using fluorine-containing resins having hydroxyl groups, a curing agent as shown in the same table was added before coating.

Each panel thus obtained was subjected to ultraviolet irradiation at 70°C for 8 hours and humidity at 50°C for 4 hours using a "Du-Panel Light Control Weather Meter" [accelerated weathering tester manufactured by Suga Test Instruments Co., Ltd.]. Changes in gloss were examined under conditions of repeated exposure for 3,000 hours, with 1 cycle being considered. Separately, similar panels were exposed outdoors for two periods to examine contamination. Stainability was evaluated based on the color difference between the painted film after exposure, which was washed with water to remove dirt, and the painted film before exposure.

Comparative Application Examples 1 to 3 Performing the same operations as in Application Examples 1 to 5, control fluororesin-based paints (SL'-1) to (SL'-3) were prepared,
A control panel was obtained which was painted and a coating was formed. Next, tests and evaluations similar to those in the application example were conducted. The results are also shown in Table 3.

As is clear from the results in Table 2, the solution-type gold-fluororesin paints (SL-1) to (SL-5) obtained using the fluororesin composition of the present invention are different from those of conventional resin compositions. Control paints (SL'1) to (SL'-
Compared to 3), it is known that even after a long-term accelerated weathering test, the gloss retention rate is excellent and the color difference hardly changes.

As is clear from Tables 2 and 3, the fluorine-containing resin composition of the present invention is known to have extremely excellent weather resistance, water and oil repellency, and stain resistance.
Therefore, it can be seen that it is an excellent new material.

teenager Reason Man

Claims (1)

[Claims] 1. A fluorine-containing copolymer (A) having a reactive polar group;
A fluororesin composition comprising a polysiloxane compound (B) having a group reactive with the reactive polar group and an organic solvent (C). 2. A fluorine-containing copolymer (A) having a reactive polar group;
A polysiloxane compound (B) having a group reactive with this reactive polar group, an organic solvent (C), and a curing agent (D) having a group reactive with the above reactive polar group. A fluororesin composition comprising: 3. A fluorine-containing copolymer (A) having a reactive polar group;
A fluororesin composition comprising a modified polymer obtained by reacting this reactive polar group with a polysiloxane compound (B) having a reactive group, and an organic solvent (C). 4. A fluorine-containing copolymer (A) having a reactive polar group;
A modified polymer obtained by reacting this reactive polar group with a polysiloxane compound (B) having a reactive group, an organic solvent (C), and a group having reactivity with the reactive polar group. A fluorine-containing resin composition comprising a curing agent (D) having the following properties. 5. Fluorine-containing copolymer having the above-mentioned reactive polar group (
Claims 1 to 4, wherein A) has at least one reactive polar group selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, and a carboxyl group.
The fluorine-containing resin composition according to any one of the above.