JP2001207004A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the coating film properties of conventional fluorine resin paint products such as water and oil repellency, stainproof property, stain resistance, durability and chemical resistance. SOLUTION: This resin composition contains a copolymer (A) of a fluoroolefin, a reactive silicone oil of general formula (1) or (2): R1-[Si(CH3)2-O]n- Si(CH3)2-R2 (1) (wherein R1 is a 1-6C alkyl group, -(CH2)rOOC(CH3)C=CH2 or CH=CH2; R2 is (CH2)r-OOC(CH3)C=CH2 or -CH=CH2; (n) is 1-420; and (r) is 1-6) or R2-Si[OSi(CH3)3]3 (2) (wherein R2 has the same meaning as defined above) and one or more polymerization units selected from an alkyl vinyl ether, an alkyl allyl ether, a methacrylate or an acrylate and an acrylic resin (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an automobile, a building, a bridge, etc., which are excellent in antifouling property, water repellency and oil repellency, and have excellent characteristics such as chemical resistance and weather resistance which are characteristics of fluororesin. The present invention relates to a fluorinated copolymer and an acrylic resin composition to be used as a paint.

[0002]

2. Description of the Related Art Solvent-soluble fluororesin coatings are generally obtained by copolymerizing a hydroxyalkyl vinyl ether and a fluoroolefin, and if necessary, an alkyl vinyl ether or an alkyl vinyl ester. Coatings based on such fluorocopolymers contain about 50 mol% of hydrocarbon monomers in order to obtain solubility in common organic solvents. For this reason, the fluorine content in the fluororesin decreases, and the coating properties such as water and oil repellency and stain resistance required for the fluororesin cannot be sufficiently obtained. On the other hand, by adding a small amount of an organic silicon compound such as silicone oil to the fluorinated copolymer, the water / oil repellency is improved. However, it is difficult to maintain long-term water and oil repellency. Furthermore, in some applications, silicone oil cannot be used because the silicone oil bleeds out from the coating film surface. Further, Japanese Patent Application Laid-Open No.
No. 535 discusses a copolymer of a fluorine-containing monomer and a monomer containing a silyl group. However, since the silyl group has a short side chain, a coating such as an antifouling property and a water / oil repellency property is required. There are problems such as insufficient film properties.

[0003]

SUMMARY OF THE INVENTION The present invention improves the properties of the conventional fluororesin coating products such as water and oil repellency, stain resistance, stain resistance, durability, chemical resistance and the like. That is the main issue.

[0004]

The present inventors have conducted intensive studies to solve the above problems, and as a result, (A)
A fluoroolefin and a compound represented by the general formula (1) or (2) R _1- [Si (CH ₃ ) ₂ -O] _n -Si (CH ₃ ) ₂ -R ₂ (1) (where R ₁ is An alkyl group of 6 or
_{(CH 2) r -OOC (CH} 3) C = CH 2 or -
Shows the CH = CH _2. R ₂ is — (CH ₂ ) _r —OOC
(CH ₃₎ shows the C = CH ₂ or -CH = CH _2.
n shows 1-420 and r shows 1-6. ) R ₂ —Si [OSi (CH ₃ ) ₃ ] ₃ (2) wherein R ₂ is as defined above, alkyl vinyl ether, alkyl allyl ether, methacrylate and acrylate The resin composition containing one or more polymerized units selected from the above and (B) an acrylic resin is excellent in long-term water and oil repellency, antifouling property, and repetitive soil removing property. Was found.

That is, the present invention relates to (A) a fluoroolefin as an essential polymerized unit of 15 to 85 mol%,
0.001 to 30 mol% of the reactive silicone oil represented by the general formula (1) or (2) and one or more selected from alkyl vinyl ethers, alkyl allyl ethers, methacrylic esters and acrylic esters. And (B) an acrylic resin, wherein the resin composition contains water and oil repellency, antifouling property, and repetition over a long period of time. The present invention provides a resin composition having excellent stain removal properties, chemical resistance, and weather resistance.

In the above-mentioned fluorine-containing copolymer, if the fluoroolefin content of the polymerized unit is less than 15 mol%, sufficient stain resistance cannot be obtained when used as a paint base, which is not preferred. On the other hand, if it is more than 85 mol%, the solubility in various solvents decreases, which is not preferable. More preferably, it is 30 to 80 mol%.

[0007] The fluoroolefin is an olefin having one or more fluorine atoms in the molecule, such as vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, and hexafluoropropylene. These fluoroolefins may be used alone or in combination of two or more, but a combination of vinylidene fluoride and tetrafluoroethylene is particularly preferred. Combination ratio of vinylidene fluoride and tetrafluoroethylene (VDF
/ TFE) is preferably 0.05 / 1 to 2.0 / 1.
A more preferred range for the fluorinated copolymer is 0.1
/ 1 to 1.5 / 1.

The ratio of the reactive silicone oil represented by the general formula (1) or (2) is 0.001 mol%.
If less, sufficient water and oil repellency in the long term,
It is not preferable because antifouling property cannot be obtained. On the other hand, if it is more than 30 mol%, sufficient chemical resistance and weather resistance cannot be obtained, which is not preferable. Further, when polymerizing a polymer having a large molecular weight (n = 200 to 400), the ratio cannot be increased due to production.
For these reasons, the proportion is more preferably 0.0
05 to 25 mol%.

Further, the reactive silicone oil represented by the general formula (1) or (2) is a methacryl-modified polydimethylsiloxane at one end, an acryl-modified polydimethylsiloxane at one end, and a methacryl-modified at both ends. Polydimethylsiloxane and the like are preferred.
These reactive silicone oils may be used alone or in combination of two or more. The number average molecular weight of these reactive silicone oils is 200 to 3
000 is preferred.

As the reactive silicone oil, silicone oils of the following formulas (3), (4), (5) and (6) are particularly preferred. CH ₂ ＣC (CH ₃ ) —COO—C ₃ H ₆ — [Si (CH ₃ ) ₂ —O] _m —Si (CH ₃ ) ₂ —R ₃ (3) (where R ₃ represents 1 carbon atom And m represents 1 to 250.) CH ₂ ＣＨCH—COO—C ₃ H ₆ — [Si (CH ₂ ) ₂ —O] _p —Si (CH ₃ ) ₂ —R ₄ (4 (Where R ₄ represents an alkyl group having 1 to 6 carbon atoms; p is 1 to 250). R ₅ -C ₃ H _6- [Si (CH ₃ ) ₂ -O] _q -C ₃ H ₆ -R _{5 (5)} (wherein R _5, the .q showing a _{-OCOC (CH 3) = CH 2} 1~250.) CH 2 = C (CH 3) COO-C 3 H 6 Si [OSi ( CH ₃ ) ₃ ] ₃ (6) Further, the proportion of the monomer selected from the group consisting of alkyl vinyl ether, alkyl allyl ether, methacrylate and acrylate is less than 1 mol%. In such a case, solubility in various solvents cannot be obtained, which is not preferable. When the content is more than 50 mol%, sufficient stain resistance,
It is not preferable because chemical resistance and weather resistance cannot be obtained.

Specific examples of the alkyl vinyl ether include ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, octadecyl vinyl ether, glycidyl vinyl ether, glycidyloxymethyl vinyl ether, glycidyloxyethyl vinyl ether, and glycidyl. Oxybutyl vinyl ether, glycidyloxypentyl vinyl ether, glycidyloxycyclohexyl vinyl ether, hydroxyethyl vinyl ether,
Examples include hydroxybutyl vinyl ether and 4-hydroxycyclohexyl vinyl ether.

Specific examples of the alkyl allyl ether include ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobutyl allyl ether, n-propyl allyl ether, allyl glycidyl ether, 3-allyloxy-1,2 propanediol, Glycerol monoallyl ether and the like can be mentioned.

Specific examples of the acrylate include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate and the like. Can be

Specific examples of the methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid. And 2-hydroxypropyl acid.

The fluorine-containing copolymer which is a component of the present invention can form a coating film having excellent water and oil repellency, antifouling property, repetitive stain removal property, chemical resistance and weather resistance over a long period of time. However, in addition to these units, other copolymerizable monomer components may be contained in an amount not exceeding 20 mol% depending on the purpose of use.

Examples of the copolymerizable monomer include olefins such as ethylene and propylene, haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl n-butyrate, vinyl isobutyrate and vinyl propionate. Esters of alkane carboxylic acid and vinyl alcohol are mentioned.

The fluorine-containing copolymer can be produced by copolymerizing a predetermined ratio of a monomer mixture using a polymerization initiator.

As the polymerization initiator, a water-soluble one or an oil-soluble one is appropriately used depending on the type of polymerization and the kind of solvent used as required.

Examples of the oil-soluble initiator include peroxyester peroxides such as t-butylperoxyisobutyrate and t-butylperoxyacetate, diisopropylperoxydicarbonate, dinormalpropylperoxydicarbonate and the like. Of dialkyl peroxydicarbonate, benzoyl peroxide, azobisisobutyronitrile, and the like.

Examples of the water-soluble initiator include a redox initiator comprising a persulfate such as potassium persulfate, hydrogen peroxide, or a combination thereof with a reducing agent such as sodium hydrogen sulfite or sodium thiosulfate. Are inorganic initiators in which a small amount of iron, ferrous salt, silver nitrate and the like coexist, and organic initiators of dibasic acid salts such as succinic peroxide, diglutaric peroxide, and monosuccinic peroxide. Is used.

The amount of these polymerization initiators used is appropriately selected according to the type thereof, copolymerization reaction conditions, etc., but is usually 0.005 to 5% by weight, preferably 0.005 to 5% by weight, based on the total amount of the monomers usually used. It is selected in the range of 0.1 to 2% by weight.

The polymerization method is not particularly limited. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be used, and ketones such as methyl ethyl ketone and acetates such as butyl acetate can be used. , A solvent polymerization method using an aromatic hydrocarbon such as xylene, an alcohol such as t-butanol, a saturated halogenated hydrocarbon having at least one fluorine atom, or an emulsion polymerization method in an aqueous solvent. Further, particularly preferred solvents for obtaining a fluorinated copolymer by a solution polymerization method include ethyl acetate, butyl acetate, xylene, toluene and methyl ethyl ketone.

In the case of copolymerization in an aqueous solvent (emulsion polymerization method, suspension polymerization method), a suspending agent or an emulsifier is usually used as a dispersion stabilizer, and a basic buffer is added to the copolymer during polymerization. It is desirable that the pH value of the reaction solution is 4 or more, preferably 6 or more.

The reaction temperature in these copolymerization reactions is as follows:
Usually, it is appropriately selected in the range of -30 ° C to 150 ° C depending on the type of the polymerization initiator and the polymerization medium. For example, when the copolymerization is carried out in a solvent, it is usually 0 ° C to 100 ° C, preferably 1 ° C to 100 ° C.
It is selected in the range of 0 ° C to 90 ° C. The reaction pressure is not particularly limited, but is usually selected in the range of 1 to 100 kg / cm ² , preferably 1 to 50 kg / cm ² . further,
The copolymerization reaction can be carried out by adding a suitable chain transfer agent.

When the resin composition of the present invention contains a hydroxyl group as a curing site, it can be cured at room temperature using polyvalent isocyanates. Preferred examples of the polyvalent isocyanates include non-yellowing diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate, adducts thereof, and polyisocyanates having isocyanurates. Among these, polyisocyanates having isocyanurates are preferred. Multivalent isocyanates are particularly effective. When curing at room temperature using isocyanates, curing can be promoted by adding a known catalyst such as dibutyltin dilaurate.

Further, the composition can be cured by heating using a melamine curing agent, a urea resin curing agent, a polybasic acid curing agent, or the like. Examples of the melamine curing agent include butylated melamine, methylated melamine, epoxy-modified melamine, and the like, and those having various degrees of modification are appropriately used according to the application, and the degree of self-condensation can also be appropriately selected. Examples of the urea resin curing agent include a methylated urea resin and a butylated urea resin. Examples of the polybasic acid curing agent include long-chain aliphatic dicarboxylic acids, aromatic polycarboxylic acids, and acid anhydrides thereof. Objects and the like.

Further, blocked polyvalent isocyanates can also be suitably used as a curing agent. When a melamine curing agent or a urea resin curing agent is used, curing can be promoted by adding an acidic catalyst.

When the resin composition of the present invention contains an epoxy group as a curing site, a curing agent such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or the like used in ordinary curable epoxy paints can be used. Aliphatic amines or modified products thereof, metaphenylene diamine, pp'-diaminodiphenylmethane, aromatic amines such as diaminophenyl sulfone or modified products thereof, phthalic anhydride, maleic anhydride,
Examples include polyvalent carboxylic acids such as oxalic anhydride, hexahydrophthalic acid, and pimelic acid, and anhydrides thereof.

When producing a fluororesin paint or a curable fluororesin paint containing a fluorine-containing copolymer as a main component of the present invention, various solvents can be used. For example, xylene, toluene and the like can be used. Examples include aromatic hydrocarbons, acetates such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethyl cellosolve, alcohols such as butanol, and various commercially available thinners. But,
Ethyl acetate, butyl acetate, xylene, toluene and butanol are particularly preferred.

Specific examples of the acrylic resin include a methyl (meth) acrylate copolymer, an ethyl (meth) acrylate copolymer, which is generally called an acrylic resin,
Butyl (meth) acrylate, (meth) acrylate copolymer containing styrene, hydroxyethyl (meth)
Acrylate copolymers and the like can be mentioned. These acrylic resins can be used alone or in a blend of two or more. It is preferable to use the fluorinated copolymer of the present invention in such a manner that the fluorinated copolymer is contained in the paint in an amount of 5 to 95% by weight, particularly 10 to 60% by weight, based on the acrylic resin. The fluorinated copolymer of the present invention has excellent compatibility with general-purpose acrylic resins, and in combination with acrylic resins, has excellent properties such as long-term water and oil repellency, antifouling properties, and repeated stain removal properties. Is given. Therefore, for applications requiring 50% by weight or more of the fluorine-containing copolymer in the coating material in order to obtain the characteristics of the conventional fluororesin, even if a small amount is added, the effect is exhibited, and the cost of the coating material can be reduced. It is possible. However, if the amount of the fluorine-containing copolymer of the present invention is too small, sufficient weather resistance may not be obtained. Therefore, for applications where weather resistance is indispensable, it is particularly preferable to add the fluorine-containing copolymer of the present invention to an amount of 10% by weight or more.

Commercially available acrylic resins include:
Acrydic A-814, Acridic A-810
-45 (manufactured by Dainippon Ink & Chemicals, Inc.), Testroid 4211-46, Testroid 4212-46 (manufactured by Hitachi Chemical Co., Ltd.), Dianal LR-620,
Diamond LR199, Diamond LR2516,
Diamond SS-792 (manufactured by Mitsubishi Rayon Co., Ltd.),
There are Hitaloid 3046C and Hitaloid 3018 (manufactured by Hitachi Chemical Co., Ltd.), and these can be used alone or in combination of two or more.

Mixing of the fluorine-containing copolymer of the present invention with a solvent for the production of a paint can be carried out by using various equipments used for ordinary paint production such as a ball mill, a paint shaker, a sand mill, a three-roll mill and a kneader. You can do it. At this time, if necessary, a pigment, a dispersion stabilizer, a viscosity modifier, a leveling agent, an ultraviolet absorber and the like can be added.

[0033]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

[0034]

Example 1 A stainless steel stirrer with an internal volume of 1 L
Toclave (withstand pressure 100kg / cm ^Two), Degassed
96 g of vinylidene fluoride (hereinafter abbreviated as VDF)
84 g of trifluoroethylene (hereinafter abbreviated as TFE)
14.9 g of tyl vinyl ether (hereinafter abbreviated as EVE),
Hydroxybutyl vinyl ether (hereinafter abbreviated as HBVE)
52.2 g, the following structural formula CH_Two= C (CH_Three) -COO-C_ThreeH₆-Si (CH
_Three)_Two-[O-Si (CH_Three)_Two]₄₄-OSi (C
H_Three)_Three Methacryl-modified silicone oil A (number average
10.5 g, butyl acetate 400 m
l, and 1.3 g of t-butyl peroxypivalate
The mixture was charged and the internal temperature was raised to 60 ° C. while stirring. afterwards,
The reaction was continued while stirring, and after 20 hours, stirring was stopped.
Response has ended. Isolate the obtained copolymer by drying under reduced pressure
did. Polymer yield 242 g, monomer conversion 94
%Met. In addition, acetyl anhydride of this copolymer
The hydroxyl value measured by the conversion method was 104 mg KOH /
g resin, fluorine content by combustion method is 47wt%, GP
The number average molecular weight measured in C is 1.9 × 10^FourMet.

The obtained fluorinated copolymer and acrylic resin (Dianal LR199 [Mitsubishi Rayon Co., Ltd.]
) Was dissolved in butyl acetate and dissolved in butyl acetate to prepare a 50% butyl acetate solution to produce a resin composition. The coating properties of the cured coating of the resin composition were examined by the following method. Table 1 shows the results. [Coating film transparency] Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was added to the above 50% mixed butyl acetate solution so that the hydroxyl group / NCO group of the polymer became 1/1, and J was added.
A 25 μm-thick test piece was applied to an ISG-3141 steel plate using an applicator and heat-treated at 80 ° C. for 24 hours, and the coating film transparency was visually evaluated.

A: Colorless and transparent B: Slightly cloudy C: Cloudy [adhesion to substrate] JIS-K5400 6.15
(Goban cellotape test). [Pencil hardness] According to JIS-K5400 6.14 (pencil scratch test). [Acid resistance] The appearance of the coating film after a 24-hour spot test with a 5% HCl solution is visually observed.

◎: No abnormality ：: Almost no change △: Slightly affected ×: Attached [Alkali resistance] The appearance of the coating film after a 24-hour spot test with a 5% NaOH solution is visually observed.

◎: No abnormality ○: Almost no change △: Slightly affected ×: Attached [oil-based magic repellency] Painted the coating surface with oil-based magic (black / red / magic ink trade name) and evaluated repellency I do. Further, after leaving this coating film at room temperature for 1 hour, it is removed by dry wiping. After repeating this 20 times, the repellency of the coating film surface is evaluated.

◎: Repels well ○: Repels △: Repels a little ×: Does not repel at all [oil-based magic repeated removal property] Oil-based magic (black
The surface of the coating film is covered with red / magic ink (brand name), left at room temperature for 1 hour, and then removed by dry wiping. Furthermore, after repeating this 20 times, the removability of the coating film surface is evaluated.

◎: No trace at all ○: Very slight trace Δ: Significant trace ×: Complete trace remaining [Water repellency] Initial and weather resistance test (Super UV 200
After 0 hour), the contact angle (unit: degree) of water was evaluated.

[0041]

Examples 2 to 3 Copolymers were obtained using the monomers shown in Table 1 in accordance with the procedure of the above example. The obtained copolymer and acrylic copolymer were mixed at a ratio (in terms of solid content) shown in Table 1 to prepare a resin composition in a 50% butyl acetate solution. The transparency and coating properties of the cured coating films of these resin compositions were examined in the same manner as in Example 1. Table 1 shows the results.

[0042]

Example 4 After degassing in a stainless steel autoclave (withstand pressure of 100 kg / cm ² ) having an internal volume of 1 L, 50 g of VDF, 78 g of TFE, 52.0 g of butyl vinyl ether (hereinafter abbreviated as BVE), and HBVE45.2
g, the following structural formula CH ₂ ＝ C (CH ₃ ) —COO—C ₃ H ₆ —Si— [O
54.6 g of methacryl-modified silicone oil C (number average molecular weight 420) represented by Si (CH ₃ ) ₃ ] ₃ , 400 ml of toluene, and 1.4 g of t-butylperoxypivalate were added, and the internal temperature was raised to 60 with stirring. The temperature was raised to ° C. Thereafter, the reaction was continued with stirring, and after 20 hours, the stirring was stopped to terminate the reaction. The obtained copolymer was isolated by drying under reduced pressure. The polymer yield was 260 g and the monomer conversion was 93%. The obtained copolymer had a hydroxyl value of 86 mgKOH / g resin measured by acetylation with acetic anhydride, a fluorine content of 32 wt% by combustion, and a number average molecular weight of 1.9 × 10 ⁴ measured by GPC. Was.

This polymer was dissolved in butyl acetate and 50
% Butyl acetate solution. The obtained fluorinated copolymer and an acrylic resin (Acrydic A-814 (manufactured by Dainippon Ink and Chemicals, Inc.)) were mixed at 1/4 (in terms of solid content), and the cured coating film of the mixture was transparent. The properties and coating properties were examined in the same manner as in Example 1. Table 1 shows the results.

[0044]

[Comparative Example 1] Stainless steel stirrer with internal volume of 1L
Toclave (withstand pressure 100kg / cm ^Two), Degassed
In addition, 96 g of VDF, 84 g of TFE, 15.1 g of EVE,
52.2 g of HBVE, 400 ml of butyl acetate, and t
-Add 1.2 g of butyl peroxypivalate and stir
Meanwhile, the internal temperature was raised to 60 ° C. Then, with stirring
Continue the reaction, stop stirring after 20 hours, and terminate the reaction.
Was. The obtained copolymer was isolated by drying under reduced pressure. Poly
The monomer yield was 230 g and the monomer conversion was 93%.
Was. Acetylation of the resulting copolymer with acetic anhydride
Therefore, the measured hydroxyl value was 110 mg KOH / g resin,
Fluorine content by combustion method is 49wt%, measured by GPC
The number average molecular weight was 1.9 × 10^FourMet.

The obtained fluorinated copolymer and Dianal LR199 were mixed at 1/2 (in terms of solid content) and dissolved in butyl acetate to prepare a 50% butyl acetate solution to prepare a resin composition. The transparency and properties of the cured coating film of this resin composition were examined in the same manner as in Example 1. Table 2 shows the results.

[0046]

Comparative Example 2 To the 50% mixed butyl acetate solution obtained in Comparative Example 1 was added 5% of TSF410 (manufactured by Toshiba Silicone Co., Ltd.) based on the polymer, and a test piece was prepared in the same manner as in the Comparative Example. These properties were investigated. Table 2 shows the results.

[0047]

Comparative Example 3 Using the monomers shown in Table 2, a copolymer was obtained according to the procedure of Comparative Example 1. The obtained copolymer and acrylic copolymer were mixed at the ratio (solid conversion) shown in Table 2 to obtain a 50% butyl acetate solution. The transparency and the properties of the cured coating film of the mixture were examined in the same manner as in Comparative Example 1. Table 2 shows the results.

[0048]

[Table 1]

[0049]

[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C09D 129/10 C09D 129/10 133/00 133/00 183/10 183/10 183/10 F term (reference) 4J002 BD12W BD14W BD15W BD16W BE04W BG04W BG04X BG05W BG05X BG06W BG06X BG07W BG07X CD19W CP17W FD140 GH01 4J038 CD091 CD092 CD111 CD112 CD121 CD122 DB131 CD132 CE051 CE052 CG141 CG142 CH03 CH1 CH2 CH03 4J100 AC24P AC26P AC26Q AC27P AC30P AE02S AE04S AE09S AE10S AL03S AL04S AL08R AL65R BA80R BA81R BC54S CA05 CA06 FA03 JA01

Claims (3)

[Claims] (A) As a polymerization unit, 15 to 85 mol% of a fluoroolefin; and the following general formula (1) or (2) R _1- [Si (CH ₃ ) ₂ -O] _n -Si ( CH ₃ ) ₂ —R ₂ (1) (where R ₁ is an alkyl group having 1 to 6 carbon atoms or —
_{(CH 2) r -OOC (CH} 3) C = CH 2 or -
Shows the CH = CH _2. R ₂ is — (CH ₂ ) _r —OOC
(CH ₃₎ shows the C = CH ₂ or -CH = CH _2.
n shows 1-420 and r shows 1-6. ) R ₂ -Si [OSi (CH _{3) 3] 3} (2) (wherein R ₂ and 0.001 mol% of the reactive silicone oil represented by the street) defined above;. Furthermore alkyl vinyl ether, A resin comprising: (B) an acrylic resin; and (B) an acrylic resin, comprising 1 to 50 mol% of at least one selected from alkyl allyl ethers, methacrylic esters, and acrylic esters. Composition. 2. The reactive silicone oil has the following formula (3), (4), (5), (6): CH ₂ ＣC (CH ₃ ) —COO—C ₃ H ₆ —Si (CH ₃ ) ₂ - _{[O-Si (C H 3)} 2 ] _m -R _{3 (3)} (. wherein R ₃ is the .m represents an alkyl group having 1 to 6 carbon atoms 1~250) CH ₂ = CH-COO —C ₃ H ₆ —Si (CH ₃ ) ₂ — [O—Si (CH ₃ ) ₂ ] _p —R ₄ (4) (where R ₄ represents an alkyl group having 1 to 6 carbon atoms. _{. 1~250) R 5 -C 3 H} 6 -Si (CH 3) 2 - [O-Si (CH _{3) 2] q -C 3 H 6 - R 5} (5) ( wherein R ₅ is - OOC (CH ₃₎ C = .q showing a CH ₂ is 1 to 250.) CH ₂ = C (CH ₃₎ pieces represented by COO-C ₃ H ₆ Si [OSi (CH _{3) 3] 3} (6) Terminal type or double terminal type modified silicone oil The resin composition according to claim 1, wherein 3. A fluorine-containing copolymer (A) in an amount of 5 to 95% by weight.
The resin composition according to claim 1, comprising: (B) 95 to 5% by weight of an acrylic resin.