JPS62187739A - Molding having coating layer of fluorocarbon polymer - Google Patents

Abstract

PURPOSE:To obtain the titled molding excellent in resistances to chemicals, water and abrasion, by coating a molding with a fluorocarbon polymer obtained from a fluoroolefin, a vinyl ether and a specified organosilicon compound. CONSTITUTION:A fluorocarbon polymer (B) is obtained by coppolymerizing 30-70mol% fluoroolefin (a) (e.g., hexafluoro-propane) with 20-60mol% vinyl ether (b) (e.g., butyl vinyl ether) and 1-80mol% organosilicon compound (c) having an olefinically unsaturated bond and a hydrolyzable group (e.g., trimethoxyvinylsilane) at -30-200 deg.C and a pressure of 0-100kg/cm<2> in an organic solvent in the presence of a radical initiator. A premolding (A) (e.g., plastic) is coated with component B to which a silanol condensation catalyst, if necessary, is added to obtain a molding having a 25mum-2mm-thick coating layer comprising at least partially crosslinked component B.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a molded product having a coating layer made of a specific fluoropolymer on the surface, and has durability such as chemical resistance, water resistance, and low friction property. Concerning molded products steeped in sexuality.

[Conventional technology]

Fluororesins such as polytetrafluoroethylene have excellent heat resistance and chemical resistance, and have excellent characteristics such as extremely low water absorption and moisture permeability.

However, because it is chemically inert, it has insufficient adhesion with low-grade materials, and cannot be injection molded or extruded like normal thermoplastic resins, so it is difficult to mold fine powder into powder. The paste is formed by compression, ram extrusion, etc.

Moreover, fluorine is expensive and its uses are naturally limited.

[Problem that the invention seeks to solve]

In view of the current situation, the technical objective of the present invention is to provide a paper-like molded product while making use of the above-mentioned special properties of fluororesin, and is made of a specific fluoropolymer. The object of the present invention is to provide a molded product having a coating layer and having excellent durability such as chemical resistance, water resistance, and abrasion resistance.

[Means for solving problems]

That is, the gist of the present invention is to provide a molded article with a coating layer containing a specific fluoropolymer as a main component, and the specific fluoropolymer includes (a) fluoroolefin, (b) vinyl ether, (C) A copolymer substantially composed of an organic silicon compound having an olefinic unsaturated bond and a hydrolyzable group, of which at least two parts are crosslinked.

[Effect]

Since the molded article is covered with a coating layer mainly composed of a fluoropolymer, which inherently has durability, it is protected from various external destructive factors.

Here, the molded article to be coated with the fluoropolymer (hereinafter referred to as
The material for the preformed product is not particularly limited as long as it has adhesive properties with the fluoropolymer, and examples of plastics include high-pressure low-density polyethylene, medium-high density polyethylene, and linear low-density polyethylene. (L
-LDPE), polypropylene, propylene-
Ethylene copolymer, poly-4-methyl-1-pentene,
Olefinic resins such as copolymers of 4-methyl-I-pentene and other α-olefins such as 1-decene, 6.6-
There are polyamide resins such as nylon and 6-nylon, polycarbonate resins, and acrylic resins, and these various plastics may be used alone or in combination.

In addition, these plastics can be filled with fillers,
It may also be used as a composition containing additives such as reinforcing agents, colorants, antistatic agents, and stabilizers.

Examples of this additive include glass fiber, glass peas,
There are plastics made of compositions filled with phenolic fibers, silica, carbon black, barium sulfate, calcium carbonate, zeolite, mica, etc.

It is desirable to form these plastics into preformed products in the desired shape in advance, and by injection molding, extrusion molding, rotational molding, etc. Shape.

In addition to plastics, other materials for the preform may be metals such as iron, steel, copper, brass, aluminum, tinplate, and galvanized iron. It is desirable to keep it.

Furthermore, other materials for the preform may be inorganic materials such as concrete or glass, or wood.

As described above, various materials can be used for the preform, but the most suitable material is plastic.

Incidentally, the fluoropolymer used in the present invention is a random copolymer consisting of at least the three types of monomer component units (a), (b), and (c) mentioned above, but it may be used within a range that does not impair the purpose of the present invention. Then, a small amount of other copolymerizable monomer components such as α-olefins, cycloolefins, unsaturated carboxylic acids, etc. may be copolymerized.

Fluoroolefin (a), which is a monomer component constituting the fluoropolymer, has at least one fluorine atom in the molecule, and preferably all hydrogen atoms of the olefin are substituted with fluorine atoms and other halogen atoms. Perfluoroolefins are preferred, and perfluoroolefins are particularly preferred. Furthermore, from the viewpoint of polymerizability and properties of the produced polymer, fluoroolefins having 2 or 3 carbon atoms, particularly perfluoroolefins, are preferred.

Examples of such fluoroolefins include CF, =CF
,, CIIP=CF,, CH,=CF,,
CHt= CIIP1CCIF= CFt, ClC
l=CF.

CCI,=CF,, CCIF=CCIF, C
F3CC1=, CI! , = CCIFlCClt =
Fluoroethylene type such as CCIF, CP, CF=C
F,, CF,CP=CHFSCF3CH=CF,,
CF3CF=CH2, CF3CF=CHF,
CHFzCF = CIIP.

CF, C11=C11,, C113CF=CF,,
CH3CII=CP3, cll 3CF=co,,
CF3CC1= CFt, CF, CC1=CF2,
CF, CF=CFCI, CF, CICC1=CP,
, CF, CICF= CFCI.

CFCI 2CF = CP t, CF3CC1 = C
CIF, CF3CC1= CC1z, CCIF, C
F= CCI, CC13CF= CF, CF, CI
CC1= CC1,, CFCl2CC1= CCI,,
CF3CF=CllCl, CICC1=ClCl.

CF, CCl=C1lCI, CI(F2CCI=C
C1,, CF2Cl1= CCl2, CF, CICC1
= ClCl, CC13CF= ClCl, CFtl
CF=CF2, CF, BrCtl= CF-5CF, C
Br= CHBr, CF, CICC1= CI.

CHpBrCF = CCl-1CF + CBr = CHt
, CF2Cl1=C11Br.

CFJrCIl= CItF, CC13CF=
Fluoropropene series such as CF, CF, CF, CF=
CF2, CF3CF= CFCF,, CF3CH=CF
CF3, cF, = CFCF, CHF, CF, CF,
CF= CH,, CF3CH= CHCF3, CF==
CFCFtCHs, CF, = CFCH,CHt.

CP, CIl, CH=CH,, CF3CH=CHCH,
,CF,=CHCHICH3,CH3CF,CH=
C) l,,CFH,CII= CI[CFH,,CII
, CF , , CI = CH3, CIL = CF
CII, C113, CFsCCFt>tcP= CPt
, CF3(CF2)3CF=CIJ, and other fluoroolefins having 4 or more carbon atoms can be mentioned.

Among these, fluoroethylene-based and fluoropropene-based are preferred, and tetrafluoroethylene (CF, = CF,) and hexafluoropropene (CF, = CFCF,) are particularly preferred, and furthermore, safety From the viewpoint of ease of handling, hexafluoropropene is preferred.

Further, in the present invention, it goes without saying that the fluoro-1-nophine may be used alone or in combination.

Vinyl ether (b) is a compound in which a vinyl group and an alkyl (including cycloalkyl) group, an aryl group, an aralkyl group, etc. are ether-bonded, and among them, an alkyl vinyl ether, especially one with a carbon atom number of 8 or less. , preferably an alkyl vinyl ether bonded with 2 to 4 alkyl groups. Furthermore, alkyl vinyl ethers in which the alkyl group is in the form of a chain are most preferred.

Examples of such vinyl ethers include linear alkyl ethers such as ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, and 4-methyl-1-pentyl vinyl ether. Vinyl ethers, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aralkyl vinyl ethers such as phenyl vinyl ether, o-, m-, p-chlorophenyl vinyl ether, aryl vinyl ethers, benzyl vinyl alkyl vinyl ether, and phenyl vinyl ether. I can do it. Among these, chain alkyl vinyl ethers and cycloalkyl vinyl ethers are particularly preferred, and ethyl vinyl ether, propyl vinyl ether, and butyl vinyl ether are more preferred. Further, in the present invention, it goes without saying that the vinyl ether may be used alone or in a mixture of two or more vinyl ethers.

The organosilicon compound (c) may have six olefinic unsaturated bonds and six hydrolyzable groups in the molecule, and specifically, those shown in the following general formulas (1) to (3) are exemplified. can do.

R'R"SiY'Y' (1) R'X5iY'Y2 (2) R'SiY'Y"Y' (3) (In the formula, R' and rt" have an olefinic unsaturated bond 12
, carbon, hydrogen and optionally oxygen, each being the same or different. X is an organic group having no olefinic unsaturated bond, and Yl, Y2, and Y3 are the same or different hydrolyzable groups. ) RI, Rt as more specific examples include vinyl allyl,
Examples include butenyl, cyclohexenyl, and cyclopentadienyl, and terminal olefinically unsaturated groups are particularly preferred. Other preferred examples include CII*= CII O(C
Ht)i~ CHt having an ester bond of the other terminal unsaturated acid, = C(CH3) Coo (CIL), -
1CI==C(CH3) COO(CHtly~O(
CL)3-1CH,=C(C11,) C00C)I
, CI, OCR, CICII, 0(CI)3-5, and the like. Among these, vinyl groups are most suitable. Specific examples of X include monovalent hydrocarbon groups such as methyl, ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl, and tolyl, and these groups are halogen-substituted hydrocarbon groups. But that's fine.

Specific examples of yl, y2, and Y3 include alkoxy groups such as methoxy, ethoxy, butoxy, and methoxyethoxy, alkoxyalkoxy groups, formiloquine,
Acyloxy groups such as acetoxy, propionoxy, oximes, e.g. ON= C(CI*)z, -ON=
CHCH1CtH6 and -ON=C(C,l(,
), or substituted amino groups and arylamino groups such as NHCHa, -NHC,11° and -NH
(C, R5), and any other hydrolyzable organic groups.

Preferably used organosilicon compounds are those represented by the general formula (3), particularly those containing groups y l, y ! ,Y
Organosilicon compounds in which 3 is equal are suitable. Among these, R1 is a vinyloxyalkyl group (CI, = CH-0(
Cut)n) or a vinyl group, and those in which Y1 to Y3 are an alkoxy group or an alkoxyalkoxy group are preferable, such as vinyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(methoxyethoxy)silane, etc. can be exemplified. However, vinylmethyljethoxysilane, vinylphenyldimethoxysilane, etc. can be used as well.

The content ratio of monomer components (a) to (c) in the fluoropolymer is based on the total number of moles of (a) to (c), (a): 30 to 70 mol%, (b): 20 ~60
Mol%, (c): I ~ 80 mol% ((a) 10Cb) +
(c) = 100), preferably c(a) = 40
~60% by mole, (b): 20-50%% by mole, (c)
: In the range of 1 to 25 mol%.

Here, (a) is set to 30 to 70 mol% because if it is less than 30 mol%, the durability will be poor, and if it is more than 70 mol%, the adhesion to the base material will be poor. The reason why it is set at 1 to 80 mol% is that if it is less than 1 mol%, it will be difficult to harden.
This is because it is difficult to form a film, and stability deteriorates when the amount exceeds 80 mol%.

The fluoropolymer used in the present invention has surface descriptions (a) to (c).
It is produced by copolymerizing each of the monomers in the presence of a well-known radical initiator (or by heating in its absence). Each component (a) to (c) is important here. For example, copolymerization does not occur with components (a) and (c) alone, but by adding component (b), (a), The components (b) and (C) are copolymerized.

Various known radical initiators can be used for copolymerization. Specifically, organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2
,5-di(peroxybenzoate)hexyne-3,
1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(
tert-butylperoxy)hexyne-3,2,5-
Dimethyl-2,5-di(tert-butylperoxy)
hexane, tert-butyl perbenzoate, tert
tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butylperu 5ec-
Octoate, tert-butylperpivalate, cumylperpivalate, tert-butylperdiedylacetate, and other aso compounds such as azobis-isobutylnitrile, dimethylazoisobutyrate, and the like. Among these are dicumyl peroxide, dite
rt-butyl peroxide, 2,5-dimethyl-2,5
-di(tert-butylperoxy)hexyne-3,
Dialkyl peroxides such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferred.

The copolymerization takes place in a reaction medium consisting of an organic solvent. The solvents used here include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-heptane, and chlorobenzene, bromobenzene, iodobenzene, and 0-bromotoluene. Examples include halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons such as tetrachloromethane, 1°1.1 trichloroethane, tetrachloroethylene, and l-chlorobutane.

Copolymerization is carried out by adding a radical initiator to the above solvent in a molar ratio of 101 to 2 x 10-' based on the total number of moles of monomers. In addition, the polymerization temperature is -30 to 200℃,
Preferably 20~ioo℃, polymerization pressure 0~100kg
/cm2・G, preferably 0 to 50kg/cm”・G
It is.

The molecular weight of the fluoropolymer thus obtained is determined by gel-pami-esotan chromatography (GPC) using tetrahydrofuran as a solvent and monodispersed polystyrene of known molecular weight as a standard substance. It is desirable that the number average molecular weight (Mn) is usually 3,000 to 200,000, preferably 5,000 to 100,000.
within the range of If the molecular weight is less than 300, it is generally difficult to form a coating layer, and if it exceeds 200,000, the solvent solubility is often poor. By adopting the above-mentioned composition ratio and the molecular weight described here, it becomes solvent-based, and after being cured by the method described below, it has excellent solvent resistance, chemical resistance, heat resistance, and weather resistance. It has excellent physical properties. Another property of fluoropolymers is that they are non-polymerized or have low crystallinity, and many are non-polymerizable. In general, the crystallinity by X-rays is 0%, and the melting point is not observed by differential scanning calorimetry (DSC). Therefore, transparency is good.

When the glass transition temperature (Tg) is measured by DSC at a heating rate of 10°C/min after cooling the sample to -120°C, the glass transition temperature (Tg) is usually ~60~+20°C1.
It is in the range of -5°C.

As an optical property, there is a refractive index (nD), which is usually 1.48.
~1.34, often in the range 1.44-1.36.

A carboxyl cap may be introduced into the molecular chain of the fluoropolymer used in the present invention in order to further improve the affinity with organic pigments and the like. An example of this is a method of graft polymerizing unsaturated carboxylic acids and their derivatives. Examples of unsaturated carboxylic acids used for this purpose include acrylic acid, methacrylic acid, α-ethyl acrylic acid,
maleic acid, fumaric acid, itaconic acid, citraconic acid,
Tetrahydrophthalic acid, methylte)-rahydrophthalic acid, endocis-bicyclo(2,2,1,1hept-5-
En-2,3-dicarboxylic acid (nadic acid ■), methyl-endocys-bicyclo(2,2,1]hept-5-
Unsaturated carboxylic acids such as ene-2,3-dicarboxylic acid (methylnadic acid), halides, amides, imides, acid anhydrides, and esters of the unsaturated carboxylic acids, i.e., maleyl chloride, maleimide, maleic anhydride, citracon anhydride. acids, monomethyl maleate, dimethyl maleate, etc.

The above-mentioned fluoropolymers are soluble in organic solvents at room temperature, and include aromatic hydrocarbons such as benzene, toluene, and xylene, acetone, ketones such as methyl ethyl ketone, dimethyl ether, dimethyl ether, and dimethyl ether. ethers, such as propyl ether,
It dissolves in alcohols such as metal and ethanol, and halogenated hydrocarbons such as tokuchloroethane, dichloroethane, and chlorobenzene.

Therefore, using a solution of a fluoropolymer in an organic solvent, the fluoropolymer is applied to the surface of a planar preform by spraying, brushing, dipping with a roll coater, etc., and then drying + U - By doing so, the molded article of the present invention can be obtained.

By the way, since the fluoropolymer has a hydrolyzable organic group derived from the a-organic silicon compound (C), when exposed to moisture, a cross-linking reaction occurs between the molecular chains of the polymer, resulting in hardening. do. Therefore, as a matter of course, moisture in the atmosphere can also cause crosslinking. Although it is clear that crosslinking will proceed even if the fluoropolymer is used alone, it is preferable to add a silanol condensation catalyst so that the fluoropolymer film applied to the preform can be rapidly cured.

In this case, a silanol condensation catalyst is added in advance to an organic solvent solution in which the fluoropolymer is dissolved, and when this is applied to the preform, the organic solvent evaporates and the curing reaction occurs at the same time as it comes into contact with the moisture in the air. occurs, and the coating layer hardens.

Known Nral catalysts can be applied, such as umbutyltin dilaurate, stannous acetate, stannous octoate, lead naphthenate, iron 2-ethylhexanoate, and cobalt naphthenate. Acid metal salts, organic bases such as ethylamine, hequinolamine, dibdelamine, piperidine, etc., acids such as mineral acids and organic fatty acids. Suitable catalysts are alkyl tin salts of carboxylic acids,
For example, dibutyltin dilaurate, dibutyltin dioctoate, diptyltin diacetate.

The crosslinking reaction proceeds sufficiently at room temperature, that is, around room temperature (0 to 40°C), but if necessary, the coated molded article may be heated to promote the crosslinking reaction of the coating layer.

Also, the thickness of the coating layer is usually 25μl to 2j! The shoulder size is normal, especially 50 to 500μ! degree is preferred. In order to improve the adhesion or adhesion of the fluoropolymer to the surface of the preform, it is preferable that the surface of the preform be subjected to a surface treatment such as coating with a primer or degreasing. As the primer, Unistol-Q (manufactured by Mitsui Petrochemical Industries, Ltd.) and the like are suitable. The coating layer made of the fluoropolymer after curing (after being left for 14 days after application) usually has a pencil hardness of 3H to 2B according to JISK 5400 (1979) 6.16, and is often in the range of H-H. K (1979) 6.16 bending resistance is usually 3m1Ilφ, and most pass 2mmφ.

In addition, the contact angle with water is usually 70 to 98°, often 78 to 9
It is 4°. Furthermore, the coefficient of static friction is usually 0.30 to 0.60.
, mostly in the range of 0.35 to 0.50. The coefficient of static friction is determined by cutting out a small piece of 3 cm x 3 cm from a steel plate that has been coated with a fluorine-based catalyst and hardened, and placing it on a steel plate that has been coated with the same polymer and hardened so that the coated surface is in contact with it. Place a 145g weight on the small piece, lift one end of the steel plate, and calculate the angle of inclination (θ) when the small piece starts to slide down.
) was determined, and tanθ was taken as the coefficient of static friction.

The light transmittance after curing is usually 95% or more, often 99% or more. Here, the light transmittance is determined by forming a film on a release base material, peeling it off after curing to form a film piece, fixing the film piece in a quartz cell and filling it with pure water, and filling it only with pure water. JIS K 6 using a quartz cell as a blank.
714.

In addition, when applying the fluoropolymer to the preformed product, pigments and dyes may be blended, and various additives commonly blended with synthetic resins may also be blended as necessary.

〔Example〕

The content of the present invention will be explained below using preferred examples, but unless otherwise specified, the present invention is not limited to these examples, and any embodiments can be made without detracting from the purpose of the present invention. It is.

80 g of benzene 1 butyl vinyl ether (BV E
)25.2g, )rimethoxyvinylsilane (T
MVS) 7.1g, dilauroyl peroxide Ig was prepared,
Solidify with acetone and dry ice and degas to remove oxygen from the system. Then hexafluoropropene (
45 g of HF P ) was introduced into an autoclave and the temperature was raised. When the temperature inside the autoclave reached 65°C, the pressure was 8.1 kg/am'. The reaction was continued for 8 hours with stirring, and when the pressure reached 4.6 kg/am'', the autoclave was cooled with water to stop the reaction.

After cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out. After concentration, the mixture was washed with a benzene-methanol mixed solvent, concentrated again, and dried. Polymer yield was 60g.

The number average molecular weight of the obtained polymer by GPC was 1. O
X 10', and the glass transition point was =14°C.

When the composition of this copolymer was analyzed using elemental analysis and NMR, HFP/BVE/TMVS=48/4
The molar ratio was 0/12.

5 kg of the polymer thus obtained was dissolved in 5 kg of toluene, and dibutyltin dilaurate (D B T DL
) 3.2g was added.

On the other hand, after applying an epoxy primer to a mesh basket-shaped preformed product obtained by injection molding from high-density polyethylene (HIZEX HOOJ manufactured by Mitsui Petrochemical Industries, Ltd.), it was placed in a toluene solution of the above fluoropolymer. After dipping, a molded article having a coating layer (thickness: 55 μm) made of a fluoropolymer on the surface was obtained by air drying at room temperature.

This molded product has excellent chemical resistance, water resistance, and low friction properties.

〔Effect of the invention〕

According to the present invention, a molded article having excellent durability such as chemical resistance, water resistance, low friction property, etc. can be obtained.

According to the present invention, molding efficiency is better than conventional fluororesin molded products, and paper storage is possible. Utilizing its properties, it can be used for chemical cleaning tanks, baskets, various chemical containers, etc., and also for automobile exteriors. It can be used for products etc.

Procedural amendment (voluntary) November 6, 1985 l Indication of case Patent application 2 dated October 18, 1985, title of invention Molded article having a fluoropolymer coating layer 3, person making the amendment Relationship to the case Patent applicant address: 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (588) Mitsui Petrochemical Industries, Ltd. 4, Agent: IO Flower Building 3, Kanda Jimbocho 3-chome, Chiyoda-ku, Tokyo 101 Furthermore, other uses of the present invention include the following.

(1) Various metal and plastic containers, tanks, storage tanks, reaction vessels, neutralization tanks, rotary tanks, etc., lined with the fluoropolymer of the present invention.

(2) Thermometer protection tubes, electrode rods, stirring rods, turn baffles, etc. whose surfaces are coated with the fluoropolymer.

(3) The inner surfaces of various types of pipes and fittings, including L-shaped pipes, T-shaped pipes, and blowing pipes, are coated with the above-mentioned fluoropolymer. In addition, when coating the inner surface of vibrators and fittings with the fluoropolymer, after cleaning the inner surface of the already laid tape, etc., inject a solution or dispersion of the fluoropolymer to line the inner surface. Things are also done.

(4) The surfaces of impellers, centrifuge liners, baskets, etc. are coated with the fluoropolymer.

(5) The inner surfaces of various cocks, liquid level gauges, metering meters, gas cylinders, etc. are coated with the fluorine-based polymer.

(6) Semiconductor cleaning baskets, safety rupture discs, crystal dishes, perforated plates, heating coils, floats, dispersion plates, electrode plates, and bottle sets whose surfaces are coated with the fluoropolymer.

(7) Coil bobbins, various terminals, and alumite forming jigs whose surfaces are coated with the fluoropolymer. ” Procedural amendment (voluntary) January 16, 1985 l Case description 1985 patent application 23276
No. 5 No. 2 Name of Proposal 8 Molded product with a coating layer of fluoropolymer 3, Relationship to the case of a person who makes hli corrections Patent applicant address 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (58g ) Mitsui Ishiura Chemical Industry Co., Ltd., Agent 11 Address: 3rd Floor, 6th Floor, Floriculture Building, 3-10-10, Kanda Jimbocho, Chiyoda-ku, Tokyo 101 Contents of Amendment (1) In the 2nd line of page 18 of the specification, there is a statement that says ``Hydrolyzable.''"Organicgroup" is replaced by "hydrolyzable organic group" and "(8) The surface of various glasses and mirrors is coated with the fluorine-based polymer. This improves the antifouling and antifogging properties. .

More specifically, the fluoropolymer is fractured on the surface of various vehicle window glasses, such as windshields, rear glasses, hack mirrors, side mirrors, headlight covers, glass test tubes, and the like.

(9) Vehicles such as passenger cars, freight cars, trains, diesel cars, etc., whose exterior surfaces are coated with the fluoropolymer. The exterior surface may be made of metal or plastic, or may be a painted exterior surface.

(10) A fluorine-based polymer coated on the exterior surface of a flying object such as an aircraft or an airship. The exterior surface may be an exterior surface made of a base material such as metal, plastic, or woven fabric, or may be an exterior surface made of a base material coated with a paint.

(11) A substance that is applied to the front or back of skis to prevent snow from adhering to them and make them easier to slip on.

(12) It is applied to rubber products coated with the fluoropolymer, such as wiper blades, rubber bushings, tires, etc., and used to prevent surface deterioration and to provide a gloss finish.

(13) An automobile interior part coated with the fluoropolymer. Effective for polishing and surface protection. ” Procedural amendment (method) 1986 GI” 3'q r 1st Commissioner of the Patent Office Kuro 1) Akio Yu 1, Indication of case 1985 Patent No. 232765 2, Title of invention Fluoropolymer coating Molded product with layers 3, relationship with the sound case to be amended Patent applicant address: 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Name (588) Mitsui Petrochemical Industries, Ltd. 4, Agent address: 101 Tokyo, Japan 7h11, 3rd floor, Flower Pill, IO, 3-chome, Jinbocho, Kanda, Chiyoda-ku.Correct content: Corrected as shown in the attached sheet.

Procedural amendment (voluntary) January 16, 1988 Commissioner of the Patent Office Kuro 1) Mr. Akio! , ,+
+-(Display of 1985 Patent Application No. 2327
No. 65 No. 2, Title of the invention Molded article having a coating layer of fluoropolymer 3, Relationship with each case for amendment Patent origin address 2-5 Kasumigashimasho-chome, Chiyoda-ku, Tokyo Name ( 588) Mitsui Petrochemical Industries Co., Ltd. 4 Agent Address: 3rd floor, Floriculture Building, 3-10 Kanda Jimbocho, Chiyoda-ku, Tokyo 101 Tel: 03 (262) 4313 (main) (2) 1985! Column for the contents of the amendment in the procedural amendment submitted on January 6th

Claims (2)

[Claims] (1) A copolymer consisting essentially of (a) a fluoroolefin, (b) a vinyl ether, and (c) an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group, the copolymer comprising at least A molded product having a coating layer mainly composed of a partially crosslinked fluoropolymer. (2) A molded article having a coating layer containing a fluoropolymer as a main component according to claim 1, wherein the crosslinking is carried out in the presence of a silanol catalyst.