JPH04180974A - Coating composition excellent in adhesiveness - Google Patents

Abstract

PURPOSE:To obtain a cold-setting coating composition having water resistance and water repellency and being excellent in adhesiveness by incorporating a specified organotin curing catalyst into a copolymer of a fluoro-olefin, an alkyl vinyl ether, and an organosilicon compound containing unsaturated groups and hydrolyzable groups. CONSTITUTION:1-30mol% fluoro-olefin of formula I (wherein R<1>, R<2>, and R<3> are each H or halogen, and R<4> is H, halogen, alkyl or haloalkyl, provided that at least one of R<1> to R<4> has a fluorine atom) is copolymerized with 1-95 mol% alkyl vinyl ether and 1-30mol% organosilicon compound of formula II, III or IV (wherein R<7> and R<8> are each an olefinically unsaturated bond; X<1> is a saturated organic group; Y<1>, Y<2>, and Y<3> are each a hydrolyzable group) to give a fluoro-copolymer. This copolymer is mixed with an organotin curing catalyst (e.g. n-butyltin trichloride) and an organic solvent to give a coating composition excellent in adhesiveness.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an M composition for fluorine fiber coatings that forms a coating film with excellent weather resistance, chemical resistance, water resistance, water repellency, etc. on a base material. In particular, it relates to a fluorocoat composition IIIi having excellent adhesion to substrates.

(Prior art and problems to be solved by the invention) Fluorine-containing copolymers have weather resistance, water resistance, i':I drug resistance, water repellency, and low jl! Since it has excellent properties such as abrasion resistance, it is expected to be applied to high performance paints. However, since fluorine-containing copolymers are usually insoluble in solvents or rust-resistant at room temperature, they are difficult to apply as solution-type coatings, and have the problem of poor adhesion to substrates.

By the way, as a result of studying to develop a resin for weather-resistant coatings that contains only a fluorine-containing copolymer and cures, the authors of this III have developed a fluorine-based ternary compound consisting of a fluoroolefin, a vinyl ether, and a specific organosilicon compound. It was discovered that the copolymer is soluble in organic solvents at room temperature, and that it cures at room temperature.
Publication No. 13).

However, paints using such conventional fluorine-containing copolymers are not necessarily satisfactory in terms of adhesion to substrates. In other words, a coating film formed on the epoxy resin undercoat surface immediately after being applied to the base material will not cause any problems in adhesion, but a coating film formed on the epoxy resin undercoat surface after a long time has elapsed. In some cases, the coating film may not have sufficient adhesion strength.

Therefore, an object of the present invention is to propose a composition for a fluorine paint that is a highly functional paint with water resistance, water repellency, etc., and is curable at room temperature and has excellent adhesion.

(Means for Solving the Problems) According to the present invention, [A] (A) a fluoroolefin (B) an alkyl vinyl ether (C) an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group; Obtained by polymerization, based on the total molar amount of components (A) to (C), component (A) is in the range of 1 to 30 mol%, and component (B) is in the range of 1 to 95 mol%. .

(C) a fluorine-containing copolymer in which the component is in the range of 1 to 30 mol%; group, X' is an alkyl group having 4 to 10 carbon atoms, Cl or OH group, Y-', y'2 are Cl, 0COR''', or OH group, and these are the same). may also be different. Provided is a coating composition characterized by comprising a curing catalyst represented by 6) in which R'' is an alkyl group, an aryl group, or an allylalkyl group, and [C] an organic solvent.

The fluoroolefin (Al) of the present invention has the formula % (R'', R', R9 are hydrogen atoms or halogen atoms, and R' is a hydrogen atom, a halogen atom, or an alkyl group.

It is a halogenated alkyl group, and one or more of R' to R1 has a fluorine atom. ).

Further, the organic silicate compound (C) of the present invention is Y'-8
i-R@... I vio Y'-5i-X... ■ R? Y'-8i-Y'... ■ 薯Y? (R', Ro have an olefinic unsaturated bond, carbon,
It consists of hydrogen and, in some cases, oxygen, and may be the same or different. X' is an organic group having no olefinic unsaturated bond, and Y', Y', and Y9 are hydrolyzable groups, and may be the same or different. )
1. It can be characterized by being an organosilicon compound (C) represented by either n, or ■.

(Function) The present invention suppresses the amount of fluorine-based polymeric components, which have excellent weather resistance, water resistance, chemical resistance, water repellency, and low friction properties as characteristics of the resin coating, to a certain amount, and also contains alkyl vinyl ether and organic silicon. This is based on the knowledge that by using the copolymer as a copolymer and dissolving it in an organic solvent together with a specific curing catalyst, a highly adhesive coating composition can be obtained.

In the present invention, it is important to suppress the amount of fluoroolefin to a certain level and form it into a copolymer with alkyl vinyl ether and organosilicon. The fluoroolefin component is 1 to 30 mol%, especially 5 to 30 mol%, based on the entire copolymer.
It is desirable that it is mol%. A composition within such a range of components is rapidly cured on the surface of the substrate by the curing catalyst, and the coating film has excellent adhesion to the substrate.

In the present invention, the alkyl vinyl ether component is desirably used in a range of 1 to 95 mol%, particularly 50 to 85 mol%, based on the entire copolymer, and the organosilicon component is preferably used in a range of 1 to 95 mol%, based on the entire copolymer. 30 mol% to 30 mol%, especially 3
It is desirable to use it in a range of 25 mol %. Also,
It is important that the organosilicon has an olefinic unsaturated bond and a hydrolyzable group. The olefinically unsaturated group is preferably a terminal olefinic group, and particularly preferably a terminally unsaturated acid ester. Typical hydrolyzable groups include alkoxy groups such as methoxy and ethoxy, acyloxy groups such as formyloxy and acetoxy, and oxime.

Alkoxy groups are preferred. These groups greatly influence when the composition cures.

The composition of the present invention also contains an organotin compound curing catalyst (B
It is important to contain E, and its content is 0.03 to 2.0 per 1100 parts by weight of the fluoropolymer (A1100 parts by weight).
In particular, a range of 0.1 to 1.5 parts by weight is desirable. The fluoropolymer is rapidly cured by such a specific curing catalyst.

When the fluoropolymer [A) and curing catalyst CB] are combined and dissolved in an organic solvent (C),
The resulting coating composition has the excellent properties of a fluororesin, has good adhesion to the substrate, and provides rapid curing. In this case, it is desirable to use a composition in which the fluoropolymer is used in an amount of 40 to 300 parts, particularly 80 to 12,011 parts, per 100 parts by weight of the organic solvent.

(Preferred Embodiments of the Invention) The fluoropolymer composition for paint according to the present invention will be specifically described below.

Components of Fluorine-based Polymer [A] The fluorine-containing copolymer used in the present invention consists of (A) fluoroolefin, [B] alkyl vinyl ether, and (C)
It is a copolymer obtained by copolymerizing an organic silicon compound having an olefinic unsaturated bond and a hydrolyzable group.

In addition, in the present invention, other copolymerizable monomers, such as unsaturated carboxylic acids or derivatives thereof, carboxylic acid vinyl esters, carboxylic acid allyl esters, α-olefins, halogenated olefins, may be used to the extent that the purpose is not impaired. or aromatic vinyl compounds may be appropriately copolymerized.

In the fluoroolefin (A), at least one fluorine atom in the molecule ψ is replaced with hydrogen, and in some cases, halogen atoms such as chlorine atoms and bromine atoms may coexist. In the present invention, preferred fluoroolefins (A) are perhaloolefins in which all fluorine atoms in the olefin are substituted with fluorine atoms, chlorine atoms, and other halogen atoms. Further, from the viewpoint of polymerizability and properties of the copolymer, fluoroolefins having 2 to 6 carbon atoms, particularly 2 or 3 carbon atoms, are preferred.

Such olefins are represented by the following formula.

R'(R',R',R' is a hydrogen atom or a halogen atom, R' is a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group, and one of R' to R' (Has at least one fluorine atom.) Specifically, the following compounds are used.

CCl=CF2. CHF=CCl,CH,=CF,
.

CH2=C)IF, CCIF=CF, , C)l
c1=cF,.

CCl2=CF? , CCl=CCl? , CHF
=CCl,.

Fluoroolefins having 2 carbon atoms (fluoroethylene type) such as CH,=CCIF, CCl=CCl2.

CF, CF=CF2. CF, CF=CHF,
CF, CHtCF, .

CF; CF=CHt, CF=CF=CHF ICH
FtCF=CHF.

CF,C)l=CH,,CH,CF=CF? , C
H, C) l=cF, .

CH, CF = CH,, CF, CCl = CF292 C
F, CCl=CF, .

CF, CF = CFCI, CF, CICCl = CF,
, CF, CCl=CCl? Product Cl=CF2 CCIFtCF =cc12. ccl, cF=cp?
, CFtCICCl=CCl? .

CCl=CCl? CCI□, CF, CF= Cl
ICl, CCIF, CF=CHCl.

CF, CCl=C) IcI, CHF, CCl=CC
l2,CF,CICH=CC]2゜CF2CICC]=
ljlCl, CCI, CH=CCl, CF, ICF=C
F2゜CF2BrCH=CF, + CF, CBr=C
HBr, CF, CICBr=C)l,.

CHJrCF=cci, CF:CBr=Cl-,
,CF? CH=CHBr.

CF2BrCH” CHF, CF, BrCF=
Fluoroolefins having 3 carbon atoms (fluoropropene type) such as CF2.

CF, CF, CF=CF,, CF, CH=CCl
,.

CF,C)l=cFcF, CHF=CCl,C
HCF2゜CF, CF7CF=CH,, CF, C) I=
CHCF,.

CF? = CFCF2CH9, CF2= CFCHzC
H.

CF,CH,C)I=CH2,CF,CH=C)IcH
,,CF,=CHCH,C)l,.

CH=CFtCH=CHt, CFH,2CH
＝CHCIII? .

CHtCF2CH= CHt, CH2= CF
CH2CH=.

CF, (CF2)2CF=CF2, CF, (CF?
), CF = CF? .

CF, CCl=CCl? , CF2= CF
CFtCCIFt.

CHF=CCl,CCI,,Cll,=CFCl,CC
l,.

CF, (CF2), CCl=CF, , CF, (CL
), fluoroolefins having 4 or more carbon atoms, such as CCl=CF2.

Among these, as mentioned above, fluoroethylene and fluoropropene are preferred, and chlorotrifluoroethylene (CCIF=CF2) is particularly preferred.

Further, in the present invention, the fluoroolefins may be used alone or in combination of two or more.

Alkyl vinyl ether (B) is a compound in which a vinyl group and an alkyl group are bonded via an ether bond. Alkyl vinyl ether (B) is represented by the following general formula.

CH7=CH-0-R"(R" is a linear, branched sheath-like, or cyclic alkyl group.) Specifically, such alkyl vinyl ethers include ethyl vinyl ether, propyl vinyl ether,
Isopropyl vinyl ether, butyl vinyl ether,
Chain alkyl vinyl ethers such as tere-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether, octyl vinyl ether, and 4-methyl-1-pentyl vinyl ether.

Cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether are used. Among these, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and the like are particularly preferred.

The above alkyl vinyl ethers may be used alone or in combination of two or more.

Organosilicon Compound (C) The organosilicon compound (C) is a compound having an olefinic unsaturated bond and a hydrolyzable group in the molecule, and can be specifically represented by the following three general formulas.

formula %formula% (R', R= have an olefinic unsaturated bond.

It consists of carbon, hydrogen, and in some cases oxygen, and they may be the same or different. X゛ is an organic group having no olefinic unsaturated bond, Y゛, Y? , Y9 are hydrolyzable groups, and may be the same or different. ).

As the group having an unsaturated bond in silicon compound #(C), vinyl, allyl, butenyl, cyclohexenyl, etc. can be specifically used. As the hydrolyzable group, an alkoxy group, an acyloxy group, an oxime group, etc. can be specifically used.

Specifically, the unsaturated bonding groups of R7 and R'' are vinyl, allyl, butenyl, cyclohexenyl, cyclopentagenyl, etc., and terminal olefinic unsaturated groups are particularly preferable. The unsaturated bond group is
CH2=C)l-CO01CH2), which has an ester bond of a terminally unsaturated acid. −.

C)1. =c(CI,)CO01CH2)! +.

CO3-C(CH=)CO01CH2)20(CTo)
g.

cH2= C(CH,)C00CH,CH,0C)12
CHCH20(CB,)-.

It can also be a group such as H. Among these, R7
Preferably, R'' to R'' do not contain oxygen and are composed of carbon and hydrogen, and a vinyl group is particularly suitable.

Specifically, the hydrocarbon of Xl is a monovalent hydrocarbon group such as methyl, ethyl, propyl, tetradecyl, octadecyl, phenyl, benzyl, tolyl, etc., and these groups may also be a halogen-substituted hydrocarbon group. good.

Specifically, Y', Y'', and Y' are methoxy.

Alkoxy groups such as ethoxy, butoxy, methoxyethoxy, alkoxyalkoxy groups, acyloxy groups such as formyloxy, acetoxy-probionoxy, oximes such as 10X=C(CI(su,

10 = cncHtctL and -ox = C(CAH9)2, etc., and any other hydrolyzable organic group.

In the present invention, the organosilicon compound is preferably a compound represented by the above-mentioned general formula, especially a compound represented by the group Y.
', Y2. Organosilicon compounds in which Y' are the same are preferred; among these, R7 is a vinyl group, and y
Particularly preferred are organosilicon compounds in which -y= is an alkoxy group or an alkoxyalkoxy group, such as vinyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(
Methoxyethoxy)silane and the like are preferred. Furthermore, vinylmethyljethoxysilane, vinylphenyldimethoxysilane, etc. can be used similarly.

Blending ratio of fluorine copolymer The fluoroolefin (A) of the fluorine-based polymer used in the present invention is contained in the copolymer in an amount of 1 to 30 mol%, preferably 5 to 30 mol%. is desirable.

When the fluoroolefins are in this range,
The copolymer maintains sufficient weather resistance, water resistance, chemical resistance, water repellency, and low friction, making it a highly functional paint. Also,
The alkyl vinyl ether (B) is in an amount of 1 to 95 mol%, preferably 50 to 85 mol%, and the organosilicon compound (C) is in an amount of 1 to 30 mol%, preferably 3 to 25 mol%.
When the copolymer is within this range, when the copolymer is used as a coating material, the adhesion to the substrate will be extremely good. Moreover, such a copolymer has good solvent selectivity when used as a coating material. In addition, if the amount of fluoroolefin is too small than the above range, sufficient water resistance, water repellency,
Weather resistance etc. cannot be obtained, and if the amount is too high, adhesion to substrates will deteriorate. Furthermore, if the amount of the organic silicon compound is too small, a tough coating film cannot be obtained after curing, and if it is too large, internal stress increases after curing, which is undesirable, causing cracks in the coating film.

Other copolymerizable monomers include acrylic acid, methacrylic acid, α-ethyl acrylic acid, crotonic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid,
7-octenoic acid, 8-nonanoic acid, 9-decanoic acid, 10-
Undecylenic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid endocys-bicyclo[2,2,1]hept-5-ene-2,3
- Unsaturated carboxylic acids such as dicarboxylic acids, monoesters or diesters of these alcohol residues having 1 to 20 carbon atoms, or maleic anhydride.

Unsaturated carboxylic acids or derivatives thereof such as olefinic acid anhydrides such as itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, caprylic vinyl acid, vinyl caprate, vinyl urarate, vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate, pt
Carboxylic acid vinyl esters such as vinyl art-butylbenzoate,! ? Allyl acid, allyl 10 pionate, allyl butyrate, allyl isobutyrate, allyl caproate, allyl caprylate, ura, allyl phosphate, allyl cyclohexanecarboxylate, allyl methylcyclohexanecarboxylate, allyl benzoate, p-tert-butylcarboxylic acid Carboxylic acid allyl esters such as allyl, α-olefins such as ethylene, propylene, butene-1, halogenated olefins such as vinyl chloride, vinylidene chloride, propylene, butene-1, styrene, α-methylstyrene, vinyltoluene. These include halogenated olefins such as styrene, α-methylstyrene, and aromatic vinyl compounds such as vinyltoluene.

Among these copolymerizable IT forms, maleic acid dialkyl esters are particularly preferred from the viewpoint of increasing the adhesion to the base material of the coating material made of the copolymer and from the viewpoint of increasing the polymerization yield of the copolymer. , the use of carboxylic acid vinyl esters is preferred.

When synthesizing the copolymer using these copolymerizable monomers, it is preferable to introduce these copolymerizable monomers within a range of 1 to 70 mol %.

In addition, in the fluorine-based polymer according to the present invention, gel and
The number average molecular weight (Mn) measured by permeation chromatography is preferably in the range of 2,000 to 300,000, particularly 3.000 to 10,000.

If the copolymer has a molecular weight within this range, the solvent selectivity will be improved in conjunction with the above-mentioned combination ratio of each component R, and it will be possible to fully utilize it for applications such as paints.

The molecular weight is measured using a monodisperse polystyrene having a known molecular weight as a standard substance, and is the number average molecule ii (Mnl) determined by gel nomeation chromatography (GPC).

Specifically, such fluorine-based polymers have the following properties at room temperature:
Examples include aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone and methyl ethyl ketone, ethers such as diethyl ether, dipropyl ether, methyl cellosolve, and ethyl cellosolve.
Dissolves in esters such as ethyl and butyl acetate, and halogenated hydrocarbons such as trichloromethane, dichloroethane, and chlorobenzene.

). , Method of Synthesis The fluorine-containing copolymer as described above can be synthesized by copolymerizing each of the monomers (A) to (C) as described above in the presence of a well-known radical initiator.

Various known radical initiators can be used as such radical initiators. Specifically, organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, and diter
t-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
tert-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, here-butylperbenzoate, tert
-Butyl perphenylacetate, tert-butyl perisobutyrate.

tert-butylperu 5ee-octoate, tert
t-butyl perbivalate, cumyl perbivalate, t
Other azo compounds such as azobisisobutyronitrile, dimethylazoisobutyrate, etc. are used, such as ert-butyl perdiethyl acetate. Among these, dicumyl peroxide, di-terL-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5
-di(tert-butylperoxy)hexane, 1,
4-bis(tert-butylperoxyisopropyl)
Dialkyl peroxides such as benzene are preferred.

In the copolymerization reaction as described above, the radical initiator is added in the above-mentioned solvent at a molar ratio of 10 to the total number of moles of monomers. The polymerization temperature is preferably 130 to 200°C, preferably 2 to 200°C.
0-100℃, polymerization pressure 0-100kg/am'・
G, preferably 0 to 50 kg/am2.G.

In the present invention, when producing a fluorine-containing copolymer using a fluoroolefin containing chlorine as a fluoroolefin, the system is It is desirable to have a chlorine scavenger present in the tank.

As such a chlorine scavenger, the following compounds can be used.

(A) M, AI, (OWL-, v-t-(A)
, ・a In formula H201, M is Mg, Ca or Z
n, A is CO, or HPO□, x-y,
z is an integer, and a is 0 or an integer. ) complex compound.

Specifically, the following compounds are used as the composite compound represented by (a).

qgJl? (OH) + CO7・4H? OMg=Al
t(OH),,CO,・5H20Mgq^1? (OH)
,,CO,・4H20Mt,A12(OH)t2cO
= ・4H20jg ＾1□(O)l), うHPOj・
4H20Ca-A12 (0 old, CO, -4) 120Z
n, A1. (OH), ecO, 4H,0 The complex compound represented by (a) may be a compound that is not exactly represented by the above formula, for example, Mg2^N0)I
A compound in which a portion of OH in L.3H20 is replaced with CO may also be used. Further, water of crystallization may be removed from these compounds.

Among such complex compounds, 1M is h, Af
Compounds that are ficO, are preferred.

(b) Basic compounds of alkaline earth metals Examples of basic compounds of alkaline earth metals include MgO, CaO
Alkaline earth metal oxides, 1 [(0 old, , Ca
Alkaline earth metal hydroxides such as (OH)p, M(CO
3, alkaline earth metal carbonates such as CaC0, etc. are used.

The basic compounds of alkaline earth metals as mentioned above are (1
It may be a double salt such as gcosu□.Mg(OH)t.5H20, and the water of crystallization may be removed from these compounds.

Among these basic compounds of alkaline earth metals,
Compounds containing M are preferred.

(c) Epoxy group-containing compounds Examples of epoxy group-containing compounds include silicon-containing epoxy compounds such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and trimethylolpropane polyglycidyl. Aliphatic epoxy compounds such as ether and neopentyl glycol diglycidyl ether are used.

Among these, epoxy compounds containing continuous chains such as γ-glycidoxypropyltrimethoxysilane are preferred.

Among the above-mentioned elemental scavengers, chlorine scavengers, which are inorganic compounds, react faster with chlorine (hydrochloric acid) than chlorine scavengers, which are organic compounds, and are suitable for polymerization or purification systems. It is preferably used because it is not dissolved and can be easily removed from the system. Particularly preferred are the composite compounds shown in (a).

By making the above-mentioned chlorine scavenger present during the double polymerization reaction, during the W phase of the obtained copolymer, or both, coloring of the obtained fluoropolymer can be effectively prevented.

When such a chlorine scavenger is used during the polymerization reaction, it is preferably used in an amount of 0.5 to 100 g, preferably 1 to 70 g, per mole of chlorine atoms contained in (A) fluoroolefin. Furthermore, in the copolymer of the present invention, the amount of salt JlllW per 100 parts by weight of the copolymer is
It is desirable to use the I scavenger in the II range of 0.2 to 100!1111.

Curing Catalyst [B] In the composition according to the present invention, a curing catalyst is used in order to accelerate the curing reaction of the fluoropolymer as described above.

The curing catalyst used in the present invention is 1% (in the formula, R" is an alkyl group having 4 to 10 carbon atoms, and
X' is an alkyl group having 4 to 10 carbon atoms, CI or OH group, Y'', Y'2 is Cl, 0COR'',
or an OH group, which may be the same or different. However, R'' is an alkyl group, an aryl group, or an allylalkyl group.

Specifically, such curing catalysts include n-C,
H, 5n(OH), Cl, n-C, H, 5n(OH)C
l? ,n-C,+Ho5nCl,-CJ+-+(OH)
2Cl-CaH, 7 (0 old CI, , C@H+, 5nCl
i,n -C-)1-5n (OH)tOcOc,l(
9,,,n C,H,5n(OH)20COC,+8
2. , n −CJ + 7sn (OH)20COCJ
+ q+n C=HI, 5n(OH)? 0COC9
,Ht? -n -C-H*5n(OCOC, Hlq),
, (n-CaHq)tsn(OCOC,,H2,)? (
n-CaHa)Jn(OCOC)l=cHcOOcH,
)2, (n-CjH,)zsn (OCOCH:CHC
OOCH? Ph) etc. are used.

Among these, CaH, 5nCl, and (C,lH*)2Sn(OCOCl-1(2112) are particularly preferred.

Cured with the above fluorine-containing copolymer fli! By using it in combination with a medium, a coating film with excellent adhesion to the substrate and weather resistance can be obtained.

Since the fluorine copolymer used in the present invention has a hydrolyzable organic group derived from the organosilicon compound (C), the degree of crosslinking between the molecular chains of the polymer can be increased by bonding with water. Spreading and hardening may occur. Therefore, as a matter of course, crosslinking can occur due to the temperature in the atmosphere. However, it is preferable to use the above-mentioned curing catalyst so that the fluorine-containing copolymer film applied to the substrate is rapidly cured.

Such a curing catalyst contains 100 g of fluorine-containing copolymer by weight.
It is used in an amount of 0.03 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight.

In the present invention, an organic solvent capable of dissolving the fluorine-containing copolymer is used in order to dissolve the above-mentioned fluorine-containing polymer and curing catalyst to form a uniform solution and use it as a paint.

Such organic solvents include toluene, xylene, #
Butyl acid, isobutyl methyl ketone, methyl cellosolve, ethyl cellosolve, or a mixture thereof is used.

The organic solvent as described above is used in an amount of 40 to 300 parts by weight, preferably 80 to 120 parts by weight, per 100 parts by weight of the fluorine-containing copolymer.

The fluorine-containing copolymer composition according to the present invention is composed of a fluorine-containing copolymer, a curing agent, and an organic solvent as described above. The solution III, which may contain all of the above-mentioned components, and the solution III prepared by dissolving the fluorine-containing copolymer in an organic solvent and the second solution prepared by dissolving the curing catalyst in an organic solvent are added immediately before use. The above fluorine-containing copolymer composition may be prepared by mixing.

Other components The fluorine-containing copolymer composition according to the present invention contains, in addition to the above-mentioned fluorine-containing copolymer, curing catalyst, and organic solvent, a pigment, a dye, a dehydrating agent (trimethyl orthoformate), a dispersant, and Other paint additives (leveling agents, wetting agents, etc.),
Alkyl silicates and their oligomers as well as their hydrolysates (tetramethyl orthosilicate oligomers, etc.)
, an organosilicon compound having an isocyanate group such as γ-cysocyanatepropyltrimethoxysilane.

The fluorine-containing copolymer composition according to the present invention can be used as a paint, and can be coated on bases such as metal, wood, plastic, ceramic, paper, glass, etc. with a brush, spray, roller coater, etc. in the same way as ordinary liquid paints. Can be applied to surfaces. The cured film has excellent weather resistance, chemical resistance, solvent resistance, water resistance, heat resistance, and low friction, as well as excellent transparency and elongation.

The curing reaction (crosslinking reaction) of the fluorine-containing copolymer composition according to the present invention is carried out at room temperature, that is, around room temperature (0 to 40
Although the reaction proceeds satisfactorily at a temperature (°C), the reaction may be carried out under heating if necessary.

(Effects of the Invention) According to the present invention, a fluoropolymer consisting of a fluoroolefin, an alkyl vinyl ether, an olefinically unsaturated gold group and an organosilicon compound having a hydrolyzable group is combined with a specific curing catalyst. By adding this composition to an organic solvent, the composition becomes a coating material with excellent weather resistance, water resistance, chemical resistance, water repellency, and low friction after curing, and also achieves rapid curing and good bonding with the base material. A pot film layer with excellent adhesion can be formed.

(Example) Below, examples of the coating composition according to the present invention and evaluation of adhesion when used as a coating material were conducted.

Note that the present invention is not limited to these examples.

Reference production example 1゜1.5i! After purging the interior of a stainless steel autoclave with a stirrer with nitrogen, under a nitrogen stream, 31.1 g of trimethoxyvinylsilane (T'4VS), 82.2 t of ethyl vinyl ether (EVE), and n-butyl vinyl ether (BVE) were added. ) 15.0g, Malein 2
1 Shimel (DMM) 108°1g, synthetic hydrotalcite (ALa, *A12(OH)7gcOg ・3..1
)120) Powder fired product (SHT) 9.3g,
``JlkIII dilauroyl 5. import benzene 500
It was dissolved in ml and charged all at once. Thereafter, 87.4 g of chlorotrifluoroethylene (CTFE) was introduced into the t-trarepe and heated to 65°C.

The reaction was carried out for 8 hours. Thereafter, the autoclave was opened, and the reaction solution was taken out into a one-bottle eggplant-shaped flask. To this reaction solution was added 15 Q g of xylene and loo
g, 9.4 g of 5HT was added and heat treated at 50'C for 1.5 hours and then at 60°C for 1.5 hours with stirring,
The residual monomer and solvent were distilled off under reduced pressure using an evaporator, then 400 g of xylene was added, and the solvent was distilled off under reduced pressure using an evaporator again. Then xylene 50
This solution was passed directly through to remove SHT, and concentrated under reduced pressure to obtain 273 g of a colorless and transparent polymer (1).

The number average molecular weight of the obtained copolymer by GPC was 640.
It was 0.

In addition, the composition of this polymer was analyzed using elemental analysis and NMR.
E/DMN/TMVS=26/30/6/30/7 (
(mol%).

Reference Production Example 2゜1. After purging the interior of an SU stainless steel autoclave with nitrogen, under a nitrogen stream, 31.1 g of trimethoxyvinylsilane (TMVS), 93.0 g of ethyl vinyl ether (EVE), and maleic acid were added. x-fk
(DEN) 206.6g, synthetic hydrotalcite (M(4,%^12(0 old, , CO, ・3.5Ht
O) Powder #! Finished product (SHT) 9.3g.

5.4 g of dilauroyl peroxide was dissolved in 500 ml of benzene and charged all at once. Then, 35.0 g of chlorotrifluoroethylene (CTFE) was introduced into an autoclave, the temperature was raised to 65°C, and reaction was carried out for 8 hours. . Thereafter, the autoclave was opened, and the reaction solution was poured into a 1U eggplant-shaped flask. Add 150 xylene to this reaction solution.
g, 100 g of methanol, 79.4 g of 5H were added, and the temperature was 1.511 at 50°C! ? 1.5 at 60” C
After heat treatment with stirring for a period of time, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then xylene 4
00g was added thereto, and the solvent was distilled off again under reduced pressure using an evaporator. Thereafter, 500 g of xylene was added, the solution was filtered to remove SHT, and concentrated under reduced pressure to obtain 290 g of colorless and transparent polymer (II).

The number average molecular weight of the obtained copolymer by GPC was 4.0.
It was 00.

In addition, the composition of this polymer was analyzed using elemental analysis and NMR. CTFE/EVE/D
EM/TMVS=12/29151/8 (mol%)
Theatu f:.

Reference Production Example 3 After purging the inside of a 1.5* stainless steel autoclave with nitrogen, add 180 m of benzene under a nitrogen stream.
1. Ethyl vinyl ether (EVE) 39.4
g, vinyl acetate (VAc) 108.6 g, trimethoxyvinylsilane (TMVS) 43.6 g, synthetic hydrotalcite (Mg-, J12(OH),, co,.
3.58? O) 13.0 g of fired powder (SHT) was charged. Then chlorotriple oleoethylene (CTFE)
) 245 g was introduced into an autoclave, and the temperature was raised to 65°C. An initiator solution of 7.6 g of dilauroyl peroxide dissolved in 120 ml of benzene was fed to the mixture thus obtained over a period of 4 hours. Further 65℃
After the reaction was carried out for 6 hours, 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 into a 1.5U eggplant type flask. 210 g of xylene and 1 methanol were added to this reaction solution.
20g, SHT 13. Add Og and heat at 50℃ for 1
The mixture was heated at 60° C. for 1.5 hours with stirring. After the treatment, residual monomers and solvent were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to form a homogeneous solution.

This solution was filtered to remove SHT and concentrated under reduced pressure to obtain 288 g of a colorless and transparent polymer (m).

The number average molecular weight of the obtained copolymer by GPC was 21,
It was 000. In addition, the composition of this polymer was analyzed using elemental analysis and NMR.

CTFE/EVE/VAc/TMVS=27/
It was 28/39/6 (%le%).

Comparative Production Example 1 The inside of a 1.5U stainless steel autoclave with a stirrer was replaced with nitrogen, and under a nitrogen flow, 180ml of benzene, 106g of ethyl vinyl ether (EVE), 21.0g of n-butyl vinyl ether (BVE), and trimethoxyvinylsilane were added. (TMVS) 62.2g,
Synthetic hydrotalcite (Mga, 5^1t (OH),
sco, ・3.5 H, O) powder fired product (SHT) 1
After that, 257 g of chlorotrifluoroethylene (CTFE) was introduced into the autoclave, and the temperature was raised to 65°C. To the mixture thus obtained, 7.6 g of dilauroyl peroxide was added to 120 ml of benzene.
An initiator solution dissolved in water was fed over a period of 4 hours.

After further reaction at 65°C for 6 hours, the autoclave was cooled with water.

The reaction was stopped. After cooling, unreacted monomers were expelled, the autoclave was opened, and the reaction solution was taken out into a 1.5XZ eggplant-shaped flask. Add xylene 2 to this reaction solution.
10g, methanol 120g-5HT13°Og
was added and heat treated at 50°C for 1.5 hours and then at 60°C for 1.5 hours with stirring. After the treatment, residual monomers and Wj medium were distilled off under reduced pressure using an evaporator, and then 550 g of xylene was added and stirred to obtain a homogeneous solution. This solution was filtered to remove SHT and concentrated under reduced pressure to obtain 366 g of a colorless and transparent polymer (IV).

The number average molecular weight of the obtained polymer by GPC was 100.
It was 00.

In addition, the composition analysis of this polymer was performed using elemental analysis and NMR.
E/TMVS =50/37/6/7 (-F nyl ratio)
telhtsuf:.

Example 1 Polymer (1) obtained in Reference Production Example 1 38.2 parts by weight, 1.9 parts by weight of tetramethyl orthosilicate oligomer, 1.9 parts by weight of methyl orthoformate, and 26 parts by weight of titanium oxide.
A paint (1) was prepared consisting of 7 parts by weight and 31.3 parts by weight of xylene.

On the other hand, galvanized steel sheet specified in JIS G 3302 +5
PG) to epoxy paint Marine SC (Mitsui Metal Paint Chemicals)
) was coated and exposed outdoors for 10 days to produce a coating substrate.

Further, a coating composition was prepared by preparing 1.9 parts by weight of a 6.3% by weight xylene solution of n-BuSnCl with respect to 100 parts by weight of the coating material (1) prepared as described above. The product was applied onto the above-mentioned coated substrate using a 100 μm applicator. After the coating film thus obtained was exposed outdoors for one week, a base grain test was conducted.

The results are shown in Table 1.

Example 2 A coating film was formed in the same manner as in Example 1 except that the polymer (II) obtained in Reference Production Example 2 was used, and after being exposed outdoors for one week, a base grain test was conducted. The results are shown in Table 1.

Example 3 Except for using the polymer (m) obtained in Reference Production Example 3,
A coating film was formed in the same manner as in Example 1, and left outside #I for 1 week.
After g+, a base test was conducted. The results are shown in Table 1.

Comparative Example 1 A coating film was formed in the same manner as in Example 1, except that the copolymer (IV) obtained in Comparative II Preparation Example 1 was used instead of the polymer (1), After one week of outdoor exposure, a substrate test was conducted.

The results are shown in Table 1.

Claims (3)

[Claims] (1) [A] (A) Fluoroolefin (B) Alkyl vinyl ether (C) Obtained by copolymerizing an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group; ) for the total molar quantity of the components (
Component A) is in the range of 1 to 30 mol%, and component (B) is in the range of 1 to 30 mol%.
A fluorine-containing copolymer in which the component (C) is in the range of 1 to 30 mol%, and [B] formula R^0^1-SnX^0^1Y^0^1Y^0
^2 (In the formula, R^0^1 is an alkyl group having 4 to 10 carbon atoms, X^1 is an alkyl group having 4 to 10 carbon atoms, C
l or OH group, and Y^0^1 and Y^0^2 are Cl
, OCOR^0^2, or OH group, which may be the same or different. However, R^0^2 is an alkyl group, an aryl group, or an arylalkyl group. )
A coating composition with excellent adhesion, characterized by comprising a curing catalyst represented by: and [C] an organic solvent. (2) The fluoroolefin (A) has the following formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (R^1, R^2, R^3 are hydrogen atoms or halogen atoms, R^4 is a hydrogen atom, The composition according to claim 1, wherein the composition is a halogen atom, an alkyl group, or a halogenated alkyl group, and has a fluorine atom in one or more of R^1 to R^4. thing. (3) The organic silicate compound (C) has the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼… I ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼… II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼… (R ^7 and R^8 have an olefinic unsaturated bond and are composed of carbon, hydrogen, and in some cases oxygen, and may be the same or different. X^1 has an olefinic unsaturated bond It is an organic group that does not have Y^1, Y^2, Y^3
are hydrolyzable groups, and may be the same or different. 2. The composition according to claim 1, wherein the composition is an organosilicon compound (C) represented by any one of I, II, or III.