JPH03281611A - Fluorocopolymer and its use - Google Patents

Abstract

PURPOSE:To obtain a fluorocopolymer improved in adhesion to substrates, comprising fluoroolefin units, vinyl ether units and specified units. CONSTITUTION:Fluoroolefin (a) (e.g. CF2=CF2) is copolymerized with a vinyl ether (b) comprising 99.5-90mol% 1-3C linear alkyl vinyl ether and 0.5-10mol% cycloalkyl vinyl ether and a monomer (c) of formula I (wherein R is alkyl; and (n) is 1-20) to obtain a solvent-soluble fluorocopolymer comprising 30-70mol% component (a) units and 20-60mol% component (b) units and 1-25mol% units of component of formula II (wherein X is H or COR) and having a number-average mol.wt. (gel permeation chromatography) of 3000-200000 and a degree of crystallinity of 0%. This copolymer and an aminoplast compound (e.g. melamine resin) or a polyisocyanate compound (e.g. hexamethylene diisocyanate) are dissolved in an organic solvent (e.g. benzene) to obtain a coating composition.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a fluorine-containing copolymer that can be dissolved in an organic solvent and rapidly cured at room temperature and has excellent adhesion to a substrate, and uses thereof. .

Technical background of the invention and its problems Weather resistance,
Paints with excellent durability are required, and high-grade exterior paints based on polyester or acrylic are used. but,
Existing paints have a short outdoor service life, and even the above-mentioned high-quality paints lose their aesthetic appearance and substrate protection effect within a few years.

On the other hand, fluoropolymers are extremely stable both thermally and chemically, and have excellent weather resistance, water resistance, chemical resistance, solvent resistance, mold releasability, low friction, and water repellency. Suitable as a surface treatment agent for various substrates. However, conventionally known fluoropolymers suffer from the above-mentioned properties,
It was difficult to form a coating film because it was soluble in organic solvents, making it extremely difficult to use it as a paint. For example, currently known paints made from fluorine-based polymers are mostly powder paints, with only a small amount of PVdF (polyvinylidene fluoride).
It is simply used as an organic solvent-dispersed paint by taking advantage of its ability to dissolve in specific solvents at high temperatures. Moreover, since these fluoropolymer paints require baking at high temperatures to form a film, their field of use has been limited to areas where heating equipment is available. In addition, the need for heating equipment and the baking process are
This is not desirable from the viewpoint of the safety of the people involved in the work and the environment of the workplace. Therefore, in recent years, attempts have been made to develop fluoropolymers that are solvent-soluble or do not require a baking process at high temperatures.

For example, JP-A-57-34107 discloses a quaternary copolymer consisting of fluoroolefins, cyclohexyl vinyl ethers, alkyl vinyl ethers, and hydroxyalkyl vinyl ethers, and this copolymer is soluble in organic solvents. It is also described that it can be cured at room temperature. However, in order to cure this copolymer at room temperature, a melamine-based curing agent or a urea resin-based curing agent is required, and as a matter of course, it is used in a two-component type, which is poor in workability. Further, the glass transition temperature of this copolymer is relatively high, at or above room temperature, that is, at or above 25°C. Furthermore, although no actual example is described in Japanese Patent Publication No. 46-39472, an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group is added to PTFE (polytetrafluoroethylene) using an organic hydroperoxide. It has been suggested that those mechanically treated in the presence of a radical initiator such as the above are crosslinked and cured by water at room temperature. However, the fluoropolymer produced by this method is a polymer in which an organosilicon compound is grafted onto PTFH, and is substantially insoluble in organic solvents.

JP-A-57609 discloses a curable fluorine-containing copolymer containing chlorotrifluoroethylene, fatty acid vinyl ester or fatty acid isopropenyl ester, and hydroxy group-containing allyl ether as essential components. .

Furthermore, JP-A No. 62-66207 discloses that a curable fluorine-containing copolymer containing trichlorofluoroethylene, a fatty acid vinyl ester or a fatty acid isopentanyl ester, and a hydroxy group-containing allyl ether as essential components is used as a sheath material. A light transmitting fiber as a component is disclosed.

In view of these current circumstances, the inventors of the present invention have developed a material that 1) dissolves in organic solvents at low temperatures, 2) does not require a special curing agent for curing, 2) cures at room temperature, and 4) can be used as a one-component paint. , ■ After curing, it has excellent weather resistance, water resistance, chemical resistance, solvent resistance, and low friction; ■ As a fluorine-containing copolymer that can be directly polymerized from monomer components, (b) a vinyl ether; (C) an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group; For the total number of moles of (c), (a
): 30-70 mol%, (b): 20-60 mol%, (
c) + 1 to 25 mol %, and has a number average molecular weight (Mn) of 3000 to 20 (I
A solvent-soluble fluorine-containing copolymer containing silicon as defined by HL and a paint prepared by dissolving this fluorine-containing polymer in an organic solvent were proposed in Japanese Patent Application No. 1982-2FI3N7.

Although this fluorine-containing copolymer has extremely excellent properties, the coating film obtained after coating a coating composition prepared by dissolving this fluorine-containing copolymer in an organic solvent on a substrate is somewhat inferior. There was a problem in that the adhesion to the base material was poor.

In view of these points, the present inventors conducted extensive studies and found that the above-mentioned results can be achieved by using the silicon-containing solvent-soluble fluorine-containing copolymer in combination with a novel solvent-soluble fluorine-containing copolymer. The present invention has been completed by discovering that the following problems can be solved. Furthermore, it was discovered that the above-mentioned novel solvent-soluble fluorine-containing copolymer itself can be used as a paint composition by dissolving it in an organic solvent, leading to the completion of the present invention.

Purpose of the Invention The present invention aims to solve the above-mentioned problems, and is capable of providing a coating film with excellent adhesion to a substrate when dissolved in an organic solvent and used as a coating material. The present invention aims to provide a novel fluorine-containing copolymer that is soluble in an organic solvent, and a coating composition prepared by dissolving this fluorine-containing copolymer in an organic solvent.

The present invention also provides a fluorine-containing copolymer composition comprising the above-mentioned silicon-containing solvent-soluble fluorine-containing copolymer and the above-mentioned novel fluorine-containing copolymer, and this fluorine-containing copolymer composition. The object of the present invention is to provide a coating composition obtained by dissolving a composition in an organic solvent.

Summary of the invention The fluorine-containing copolymer [I] according to the present invention comprises [A](i)
A unit derived from a fluoroolefin, (i) a unit derived from a vinyl ether, and (i) a unit (CH2) represented by the following formula. ox (wherein X is a hydrogen atom or a -COR group (wherein R is an alkyl group), and n is a number from 1 to 20), (i), (i) and (i
), (i) is in an amount of 30 to 70 mol%, (i) is in an amount of 20 to 60 mol%, and (i) is in an amount of 1 to 60 mol%.
25 mol %, and the number average molecular weight (Mn) measured by Cl gel permeation chromatography is 3000-20
OO (characterized by being within the range of 10).

Further, the first coating composition according to the present invention is characterized in that the above-mentioned fluorine-containing copolymer [I] is dissolved in an organic solvent.

Further, the fluorine-containing copolymer composition according to the present invention comprises [I] the above-mentioned fluorine-containing copolymer [I], [Ir] (^) (a) fluoroolefin (b) vinyl ether (c) olefin A copolymer of an organosilicon compound having a sexually unsaturated bond and a hydrolyzable group, [B] based on the total number of moles of (a), (h), and (C) forming the copolymer. , (a) is in an amount of 30 to 70 mol%, (b) is in an amount of 20 to 60 mol%, (C) is in an amount of 1 to 25 mol%, and The number average molecular weight (!Wn) measured by chromatography is 3000 to 20.
The solvent-soluble fluorine-containing copolymer [II] is characterized in that G [100] is within the range.

Further, the second coating composition according to the present invention is characterized in that it is formed by dissolving the above-mentioned fluorine-containing copolymer in an organic solvent.

DETAILED DESCRIPTION OF THE INVENTION The fluorine-containing copolymer [1] according to the present invention and the coating composition containing the same will be specifically described below.

First, the fluorine-containing copolymer [I] according to the present invention will be explained. This fluorine-containing copolymer has (i) a unit derived from a fluoroolefin, (i) a unit derived from a vinyl ether, and (i) a unit derived from a vinyl ether. ) A unit represented by the following formula (CH2), OX (wherein, X is a hydrogen atom or a -COR group (however, R is an alkyl group), and n is a number from 1 to 20) The above-mentioned structural units are arranged at random. However, within the scope that does not impair the purpose of the present invention, small amounts of other copolymerizable monomer components such as α-olefins, cycloolefins,
It does not matter if unsaturated carboxylic acids or the like are copolymerized.

The fluoroolefins (i) used in the present invention have at least one fluorine atom in the molecule, and are preferably perhaloolefins in which all hydrogen atoms of the olefin are substituted with fluorine atoms and other halogen atoms. , particularly perfluoroolefins.

Furthermore, from the viewpoint of polymerizability and properties of the resulting polymer, fluoroolefins having 2 or 3 carbon atoms, particularly perfluoroolefins, are preferred.

Specifically, the following compounds are used as such fluoroolefins.

CF=CF, CF3C1, CH2=2 2
2 CF, CH2=CHFXC'CIF=CF2, CH
Cl=CF, CCI=CF
, CCI F2 2 2 =OCA' FSCHF=CCI 5CH2=CHF
.

CCI 2 = Fluoroethylene type such as CCl F.

CF　CF=CF　5CF3CF=CHF.

2 CF　CH=CF　　, CF3CClCH2, 2 CF3CF=CHFSCHF2CF=CHF.

CF CH=CH5CH3CF=CF2, 2 CHCH=CF, CH3CF=CH2, 2 CF2CICF=CF2, CF30C1-CF2, CF
3CF=CFCA'.

CF2ClCC1=CF2, CF2clCF=CFC1
1CFC12CF=CF2, CF3CCl=CCl F, CF3CCl=CC1
, CCIF2CF=CC12, CCJ CF=CF , CF2Cl CCJ =2 CCI , CFCI 2CCI = CCl 2, CF
3CF=CHC/, CCI F2CF=CHCI 5C
F3CCA'=CHCf.

CHF CCf =CC1, CF2CIICI(=2 CCI 5CF2CI CCI =CHC1,2 CCI CH=CHCA', CF,, l'cF=c
F2, CF B fCH; CF 1CF 3CB
t = 2 CHBr, CF CICB+ = CH2, CHB
t CF = CCl, CF 3CB r=2 CH1CF CH= CHB t, CF 2
Fluoropropene type such as B r CH2 = CHF SCF B + CF = CF2.

CF CF CH=CH2, 2 CF CF=CFCF S CF3CH=3 CFCF 5CF2=CFCF2 CHF2, CF
CF CF=CH, CF3 CH=3 2
2 CHCF, CF = CFCF CH5CF3
2 23 2 = CFCHCH, CF3CH2CH=CH2, 3 CF CH=CH2H, CF2= 3 CHCHCH, CHCF2CH=CH2, 233 CFHCH=CHCFHSCH3CF,, CH2 = CH, CH=CFCH2CH3, 2 CF (CF2)2 0F=CF2, CF ( CF2) Fluoroolefins having 4 or more carbon atoms such as 3CF=CF2.

Among these, fluoroethylene and fluoropropene are preferable as mentioned above, and tetrafluoroethylene (CF2=CF2) and chlorotrifluoroethylene (CF2=CF2I) are particularly preferable, and furthermore, they are safe and easy to handle. From this point of view, chlorotrifluoroethylene is preferred.

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

The vinyl ether (i) used in the present invention is a compound in which a vinyl group and an alkyl group, cycloalkyl group, aryl group, aralkyl group, etc. are ether bonded.

Specifically, such vinyl ethers include ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, ier+
-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, isohexyl vinyl ether,
Chain alkyl vinyl ethers such as octyl vinyl ether and 4-methyl-1-pentyl vinyl ether, cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether, aryl vinyl ethers such as phenyl vinyl ether and o-1m-194'rivinyl ether, benzyl vinyl ether , phenethyl vinyl ether, and other aralkyl vinyl ethers can be used.

Among these, the number of carbon atoms is preferably 8 or less, preferably 2 to 4.
and a chain alkyl vinyl ether having 5 to 5 carbon atoms.
6 is preferred, and ethyl vinyl ether, propyl vinyl ether, and butyl vinyl ether are more preferred.

Further, in the present invention, the above-mentioned vinyl ethers may be used alone or in combination.

In the present invention, as vinyl ether (i), (
a) a linear alkyl vinyl ether having 1 to 3 carbon atoms;
(b) By using a cycloalkyl vinyl ether or a branched alkyl vinyl ether in combination, a fluorine-containing copolymer that can provide a coating film with excellent stain resistance can be obtained. At this time, (a) linear alkyl vinyl ether is (
The amount of (b) cycloalkyl vinyl ether or branched alkyl vinyl ether is preferably 0.5 to 10 mol%, based on the total number of moles of (b).

Units derived from such vinyl ethers (wherein
RI is a straight or branched alkyl group or a cycloalkyl group. ).

The fluorine-containing copolymer [I] according to the present invention comprises (i) a unit derived from a fluoroolefin as described above;
) units derived from vinyl ether, and (i) the following formula % formula %) (wherein, X is a hydrogen atom or a -COR group (however, R is an alkyl group), and n is a number from 1 to 20. It consists essentially of the units represented by

The unit represented by the above formula is derived by using the following monomers.

C1l=CFI(CH2)OCOCH3C1l
=CII(CI(2) ,, OCOCH3CI(=
CH(CH2) 3 0COCH! C1l=CH(
CH2) OCOCH5CI(=CH(C112) 2
ococ2H5CH=CH(CH2') 30COC2
H5CO= CM (CH2) 0CON-C3H7C
B=CH(CH2)OCOi−C3H7CB”
”CB (0M2) 20CON-C3H7CD =
CH(CH2) 20COi-C3H7CO2”CH(
CH2) 30CON-C3H7CB =CHCCH
2) 30COi-C3it7CB =CH(CH2
) 0CON-C4H9CH= CH(CH,,) 0
COi-C4H9=CH(C112) =CH(CH2) Engineering C1((C112) =CH(CH,,) =CH(CH2) =CII (CH2) =CH(CH,,) =CH(C12) =CH (C12) =CH(C112) = CH(CH,,) = CH(CB2) =CII (C112) =CII (CH2) =CII (CH2) =CH(CH,,) =CH(CH2) =C[ I (CI(2) =CII (CH,,) =CH(CH2) OCO+-C4H9 20COn-C4H9 20COi-C4H9 20COt-C4H9 30COn-C41(9 30COi-C4H.

30COt-C4H9 0CON-C5H1゜ OCO knee C5H,.

0COOneo-C5H,.

QC(N-C5H11 20CON-C5H,.

20COi-C5II,.

20COneo-C5H,.

20COt-C5H,.

30CON-C5H11 3ocoi-c5ft.

30COneo-C5H.

30CO1-C5H11 OH C)l =C1l (C)+2) 20)1C)l
=CH(CH2) 30H C1l =CH(CH2)40f (In the present invention, a monomer represented by CH2=CH(CH2) and 0COR as described above is also used to add units to the fluorine-containing copolymer. and hydrolyze this structural unit (CH
2). A unit represented by OH may be introduced into the fluorine-containing copolymer.

In the fluorine-containing copolymer [I] according to the present invention, (i) to (
The content ratio of the monomer component of i) is 30 to 70 mol%, preferably 40 to 60 mol% of (1), based on the total number of moles of (i) to (i), and (i) is 20-6
0 mol%, preferably 20-50 mol%, (i
) is in an amount of 1 to 25 mol%, preferably 3 to 20 mol%.

The molecular weight of such a fluorine-containing copolymer [I] is determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and monodisperse polystyrene of known molecular weight as a standard substance. The number average molecular weight (Mn) is usually 3000 to 200000,
Many are in the 500G-100,000 range.

The fluorine-containing copolymer [1] according to the present invention is also non-quality or has low crystallinity, and is often non-quality, and generally has a crystallinity of 0% by X-rays and a differential scanning calorimeter (D SC)
Often no melting point is observed. Therefore, the fluorine-containing copolymer according to the present invention has good transparency.

By adopting such a composition ratio and molecular weight, the fluorine-containing copolymer according to the present invention becomes solvent soluble and has excellent film coating properties, and after being cured by the method described below, it becomes solvent resistant. It has excellent properties such as hardness, chemical resistance, weather resistance, heat resistance, mechanical properties, and adhesion to the substrate.

Such a fluorine-containing copolymer [I] according to the present invention can be used at room temperature to contain, for example, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone and methyl ethyl ketone, diethyl ether, and dipropyl ether. Alcohols such as ethers and ethanol,
Soluble in halogenated hydrocarbons such as trichloromethane, dichloroethane, and chlorobenzene.

Therefore, a coating composition can be prepared by dissolving the above-mentioned fluorine-containing copolymer [I] in the above-mentioned organic solvent.

When preparing a coating composition from the above-mentioned fluorine-containing copolymer [I], toluene, xylene, butyl acetate, isobutyl methyl ketone, methyl cellosolve, ethyl cellosolve, or a mixture thereof is used as an organic solvent. It is preferable.

A coating composition prepared by dissolving such a fluorine-containing copolymer [I] in an organic solvent can be cured as follows.

That is, examples of the curing agent include aminoplast compounds, polyvalent isocyanate compounds, epoxy group-containing compounds, polybasic acids or their anhydrides, metal alkoxides or derivatives thereof, etc., which can react with the hydroxyl group of [I]. From the viewpoint of properties, it is preferable to heat cure using an aminoplast compound or to cure at room temperature using a polyvalent isocyanate. Examples of the aminoplast compound include melamine resin, urea resin, benzoguanamine resin, and acetoguanamine resin, and examples of the polyvalent isocyanate compound include hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, and the like. Further, as the polyvalent isocyanate compound, polyvalent isocyanates blocked with blocking agents such as alcohols, phenols, oximes, and amines can also be employed. The amount of the curing agent added and mixed is such that the number of functional groups in the curing agent/the number of hydroxyl groups in the copolymer [I] is 0.5 to 1.
Preferably, the amount is 5.

The present invention also provides a composition comprising the above-mentioned fluorine-containing copolymer according to the present invention [1] and the following silicon-containing solvent-soluble fluorine-containing copolymer [11] .

That is, the silicon-containing solvent-soluble fluorine-containing copolymer [■] used in combination with the fluorine-containing copolymer [I] according to the present invention is [^] (a) fluoroolefin (b) vinyl ether (c) olefin A copolymer of an organosilicon compound having a sexually unsaturated bond and a hydrolyzable group, [Bl based on the total number of moles of (a), (b) and (C) forming the copolymer, (Ri is 30-70 mol%
(b) in an amount of 20 to 60 mol%, and (C) in an amount of 1
~25 mol%, and [number average molecular weight (Mn) measured by Cl gel permeation chromatography of 3000 to 200]
It is a fluorine-containing copolymer in the range of 00G.

This silicon-containing solvent-soluble fluorine-containing copolymer [I[
], the (i) fluoroolefins as described above are used as (a) the fluoroolefins, and (b)
As the vinyl ether, (i) vinyl ether as described above is used.

Further, the organosilicon compound (C) used in this silicon-containing fluorine-containing copolymer [n] is a compound having an olefinic unsaturated bond and a hydrolyzable group in the molecule, and specifically, Compounds represented by the following formulas (1) to (3) can be exemplified.

R' R2Si Y' Y2 (1) R' XS
i Y' Y2 (2) R' Si Y' Y
2Y3 (3)2 (wherein RSR has an olefinically unsaturated bond and is composed of carbon, hydrogen, and optionally oxygen, each of which is the same or different. X is a group having an olefinically unsaturated bond. 1 2 3 , and Y SY and Y are the same or different hydrolyzable groups, respectively.) R1 or R2 is specifically, vinyl, allyl (al
171), butenyl, cyclohexenyl, cyclopentagenyl, etc., and terminal olefinically unsaturated groups are particularly preferred. Further, R or R2 is CH=CH-Coo (CH,,) 3-1CH2= having an ester bond of a terminal unsaturated acid.
C(CH3) COO(CH2) 3CH2-C(CH
3) It can also be a group such as COO(CH2)2-0(CH2)3 CH2=C(CH3)COOCH2CH2. Among these, it is preferable that R and R2 do not contain oxygen and are composed of carbon and hydrogen, and a vinyl group is particularly suitable.

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

YI Yl, Y3 are specifically alkoxy groups such as methoxy, ethoxy, butoxy, methoxyethoxy,
Alkoxyalkoxy group, formyloxy, acetoxy,
Acyloxy groups such as propionoxy, oximes such as 10N=C(CH3) 2. 0N=CHCH2C2H5 and ON"C(c6H5)2 or substituted amino groups and arylamino groups such as -NHCH3, -NHCH and -NH(C6H5), and any other hydrolyzable organic group.

In the present invention, the organosilicon compound [I[] is preferably a compound represented by the general formula (3), particularly the group Y
, Yl, and Y3 are preferably the same.

Among these, organosilicon compounds in which R1 is a vinyl group and Yl-Y3 is an alkoxy group or an alkoxyalkoxy group are particularly preferred, such as vinyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(methoxy Ethoxy)silane and the like are preferred. Furthermore, vinylmethyljethoxysilane, vinylphenyldimethoxysilane, etc. can be used similarly.

In such a silicon-containing fluorine-containing copolymer [Ir], the content ratio of monomer components (a) to (C) is i)
Based on the total number of moles of ~(c), (a) is 30-7
0 mol%, preferably 40 to 60 mol%, (b
) is in an amount of 20 to 60 mol%, preferably 20 to 50 mol%, and (C) is in an amount of 1 to 25 mol%, preferably 3 to 20 mol%.

The molecular weight of this silicon-containing fluorine-containing copolymer [11] was determined by measuring by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and monodisperse polystyrene of known molecular weight as a standard substance. The number average molecular weight (Mn) is usually 3000 to 200.
000, mostly in the range of 4000 to 100 [100].

In addition, this silicon-containing fluorine-containing copolymer [11]
In addition, it is of poor quality or has low crystallinity, and in many cases it is of poor quality, and the degree of crystallinity by X-rays is generally 0%, and the degree of crystallinity by differential scanning calorimeter (
Often no melting point is observed in DSC). Therefore, this silicon-containing fluorine-containing copolymer [n] has good transparency.

In addition, this silicon-containing fluorine-containing copolymer [I[] is
When the glass transition temperature (Tg) is measured by DSC at a temperature increase rate of 10°C/min after cooling the sample to 120°C, it is usually in the range of -60 to +20°C, and often in the range of -40 to +5°C. . In addition, this fluorine-containing copolymer usually has a 1.4
They have refractive indices ranging from 8 to 1.34, often from 1.44 to 1.36.

Such silicon-containing fluorine-containing copolymers [n] can also be used at room temperature for example, aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as acetone and methyl ethyl ketone, diethyl ether, dipropyl ether, etc. It dissolves in ethers, alcohols such as ethanol, and halogenated hydrocarbons such as trichloromethane, dichloroethane, and chlorobenzene.

Therefore, a coating composition is prepared by dissolving a composition comprising the fluorine-containing copolymer [I] according to the present invention as described above and the fluorine-containing copolymer containing silicon [n] in the organic solvent as described above. It can be prepared.

When preparing a coating composition from the above-mentioned fluorine-containing copolymer [I] and silicon-containing fluorine-containing copolymer [■], toluene, xylene, butyl acetate, isobutyl methyl can be used as the organic solvent. It is preferable to use ketone, methyl cellosolve, ethyl cellosolve, or a mixture thereof.

Fluorine-containing copolymer containing silicon as described above [Ir]
Since it has a hydrolyzable organic group derived from the organosilicon compound (c), when it comes into contact with moisture, a cross-linking reaction occurs between the molecular chains of the polymer and it is cured. Therefore, as a matter of course, moisture in the atmosphere can also cause crosslinking. This silicon-containing fluorine-containing copolymer [1
It is clear that crosslinking will proceed even if 1] is used alone, but when used as a paint, a silanol condensation catalyst is added to the paint composition so that the fluorine-containing copolymer film applied to the base material cures quickly. It is preferable to add it to the product. In this case, a silanol condensation catalyst is added in advance to an organic solvent solution in which the silicon-containing fluorine-containing copolymer [■] and the fluorine-containing copolymer [I] according to the present invention are dissolved, and the silanol condensation catalyst is added to the base material. When applied to a surface, the organic solvent evaporates and comes into contact with moisture in the air, at the same time a curing reaction occurs and the film hardens.

Therefore, it becomes a one-component fluorine-containing copolymer coating composition.

As the silanol catalyst, known ones can be used, specifically, dibutyltin dilaurate, stannous acetate, stannous octoate, lead naphthenate, iron 2-ethylhexanoate, cobalt naphthenate, etc. carboxylic acid metal salt,
Organic bases such as ethylamine, hexylamine, dibutylamine, piperidine, and acids such as inorganic acids and organic fatty acids are used. Among these, alkyltin carboxylates such as dibutyltin diurarate, dibutyltin dioctoate, and dibutyltin diacetate are preferred.

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

When the fluorine-containing copolymer [I] according to the present invention and the silicon-containing fluorine-containing copolymer [II] are used as a coating material, it is preferable to use the one-component type as described above. This coating composition can be applied to the surface of substrates such as metal, wood, plastic, ceramic, paper, and glass using a brush, spray roller coater, etc. in the same way as ordinary liquid coatings.

The cured film has excellent weather resistance, chemical resistance, solvent resistance, water resistance, heat resistance, and low friction, as well as excellent transparency, gloss, and adhesion to the substrate.

That is, the film made of the fluorine-containing copolymer [I] and [I[] after curing (after being left for 14 days after application) is
K 5400 (1979) 6. Pencil hardness according to JIS 14 is usually 3H to 2B, often in the range of H-B.
K 5400 (1979) 6. The bending resistance according to No. 16 is usually 3 strokes φ, and most are 2 mφ or less.

Furthermore, the coating made of the fluorine-containing copolymers [1] and [■] after curing has a contact angle with water of usually 70 to 98°, often 78 to 94°, and a coefficient of static friction of usually 0.30 to 94°. 0
．． 60, mostly in the range of 0.35 to 0.50. Note that the coefficient of static friction here is calculated by cutting out a small piece of 3 an x 3 cm from a steel plate coated with a fluorine-containing copolymer and hardening it, and cutting it so that the coated film surface is in contact with a steel plate coated with the same polymer and hardened. A 145 g weight was placed on the small piece, one end of the steel plate was lifted, and the angle of inclination (θ) when the small piece slid down was determined, and tzn θ was taken as the coefficient of static friction.

The coating made of the fluorine-containing copolymers [I] and [II] after curing usually has a light transmittance of 95% or more, often 99%.
That's all. 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 adding drops of pure water. A quartz cell filled with JIS K 67 is used as a blank.
It was carried out according to 14.

Further, the cured coating made of the fluorine-containing copolymers [I] and [1] also has excellent adhesion to the substrate as described above. Here, the adhesion of the fluorine-containing copolymer to the substrate was evaluated as follows.

rllsK5400 on the surface of the coating film applied to the steel plate.
Cuts were made in accordance with 1979 General Test Methods for Paints 6.15 Base Test. Next, apply a width of 2
A piece of cellophane adhesive tape of 0.0 mm was applied, and the tape was brought into close contact with the surface of the coating film by rubbing strongly with a spatula having a width of 7 cm, and then the cellophane tape was rapidly pulled vertically upward and peeled off. This cellophane tape was adhered and peeled off a total of four times from each direction of the four sides of the base grains, and the number of base grains that remained without being removed was determined, and the test results were expressed as the number.

The fluorine-containing copolymer [I] according to the present invention can be produced by copolymerizing the above monomers (i) to (i) in the presence of a known radical initiator. Here, each of the components (1) to (i) must be present; for example, copolymerization does not occur with components (i) and (i) alone, but adding component (i) Components (1), (i), and (i) are copolymerized by this.

When producing the fluorine-containing copolymer [I] according to the present invention, various known radical initiators can be used. Specifically, organic peroxides, organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-16
N-butyl peroxide, 2,5-dimethyl-2,5-
Di(peroxybenzoate)hexyne-3,1,4-
Bis(tert-butylperoxyisopropyl)
Benzene, lauroyl peroxide, tel-butyl peracetate, 25-dimethyl-2,5-di(te
r t-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tel-butylperoxy)hexane, te+l-butylperbenzoate, te+t-
Butylperphenylacetate, 1er(-butylperisobutyrate, jcrt-butylperu1ee-octoate, 1erl-butylperpivalate, cumylperpivalate, 1ert-butylperdiethyl acetate, etc.), and other azo compounds such as azobis-isobutylnitrile. , dimethyl azoisobutyrate, etc. Among these, dicumyl peroxide, di-ten+-
Butyl peroxide, 25-dimethyl-2,5-di(t
e r f-butylperoxy)hexyne-3,2,
5-dimethyl-2,5-di(l e t + -butylperoxy)hexane, 1,4-bis(l er t-
Dialkyl peroxides such as butylperoxyisopropyl)benzene are preferred.

The copolymerization reaction as described above is preferably carried out in a reaction medium consisting of an organic solvent. Examples of such organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as rhohexane, cyclohexane, and n-heptane, and halogens such as chlorobenzene, bromobenzene, iodobenzene, and 0-bromotoluene. aromatic hydrocarbon, tetrachloromethane, 1. I,i
) Halogenated aliphatic hydrocarbons such as dichloroethane, tetrachloroethylene, and 1-chlorobutane can be used.

In the copolymerization reaction as described above, the radical initiator is added at a molar ratio of 1 to the total number of moles of monomers in the solvent as described above.
It is preferable to add in a range of 0.02 to 2.times.10'. The polymerization temperature is -30 to 200°C, preferably 20 to 200°C.
The polymerization pressure is 100° C. and 0 to 100 kg/cnf-G, preferably 0 to 50 kg/cd-G.

In order to further improve the affinity between the fluorine-containing copolymer [I] according to the present invention and organic pigments, a carboxyl group can be further introduced into the molecular chain of the fluorine-containing copolymer. Specifically, an unsaturated carboxylic acid and a derivative thereof may be graft-polymerized onto a fluorine-containing copolymer. 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, methyltetrahydrophthalic acid, endocys-bicyclo [2,2,11hept-5-ene-2,
3-dicarboxylic acid (nadic acid ■), methyl-endocys-bicyclo[2,2,II hept-5-ene-2,
Unsaturated carboxylic acids such as 3-dicarboxylic acid (methylnadic acid ■), halides, amides of the unsaturated carboxylic acids,
Imides, acid anhydrides, esters, ie maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, monoethyl maleate, diethyl maleate, and the like.

Note that the silicon-containing fluorine-containing copolymer [Ir] used in the present invention is also the same as the above-mentioned fluorine-containing copolymer [II
It can be manufactured in the same manner as.

As for the field of application of the fluorine-containing copolymer [1] according to the present invention, as described above, it is best to use it as a coating composition in the form of a solution in various organic solvents. In this case, pigments or dyes may be added to the paint composition to form a colored paint, and if necessary, various additives commonly added to synthetic resins may also be added. Further, the above-described fluorine-containing copolymer may be used as a modifier for resins having alkoxysilyl groups or silanol groups, such as silylated acrylic resins, silicone paints, and silylated polyolefins.

Effects of the Invention The fluorine-containing copolymer [II of the present invention: (i) dissolves in an organic solvent at room temperature; (i) the curing reaction proceeds at room temperature in the presence of moisture; (i)
It has excellent transparency and, after curing, has excellent properties such as weather resistance, chemical resistance, mechanical properties, low friction, and adhesion to substrates. When used in combination with copolymer [1], (IV) it can be used as a one-component paint, (V) it does not require a baking process even though it is a fluorine-based paint, and (vl) it has good adhesion to the substrate. It exhibits characteristics such as superior performance. Therefore, it can be used as a coating agent for metals, wood, plastics, ceramics, paper, etc., and as a surface coating for optical fibers, optical disks, and liquid crystal display substrates.

〔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 are possible without impairing the purpose of the present invention. .

Example 1 The inside of a 1.51 autoclave equipped with a stirrer was replaced with nitrogen,
Benzene 180ml under nitrogen stream, ethyl bee/l/
x-thyl (EVE) 106g, n-butyl vinyl ether (BVE) 21.0g, trimethoxyvinylsilane (TMVS) 62.2g, synthetic hydrotalcite (M
g Al1 (OH) 1365 co ・3.5820) Powder fired product (SHT) 13
．． 0g was charged. Thereafter, 257 g of chlorotrifluoroethylene (CTFE) was introduced into the autoclave, and the temperature was raised to 65°C.

An initiator solution of 7.6 g of dilauroyl peroxide dissolved in benzene 1201 was added to the mixture thus obtained.
I took my time to feed it. After further reacting at 65° C. 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 1.51 eggplant flask.

Add 210 g of xylene and 120 g of methanol to this reaction solution.
, 5H713,Og were added thereto, and the mixture was heated at 50°C for 1.5 hours and then 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 366 g of a colorless and transparent polymer.

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

Furthermore, when the composition of this polymer was analyzed using elemental analysis and NMR, it was found that CTFE/EVE/BVE/TM
VS=50/37/6/7 (molar ratio).

A paint was prepared consisting of 38.2 parts by weight of the polymer obtained by the above method, 1.9 parts by weight of tetramethylorthosilicate oligomer, 26.7 parts by weight of titanium oxide, and 31.3 parts by weight of xylene.

On the other hand, after replacing the interior of a 1.51 stainless steel autoclave with a stirrer with nitrogen, 500+ benzene was added under a nitrogen stream.
I, 4-hydroxybutyl vinyl ether (HBVE)
23.2 g, ethyl vinyl ether (EVE) 50
．． 5g, cyclohexylvinyl x-thyl (CyHVE)
12.6 g1 dilauroyl peroxide I, sg, and 2.1 g of potassium carbonate were charged.

Next, chlorotrifluoroethylene (CT F E) 1
16.5g was introduced into an autoclave and the temperature was raised to 65°C. After reacting at 65° C. for 7.5 hours, the autoclave was cooled with water to stop the reaction. Thereafter, it was concentrated under reduced pressure to obtain 193.7 g of a colorless and transparent polymer [111r]. The number average molecular weight of the obtained polymer was determined by GPC to be 10,000.

In addition, compositional analysis of the polymer was performed using elemental analysis and NMR, and it was found that CTFE/EVE/HBVE/CyH
VE=48/36/6/10.

To 100 parts by weight of the paint prepared by the above method, 5.5 parts by weight of a 69.6% by weight xylene solution of the polymer [III] obtained by the above method, and 6.5 parts by weight of a 69.6% by weight xylene solution of the polymer [III] obtained by the above method, and 6.5 parts by weight of a 69.6% by weight xylene solution of the polymer [III] obtained by the above method. A fluorine-containing copolymer composition was prepared by mixing 3.8 parts by weight of a 3% by weight xylene solution, and this composition was applied to a 100 μm thick coating on a coating film produced in the same manner as in Example 1.
It was applied using an 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 After replacing the interior of a 1.51 stainless steel autoclave with a stirrer with nitrogen, 500 ml of benzene, 3 Q g of allyl acetate (AA c), 86.5 g of ethyl vinyl ether (EVE), and 5 g of dilauroyl peroxide were added under a nitrogen stream.
．． I prepared 4g.

Then, chlorotrifluoroethylene (CTFE)18
3g was introduced into an autoclave and the temperature was raised to 65°C. After reacting at 65° C. for 7.5 hours, the autoclave was cooled with water to stop the reaction. Thereafter, it was concentrated under reduced pressure to obtain 254 g of a colorless and transparent polymer.

The number average molecular weight of the obtained polymer by GPC was 120.
It was 00.

Furthermore, when the composition of this polymer was analyzed using elemental analysis and NMR, it was found that CTFE/EVE/AAc=43
/49/8 (mol%).

200 g of the polymer obtained by the above method was dissolved in 234 g of xylene in 11 glass reactors equipped with a stirrer.
After heating to 0° C., 106 g of a 1.6% methanol solution of sodium methoxide was added over 3 hours, and the mixture was further stirred for 1 hour. Methanol and the produced methyl acetate were distilled off under reduced pressure, and the mixture was cooled.

This concentrate is 1.5! The procedure of reprecipitating in methanol, removing the supernatant liquid, adding methanol 11 and stirring was repeated four times.

Methanol was distilled off under reduced pressure, and 11 xylene was added.
The mixture was filtered through a 2μ membrane filter and concentrated to obtain 120 g of a copolymer hydrolyzate. As a result of measuring the IR spectrum of the hydrolyzate, the absorption of ester completely disappeared;
New absorption of hydroxyl groups was observed.

A paint was prepared consisting of 39.7 parts by weight of the polymer obtained by the above method, 27.8 parts by weight of titanium oxide, and 32.5 parts by weight of xylene.

On the other hand, galvanized steel sheet (SP) specified in JIS G3302
G) Epoxy paint Marine SC (Mitsui Metal Paint Chemical ■)
A base material for coating was prepared by applying the above and exposing it outdoors for 10 days.

Coronate EH (isocyanate curing agent manufactured by Nippon Polyurethane Co., Ltd., hexamethylene diisocyanate cyclic trimer) was added to 100 parts by weight of the paint prepared as described above.
29.6 parts by weight of a 60% by weight xylene solution, and 3 parts by weight of a 6.3% by weight xylene solution of n-butyltin dilaurate.
．． A fluorine-containing copolymer composition was prepared by mixing 8 parts by weight,
This composition was applied to the coating substrate prepared by the above method for 10 minutes.
Application was performed using a 0 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.

Comparative Example 1 3.8 parts by weight of a 6.3% by weight xylene solution of n-butyltin dilaurate was mixed with 100 parts by weight of the paint prepared in Example 1 to prepare a fluorine-containing copolymer composition.

On the other hand, 10
Application was performed using a 0 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.

table

Claims (4)

[Claims] (1) [A] (i) Units derived from fluoroolefins, (ii) Units derived from vinyl ethers, and (iii) Units represented by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, X is a hydrogen atom or a -COR group (wherein R is an alkyl group, and n is a number from 1 to 20); (ii) and (
With respect to the total number of moles of (iii), (i) is present in an amount of 30 to 70 mol%, (ii) is in an amount of 20 to 60 mol%, and (i)
ii) is in an amount of 1 to 25 mol%, and has a number average molecular weight (@M@_n) of 3000 to 2 as measured by [C] gel permeation chromatography.
00000. (2) A coating composition prepared by dissolving the fluorine-containing copolymer according to claim 1 in an organic solvent. (3) [I] [A] (i) Units derived from fluoroolefins, (ii) Units derived from vinyl ethers, and (iii) Units expressed by the following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( [B] Forming the copolymer ( i), (ii) and (
With respect to the total number of moles of (iii), (i) is present in an amount of 30 to 70 mol%, (ii) is in an amount of 20 to 60 mol%, and (i)
ii) is in an amount of 1 to 25 mol%, and has a number average molecular weight (@M@_n) of 3000 to 2 as measured by [C] gel permeation chromatography.
00000, and [II] [A] (a) fluoroolefin (b) vinyl ether (c) an olefinic unsaturated bond and a hydrolyzable group; A copolymer of an organosilicon compound comprising: [B] (a), (b) and (c) forming the copolymer;
), (a) is in an amount of 30 to 70 mol%, (b) is in an amount of 20 to 60 mol%, and (c) is in an amount of 1 to 60 mol%.
25 mol%, and the number average molecular weight (@M@_n) measured by [C] gel permeation chromatography is 3000 to 2
1. A solvent-soluble fluorine-containing copolymer composition comprising a solvent-soluble fluorine-containing copolymer, characterized in that the fluorine-containing copolymer composition is within the range of 00,000. (4) A coating composition obtained by dissolving the fluorine-containing copolymer composition according to claim 3 in an organic solvent.