JPS6067518A - Fluorine-contained copolymer and its composition - Google Patents

Abstract

PURPOSE:A solvent-soluble fluorine-contained copolymer providing a film having improved heat resistance, antifouling properties, etc. after curing, comprising a specific fluorovinylene structural unit and a functional vinylene unit. CONSTITUTION:The desired copolymer comprising (A) a structural unit shown by the formula I (X is F, or Cl), (B) one shown by the formula II (X<1> and X<2> are F, or CF3; Y is H, Cl, or F; n is 1-3; m is 0-6 integer) (with the proviso that 2,2,3,3-tetrafluoropropyl vinyl ether is omitted), and (C) one shown by the formula III (Z is OH, or group shown by the formula IV; p is 2-5 integer). A curtable composition is obtained from this copolymer and a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a crosslinkable fluorine-containing copolymer with excellent solvent solubility, and a curing composition comprising this copolymer and a curing agent.

Conventional fluorine-containing polymers have been used in a variety of applications that take advantage of their excellent properties such as chemical resistance, stuttering resistance, stain resistance, and heat resistance.

However, when this fluoropolymer is used in a room-temperature curing paint, for example, this fluoropolymer has poor solubility in ordinary solvents, and even when it can be dissolved, the types of solvents that can be used are limited. In addition, these solvents have high boiling astringency,
Because of this, it has drawbacks such as the need for heat treatment at high temperatures to remove coating solvents.

In order to solve the above-mentioned drawbacks, various fluorine-containing copolymers have been researched, and fluoroolefins have been developed for the purpose of room-temperature curing paints. , cyclohexyl vinyl ether and other copolymerizable monomer components have been proposed (JP-A-55-25414, JP-A-57-841).
No. 07 and Japanese Unexamined Patent Publication No. 57-84108). However, all of the above copolymers have insufficient heat resistance and stain resistance, and have improved solvent solubility at the expense of the properties of fluorine-containing polymers.

Therefore, the present inventors developed a fluorine-containing copolymer that has sufficient heat resistance, weather resistance, stain resistance, and chemical resistance, has good solvent solubility, and can be easily cured at room temperature when mixed with a curing agent. As a result of intensive research on coalescence, it was discovered that a fluorine-containing copolymer having a specific structural unit satisfies the above properties, and the present invention was completed.

That is, the gist of the present invention is the structural unit: a) -CFX-CF2- (xFiF''!! or C1.) (Xl and x2 are the same or different and represent F'' or CF
s, Y is H%CI or FiFs n is 1~Bm is 0~6
indicates an integer. ) and c) -CHx -CH- 0-(CHg)pZ Indicates an integer. ) (excluding 2.2.8.8-tetrafluoropropyl vinyl ether in component b)) and a cured composition comprising the above fluorine-containing copolymer and a curing agent. exists in

The fluorine-containing copolymer according to the present invention usually contains 40 to 60 mol% of the component a), and the monomer forming the basis of the component a) is usually tetrafluoroethylene or tarolotrifluoroethylene. It is.

Component a) in the copolymer is 40 to 60 mol% as described above.
When it is contained, the copolymer has good heat resistance and weather resistance.

Specific examples of monomers that are usually the basis of component b) include CH2=CH0CIhCFs, CH2=CH0CHg
CF tCF@, CH2=CHOCH2(CFg)z
cFB, CH2=CHOCH2(CF2)gcFs, C
H2=CH0CH2(CF2)4CF8, CI(2=C
HOCH2(CFg)6CF,, CH2=CH0CH2
(CF2)4 CF[l, CHg=CHOCHgCFt
CF2H, CH2=CHOCHg (CFgCFlri2H
SCH2=CHOCH2(CF2CF2)sH,CH2
=CH0CH2HOCH2(CF2)4C name, CH2=
CH0CH2CH2CFa, CH2=CH0CH2CH
2CF2CFa, CH2=CH0CH2CH2(CF2
)2CFs, CHg=CH0C port 2CH2 (CF2)
8CFB, CH2=CH0C2H2(CFg)4CF
s, CH2=CH0CH2CH2(CF2)6CF8,
CH2=CH0C2Hg(CFg)gcFs, CH! =
CH0CH2cH2cF2cF2H% CH2=CHO
CHtCHg(CFgCFg)zH1CHz=CHOC
H2CHg(CFgCFg)sH, CHg=CHOCH
2CHzHg=CHOCHgCHgCIhCFtCFs
, CHg=CHOCH2CH2 or more are used.

In the general formula of component b), cases where m is 4 or more and n is 7 or more are not advantageous in terms of physical properties or synthesis, and are therefore excluded, but it is of course possible to use these vinyl ethers.

The amount of component b) contained in the copolymer is 20 to 5
A range of 0 mol % is preferable in order to obtain solvent solubility, heat resistance, stain resistance, etc.

Specific examples of monomers that are the basis of component C) include C)
H2=CH0CH2CH20H, CH2=CH0CH2
CH2CHzOH, CHg=CH0(CHz)40H,
CH2=CH0(CH2)i.

Or two or more types are used.

Since component C) has the function of curing the cured composition according to the present invention by performing a crosslinking reaction with the curing agent, the copolymer content of component C) is appropriately determined so as to satisfy the desired physical properties of the cured product. is usually preferably in the range of 0.5 to 30 mol%, and 2 to 30 mol%.
A range of 20 mol% is more preferred.

In addition to the constituent components of the copolymer of the present invention, CH, =C
F2,CHF=CF2,CH,=CHF%CF2=C
FCF8,CF2=CFOCF8,CF2=CFO
Fluorine-containing monomers such as CF2CF, CF=CFOCIIF7, CH2=CH0CHa, CH2=CHOC
2Ha, CH2=CH0C8H7, CH2=CH0C2
It is also possible to copolymerize other hydrocarbon monomers.

The solvent solubility of the copolymer of the present invention is particularly influenced by the fluorine content of the fluoroalkyl group of the component (a) of the acid components. When the fluorine content of the fluoroalkyl group is low, the polymer of the present invention can be used in NTE 1V solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and cellosolve acetate, acetone, and aromatic hydrocarbon solvents such as toluene and xylene as a medium. It can be used within the range of 0 to 80 weight percent relative to the solvent. When the fluorine content of the fluoroalkyl group is high, cyclic ethers such as tetrahydrofuran, N,N-dimethylformamide, N,N, which are more polar than the ester-based or ketone thread solvents, are used.
-Amides such as dimethylacetamide, methyl alcohol, ethyl alcohol-/I/1 Easily dissolves in alcohols such as butyl alcohol. The solubility in a solvent is also influenced by the amount of component C), and as the amount of component C) increases, it becomes easier to dissolve in polar solvents.

As a method for producing the copolymer of the present invention, any method such as solution polymerization, suspension polymerization, or emulsion polymerization can be used. , a redocne polymerization initiator using the persulfate and a sulfite such as potassium sulfite or sodium sulfite and/or an acidic sulfite such as acidic potassium or sodium sulfite, Jimmy propyl peroxydicarbonate, rubutyl peroxy Peroxide-based polymerization initiators such as bunarate or benzyi V peroxide, azo thread polymerization initiators such as azobinuisoptilonitrile, and the like are preferably used. The amount of polymerization initiator used is usually 0.01 to 5% based on the total amount of the monomers.
The weight is preferably 0.05 to 1.0% by weight.

Polymerization temperature [7] -20 to 150°C, preferably 5 to 150°C
The 95°C1 polymerization pressure is θ~80 kg, -〇, preferably 10 kg/G or less.

The solvent used for solution polymerization is trichlorol-I7fluoroethane%l, 1. l, 2-tetrachloro-2
, 2-difluoroethane, methyl V ethyl ketone, methyl isobutyl ketone, ethyl acetate, propy V acetate, etc. are used depending on the solubility of the above-mentioned copolymer.

Examples of emulsifiers used in emulsion polymerization include ammonium salts and sodium salts such as perfluorocarboxylic acid and ω-hydroper 7M orocarboxylic acid.

The curing agent blended into the curing composition of the present invention is -2°C~
Any material can be used as long as it reacts with hydroxyl groups and epoxy groups in the temperature range of 200°C and has a crosslinked structure, and the reaction temperature is preferably in the range of 5 to 150°C, except in special cases. used.

As examples of curing agents that react with hydroxyl groups and epoxy groups, the following curing agents can be used, but the curing agents are not limited thereto.

[Curing agent example]

A compound having the following structural formula.

(In the formula, MXr, l+n BF4, PFa%5bF
s, m#-1: integer, A represents an organic substituent.) AICIIs, 5bClls, BFs,
BCIIs, BeC15, Fecllx.

FeBrs, Tice4. ZnC1z,
Alcohols such as methylated alcohol, isobutyl alcohol, and isobutyl alcohol, which are made by methylolizing melamine resin lamin such as PFs.
Compounds obtained by converting ether to V with V, urea resins, compounds formed by condensing urea and formaldehyde, and compounds having an epoxy group or incyanate group consisting of the structural formula shown below (Lzo, lower, 6th group) \: 81 roll) 13- Product name [EPE-1859J (manufactured by Ciba Geigy) r
QT-8476J (manufactured by Dow Chemical Company) 14-Hs 0 Product name [Epon 1081 J "ERRA-0158J (manufactured by UC, C Company) 1 Product name rDEN4881 (n=1.8) rDEN4
89J "Epicoat 152J (Io=0-1)"Ebiko
154 J (n=1.5 or more) or more (manufactured by Shell Chemical Co., Ltd.) Tolylene diisocyanate (TDI) 8.8A-Tolylene-4,4'-diisocyanate diphenylmethane-4,4'-diisocyanate (MD
I) Triphenylmethane-P,P',P'-1-diisocyanate (TM) GO 2,4-tolylene timer (TT) 17-naphthalene-1,5-diisocyanate CN Tris(4-phenylisocyanate) thiophosphate product Desmodur RFJ (manufactured by Bayf L/Company) crude (MDI) CO 1g- TDI trimer CHs dicyclohexameta2-4,4'-diisocyanate) (
HMDI) Hydrogenated TDI (HTDI) Kan〉ICO Metaxylene diisocyanate (XDT), Hexahydrometaxylene diisocyanate 1-(HXDI) Hexamethylene diisocyanate (HMD I) OC
N -CHz CH2CHx CHz CH2CH2-
NGO trimethylpropane-1-methyl-2-isocyano-4-cababamate Trade name Desmodur L J (Bayer AG tn) Polymethylene polyphenylisocyanate n = Q~
3 Product name 1'-PAPIJ 8. 3'-dimethoxy-4,4'-diphenyl diisocyanate Product name "DADIJ Diphenyl ether, -2,4,4'-triisocyanate 2l- C) I2 Hot O CH3 Product name 11) esmodur THJ (manufactured by Bayer) ■ O H (CH2) @ GO Product name: “Degmodur HHJ (manufactured by Bayer)
Furthermore, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic anhydride (HHPA), tetrahydrophthalic anhydride (HHPA), 8.6-nindomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride II, 3.6-nindomethylenetetrachlorophthalic anhydride, l 23- Adipic acid HOOC(CH2)4 C0OH Sepatic acid HOOC(CH2)s C0OH Ethyleneamine group Hz N (CHz CH2NH)□1HN-Aminoethylpuberazine metaxylylenediamine 1.8-His(aminomethyl)cyclohexane 25- 24- Paramethanediamine CHz Metsphoronediaminebis-(4-amino-3-methylcyclohexyl)methanemethphenylenediamine 26-4.4'-Diaminodiphenylmethane 4.4'-Diaminodiphenylnulfonediaminodiphenyl ether melamine NH.

11 Pyromet acid etc.

(1.4 engineering, tb 鐸国 1ζ栴剋KU) 27- The above-mentioned curing agent can be used in an amount of 0.5 to 2 equivalents based on the functional group of the copolymer. At this time, it is also possible to use curing accelerators such as amine compounds and organometallic compounds.

Pigments, viscosity modifiers, leveling agents, anti-gelling agents, ultraviolet absorbers, anti-scald agents, etc. can also be added to the copolymer of the present invention as a curing composition, and these can be added by ball milling,
It can be mixed using equipment commonly used for mixing paints, such as sand mills, paint shakers, and triple rolls.

The curing composition of the present invention can be cured in several minutes to several days by appropriately selecting the content of hydroxyl groups or epoxy groups, the type of curing agent, the curing temperature, etc. When using the composition as a coating material, Heat resistance, stain resistance, chemical resistance,
A coating film with good weather resistance can be formed.

The cured composition of the present invention is used as an outdoor or indoor paint on metal, wood, concrete, glass, plastic, etc., and is used in fields where the chemical resistance, weather resistance, stain resistance, heat resistance, etc. of the paint film are utilized. 29-121i'-I can use it. Further, since the cured composition of the present invention has high transparency and a refractive index in the range of 1.35 to 1.45, it can also be used as a sheath material for optical fibers. Further, the cured composition of the present invention has a volume resistivity of 1013 to 10170·■, has high triboelectric charging properties, and has good stain resistance, and is therefore useful as a carrier coating material for electronic copying machines.

Next, the copolymers and compositions of the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 A 1000 rnl glass autoclave 1 was charged with 850 g of ion-exchanged water, 1 g of carbonic acid, and 1 g of thorium, and the space was sufficiently replaced with nitrogen gas to remove oxygen. 2.2.2 = ) 25.5 g of fluoroether vinyl ether, hydroxybutyl vinyl ether/
L'5.8g and 70-mouth trifluoroethylene 80g
I prepared it. Heat to 45°C without stirring, and add 0% diisopropyl peroxydicarbonate as a polymerization initiator.
．． 85 g was added and polymerized at the same temperature for 8 hours.

30- The pressure at the start of polymerization was 2.1 kg/lry G, and after the end of polymerization it was 0.2 kg/lry G. The polymer is trichloro1
- It was dissolved in refluoroethane, and this was added to petroleum ether with stirring and reprecipitated. Thereafter, the polymer was dried under reduced pressure to obtain 48 g of polymer (polymerization rate: 80%).

The intrinsic viscosity of the obtained polymer at 35°C in methyl ether ketone was 0.88 (dsig), and the thermal decomposition temperature (weight loss in air at a heating rate of 10°C/min) was 0.88 (dsig). % temperature) is 3
The glass transition temperature measured using a differential scanning calorimeter (hereinafter referred to as DSC) at 70°C (heating rate 10°C/min) was 5.
It was 3°C.

In addition, the obtained polymer was subjected to infrared absorption analysis and the presence of hydroxyl groups was confirmed, and the hydroxyl groups were quantitatively determined using the acetic anhydride-pyridine method (JIS KOO70).
There was a hydroxyl group corresponding to the mol% content @ When the overall composition of the copolymer was analyzed by elemental analysis, it was found that carbon was 31.7%, fluorine was 42.9%, and chlorine was 15.0%. %, and the resulting copolymer is approximately chlorotrifluoroethylene/trifluoroethyl vinyl ether/hydroxybutyl vinyl ether-5/4/1 (mol/
It was found that it was a copolymer of L/).

Examples 2 to 15 Each monomer shown in Table 1 was copolymerized in the same manner as in Example 1. Table 1 shows the composition, intrinsic viscosity, thermal decomposition temperature and glass transition temperature of the obtained copolymer. The monomers were copolymerized. Composition and intrinsic viscosity of the obtained copolymer.

The thermal decomposition temperatures and glass transition temperatures are shown in the same Table 2.

Table 2 34- The constituent monomers of each copolymer in Tables 1 and 2 are abbreviated as shown.

CTFE = Chlorotrif/L/Oroethylene 8FVB
=2.2.2-) Lifluoroethyl vinyl ether 4F
VE = 2.2,8.8 ~ Tetrafluoropropyl vinyl 7 ether 5FVE = 2.2, 8, 8.8 Bentafuloprohyro(vinyl ether 6FVE = 2.2,
8,4,4,4△ki+7A/oroptirubi=iVl
-f 1ly7FVE=2dolifluoromethi/L'-2
, 8,8,8 tetrafluoropropyl vinyl ether 8FVE = 2.2,8,8,4,4,5.5-octa71L/orohentyl vinyl ether 18FVB = 2.2,8. a, 4, 4, 5, 5, 6,
6,7,7.7dolidecafluorononyl vinyl ether TFE -tetrafluoroethylene HBVE = hydroxygutyl vinyl ethyl GVE =
glycidium vinyl ether MVE - methylvinyl ether EVE = ethyl vinyl ether PrvE - propyl vinyl ether BVE - butyl vinyl ether 1 BVE - isobutyl vinyl A/, : 11 - thyl Copolymers shown in Examples and copolymers shown in Comparative Examples As is clear from comparing the glass transition temperature and thermal decomposition temperature of , the fluorine-containing copolymer of the present invention has excellent heat resistance properties.

Next, Examples of cured compositions will be shown to explain the features of the copolymer of the present invention.

Example] 6 The copolymer obtained in Example 1 was dissolved in a mixed solvent of methyl ether ketone and butyl acetate (1/1 weight) to prepare a copolymer having a weight of 20 weight. Said solution 10
7 parts by weight of Dinumodur TP-KL5-2444 (manufactured by Sumitomo Bayer), which is a hexamethylene diisocyanate trimer, and 1 part by weight of triethylamine were added and thoroughly mixed with respect to the weight of zinc phosphate, treated 0,
A 5 m steel plate (Nippon Tent Panel Co., Ltd.) was spray-painted and cured at room temperature for 3 days. The obtained cured coating film was a glossy, hard coating film with a thickness of 38 μm.

Table 5 shows the chemical resistance, solvent resistance, boiling water resistance, and stain resistance of the paint films obtained in Examples 16 to 29 and Comparative Examples 12 to 19.

! l! Examples 17 to 29 Paint films were obtained in the same manner as in Example 16 using the curing agents and copolymers shown in Table 3.

(P person': Sho-white, ; Central 1i1 = Shake no 87- Table 8 -3? r- Comparative Examples 12-19 The following coating film trial was prepared in the same manner as in Example 16.

Table 4 Table 5 From these results, it can be seen that chemical resistance, solvent resistance, and stain resistance are excellent.

that's all Patent applicant: Daikin Industries, Ltd.

Claims (1)

[Claims] 1. Structural unit: a) -CFX -CF2- (X represents F or C1) (Xl and x2 are the same or different, F or CF,
, Y represents H, CI- or F, n represents an integer of 1 to 8, and m represents an integer of θ to 6. ) and c) -CH2-CH- o-(cHg) pz (However, in component b) 2.2.8.8-tetrafluoropropyl e'; This is the same as the 7 series. (Engineering/Irishitai Jinpaku Takajo (2 μ anti-ko) 2, Structural unit a) -CFX-CFz - (X indicates F or CI.) (Xl and X2 are the same or different, F or FiCF
,, Y is H, CI''! or F, n is 1 to 8, m is θ to 6
indicates an integer. ) and c) -CH2-CH- 0-(CH2)pZ (with the exception of 2.2.8.8-tetrafluorofuvir vinyl ether e< in component b). ) and a curing agent.