JP2002327018A - Fluorine-containing copolymer, composition and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing copolymer which has excellent adhesion to a non-fluorine polymer and gives a laminate with the polymer by co- extrusion molding and to provide the laminate. SOLUTION: The copolymer contains a polymer unit of (A) tetrafluoroethylene or chlorotrifluoroethylene, (B) ethylene, (C) vinyl acetate and (D) a compound represented by the formula CH2 =CX(CF2 )n Y (X and Y are respectively a hydrogen atom or fluorine atom, n is an integer of 2-10) at the molar rate of A/B=1/4-4/1, C/(A+B)=1/1000-3/20, D/(A+B)=1/1000-3/20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorinated copolymer having excellent adhesion to a non-fluorinated polymer and a laminate containing the same.

[0002]

2. Description of the Related Art Fluoropolymers such as polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer and ethylene / tetrafluoroethylene copolymer (hereinafter referred to as ETFE) have heat resistance. It has excellent properties such as chemical resistance, weather resistance and gas barrier properties, and is used in various fields such as the semiconductor industry and the automobile industry. With the spread of applications, development of fluoropolymers having characteristics such as higher rigidity and higher strength than usual has been demanded. As one of the development means, there is a method of laminating a fluorine-based polymer and a non-fluorine-based polymer.

[0003] Fluoropolymers are usually surface-treated by a method such as chemical treatment, corona discharge treatment, plasma discharge treatment and the like to introduce various adhesive functional groups to the surface, and then, if necessary, using an adhesive. Laminated with other materials. However, such a lamination method requires complicated steps and low productivity. Therefore, it is desirable to obtain a laminated film or a laminated hose without a surface treatment of the fluoropolymer and using a simpler molding method such as a co-extrusion method.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorine-containing copolymer and a fluorine-containing copolymer composition which are excellent in adhesiveness to a non-fluorine-based polymer and give a laminate by a co-extrusion method.
Another object of the present invention is to provide a laminate in which a fluorinated copolymer and a non-fluorinated polymer are firmly bonded.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a tetrafluoro compound.
Heavy based on ethylene or chlorotrifluoroethylene
Combined unit (A), polymerized unit based on ethylene (B), acetic acid
Polymerized units (C) based on vinyl and the general formula CH₂= CX
(CF₂)_nY (where X and Y are each independently hydrogen
And n is an integer of 2 to 10.
You. ) Containing a polymerized unit (D) based on the compound represented by
(A) / (B) is a mole of
The ratio is 20/80 to 80/20, and (C) / ((A)
+ (B)) is 1/1000 to 15/100 in molar ratio.
(D) / ((A) + (B)) is 1/100 in molar ratio.
0 to 15/100 and the volume flow rate is 1 to 1000
mm ³/ Sec.
provide.

Further, the present invention relates to the above-mentioned fluorine-containing copolymer 1
0.01 to 10 parts of an organic peroxide is compounded with respect to 00 parts, and a fluorinated copolymer composition characterized by being heat-treated, and a layer of the fluorinated copolymer composition. A laminate comprising a non-fluorine-based polymer layer. In this specification, “parts” means “parts by mass”.

In the present invention, a polymerization unit (A) based on tetrafluoroethylene (hereinafter referred to as TFE) or chlorotrifluoroethylene (hereinafter referred to as CTFE) and a polymerization unit based on ethylene (hereinafter referred to as E). The molar ratio of B) is from 20/80 to 80/20, preferably from 50/50 to 70/30. (A) /
If the molar ratio of (B) is too small, the heat resistance, weather resistance, chemical resistance, gas barrier properties, etc. of the fluorinated copolymer will decrease, and if the molar ratio is too large, the mechanical strength, melt moldability, etc. will decrease. . TFE and CTFE may be used alone or in combination.

In the fluorine-containing copolymer of the present invention, the content of the polymerized unit (C) based on vinyl acetate (hereinafter referred to as VOAc) is (C) / ((A) + (B)) in a molar ratio. 1/1000 to 15/100, preferably 1 /
It is 100 to 1/10. If the content of (C) is too small, the adhesion between the fluorinated copolymer and the non-fluorinated polymer will be reduced, and if it is too large, heat resistance, oil resistance, chemical resistance, etc. will be reduced.

In the fluorine-containing copolymer of the present invention, the content of the polymerized unit (D) based on the compound represented by the general formula CH ₂ ＣCX (CF ₂ ) _n Y (hereinafter referred to as FAE) is as follows: D) / ((A) + (B)) is 1/10 in molar ratio
00 to 15/100, preferably 1/100 to 3
/ 100. If the content of (D) is too small, crack resistance decreases, and a destructive phenomenon such as cracking of the fluorinated copolymer tends to occur under stress. If the content is too large, the strength of the fluorinated copolymer decreases. .

[0010] FAE, as described above, the general formula _CH 2 =
A compound represented by CX (CF ₂ ) _n Y (where X and Y are each independently a hydrogen atom or a fluorine atom, and n is an integer of 2 to 10). As FAE, C
_{H 2 = CF (CF 2)} 4 F, CH 2 = CF (CF 2) 5
_{F, CH 2 = CF (CF} 2) of ₅ H such as _CH 2 = CF (C
Although a compound represented by F ₂ ) _n Y can be used, CH ₂ =
CH (CF ₂ ) ₃ F, CH ₂ ＣＨCH (CF ₂ ) ₄ F, C
H ₂ ＣＨCH (CF ₂ ) ₄ H, CH ₂ ＣＨCH (CF ₂ ) ₅
CH ₂ ＣＨCH (C such as F, CH ₂ ＣＨCH (CF ₂ ) ₈ F
A compound represented by F ₂ ) _n Y is preferable, and CH ₂ ＣＨCH
A compound represented by (CF ₂ ) _m F (m is an integer of 2 to 8) is more preferable.

The volume flow rate (hereinafter referred to as Q value) of the fluorinated copolymer of the present invention is from 1 to 1000 mm ³ / sec. The Q value is an index indicating the melt fluidity of the fluorinated copolymer and serves as a measure of the molecular weight. A large Q value indicates a low molecular weight, and a small Q value indicates a high molecular weight. The Q value in the present invention was measured at a temperature of 2 using a flow tester manufactured by Shimadzu Corporation.
This is the extrusion rate of the fluorocopolymer when it is extruded into an orifice having a diameter of 2.1 mm and a length of 8 mm under a temperature of 97 ° C. and a load of 7 kg. If the Q value is too small, extrusion molding becomes difficult, and if it is too large, the mechanical strength of the fluorocopolymer decreases. Q value is preferably 10 to 500 mm ³ / sec.

The fluorinated copolymer of the present invention preferably has a molding temperature close to the molding temperature of the non-fluorinated polymer so that it can be co-extruded with the non-fluorinated polymer. Therefore, it is preferable to appropriately adjust the content ratio of (A), (B), (C) and (D) within the above range to optimize the molding temperature of the fluorinated copolymer.

The method for producing the fluorine-containing copolymer of the present invention is not particularly limited, and a polymerization method using a generally used radical polymerization initiator is used. As the polymerization method,
Bulk polymerization, solution polymerization using an organic solvent such as a fluorocarbon, chlorohydrocarbon, fluorinated chlorohydrocarbon, alcohol, hydrocarbon, suspension polymerization using an aqueous medium and an appropriate organic solvent if necessary, Emulsion polymerization using an aqueous medium and an emulsifier is exemplified.

The radical polymerization initiator has a half-life of 1
The decomposition temperature at 0 hours is preferably 0 ° C to 100 ° C,
0-90 degreeC is more preferable. Specific examples include azo compounds such as azobisisobutyronitrile, non-fluorinated diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, and lauroyl peroxide, and peroxydioxides such as diisopropylperoxydicarbonate. Carbonate, t
Peroxyesters such as tert-butylperoxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, (Z (C
F ₂ ) _p COO) ₂ (where Z is a hydrogen atom, a fluorine atom or a chlorine atom, and p is an integer of 1 to 10.)
And inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate.

The polymerization conditions are not particularly limited.
C. to 100 C. are preferred, and 20 to 90 C. are more preferred. The polymerization pressure is preferably 0.1 to 10 MPa, and 0.5 to 10 MPa.
-3 MPa is more preferable. The polymerization time is preferably 1 to 30 hours.

An organic peroxide is blended with the fluorinated copolymer of the present invention and then heat-treated (modified fluorinated copolymer, fluorinated copolymer compound, fluorinated copolymer) A polymer blend is also preferred, since the adhesiveness to a non-fluorinated polymer is further improved as compared with a fluorinated copolymer.

The organic peroxide used here includes:
The decomposition temperature at which the half life is 1 minute is preferably from 150 to 280C, more preferably from 170 to 240C. Specific examples include 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, ditert-butyl peroxide, and 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3. Aliphatic peroxides such as 1,4-bis (α-tert-butylperoxyisopropyl) benzene, aromatic peroxides such as tert-butyl cumyl peroxide, dicumyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, benzoyl Diacyl peroxides such as peroxides, peroxydicarbonates such as diisopropylperoxydicarbonate, alkylperoxyesters such as tert-butylperoxyisobutyrate, and hydropeides such as tert-butylhydroperoxide. Oxides, and the like. The organic peroxide can be used in liquid or solid form. The amount of the organic peroxide is 0.01 to 10 parts, preferably 0.1 to 5 parts, per 100 parts of the fluorinated copolymer.

As a method of blending an organic peroxide with the fluorinated copolymer and heat-treating the mixture, the organic peroxide is mixed with the powdery or particulate fluorinated copolymer using a mixer. The method of melt extrusion is preferred. When this method is used, the organic peroxide is added to the fluorine-containing copolymer and heat-treated at the same time, whereby a pellet-shaped fluorine-containing copolymer composition is obtained. The heat treatment temperature is preferably from 150 to 280 ° C, and is from 220 to 280 which is higher than the melting point of the fluorine-containing copolymer.
C is more preferred. The heat treatment time is preferably short, more preferably 0.1 to 30 minutes, and even more preferably 0.5 to 10 minutes.

It is preferable to use a single or twin screw extruder for melt extrusion. The cylinder temperature of the extruder is 1
The temperature is preferably from 200 to 350 ° C., and the crosshead temperature and the die temperature are each preferably from 200 to 350 ° C. The screw rotation speed is not particularly limited, but is preferably from 10 to 200 rotations / minute. The residence time of the fluorocopolymer in the extruder is 1
Preferably 10 minutes to 10 minutes. Die discharge hole is 2-20mm in diameter
Is preferred. The cord-like fluorine-containing copolymer melted and discharged from the discharge hole is cooled and solidified with water or air while being stretched, cut with a cutter, and has a length of 1 to 5 mm and a diameter of 1 mm.
A columnar pellet of ５5 mm is obtained.

Further, in the present invention, a compound having an organic peroxide and a graftable bonding group and a functional group imparting adhesiveness to the fluorine-containing copolymer (hereinafter referred to as a grafting compound) is used. The blended, heat-treated, grafted fluorine-containing copolymer composition is improved in adhesiveness with the non-fluorine-based polymer as compared to the fluorine-containing copolymer to at least the same level as the fluorine-containing copolymer composition. It is preferred. By such heat treatment, the grafting compound is grafted on the fluorinated copolymer, and a functional group imparting adhesiveness is introduced into the fluorinated copolymer.

The functional group imparting adhesiveness is a group having reactivity or polarity, such as a carboxyl group and 2 groups in one molecule.
Residues in which two carboxyl groups are dehydrated and condensed (hereinafter referred to as carboxylic anhydride residues), epoxy groups, hydroxyl groups, isocyanate groups, ester groups, amide groups, aldehyde groups, amino groups, hydrolyzable silyl groups, cyano groups, Preferred are a carbon-carbon double bond, a sulfonic acid group and an ether group. Among them, a carboxyl group, a carboxylic anhydride residue, an epoxy group, a hydrolyzable silyl group and a carbon-carbon double bond are preferred. Such functional groups are
Two or more different types may be present in one molecule of the fluorinated copolymer, or two or more may be present in one molecule.

The graft compound is a compound having a functional group such as the above-mentioned carboxyl group and a binding group such as an organic group having a reactive unsaturated double bond, a peroxy group and an amino group. Examples include unsaturated carboxylic acids, epoxy group-containing unsaturated compounds, hydrolyzable silyl group-containing unsaturated compounds, and epoxy group-containing peroxy compounds. Unsaturated carboxylic anhydrides such as maleic anhydride and fumaric anhydride are preferred, and maleic anhydride is more preferred. The grafting compound is preferably used in an amount of 0.01 to 100 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the fluorinated copolymer.

The laminate of the present invention comprises a layer (E) of the above-mentioned fluorinated copolymer, fluorinated copolymer composition or grafted fluorinated copolymer composition and a layer (F) of a non-fluorinated polymer. )
And For example, an (E) / (F) laminate composed of two layers (E) and (F), and a three-layer (E) and (F) further laminated with a fluoropolymer layer (G) ( G) /
(E) / (F) laminates, and multilayer laminates such as (G) / (E) / (F) / (F) laminates in which the number of layers to be further laminated are increased. Here, it is important that the layers (E) and (F) are laminated so as to be in direct contact with each other, whereby a strongly bonded laminate is obtained.

Such a laminate is made of a fluorine-containing copolymer,
It is preferable to obtain the fluorinated copolymer composition or the grafted fluorinated copolymer composition and a non-fluorinated polymer by coextrusion molding. Usually, coextrusion methods involve film,
This is a method of obtaining a laminate of two or more layers in the shape of a tube or the like. The melt coming out of the discharge ports of two or more extruders is formed into a laminate through a die while contacting in a molten state. As for the extrusion temperature, the screw temperature is 100 to 3
The temperature is preferably 50 ° C, and the die temperature is preferably 200 to 350 ° C. The screw rotation speed is not particularly limited, but is 10 to 20.
0 revolutions / minute is preferred. The residence time of the melt in the extruder is preferably 1 to 20 minutes.

According to the present invention, a laminate in which the fluorine-containing copolymer layer and the non-fluorine-containing polymer layer are firmly adhered to each other is obtained. The mechanism by which the adhesion between the two layers is excellent is not clear, but is considered as follows. The fluorinated copolymer is (A)
Since it contains (C) having a higher polarity than (B) and (D) and having an ester bond, the adhesiveness to a non-fluorinated polymer is improved. Further, an organic peroxide is blended with the fluorinated copolymer, and when heat-treated, the organic peroxide is decomposed, and the fluorinated copolymer undergoes some modification, so that the fluorinated copolymer composition and the non-fluorinated It is considered that the adhesion to the system polymer is further improved. Furthermore, since the grafted fluorine-containing copolymer composition to which the graft compound has been grafted has an adhesive functional group, it is considered that the adhesiveness with the non-fluorine-based polymer is further improved.

The non-fluorinated polymer used for lamination with the fluorine-containing copolymer and the fluorine-containing copolymer composition of the present invention includes polyamide 6, polyamide 66 and polyamide 4
6, polyamide 11, polyamide 12, polyamide MX
Polyamides such as D6 (semi-aromatic polyamide), polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene, poly (ethylene / vinyl acetate), polypropylene, polystyrene, polyvinylidene chloride , Polyvinyl acetate, polyvinyl alcohol, poly (ethylene / vinyl alcohol), polyacrylonitrile, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyamideimide, polyetherimide, polysulfone, polyaryleate and the like.

More preferred as the non-fluorinated polymer are polyamide 6, polyamide 66, polyamide 46,
Polyamide 11, Polyamide 12, Polyamide MXD
6. Polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyvinylidene chloride, poly (ethylene / vinyl alcohol), and polyacrylonitrile.

The fluorinated copolymers, fluorinated copolymer compositions, grafted fluorinated copolymer compositions and laminates of the present invention are used for automotive fuel hoses, industrial multilayer hoses, food multilayers. Examples include hoses, weather-resistant multilayer films, chemical-resistant linings, weather-resistant linings, and adhesives between a fluorine-based polymer and a non-fluorine-based polymer.

[0029]

EXAMPLES The present invention will be described below with reference to Examples (Examples 1 to 3 and 7) and Comparative Examples (Examples 4 to 6), but the present invention is not limited thereto. The MIT bending test was measured by the following method.

[MIT Bending Test] ASTM D21
It measured according to 76. That is, a test piece having a width of 12.5 mm, a length of 130 mm, and a thickness of 0.23 mm was mounted on an MIT measuring device manufactured by Toyo Seiki Seisaku-sho, and the load was 1.25 kg, the bending angle on each side was 135 degrees, and the number of times of bending was 175.
The test piece was bent under the conditions of times / minute, and the number of times until the test piece was cut was measured. This test is a bending fatigue resistance test of the fluorine-containing copolymer and serves as an index of crack resistance.
The higher the number, the better the crack resistance.

Example 1 A 430 L polymerization tank equipped with stirring blades was degassed, and 314 k of 1-hydrotridecafluorohexane was added.
g, 105 kg of 1,3-dichloro-1,1,2,2,3-pentafluoropropane (manufactured by Asahi Glass Co., Ltd .; hereinafter, referred to as AK225cb), 0.506 kg of VOAc,
(Perfluorobutyl) ethylene CH ₂ ＣＨCH (C
0.184 k of F ₂ ) ₄ F (hereinafter referred to as PFBE)
g, 13.0 kg of TFE and 0.69 kg of E were charged, and the temperature in the polymerization tank was raised to 74 ° C.

Tert-butyl peroxypivalate as a polymerization initiator (having a half-life of 10 hours and a decomposition temperature of 5 hours)
Polymerization was started by charging 20 ml of a 1: 1 (mass ratio) mixed solution of 4.6 ° C.) and AK225cb. Since the pressure in the tank was lowered as the polymerization proceeded, a mixed gas of TFE / E = 60/40 (molar ratio) was continuously charged so as to keep the pressure constant. Further, VOAc in an amount corresponding to 5 mol% based on the total number of moles of TFE and E charged during the polymerization was continuously charged. When the total amount of TFE and E charged during the polymerization reached 28 kg, the charging of VOAc was stopped. When the polymerization proceeded and the total amount of TFE and E charged during the polymerization reached 36 kg, the internal temperature of the polymerization tank was cooled to room temperature, and unreacted TFE and E were purged to normal pressure.

The obtained slurry-like fluorine-containing copolymer a
Was charged into an 800 L granulation tank charged with 300 kg of water, and then heated to 105 ° C. with stirring and granulated while distilling off and removing the solvent. The obtained granulated product is heated at 135 ° C. for 3 hours.
After drying for 38 hours, 38 kg of a granulated product a of the fluorine-containing copolymer a was obtained.

From the results of the melt NMR analysis and the fluorine content analysis, the composition of the fluorine-containing copolymer a was found to be TFE / E / V
60/4 in molar ratio of polymerized units based on OAc / PFBE
0 / 5.0 / 0.15. Q value is 310 mm ³ /
Second, the number of MIT bending was 8,500 times.

The granulated product a is extruded at 260 ° C.
Pellets a were produced by melt-kneading with a residence time of 2 minutes. ETFE (ETFE containing no polymerized unit based on VOAc) in the cylinder forming the lower layer; Aflon LM7 manufactured by Asahi Glass Co., Ltd.
30A), nylon 6 (Ube Industries, Ltd., 1022B) was supplied to the cylinder forming the upper layer, and pellet a was supplied to the cylinder forming the intermediate layer, and each was transferred to the transport zone of the cylinder. The heating temperature in the transport zone of ETFE, nylon 6 and pellet a was 290 ° C, 260 ° C and 260 ° C, respectively. A three-layer co-extrusion was performed at a co-die temperature of 270 ° C., and a 1 mm-thick and 10 cm-wide ETFE / fluorinated copolymer a / nylon 6
Was formed into a three-layer laminated sheet. The thickness of each of the ETFE layer, the fluorine-containing copolymer a layer, and the nylon 6 layer is 0.3 m.
m, 0.2 mm, and 0.5 mm.

The peel strength between each layer was measured using a test piece having a width of 1 cm and a length of 10 cm obtained by cutting the obtained three-layer laminated sheet. The fluorinated copolymer a layer and the ETFE layer could not be peeled off, and the material was partially destroyed and showed high adhesive strength. The peel strength between the fluorine-containing copolymer a layer and the nylon 6 layer was 25.4 N / cm.

[Example 2] The charged amount of PFBE was 0.55 kg.
38 kg of a fluorinated copolymer b was obtained in the same manner as in Example 1 except that Further, a granulated product b was obtained from the fluorine-containing copolymer b in the same manner as in Example 1. As a result of the melt NMR analysis and the fluorine content analysis, the composition of the fluorine-containing copolymer b was TFE.
The molar ratio of polymerized units based on / E / VOAc / PFBE was 60/40 / 5.0 / 0.5. Q value is 340m
m ³ / sec, and the number of MIT bends was 15,300.

Pellets b were obtained in the same manner as in Example 1 using the granules b. Conductive ETFE on the cylinder forming the lower layer
(Aflon LM CB4015L, manufactured by Asahi Glass Co., Ltd.), nylon 12 (3030 JLX2, manufactured by Ube Industries, Ltd.) is supplied to the cylinder that forms the upper layer, and pellet b is supplied to the cylinder that forms the intermediate layer, and each cylinder is transported. Transferred to the zone. The heating temperature in the transport zone of ETFE, nylon 12 and pellet b was set to 31 respectively.
0 ° C, 240 ° C, and 260 ° C. The temperature of the die is 26
Three-layer coextrusion was performed at 0 ° C. to obtain a three-layer laminated tube of conductive ETFE / fluorinated copolymer b / nylon 12. The outer diameter of the laminated tube is 8 mm, the inner diameter is 6 mm, the thickness is 1 mm, the thickness of the conductive ETFE layer, the fluorine-containing copolymer b layer, and the thickness of the nylon 12 layer are each 0.2 mm,
0.1 mm and 0.7 mm.

The peel strength between the layers was measured in the same manner as in Example 1. The fluorinated copolymer b layer and the conductive ETFE layer could not be peeled off, and the material was partially destroyed and showed high adhesive strength. The peel strength between the fluorine-containing copolymer b layer and the nylon 12 layer is 3
It was 2.5 N / cm.

The obtained three-layer laminated tube was subjected to CE10 (isooctane / toluene / ethanol = 45/45/10).
(Volume alcohol mixed fuel) at 60 ° C. for 240 hours. After immersion, the peel strength between the respective layers was measured. The fluorine-containing copolymer b layer and the conductive ETFE layer did not peel off, and showed high adhesive strength. The peel strength between the fluorine-containing copolymer b layer and the nylon 12 layer was 30.5 N / cm.

[Example 3] 100 of the granulated product a obtained in Example 1
Parts of ditert-butyl peroxide (having a half-life of 1
(Decomposition temperature of 185.9 ° C) is uniformly mixed, and then mixed and kneaded with a twin screw extruder at 260 ° C and a residence time of 3 minutes to mix the organic peroxide. Thus, pellets c of the heat-treated fluorinated copolymer composition a were obtained. A three-layer co-extruded laminated sheet was formed in the same manner as in Example 1 using the pellet c. The thickness of each of the ETFE layer, the fluorine-containing copolymer composition a layer, and the nylon 6 layer is 0.0
They were 5 mm, 0.02 mm, and 0.13 mm.

The peel strength between the layers was measured in the same manner as in Example 1. The fluorinated copolymer composition a layer and the ETFE layer could not be peeled off, and the material was partially broken, showing high adhesive strength. The peel strength between the fluorine-containing copolymer composition a layer and the nylon 6 layer was 37.6 N / cm.

[Example 4] Example 1 except that PFBE was not charged.
38.5 kg of a fluorinated copolymer c was obtained in the same manner as described above. As a result of the melt NMR analysis and the fluorine content analysis, the composition of the fluorine-containing copolymer c was 60/40 / 5.0 in a molar ratio of TFE / E / VOAc. Q value is 280 mm ³ /
Seconds, the number of MIT bending was 1500 times.

[Example 5] ETFE instead of pellet b
A three-layer laminated sheet of conductive ETFE / ETFE / nylon 12 was formed in the same manner as in Example 2 except that (Aflon LM730A, manufactured by Asahi Glass) was used. Conductive ETFE
Layer, ETFE layer, and 12 layers of nylon each have a thickness of 0.
They were 3 mm, 0.2 mm, and 0.5 mm.

The peel strength between the layers was measured in the same manner as in Example 2. The conductive ETFE layer and the ETFE layer could not be peeled off, causing partial material destruction and exhibiting high adhesive strength. On the other hand, E
Peel strength between TFE layer and nylon 12 layer is 1N / cm
And the adhesive strength was low.

[Example 6] ETFE instead of pellet a
A three-layer laminated tube of ETFE / ETFE / nylon 6 was obtained in the same manner as in Example 1 except that (Aflon LM730A, manufactured by Asahi Glass Co., Ltd.) was used. ETFE layer, intermediate ETF
The thicknesses of the E layer and the nylon 6 layer are 0.2 mm and 0.
They were 1 mm and 0.7 mm.

The peel strength between the layers was measured in the same manner as in Example 1. It was found that the ETFE layer and the ETFE layer could not be peeled off and were partially adhered to each other because the material was partially broken.
On the other hand, the peel strength between the intermediate ETFE layer and the nylon 6 layer was 1 N / cm, and the adhesive strength was low.

Example 7 100 of the granulated product a obtained in Example 1
After uniformly mixing 1.5 parts of di-tert-butyl peroxide and 0.08 part of maleic anhydride per part,
The mixture was melt-kneaded at 260 ° C. for 3 minutes using a screw extruder, thereby blending an organic peroxide and a grafting compound to obtain pellets d of the heat-treated fluorocopolymer composition a. Using the pellets d, a three-layer co-extruded laminated sheet was formed in the same manner as in Example 1. The thicknesses of the ETFE layer, the grafted fluorine-containing copolymer composition a layer, and the nylon 6 layer were 0.2 mm, 0.1 mm, and 0.7 mm, respectively.

The peel strength between the layers was measured in the same manner as in Example 1. The grafted fluorinated copolymer composition a layer and the conductive ETFE layer could not be peeled off, and the material was partially destroyed and exhibited high adhesive strength. The peel strength between the grafted fluorine-containing copolymer composition a layer and the nylon 6 layer was 35.5 N / cm.

The obtained three-layer laminated tube was subjected to CE10 (isooctane / toluene / ethanol = 45/45/10).
(Volume alcohol mixed fuel) at 60 ° C. for 240 hours. After immersion, the peel strength between the respective layers was measured. The grafted fluorinated copolymer composition a layer and the conductive ETFE layer did not peel off and exhibited high adhesive strength. The peel strength between the grafted fluorine-containing copolymer composition a layer and the nylon 6 layer was 34.
It was 5 N / cm.

[0051]

The fluorinated copolymer of the present invention can be co-extruded with other fluorinated polymers or non-fluorinated polymers to form a laminate having excellent adhesion and excellent crack resistance. give.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08J 3/00 CEW C08J 3/00 CEW // (C08F 214/24 C08F 210: 02 210: 02 218: 08 218: 08 214: 18 214: 18) C08L 27:12 (C08F 214/26 210: 02 218: 08 214: 18) C08L 27:12 (72) Inventor Eiichi Nishi 10 Goi Kaigan, Ichihara City, Chiba Prefecture Asahi Glass Co., Ltd. 72) Inventor Masahide Yodogawa 10 Asahi Glass Co., Ltd., Ichihara-shi, Chiba Pref. Asahi Glass Co., Ltd. AC56 AE08 AE24 BA05 BB02 BB08 GA05 GC08 4F100 AK04A AK17B AK18A AK22A AK46 AL01A AL05A BA02 EH20 EH202 GB66 JL11 4J026 AA12 AA26 AA38 AC06 BA25 BA30 BA35 BA43 DB05 DB15 GA01 AC02 AC08 AC10 AC02 JA03

Claims (5)

[Claims] 1. A polymerization unit based on tetrafluoroethylene or chlorotrifluoroethylene (A), a polymerization unit based on ethylene (B), a polymerization unit based on vinyl acetate (C), and a general formula CH ₂ ＣCX (CF ₂ ) _n Y (where X and Y are each independently a hydrogen atom or a fluorine atom, and n is an integer of 2 to 10). (A) / (B) in a molar ratio of 20/80 to 80 /
20, and (C) / ((A) + (B)) is 1 in a molar ratio.
/ 1000 to 15/100, and (D) / ((A) +
(B)) is a molar ratio of 1/1000 to 15/100, and the volume flow rate is 1 to 1000 mm ³ / sec. Wherein said general formula _{CH 2 = CX (CF 2)} X in the _n Y is a hydrogen atom, a fluorine-containing copolymer according to claim 1 Y is a fluorine atom. 3. A fluorine-containing composition obtained by mixing 0.01 to 10 parts of an organic peroxide with 100 parts of the fluorine-containing copolymer according to claim 1 or 2 and heat-treating the mixture. Copolymer composition. 4. A method for imparting 0.01 to 10 parts of an organic peroxide and a graftable bonding group and adhesion to 100 parts of the fluorinated copolymer according to claim 1 or 2. 0.01 to 100 parts of a compound having a functional group are blended,
A grafted fluorine-containing copolymer composition, which is heat-treated. 5. A composition comprising the layer of the fluorine-containing copolymer composition according to claim 3 or the layer of the grafted fluorine-containing copolymer composition according to claim 4 and a layer of a non-fluorine-containing polymer. Characteristic laminate.