JP2010053209A - Fluorine-containing copolymer and its usage - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing copolymer excellent in heat resistance, chemical resistance, weatherability and stress crack resistance as well as excellent in adhesiveness, and to provide a laminate of the copolymer and a coated article. <P>SOLUTION: The fluorine-containing copolymer contains a repeating unit (a) based on tetrafluoroethylene, a repeating unit (b) based on CF<SB>2</SB>=CFOCF<SB>2</SB>CF<SB>2</SB>CF<SB>3</SB>, a repeating unit (c) based on CF<SB>2</SB>=CFOCF<SB>3</SB>and/or CF<SB>2</SB>=CFOCF<SB>2</SB>CF<SB>3</SB>, and a repeating unit (d) based on a polymerizable hydrocarbon monomer having a dicarboxylic acid anhydride group. Based on the total molar amount of the repeating unit (a), repeating unit (b), repeating unit (c) and repeating unit (d), the copolymer contains the repeating unit (a) by from 75 to 99.79 mol%, the repeating unit (b) by from 0.1 to 10.0 mol%, the repeating unit (c) by from 0.1 to 10.0 mol%, and the repeating unit (d) by from 0.01 to 5.0 mol%, and has a volume flow rate of 0.1 to 1,000 mm<SP>3</SP>/sec. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a fluorine-containing copolymer and its use.

  Fluoropolymers such as polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers, and ethylene / tetrafluoroethylene copolymers are used in various fields such as the semiconductor industry and the automobile industry.

  The fluorine-containing polymer is excellent in heat resistance, chemical resistance, weather resistance, gas barrier properties, and the like, but has insufficient adhesion to other materials. For example, in order to adhere to synthetic resin, metal, metal oxide, glass, ceramics, etc., the surface of the fluoropolymer is subjected to corona discharge treatment, sodium etching treatment, etc., and then applied with an adhesive and adhered. A method or the like is used. Such an adhesion method requires complicated development, low productivity, and development of a fluorine-containing polymer that adheres to other materials by a simpler method.

  As a method of forming a fluoropolymer film on the surface of a metal substrate, an uneven shape is formed on the surface in advance by sandblasting or the like, a primer is applied, and the fluoropolymer particles are then adhered to the surface. Examples thereof include a method of melting at a temperature equal to or higher than the melting point of the fluoropolymer. Also in this case, from the viewpoint of cost reduction and productivity improvement, there is a demand for the development of a fluorine-based polymer that does not require a primer and has excellent adhesion to a metal or the like.

  In recent years, laminates of fluoropolymers and polyamides have been studied as materials for paint piping for coating robots, chemical piping for semiconductor manufacturing equipment, fuel hoses, and the like. In this application, it is necessary that the fluoropolymer layer and the polyamide layer be firmly bonded. Therefore, the surface of the fluoropolymer tube is subjected to surface treatment by a method such as chemical treatment, corona discharge treatment, plasma discharge treatment, etc., and an adhesive is applied to the surface as necessary. A method of improving the adhesion between the fluoropolymer layer and the polyamide layer by extruding and laminating polyamide on the outside is used. However, since this method is complicated and the productivity is low, development of a fluoropolymer capable of forming a laminate having excellent interlayer adhesion without requiring surface treatment of the fluoropolymer layer is required. Is requested.

  As such a fluoropolymer, Patent Document 1 describes a copolymer containing a repeating unit based on tetrafluoroethylene / a repeating unit based on a fluorine-containing monomer / a repeating unit based on itaconic anhydride. However, the tetrafluoroethylene copolymer has insufficient heat resistance in a high temperature region of 300 ° C.

  Patent Document 2 discloses a fluorine-containing copolymer containing a repeating unit based on 5-norbornene-2,3-dicarboxylic acid anhydride. The fluorine-containing copolymer has improved adhesiveness with other materials, but lacks flexibility, and has insufficient mechanical strength such as stress crack resistance as a material for paint piping for paint robots, fuel hoses, etc. .

Japanese Patent Laid-Open No. 2004-277789 JP 2006-152234 A

  The object of the present invention is to be developed against the background as described above, and is excellent in heat resistance, chemical resistance, weather resistance, stress crack resistance, and adhesion to thermoplastic resins and substrates. It is to provide a fluorine-containing copolymer having excellent resistance.

The invention relates to repeating units based on tetrafluoroethylene (a), repeating units based on CF ₂ ═CFOCF ₂ CF ₂ CF ₃ (b), CF ₂ ═CFOCF ₃ and / or CF ₂ ═CFOCF ₂ CF ₃ Unit (c), containing a repeating unit (d) based on a polymerizable hydrocarbon monomer having a dicarboxylic anhydride group, the repeating unit (a), the repeating unit (b), the repeating unit (c), the repeating unit (d ), The repeating unit (a) is 75 to 99.79 mol%, the repeating unit (b) is 0.1 to 10.0 mol%, and the repeating unit (c) is 0. a .1～10.0 mol%, the repeating units (d) is the 0.01 to 5.0 mol%, fluorine-containing, wherein the volume flow rate is 0.1~1000mm ³ / sec To provide a copolymer.

  The present invention also provides a laminate in which a layer of the fluorine-containing copolymer and a layer of a thermoplastic resin other than the fluorine-containing copolymer are directly laminated, and a substrate made of the fluorine-containing copolymer. Provided is a coated article having a surface coated.

  The fluorine-containing copolymer of the present invention is excellent in adhesion to resins, metals, metal oxides, glass, ceramics, etc., and is excellent in heat resistance, chemical resistance, and stress crack resistance.

  The fluorine-containing copolymer of the present invention is excellent in coextrusion moldability with a thermoplastic resin other than the fluorine-containing polymer. The laminate obtained by directly laminating the obtained fluorine-containing copolymer layer and the thermoplastic resin layer is excellent in interlayer adhesion.

  The fluorine-containing copolymer of the present invention can form a film of a fluorine-containing copolymer on a substrate such as resin, metal, metal oxide, glass, or ceramic without using a primer, and can adhere to the substrate. A coated article having excellent properties is provided. The coated article is excellent in heat resistance, chemical resistance, corrosion resistance, oil resistance, weather resistance, wear resistance, lubricity, and the like.

The fluorine-containing copolymer of the present invention comprises a repeating unit (a) based on tetrafluoroethylene, a repeating unit (b) based on CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₃ and / or CF ₂ = CFOCF. _{2 The} repeating unit (c) based on CF ₃ and the repeating unit (d) based on a hydrocarbon monomer having a dicarboxylic anhydride group are contained.

Hereinafter, CF ₂ = CFOCF ₂ CF ₂ CF _{3 is referred} to as PPVE, CF ₂ = CFOCF ₂ CF ₃ as PEVE, and CF ₂ = CFOCF ₃ as PMVE.

  The repeating unit (a) is 75 to 99.79 mol% based on the total molar amount of the repeating unit (a), the repeating unit (b), the repeating unit (c), and the repeating unit (d), and the repeating unit The unit (b) is 0.1 to 20.0 mol%, the repeating unit (c) is 0.1 to 10.0 mol%, and the repeating unit (b) is 0.1 to 10.0 mol%. It is.

Preferably, the repeating unit (a) is 85 to 98.97 mol%, the repeating unit (b) is 0.5 to 7 mol%, the repeating unit (c) is 0.5 to 7 mol%, and the repeating unit (d ) Is 0.03 to 1 mol%, more preferably the repeating unit (a) is 89.5 to 97.97 mol%, the repeating unit (b) is 1.0 to 5 mol%, and the repeating unit ( c) is 1.0 to 5 mol%, and the repeating unit (d) is 0.03 to 0.5 mol%. When the repeating unit (a), the repeating unit (b), and the repeating unit (c) are within this range, the fluorinated copolymer is excellent in heat resistance and chemical resistance, and has a machineability such as moldability and stress crack resistance. Excellent physical properties.
Furthermore, when the mol% of the repeating unit (d) is in this range, the fluorine-containing copolymer is excellent in adhesiveness with a thermoplastic resin other than the fluorine copolymer or a substrate.

  In the present invention, the “polymerizable hydrocarbon monomer having a dicarboxylic anhydride group” is a compound having a dicarboxylic anhydride group (—CO—O—CO—) and a polymerizable unsaturated group, and an aliphatic dicarboxylic acid. Examples thereof include anhydrides and anhydrides of dicarboxylic acids having a hydrocarbon ring. In addition, a part of hydrogen atoms bonded to carbon atoms in the polymerizable hydrocarbon monomer may be substituted with a halogen atom, an alkyl group, a halogenated alkyl group or other substituents.

  The polymerizable hydrocarbon monomer preferred in the present invention is a dicarboxylic acid anhydride having a hydrocarbon ring. The hydrocarbon ring is a ring composed of only carbon atoms, and the hydrocarbon ring may be any of a monocyclic ring, a condensed polycyclic ring, a bridged polycyclic ring, an aggregated polycyclic ring, an alicyclic ring or an aromatic ring. It may be. The polymerizable unsaturated group may exist between the carbon atoms constituting the ring, or may exist between the carbon atoms constituting the ring and the carbon atoms constituting the ring or between the carbon atoms constituting the ring. The two bonds of the dicarboxylic anhydride group are each bonded to a carbon atom constituting the ring or a carbon atom outside the ring. The hydrocarbon ring is preferably an alicyclic ring having a monocyclic, condensed polycyclic or bridged polycyclic structure. Further, the dicarboxylic anhydride group is preferably bonded to two carbon atoms constituting the alicyclic ring, and particularly preferably bonded to two adjacent carbon atoms constituting the alicyclic ring.

  Specific examples of the polymerizable cyclic hydrocarbon monomer having a dicarboxylic acid anhydride group include 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as NAH), and the following formulas (1) to (3): The acid anhydride etc. which are represented are mentioned. NAH is preferable.

  The fluorine-containing copolymer of the present invention contains a repeating unit (e) based on another monomer in addition to the repeating unit (a), the repeating unit (b), the repeating unit (c), and the repeating unit (d). It is also preferable.

Examples of the other monomers include hexafluoropropylene (hereinafter referred to as HFP), vinyl fluoride, vinylidene fluoride (hereinafter referred to as VdF), trifluoroethylene, CF ₂ = CFOR ^f ₂ SO ₂ X ¹ (R ^f2 is A perfluoroalkylene group having 1 to 10 carbon atoms and optionally containing an oxygen atom between carbon atoms, X ¹ is a halogen atom or a hydroxyl group), CF ₂ = CFOR ^f ₂ CO ₂ X ² (where R ^f2 is the same as above, X ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.), CF ₂ = CF (CF ₂ ) _p OCF═CF ₂ (where p is 1 or 2), CH ₂ = CX ³ (CF ₂ ) _Q X ⁴ (wherein X ³ and X ⁴ are each independently a hydrogen atom or a fluorine atom, q is an integer of 2 to 10), perfluoro (2-methylene-4-methyl-1, 3-dioxolane), perfluoro (2,2-dimethyl-1,3-dioxole), perfluoro (4-methoxy-1,3-dioxole), ethylene, propylene, isobutene and other olefins having 2 to 4 carbon atoms, vinyl acetate And vinyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether. Other monomers may be used alone or in combination of two or more.

As CH ₂ = CX ³ (CF ₂ ) _q X ⁴ , CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ ═CF (CF ₂ ) ₃ H, CH ₂ ═CF (CF ₂ ) ₄ H, and the like. Preferably, CH ₂ ═CH (CF ₂ ) ₄ F or CH ₂ ═CH (CF ₂ ) ₂ F.
The other monomer is preferably at least one selected from the group consisting of HFP, VdF, CH ₂ ═CX ³ (CF ₂ ) _q X ⁴ , ethylene, propylene and vinyl acetate, and more preferably HFP, ethylene And CH ₂ = CX ³ (CF ₂ ) _q X ⁴ is at least one selected from the group consisting of Most preferred is HFP.

  Preferable specific examples of the fluorine-containing copolymer of the present invention include TFE / PPVE / PMVE / NAH copolymer, TFE / PPVE / PEVE / NAH copolymer, TFE / HFP / PPVE / PMVE / NAH copolymer, Examples include TFE / HFP / PPVE / PEVE / NAH copolymer.

  150-320 degreeC is preferable and, as for melting | fusing point of the fluorine-containing copolymer of this invention, 200-310 degreeC is more preferable. Within this range, the melt coextrusion moldability with the thermoplastic resin is excellent. The melting point is preferably adjusted by appropriately selecting the content ratio of the repeating unit (a), the repeating unit (b), the repeating unit (c), and the repeating unit (d) within the above range.

  When the fluorine-containing copolymer of the present invention has an adhesive functional group such as an ester group, a carbonate group, a hydroxyl group, a carboxyl group, a carbonyl fluoride group, or an acid anhydride residue as a polymer terminal group, a thermoplastic resin or Since it is excellent in adhesiveness with a substrate, it is preferable. The polymer end group having an adhesive functional group is preferably introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent, etc. during the production of the fluorine-containing copolymer.

The volume flow rate (hereinafter referred to as Q value) at 380 ° C. of the fluorinated copolymer of the present invention is 0.1 to 1000 mm ³ / sec. The Q value is an index representing the melt fluidity of the fluorinated copolymer and is 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 is the value when extruded into an orifice having a diameter of 2.1 mm and a length of 8 mm under a load of 7 kg at a temperature 50 ° C. higher than the melting point of the fluorine-containing copolymer using a flow tester manufactured by Shimadzu Corporation. This is the extrusion rate of the fluorinated copolymer. When the Q value is too small, extrusion molding becomes difficult. When the Q value is too large, the stress crack resistance of the fluorine-containing copolymer is not sufficient. Q value of the fluorocopolymer of the present invention is preferably from 5 to 500 mm ³ / sec, 10 to 200 mm ³ / sec is more preferable.

The MIT bending life of the fluorine-containing copolymer in the present invention is 1 million times or more. Here, the MIT bending life is the number of bendings until the sample breaks in a bending test performed in accordance with ASTM D2176. It shows that it is excellent in stress crack resistance, so that this value is large. Preferably it is 2 million times or more, More preferably, it is 3 million times or more.

  The method for producing the fluorine-containing copolymer of the present invention is not particularly limited, and a radical polymerization method using a radical polymerization initiator is used. Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, fluorinated hydrocarbon ethers, chlorinated hydrocarbons, fluorinated chlorinated hydrocarbons, alcohols, hydrocarbons, aqueous media, and as required. Examples thereof include suspension polymerization using an appropriate organic solvent, and emulsion polymerization using an aqueous medium and an emulsifier, and solution polymerization is particularly preferable.

As the radical polymerization initiator, the temperature at which the half-life is 10 hours is preferably 0 ° C to 100 ° C, more preferably 20 to 90 ° C. Specific examples thereof include azo compounds such as azobisisobutyronitrile, non-fluorine diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxy. peroxydicarbonate such dicarbonate, tert- butyl peroxypivalate, tert- butylperoxy isobutyrate, peroxy esters such as tert- butylperoxy _{acetate, 2} (where _{(Z (CF 2) r COO} ), Z is hydrogen An atom, a fluorine atom, or a chlorine atom, and r is an integer of 1 to 10.) Fluorine-containing diacyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, etc. Peroxides and the like.

  In the present invention, it is also preferable to use a chain transfer agent in order to control the Q value of the fluorine-containing copolymer. Chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, Hydrocarbons such as pentane, hexane, and cyclohexane are listed. Examples of the chain transfer agent for introducing an adhesive functional group to the polymer terminal of the fluorinated copolymer include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.

  In the present invention, the polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.

  The concentration of the polymerizable hydrocarbon monomer having a dicarboxylic acid anhydride group during the polymerization is preferably 0.01 to 5 mol%, more preferably 0.05 to 3 mol%, more preferably 0.05 to 1 with respect to the total monomers. Mole% is most preferred. When the concentration of the polymerizable hydrocarbon monomer having a dicarboxylic acid anhydride group is too high, the polymerization rate tends to decrease. Within the above range, the polymerization rate during production does not decrease, and the fluorinated copolymer is excellent in adhesiveness. During the polymerization, as the polymerizable hydrocarbon monomer having a dicarboxylic anhydride group is consumed in the polymerization, the consumed amount is continuously or intermittently supplied into the polymerization tank, and the polymerization property having the dicarboxylic anhydride group is obtained. It is preferred to maintain the concentration of the hydrocarbon monomer within this range.

  The laminate of the present invention is obtained by directly laminating a fluorine-containing copolymer layer and a thermoplastic resin layer other than the fluorine copolymer. The lamination of the fluorine-containing copolymer and the thermoplastic resin is preferably performed by a melt molding method, and the co-extrusion molding method is more preferable because it is excellent in productivity. The coextrusion molding method is a method for obtaining a laminate of two or more layers in the shape of a film, a tube or the like. The melt coming out from the discharge ports of two or more extruders passes through the die while being in contact in the molten state, and is formed into a laminate. For coextrusion molding, the fluorinated copolymer and the thermoplastic resin preferably have molding temperatures close to each other. The extrusion temperature is determined from the viewpoints of the melting point and decomposition temperature of the fluorine-containing copolymer and the thermoplastic resin. The screw temperature is preferably 100 to 400 ° C, and the die temperature is preferably 150 to 400 ° C. The screw rotation speed is not particularly limited, but is preferably 10 to 200 rotations / minute. The residence time of the fluorine-containing copolymer in the extruder is preferably 1 to 20 minutes.

  Examples of the thermoplastic resin other than the fluorine-containing copolymer in the laminate of the present invention include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, polyamide 6, polyamide 66, polyamide 46, and polyamide. 11. Polyamides such as polyamide 12, polyamide MXD6 (semi-aromatic polyamide), polyolefins such as polyethylene and polypropylene, polyvinyl acetate, poly (ethylene / vinyl acetate), polyvinyl alcohol, poly (ethylene / vinyl alcohol), Polystyrene, polyvinylidene chloride, polyacrylonitrile, polyoxymethylene, polyphenylene sulfide, polyphenylene ether, polycarbonate, polyamideimide, polyetherimide Polysulfone, Poriarireeto, and the like.

The coated article of the present invention is formed by coating the surface of a substrate with a fluorine-containing copolymer. Examples of the base material include organic materials such as thermoplastic resins other than the fluorine-containing polymer, metal materials such as iron, stainless steel, copper, brass, aluminum, nickel, magnesium alloy, and titanium, and inorganic materials such as glass and ceramics. Can be mentioned.
As a method for coating the substrate, an electrostatic powder molding method, a rotational molding method, a thermal spray molding method, a fluidized immersion method, a dispersion method, a solvent casting method, or the like can be employed.

In the electrostatic powder molding method, a negative high voltage is applied to the powder of the fluorine-containing copolymer to be charged and adhered to the surface of the substrate, and then the adhered fluorine-containing copolymer is not lower than its melting point and not higher than the decomposition point. It is preferable to heat and melt at a temperature for 5 minutes to 1 hour to form a fluorine-containing copolymer film having a certain thickness on the surface of the substrate.
In the rotational molding method, the fluorine-containing copolymer powder is inserted into the inside of a can-like or cylindrical substrate, and the temperature of the melting point of the fluorine-containing copolymer is not lower than the decomposition point while rotating the substrate. It is preferable to heat the substrate for 1 hour to melt the fluorine-containing copolymer and form a film of the fluorine-containing copolymer having a uniform thickness on the inner surface of the substrate.

In the thermal spray molding method, it is preferable to form a coating film of the fluorinated copolymer on the surface of the substrate by spraying a semi-molten fluorinated copolymer onto a preheated substrate.
In the fluidized immersion method, the powder of the fluorinated copolymer is placed in a container having a gas-permeable porous plate at the bottom, and the powder is fluidized by sending gas from the porous plate. It is preferable to form a uniform fluorine-containing copolymer film on the substrate surface by immersing the substrate heated to the melting point or more and the decomposition point or less of the coalescence for 1 minute or more and 1 hour or less.

  In the dispersion method, a fine powder of a fluorine-containing copolymer is suspended in water or a solvent, or suspended in a liquid, and sprayed onto a substrate to evaporate the water or the solvent, thereby depositing a uniform powder. To form. Next, it is preferable to heat and melt for 1 minute to 1 hour below the melting point and below the decomposition point of the fluorine-containing copolymer to form a film of the fluorine-containing copolymer on the substrate surface.

When the fluorine-containing copolymer can be dissolved in a solvent, it is also preferable to form a film of the fluorine-containing copolymer by coating it on the surface of the substrate by casting, dipping or the like.
It is also preferable that the surface of the substrate is pretreated in order to improve adhesion. Examples of the pretreatment method include sandblast treatment, phosphate treatment, hydrochloric acid treatment, and sulfuric acid treatment.

  EXAMPLES Although Examples 1-4 and Comparative Examples 1-4 are given below and this invention is demonstrated, this invention is not limited to these. The adhesive strength, stress crack resistance, and NAH content were measured by the following methods.

[Adhesive strength (unit: N / cm)]
A 100 μm-thick fluorine-containing copolymer film and a 100 μm-thick polyamide 12 (Ube Industries, Ltd., 3030JLX, hereinafter referred to as PA12) film, a copper foil or an aluminum foil are overlaid, and a heat sealer ( Using Fuji Impulse Co., Ltd., melt bonding was performed at a setting of a heating level 9 (attainment temperature 280 ° C.). The obtained laminated film was cut into strips having a length of 10 cm and a width of 1 cm to prepare test pieces. The peel strength of the test piece was measured using a tensile tester to obtain the adhesive strength.

  Similarly, the adhesive strength between a 100 μm-thick fluorine-containing copolymer film and a 20 μm-thick copper foil (electrolytic copper foil SV manufactured by Fukuda Metal Foil Powder Co., Ltd.), a 100 μm-thick aluminum foil (Tokai Aluminum) The adhesive strength with a hard aluminum foil manufactured by Foil Co., Ltd. was measured.

[Stress crack resistance test (MIT bending life)]
A film having a thickness of 0.220 to 0.236 μm obtained by compression molding the fluorine-containing copolymer at 340 ° C. was punched into a strip having a width of 12.5 mm to obtain a measurement sample. In accordance with ASTM D2176, a bending test of the measurement sample was performed using a bending tester MIT-D (manufactured by Toyo Seiki Seisakusho) at a load of 1.25 kg, a bending angle of ± 135 degrees, and room temperature. The number of folds until rupture was defined as the MIT fold life. It shows that it is excellent in stress crack resistance, so that this value is large.

[Content of repeating unit based on NAH (unit: mol%)]
An infrared absorption spectrum was measured using a 100 μm fluorine-containing copolymer film. Since the absorption peak of NAH in the infrared absorption spectrum appears at 1778 cm ⁻¹ , the absorbance of the peak was measured. The content of repeating units based on NAH was calculated using a molar extinction coefficient of NAH of 1340 l · mol ⁻¹ · cm ⁻¹ .

[Content of repeating unit based on PMVE, PEVE, PPVE, HFP (unit: mol%)]
In accordance with the method described in Asahi Glass Research Report 40 (1), 75 (1990), it was calculated by melt NMR analysis.

[Example 1 (TFE / PPVE / PMVE / NAH copolymer)]
The polymerization tank with a stirrer having an internal volume of 1.2 L was degassed, and 1,1,2,2, -tetrafluoroethyl-2,2,2, -trifluoroethyl ether (AE-3000 manufactured by Asahi Glass Co., Ltd. AE-3000), 1131 g of PPVE, 35 g of PPVE, 22 g of PMVE, and 5 g of methanol. Next, the temperature inside the polymerization tank was raised to 50 ° C., 155 g of TFE was charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm ³ of the peroxide and the polymerization was started and charged with 1 cm ³ of the polymerization initiator solution every 10 minutes thereafter. Further, TFE was continuously charged so that the pressure during polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 5.6 hours after the start of polymerization, when 50 g of TFE was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

The slurry of the obtained fluorinated copolymer 1 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 45 g of fluorinated copolymer 1.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 1 is as follows: repeating unit based on TFE / repeating unit based on PPVE / repeating unit based on PMVE / repeating unit based on NAH = 95 0.8 / 2.0 / 2.1 / 0.1 (mol%). The melting point was 285 ° C., and the Q value was 28 mm ³ / sec. The MIT bending life was 2.2 million times, and it was found to be excellent in stress crack resistance. The adhesive strength between the fluorine-containing copolymer 1 film and the PA12 film is 14.1 N / cm, the adhesive strength with the copper foil is 10.5 N / cm, and the adhesive strength with the aluminum foil is 9. 3 N / cm, both of which were found to be excellent in adhesiveness. The physical properties of the resulting fluorinated copolymer 1 are shown in Table 1.

[Example 2 (TFE / PPVE / PEVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 35 g of PPVE, 29 g of PEVE, and 5 g of methanol. Next, the temperature inside the polymerization tank was raised to 50 ° C., 160 g of TFE was charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm ³ of the peroxide and the polymerization was started and charged with 1 cm ³ of the polymerization initiator solution every 10 minutes thereafter. Further, TFE was continuously charged so that the pressure during polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 5.6 hours after the start of polymerization, when 50 g of TFE was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

The slurry of the obtained fluorinated copolymer 2 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 46 g of fluorinated copolymer 2.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 2 is as follows: repeating unit based on TFE / repeating unit based on PPVE / repeating unit based on PEVE / repeating unit based on NAH = 95 0.6 / 2.1 / 2.2 / 0.1 (mol%). The melting point was 287 ° C., and the Q value was 30 mm ³ / sec. The MIT bending life was 2.3 million times, and it was found to be excellent in stress crack resistance. The adhesive strength between the fluorine-containing copolymer 2 film and the polyamide 12 film is 13.2 N / cm, the adhesive strength with the copper foil is 9.5 N / cm, and the adhesive strength with the aluminum foil is 9 It was found to be excellent in adhesiveness. The physical properties of the resulting fluorinated copolymer 2 are shown in Table 1.

[Comparative Example 1 (TFE / PPVE copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 40 g of PPVE, and 5 g of methanol. Next, the temperature inside the polymerization tank was raised to 50 ° C., 169 g of TFE was charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm ³ of the peroxide and the polymerization was started and charged with 1 cm ³ of the polymerization initiator solution every 10 minutes thereafter. Further, TFE was continuously charged so that the pressure during polymerization was maintained at 0.99 MPa / G. After 5 hours from the start of polymerization, when 50 g of TFE was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

The slurry of the obtained fluorinated copolymer 3 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 45 g of fluorinated copolymer 3.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 3 was a repeating unit based on TFE / repeating unit based on PPVE = 98.0 / 2.0 (mol%). It was. The melting point was 300 ° C., and the Q value was 20 mm ³ / sec. The MIT bending life was 500,000 times. The film of fluorine-containing copolymer 3 did not adhere to any of PA12 film, copper foil, and aluminum foil. The physical properties of the resulting fluorinated copolymer 3 are shown in Table 1.

[Comparative Example 2 (TFE / PPVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 40 g of PPVE, and 5 g of methanol. Next, the temperature inside the polymerization tank was raised to 50 ° C., 169 g of TFE was charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm ³ of the peroxide and the polymerization was started and charged with 1 cm ³ of the polymerization initiator solution every 10 minutes thereafter. Further, TFE was continuously charged so that the pressure during polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 5.5 hours after the start of polymerization, when 50 g of TFE was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

The slurry of the obtained fluorinated copolymer 4 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 46 g of fluorinated copolymer 4.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 4 is as follows: repeating unit based on TFE / repeating unit based on PPVE / repeating unit based on NAH = 97.9 / 2.0. /0.1 (mol%). The melting point was 300 ° C., and the Q value was 23 mm ³ / sec. The MIT bending life was 300,000 times. The adhesive strength between the fluorine-containing copolymer 4 film and the PA12 film is 13.5 N / cm, the adhesive strength with the copper foil is 9.5 N / cm, and the adhesive strength with the aluminum foil is 8. 4 N / cm, both of which were found to be excellent in adhesiveness. Table 1 shows the physical properties of the obtained fluorinated copolymer.

[Example 3 (TFE / HFP / PPVE / PMVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 15 g of PPVE, 10 g of PMVE, and 5 g of methanol. Next, the temperature in the polymerization tank was raised to 50 ° C., 25 g of TFE and 300 g of HFP were charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm ³ of the peroxide and the polymerization was started and charged with 1 cm ³ of the polymerization initiator solution every 10 minutes thereafter. In addition, a mixed gas of TFE / HFP = 91/9 (molar ratio) was continuously charged so that the pressure during the polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 6.1 hours after the start of polymerization, when 50 g of a mixed gas of TFE / HFP = 91/9 (molar ratio) was charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.

The slurry of the obtained fluorinated copolymer 5 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 47 g of fluorinated copolymer 5.
From the results of the melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 5 is as follows: repeating unit based on TFE / repeating unit based on HFP / repeating unit based on PPVE / repeating unit based on PMVE / NAH The repeating unit based on the formula was 88.1 / 8.1 / 1.6 / 2.1 / 0.1 (mol%). The melting point was 246 ° C., and the Q value was 56 mm ³ / sec. The MIT bending life was 2 million times, and it was found to be excellent in stress crack resistance. The adhesive strength between the fluorine-containing copolymer 5 film and the PA12 film is 14.1 N / cm, the adhesive strength with the copper foil is 12.1 N / cm, and the adhesive strength with the aluminum foil is 12.1. It was 5 N / cm, and it was found that both were excellent in adhesiveness. The physical properties of the resulting fluorinated copolymer 5 are shown in Table 1.

[Example 4 (TFE / HFP / PPVE / PEVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated, and charged with 1131 g of AE-3000, 15 g of PPVE, 12.5 g of PEVE, and 5 g of methanol. Next, the temperature in the polymerization tank was raised to 50 ° C., 25 g of TFE and 300 g of HFP were charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm ³ of the peroxide and the polymerization was started and charged with 1 cm ³ of the polymerization initiator solution every 10 minutes thereafter. In addition, a mixed gas of TFE / HFP = 91/9 (molar ratio) was continuously charged so that the pressure during the polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 6.3 hours after the start of polymerization, when 50 g of a mixed gas of TFE / HFP = 91/9 (molar ratio) was charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.

The slurry of the obtained fluorinated copolymer 6 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 46 g of fluorinated copolymer 6.
From the results of the melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 6 is as follows: repeating unit based on TFE / repeating unit based on HFP / repeating unit based on PPVE / repeating unit based on PEVE / NAH The repeating unit based on the formula was 88.2 / 8.0 / 1.7 / 2.0 / 0.1 (mol%). The melting point was 245 ° C., and the Q value was 56 mm ³ / sec. The MIT bending life was 2.1 million times, and it was found to be excellent in stress crack resistance. The adhesive strength between the fluorine-containing copolymer 6 film and the PA12 film is 13.6 N / cm, the adhesive strength with the copper foil is 11.9 N / cm, and the adhesive strength with the aluminum foil is 13. 7 N / cm, both of which were found to be excellent in adhesiveness. The physical properties of the obtained copolymer are shown in Table 1.

[Comparative Example 3 (TFE / HFP / PPVE copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 15 g of PPVE, and 5 g of methanol. Next, the temperature in the polymerization tank was raised to 50 ° C., 25 g of TFE and 300 g of HFP were charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm ³ of the peroxide and the polymerization was started and charged with 1 cm ³ of the polymerization initiator solution every 10 minutes thereafter. In addition, a mixed gas of TFE / HFP = 91/9 (molar ratio) was continuously charged so that the pressure during the polymerization was maintained at 0.99 MPa / G. Six hours after the start of the polymerization, when 50 g of a mixed gas of TFE / HFP = 91/9 (molar ratio) was charged, the polymerization tank internal temperature was lowered to room temperature and purged to normal pressure.

The slurry of the obtained fluorinated copolymer 7 was filtered through a glass filter to separate the solvent, and then dried at 150 ° C. for 15 hours to obtain 46 g of fluorinated copolymer 7.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 7 is as follows: repeating unit based on TFE / repeating unit based on HFP / repeating unit based on PPVE = 90.5 / 8.0 /1.5 (mol%). The melting point was 262 ° C., and the Q value was 50 mm ³ / sec. The MIT bending life was 250,000 times. The film of fluorine-containing copolymer 7 did not adhere to any of PA12 film, copper foil, and aluminum foil. Table 1 shows the physical properties of the obtained fluorinated copolymer.

[Comparative Example 4 (TFE / HFP / PPVE / NAH copolymer)]
The polymerization tank equipped with a stirrer with an internal volume of 1.2 L was deaerated and charged with 1131 g of AE-3000, 15 g of PPVE, and 5 g of methanol. Next, the temperature in the polymerization tank was raised to 50 ° C., 25 g of TFE and 300 g of HFP were charged, and the pressure was increased to 0.99 MPa / G. The polymerization initiator solution as charged (perfluoro-butyryl) 0.1 wt% AE-3000 solution 1 cm ³ of the peroxide and the polymerization was started and charged with 1 cm ³ of the polymerization initiator solution every 10 minutes thereafter. In addition, a mixed gas of TFE / HFP = 91/9 (molar ratio) was continuously charged so that the pressure during the polymerization was maintained at 0.99 MPa / G. In addition, a 0.3 mass% AE-3000 solution of NAH in an amount corresponding to 0.2 mol% with respect to the number of moles of TFE charged during the polymerization was continuously charged. 6.1 hours after the start of polymerization, when 50 g of a mixed gas of TFE / HFP = 91/9 (molar ratio) was charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.

46 g of the fluorinated copolymer 8 was obtained by filtering the slurry of the obtained fluorinated copolymer 8 through a glass filter and separating the solvent, followed by drying at 150 ° C. for 15 hours.
From the results of melt NMR analysis and infrared absorption spectrum analysis, the copolymer composition of the fluorinated copolymer 8 is as follows: repeating unit based on TFE / repeating unit based on HFP / repeating unit based on PPVE / repeating unit based on NAH = 90 2 / 8.1 / 1.6 / 0.1 (mol%). The melting point was 260 ° C., and the Q value was 55 mm ³ / sec. The MIT bending life was 150,000 times. The adhesive strength between the fluorine-containing copolymer 8 film and the PA12 film is 14.0 N / cm, the adhesive strength with the copper foil is 10.2 N / cm, and the adhesive strength with the aluminum foil is 12. It was 5 N / cm, and it was found that both were excellent in adhesiveness. Table 1 shows the physical properties of the obtained fluorinated copolymer.

  The fluorine-containing copolymer and laminate of the present invention are excellent in heat resistance, chemical resistance, corrosion resistance, oil resistance, weather resistance and the like, and are excellent in stress crack resistance. Suitable for chemical liquid piping, automotive fuel hoses, industrial hoses, food hoses, weather resistant laminated films, weather resistant laminated sheets, IC substrates, adhesives, etc.

  Further, the coated article of the present invention is excellent in heat resistance, chemical resistance, corrosion resistance, oil resistance, weather resistance, abrasion resistance, lubricity, etc., so it is used for food, medical use, semiconductor use, chemical plant use, etc. Suitable for applications such as reactors, containers, pipes, tank trucks for transporting chemicals, shatterproof glass plates, shatterproof glass bottles, and wear-resistant ceramic parts.

Claims (4)

Repeating units based on tetrafluoroethylene _(a), repeating units based on _{CF 2 = CFOCF 2 CF 2 CF} 3 (b), CF 2 = CFOCF 3 and / or _CF 2 = CFOCF repeating units based on ₂ CF ₃ (c) , Containing a repeating unit (d) based on a polymerizable hydrocarbon monomer having a dicarboxylic anhydride group, the total mole of the repeating unit (a), the repeating unit (b), the repeating unit (c) and the repeating unit (d). The repeating unit (a) is 75 to 99.79 mol%, the repeating unit (b) is 0.1 to 10.0 mol%, and the repeating unit (c) is 0.1 to 10% with respect to the amount. 2.0 the mole%, a repeating unit (d) is 0.01 to 5.0 mol%, the fluorine-containing copolymer, wherein the volume flow rate is 0.1~1000mm ³ / sec   The fluorine-containing copolymer according to claim 1, wherein the polymerizable hydrocarbon monomer having a dicarboxylic acid anhydride group is 5-norbornene-2,3-dicarboxylic acid anhydride.   A laminate comprising the fluorine-containing copolymer layer according to claim 1 and a thermoplastic resin layer other than the fluorine-containing copolymer directly laminated.   A coated article obtained by coating the surface of a substrate with the fluorine-containing copolymer according to claim 1.