WO2015125930A1 - フッ素樹脂積層体およびその製造方法 - Google Patents
フッ素樹脂積層体およびその製造方法 Download PDFInfo
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- WO2015125930A1 WO2015125930A1 PCT/JP2015/054837 JP2015054837W WO2015125930A1 WO 2015125930 A1 WO2015125930 A1 WO 2015125930A1 JP 2015054837 W JP2015054837 W JP 2015054837W WO 2015125930 A1 WO2015125930 A1 WO 2015125930A1
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- Prior art keywords
- repeating unit
- copolymer
- layer
- ethylene
- fluorine
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- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002490 poly(thioether-sulfone) polymer Polymers 0.000 description 1
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- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
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- 229920001601 polyetherimide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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- 239000007870 radical polymerization initiator Substances 0.000 description 1
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Classifications
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- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Definitions
- the present invention relates to a fluororesin laminate having a fluorine-containing copolymer layer and a method for producing the same.
- Fluorine-containing copolymers such as polytetrafluoroethylene, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers, and ethylene / tetrafluoroethylene copolymers have chemical resistance, heat resistance, weather resistance, and low friction. It has excellent properties such as electrical properties and electrical insulation, and is used in various fields such as the semiconductor industry, the aircraft and automobile industries.
- fluorine-containing copolymers Since these fluorine-containing copolymers have low mechanical strength and are expensive, attempts have been made to form laminates with other inexpensive general-purpose resin materials having excellent mechanical strength. However, the fluorine-containing copolymer has poor adhesion to other materials, and it has been difficult to obtain a laminate in which the fluorine-containing copolymer and other materials are firmly bonded.
- Patent Document 1 discloses that a fluorine-containing copolymer is provided by providing an epoxy group-containing ethylene copolymer layer between a specific fluorine-containing copolymer layer and a polyolefin resin layer. A technique for firmly bonding the layer and a layer made of a polyolefin resin or the like is disclosed.
- An object of the present invention is to provide a fluororesin laminate in which a fluorine-containing copolymer layer and a vinyl chloride copolymer layer are firmly bonded, and a method for producing the same.
- a fluorine-containing copolymer layer and a vinyl chloride copolymer layer can be obtained by using a fluorine-containing copolymer having a crystallization temperature in a specific range.
- the inventors have found that a fluororesin laminate strongly bonded through an epoxy group-containing ethylene-based copolymer layer can be obtained, and the present invention has been completed.
- the present invention has the following configuration.
- the fluorine-containing copolymer (1) comprises a repeating unit (A) based on tetrafluoroethylene, a repeating unit (B) based on ethylene, itaconic acid, itaconic anhydride, 5-norbornene-2,3-dicarboxylic acid, Containing a repeating unit (C) based on one or more selected from the group consisting of 5-norbornene-2,3-dicarboxylic anhydride, citraconic acid and citraconic anhydride, and repeating unit (A) and repeating unit (B ) And the repeating unit (C), the repeating unit (A) is 25
- the epoxy group-containing ethylene copolymer includes a repeating unit (E) based on ethylene and a repeating unit based on an epoxy group-containing monomer (F And an epoxy group-containing ethylene copolymer comprising 50 mass% or more of the epoxy group-containing ethylene copolymer [1]. ] Fluororesin laminate.
- the vinyl chloride copolymer or composition (3) thereof the vinyl chloride copolymer is a polyvinyl chloride copolymer, a chlorinated polyvinyl chloride copolymer, or a polyvinyl chloride copolymer.
- the fluorine-containing copolymer (1) further contains a repeating unit (D) based on another monomer, and the molar ratio of the repeating unit (A) to the repeating unit (D) [(A) / (D)] is a fluororesin laminate of [1], [2] or [3], wherein the ratio is 70/30 to 99.9 / 0.1.
- a fluororesin laminate in which the fluorine-containing copolymer layer and the vinyl chloride copolymer layer are firmly bonded can be obtained.
- a fluororesin laminate in which a fluorine-containing copolymer layer and a vinyl chloride copolymer layer are firmly bonded can be produced.
- the fluororesin laminate of the present invention comprises a layer (I) containing a fluorinated copolymer (1), a layer (II) comprising an epoxy group-containing ethylene copolymer or a composition (2) thereof, It includes a laminate [(I) / (II) / (III)] in which a layer (III) made of a vinyl copolymer or its composition (3) is sequentially laminated.
- the fluorine-containing copolymer (1) includes a repeating unit (A) based on tetrafluoroethylene (hereinafter referred to as “TFE”), a repeating unit (B) based on ethylene, and itaconic acid (hereinafter referred to as “IAC”). ), Itaconic anhydride (hereinafter referred to as “IAH”), 5-norbornene-2,3-dicarboxylic acid (hereinafter referred to as “NAC”), 5-norbornene-2,3-dicarboxylic anhydride (hereinafter referred to as “NAC”).
- IAH Itaconic anhydride
- NAC 5-norbornene-2,3-dicarboxylic acid
- NAC 5-norbornene-2,3-dicarboxylic anhydride
- a repeating unit (C) based on one or more selected from the group consisting of citraconic acid (hereinafter referred to as “CAC”) and citraconic anhydride (hereinafter referred to as “CAH”). And the crystallization temperature is 100 to 220 ° C.
- a fluorine-containing copolymer (1) may be used individually by 1 type, or may use 2 or more types together.
- the repeating unit (A) is 25 to 80 mol% and the repeating unit (B) is 20 to 75 mol% based on the total molar amount of the repeating unit (A), the repeating unit (B) and the repeating unit (C).
- the repeating unit (C) is 0.01 to 5 mol%, the repeating unit (A) is 40 to 65 mol%, the repeating unit (B) is 35 to 50 mol%, and the repeating unit (C) is It is preferably 0.03 to 3 mol%, the repeating unit (A) is 45 to 63 mol%, the repeating unit (B) is 37 to 55 mol%, and the repeating unit (C) is 0.05 to 1 mol%. More preferably, it is mol%.
- the fluorinated copolymer (1) is excellent in chemical resistance and heat resistance.
- the content of the repeating unit (B) is within the above range, chemical resistance and heat resistance are excellent.
- the content of the repeating unit (C) is in the above range, the fluorinated copolymer (1) is excellent in adhesiveness to other layers.
- the molar ratio [(A) / (B)] of the repeating unit (A) to the repeating unit (B) is preferably 25/75 to 80/20, more preferably 40/60 to 65/35, / 58 to 63/37 is more preferable, and 45/55 to 61/39 is most preferable.
- the molar ratio [(A) / (B)] is less than or equal to the upper limit of the above range, the mechanical strength of the fluorocopolymer (1) is more excellent, and when it is greater than or equal to the lower limit of the above range, The heat resistance of the copolymer (1) is more excellent.
- the mechanical strength and heat resistance of the fluorinated copolymer (1) are both excellent.
- the repeating unit (C) is a repeating unit based on one or more selected from the group consisting of IAC, IAH, NAC, NAH, CAC and CAH, and is preferably a repeating unit based on IAH from the viewpoint of excellent polymerizability.
- IAC, IAH, NAC, NAH, CAC, and CAH is used, conventionally, for example, when maleic anhydride described in JP-A-11-19312 is used, A fluorine-containing copolymer having a repeating unit based on these acid monomers can be easily produced without using a special polymerization method.
- the fluorinated copolymer (1) has a repeating unit (D) based on other monomers in addition to the repeating units (A) to (C), so that the crystallization temperature of the fluorinated copolymer (1) Is preferable because the crystallization temperature is easily controlled within the above range.
- Other monomers constituting the repeating unit (D) are monomers other than TFE, ethylene, IAC, IAH, NAC, NAH, CAC and CAH, and examples thereof include fluorine-containing monomers and non-fluorine-containing monomers. Other monomers may be used alone or in combination of two or more.
- the fluorine-containing monomer constituting the repeating unit (D) is a monomer other than TFE having a fluorine atom.
- VDF vinyl fluoride
- HFP Hexafluoropropylene
- chlorotrifluoroethylene CH 2 ⁇ CH (CF 2 ) Q1 F (where Q1 is an integer of 2 to 10), CH 2 ⁇ CF (CF 2) Q2 H (provided that, Q2 2-10 integers.) and the like of the fluorine-containing olefin
- the fluorine-containing monomer may be linear or branched. Moreover, a fluorine-containing monomer may be used individually by 1 type, or may use 2 or more types together.
- Each of R 1 to R 3 is preferably a fluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms of the fluoroalkyl group in R 1 to R 3 is preferably 1 to 6, and more preferably 1 to 4.
- a perfluoroalkyl group such as CF 3 group, C 2 F 5 group, C 3 F 7 group and the like is particularly preferable.
- CH 2 CH (CF 2) Q1 F Q 1 of a polymerizable, in terms of continuous operation, preferably an integer of 2-6.
- the non-fluorine-containing monomer constituting the repeating unit (D) is a monomer having no fluorine atom other than ethylene, IAC, IAH, NAC, NAH, CAC and CAH.
- methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether examples thereof include vinyl ethers such as tert-butyl vinyl ether, methoxyethyl vinyl ether and ethoxyethyl vinyl ether; ⁇ -olefins such as propylene, butene and isobutene.
- a non-fluorine-containing monomer may be used individually by 1 type, or may use 2 or more types together.
- the fluorinated copolymer (1) it is preferable to use a fluorinated monomer as the other monomer constituting the repeating unit (D).
- a fluorinated monomer As the fluorine-containing monomer constituting the repeating unit (D), it is preferable to use at least HFP.
- the repeating unit (D) includes the repeating unit (D1) based on HFP, the crystallization temperature of the fluorinated copolymer (1) is increased without reducing the heat resistance of the fluorinated copolymer (1). Easy to control to range.
- the repeating unit (D) includes the repeating unit (D1) based on HFP and the repeating unit (D2) based on CH 2 ⁇ CH (CF 2 ) Q1 F, the repeating unit (D1) is included.
- the molar ratio [(A) / (D)] of the repeating unit (A) based on TFE and the repeating unit (D) based on another monomer is 60/40 to 99.9 / 0.1. Preferably, 65/35 to 98/2 is more preferable, and 68/32 to 95/5 is most preferable.
- the molar ratio [(A) / (D)] is less than or equal to the upper limit of the above range, the crystallization temperature of the fluorinated copolymer (1) is lowered, and the crystallization temperature is easily controlled within the above range.
- the molar ratio [(A) / (D)] is not less than the lower limit of the above range, the fluorinated copolymer (1) is excellent in chemical resistance and heat resistance.
- the molar ratio [(D1) / (D2)] of the repeating unit (D1) to the repeating unit (D2) is 75 / It is preferably 25 to 97/3, more preferably 80/20 to 96/4, and most preferably 85/15 to 95/5.
- the molar ratio [(D1) / (D2)] is not more than the upper limit of the above range, the stress crack resistance and moldability of the fluorinated copolymer (1) are more excellent.
- the molar ratio [(D1) / (D2)] is at least the lower limit of the above range, the crystallization temperature of the fluorinated copolymer (1) can be easily controlled by the above range.
- Examples of the fluorinated copolymer (1) include copolymers comprising the following repeating units (1) to (5). Among these, the following (5) is preferred.
- the fluorine-containing copolymer (1) has a repeating unit (D1), all the repeating units other than the repeating unit (D1) and the repeating unit (D1) constituting the fluorine-containing copolymer (1) (
- the molar ratio [(M1) / (D1)] to M1) is preferably 85/15 to 94/6, more preferably 90/10 to 93/7.
- the crystallization temperature of the fluorinated copolymer (1) does not become too high and the moldability is excellent.
- the molar ratio [(M1) / (D1)] is greater than or equal to the lower limit of the above range, the polymerization reaction during the production of the fluorinated copolymer (1) proceeds without problems, and the productivity is excellent. The heat resistance and moldability of the polymer (1) are more excellent. When the molar ratio [(M1) / (D1)] is within the above range, the productivity, heat resistance and moldability of the fluorinated copolymer (1) are excellent.
- the fluorine-containing copolymer (1) has a repeating unit (P) based on propylene, all the units other than the repeating unit (P) and the repeating unit (P) constituting the fluorine-containing copolymer (1)
- the molar ratio [(M2) / (P)] with the repeating unit (M2) is preferably 80/20 to 94/6, and more preferably 85/15 to 93/7.
- the molar ratio [(M2) / (P)] is less than or equal to the upper limit of the above range, the crystallization temperature of the fluorinated copolymer (1) does not become too high, the moldability is excellent, and the molar ratio [(M2 ) / (P)] is equal to or greater than the lower limit of the above range, the polymerization reaction of the fluorinated copolymer (1) proceeds without problems, and is excellent in productivity, and the heat resistance of the fluorinated copolymer (1). Excellent in moldability and moldability.
- the crystallization temperature of the fluorinated copolymer (1) is 100 to 220 ° C, preferably 120 to 205 ° C, more preferably 150 to 200 ° C.
- the layer (I) of the fluorinated copolymer (1) and the later-described epoxy group-containing When producing a fluororesin laminate having a layer (II) of an ethylene copolymer or its composition (2) and a layer (III) of a vinyl chloride copolymer or its composition (3),
- the temperature of the thermal lamination process can be set to a low temperature of 150 to 260 ° C., for example.
- the thermal decomposition of the vinyl chloride copolymer or its composition (3) when producing the fluororesin laminate is suppressed, and the layer (III) is firmly attached to the layer (I) via the layer (II).
- a bonded fluororesin laminate is obtained.
- the crystallization temperature of the fluorinated copolymer (1) is at least the lower limit of the above range, the heat-resistant discoloration of the fluorinated copolymer (1) is excellent.
- the crystallization temperature of the fluorinated copolymer (1) can be adjusted by, for example, the content of the repeating unit (D) based on other monomers, and is included in all the repeating units constituting the fluorinated copolymer (1).
- the crystallization temperature is the maximum of the crystallization peak when a differential scanning calorimeter is used and about 5 mg of sample is held at 300 ° C. for 10 minutes under a flow of dry air, and then the temperature is lowered to 100 ° C. at a rate of 10 ° C./min. The temperature corresponding to the value.
- the fluorine-containing copolymer (1) has a volume flow rate (hereinafter sometimes referred to as “Q value”) of 0.1 to 1000 mm at a temperature 20 to 50 ° C. higher than the crystallization temperature of the copolymer.
- Q value volume flow rate
- the fluorine-containing copolymer (1) is a copolymer having a temperature at which the Q value is 0.1 to 500 mm 3 / sec at a temperature 20 to 50 ° C. higher than the crystallization temperature of the copolymer.
- the copolymer has a temperature of 0.1 to 200 mm 3 / sec, and it is most preferable that the copolymer has a temperature of 0.2 to 100 mm 3 / sec. preferable.
- the Q value is a measure of molecular weight. If Q value is more than the lower limit of the said range, it will be excellent in the moldability of a fluorine-containing copolymer (1). If Q value is below the upper limit of the said range, the fluororesin laminated body which has a layer of a fluorine-containing copolymer (1) has the intensity
- the Q value is a value measured for the fluorine-containing copolymer (1) as a measurement object under the conditions of 20 to 50 ° C. higher than the crystallization temperature and a load of 68.6 N. is there. Specifically, in the Koka flow tester, the speed (mm 3 / sec) of the resin flowing out from a nozzle having a diameter of 2.1 mm and a length of 8 mm in 10 minutes.
- Q value of each fluorine-containing copolymer (1) used by the below-mentioned Example is a value measured on condition of temperature 220 degreeC and load 68.6N.
- a fluorine-containing copolymer (1) One or more types chosen from the group which consists of TFE, ethylene, IAC, IAH, NAC, NAH, CAC, and CAH, and as needed It is possible to employ a method in which other monomers to be used are charged into a reactor and copolymerized using a generally used radical polymerization initiator. For example, it may be produced according to the polymerization method described in Patent Document 1.
- the layer (II) comprising the epoxy group-containing ethylene copolymer or its composition (2) is composed of a layer (I) containing the fluorine-containing copolymer (1), a vinyl chloride copolymer described later, or a layer thereof. It acts as an adhesive layer with the layer (III) comprising the composition (3).
- the epoxy group-containing ethylene copolymer used for the layer (2) includes a copolymer comprising a repeating unit (E) based on ethylene and a repeating unit (F) based on an epoxy group-containing monomer; a repeating unit based on ethylene (E), a copolymer comprising a repeating unit (F) based on an epoxy group-containing monomer and a repeating unit (G) based on another monomer; and the like.
- Epoxy group-containing ethylene copolymers may be used alone or in combination of two or more.
- epoxy group-containing monomer examples include unsaturated glycidyl ethers (for example, allyl glycidyl ether, 2-methylallyl glycidyl ether, vinyl glycidyl ether, etc.) and unsaturated glycidyl esters (for example, glycidyl acrylate, glycidyl methacrylate, etc.). ) And the like. In these, since adhesiveness is improved more, glycidyl methacrylate is preferable.
- An epoxy group containing monomer may be used individually by 1 type, or may use 2 or more types together.
- Examples of other monomers constituting the repeating unit (G) include ethylenically unsaturated esters and ⁇ -olefins other than ethylene.
- ethylenically unsaturated esters include acrylic acid esters (for example, acrylic acid). Methyl, ethyl acrylate, etc.), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, etc.), and fatty acid vinyl esters such as vinyl acetate. Of these, ethylenically unsaturated esters are preferred.
- Other monomers may be used alone or in combination of two or more.
- a copolymer having a repeating unit (E) based on ethylene and a unit (F1) based on glycidyl methacrylate is preferable.
- Specific examples of the copolymer include an ethylene-glycidyl methacrylate copolymer.
- adhesion between layers is more excellent.
- a copolymer comprising a repeating unit (E) based on ethylene, a repeating unit (F1) based on glycidyl methacrylate, and a repeating unit (G1) based on an ethylenically unsaturated ester also has moldability and mechanical properties. This is preferable.
- the copolymer examples include ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, and ethylene-ethyl acrylate-glycidyl methacrylate copolymer. .
- ethylene-methyl acrylate-glycidyl methacrylate copolymer and ethylene-ethyl acrylate-glycidyl methacrylate copolymer are preferable from the viewpoint of adhesiveness.
- the content of the repeating unit (E) based on ethylene in all the repeating units constituting the epoxy group-containing ethylene copolymer is preferably 55 to 99.9 mol%, more preferably 70 to 94 mol%.
- the content of the repeating unit (F) based on the epoxy group-containing monomer in the total repeating units constituting the epoxy group-containing ethylene-based copolymer is preferably 0.1 to 15 mol%, and preferably 1 to 10 mol%. More preferred.
- the layer (II) is excellent in adhesiveness with other layers.
- the repeating unit based on the other monomer occupies in all the repeating units constituting the epoxy group-containing ethylene-based copolymer
- the content of (G) is preferably 1 to 30 mol%, more preferably 10 to 30 mol%.
- the method for producing the epoxy group-containing ethylene-based copolymer there are no particular restrictions on the method for producing the epoxy group-containing ethylene-based copolymer.
- ethylene, an epoxy group-containing monomer, and other monomers used as necessary are reacted under a pressure of 50 to 250 MPa.
- the polymer is charged into a vessel and radical polymerization may be performed at 120 to 300 ° C. in the presence of a suitable radical generator.
- the polymerization method include known bulk polymerization, solution polymerization, suspension polymerization and the like.
- the polymerization can be carried out by a batch operation or continuous operation using a single tank or multi-tank type stirring polymerization apparatus, tube polymerization apparatus, and the like.
- epoxy group-containing ethylene copolymer a commercially available product can also be used.
- Commercially available products include "Bond Fast E (trade name, manufactured by Sumitomo Chemical Co., Ltd.)" which is an ethylene-glycidyl methacrylate copolymer, and "Bond Fast 7M” (product) which is an ethylene-methyl acrylate-glycidyl methacrylate copolymer. Name, manufactured by Sumitomo Chemical Co., Ltd.).
- an epoxy group-containing ethylene copolymer composition containing 50 mass% or more of the epoxy group-containing ethylene polymer can be used for the layer (II).
- components other than the epoxy group-containing ethylene copolymer that may be contained in the epoxy group-containing ethylene copolymer composition in a range of less than 50% by mass include rubber, thermoplastic elastomer, and epoxy group-containing ethylene Examples include modifiers such as ethylene copolymers other than copolymers; various additives such as heat stabilizers, lubricants, and pigments.
- the ethylene copolymer other than the epoxy group-containing ethylene copolymer is preferably an ethylene-ethylenically unsaturated ester copolymer from the viewpoint of excellent compatibility with the epoxy group-containing ethylene copolymer.
- the thermoplastic elastomer include olefinic TPO (thermoplastic polyolefin elastomer) in terms of excellent compatibility with the epoxy group-containing ethylene copolymer.
- vinyl chloride copolymer or composition thereof (3) examples include a polyvinyl chloride copolymer having a repeating unit (H) based on vinyl chloride and a chlorinated polyvinyl chloride copolymer obtained by chlorinating the copolymer. These may be used alone or in combination.
- the polyvinyl chloride copolymer may have a repeating unit (J) based on ⁇ -olefin in addition to the repeating unit (H) based on vinyl chloride.
- ⁇ -olefin constituting the repeating unit (J) include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1 - ⁇ -olefins having about 2 to 10 carbon atoms such as octene and 1-decene.
- the content of the repeating unit (H) in the total of the repeating unit (H) and the repeating unit (J) is preferably 50 to 99.9 mol%, more preferably 90 to 99.5 mol%, 99.5 mol% is most preferred.
- the content of the repeating unit (J) is preferably from 0.1 to 50 mol%, more preferably from 0.5 to 10 mol%, most preferably from 0.5 to 5 mol%.
- the polyvinyl chloride copolymer may have a repeating unit (K) based on an epoxy group-containing monomer in addition to the repeating unit (H) and the repeating unit (J).
- the epoxy group-containing monomer constituting the repeating unit (K) include glycidyl esters, glycidyl ethers, and glycidyl amines having an ethylenically unsaturated group that can be copolymerized with ethylene.
- glycidyl esters include glycidyl acrylate, glycidyl methacrylate, monoglycidyl maleate, diglycidyl maleate, monoglycidyl fumarate, diglycidyl fumarate, glycidyl crotonic acid, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl citraconic acid, Examples include citraconic acid diglycidyl, glutaconic acid monoglycidyl ester, glutaconic acid diglycidyl ester, mesaconic acid monoglycidyl ester, and mesaconic acid diglycidyl ester.
- glycidyl ethers examples include allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, isopropenyl glycidyl ether, 1-butenyl glycidyl ether, 2-butenyl glycidyl ether, and 2-pentenyl glycidyl ether.
- glycidyl methacrylate is preferable from the viewpoints of availability, price, and effects.
- the polyvinyl chloride copolymer is a copolymer comprising a repeating unit (H), a repeating unit (J) and a repeating unit (K), the repeating unit (H), the repeating unit (J) and the repeating unit (H).
- the content of the repeating unit (H) in the total of K) is preferably from 50 to 99.9 mol%, more preferably from 80 to 95.5 mol%.
- the content of the repeating unit (J) is preferably from 0.1 to 10 mol%, more preferably from 0.5 to 5 mol%.
- the content of the repeating unit (K) is preferably more than 0 and 20 mol%, and preferably 1 to 15 mol%.
- the method for producing the polyvinyl chloride copolymer there is no particular limitation on the method for producing the polyvinyl chloride copolymer.
- vinyl chloride and, if necessary, ⁇ -olefin and epoxy group-containing monomer are used in the reactor under a pressure of 0.5 to 2 MPa.
- the radical polymerization may be carried out at 20 to 100 ° C. in the presence of a suitable radical generator.
- the polymerization method include known bulk polymerization, solution polymerization, suspension polymerization and the like.
- the polymerization can be carried out by a batch operation or continuous operation using a single tank or multi-tank type stirring polymerization apparatus, tube polymerization apparatus, and the like.
- a commercial item can also be used for a polyvinyl chloride copolymer.
- the average degree of polymerization of the polyvinyl chloride copolymer is preferably 500 to 4000, more preferably 500 to 2000, particularly preferably 600 to 1000, and most preferably 600 to 800 from the viewpoint of moldability.
- the chlorinated polyvinyl chloride copolymer is a copolymer in which one or more hydrogen atoms in the repeating unit (H) of the vinyl chloride copolymer are substituted with chlorine.
- the number of chlorine atoms in each repeating unit (H) may be the same or different.
- the chlorinated polyvinyl chloride copolymer is preferably a chlorinated polyvinyl chloride copolymer of the above preferred embodiment. Commercial products can also be used as the chlorinated polyvinyl chloride copolymer.
- the layer (3) includes a polyvinyl chloride copolymer, a chlorinated polyvinyl chloride copolymer obtained by chlorinating the copolymer, a vinyl chloride copolymer composed of any of these, and the chloride.
- a vinyl chloride copolymer composition containing a vinyl copolymer as a matrix and containing at least one selected from carbon black, an elastomer component, glass fiber, and carbon fiber can also be used.
- the content of carbon black, elastomer component, glass fiber and carbon fiber is preferably 50% by mass or less in the vinyl chloride copolymer composition. That is, the vinyl chloride copolymer composition is a vinyl chloride copolymer composition containing more than 50% by mass of the vinyl chloride copolymer.
- a thermoplastic elastomer etc. are mentioned as an elastomer component.
- the vinyl chloride copolymer composition may contain, for example, a stabilizer, a lubricant, a plasticizer, a filler, a colorant, rubber, a modifier such as an ethylene copolymer that does not fall under the vinyl chloride copolymer.
- a stabilizer for example, a stabilizer, a lubricant, a plasticizer, a filler, a colorant, rubber, a modifier such as an ethylene copolymer that does not fall under the vinyl chloride copolymer.
- ethylene copolymer chlorinated polyethylene or the like is preferable because it can modify low-temperature impact strength and is excellent in compatibility with a vinyl chloride copolymer.
- the fluororesin laminate of the present invention comprises a layer (I) containing a fluorinated copolymer (1), a layer (II) comprising an epoxy group-containing ethylene copolymer or a composition (2) thereof, A layered body [(I) / (II) / (III)] in which the layer (III) made of the vinyl copolymer or the composition (3) thereof is laminated in this order is included.
- the layer (I) containing the fluorine-containing copolymer (1) is a layer containing 50% or more, preferably 75% or more, more preferably 90% or more of the fluorine-containing copolymer.
- the fluororesin laminate of the present invention may be a laminate in which one or more other layers are laminated on the outside of the layer (III).
- another resin layer (IV) on the outside of the layer (III) Laminate [(I) / (II) / (II) / (III) / (IV)], resin layer (IV) and resin layer (V). / (III) / (IV) / (V)] and the like.
- the fluororesin laminate of the present invention has a laminate [(I) / (II) / (III)], the total number of layers is not limited.
- the layers (I) and (II) are extremely firmly bonded by being laminated under heating.
- This is an acid group of a monomer selected from the group consisting of IAC, IAH, NAC, NAH, CAC, CAH that forms the repeating unit (C) in the fluorine-containing copolymer (1) that forms the (I) layer or
- the acid anhydride group and the epoxy group in the epoxy group-containing ethylene copolymer forming the layer (II) undergo some kind of reaction (for example, an epoxy ring-opening reaction with an acid) at the laminated interface. It is thought to be due to combining.
- the fluorinated copolymer (1) forming the layer (I) has a low crystallization temperature of 100 to 220 ° C.
- a laminate [(I) / (II) / (III)] is produced. It is possible to set the temperature at the time of heating to a low temperature of 150 to 260 ° C., for example. Therefore, when manufacturing a laminated body, the thermal decomposition of the vinyl chloride copolymer used for the layer (III) is suppressed, and the layer (III) is firmly attached to the layer (I) via the layer (II). Glue.
- the layer (III) acts as an adhesive layer. Then, the laminate [(I) / (II) / (III)] and the other resin layer (IV) are firmly bonded.
- the resin forming the layer (layer (IV), layer (V),%) Laminated on the outside of the layer (III) is not particularly limited.
- polyethylene high density polyethylene, medium density
- Polyethylene low density polyethylene, ultra-low density polyethylene, etc.
- polypropylene polybutene, polybutadiene, ABS resin, polystyrene, methacrylic resin, norbornene resin, polyvinylidene chloride, polybutylene terephthalate, polyethylene naphthalate, polyester, polycarbonate, polyamide, Polyimide, thermoplastic polyimide, polyamino bismaleimide, polysulfone, polyphenylene sulfide, polyether ether ketone, polyether imide, polyether ketone, polyether sulfone, polythioether sulfone, polyester Polyether nitrile, polyphenylene ether, thermosetting epoxy resins, urethane resins, urea resins, phenol resins, melamine resins
- each layer in the fluororesin laminate is not particularly limited.
- the layer (I) has a thickness of 3 to 2000 ⁇ m
- the layer (II) has a thickness of 2 to 1500 ⁇ m
- the layer (III) has a thickness of about 50 to 100,000 ⁇ m.
- the ratio of each layer is not particularly limited.
- the layer (I) is 0.003 to 98%
- the layer (II) is 0.002 to 97%
- the layer (III) is based on the total thickness. Is 1.4 to 99.99%.
- the total thickness of the fluororesin laminate (that is, the total thickness of the three layers of layer (I), layer (II) and layer (III), excluding the thickness of the additional layer))
- it is 50 to 100,000 ⁇ m, preferably 100 to 30,000 ⁇ m.
- the fluororesin laminate may be in the form of a sheet, a three-dimensional shape obtained by three-dimensionally forming a sheet, a tube shape, or the like, and the shape is not limited.
- the fluororesin laminate of the present invention has a multilayer extrusion molding (coextrusion molding), an extrusion laminate molding, a multilayer laminate molding using a heating roll and a heating press, a multilayer injection molding, and a multilayer blow molding because of the ease of molding and productivity. It can manufacture suitably by the method which has thermal lamination processes, such as. Specifically, layer (I), layer (II), layer (III) and other layers provided as needed are laminated and bonded in a single-stage thermal lamination process such as multilayer extrusion molding or multilayer laminate molding. And a method of forming a fluororesin laminate.
- a first thermal lamination step of laminating the layer (I) and the layer (II) by multilayer extrusion molding or extrusion lamination molding is performed, and then the layer (I) obtained in the first thermal lamination step
- a method of performing a second thermal lamination step in which the layer (III) is hot-pressed on the laminate comprising the layer (II) is performed, and then a method of performing a third thermal lamination process in which another layer is further heated and pressed; a method of producing by a multistage thermal lamination process of two or more stages, and the like.
- the thermal lamination process in which the layer (III) and the layers other than the layer (III) are laminated under heating is preferably performed at 150 to 260 ° C., more preferably 180 to 250 ° C. Adhesion can be sufficiently achieved when the temperature in the thermal lamination step of laminating the layer (III) and a layer other than the layer (III) is at least the lower limit of the above range. When the amount is not more than the upper limit of the above range, the thermal decomposition of the vinyl chloride copolymer constituting the layer (III) is suppressed, and the adhesive force becomes sufficient.
- a first heat lamination process is performed in which a laminate [(I) / (II)] is formed by multilayer extrusion molding or extrusion lamination molding, and then the layer (III) is hot pressed to form a fluororesin laminate.
- a laminate [(I) / (II)] is formed by multilayer extrusion molding or extrusion lamination molding, and then the layer (III) is hot pressed to form a fluororesin laminate.
- the heating and holding time in each thermal lamination step is preferably 0.1 second to 1 hour. If it is 0.1 second or more, the adhesive force is stable, and if it is 1 hour or less, the productivity is excellent.
- the thermal lamination step may be performed in the air, in an inert gas, or under reduced pressure.
- it is preferable to carry out in an inert gas or under reduced pressure.
- the fluororesin copolymer of the present invention uses the fluorocopolymer (1) having a crystallization temperature in a specific range, the thermal decomposition of the layer (III) in the production process is suppressed. The three layers are firmly bonded.
- Crystallization temperature Using a differential scanning calorimeter (DSC-7020, manufactured by SII Corporation), about 5 mg of a sample was held at 300 ° C. for 10 minutes under a flow of dry air, and then lowered to 100 ° C. at a rate of 10 ° C./min. The temperature corresponding to the maximum value at the crystallization peak was taken as the crystallization temperature.
- composition of fluorinated copolymer (1) It was determined by melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis.
- the fluorinated copolymer (1-1) is The ratio of the repeating unit based on HFP / the repeating unit based on CH 2 ⁇ CH (CF 2 ) 4 F / the repeating unit based on IAH / the repeating unit based on ethylene is 46.2 / 9.4 / 1.0 / 0. It was 4 / 43.0 (molar ratio). Further, the Q value of the fluorinated copolymer (1-1) (measured with a flow tester manufactured by Shimadzu Corporation. Measurement temperature is 220 ° C., load is 68.6 N) is 7.2 mm 3 / second, crystal The conversion temperature was 170 ° C.
- an epoxy group-containing ethylene-based copolymer having a repeating unit based on glycidyl methacrylate / an ethylene repeating unit of 2.6 / 97.4 (molar ratio) (trade name; Bondfast E, manufactured by Sumitomo Chemical Co., Ltd.)
- a polyvinyl chloride copolymer (trade name: TH-640, manufactured by Taiyo PVC Co., Ltd., average polymerization degree 620 to 660).
- the inner layer was the above-mentioned fluorinated copolymer (1-1), the intermediate layer was “Bond Fast E”, and the outer layer was “TH-640”.
- the extruder for the inner layer one having a diameter of 40 mm was used, and the cylinder temperature was set to 220 to 240 ° C.
- An intermediate layer extruder having a diameter of 30 mm was used, and the cylinder temperature was set to 180 to 220 ° C.
- the outer layer extruder used had a diameter of 50 mm, and the cylinder temperature was set to 180 to 200 ° C.
- the temperature of the die after the resins forming the three layers merged was 240 ° C.
- middle layer extruder was hold
- the discharge amount of each extruder and the take-up speed of the tube were adjusted so that the final tube shape was 6 mm inside diameter, 8 mm outside diameter, and the wall thickness was 0.1 mm inner layer, 0.1 mm intermediate layer, and 0.8 mm outer layer. Thus, the take-up speed was 10 m / min.
- the tube discharged from the die passed through the vacuum sizing part, and then cooled in the water tank to fix the final shape.
- the obtained three-layer tube comprises (1) a fluorine-containing copolymer layer (I), (2) an epoxy group-containing ethylene copolymer layer (II), and a polyvinyl chloride copolymer.
- This corresponds to a fluororesin laminate [(I) / (II) / (III)] in which the layer (III) is sequentially laminated.
- the outer diameter of the laminate was read with an infrared outer diameter measuring device after cooling, and the inner diameter and the thickness of each layer were cut by cutting a molded tube and the cross section was taken with an optical microscope at a magnification of 20 times.
- This three-layer tube was cut out to a length of 75 mm and then opened in the longitudinal direction to obtain a rectangular sample having a length of 75 mm in the longitudinal direction and a side length of 10 mm perpendicular to the longitudinal direction. Then, the laminate interface between the sample layer (II) and the layer (III) was peeled by about 1 cm in the longitudinal direction by hand to obtain a test piece. At this time, the layer (I) and the layer (II) could not be peeled by hand.
- the peel strength (adhesive strength) was calculated by dividing the load when the laminate interface between layer (II) and layer (III) of this test piece was peeled off at 30 mm / min with a tensile tester by the test piece width. . The peel strength was as high as 15.1 N / cm.
- Example 2 Example 1 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation) was used in place of the polyvinyl chloride copolymer as a material for forming the layer (III). A three-layer tube was produced in the same manner. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation
- the fluorinated copolymer (1-2) is The ratio of the repeating unit based on HFP / the repeating unit based on CH 2 ⁇ CH (CF 2 ) 4 F / the repeating unit based on IAH / the repeating unit based on ethylene is 46.9 / 9.0 / 1.0 / 0. It was 4 / 42.7 (molar ratio). Further, the Q value of the fluorine-containing copolymer (1-2) (measured with a flow tester manufactured by Shimadzu Corporation. Measurement temperature is 220 ° C., load is 68.6 N) is 15.3 mm 3 / second, crystal The conversion temperature was 171 ° C.
- Example 1 Three layers are formed in the same manner as in Example 1 except that the fluoropolymer (1-2) is used instead of the fluorocopolymer (1-1) as a material for forming the layer (I).
- a tube was manufactured. The peel strength of this tube was as high as 16 N / cm, and the peel location was the laminated interface between the layer (II) and the layer (III), as in Example 1.
- the obtained slurry-like fluorine-containing copolymer (1-3) is put into a 200 L granulation tank charged with 77 kg of water, heated to 105 ° C. with stirring, and the solvent is distilled off. Granulated while removing. The obtained granulated product was dried at 150 ° C. for 15 hours to obtain 6.9 kg of a dry granulated product of the fluorinated copolymer (1-3). From the results of melt NMR analysis, fluorine content analysis, and infrared absorption spectrum analysis of the fluorinated copolymer (1-3), the fluorinated copolymer (1-3) is a repeating product based on tetrafluoroethylene.
- the ratio of the repeating unit based on unit / CH 2 ⁇ CH (CF 2 ) 2 F / the repeating unit based on IAH / ethylene was 58.6 / 2.0 / 0.3 / 39.1 (molar ratio).
- the Q value of the fluorinated copolymer (1-3) (measured with a flow tester manufactured by Shimadzu Corporation. Measurement temperature is 297 ° C., load is 68.6 N) is 30 mm 3 / sec, crystallization temperature was 223 ° C.
- the inner layer was the above-mentioned fluorine-containing copolymer (1-3), the intermediate layer was “Bond Fast E”, and the outer layer was “TH-640”.
- the extruder for the inner layer one having a diameter of 40 mm was used, and the cylinder temperature was set at 270 to 300 ° C.
- An intermediate layer extruder having a diameter of 30 mm was used, and the cylinder temperature was set to 180 to 220 ° C.
- the outer layer extruder used had a diameter of 50 mm, and the cylinder temperature was set to 180 to 200 ° C.
- the temperature of the die after the resins forming the three layers merged was set to 300 ° C.
- middle layer extruder was hold
- the discharge amount of each extruder and the take-up speed of the tube were adjusted so that the final tube shape was 6 mm inside diameter, 8 mm outside diameter, and the wall thickness was 0.1 mm inner layer, 0.1 mm intermediate layer, and 0.8 mm outer layer. As a result, the take-up speed was 10 m / min.
- the tube discharged from the die passed through the vacuum sizing part, and then cooled in the water tank to fix the final shape.
- Comparative Example 2 Comparative Example 1 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation) was used as a material for forming the layer (III) instead of the polyvinyl chloride copolymer. Thus, a three-layer tube was manufactured. The peel strength of this tube was 3 N / cm, and the peel location was the laminated interface between layer (II) and layer (III), as in Example 1.
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation
- Comparative Example 3 A three-layer tube was manufactured in the same manner as in Comparative Example 1 except that the cylinder temperature of the inner layer extruder was set to 220 to 240 ° C. However, the set temperature of the cylinder was low, and the resin could be extruded stably. There wasn't.
- the fluorinated copolymer (1-4) is a repeating unit / based on TFE /
- the ratio of the repeating unit based on HFP / the repeating unit based on CH 2 ⁇ CH (CF 2 ) 4 F / the repeating unit based on IAH / the repeating unit based on ethylene is 48.7 / 10.2 / 0.8 / 0. It was 3 / 40.0 (molar ratio).
- the Q value of the fluorine-containing copolymer (1-4) (measured with a flow tester, manufactured by Shimadzu Corporation. Measurement temperature is 220 ° C., load is 68.6 N) is 10.0 mm 3 / second, crystal The conversion temperature was 161 ° C.
- a fluorine-containing copolymer (1-4) is used instead of the fluorine-containing copolymer (1-1), and the cylinder temperature of the inner layer extruder is 210 to
- a three-layer tube was produced in the same manner as in Example 1 except that the temperature was set to 230 ° C.
- the peel strength of this tube was as high as 14 N / cm, and the peel location was the laminated interface between layer (II) and layer (III), as in Example 1.
- Example 5 Example 4 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation) was used in place of the polyvinyl chloride copolymer as a material for forming the layer (III). A three-layer tube was produced in the same manner. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation
- the fluorine-containing copolymer (1-5) is a repeating unit / based on TFE /
- the ratio of the repeating unit based on HFP / the repeating unit based on CH 2 ⁇ CH (CF 2 ) 4 F / the repeating unit based on IAH / the repeating unit based on ethylene is 54.3 / 9.1 / 0.9 / 0. 3 / 35.4 (molar ratio).
- the Q value of the fluorinated copolymer (1-5) (measured with a flow tester, manufactured by Shimadzu Corporation. Measurement temperature is 220 ° C., load is 68.6 N) is 19.0 mm 3 / sec, crystal The conversion temperature was 162 ° C.
- a fluorine-containing copolymer (1-5) is used instead of the fluorine-containing copolymer (1-1), and the cylinder temperature of the extruder for the inner layer is set to 210 to
- a three-layer tube was produced in the same manner as in Example 1 except that the temperature was set to 230 ° C.
- the peel strength of this tube was as high as 15 N / cm, and the peel location was the laminated interface between the layer (II) and the layer (III), as in Example 1.
- Example 7 Example 6 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Co., Ltd.) was used in place of the polyvinyl chloride copolymer as a material for forming the layer (III).
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Co., Ltd.
- a three-layer tube was produced in the same manner. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- the fluorine-containing copolymer (1-6) is The ratio of the repeating unit based on HFP / the repeating unit based on CH 2 ⁇ CH (CF 2 ) 4 F / the repeating unit based on IAH / the repeating unit based on ethylene is 38.0 / 17.0 / 0.4 / 0. 3 / 44.3 (molar ratio). Further, the Q value of the fluorinated copolymer (1-6) (measured with a flow tester manufactured by Shimadzu Corporation. Measurement temperature is 150 ° C., load is 68.6 N) is 40 mm 3 / sec, crystallization temperature Was 122 ° C.
- a fluorine-containing copolymer (1-6) is used instead of the fluorine-containing copolymer (1-1), and the cylinder temperature of the extruder for the inner layer is set to 170 to
- a three-layer tube was produced in the same manner as in Example 1 except that the temperature was set to 190 ° C.
- the peel strength of this tube was as high as 13 N / cm, and the peel location was the laminated interface between layer (II) and layer (III), as in Example 1.
- Example 9 Example 8 and Example 8 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation) was used as a material for forming the layer (III) instead of the polyvinyl chloride copolymer.
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation
- a three-layer tube was produced in the same manner. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- CH 2 ⁇ CH (CF 2 ) 4 F in an amount corresponding to 4 mol% and IAH in an amount corresponding to 0.3 mol% are continuously added to the total number of moles of TFE and ethylene charged during the polymerization.
- IAH in an amount corresponding to 0.3 mol%
- the fluorinated copolymer (1-7) is The ratio of the repeating unit based on HFP / the repeating unit based on CH 2 ⁇ CH (CF 2 ) 4 F / the repeating unit based on IAH / the repeating unit based on ethylene is 49.0 / 4.3 / 1.8 / 0. 3 / 44.6 (molar ratio). Further, the Q value of the fluorinated copolymer (1-7) (measured by a flow tester, manufactured by Shimadzu Corporation. The measurement temperature is 220 ° C., the load is 68.6 N) is 3.9 mm 3 / sec, crystal The conversion temperature was 196 ° C.
- a fluorine-containing copolymer (1-7) is used instead of the fluorine-containing copolymer (1-1), and the cylinder temperature of the inner layer extruder is 240 to
- a three-layer tube was produced in the same manner as in Example 1 except that the temperature was set to 260 ° C.
- the peel strength of this tube was as high as 16 N / cm, and the peel location was the laminated interface between the layer (II) and the layer (III) as in Example 1.
- Example 11 Example 10 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation) was used as a material for forming the layer (III) instead of the polyvinyl chloride copolymer. A three-layer tube was produced in the same manner. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation
- Example 3 In the same manner as in Example 1, except that the fluorine-containing copolymer (1-8) was used instead of the fluorine-containing copolymer (1-1) as a material for forming the layer (I). A layer tube was produced. The peel strength of this tube was as high as 13 N / cm, and the peel location was the laminated interface between layer (II) and layer (III), as in Example 1.
- Example 13 Example 12 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation) was used in place of the polyvinyl chloride copolymer as a material for forming the layer (III).
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation
- a three-layer tube was produced in the same manner. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- Example 3 In the same manner as in Example 1, except that the fluorine-containing copolymer (1-9) was used instead of the fluorine-containing copolymer (1-1) as a material for forming the layer (I). A layer tube was produced. The peel strength of this tube was as high as 11 N / cm, and the peel location was the laminated interface between layer (II) and layer (III), as in Example 1.
- Example 15 Example 14 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation) was used in place of the polyvinyl chloride copolymer as a material for forming the layer (III).
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation
- a three-layer tube was produced in the same manner. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- the fluorinated copolymer (1-10) is The ratio of the repeating unit based on HFP / the repeating unit based on CH 2 ⁇ CH (CF 2 ) 2 F / the repeating unit based on IAH / the repeating unit based on ethylene is 46.4 / 9.3 / 0.9 / 0. It was 4 / 43.0 (molar ratio). Further, the Q value of the fluorinated copolymer (1-10) (measured with a flow tester manufactured by Shimadzu Corporation. Measurement temperature is 220 ° C., load is 68.6 N) is 5.8 mm 3 / sec, crystal The conversion temperature was 173 ° C.
- Example 3 In the same manner as in Example 1, except that the fluorinated copolymer (1-10) was used instead of the fluorinated copolymer (1-1) as a material for forming the layer (I). A layer tube was produced. The peel strength of this tube was as high as 14 N / cm, and the peel location was the laminated interface between layer (II) and layer (III), as in Example 1.
- Example 17 Example 16 and Example 16 except that chlorinated polyvinyl chloride (trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation) was used as a material for forming the layer (III) instead of the polyvinyl chloride copolymer.
- chlorinated polyvinyl chloride trade name; heat-resistant Kane Vinyl H-536, manufactured by Kaneka Corporation
- a three-layer tube was produced in the same manner. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- Bondfast 7M manufactured by Sumitomo Chemical Co., Ltd.
- polyvinyl chloride copolymer trade name; TH-640, manufactured by Taiyo PVC Co., Ltd., average polymerization degree 620 to 660.
- the obtained three-layer tube comprises (1) a fluorine-containing copolymer layer (I), (2) an epoxy group-containing ethylene copolymer layer (II), and a polyvinyl chloride copolymer layer ( III) corresponds to the fluororesin laminate [(I) / (II) / (III)] laminated in order.
- the peel strength of this tube was as high as 52 N / cm, and the peel location was the laminated interface between the layer (II) and the layer (III) as in Example 1.
- Example 1 containing ethylene-based copolymer (trade name; Bondfast 7M, manufactured by Sumitomo Chemical Co., Ltd.) and chlorinated polyvinyl chloride (trade name; heat-resistant Kane vinyl H-536, manufactured by Kaneka Co., Ltd.)
- a three-layer tube was produced by multilayer extrusion molding in the same manner as described above.
- the obtained three-layer tube is composed of (1) a fluorine-containing copolymer layer (I), (2) an epoxy group-containing ethylene copolymer layer (II), and a chlorinated polyvinyl chloride layer (III ) Corresponds to the fluororesin laminate [(I) / (II) / (III)] laminated in order. This tube could not be peeled by hand between layer (I) and layer (II) or between layer (II) and layer (III).
- the molar ratio of the repeating units of each component (AD) of the fluorinated copolymer, the repeating unit of each component (AD) of the fluorinated copolymer Tables 1 and 2 show the molar amount and ratio, the production conditions of the fluororesin laminate, the layer configuration of the fluororesin laminate, the peel strength, the peel location, the crystallization temperature, and the like.
- the fluororesin laminate composed of the layer (I), the layer (II) and the layer (III) of the present invention, or a fluororesin laminate composed of 4 or more layers in combination with other layers has weather resistance, electrical insulation, Excellent acid / alkaline resistance, flame resistance, gas permeability, protection of laminated printed wiring boards, wiring / piping cover ducts (protection pipes), aircraft parts, vehicle parts, exterior parts of building components called exteriors, Construction hose for outer wall protection and inner wall, electrical parts, industrial hoses for transportation of oils, chemicals, paints, fruit juices, pasty foods, etc., fuel transportation hoses for gasoline, light oil, alcohol etc., for hot water supply Release of industrial films such as hoses, chemical tanks, fuel tanks, packaging, agricultural houses, release films for cast film manufacture, semiconductor green sheets, release films for IC chip manufacture, etc. Irumu, food film, can be used for wire coating, rubber processing core material or the like. It should be noted that the entire content of the specification, claims, and abstract of Japanese Patent Application No
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Abstract
Description
[1]含フッ素共重合体(1)を含有する層(I)と、エポキシ基含有エチレン系共重合体またはその組成物(2)からなる層(II)と、塩化ビニル系共重合体またはその組成物(3)からなる層(III)とが順次積層したフッ素樹脂積層体であって、
含フッ素共重合体(1)が、テトラフルオロエチレンに基づく繰り返し単位(A)と、エチレンに基づく繰り返し単位(B)と、イタコン酸、無水イタコン酸、5-ノルボルネン-2,3-ジカルボン酸、5-ノルボルネン-2,3-ジカルボン酸無水物、シトラコン酸および無水シトラコン酸からなる群より選ばれる1種以上に基づく繰り返し単位(C)とを含有し、繰り返し単位(A)と繰り返し単位(B)と繰り返し単位(C)との合計モル量に対して、繰り返し単位(A)が25~80モル%、繰り返し単位(B)が20~75モル%、繰り返し単位(C)が0.01~5モル%であり、前記含フッ素共重合体(1)の結晶化温度が100~220℃であることを特徴とするフッ素樹脂積層体。
[2]前記エポキシ基含有エチレン系共重合体またはその組成物(2)において、エポキシ基含有エチレン系共重合体は、エチレンに基づく繰り返し単位(E)とエポキシ基含有モノマーに基づく繰り返し単位(F)とからなるエポキシ基含有エチレン系共重合体であり、その組成物は、前記エポキシ基含有エチレン系共重合体を50質量%以上含有するエポキシ基含有エチレン系共重合体組成物である[1]のフッ素樹脂積層体。
[3]前記塩化ビニル系共重合体またはその組成物(3)において、塩化ビニル系共重合体は、ポリ塩化ビニル共重合体、塩素化ポリ塩化ビニル共重合体、またはポリ塩化ビニル共重合体と塩素化ポリ塩化ビニル共重合体との混合物であり、その組成物は、前記塩化ビニル系共重合体を50質量%超含有する塩化ビニル系共重合体組成物である[1]または[2]のフッ素樹脂積層体。
[4]前記含フッ素共重合体(1)が、その他のモノマーに基づく繰り返し単位(D)をさらに含有し、前記繰り返し単位(A)と前記繰り返し単位(D)とのモル比[(A)/(D)]が、70/30~99.9/0.1である、[1]、[2]または[3]のフッ素樹脂積層体。
[5]前記繰り返し単位(D)が、その他のモノマーであるヘキサフルオロプロピレンに基づく繰り返し単位(D1)を含む、[4]のフッ素樹脂積層体。
[6]前記繰り返し単位(D)が、その他のモノマーであるCH2=CH(CF2)Q1F(ただし、Q1は2~10の整数。)に基づく繰り返し単位(D2)をさらに含む、[5]のフッ素樹脂積層体。
[7]前記[1]~前記[4]のいずれかに記載のフッ素樹脂積層体の製造方法であって、前記層(III)と該層(III)以外の層とを加熱下で積層する熱積層工程を有し、該熱積層工程の温度が150~260℃であることを特徴とするフッ素樹脂積層体の製造方法。
本発明のフッ素樹脂積層体の製造方法によれば、含フッ素共重合体の層と塩化ビニル系共重合体の層とが強固に接着したフッ素樹脂積層体を製造できる。
含フッ素共重合体(1)は、テトラフルオロエチレン(以下、「TFE」という。)に基づく繰り返し単位(A)と、エチレンに基づく繰り返し単位(B)と、イタコン酸(以下、「IAC」という。)、無水イタコン酸(以下、「IAH」という。)、5-ノルボルネン-2,3-ジカルボン酸(以下、「NAC」という。)、5-ノルボルネン-2,3-ジカルボン酸無水物(以下、「NAH」という。)、シトラコン酸(以下、「CAC」という。)および無水シトラコン酸(以下、「CAH」という。)からなる群より選ばれる1種以上に基づく繰り返し単位(C)とを含有し、結晶化温度が100~220℃である。含フッ素共重合体(1)は、1種を単独で使用しても、2種以上を併用してもよい。
各繰り返し単位(A)~(C)の含有量が上記範囲内であると、含フッ素共重合体(1)は、耐薬品性、耐熱性に優れる。繰り返し単位(B)の含有量が上記範囲であると、耐薬品性、耐熱性が優れる。繰り返し単位(C)の含有量が上記範囲であると、含フッ素共重合体(1)は、他の層との接着性に優れる。
繰り返し単位(D)を構成するその他のモノマーは、TFE、エチレン、IAC、IAH、NAC、NAH、CACおよびCAH以外のモノマーであり、含フッ素モノマーと非含フッ素モノマーとが挙げられる。その他のモノマーは、1種単独で使用しても2種以上を併用してもよい。
R1~R3は、それぞれ、炭素数1~10のフルオロアルキル基であることが好ましい。
R1~R3におけるフルオロアルキル基の炭素数は、1~6が好ましく、1~4がより好ましい。フルオロアルキル基としては、CF3基、C2F5基、C3F7基等のパーフルオロアルキル基が特に好ましい。
CF2=CFOR1の具体例としては、CF2=CFOCF3、CF2=CFOCF2CF3、CF2=CFOCF2CF2CF3、CF2=CFOCF2CF2CF2CF3、CF2=CFO(CF2)8F等が挙げられ、CF2=CFOCF2CF2CF3が好ましい。
CH2=CF(CF2)Q2Hの具体例としては、CH2=CF(CF2)3H、CH2=CF(CF2)4H等が挙げられる。
繰り返し単位(D)を構成する含フッ素モノマーとしては、HFPを少なくとも用いることが好ましい。繰り返し単位(D)がHFPに基づく繰り返し単位(D1)を含むと、含フッ素共重合体(1)の耐熱性を低下させることなく、該含フッ素共重合体(1)の結晶化温度を上記範囲に制御しやすい。
繰り返し単位(D)を構成する含フッ素モノマーとしては、上述のHFPと、VDF、CF2=CFOR1、CH2=CH(CF2)Q1FおよびCH2=CF(CF2)Q2Hからなる群より選ばれる1種とを併用することがより好ましく、HFPとCH2=CH(CF2)Q1Fとを併用することが最も好ましい。繰り返し単位(D)がHFPに基づく繰り返し単位(D1)とCH2=CH(CF2)Q1Fに基づく繰り返し単位(D2)とを含むと、繰り返し単位(D1)を含むことに起因して、含フッ素共重合体(1)の結晶化温度を上記範囲に制御しやすい。
また、繰り返し単位(D2)を含むことに起因して、含フッ素共重合体(1)の結晶化温度を上記範囲に制御しやすいとともに、含フッ素共重合体(1)の耐ストレスクラック性および成形性が優れる。
また、繰り返し単位(D1)と繰り返し単位(D2)とを含むと、含フッ素共重合体(1)の生産性を良好に維持できる。
モル比[(A)/(D)]が上記範囲の上限値以下であると、含フッ素共重合体(1)の結晶化温度が低下し、該結晶化温度を上記範囲に制御しやすい。モル比[(A)/(D)]が上記範囲の下限値以上であると、含フッ素共重合体(1)は、耐薬品性、耐熱性により優れる。
モル比[(D1)/(D2)]が上記範囲の上限値以下であると、含フッ素共重合体(1)の耐ストレスクラック性および成形性がより優れる。モル比[(D1)/(D2)]が上記範囲の下限値以上であると、含フッ素共重合体(1)の結晶化温度を上記範囲により制御しやすい。
(1)繰り返し単位(A)/繰り返し単位(B)/繰り返し単位(C);
(2)繰り返し単位(A)/繰り返し単位(B)/繰り返し単位(C)/繰り返し単位(D1);
(3)繰り返し単位(A)/繰り返し単位(B)/繰り返し単位(C)/プロピレンに基づく繰り返し単位(P);
(4)繰り返し単位(A)/繰り返し単位(B)/繰り返し単位(C)/繰り返し単位(D2)/プロピレンに基づく繰り返し単位(P);
(5)繰り返し単位(A)/繰り返し単位(B)/繰り返し単位(C)/繰り返し単位(D1)/繰り返し単位(D2)。
モル比[(M1)/(D1)]が上記範囲の上限値以下であると、含フッ素共重合体(1)の結晶化温度が高くなりすぎず、成形性に優れる。モル比[(M1)/(D1)]が上記範囲の下限値以上であると、含フッ素共重合体(1)製造時の重合反応が問題なく進行し、生産性に優れるとともに、含フッ素共重合体(1)の耐熱性、成形性がより優れる。モル比[(M1)/(D1)]が上記範囲内であると、含フッ素共重合体(1)の生産性、耐熱性および成形性が優れる。
モル比[(M2)/(P)]が上記範囲の上限値以下であると、含フッ素共重合体(1)の結晶化温度が高くなりすぎず、成形性に優れ、モル比[(M2)/(P)]が上記範囲の下限値以上であると、含フッ素共重合体(1)の重合反応が問題なく進行し、生産性に優れるとともに、含フッ素共重合体(1)の耐熱性、成形性がより優れる。
Q値が上記範囲の下限値以上であれば、含フッ素共重合体(1)の成形性に優れる。Q値が上記範囲の上限値以下であれば、含フッ素共重合体(1)の層を有するフッ素樹脂積層体が実用途に使用可能な強度を有する。
なお、後述の実施例で用いた各含フッ素共重合体(1)のQ値は、温度220℃、荷重68.6Nの条件で測定される値である。
具体的には、公知の塊状重合;フッ化炭化水素、塩化炭化水素、フッ化塩化炭化水素、アルコール、炭化水素等の有機溶媒を使用する溶液重合;水性媒体および必要に応じて適当な有機溶剤を使用する懸濁重合;水性媒体および乳化剤を使用する乳化重合等で行うことができ、溶液重合が好ましい。重合は、一槽または多槽式の撹拌型重合装置、管型重合装置等を使用し、回分式または連続式操作で実施できる。
エポキシ基含有エチレン系共重合体またはその組成物(2)からなる層(II)は、含フッ素共重合体(1)を含有する層(I)と、後述の塩化ビニル系共重合体またはその組成物(3)からなる層(III)との接着層として作用する。
層(2)に用いられるエポキシ基含有エチレン系共重合体としては、エチレンに基づく繰り返し単位(E)およびエポキシ基含有モノマーに基づく繰り返し単位(F)とからなる共重合体;エチレンに基づく繰り返し単位(E)、エポキシ基含有モノマーに基づく繰り返し単位(F)およびその他のモノマーに基づく繰り返し単位(G)からなる共重合体;等が挙げられる。エポキシ基含有エチレン系共重合体は、1種単独で用いても、2種以上を併用してもよい。
該共重合体としては、具体的には、エチレン-メタクリル酸グリシジル共重合体が挙げられる。該共重合体を用いると、層間の接着性がより優れる。
また、エチレンに基づく繰り返し単位(E)と、メタクリル酸グリシジルに基づく繰り返し単位(F1)と、エチレン性不飽和エステルに基づく繰り返し単位(G1)とからなる共重合体も、成形性、機械的特性の点で好ましい。
該共重合体の具体例としては、エチレン-メタクリル酸グリシジル-酢酸ビニル共重合体、エチレン-アクリル酸メチル-メタクリル酸グリシジル共重合体、エチレン-アクリル酸エチル-メタクリル酸グリシジル共重合体が挙げられる。これらの中でも、接着性の点で、エチレン-アクリル酸メチル-メタクリル酸グリシジル共重合体、エチレン-アクリル酸エチル-メタクリル酸グリシジル共重合体が好ましい。
エポキシ基含有エチレン系共重合体を構成する全繰り返し単位中に占める、エポキシ基含有モノマーに基づく繰り返し単位(F)の含有量は、0.1~15モル%が好ましく、1~10モル%がより好ましい。エポキシ基含有モノマーに基づく繰り返し単位(F)の含有量が上記範囲の下限値以上であると、層(II)は他の層との接着性に優れる。
エポキシ基含有エチレン系共重合体組成物に50質量%未満の範囲で含まれてもよいエポキシ基含有エチレン系共重合体以外の成分としては、たとえば、ゴム、熱可塑性エラストマー、エポキシ基含有エチレン系共重合体以外のエチレン共重合体等の改質材;熱安定剤、滑剤、顔料等の各種添加剤等;が挙げられる。
エポキシ基含有エチレン系共重合体以外のエチレン共重合体としては、エポキシ基含有エチレン系共重合体との相溶性に優れる点で、エチレン-エチレン系不飽和エステル共重合体が好ましい。
熱可塑性エラストマーとしては、たとえば、エポキシ基含有エチレン系共重合体との相溶性に優れる点で、オレフィン系のTPO(熱可塑性ポリオレフィン系エラストマー)が挙げられる。
塩化ビニル系共重合体としては、塩化ビニルに基づく繰り返し単位(H)を有するポリ塩化ビニル共重合体および該共重合体を塩素化した塩素化ポリ塩化ビニル共重合体が挙げられる。これらは1種単独で使用しても混合して使用してもよい。
繰り返し単位(K)を構成するエポキシ基含有モノマーとしては、エチレンと共重合しうるエチレン性不飽和基を有するグリシジルエステル類、グリシジルエーテル類、グリシジルアミン類等が挙げられる。
グリシジルエステル類としては、たとえばアクリル酸グリシジル、メタクリル酸グリシジル、マレイン酸モノグリシジル、マレイン酸ジグリシジル、フマル酸モノグリジル、フマル酸ジグリシジル、クロトン酸グリシジル、イタコン酸モノグリシジル、イタコン酸ジグリシジル、シトラコン酸モノグリシジル、シトラコン酸ジグリシジル、グルタコン酸モノグリシジルエステル、グルタコン酸ジグリシジルエステル、メサコン酸モノグリシジルエステル、メサコン酸ジグリシジルエステル等が挙げられる。
グリシジルエーテル類としては、アリルグリシジルエーテル、2-メチルアリルグリシジルエーテル、スチレン-p-グリシジルエーテル、イソプロペニルグリシジルエーテル、1-ブテニルグリシジルエーテル、2-ブテニルグリシジルエーテル、2-ペンテニルグリシジルエーテル等が挙げられる。
これらの中では、メタクリル酸グリシジルが入手容易性、価格、効果等の点から好ましい。
ポリ塩化ビニル共重合体は、市販品も使用できる。
塩素化ポリ塩化ビニル共重合体としては、上記好ましい態様のポリ塩化ビニル共重合体を塩素化したものが好ましい。
塩素化ポリ塩化ビニル共重合体は、市販品も使用できる。
たとえば、エラストマー成分としては、熱可塑性エラストマー等が挙げられる。
本発明のフッ素樹脂積層体は、含フッ素共重合体(1)を含有する層(I)と、エポキシ基含有エチレン系共重合体またはその組成物(2)からなる層(II)と、塩化ビニル系共重合体またはその組成物(3)からなる層(III)とがこの順序で積層した積層体〔(I)/(II)/(III)〕を含む。
本発明において、含フッ素共重合体(1)を含有する層(I)とは、含フッ素共重合体を50%以上、好ましくは75%以上、より好ましくは90%以上含有する層である。
本発明のフッ素樹脂積層体は、層(III)の外側にさらに他の層が1層以上積層した積層体でもよく、たとえば、層(III)の外側に他の1層の樹脂層(IV)が積層した積層体〔(I)/(II)/(III)/(IV)〕、樹脂層(IV)および樹脂層(V)の2層が積層した積層体〔(I)/(II)/(III)/(IV)/(V)〕等が挙げられる。本発明のフッ素樹脂積層体は、積層体〔(I)/(II)/(III)〕を有する限り、層の総数には制限はない。
また、層(I)を形成している含フッ素共重合体(1)は、結晶化温度が100~220℃と低いため、積層体〔(I)/(II)/(III)〕を製造する際の温度を、たとえば150~260℃の低温とすることが可能となる。よって、積層体を製造する際において、層(III)に使用される塩化ビニル系共重合体の熱分解が抑制され、層(III)が層(II)を介して層(I)に強固に接着する。
また、該樹脂には、該樹脂をマトリックスとしてカーボンブラック、各種のエラストマー成分、ガラス繊維、カーボン繊維等が含まれていてもよい。
フッ素樹脂積層体の総厚み(すなわち、層(I)、層(II)および層(III)の3層の合計厚みであって、付加層の厚みは除かれた総厚み)には特に制限はないが、たとえば、50~100000μmであり、好ましくは100~30000μmである。
フッ素樹脂積層体は、シート状でも、シートが立体成形された立体形状でも、チューブ状等であってもよく、その形状に制限はない。
本発明のフッ素樹脂積層体は、成形の簡便性、生産性から、多層押し出し成形(共押し出し成形)、押し出しラミネート成形、加熱ロール、加熱プレスを用いた多層ラミネート成形、多層射出成形、多層ブロー成形等の熱積層工程を有する方法により、好適に製造できる。
具体的には、多層押し出し成形や多層ラミネート成形等の一段の熱積層工程で、層(I)と層(II)と層(III)と必要に応じて設けられる他の層とを積層、接着し、フッ素樹脂積層体を形成する方法が挙げられる。また、たとえば、層(I)と層(II)とを多層押し出し成形や押し出しラミネート成形で積層する第1の熱積層工程を行い、ついで、第1の熱積層工程で得られた層(I)と層(II)からなる積層体に、層(III)を加熱プレスする第2の熱積層工程を行う方法;上述の第1の熱積層工程と第2の熱積層工程とを行った後、必要に応じて、さらに他の層を加熱プレスする第3の熱積層工程を行う方法;等、2段以上の多段の熱積層工程により製造する方法が挙げられる。
たとえば、積層体〔(I)/(II)〕を多層押し出し成形や押し出しラミネート成形で形成する第1の熱積層工程を行い、ついで、これに層(III)を熱プレスして、フッ素樹脂積層体を〔(I)/(II)/(III)〕を得る第2の熱積層工程を行う場合には、第2の熱積層工程を上記温度範囲で行うことが好ましい。
熱積層工程は、大気中で行っても、不活性ガス中で行っても、減圧下で行ってもよい。たとえば、層(II)を構成するエポキシ基含有エチレン系共重合体における繰り返し単位(F)の熱分解を抑制する目的等においては、不活性ガス中または減圧下で行うことが好ましい。
なお、「%」とあるものは、特に断りがない限り、「質量%」を意味する。
各例における測定および試験は、以下のようにして実施した。
示差走査熱量計(SII株式会社製、DSC-7020)を用い、試料約5mgを乾燥空気流通下に300℃で10分保持した後、100℃まで10℃/分の降温速度で降温したときの結晶化ピークにおける極大値に対応する温度を結晶化温度とした。
溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析で求めた。
JIS K 6854-2:1999に準じて実施した。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの237.2kg、1,3-ジクロロ-1,1,2,2,3-ペンタフルオロプロパン(旭硝子社製、AK225cb、以下「AK225cb」という。)の49.5kg、HFPの122kg、CH2=CH(CF2)4F(以下、C4olf、またはC4とも記す。)の1.31kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレン(以下、エチレンをEとも記す。)の混合ガス(TFE/エチレン=89/11(モル比))で、1.5MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの2%1-ヒドロトリデカフルオロヘキサン溶液の2.5Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=54/46(モル比))を連続的に仕込んだ。また、重合中に仕込むTFEとエチレンの合計モル数に対して1モル%に相当する量のCH2=CH(CF2)4Fと0.4モル%に相当する量のIAHを連続的に仕込んだ。重合開始9.3時間後、モノマー混合ガスの29kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-1)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-1)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)4Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、46.2/9.4/1.0/0.4/43.0(モル比)であった。
また、含フッ素共重合体(1-1)のQ値(島津製作所社製、フローテスターにて測定。測定温度は220℃、荷重は68.6N。)は、7.2mm3/秒、結晶化温度は、170℃であった。
三層を形成する樹脂が合流後のダイの温度、すなわち、熱積層工程の温度は、240℃とした。なお、中間層押出機の供給部は、材料の熱分解を抑制する目的で、窒素雰囲気に保持した。最終チューブ形状が内径6mm、外径8mm、肉厚が内層0.1mm、中間層0.1mm、外層0.8mmとなるように、各押出機の吐出量およびチューブの引き取り速度を調整した。これにより、引き取り速度は、10m/分とした。ダイより吐出したチューブは、真空サイジング部を通り、その後水槽内で冷却して最終形状を固定した。
また、当該積層体の外径は、冷却後に赤外線外径測定器で読みとり、内径および各層肉厚は成形チューブを切断してその断面を光学顕微鏡で20倍の拡大写真にとり、読みとった。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)を用いた以外は、実施例1と同様にして三層チューブを製造した。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの237.0kg、AK225cbの53.4kg、HFPの119kg、CH2=CH(CF2)4Fの1.31kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=89/11(モル比))で1.5MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの3.1%1-ヒドロトリデカフルオロヘキサン溶液の2.5Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=54/46(モル比))を連続的に仕込んだ。また、重合中に仕込むTFEとエチレンの合計モル数に対して1モル%に相当する量のCH2=CH(CF2)4Fと0.4モル%に相当する量のIAHを連続的に仕込んだ。重合開始6.5時間後、モノマー混合ガスの30kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-2)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-2)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)4Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、46.9/9.0/1.0/0.4/42.7(モル比)であった。
また、含フッ素共重合体(1-2)のQ値(島津製作所社製、フローテスターにて測定。測定温度は220℃、荷重は68.6N。)は、15.3mm3/秒、結晶化温度は、171℃であった。
このチューブの剥離強度は、16N/cmと高いものであり、剥離箇所は、実施例1と同様に、層(II)と層(III)との積層界面であった。
(1)内容積が94リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの71.3kg、AK225cbの20.4kg、CH2=CH(CF2)2Fの562g、IAHの4.45gを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=89/11(モル比))で1.5MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの0.7%1-ヒドロトリデカフルオロヘキサン溶液の1Lを仕込み、重合を開始させた。重合中圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=60/40(モル比))を連続的に仕込んだ。
また、重合中に仕込むTFEとエチレンの合計モル数に対して3.3モル%に相当する量のCH2=CH(CF2)2Fと0.5モル%に相当する量のIAHを連続的に仕込んだ。重合開始9.9時間後、モノマー混合ガスの7.28kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-3)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-3)は、テトラフルオロエチレンに基づく繰り返し単位/CH2=CH(CF2)2Fに基づく繰り返し単位/IAH/エチレンに基づく繰り返し単位の比が、58.6/2.0/0.3/39.1(モル比)であった。
また、含フッ素共重合体(1-3)のQ値(島津製作所社製、フローテスターにて測定。測定温度は297℃、荷重は68.6N。)は、30mm3/秒、結晶化温度は、223℃であった。
三層を形成する樹脂が合流後のダイの温度、すなわち、熱積層工程の温度は、300℃とした。なお、中間層押出機の供給部は、材料の熱分解を抑制する目的で、窒素雰囲気に保持した。最終チューブ形状が内径6mm、外径8mm、肉厚が内層0.1mm、中間層0.1mm、外層0.8mmとなるように、各押出機の吐出量およびチューブの引き取り速度を調整した。これにより、引き取り速度は10m/分とした。ダイより吐出したチューブは、真空サイジング部を通り、その後水槽内で冷却して最終形状を固定した。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製)を用いた以外は、比較例1と同様にして成形して三層チューブを製造した。
このチューブの剥離強度は、3N/cmであり、剥離箇所は、実施例1と同様、層(II)と層(III)との積層界面であった。
内層用の押し出し機のシリンダー温度を220~240℃に設定した以外は、比較例1と同様にして三層チューブを製造したが、シリンダーの設定温度が低く、安定して樹脂を押し出すことができなかった。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの257.4kg、AK225cbの35.2kg、HFPの145kg、CH2=CH(CF2)4Fの0.87kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=92/8(モル比))で、1.47MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの2%1-ヒドロトリデカフルオロヘキサン溶液の3.7Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=60/40(モル比))を連続的に仕込んだ。
また、重合中に仕込むTFEとエチレンの合計モル数に対して0.7モル%に相当する量のCH2=CH(CF2)4Fと0.3モル%に相当する量のIAHを連続的に仕込んだ。重合開始2.7時間後、モノマー混合ガスの24kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-4)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-4)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)4Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、48.7/10.2/0.8/0.3/40.0(モル比)であった。
また、含フッ素共重合体(1-4)のQ値(島津製作所社製、フローテスターにて測定。測定温度は220℃、荷重は68.6N。)は、10.0mm3/秒、結晶化温度は、161℃であった。
このチューブの剥離強度は、14N/cmと高いものであり、剥離箇所は、実施例1と同様に、層(II)と層(III)との積層界面であった。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)を用いた以外は、実施例4と同様にして三層チューブを製造した。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの234.2kg、AK225cbの32.0kg、HFPの117kg、CH2=CH(CF2)4Fの0.81kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=94/6(モル比))で、1.35MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの2%1-ヒドロトリデカフルオロヘキサン溶液の3.1Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=65/35(モル比))を連続的に仕込んだ。
また、重合中に仕込むTFEとエチレンの合計モル数に対して0.7モル%に相当する量のCH2=CH(CF2)4Fと0.3モル%に相当する量のIAHを連続的に仕込んだ。重合開始3.4時間後、モノマー混合ガスの24kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-5)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-5)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)4Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、54.3/9.1/0.9/0.3/35.4(モル比)であった。
また、含フッ素共重合体(1-5)のQ値(島津製作所社製、フローテスターにて測定。測定温度は220℃、荷重は68.6N。)は、19.0mm3/秒、結晶化温度は、162℃であった。
このチューブの剥離強度は、15N/cmと高いものであり、剥離箇所は、実施例1と同様に、層(II)と層(III)との積層界面であった。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)を用いた以外は、実施例6と同様にして三層チューブを製造した。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの191.6kg、HFPの193kg、CH2=CH(CF2)4Fの0.33kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=89/11(モル比))で、1.57MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの2%1-ヒドロトリデカフルオロヘキサン溶液の4.8Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=54/46(モル比))を連続的に仕込んだ。また、重合中に仕込むTFEとエチレンの合計モル数に対して0.4モル%に相当する量のCH2=CH(CF2)4Fと0.4モル%に相当する量のIAHを連続的に仕込んだ。重合開始3.5時間後、モノマー混合ガスの24kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-6)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-6)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)4Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、38.0/17.0/0.4/0.3/44.3(モル比)であった。
また、含フッ素共重合体(1-6)のQ値(島津製作所社製、フローテスターにて測定。測定温度は150℃、荷重は68.6N。)は、40mm3/秒、結晶化温度は、122℃であった。
このチューブの剥離強度は、13N/cmと高いものであり、剥離箇所は、実施例1と同様に、層(II)と層(III)との積層界面であった。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)を用いた以外は、実施例8と同様にして三層チューブを製造した。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの274.9kg、HFPの74.5kg、CH2=CH(CF2)4Fの2.8kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=90/10(モル比))で、1.48MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの2%1-ヒドロトリデカフルオロヘキサン溶液の2.0Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=54/46(モル比))を連続的に仕込んだ。
また、重合中に仕込むTFEとエチレンの合計モル数に対して4モル%に相当する量のCH2=CH(CF2)4Fと0.3モル%に相当する量のIAHを連続的に仕込んだ。重合開始3.5時間後、モノマー混合ガスの24kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-7)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-7)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)4Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、49.0/4.3/1.8/0.3/44.6(モル比)であった。
また、含フッ素共重合体(1-7)のQ値(島津製作所社製、フローテスターにて測定。測定温度は220℃、荷重は68.6N。)は、3.9mm3/秒、結晶化温度は、196℃であった。
このチューブの剥離強度は、16N/cmと高いものであり、剥離箇所は実施例1と同様に、層(II)と層(III)との積層界面であった。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)を用いた以外は、実施例10と同様にして三層チューブを製造した。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの239.9kg、AK225cbの51.5kg、HFPの119kg、CH2=CH(CF2)4Fの1.32kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=89/11(モル比))で、1.50MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの1%1-ヒドロトリデカフルオロヘキサン溶液の2.5Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=54/46(モル比))を連続的に仕込んだ。
また、重合中に仕込むTFEとエチレンの合計モル数に対して1.0モル%に相当する量のCH2=CH(CF2)4Fと0.4モル%に相当する量のIAHを連続的に仕込んだ。重合開始8.4時間後、モノマー混合ガスの30kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-8)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-8)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)4Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、47.1/8.1/1.2/0.4/43.2(モル比)であった。
また、含フッ素共重合体(1-8)のQ値(島津製作所社製、フローテスターにて測定。測定温度は220℃、荷重は68.6N。)は、5.5mm3/秒、結晶化温度は172℃であった。
このチューブの剥離強度は、13N/cmと高いものであり、剥離箇所は、実施例1と同様に、層(II)と層(III)との積層界面であった。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)を用いた以外は、実施例12と同様にして三層チューブを製造した。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの237.2kg、1,3-ジクロロ-1,1,2,2,3-ペンタフルオロプロパン(旭硝子社製、AK225cb、以下「AK225cb」という。)の49.5kg、HFPの122kg、CH2=CH(CF2)6Fの1.84kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=89/11(モル比))で、1.5MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの2%1-ヒドロトリデカフルオロヘキサン溶液の3.0Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=54/46(モル比))を連続的に仕込んだ。
また、重合中に仕込むTFEとエチレンの合計モル数に対して1モル%に相当する量のCH2=CH(CF2)6Fと0.4モル%に相当する量のIAHを連続的に仕込んだ。重合開始8.1時間後、モノマー混合ガスの29kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-9)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-9)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)6Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、46.3/9.2/1.0/0.4/43.1(モル比)であった。
また、含フッ素共重合体(1-9)のQ値(島津製作所社製、フローテスターにて測定。測定温度は220℃、荷重は68.6N。)は、10.4mm3/秒、結晶化温度は、171℃であった。
このチューブの剥離強度は、11N/cmと高いものであり、剥離箇所は、実施例1と同様に、層(II)と層(III)との積層界面であった。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)を用いた以外は、実施例14と同様にして三層チューブを製造した。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
(1)内容積が430リットルの撹拌機付き重合槽を脱気し、1-ヒドロトリデカフルオロヘキサンの237.2kg、1,3-ジクロロ-1,1,2,2,3-ペンタフルオロプロパン(旭硝子社製、AK225cb、以下「AK225cb」という。)の49.5kg、HFPの122kg、CH2=CH(CF2)2Fの0.78kgを仕込み、重合槽内を66℃に昇温し、TFEとエチレンの混合ガス(TFE/エチレン=89/11(モル比))で、1.5MPa/Gまで昇圧した。重合開始剤として、tert-ブチルペルオキシピバレートの2%1-ヒドロトリデカフルオロヘキサン溶液の2.5Lを仕込み、重合を開始させた。重合中、圧力が一定になるようにTFEとエチレンのモノマー混合ガス(TFE/エチレン=54/46(モル比))を連続的に仕込んだ。
また、重合中に仕込むTFEとエチレンの合計モル数に対して1モル%に相当する量のCH2=CH(CF2)2Fと0.4モル%に相当する量のIAHを連続的に仕込んだ。重合開始7.5時間後、モノマー混合ガスの29kgを仕込んだ時点で、重合槽内温を室温まで降温するとともに、常圧までパージした。
含フッ素共重合体(1-10)についての、溶融NMR分析、フッ素含有量分析および赤外吸収スペクトル分析の結果から、当該含フッ素共重合体(1-10)は、TFEに基づく繰り返し単位/HFPに基づく繰り返し単位/CH2=CH(CF2)2Fに基づく繰り返し単位/IAHに基づく繰り返し単位/エチレンに基づく繰り返し単位の比が、46.4/9.3/0.9/0.4/43.0(モル比)であった。
また、含フッ素共重合体(1-10)のQ値(島津製作所社製、フローテスターにて測定。測定温度は220℃、荷重は68.6N。)は、5.8mm3/秒、結晶化温度は、173℃であった。
このチューブの剥離強度は、14N/cmと高いものであり、剥離箇所は、実施例1と同様に、層(II)と層(III)との積層界面であった。
層(III)を形成する材料として、ポリ塩化ビニル共重合体の代わりに塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)を用いた以外は、実施例16と同様にして三層チューブを製造した。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
実施例1と同様にして得られた含フッ素共重合体と、グリシジルメタクリレートに基づく繰り返し単位/アクリル酸メチルに基づく繰り返し単位/エチレンに基づく繰り返し単位=6/27/67(重量比)のエポキシ基含有エチレン系共重合体(商品名;ボンドファスト7M、住友化学社製)と、ポリ塩化ビニル共重合体(商品名;TH-640、大洋塩ビ社製、平均重合度620~660。)をそれぞれ準備し、実施例1に示した方法と同様にして多層押し出し成形し、三層チューブを製造した。得られた三層チューブは、(1)含フッ素共重合体の層(I)と、(2)エポキシ基含有エチレン系共重合体の層(II)と、ポリ塩化ビニル共重合体の層(III)とが順に積層したフッ素樹脂積層体〔(I)/(II)/(III)〕に相当する。
このチューブの剥離強度は、52N/cmと高いものであり、剥離箇所は、実施例1と同様に、層(II)と層(III)との積層界面であった。
実施例1と同様にして得られた含フッ素共重合体と、グリシジルメタクリレートに基づく繰り返し単位/アクリル酸メチルに基づく繰り返し単位/エチレンに基づく繰り返し単位=6/27/67(重量比)のエポキシ基含有エチレン系共重合体(商品名;ボンドファスト7M、住友化学社製)と、塩素化ポリ塩化ビニル(商品名;耐熱カネビニールH-536、カネカ社製。)をそれぞれ準備し、実施例1に示した方法と同様にして多層押し出し成形し、三層チューブを製造した。得られた三層チューブは、(1)含フッ素共重合体の層(I)と、(2)エポキシ基含有エチレン系共重合体の層(II)と、塩素化ポリ塩化ビニルの層(III)とが順に積層したフッ素樹脂積層体〔(I)/(II)/(III)〕に相当する。
このチューブは、層(I)と層(II)の間でも、層(II)と層(III)の間でも手で剥離することができなかった。
なお、2014年2月21日に出願された日本特許出願2014-032232号の明細書、特許請求の範囲、および要約書の全内容をここに引用し、本発明の開示として取り入れるものである。
Claims (7)
- 含フッ素共重合体(1)を含有する層(I)と、エポキシ基含有エチレン系共重合体またはその組成物(2)からなる層(II)と、塩化ビニル系共重合体またはその組成物(3)からなる層(III)とが順次積層したフッ素樹脂積層体であって、
含フッ素共重合体(1)が、テトラフルオロエチレンに基づく繰り返し単位(A)と、エチレンに基づく繰り返し単位(B)と、イタコン酸、無水イタコン酸、5-ノルボルネン-2,3-ジカルボン酸、5-ノルボルネン-2,3-ジカルボン酸無水物、シトラコン酸および無水シトラコン酸からなる群より選ばれる1種以上に基づく繰り返し単位(C)とを含有し、繰り返し単位(A)と繰り返し単位(B)と繰り返し単位(C)との合計モル量に対して、繰り返し単位(A)が25~80モル%、繰り返し単位(B)が20~75モル%、繰り返し単位(C)が0.01~5モル%であり、前記含フッ素共重合体(1)の結晶化温度が100~220℃であることを特徴とするフッ素樹脂積層体。 - 前記エポキシ基含有エチレン系共重合体またはその組成物(2)において、エポキシ基含有エチレン系共重合体は、エチレンに基づく繰り返し単位(E)とエポキシ基含有モノマーに基づく繰り返し単位(F)とからなるエポキシ基含有エチレン系共重合体であり、その組成物は、前記エポキシ基含有エチレン系共重合体を50質量%以上含有するエポキシ基含有エチレン系共重合体組成物である請求項1に記載のフッ素樹脂積層体。
- 前記塩化ビニル系共重合体またはその組成物(3)において、塩化ビニル系共重合体は、ポリ塩化ビニル共重合体、塩素化ポリ塩化ビニル共重合体、またはポリ塩化ビニル共重合体と塩素化ポリ塩化ビニル共重合体との混合物であり、その組成物は、前記塩化ビニル系共重合体を50質量%超含有する塩化ビニル系共重合体組成物である請求項1または2に記載のフッ素樹脂積層体。
- 前記含フッ素共重合体(1)が、その他のモノマーに基づく繰り返し単位(D)をさらに含有し、前記繰り返し単位(A)と前記繰り返し単位(D)とのモル比[(A)/(D)]が、70/30~99.9/0.1である、請求項1、2または3に記載のフッ素樹脂積層体。
- 前記繰り返し単位(D)が、その他のモノマーであるヘキサフルオロプロピレンに基づく繰り返し単位(D1)を含む、請求項4に記載のフッ素樹脂積層体。
- 前記繰り返し単位(D)が、その他のモノマーであるCH2=CH(CF2)Q1F(ただし、Q1は2~10の整数。)に基づく繰り返し単位(D2)をさらに含む、請求項5に記載のフッ素樹脂積層体。
- 請求項1~6のいずれか一項に記載のフッ素樹脂積層体の製造方法であって、
前記層(III)と該層(III)以外の層とを加熱下で積層する熱積層工程を有し、
該熱積層工程の温度が150~260℃であることを特徴とするフッ素樹脂積層体の製造方法。
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- 2015-02-20 JP JP2016504194A patent/JPWO2015125930A1/ja active Pending
- 2015-02-20 EP EP15752096.6A patent/EP3109046A4/en not_active Withdrawn
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JP2006297843A (ja) * | 2005-04-25 | 2006-11-02 | Asahi Glass Co Ltd | フッ素樹脂積層体 |
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WO2018216741A1 (ja) * | 2017-05-26 | 2018-11-29 | Agc株式会社 | 加飾フィルム |
JPWO2018216741A1 (ja) * | 2017-05-26 | 2020-03-26 | Agc株式会社 | 加飾フィルム |
JP7044110B2 (ja) | 2017-05-26 | 2022-03-30 | Agc株式会社 | 加飾フィルム |
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US20160339677A1 (en) | 2016-11-24 |
EP3109046A1 (en) | 2016-12-28 |
JPWO2015125930A1 (ja) | 2017-03-30 |
EP3109046A4 (en) | 2017-11-01 |
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