JP2014233893A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate with high interlayer adhesion.SOLUTION: A laminate comprises (A) a layer composed of polychlorotrifluoroethylene, and (B) a layer composed of fluorine-free organic material or metal. The polychlorotrifluoroethylene has 90-100 mol% of polymerization units based on chlorotrifluoroethylene, and has a carbonyl group-containing functional group at a main chain terminal.

Description

The present invention relates to a laminate.

Fluoropolymers have excellent properties not found in other resins, such as non-adhesiveness, antifouling properties, heat resistance, chemical resistance, transparency, UV degradation resistance, weather resistance, and water and oil repellency. ing. For this reason, the laminated body which has a layer which consists of a fluororesin is utilized for various uses, such as an electronic component, medical supplies, and building materials.

The cited document 1 includes a layered product including a layer made of a fluorine-containing polymer and / or a fluorine-free organic material and a layer made of a chlorotrifluoroethylene copolymer. A fluid transfer member having both stress cracking properties and low chemical solution permeability has been proposed.

International Publication WO2005 / 108051

However, the fluororesin is difficult to laminate with other materials because of its non-adhesive property, and in particular, a laminate having a layer made of polychlorotrifluoroethylene is made of a layer made of another organic material or a metal. The interlaminar adhesion with the resulting layer has not been sufficient, and improvement has been required.

An object of the present invention is to provide a laminate having high interlayer adhesion in view of the above-described present situation.

The present inventors have found that by using a specific polychlorotrifluoroethylene, interlayer adhesion between a layer made of polychlorotrifluoroethylene and a layer made of a fluorine-free organic material or metal can be improved, The present invention has been completed.

That is, the present invention includes a layer (A) made of polychlorotrifluoroethylene and a layer (B) made of a fluorine-free organic material or metal, and the polychlorotrifluoroethylene is a polymerization based on chlorotrifluoroethylene. The laminate has a unit of 90 to 100 mol% and has a carbonyl group-containing functional group at the end of the main chain.
The fluorine-free organic material includes polyamide resin, polyolefin resin, ethylene / vinyl alcohol copolymer resin, polyvinyl alcohol resin, polyurethane resin, polyester resin, polyaramid resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyacetal. Resin, polycarbonate resin, acrylic resin, styrene resin, acrylonitrile / butadiene / styrene resin, vinyl chloride resin, cellulose resin, polyetheretherketone resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, and It is preferably at least one resin selected from the group consisting of polyphenylene sulfide resins.
The fluorine-free organic material is preferably at least one resin selected from the group consisting of polyamide resins, ethylene / vinyl alcohol copolymer resins, polyvinyl alcohol resins, polyester resins, and polyimide resins.
The amount of the carbonyl group-containing functional group of the polychlorotrifluoroethylene is preferably 50 to 400 per 10 ⁶ main chain carbon atoms.
The carbonyl group-containing functional group is preferably a carbonate group and / or a carboxylic acid halide group.
The polychlorofluoroethylene is preferably a suspension polymer.
The layer (B) is preferably made of a fluorine-free organic material.
The metal is preferably at least one selected from the group consisting of aluminum, silicon, titanium, zinc, zirconium, magnesium, tin, copper, and iron.
The present invention is described in detail below.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in interlayer adhesiveness can be provided.

The present invention comprises a layer (A) made of polychlorotrifluoroethylene and a layer (B) made of a fluorine-free organic material or metal, and the polychlorotrifluoroethylene has polymerized units based on chlorotrifluoroethylene. It is 90-100 mol%, and is a laminated body characterized by having a carbonyl group-containing functional group at the end of the main chain.
For this reason, the laminated body of this invention is excellent in interlayer adhesiveness.

The laminate of the present invention has a layer (A) made of polychlorotrifluoroethylene (PCTFE).
PCTFE is a homopolymer of chlorotrifluoroethylene (CTFE) or a copolymer of polymerized units based on CTFE (CTFE units) and polymerized units based on a monomer (α) copolymerizable with CTFE. . Especially, it is more preferable that it is a homopolymer of CTFE at the point which is excellent in gas barrier property and water vapor | steam barrier property.

The PCTFE has 90 to 100 mol% of polymerized units based on chlorotrifluoroethylene (CTFE).
If the polymerized unit based on CTFE is less than 90 mol%, gas barrier properties and water vapor barrier properties may be deteriorated.
The PCTFE is more preferably 98 to 100 mol%, more preferably 99 to 100 mol%, based on CTFE.
A structural unit such as a CTFE unit is a value obtained by performing ¹⁹ F-NMR analysis. Specifically, it is a value obtained by appropriately combining NMR analysis, infrared spectrophotometer (IR), elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.

The monomer (α) polymerizable with CTFE is not particularly limited as long as it is a monomer copolymerizable with CTFE. For example, tetrafluoroethylene (TFE), ethylene (Et), vinylidene fluoride (VdF) ), Perfluoro (alkyl vinyl) ether (PAVE), the following general formula (I)
CX ³ X ⁴ = CX ¹ (CF ₂ ) _n X ² (I)
(Wherein X ¹ , X ³ and X ⁴ are the same or different and represent a hydrogen atom or a fluorine atom, X ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and n is an integer of 1 to 10) And a vinyl monomer represented by the following general formula (II):
_{CF 2 = CF-OCH 2 -Rf} (II)
And alkyl perfluorovinyl ether derivatives represented by the formula (wherein Rf is a C 1-5 perfluoroalkyl group).

Examples of the PAVE include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether).

Although it does not specifically limit as a vinyl monomer represented by the said general formula (I), For example, hexafluoropropylene (HFP), perfluoro (1,1,2- trihydro-1-hexene), perfluoro ( 1,1,5-trihydro-1-pentene), the following general formula (III)
H ₂ C═CX ⁵ Rf ⁵ (III)
(Wherein, X ⁵ is H, F, or CF ₃ , and Rf ⁵ is a perfluoroalkyl group having 1 to 10 carbon atoms).
As the perfluoro (alkyl) ethylene, perfluoro (butyl) ethylene is preferable.

As the alkyl perfluorovinyl ether derivative represented by the general formula (II), those in which Rf is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable. preferable.

The monomer (α) polymerizable with CTFE is at least one selected from the group consisting of TFE, Et, VdF, PAVE, and the vinyl monomer represented by the general formula (I). It is preferable.
1 type (s) or 2 or more types may be sufficient as the said monomer ((alpha)).

As the monomer (α), unsaturated carboxylic acids copolymerizable with CTFE may also be used.
The unsaturated carboxylic acids are not particularly limited, and examples thereof include unsaturated compounds having 3 to 6 carbon atoms such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and aconitic acid. Examples thereof include aliphatic carboxylic acids, and may be unsaturated aliphatic polycarboxylic acids having 3 to 6 carbon atoms.

The unsaturated aliphatic polycarboxylic acids are not particularly limited, and examples thereof include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid and the like, and acids such as maleic acid, itaconic acid, citraconic acid and the like. What can be an anhydride may be an acid anhydride.

The monomer (α) may be two or more, but when one of them is VdF, PAVE and / or HFP, it is not used in combination with itaconic acid, citraconic acid and acid anhydrides thereof. May be.

The PCTFE has a carbonyl group-containing functional group at the main chain end.
By having a carbonyl group-containing functional group, it is possible to adhere well to other materials.

The carbonyl group is a carbon divalent group composed of a carbon-oxygen double bond, and is represented by a group represented by -C (= O)-.
The carbonyl group-containing functional group is not particularly limited, and examples thereof include a carbonate group, a carboxylic acid halide group (halogenoformyl group), a formyl group, a carboxyl group, an ester bond (—C (═O) O—), and an acid anhydride. Bond (—C (═O) O—C (═O) —), isocyanate group, amide group, imide group (—C (═O) —NH—C (═O) —), urethane bond (—NH—) C (═O) O—), carbamoyl group (NH ₂ —C (═O) —), carbamoyloxy group (NH ₂ —C (═O) O—), ureido group (NH ₂ —C (═O)) Examples include —NH— and oxamoyl groups (NH ₂ —C (═O) —C (═O) —) that contain a carbonyl group as part of the chemical structure.

The carbonate group is represented by —OC (═O) O—R ¹ (wherein R ¹ represents an organic group).

The amide group has the following general formula

(Wherein R ² represents a hydrogen atom or an organic group, and R ³ represents an organic group).

In the amide group, imide group, urethane bond, carbamoyl group, carbamoyloxy group, ureido group, oxamoyl group, etc., the hydrogen atom bonded to the nitrogen atom may be substituted with a hydrocarbon group such as an alkyl group, for example. .

Among them, the carbonyl group-containing functional group is preferably a carbonate group and / or a carboxylic acid halide group in terms of easy introduction and good adhesiveness.

The PCTFE preferably has a carbonyl group-containing functional group amount of 50 to 400 per 10 ⁶ main chain carbon atoms. Within the above range, the interlayer adhesion between the layer (A) and the layer (B) becomes better. The amount of the carbonyl group-containing functional group is more preferably 70 or more per 10 ⁶ main chain carbon atoms, still more preferably 80 or more, more preferably 350 or less, and still more preferably 340 or less.

The carbonyl group-containing functional group is usually formed at the end of the main chain by the addition of a chain transfer agent or a polymerization initiator used during polymerization, and is derived from the structure of the chain transfer agent or polymerization initiator It is.

The number of the carbonyl group-containing functional groups is a film sheet having a thickness of 0.25 to 0.30 mm obtained by compression-molding the PCTFE powder at a molding temperature of 50 ° C. higher than its melting point and a molding pressure of 5 MPa. The infrared absorption spectrum was analyzed using an infrared spectrophotometer, and the type of characteristic absorption of the above carbonyl group-containing functional group was determined by comparison with the infrared absorption spectrum of a known film. It is the number calculated by.

Number of terminal groups (per 1 × 10 ⁶ carbon atoms) = (l × K) / t
l: Absorbance K: Correction coefficient t: Film thickness (mm)
Table 1 shows the correction coefficient of the target carbonyl group-containing functional group.

The correction coefficient in Table 1 is a value determined from the infrared absorption spectrum of the model compound in order to calculate the terminal group per 1 × 10 ⁶ main chain carbon atoms.

As a method for introducing the carbonyl group-containing functional group into the terminal, a method for introducing a carbonyl group-containing monomer (β) by copolymerization, a method for using a compound having or resulting from a carbonyl group as a polymerization initiator, carbonyl Examples thereof include a method of using a compound having or generated a group as a chain transfer agent, a method of introducing a carbonyl group into a fluoropolymer by a polymer reaction, a method of combining these methods, and the like.

In the present invention, a method using a compound having or generating a carbonyl group as a polymerization initiator and a method using a compound having or generating a carbonyl group as a chain transfer agent are preferred. By polymerizing PCTFE using a compound having or resulting from a carbonyl group as a polymerization initiator or chain transfer agent, a polymer having a carbonyl group-containing functional group at the end of the main chain is obtained.

The PCTFE can be obtained by a conventionally known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization or bulk polymerization. Among these, from the viewpoint of industrial productivity, the PCTFE is preferably a suspension polymer.
In the above polymerization, the conditions such as temperature and pressure, the polymerization initiator and other additives can be appropriately set according to the composition and amount of PCTFE.
In order to obtain PCTFE having a carbonyl group-containing functional group at the end of the main chain, as a polymerization initiator or chain transfer agent, diisopropyl peroxydicarbonate (IPP), di-n-propyl peroxydicarbonate, t-butylperoxy It is preferable to use isopropyl carbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-pethylhexyl peroxydicarbonate, or the like.

The PCTFE preferably has a melt flow rate (MFR) of 1 g / 10 min or more. The MFR is more preferably 3 g / 10 min or more, and further preferably 5 g / 10 min or more. The upper limit of MFR is, for example, 30 g / 10 minutes.
The MFR is a value that can be measured under the conditions of a temperature of 265 ° C. and a load of 10.0 kg in accordance with ASTM D3307.

The layer (A) made of PCTFE may contain other components as needed in addition to PCTFE. Examples of other components include additives such as fillers, pigments, conductive materials, heat stabilizers, reinforcing materials, and ultraviolet absorbers.
Among these, examples of the conductive material include carbon fibrils described in U.S. Pat. No. 4,663,330, JP-A-3-174018, and the like.
Additives such as the above fillers are preferably added within a range that does not impair the properties of the PCTFE copolymer.

The method for forming the layer (A) is not particularly limited, and may be formed by applying a known method such as melt extrusion molding.

The thickness of the layer (A) is preferably 1 to 500 μm. The thickness is more preferably 5 μm or more, further preferably 10 μm or more, more preferably 300 μm or less, and even more preferably 200 μm or less, in that it can be molded into a required shape after laminating.

The laminate of the present invention further includes a layer (B) made of a fluorine-free organic material or metal.
The layer (B) is preferably made of a fluorine-free organic material from the viewpoint of imparting mechanical strength and improving post-processability.

The fluorine-free organic material constituting the layer (B) is an organic material that does not contain a fluorine atom.
The fluorine-free organic material is preferably a resin that can be coextruded with PCTFE constituting the layer (A), press-moldable, and roll-to-roll laminated.

Examples of the fluorine-free organic material include polyamide resin, polyolefin resin, ethylene / vinyl alcohol copolymer resin, polyvinyl alcohol resin, polyurethane resin, polyester resin, polyaramid resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, Polyacetal resin, polycarbonate resin, acrylic resin, styrene resin, acrylonitrile / butadiene / styrene resin, vinyl chloride resin, cellulose resin, polyetheretherketone resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, and The resin is preferably at least one resin selected from the group consisting of polyphenylene sulfide resins.

Among these, the fluorine-free organic material is at least selected from the group consisting of a polyamide-based resin, an ethylene / vinyl alcohol copolymer resin, a polyvinyl alcohol resin, a polyester resin, and a polyimide resin from the viewpoint of adhesiveness. One type of resin is more preferable, and a polyvinyl alcohol resin is still more preferable from the viewpoint of gas barrier properties.

The polyamide-based resin is made of a polymer having an amide bond [—NH—C (═O) —] as a repeating unit in the molecule.
As the polyamide resin, a so-called nylon resin composed of a polymer in which an amide bond in a molecule is bonded to an aliphatic structure or an alicyclic structure, or a polymer in which an amide bond in a molecule is bonded to an aromatic structure Any of so-called aramid resins may be used.

The nylon resin is not particularly limited. For example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 66/12, nylon 46, metaxylylenediamine / adipic acid What consists of polymers, such as a copolymer, is mentioned, You may use combining 2 or more types from these.
The aramid resin is not particularly limited, and examples thereof include polyparaphenylene terephthalamide and polymetaphenylene isophthalamide.

The polyamide-based resin may be composed of a polymer in which a structure having no amide bond as a repeating unit is block-copolymerized or graft-copolymerized in a part of the molecule. Examples of such polyamide resins include nylon elastomers such as nylon 6 / polyester copolymers, nylon 6 / polyether copolymers, nylon 12 / polyester copolymers, and nylon 12 / polyether copolymers. And the like. These polyamide-based elastomers are obtained by block copolymerization of nylon oligomers and polyester oligomers via ester bonds, or by block copolymerization of nylon oligomers and polyether oligomers via ether bonds. It is obtained. Examples of the polyester oligomer include polycaprolactone and polyethylene adipate, and examples of the polyether oligomer include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. As the polyamide elastomer, nylon 6 / polytetramethylene glycol copolymer and nylon 12 / polytetramethylene glycol copolymer are preferable.

As the polyamide-based resin, sufficient mechanical strength can be obtained even if the layer made of the polyamide-based resin is thin. Among them, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 66/12, nylon 6 / polyester copolymer, nylon 6 / polyether copolymer, nylon 12 / polyester copolymer, nylon 12 / polyether copolymer, and the like. Two or more of them may be used in combination.

The ethylene / vinyl alcohol copolymer resin is preferably a copolymer consisting of 10 to 60 mol% ethylene and 90 to 40 mol% vinyl alcohol, 20 to 50 mol% ethylene, and 80 to 50 mol vinyl alcohol. It is more preferable that the copolymer is composed of%. Further, it may contain a third component, and the third component is an α-olefin such as propylene, isobutylene, 4-methylpentene-1, 1-hexene, 1-octene; vinyl acetate, vinyl propionate , Vinyl esters of versatic acid, vinyl esters of pivalic acid, vinyl esters of valeric acid, vinyl esters of capric acid, vinyl esters of benzoic acid; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride Or a derivative thereof (eg, salt, ester, nitrile, amide, anhydride, etc.); vinylsilane compound such as vinyltrimethoxysilane; unsaturated sulfonic acid or salt thereof; N-methylpyrrolidone; Of ethylene and vinyl alcohol Relative to the amount is preferably 10 mol% or less.

Polyester terephthalate [PET], polybutylene terephthalate [PBT], polytrimethylene terephthalate [PTT], polyethylene naphthalate [PEN], polybutylene naphthalate [PBN], parahydroxybenzoic acid / ethylene terephthalate Examples thereof include a polymer, a hydroxynaphthoic acid / parahydroxybenzoic acid copolymer, and a biphenol / parahydroxybenzoic acid / phthalic acid copolymer.

The polyimide resin is not particularly limited as long as it is a resin composed of a polymer having an imide bond in the molecular structure. For example, it can be obtained by a reaction of an aromatic tetravalent carboxylic anhydride such as pyromellitic anhydride. Examples thereof include resins made of molecular weight polymers.

The fluorine-free organic material preferably has a melting point of 50 to 400 ° C. A more preferred lower limit is 100 ° C, and even more preferred is 150 ° C. A more preferable upper limit is 300 ° C., and further preferably 250 ° C.
The said melting | fusing point is the value calculated | required as temperature corresponding to the maximum value in the heat of fusion curve when it heats up at a speed | rate of 10 degree-C / min using a differential scanning calorimeter (DSC) apparatus (made by Seiko).

The layer made of the fluorine-free organic material can be made conductive by further blending the fluorine-free organic material with a conductive material. The conductive material is not particularly limited, and examples thereof include conductive simple powders such as metals and carbon or conductive single fibers; conductive compound powders such as zinc oxide: surface conductive powder.

The conductive single powder or conductive single fiber is not particularly limited, and examples thereof include metal powders such as copper and nickel; metal fibers such as iron and stainless steel; carbon black and carbon fibers.

In addition to the conductive material, the layer (B) made of the fluorine-free organic material is within a range that does not impair the object of the present invention, for example, a stabilizer such as a heat stabilizer, a reinforcing agent, a filler, and an ultraviolet absorber. In addition, various additives such as pigments may be contained.

The method for forming the layer (B) made of the fluorine-free organic material is not particularly limited, and a known method such as melt extrusion molding may be used according to the characteristics of the material.

The metal forming the layer (B) is preferably at least one selected from the group consisting of aluminum, silicon, titanium, zinc, zirconium, magnesium, tin, copper, and iron. When the layer (B) is made of these metals, the interlayer adhesion with the layer (A) described above becomes better.
The metal is more preferably at least one selected from the group consisting of aluminum, copper, and iron.

The layer (B) made of the metal may be a layer formed by sputtering, vacuum deposition or the like, or may be formed by bonding a metal foil. Among these, a metal foil is preferable because it can be laminated and pressed.

The thickness of the layer (B) is preferably 1 to 10000 μm, more preferably 5 μm or more, further preferably 7 μm or more, more preferably 1000 μm or less, and further preferably 500 μm or less.

The laminate of the present invention may further include other layers.
Examples of the other layer include a layer made of a fluororesin or a non-fluororesin.

The method for producing the laminate of the present invention is not particularly limited, and after forming each layer, both layers may be laminated and bonded to obtain a laminate, or after forming one layer, Another layer may be formed on that layer to obtain a laminate.

For example, when the layer (B) is made of a fluorine-free organic material, the layer (A) and the layer (B) are formed, and both layers are laminated and bonded by hot pressing to obtain a laminate. Alternatively, after one layer is formed, it may be melt-extruded on that layer to obtain a laminate, or two layers may be simultaneously formed by co-extrusion and laminated.
The hot pressing or extrusion may be appropriately performed by a known method according to the material to be used.

When the layer (B) is made of metal, after forming the layer (A), the layer (A) and the layer (B) made of metal foil are laminated and hot pressed to obtain a laminate, or the layer (A ) May be vacuum-deposited on the surface to form a layer (B) to obtain a laminate.

The laminate of the present invention can have various shapes such as a film shape, a sheet shape, a tube shape, a hose shape, a bottle shape, and a tank shape. The film shape, sheet shape, tube shape, and hose shape may be a corrugated shape or a convoluted shape.

The laminated body of this invention consists of a structure mentioned above. For this reason, it is excellent in interlayer adhesiveness. The laminate of the present invention is excellent in chemical resistance and crack resistance. Moreover, it is excellent also in water vapor | steam barrier property and gas barrier property. For this reason, the laminated body of the present invention can be used for piping materials such as tubes (tubes) and joints, fluid transfer members such as films used in diaphragm pumps, packaging materials such as pharmaceuticals, foods, electronic / precision machine products, etc. Can be applied.

Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited only to this example.

Preparation Example 1
A 50 μm-thick PCTFE film (CTFE homopolymer, MFR (265 ° C.) 23.0 g / 10 min, main chain terminal carboxylic acid halide group number: 212 per 10 ⁶ main chain carbon atoms) was prepared by melt extrusion molding. .

Preparation Example 2
Using a vacuum heat press machine (model number: MKP-1000HV-WH-S7, manufactured by Mikado Technos), pellets of polyamide resin (polyamide 12, trade name “Daiamide”, melting point 175 ° C., manufactured by Daicel Evonik) Film A having a thickness of 400 μm was produced by hot pressing at a pressing temperature of 260 ° C., a preheating time of 300 seconds, a pressing force of 3.0 MPa, and a pressing time of 120 seconds.

Preparation Example 3
Pellets of polyamide resin (polyamide 12, trade name “Vestamide”, melting point 178 ° C., manufactured by Daicel Evonik Co., Ltd.) were pressed using the above vacuum heat press machine at a press temperature of 260 ° C., a preheating time of 300 seconds, and a pressure of 3.0 MPa. The film B having a thickness of 400 μm was produced by hot pressing with a pressurization time of 120 seconds.

Preparation Example 4
A pellet of nylon resin (nylon 6, trade name “Amilan”, melting point 225 ° C., manufactured by Toray Industries, Inc.) was melt-extruded to prepare a film C having a thickness of 400 μm.

Preparation Example 5
A pellet of ethylene / vinyl alcohol copolymer resin (trade name “EVAL”, melting point 180 ° C., manufactured by Kuraray Co., Ltd.) was melt-extruded to produce a film D having a thickness of 400 μm.

Example 1
By laminating and bonding the PCTFE film obtained above and the film A, a two-layered laminate (sample A) was obtained. Adhesion was performed by hot pressing using the above vacuum heat press machine at a pressing temperature of 220 ° C., a preheating time of 30 seconds, a pressing force of 3.0 MPa, and a pressing time of 90 seconds.

(Example 2)
A laminated body (sample B) of the PCTFE film and the film B was obtained in the same manner as in Example 1 except that the film B was used instead of the film A.

Example 3
A laminate (sample C) of the PCTFE film and the film C was obtained in the same manner as in Example 1 except that the film C was used instead of the film A.

Example 4
A laminate (sample D) of a PCTFE film and a film D was obtained in the same manner as in Example 1 except that the film D was used instead of the film A.

(Example 5)
A PCTFE film and a film E were used in the same manner as in Example 1 except that instead of the film A, a polyvinyl alcohol (PVA) resin film E (trade name “Boblon”, manufactured by Nippon Synthetic Chemical Co., Ltd., thickness: 200 μm) was used. A laminate (Sample E) was obtained.

(Example 6)
Instead of the film A, an ethylene / vinyl acetate copolymer (EVA) resin film F (trade name “Solar Eva”, manufactured by Mitsui Chemicals, Inc., thickness 200 μm) was used, and the press temperature was 150 ° C. In the same manner as in Example 1, a laminate (sample F) of the PCTFE film and the film F was obtained.

(Peel test)
About the laminated body obtained in Examples 1-6, the integral strength of the peeling strength, the maximum average, and the maximum point were calculated | required with the following method, and adhesive force was evaluated.

Method for measuring peel strength The obtained laminate was cut into a width of 10 mm, and one end was bent into a T shape and peeled to obtain a test piece for a peel test.
Based on the T-type peel test method of JIS K6854-3-1999, a Tensilon universal testing machine manufactured by Shimadzu Corporation was used, measured at room temperature at a crosshead speed of 25 mm / min, and determined by the area method.

(Integral average)
The load in the measurement section was averaged.
(Maximum average)
It calculated | required as an average value load of the maximum point in a measurement area.
(Maximum point)
The maximum load point in the measurement section was obtained.
The measurement results are shown in Table 2.

The laminate of the present invention can be applied to fluid transfer members, pharmaceuticals, foods, packaging materials for electronic / precision equipment products, and the like.

Claims (8)

A layer (A) comprising polychlorotrifluoroethylene;
A layer (B) made of a fluorine-free organic material or metal,
The polychlorotrifluoroethylene has a polymerization unit based on chlorotrifluoroethylene of 90 to 100 mol%, and has a carbonyl group-containing functional group at the main chain terminal. Non-fluorine-containing organic materials are polyamide resin, polyolefin resin, ethylene / vinyl alcohol copolymer resin, polyvinyl alcohol resin, polyurethane resin, polyester resin, polyaramid resin, polyimide resin, polyamideimide resin, polyphenylene oxide resin, polyacetal resin. , Polycarbonate resin, acrylic resin, styrene resin, acrylonitrile / butadiene / styrene resin, vinyl chloride resin, cellulose resin, polyetheretherketone resin, polysulfone resin, polyethersulfone resin, polyetherimide resin, and polyphenylene The laminate according to claim 1, wherein the laminate is at least one resin selected from the group consisting of sulfide resins. The fluorine-free organic material is at least one resin selected from the group consisting of a polyamide-based resin, an ethylene / vinyl alcohol copolymer resin, a polyvinyl alcohol resin, a polyester resin, and a polyimide resin. The laminated body of description. The laminate according to claim 1 or 2, wherein the amount of the carbonyl group-containing functional group of polychlorotrifluoroethylene is 50 to 400 per 10 ⁶ main chain carbon atoms. The laminate according to claim 1, 2, 3 or 4, wherein the carbonyl group-containing functional group is a carbonate group and / or a carboxylic acid halide group. The laminate according to claim 1, 2, 3, 4, or 5, wherein the polychlorofluoroethylene is a suspension polymer. The layered product according to claim 1, 2, 3, 4, 5 or 6, wherein the layer (B) is made of a fluorine-free organic material. The metal according to claim 1, 2, 3, 4, 5, or 6, wherein the metal is at least one selected from the group consisting of aluminum, silicon, titanium, zinc, zirconium, magnesium, tin, copper, and iron. Laminated body.