JP2003191402A - Fluoropolymer laminate - Google Patents

Abstract

(57) [Problem] To provide a laminate containing a fluororesin layer (A) and a non-fluororesin layer (B), which is excellent in adhesion and transparency between the fluororesin layer and the non-fluororesin layer. . A laminate comprising a fluororesin layer (A) and a non-fluororesin layer (B), obtained by coextrusion molding, comprising a fluororesin layer (A) and a non-fluororesin layer (B). Are directly bonded, and the laminate has a haze of 0.1 to 10%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminate containing a fluororesin layer and a non-fluorine resin layer.

[0002]

2. Description of the Related Art Tubes used for transporting liquids such as drinking water, ink and paints have chemical resistance, antifouling property, abrasion resistance, non-elution property, gas barrier property, toughness, water resistance and resistance. In addition to properties such as aging property and flexibility, it is necessary to have a property capable of visually confirming the transportation status of the liquid.

For example, a beer dispenser tube has chemical resistance, antifouling property, abrasion resistance, non-elution property, gas barrier property, toughness, water resistance, aging resistance, flexibility and the like. Transparency is required so that the mixed state of beer liquid and carbon dioxide can be visually observed.

Conventionally, a tube of soft vinyl chloride (PVC) has been used as a tube for a beer dispenser. However, although PVC tubes are excellent in transparency and flexibility, they have insufficient abrasion resistance, and there is a problem that stains adhere to the tubes due to the pigment of beer after long-term use.

For this improvement, a tube having two inner and outer layers has been proposed.

For example, a two-layer tube having an inner layer made of polypropylene (PP), which is less likely to adsorb pigments, fine particles, etc., and an outer layer made of an olefin elastomer having excellent heat resistance, transparency and flexibility, and an inner layer. Adhesive polyolefin resin, ethylene-vinyl acetate copolymer resin (EVA) on outer layer
A tube having a two-layer structure and the like has been proposed. These two-layer tubes have compatibility with the Food Sanitation Law, but the inner layer is insufficient in dye adhesion resistance and stain resistance, and it is necessary to wash and remove stains after a certain period of use.

The fluororesin tube is excellent in chemical resistance, antifouling property, non-elution property, gas barrier property, toughness, water resistance, aging resistance and dye adhesion resistance, but it is expensive. Lamination with a non-fluorine resin is preferable in order to reduce the amount of the fluororesin used, but since the fluororesin is essentially non-adhesive, sufficient adhesion cannot be obtained between the fluororesin layer and the non-fluorine resin layer.

In order to improve the adhesiveness, a multi-layered tube in which a fluororesin tube is surface-treated by chemical etching or corona discharge and an outer layer is coated around the tube has been proposed, but the adhesiveness is improved, The number of steps is large, resulting in an expensive product. Further, when a fluororesin tube is etched with sodium, the tube is colored and the transparency is lowered.

JP-A-8-142151 discloses a two-layer tube in which polyvinylidene fluoride (hereinafter referred to as PVDF) is used for the inner layer and a polyurethane resin or a polyurethane-based elastomer is used for the outer layer to improve the adhesion by coextrusion molding. Is listed. The PVDF layer of this two-layer tube has a high hardness and is whitened when bent. In particular, it becomes brittle in the low temperature region and cannot be applied to transport of cold liquid.

In Japanese Unexamined Patent Publication No. 10-286897, P is used for the inner layer.
A two-layer tube in which a copolymer resin of VDF and hexafluoropropylene (hereinafter referred to as HFP) is used and a polyurethane elastomer is used as an outer layer is described. The adhesive strength of both layers is not sufficient. Since non-fluorine resin is limited to polyurethane elastomer, it has hydrolyzability,
Not suitable for applications such as beverage piping.

Japanese Patent Laid-Open No. 2001-193872 discloses PVD.
A two-layer tube coextruded with F and an acrylic elastomer or a styrene elastomer is described. Also in this case, the non-fluorine resin cannot be arbitrarily selected.

Japanese Unexamined Patent Publication (Kokai) No. 9-131833 describes a multi-layer tube obtained by co-extruding a polymer alloy of a fluororesin and a non-fluorine resin as an intermediate layer. Low transparency.

[0013]

An object of the present invention is a laminate containing a fluororesin layer and a non-fluororesin layer obtained by coextrusion molding, which comprises a fluororesin layer and a non-fluorine resin layer. To provide a laminate having excellent adhesiveness and transparency.

[0014]

The present invention relates to a laminate obtained by coextrusion molding, which comprises a fluororesin layer (A) and a non-fluorine resin layer (B), and is a fluororesin layer (A). And the non-fluorine resin layer (B) are directly adhered to each other, and the haze of the laminate is 0.1 to 30%.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The laminate of the present invention contains a fluororesin layer (A) and a non-fluorine resin layer (B).

The fluororesin used in the fluororesin layer (A) includes ethylene-tetrafluoroethylene copolymer (hereinafter referred to as ETFE), polychlorotrifluoroethylene (hereinafter referred to as PCTFE), and ethylene-chlorotrifluoro. Ethylene copolymer (hereinafter referred to as ECTF
E), tetrafluoroethylene-hexafluoropropylene copolymer, perfluoroalkyl vinyl ether (hereinafter referred to as PFA), PVDF, soft fluororesin, and the like. More preferably ETFE or EC
It is TFE.

The composition of ETFE or ECTFE is as follows: polymerized units (c1) based on tetrafluoroethylene or chlorotrifluoroethylene, polymerized units (c2) based on ethylene, and polymerized units (c3) based on vinyl acetate.
And a polymerized unit (c4) based on polyfluoroalkylethylene is (c1) / (c2) / (c3) / (c4)
= 40-60 / 30-50 / 1-20 / 0.01-5 The fluorine-containing copolymer (C) contained at a molar ratio is preferable.
Within this composition range, chemical resistance, antifouling property, non-elution property,
In addition to excellent properties such as gas barrier properties and aging resistance, the adhesiveness and transparency are excellent, which is preferable.

In the present invention, the fluororesin constituting the fluororesin layer (A) is the fluorocopolymer (C) containing the organic peroxide (D) (C) / (D) = 100/0. .0
It is preferable that the fluorine-containing copolymer composition (E) is obtained by mixing in a mass ratio of 1 to 10 and heat-treated. More preferably, the mass ratio is (C) / (D) = 100 / 0.1-5. By using the fluorine-containing copolymer composition (E), the adhesiveness with the non-fluorine resin is improved.

The fluororesin constituting the fluororesin layer (A) is obtained by blending the fluorocopolymer (C) with an organic peroxide (D) and an unsaturated dicarboxylic acid or its derivative (F). , A fluorine-containing copolymer composition (E
2) is preferable. Blending of the unsaturated dicarboxylic acid or its derivative (F) further improves the adhesiveness, which is preferable. The compounding amount of the unsaturated dicarboxylic acid or its derivative (F) is (C) / (F) = 100 / 0.01
A mass ratio of 10 to 10 is preferable, and a mass ratio of 100 / 0.1 to 5 is more preferable.

The melt flow rate (hereinafter referred to as MFR) of the fluorine-containing copolymer composition (E1) or (E2) is preferably 1 to 300 g / 10 min at 297 ° C., more preferably 10 to 50 g / 10 min. . MF
R is a measure of molecular weight, with large values representing low molecular weight.
When the MFR is in this range, the moldability is good.

The organic peroxide preferably has a half-life of 1 minute and a decomposition temperature of 150 to 280 ° C, more preferably 170 to 240 ° C. As a specific example, 2,5-dimethyl-2,5-bis (ter
t-butylperoxy) hexane, ditert-butylperoxide, 2,5-dimethyl-2,5-bis (te
rt-Butylperoxy) hexyne-3, di-tert
-Aliphatic peroxides such as butyl peroxide, 1,
Aromatic peroxides such as 4-bis (α-tert-butylperoxyisopropyl) benzene, tert-butyl = cumyl peroxide, and dicumyl peroxide,
Ketone peroxides such as methyl ethyl ketone peroxide, diacyl peroxides such as benzoyl peroxide, peroxydicarbonates such as diisopropyl peroxydicarbonate, alkyl peroxy esters such as tert-butyl peroxyisobutyrate,
Hydroperoxides such as tert-butyl hydroperoxide can be mentioned. The organic peroxide can be used in liquid form or solid form.

Specific examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, itaconic acid and the like.

Derivatives of unsaturated dicarboxylic acids include acid anhydrides, esters, amides, imides, and the like. Specific examples include maleic anhydride, citraconic anhydride, itaconic anhydride, maleic acid monomethyl ester, and dimethyl maleate. Ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, maleic acid monoamide, maleic acid diamide, maleic acid mono N-ethylamide, maleic acid bis N-ethylamide, maleic acid mono N, N-diethylamide, maleic acid mono N-butylamide, Maleic acid mono N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid mono N-ethylamide, fumaric acid bis N-ethylamide, fumaric acid mono N,
N-diethylamide, fumaric acid mono N-butylamide,
Fumaric acid mono N, N-dibutylamide, maleimide, N
-Butyl maleimide, N-phenyl maleimide, etc. are mentioned.

As a method for blending the fluorine-containing copolymer (C) with the organic peroxide (D) or the unsaturated dicarboxylic acid or its derivative (F) and the organic peroxide (D) and subjecting to heat treatment, powdery A method in which the fluorine-containing copolymer (C) in the form of particles, pellets or the like is preliminarily mixed with the organic peroxide (D) in a mixer, and then melt-extruded, or powder, particles, pellets or the like are contained. A method in which the fluorocopolymer (C) is supplied to the extruder and the organic peroxide (D) or unsaturated dicarboxylic acid or its derivative (F) and the organic peroxide (D) are continuously supplied to the extruder is known. preferable. When these methods are used, the organic peroxide (D) or the unsaturated dicarboxylic acid or its derivative (F) and the organic peroxide (D) are heat-treated at the same time as being mixed with the fluorine-containing copolymer (C). A pelletized fluorocopolymer composition (E) is obtained. The heat treatment temperature is preferably 100 to 300 ° C, more preferably 150 to 250 ° C. Also, the heat treatment time is preferably short,
0.1 to 30 minutes is more preferable, and 0.5 to 10 minutes is still more preferable.

The laminate of the present invention is a laminate obtained by coextrusion molding. Coextrusion refers to melt coextrusion. A single-screw or twin-screw extruder is preferably used for melt coextrusion. The cylinder temperature of the extruder is 100-350.
C. is preferable, the crosshead temperature and the die temperature are each preferably 200 to 350.degree. C., and the screw rotation speed is not particularly limited, but is preferably 10 to 200 rotations / minute. The residence time of the fluorocopolymer in the extruder is preferably 1 to 10 minutes. The discharge hole of the die preferably has a diameter of 2 to 20 mm.
The strand-shaped fluorine-containing copolymer melted and discharged from the discharge hole is cooled and solidified with water or air while being stretched, cut by a cutter, and has a length of 1 to 5 mm and a diameter of 1 to 1.
A 5 mm cylindrical pellet is obtained.

As the non-fluorine resin constituting the non-fluorine resin layer (B) in the present invention, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, acrylic resin, polyethylene terephthalate, polyacetal, polycarbonate, polyamide,
Examples thereof include polyimide resin, phenol resin, amino resin, epoxy resin and polyester.

More preferably, it is transparent and flexible,
Polyamide 6, polyamide 66, polyamide 11, polyamide 12, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH), polyethylene (PE), polypropylene (PP), which have excellent durability and the like. It is a polyurethane resin (PU).

The laminate of the present invention contains the above-mentioned fluororesin layer (A) and non-fluororesin layer (B). For example,
(A) / (B) laminate comprising two layers of (A) and (B),
A fluoropolymer composition (E1) is provided between (A) and (B).
Alternatively, (A) / (E consisting of three layers in which (E2) layers are laminated.
1) or (E2) / (B) laminate, and (A) / (E1) or (E2) / (B) / in which the number of layers to be laminated is increased.
Examples thereof include a four-layer laminate of (B) and a five-layer laminate of (A) / (A) / (E1) or (E2) / (B) / (B).

The thickness of the fluororesin layer (A) is 1 μm to 1 m.
m is preferable, 1 to 0.5 mm is more preferable, 1 μm
The most preferable is 0.2 mm. Further, the thickness of the non-fluorine resin layer (B) is preferably 1 μm to 5 mm, and 1 μm to 1
mm is more preferable, and 1 μm to 0.8 mm is the most preferable. When the thickness of each layer is within this range, good adhesiveness is obtained and transparency is also excellent, which is preferable.

Such a laminate is obtained by co-extruding a fluororesin and a non-fluororesin. Usually, the co-extrusion molding method is a method of obtaining a laminate having two or more layers in the shape of a film, a tube or the like. Melts discharged from two or more extruders pass through a die while being in contact with each other in a molten state to form a laminate. For extrusion temperature, screw temperature is 100
˜350 ° C. is preferable, and the die temperature is preferably 200 to 350 ° C. The screw rotation speed is not particularly limited, but is 10
200 revolutions / minute is preferred. The residence time of the melt in the extruder is preferably 1 to 20 minutes.

In the laminate of the present invention, the fluororesin layer (A) and the non-fluororesin layer (B) are directly bonded.
Thereby, the fluororesin layer (A) and the non-fluorine resin layer (B)
A laminated body in which is firmly adhered is obtained. The adhesive strength between the fluororesin layer (A) and the non-fluororesin layer (B) is 5 to 60.
N / cm is preferred. More preferably 15 to 60 N / c
m, most preferably 30 to 60 N / cm. When the adhesive strength is in this range, peeling due to bending does not occur and the transparency is not deteriorated.

The haze of the laminate of the present invention is 0.1 to 30%.
Is. When the haze is within this range, the laminate has transparency, and the liquid to be transported has high visibility. The haze of the laminate is more preferably 0.1 to 15%, most preferably 0.1 to 10%.

The laminate of the present invention is formed into various shapes such as a tube shape, a film shape and a bottle shape.

The application of the laminate of the present invention includes beverage transport pipes, paint transport pipes, chemical liquid transport pipes, medical tubes, optical fiber pressure feed pipes, barrier packaging materials, weather resistant wallpaper, translucent filters. Etc.

[0035]

The present invention will be described in detail with reference to the following examples and comparative examples, but the present invention is not limited thereto. Example 1
6 to 6 are Examples, and Examples 7 to 8 are Comparative Examples. In addition,
MFR, adhesive strength and haze were measured according to the following methods.

[MFR (unit: g / 10 min)] AS
297 ° C according to TM D-3159 (1238)
After heating for 5 minutes, a load of 5 kg was applied for measurement.

[Adhesive strength (unit: N / cm)] The laminate was cut into a sample having a width of 1 cm and a length of 20 cm. In the case of a laminated tube, it was cut into a length of 20 cm and further cut in the longitudinal direction to prepare a sample. The width of the stack is 1c
When it was less than m, the measured value was converted into a width of 1 cm. The layer between the fluororesin layer (A) and the non-fluorine resin layer (B) of the laminate is peeled off by 3 cm or more from the end, and Tensilon is used as the equipment to prevent the unpeeled portion from coming into contact with the equipment. One of the scissors was peeled 180 degrees at a speed of 30 mm / min. The measurement was performed on two samples, and the average value of the strength (N / cm) required for the peeling was defined as the adhesive strength.

[Haze (unit:%)] JIS K713
According to 6, the measurement was performed using an SM color computer (manufactured by Suga).

[Synthesis Example 1] By solution polymerization, the copolymerization composition is tetrafluoroethylene-based polymer units / ethylene-based polymer units / vinyl acetate-based polymer units / (perfluorobutyl) ethylene-based polymer units = 51 /
Fluorine-containing copolymer (C: 31/15/3 (molar ratio))
-1) was produced. MF of fluorinated copolymer (C-1)
R was 153g / 10min. The fluorocopolymer (C-1) was compression molded at a temperature of 280 ° C. for 5 minutes to obtain a sheet having a thickness of 0.05 mm. The haze of the sheet was 3.5%.

[Synthesis Example 2] By suspension polymerization, the copolymerization composition was tetrafluoroethylene-based polymer units / ethylene-based polymer units / vinyl acetate-based polymer units / (perfluorobutyl) ethylene-based polymer units = 51. /
A fluorinated copolymer (C-2) having a ratio of 43 / 3.6 / 2.4 (molar ratio) was produced. Fluorine-containing copolymer (C-2)
Had an MFR of 90 g / 10 min. The fluorocopolymer (C-2) was compression molded at a temperature of 280 ° C. for 5 minutes to obtain a sheet having a thickness of 0.05 mm. The haze of the sheet was 2.8%.

[Synthesis Example 3] By solution polymerization, the copolymerization composition is tetrafluoroethylene-based polymer units / ethylene-based polymer units / vinyl acetate-based polymer units / (perfluorobutyl) ethylene-based polymer units = 57 /
A fluorinated copolymer (C-3) having a molar ratio of 38 / 4.9 / 0.1 was produced. Fluorine-containing copolymer (C-3)
The MFR of was measured to be 200 g / 10 min. The fluorocopolymer (C-3) was compression molded at a temperature of 280 ° C. for 5 minutes to obtain a sheet having a thickness of 0.05 mm. The haze of the sheet was 1.7%.

[Synthesis Example 4] Fluorine-containing copolymer (C-1)
1 kg and 2,5-dimethyl-2,5-bis (ter
t-butylperoxy) hexane (Perhexa 25B,
30 g of Nippon Oil & Fats Co., Ltd. was continuously fed to the twin-screw extruder in the same direction, and the melting zone of the cylinder was adjusted to 230 ° C. for kneading. The discharged strand was air-cooled and cut with a pelletizer to prepare a fluorinated copolymer composition (E-1).
The MFR of the fluorinated copolymer composition (E-1) was 17 g /
It was 10 minutes. Fluorine-containing copolymer composition (E-
1) was subjected to pressure compression molding at a temperature of 280 ° C. for 5 minutes to give a thickness of 0.
A 05 mm sheet was obtained. The haze of the sheet is 5.5.
%Met.

[Synthesis Example 5] Fluorine-containing copolymer (C-2)
1 kg, 15 g of maleic anhydride and 15 g of dicumyl peroxide (Percumyl D, manufactured by NOF CORPORATION) were uniformly mixed in advance, and this was continuously supplied to a twin-screw extruder in the same direction, and the melting zone of the cylinder was heated to 270 ° C. And kneaded. The discharged strand was air-cooled and cut with a pelletizer to prepare a fluorinated copolymer composition (E-2). The MFR of the fluorinated copolymer composition (E-2) was 26.
It was g / 10 min. Fluorine-containing copolymer composition (E
-2) is compression molded at a temperature of 280 ° C. for 5 minutes to give a thickness of 0.0
A 5 mm sheet was obtained. The haze of the sheet is 3.9%
Met.

[Synthesis Example 6] Fluorine-containing copolymer (C-3)
1 kg and 5 g of di-tert-butyl peroxide (Perbutyl D, manufactured by NOF CORPORATION) were continuously supplied to a twin-screw extruder in the same direction, and kneading was performed by setting the melting zone of the cylinder at 250 ° C. The discharged strand was air-cooled and cut with a pelletizer to prepare a fluorinated copolymer composition (E-3). The MFR of the fluorinated copolymer composition (E-3) was 30 g / 10 min. The fluorinated copolymer composition (E-3) was compression molded at a temperature of 280 ° C. for 5 minutes to obtain a sheet having a thickness of 0.05 mm. The haze of the sheet was 2.1%.

Example 1 Using a three-layer coextruder, the inner layer /
The inner layer / outer layer has an inner diameter of 6 mm, and the inner layer / intermediate layer / outer layer has a thickness of 0.2 mm / 0.1 mm / 0.
A laminated tube that is 7 mm was molded. The ETFE (Aflon COP LM740,
Asahi Glass Co., Ltd. was supplied, and polyamide 11 (Rilsan B, manufactured by Atofina Co., Ltd.) was supplied to the cylinder forming the outer layer. The fluorine-containing copolymer composition (E-1) was supplied to the cylinder forming the intermediate layer. The processing temperatures in the transport zones of ETFE, the fluorocopolymer composition (E-1) and the polyamide 11 are 230 ° C., 250 ° C. and 2 respectively.
The temperature was 40 ° C., and the temperature of the co-die was 240 ° C. Regarding the adhesive strength of the obtained three-layer laminated tube, material destruction occurred between the ETFE layer and the fluorine-containing copolymer composition (E-1) layer. It was 38 N / cm between the fluorinated copolymer composition (E-1) layer and the polyamide 11 layer, and showed good adhesiveness. The laminated tube had a haze of 16.8% and was transparent enough to confirm the internal fluid.

Example 2 Using a three-layer coextruder, the inner layer /
The inner layer / outer layer has an inner diameter of 3 mm, and the inner layer / intermediate layer / outer layer has a thickness of 0.1 mm / 0.1 mm / 0.
A 3-layer laminated tube that is 3 mm was molded. ETFE (Aflon COP LM-7 is used for the cylinder that forms the inner layer.
40, manufactured by Asahi Glass Co., Ltd., and polyamide 11 (Rilsan B, manufactured by Atofina) was supplied to the cylinder forming the outer layer. The fluorine-containing copolymer composition (E-2) was supplied to the cylinder forming the intermediate layer. The processing temperature in the transport zone of ETFE, the fluorocopolymer composition (E-2), and the polyamide 11 is 280 ° C. and 270 ° C., respectively.
And 240 ° C., and the temperature of the co-die was 260 ° C. The adhesive strength of the obtained three-layer laminated tube was material-damaged between the ETFE layer and the fluorocopolymer composition (E-2) layer,
Fluorine-containing copolymer composition (E-2) layer and polyamide 11
It was 25 N / cm between the layers, indicating good adhesion.
The laminated tube had a haze of 15.5% and was transparent enough to confirm the internal fluid.

Example 3 Using a two-layer coextruder, the inner layer /
A two-layer laminated tube having an outer layer structure having an inner diameter of 3 mm and inner layer / outer layer thicknesses of 0.1 mm / 0.4 mm was molded. The fluorinated copolymer composition (E-1) was supplied to the cylinder forming the inner layer. EVOH (Eval, manufactured by Kuraray Co., Ltd.) is supplied to the cylinder forming the outer layer,
Fluorine-containing copolymer composition (E-1) and EVOH were processed at processing temperatures of 270 ° C. and 220, respectively.
C. and the codie temperature was 230.degree. The adhesive strength of this laminated tube was 19 N / cm, indicating adhesiveness. Also, this laminated tube has a haze of 13.2%,
It was transparent enough to confirm the internal fluid.

Example 4 Using a three-layer coextruder, the inner layer /
The inner layer / outer layer has an inner diameter of 6 mm, and the inner layer / intermediate layer / outer layer has a thickness of 0.2 mm / 0.1 mm / 0.
A 3-layer laminated tube that is 7 mm was molded. ETFE (Aflon COP LM-7 is used for the cylinder that forms the inner layer.
40, manufactured by Asahi Glass Co., Ltd., and polyamide 12 (Uvesta PA12, manufactured by Ube Industries, Ltd.) was supplied to the cylinder forming the outer layer. The fluorine-containing copolymer composition (E-3) was supplied to the cylinder forming the intermediate layer. ETFE,
Fluorine-containing copolymer composition (E-3) and polyamide 12
Processing temperature in the transportation zone of
The temperature was 50 ° C. and 240 ° C., and the temperature of the co-die was 220 ° C. The adhesive strength of the obtained three-layer laminated tube was ETFE.
The material was destroyed between the layer and the fluorine-containing copolymer composition (E-3) layer, and 50 N / cm between the fluorine-containing copolymer composition (E-3) layer and the polyamide 12 layer, showing good adhesion. It was Also, this laminated tube has a haze of 12.2%.
It was transparent enough to confirm the internal fluid.

[Example 5] Using a coextrusion film molding machine, the thickness of each layer of the fluorocopolymer composition (E-1) and EVOH (Eval, manufactured by Kuraray Co., Ltd.) was 0.1 mm, and the total thickness was A two-layer laminated film having a size of 0.2 mm was formed. The fluorine-containing copolymer composition (E-1) was placed in the cylinder forming one layer, and E was placed in the cylinder forming the other layer.
VOH is supplied, and the processing temperature in the transport zone of the fluorine-containing copolymer composition (E-1) and EVOH is 2 each.
The temperature of the co-die was set to 220 ° C. and 30 ° C. and 220 ° C. The adhesive strength of this two-layer laminated film was 25 N / cm, which showed good adhesiveness. In addition, this laminated film had a haze of 7.3% and had good transparency.

Example 6 Using a coextrusion film molding machine, the fluorocopolymer composition (E-3) and polyamide 6 were used.
(Uvesta PA6, manufactured by Ube Industries, Ltd.) has a thickness of 0.
A two-layer laminated film having a thickness of 1 mm and a total thickness of 0.2 mm was formed. The fluorine-containing copolymer composition (E-3) was supplied to the cylinder forming one layer, and the polyamide 6 was supplied to the cylinder forming the other layer to obtain a fluorine-containing copolymer composition (E-3) and The processing temperature in the transport zone of polyamide 6 was 230 ° C and 230 ° C, respectively, and the temperature of the co-die was 210 ° C. The adhesive strength of this two-layer laminated film was 28 N / cm, which showed good adhesiveness. Moreover, this laminated film had a haze of 8.9% and had good transparency.

Example 7 (Comparative Example) Using a three-layer coextrusion machine, the inner layer / intermediate layer / outer layer had an inner diameter of 6 mm and the inner layer / intermediate layer / outer layer had a thickness of 0.2 mm / 0. .1
A 3-layer laminated tube having a size of mm / 0.7 mm was formed.
ETFE (Aflon LM,
Asahi Glass Co., Ltd. was supplied, and polyamide 11 (Rilsan B, manufactured by Atofina Co., Ltd.) was supplied to the cylinder forming the outer layer. The fluorine-containing copolymer (C-2) was supplied to the cylinder forming the intermediate layer. The processing temperatures in the transport zones of ETFE, the fluorinated copolymer (C-2) and the polyamide 11 were 230 ° C, 250 ° C and 240 ° C, respectively, and the temperature of the co-die was 240 ° C. Regarding the adhesive strength of the obtained three-layer laminated tube, material destruction occurred between the ETFE layer and the fluorocopolymer (C-2) layer, but it was manually broken between the fluorocopolymer (C-2) layer and the polyamide 11 layer. It could be easily peeled off and the adhesiveness was insufficient. The laminated tube was transparent enough to confirm the internal fluid.

[Example 8 (Comparative Example)] A two-layer laminate was prepared in the same manner as in Example 6 except that the fluorinated copolymer (C-3) was used instead of the fluorinated copolymer composition (E-3). A film was produced. This laminated film was easily peeled off by hand, and its adhesiveness was insufficient.

[0053]

The laminate of the present invention has excellent adhesiveness and transparency between the fluororesin layer and the non-fluorine resin layer. It has the excellent characteristics of fluororesin such as chemical resistance, solvent resistance, oil resistance, gas barrier property, water repellency, oil repellency, weather resistance, corrosion resistance, waterproof property, antifouling property, etc. Can be used in the field. Further, the non-fluorine resin layer also has excellent abrasion resistance.

Continued front page    F term (reference) 3H111 AA02 BA15 BA34 CB03 DA08                       DA09 DA26 DB03 DB10 DB27                       EA04 EA12                 4F100 AK01A AK17B AK17K AK18B                       AK18J AK22B AK22J AL01B                       BA02 EH20 GB16 JB01 JB07                       JK01 JK06 JK09 JK13 JK17                       JL06 JL09 JN08 YY00                 4J100 AA02Q AC23S AC26P AC31P                       AG04R CA06 CA31 HA01                       HA57 HC29 HC30 HC36

Claims (5)

[Claims] 1. A laminate obtained by coextrusion molding, which comprises a fluororesin layer (A) and a non-fluorine resin layer (B), comprising a fluororesin layer (A) and a non-fluorine resin layer (B). ) And the haze of the laminate is 0.1 to 30%.
It is a laminated body characterized by being. 2. The adhesive strength between the fluororesin layer (A) and the non-fluorine resin layer (B) is 5 to 60 N / cm.
The laminated body according to. 3. The fluororesin comprises tetrafluoroethylene- or chlorotrifluoroethylene-based polymerized units (c1), ethylene-based polymerized units (c2), vinyl acetate-based polymerized units (c3) and polyfluoroalkylethylene. Based on the polymerized units (c4), (c1) /
(C2) / (c3) / (c4) = 40-60 / 30-5
The layered product according to claim 1 or 2, which is the fluorocopolymer (C) contained in a molar ratio of 0/1 to 20 / 0.01 to 5. 4. The fluororesin comprises an organic peroxide (D) in the fluorocopolymer (C), and (C) / (D) = 10.
The layered product according to claim 3, which is a fluorocopolymer composition (E1) obtained by blending in a mass ratio of 0 / 0.01 to 10 and heat-treated. 5. The fluororesin comprises a fluorocopolymer (C), an organic peroxide (D) and an unsaturated carboxylic acid or a derivative thereof (F), (C) / (D) = 100 / 0.0
1 to 10 and (C) / (F) = 100 / 0.01 to 10
The fluorine-containing copolymer composition (E2) obtained by blending in a mass ratio of and heat-treated.