JPH08207217A - Manufacture of multilayer structure - Google Patents

Abstract

PURPOSE: To provide a method for obtaining a multilayer structure made of a polyvinylidene fluoride resin and other material by improving the adhesive properties of the resin to the other material. CONSTITUTION: A method for manufacturing a multilayer structure comprises the step of disposing a layer of 100% polyether-polyester block copolymer or a layer of resin composition containing 20wt.% polyether-polyester block copolymer between a polyvinylidene resin layer and other material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for adhering a polyvinylidene fluoride resin to a metal or polymer which is originally non-adhesive.
Steel pipe linings, chemical plant parts, which require corrosion resistance, weather resistance, and chemical resistance for the lamination method,
It is applied to marking films.

[0002]

2. Description of the Related Art Polyvinylidene fluoride resin (hereinafter referred to as P
VDF (abbreviated as VDF) is a melt-moldable fluororesin having excellent weather resistance and chemical resistance, and is used in paints, electric / electronic parts, steel pipe linings, chemical plant parts, weatherproof antifouling films and the like. However, since it has almost no adhesiveness to other materials, it has a drawback that it cannot be composited or modified with multiple materials.

Therefore, in order to remedy this drawback, PVD
Attempts have been made to mix F with other polymers, but PVD
Few polymers have adhesiveness or compatibility with F,
In addition, the application range was extremely limited because it adversely affected the physical properties of PVDF.

For example, polymethylmethacrylate resin (hereinafter abbreviated as PMMA) is known as a material having a good compatibility with PVDF (Japanese Patent Publication No. 43-122012).
JP-B-51-18197) and the like, PMMA has a glass transition temperature extremely higher than that of PVDF, so that the mixture thereof has a drawback that it lacks flexibility. In addition, composites with polycarbonate (JP-A-57-8244, etc.), polyolefins (JP-B-3-22901, etc.), modified polyolefins having functional groups (JP-A-62-57448, etc.), polyimides (Japanese Patent Application Laid-Open No. 2-308856, etc.) and the like have been proposed, but these combinations have poor compatibility and were not always sufficient when used for coating other materials.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method of improving the adhesion of PVDF to other materials and obtaining a multilayer material of PVDF and other materials.

[0006]

The present inventors have found that a polyether / polyester block copolymer (hereinafter referred to as TPEE
(Hereinafter abbreviated as) is adhesive and compatible with PVDF, and that TPEE itself and a mixture of TPEE and plastics are adhesive with respect to many materials, and these properties are PVDF. It has been found to be effective in the production of multilayer materials.

[0007]

According to the present invention, when the polyvinylidene fluoride resin and the non-adhesive material A are laminated, a layer of 100% polyether / polyester block copolymer or a polyether / polyester block copolymer is used. 2
The present invention relates to a method for producing a multilayer structure in which a layer of a resin composition containing 0% by weight or more is present between a polyvinylidene fluoride resin layer and a material A layer and used as an adhesive layer between the two.

The PVDF used in the present invention is obtained by a commonly used polymerization method such as emulsion polymerization and suspension polymerization, and has an MFR value of 0.01 to 500 g / 10 minutes (230
C., 2.16 kg load).

Further, the PVDF referred to here is not limited to polyvinylidene fluoride homopolymer, but includes a copolymer of vinylidene fluoride and another monomer copolymerizable therewith, and the vinylidene fluoride component in the copolymer is It may be 50% by weight or more. Other copolymerizable monomers include tetrafluoroethylene, hexafluoropropylene, trifluoroethylene,
Examples thereof include trifluorochloroethylene, vinyl fluoride and the like, and one or more of these may be used.

The PVDF and the originally non-adhesive material A may be thermoplastic resin, thermosetting resin, rubber, metal, glass, ceramic, wood, paper, etc., and these may be used alone. You may use it as a mixture.

Here, as the thermoplastic resin, polyvinyl chloride, acrylic modified polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate-vinyl chloride copolymer, EVA resin, polyethene, polypropylene,
Ethylene-α-olefin copolymer, olefin-vinyl alcohol copolymer, polystyrene, ABS resin, methacrylic acid ester-styrene copolymer, polyurethane, polyamide (polyamide 66, polyamide 6, polyamide 12, polyamide 11 polyamide 46, reinforced Polyamide, etc.), polybutylene terephthalate, polyethylene terephthalate, aromatic polyester, polyarylate, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether sulfone, polyetherimide, polysulfone, polyacetal, polyimide, cellulose Examples include plastics, polyvinyl alcohol, and various thermoplastic elastomers. Among them, in the case of polyolefin resin or polystyrene resin, PVD is obtained by copolymerizing a monomer having a polar group (maleic anhydride, etc.) in an amount of about 0.1 to 15% by weight.
The adhesiveness with F can be improved.

Examples of the thermosetting resin include polyurethane resin, epoxy resin, phenol resin, alkyd resin, urea resin, melamine resin, benzoguanamine resin, bismaleimide triazine resin and unsaturated polyester resin.

As the metal used for the material A,
There are iron, stainless steel, aluminum, copper, nickel, chromium, titanium and the like.

The polyether used in the present invention
The polyester block copolymer is a polyester which is a polymer of a poly (oxyalkylene) chain (a) and an oxycarboxylic acid having 6 or more carbon atoms or a dihydroxy compound having 2 or more carbon atoms and a dicarboxylic acid having 6 or more carbon atoms. Chain (b)
And are connected. This polyether / polyester block copolymer has a temperature of 200 ° C. and 2.16 k
Melt flow rate (MFR) under g load is 0.1
Is preferably 50 to 50, more preferably 0.
5 to 20.

In the present invention, poly (oxyalkylene)
Examples of the chain (a) include poly (oxyethylene), poly (oxy-1,2- and 1,3-propylene), poly (oxytetramethylene), poly (oxyhexamethylene), ethylene oxide and propylene oxide. A block or random copolymer, a block or random copolymer of ethylene oxide and tetrahydrofuran, etc. are exemplified, and those having an alkylene part having 2 to 4 carbon atoms are preferable, and examples of the terminal group include a hydroxyl group and a carboxyl group. It

The number average molecular weight of the polyoxyalkylene chain is preferably in the range of 300 to 20,000, and 50
0 to 4000 is particularly preferable.

Examples of the above-mentioned polymer (b) of an oxycarboxylic acid having 6 or more carbon atoms or a dihydroxy compound having 2 or more carbon atoms and a dicarboxylic acid having 6 or more carbon atoms include, for example, p-oxybenzoic acid and p-hydroxyethoxy. Benzoic acid, oxynaphthoic acid, hydroxyethoxynaphthoic acid; ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, cyclohexane dimethanol, terephthalic acid, isophthalic acid, diphenyl dicarboxylic acid Polyesters from diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ketone dicarboxylic acid, naphthalene dicarboxylic acid and the like. You may use 2 or more types of these components.

Among these, butylene terephthalate, butylene terephthalate / isophthalate, ethylene terephthalate, butylene naphthalate and the like are preferably used, depending on the purpose. In addition, these components (b) are
Two or more kinds may be used in combination.

The polyether used in the present invention
In the polyester block copolymer, the ratio of the component (a) to the component (b) depends on the purpose and application, but is generally a / b = 20/80 to 90/10 by weight ratio, preferably It is 40 / 60-80 / 20.

TPEE may be used as it is as an adhesive layer, or may be used as a composition obtained by mixing TPEE with another resin. In the latter case, it is desirable that the TPEE content of the composition is 20% by weight or more,
More preferably, it is 30% by weight or more. T in the composition
If the PEE content is less than this range, sufficient adhesion with other materials cannot be obtained.

The other resins mentioned herein include polymethacrylic acid esters (polymethylmethacrylate, etc.), polyvinyl acetate, EVA resin, ethylene-acrylic acid ester copolymer, polyolefins (polyethylene, polypropylene, ethylene-). α-Olefin copolymer, maleic anhydride modified product thereof, etc.), polybutylene terephthalate, polyethylene terephthalate, aromatic polyester, polyarylate, polycarbonate, polyacetal, methacrylic acid ester-styrene copolymer, polyvinyl chloride, polyurethane, Polyamide (Polyamide 6
6, polyamide 6, polyamide 12, polyamide 11,
Polyamide 46, reinforced polyamide, etc.), PVDF, various thermoplastic elastomers, etc.

A resin composition comprising TPEE and another resin can be prepared by melt-kneading both.
Here, as a method of melt-kneading, a conventionally known method can be used, and a compatibilizing agent can be used if necessary. For example, Banbury mixer, rubber roll machine,
Using a uniaxial or biaxial extruder, etc., usually 100 ~
300 ° C, preferably 150-260 ° C depending on the composition
The resin composition is obtained by melt-kneading at the temperature of.

Further, the PVDF and other resin compositions of the present invention include conventionally known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (dyes, pigments),
Adhesion aids, pressure-sensitive adhesives and the like can be optionally contained.

The multi-layer structure material as used in the present invention means an extruded product (film, sheet, plate, pipe, bar, profile extruded product,
Strands, monofilaments, fibers, etc.), injection molded products, press molded products, etc., and are not particularly limited. Examples of production methods include calendaring, coextrusion, extrusion lamination, multi-layer injection, fluidized dip coating, dipping, spray coating, and coating on the surface of a molded body.

The present invention will be described below with reference to examples.
The present invention is not limited to the examples.

[0026]

EXAMPLES The polymer pellets used in the present invention are as follows. However, the melt flow rate (MFR) of PVDF was measured at 230 ° C. under a load of 2.16 kg (unit: g / 10 minutes), and the MFR of TPEE was 200.
Measured value under C, 2.16 kg load (unit: g / 10
Minutes).

PVDF-1: 100% PVDF, MRF
= 2. PVDF-2: PVDF with 11% by weight of hexafluoropropylene introduced as a copolymerization component, MFR = 1.5. PVDF-3: PVDF in which 15% by weight of chlorotrifluoroethylene was introduced as a copolymerization component, MFR = 0.9.

TPEE-1: Butylene terephthalate reacted with polyoxytetramethylene glycol having a number average molecular weight of 2,000 at a weight ratio of 1/1. MFR
= 8. TPEE-2: a mixture of butylene terephthalate and isophthalate (75/25) and a number average molecular weight of 2,000.
It was reacted with polyoxytetramethylene glycol of 0 at a weight ratio of 1/2. MFR = 7.

Adhesiveness was evaluated by cutting a plate or film having a PVDF film adhered on its surface into 5 mm square pieces, sandwiching them between two adhesive tapes, and peeling off the tape vigorously. It was performed by observing the degree of peeling of the film.

In Examples 1 and 2 and Comparative Example 3 three extruders (A, B, C) are used to feed the molten resin to the coextrusion head in order to obtain a three-layer thermoplastic structure. . The extruder A has a screw with L / D = 20 and a compression ratio of 2, and is used for extruding the material A. Extruder B is L
It has a screw with a compression ratio of 4 at / D = 20 and is used for extrusion of the adhesive layer. The extruder C has a screw with L / D = 15 and a compression ratio of 3.5, and is used for extrusion of PVDF. The heating temperature is appropriately set according to the resin used.

The coextrusion head has one flow distributor, three inlet channels and one outlet channel. Material A, adhesive and PVDF are each fed from three inlets to form a thermoplastic structure with three layers at the outlet channels. The resin flow through the three extruders is such that the thickness of the material A layer of the three layer structure extruded from the coextrusion die is about 0.
25 mm, and the thickness of the adhesive layer and PVDF is adjusted to 0.1 mm.

Further, Examples 4 to 6 and Comparative Examples 1, 4 and
In and 5 two extruders (B, C) are used to feed the molten resin to the coextrusion head to obtain a two layer thermoplastic structure. The extruder B has a screw with a compression ratio of 4 at L / D = 20 and is used for extrusion of the adhesive layer. The extruder C has a screw with L / D = 15 and a compression ratio of 3.5, and is used for extrusion of PVDF. The co-extrusion head has one flow distributor, two inlet channels and one outlet channel. The adhesive (or material A) and PVDF are each fed from two inlets to form a thermoplastic structure having two layers at the outlet channels. Two
The resin flow through the two extruders is such that the adhesive layer of the two-layer structure extruded from the coextrusion die and the PVDF thickness is 0.1.
It is adjusted to be mm.

[0033]

Example 1 Polyamide 12 (AES N O P40-TL, manufactured by Elf Atchem) as material A, TPEE-1 as an adhesive, and PVDF-1 as a PVDF resin were coextruded to form a sheet having a three-layer structure. Obtained. At this time, the cylinder temperatures of the extruders A, B, and C were 180 to 240 ° C., 150 to 220 ° C., and 170 to 230 ° C., respectively. In this sheet, peeling did not occur even after repeating the peeling test with an adhesive tape 20 times, and these layers adhered very strongly. Further, it had flexibility, and the PVDF surface showed strong durability against sulfuric acid and chromic acid aqueous solution.

[0034]

Example 2 In Example 1, PVD was used as an adhesive.
A sheet having a three-layer structure was obtained in the same manner as in Example 1 except that 100 parts by weight of the F-1 pellets and 50 parts by weight of the TPEE-1 pellets were mixed by a blender.
This sheet also showed the same properties as in Example 1.

[0035]

Example 3 100 parts by weight of PVDF-1 pellets and T
100 parts by weight of PEE-2 pellets were put in a blender and mixed, and then a film (adhesive) having a thickness of about 0.1 mm was extruded using a uniaxial extruder set to a cylinder temperature of 170 to 240 ° C. A film made of PVDF-1 alone was extruded at the same cylinder temperature with another extruder. These were subjected to the following extrusion lamination.

100 parts by weight of vinyl chloride resin having a degree of polymerization of 800, 2 parts by weight of tin stabilizer, 10 parts by weight of MBS resin, and 3 parts by weight of epoxidized soybean oil were roll-kneaded at 170 ° C. A 3 mm vinyl chloride film was prepared by a calender, and the above adhesive and PVDF were continuously applied.
-1 was pressure-bonded to obtain a three-layer film composed of vinyl chloride resin / adhesive / PVDF. This film also did not peel even if the peeling test with the adhesive tape was repeated 20 times,
These layers adhered very tightly.

[0037]

Example 4 PVDF-3 was prepared using the two-layer coextruder described above.
And a two-layer film made of TPEE-2 was prepared. At this time, the cylinder temperatures of extruders B and C are 15
The temperature was 0 to 220 ° C and 160 to 230 ° C. The thickness of the obtained two-layer film is 0.2 m so that the adhesive layer contacts the steel plate.
m to a steel plate at 230 ° C. No peeling occurred even after repeating the peeling test using the adhesive tape 10 times, and the PVDF layer was very strongly adhered to the steel sheet. Also, PV of this steel plate
The DF surface did not change at all even when it was contacted with 50 ° C. and 2N sulfuric acid for 2 months.

[0038]

Example 5 100 parts by weight of pellets of polymethylmethacrylate (Acrypet V manufactured by Mitsubishi Rayon Co., Ltd.) and TPE
100 parts by weight of E-1 pellets were put into a blender, mixed, and then extruded from an extruder to prepare adhesive pellets.
Next, a two-layer film composed of PVDF-1 and the obtained adhesive pellets was produced using the above-mentioned two-layer coextruder.
At this time, the cylinder temperatures of extruders B and C are
It was set to 150 to 220 ° C and 160 to 230 ° C.

The obtained two-layer film was pressure-bonded to a steel plate having a thickness of 0.2 mm at 230 ° C. so that the adhesive layer contacted the steel plate. No peeling occurred even after repeating the peeling test using the adhesive tape 10 times, and the PVDF layer was very strongly adhered to the steel sheet. Further, the PVDF surface of this steel plate did not change at all even when it was contacted with 50 ° C. and 2N sulfuric acid for 2 months.

[0040]

[Example 6] PVDF-3 and TPE produced in Example 4
Two-layer film consisting of E-2 and 50% by weight of polyphenylene ether and 50% by weight of polystyrene as material A
Polymer alloy (made by GE Plastics, Nory
1 731) having a thickness of 0.2 mm,
Both were pressure-bonded at 230 ° C. so that the adhesive layer of the two-layer film was in contact with the material A. 20 peel tests with adhesive tape
Peeling did not occur even after repeated times, and the PVDF layer adhered to the material A very strongly. Further, the PVDF surface of this material A did not change at all even when it was brought into contact with 50 ° C. and 2N sulfuric acid for 2 months.

[0041]

Comparative Example 1 Polyamide 12 and PVD used in Example 1
The pellet of F-1 was supplied to the two-layer coextruder, and the two-layer film was produced. At this time, the cylinder temperatures of the extruders B and C were both 170 to 230 ° C. In the peel test using the adhesive tape, this film peeled at the third time, and the adhesion between the two layers was weak.

[0042]

Comparative Example 2 A sheet having a three-layer structure was obtained in the same manner as in Example 1 except that TPEE-1 was changed to polymethylmethacrylate (Acrypet V manufactured by Mitsubishi Rayon Co., Ltd.). This sheet was peeled when the peeling test with an adhesive tape was repeated 5 times, and the adhesion between layers was not large. In addition, this sheet was inferior in flexibility to the sheet obtained in Example 1.

[0043]

Comparative Example 3 In Example 3, TPEE was used as an adhesive.
A double-layer film made of PVDF-1 and the same vinyl chloride resin as in Example 4 was produced by extrusion lamination under the same conditions without using -2. In the peel test with the adhesive tape, this film peeled at the fourth time, and the adhesiveness between the two layers was weak.

[0044]

[Comparative Example 4] In Example 4, TPEE was used as an adhesive.
In place of -2, the same methyl methacrylate as in Comparative Example 2 was used, and the PVDF-3 film and a steel plate having a thickness of 0.2 mm were pressure bonded in the same manner as in Example 4. In the peel test using the adhesive tape, the PVDF layer was peeled after four times, and the adhesion between the two layers was weak.

[0045]

Comparative Example 5 The PVDF / methyl methacrylate bilayer film prepared in Comparative Example 4 was used in the same manner as in Example 6 to
It was pressure-bonded to a 0.2 mm-thick sheet of 1731. In the peel test using the adhesive tape, the PVDF layer was peeled off twice, and the adhesion between the two layers was weak.

[0046]

INDUSTRIAL APPLICABILITY The method for producing a multi-layer structure of the present invention can be applied to various molded articles, and is a component that constitutes a device requiring chemical inertness in the chemical, pharmaceutical and food industries, and can be used for a long period of time. It is useful in many fields such as outdoor building materials and agricultural films that require weather resistance over a wide range.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuyoshi Ohashi 1st Awata-cho, Nakado-ji, Shimogyo-ku, Kyoto-shi, Kyoto Elf Atchem Japan Co., Ltd. Kyoto Technical Center

Claims (6)

[Claims] 1. A layer of 100% polyether / polyester block copolymer or 20% of polyether / polyester block copolymer is used for laminating a polyvinylidene fluoride resin and the non-adhesive material A which is originally non-adhesive. A method for producing a multilayer structure, wherein a layer of a resin composition containing at least wt% is present between a polyvinylidene fluoride resin layer and a material A layer and used as an adhesive layer between the two. 2. The method for producing a multilayer structure according to claim 1, wherein the polyvinylidene fluoride-based resin is a vinylidene fluoride homopolymer or a copolymer composed of 50% by weight or more of vinylidene fluoride monomer. 3. The method for producing a multilayer structure according to claim 1, wherein the content of the polyether component in the polyether / polyester block copolymer is 40 to 80% by weight of the block copolymer. 4. The method for producing a multilayer structure according to claim 3, wherein the polyether block of the polyether / polyester block copolymer is selected from polyethylene glycol, polypropylene glycol and polytetramethylene glycol. 5. The method for producing a multilayer structure according to claim 1, wherein the material A is a metal. 6. The method for producing a multilayer structure according to claim 1, wherein the material A is a thermoplastic resin.