JPH01193350A - Polyvinylidene fluoride resin composition and laminate thereof - Google Patents

Abstract

PURPOSE:To obtain the title composition having improved adhesiveness between a polyvinylidene fluorine(PVDF) and polyolefines, by blending a resin composition comprising a PVDF or vinylidene fluoride copolymer and optionally a polyolefin with inorganic solid fine particles. CONSTITUTION:(A) A polyvinylidene fluorine or vinylidene fluoride copolymer is blended with (B) inorganic solid fine particles (e. g., iron oxide or glass beads) having <=10mum, preferably 1-0.01mum particle diameter and optionally (C) a polyolefin. The preferable blending ratio is 18-94wt.%, especially 32-88wt.% component A, 82-6wt.%, especially 68-12wt.% component C and 0. 5-30vol.%, especially 2-5vol.% based on sum of the components A and C of the component B.

Description

Detailed Description of the Invention Industrial Field of Application The present invention relates to polyvinylidene fluoride (hereinafter abbreviated as PvDF) and vinylidene fluoride coelectrolyte (hereinafter abbreviated as VDF copolymer) (both collectively referred to as pvpirs). This invention relates to a PVDF resin composition that enables adhesion between a polyolefin and a PVDF resin composition, and a laminate using the same.

Conventional technology PVDF has excellent properties such as chemical resistance, flexibility, weather resistance, and electrical properties, and VDF copolymer is
The modulus of elasticity has been changed and the heat resistance has been improved while maintaining the characteristics of . By making it possible to bond pvDFs and polyolefin resins, it is possible to improve the functionality of polyolefin Vfi resin molded products and materials having polyolefin resins in their surface layers.

However, PVDF is known to be difficult to adhere to different materials without a special surface layer, and its adhesion to polyolefins has not been known.

Problems to be Solved by the Invention The object of the present invention is to obtain an adhesive PVDF resin composition that allows easy adhesion of PVDF and polyolefin, and a product using the same.

Means for Solving Point J In view of the above objectives, as a result of intensive research, we have found that a resin composition containing PVDFs and inorganic solid particles or PVDFs and polyolefin in a specific mixing ratio is blended with inorganic solid particles. The inventors have discovered that the object of the present invention can be achieved and have completed the present invention.

That is, the present invention provides (1) (a) PVDF or VDF
A PVDF resin composition comprising (2)) a pvDF or VDF copolymer, (b) an inorganic solid fine particle, and (2) a polymer and (b) an inorganic solid fine particle. (3) a composition comprising a PVDF or VDF copolymer and (b) an inorganic solid fine particle, or a composition comprising (b) an inorganic solid fine particle; ) Composition containing polyolefin and %
The gist is a laminate consisting of PVDF or VDF copolymer and/or polyolefin.

Each component of the PVDF resin composition of the present invention will be explained below.

PVDF in the present invention is a polymer having the following molecular structure.

←CHj-CF, -CH, -○F, 鈷As the PVDF having the above molecular structure, injection molding, extrusion molding grade, etc. can be used. In Japan, this type of PVDF is produced and sold under the trademarks such as Prefectural Chemical Industry ■ ``KF Polymer'' and Daikin Industries ■ ``Neoflon VDF J.''

In addition, VDF copolymer is made of vinylidene fluoride and tetrafluoride.
It is a copolymer whose main monomers are ethylene, hexafluoropropylene, and other monomers. Also, radiation,
Also included are graft reaction copolymers using peroxides in the trunk, branches, or side chain structures of catalysts or polymer structures.

The polyolefin in the present invention includes ethylene, propylene, butene-1, pentene-1% hexene-1,
Homopolymers of α-olefins such as methylpentene-1,
Examples include copolymers of ethylene and propylene or other α-olefins, or copolymers of two or more of these α-olefins. Among the above polyolefins, the low ',! IF degree polyethylene (hereinafter referred to as LD)
PE), linear low density polyethylene (LLDP)
E), medium density polyethylene (hereinafter referred to as MDPE), high density polyethylene (hereinafter referred to as HDPE), polyethylene of various densities, polypropylene (hereinafter referred to as PP), and random combinations of ethylene and propylene or other α-olefins. Alternatively, block copolymers and the like are preferred. Furthermore, polyolefins that have been improved by grafting reactions with unsaturated carbon acids, derivatives thereof, etc. can also be used.

The inorganic solid fine particles in the present invention need to be chemically and morphologically stable at the 1-solution temperature of the PVDF resin composition. The particle size of the inorganic solid fine particles is preferably 10 μm or less, more preferably 1 to 0.01 μm, from the standpoint of further improving adhesiveness.

Examples of inorganic solid particles include oxide particles, glass beads,
Silas paroon, chromium oxide, aluminum oxide, boron nitride, turquoise, silica, carbonic acid, asbestos, clay, gypsum, bentonite, mica, nickel ν,
Examples include nickel-iron alloys and abrasive jewelry.

The mixing ratio of the PVDF resin composition of the present invention is 18 to 94% by weight of pVDF' when the total amount of supplied polymer is 100%.
is preferable, more preferably 32 to 88% by weight, and preferably 68 to 6% by weight, and more preferably 68 to 12% by weight. It is preferably 5 to 3% by volume, more preferably 2 to 5% by volume, based on the total amount of the resin composition. The mixing of the inorganic solid fine particles further improves the adhesion between the PVDF and the polyolefin compared to a composition that does not contain the inorganic solid particles. Further, in order to obtain good adhesion between pvDF and polyolefin, it is preferable that the mixing ratio of each component is within the above range.

Note that true specific gravity is used as the specific gravity used in calculations when collecting the above-mentioned inorganic solid fine particle component.

The composition of the present invention is obtained by melt-kneading a mixture of the above-mentioned PVDF, polyolefin, and inorganic solid fine particles. For example, it can be obtained by melting PVDF at a temperature higher than its melting point, for example 200°C, adding polyolefin and inorganic solid fine particles thereto, and stirring mechanically. Note that the above-mentioned mixture, which has been tri-blended in advance, is subjected to P using a Banbury mixer 1 extruder or the like.
The mixture may be kneaded at a temperature higher than the melting point of VDF.

The PVDF resin composition of the present invention according to the above has pvpFa
and polyolefin can be used as an adhesive to bond them together.

As an example of bonding the molded product, generally the composition of the present invention, PVDF, and polyolefin are formed into a film, plate, rod, etc., and then bonded between the PVDFa and the polyolefin molded product. Heat compression bonding is performed with the composition interposed. The adhesion temperature is higher than the melting point of PVDF, for example 20
0-250°C is preferred. Extremely high temperatures are undesirable because the oxidation of the polyolefin becomes significant. Further, the pressing force is sufficient to bring the surfaces of each layer into close contact with each other. As other adhesion methods, coextrusion using an extruder or extrusion coating may be used.

In the case of a laminate, the structure is composed of the composition of the present invention and the above-mentioned P.
It is based on a 2.1 or 3m6It construction with one selected from VDFs and polyolefins. For example, combinations such as composition/PVDF, composition/polyolefin, polyolefin/compound/PVDF, etc. may be further combined, or other materials may be added to the basic structure, such as other thermoplastic resins. , metal, fiber, paper, wood, etc. may be combined. The thickness of the composition layer in these pickles and VI products is 1
It is preferable that it is 0-50011 m.

In addition, the composition of the present invention may contain various stabilizers,
A coloring agent or the like may be added.

Example The present invention will be explained in further detail by the following examples.

Example PVDF used was KF Polymer (trade name) manufactured by Kureha Kagaku Kogyo ■. As the VDF copolymer, grafted PVDF synthesized by a two-step reaction was used. In the first stage, the graft-type PVDF polymerization reaction was carried out using 1 part of buty-μ peroxyallicarbonate, 7G parts of VDF, and 53 parts of hexafluoropropene as polymerization monomers, and using a radical polymerization catalyst and an autoclave, the reaction was carried out at 55°C for 17 hours. went. In the second stage reaction, approximately 40 parts of VDF was added to 60 parts of the reaction polymer, and the mixture was heated at 95°C in an autoclave at 2.
A polymer was obtained by conducting a polymerization reaction for 4 hours.

Regarding HDPE as a polyolefin, Showa Denko ■
Manufactured by 5HOWLEX 56006M (product name) and p
For p, manufactured by Mitsui Petrochemical ■, Mitsui Polypro J600
(product name) was used.

As inorganic solid fine particles, ferrite [manufactured by Toda Kogyo ■,
7-Fe103-KFA-NH (trade name), average particle size 1
5~1lL6μm, hereinafter abbreviated as FeO] and alumina (
Baikowski Chemie Balkalo
x GR, As (trade name) and average particle size (LO5 μm) were used.

The above raw materials were mixed according to the following procedure at a predetermined mixing ratio to prepare a composition and form a sheet.

PVDF pellets are fed into the mixing cell of Pustomy/I/ (newly manufactured by Toyo Seiki Seisakusho) at a temperature of 200°C and the mixing mixer is rotating, and after this is melted, polyolefin pellets are fed, and at the end of this feeding or at the feeding stage. The filler was supplied, and the mixer was rotated for several minutes after the supply was completed to mix.

This molten resin mass was sucked out and molded into an adhesive sheet with a thickness of 13 mm using a heat press.

The test piece for evaluating adhesion was made of PVDF or polyolefin as the adherend material and had a diameter of 6 mm and a length of 3 to 7 mm.
Heat-seal a 3 x 4 x 131 flat plate to the tip of the tx round bar,
The flat plate portion was used as the gripping portion during the tensile test, and the tips of the round bars were used for bonding.

To bond PVDF and polyolefin, cut out a sheet with a diameter of 5 fi from the above adhesive sheet, use a heated metal plate with a smooth surface and a thin sheet of polytetrafluoroethylene as a release material, and attach the adhesive sheet to the tip of one round bar. was fused. Next, heat this round rod and the two tips of the round rod to be bonded to it with an air burner, and after confirming that the tips have melted,
These tips were brought into contact and lightly pressed to fuse them in a straight line and then cooled to perform adhesion. Note that the heating of the metal plate and the temperature of the heating air were controlled to around 220 to 250°C.

The adhesive force of the obtained adhesive round bar was measured using Tennron UTM.
The tensile strength was measured using Type 3 at a tensile rate of 4/min, and the value obtained by dividing the tensile strength by the fracture surface area was defined as the adhesive strength. The results are shown in Table-1.

Note that the specific gravity (true specific gravity) used in the calculation when mixing ferrite and alumina is 5.24 for ferrite and 598 for alumina.

In addition to the effects of the invention, the PVDF resin composition of the present invention improves the adhesiveness between PVDF and polyolefin, and facilitates the adhesion or lamination of PVDF and polyolefin.

Therefore, by adhesively laminating PVDF, which has excellent properties such as chemical resistance, weather resistance, and electrical properties, and relatively inexpensive polyolefin, polyolefin molded products, polyolefin,
It is possible to improve the functionality of materials that have on the surface.

Claims (3)

[Claims] (1) A polyvinylidene fluoride resin composition comprising (a) polyvinylidene fluoride or vinylidene fluoride copolymer and (b) inorganic solid fine particles. (2) A polyvinylidene fluoride resin composition comprising (a) polyvinylidene fluoride or vinylidene fluoride copolymer, (b) inorganic solid fine particles, and (c) polyolefin. (3) A composition comprising (a) polyvinylidene fluoride or vinylidene fluoride copolymer and (b) inorganic solid fine particles, or a composition comprising (c) polyolefin blended with the composition, and polyvinylidene fluoride. Alternatively, a laminate comprising a vinylidene fluoride copolymer and/or a polyolefin.