JPH08132568A - Laminate - Google Patents

Abstract

PURPOSE: To provide a laminate which has an intermediate layer between a layer comprising a vinylidene fluoride resin and a layer comprising a polyolefin polymer and which has good adhesive properties between the layers and an excellent chemical resistance. CONSTITUTION: A laminate is provided wherein an intermediate layer between a layer comprising a vinylidene fluoride resin and a layer comprising an olefin polymer is used as an adhesive layer comprising an unsaturated compound having at least one kind of functional groups selected from among a carboxyl group, an acid anhydride group, a maleimide group and a hydroxyl group and/or a copolymer of a maleimide compound and a nonpolar α-olefin monomer, or these modified substances.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having good adhesion between layers and having excellent chemical resistance, such as pesticides, fuel oils and industrial chemicals (hydrocarbon solvents).

2. Description of the Related Art Conventionally, containers such as polyethylene and polypropylene have been generally used for pesticides and hydrocarbon solvents. However, due to insufficient chemical resistance, swelling of containers,
There were problems such as cracks and there was a limit to its use. In order to supplement the chemical resistance of polyolefins, a container having good chemical resistance has been developed by extrusion-molding a polyamide resin and polyolefin having good chemical resistance, both in multilayers. However, even such a resin does not show resistance to all chemicals, and a polyamide resin has a drawback that it is extremely weak against phenols, alcohols, strong acids and the like.
Therefore, fluororesin, which is generally known as a resin that is resistant to all chemicals, can be considered, but since it is generally very expensive, it is only used in some special fields. It was Further, since a fluororesin is generally excellent in non-adhesiveness, it is difficult to laminate it with another resin.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and an object of the present invention is to provide a laminate having excellent interlayer adhesion and chemical resistance.

[0002]

According to the present invention, an intermediate layer between a layer (A) made of a vinylidene fluoride resin and a layer (B) made of an olefin polymer is a carboxyl group, an acid anhydride group or a maleimide. Of an unsaturated compound and / or a maleimide compound having at least one functional group selected from a group and a hydroxyl group and a non-polar α-olefin monomer, or a modified product thereof (C ) Is provided. Examples of the vinylidene fluoride resin of the layer (A) used in the present invention include vinylidene fluoride resin, vinylidene fluoride content of 50 mol% or more, preferably 90 mol% or more of copolymer resin such as tetrafluoride. Examples thereof include ethylene-vinylidene fluoride copolymer resin. Further, it may be a composition comprising polyvinylidene fluoride and an acrylic resin such as polymethacrylate and the like, containing at least 40% by weight, preferably 75% by weight or more of polyvinylidene fluoride. Among them, polyvinylidene fluoride resin and tetrafluoroethylene-vinylidene fluoride copolymer resin are preferable, and vinylidene fluoride resin is more preferable.

The polyolefin polymer of the layer (B) used in the present invention includes high-, medium-, and low-density polyethylene,
Examples thereof include polypropylene and ethylene-propylene copolymer. Among them, high density polyethylene is preferable. Further, a filler such as glass fiber, carbon fiber, metal fiber, glass beads, wollastonite, talc, mica, glass flake, milled fiber, kaolin, barium sulfate may be used alone or in combination with the polyolefin polymer. can do. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. These fillers are usually used in the range of 5 to 150 parts by weight based on 100 parts by weight of the polyolefin polymer.

Examples of the non-polar α-olefin monomer used in the adhesive layer (C) of the present invention include ethylene, propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1. Is mentioned. Of these, ethylene is preferred. Examples of the carboxyl group-containing unsaturated compound used here include acrylic acid, methacrylic acid, and maleic acid. Examples of the unsaturated compound containing an acid anhydride group include maleic anhydride, itaconic anhydride and citraconic anhydride. As the hydroxyl group-containing unsaturated compound,
Hydroxystyrene, 3-hydroxy-1-propene,
4-hydroxy-1-butene, cis-4-hydroxy-
2-butene, trans-4-hydroxy-2-butene,
There are 3-hydroxy-2-methyl-1-propene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and the like. Further, examples of the maleimide compound include maleimide compounds of α- or β-unsaturated dicarboxylic acids such as maleimide, N-methylreimide, N-butylmaleimide and N-cyclohexylmaleimide. Further, a carboxyl group, a carboxyl group in the copolymer of an acid anhydride group-containing unsaturated compound and a non-polar α-olefin monomer, the acid anhydride group is esterified with a polyol component, the hydroxyl group, In addition, a copolymer of an acid anhydride group-containing unsaturated compound and a non-polar α-olefin monomer and a general formula NH ₂ —R—OH (wherein R is a carbon number 2
What is obtained by reacting with (about 30 to 30 hydrocarbons) can be used as the adhesive layer (C) of the present invention. Also,
The unsaturated compound having a functional group selected from a carboxyl group, an acid anhydride group and a hydroxyl group and / or a modified product of a copolymer of a maleimide compound and a non-polar α-olefin monomer is the above-mentioned copolymer. It is composed of a graft copolymer of a polymer and a polymer copolymerizable therewith, or a vinyl-based (co) polymer of the above-mentioned copolymer, one (co) polymer of which is in the other (co) polymer. The particles are dispersed and the particle size is 0.
It may be a thermoplastic resin having a multi-phase structure of 001 to 10 μm. Examples of the vinyl (co) polymer used here include styrene, nucleus-substituted styrenes such as methylstyrene, dimethylstyrene, α-substituted styrenes such as α-.
A vinyl aromatic monomer such as methylstyrene; an alkyl ester of acrylic acid or methacrylic acid having 1 to 7 carbon atoms, for example, methyl-, ethyl- of (meth) acrylic acid,
(Meth) such as propyl-, isopropyl-, butyl-
Acrylic acid ester monomers; (meth) acrylic acid hydroxyalkyl ester monomers such as 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate; vinyl cyanide such as acrylonitrile or methacrylonitrile. Monomers; vinyl ester monomers such as vinyl acetate and vinyl propionate; (meth) acrylamide monomers such as acrylamide and methacrylamide; (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, It is a (co) polymer obtained by polymerizing one or more vinyl monomers such as unsaturated carboxylic acids such as crotonic acid and derivatives thereof such as amides, imides, esters and anhydrides. The term "multiphase thermoplastic resin" as used herein means an unsaturated compound having a functional group and a nonpolar α-
It is composed of a copolymer with an olefin monomer and a vinyl (co) polymer, and one (co) polymer is spherically and uniformly dispersed. The particle size of the dispersed (co) polymer is usually 0.001 to 10 μm, preferably 0.0.
It is 1 to 5 μm. If the dispersed particle system is less than 0.001 μm or exceeds 10 μm, the interlayer adhesion resistance of the obtained laminate is deteriorated, which is not preferable.

The laminate of the present invention can be molded by a known molding method such as a conventional multilayer extrusion blow molding method and a multilayer sheet extrusion molding method. The laminate of the present invention is
The component (A) component / (C) component / (B) component of the present invention, the component (B) / (C) / (A) / (C) / (B), and the like may be used in appropriate combination. it can. Specific examples of the use of the laminate of the present invention include blow molded articles, tanks for general gasoline and alcohol mixed gasoline, agricultural chemicals, hydrocarbon solvents, gasoline additives,
Examples include containers for storing acid and alkaline solutions, and examples of sheets include chemical plant vessel linings, FRP tank linings, chemical solution tanks, acid storage tanks, and plating tank linings. Depending on the usage conditions, a vinylidene fluoride resin for the inner layer, a polyolefin polymer for the outer layer, or a polyolefin polymer for the inner layer, a vinylidene fluoride resin for the outer layer, and the above-mentioned five-layer laminate can be used.

[0006]

EXAMPLES The present invention will be further described below with reference to examples. Various evaluations in the examples are values measured as follows. A sample cut out from the molded product after the chemical permeable multilayer sheet is molded,
Set the (A) layer on one wall of the container so that it touches the content liquid (chemicals), and measure the weight change in the state of 40 ° C after filling the chemicals every day for up to one week. I calculated the average. The chemical used was toluene / isooctane = 5/5. The adhesive strength was measured at a peeling speed of 100 mm / min. <Example 1> Polyvinylidene fluoride resin for vinylidene fluoride resin, Showa Denko KK for polyolefin polymer
Made of high density polyethylene 4551H, ethylene-maleic anhydride copolymer (maleic anhydride content 2
0% by weight) was used to mold a sheet having a three-layer structure with a multilayer sheet extrusion molding machine. <Example 2> A vinylidene fluoride resin and a polyolefin polymer, which are the same as those in Example 1, and an ethylene-acrylic acid copolymer (acrylic acid content is 15% by weight) are used for the adhesive layer. A sheet similar to that was molded. <Comparative Example 1> Using the high-density polyethylene used in Example 1, a single layer sheet similar to that of Example 1 was molded.

[0007]

[Table 1]

Examples 1 and 2 obtained by the present invention are excellent in interlayer adhesion resistance and chemical resistance.

[0009]

EFFECT OF THE INVENTION The laminate of the present invention has excellent chemical resistance and interlayer adhesion, and can be used for storing agricultural chemicals, fuel oils, industrial chemicals (hydrocarbon solvents) and the like.

Front page continued (72) Inventor Hisao Nagai 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. An intermediate layer between a layer (A) made of a vinylidene fluoride resin and a layer (B) made of an olefin polymer is selected from a carboxyl group, an acid anhydride group, a maleimide group and a hydroxyl group. An adhesive layer (C) comprising a copolymer of an unsaturated compound and / or a maleimide compound having at least one functional group and a nonpolar α-olefin monomer, or a modified product thereof. Laminate.