JPS61106244A - Vinyl chloride group resin laminate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a vinyl chloride resin laminate.

Specifically, the present invention relates to a vinyl chloride resin laminate with excellent interlayer adhesion in which a specific adhesive resin composition is interposed between the vinyl chloride resin and the base material.

[Conventional technology]

Vinyl chloride resin has many excellent properties such as toughness and transparency, and by using plasticizers such as dioctyl phthalate, it can have a wide range of properties from highly rigid hard products to flexible soft products. can, film, sheet,
Molded products, etc. - Used in an extremely wide range of applications.

However, vinyl chloride resins having the above-mentioned excellent properties have the drawback of extremely poor adhesion to the base material 1, such as synthetic resin, metal, or wood.

In order to improve this adhesive property, various attempts have been made to interpose an adhesive layer between the vinyl chloride resin layer and the base material.

for example.

■ How to apply acrylic or epoxy adhesives.

■ Ethylene-vinyl acetate copolymer or rosin, indene, coumaron, modified rosin.

A method in which a material containing a tackifier such as aromatic petroleum resin is used as an adhesive layer.

(2) A method in which a modified ethylene-vinyl acetate copolymer is graft-polymerized with an unsaturated carboxylic acid or its anhydride and used as an adhesive layer (see No. 7673/1983).

■ A method in which a mixture of carboxylated ethylene-vinyl acetate copolymer and petroleum resin is used as an adhesive layer (see JP-A-Sho, 1-, ?-/1&!3).

(2) A method in which a mixture of ethylene-vinyl acetate copolymer and polyethylene is graft-polymerized with an unsaturated carboxylic acid or its anhydride to form a modified adhesive layer (see Japanese Patent Application Laid-open No. Sho JμmtIo).

■ A method in which a polyolefin modified with an unsaturated carboxylic acid or its anhydride is blended with an ethylene-vinyl acetate copolymer and an aliphatic petroleum resin as an adhesive layer. See JlI No. 4, etc. have been proposed.

[Problem that the invention seeks to solve]

Moreover, it requires complicated processes such as coating and drying, and is complicated to operate, and there is also the problem of deterioration of the production environment due to the use of screener solvents. In addition, the above-mentioned methods (1) to (2) have a problem in that interlayer adhesion is somewhat insufficient, and when the adhesive layer is formed into a film, the films tend to block each other, resulting in poor workability.

Furthermore, in methods (1) and (2) above, when the adhesive layer is formed into a film, it has the advantage of no blocking property and good workability.

There is a problem that interlayer adhesion is somewhat insufficient.

[Failure to solve the problem]

In view of the above-mentioned prior art, the present inventors have conducted extensive studies on improving interlayer adhesion when laminating a vinyl chloride resin layer and a base material by an adhesive layer interposition method. By using an adhesive polyolefin resin composition in which polyolefin modified by graft polymerization of unsaturated carvone 111 or its anhydride and a specific amount of vinyl chloride resin is used as an adhesive layer between the material and the material, one layer can be formed. Adhesion is significantly improved.

Furthermore, the present invention was completed by discovering that when the adhesive layer is formed into a film, there is no blocking property and the workability is good.

That is, 1 the gist of the present invention is a vinyl chloride resin laminate comprising a vinyl chloride resin layer, an adhesive layer, and a base material, in which the adhesive layer contains polyolefin with 0.0.0 of an unsaturated carboxylic acid or its anhydride. /~/, Q weight'i% based on 95 to -0 parts by weight of the grafted modified polyolefin.

A vinyl chloride resin laminate characterized by being an adhesive polyolefin resin composition containing 0 parts by weight of a vinyl chloride resin j-ff.

The present invention will be explained in more detail below.

As the vinyl chloride resin used in the present invention,
Polymerization degree of polymerized vinyl chloride monomer is generally 00~
Hiroshi, 000. Preferably, a homopolymer with a polymerization degree of 300 to 300, obtained by copolymerizing vinyl chloride and vinyl acetate, and a copolymer obtained by grafting vinyl chloride onto an ethylene-vinyl acetate copolymer. Examples include copolymers of vinyl chloride and small amounts of monomers copolymerizable with vinyl chloride, such as ethylene, propylene, acrylic esters, and vinylidene chloride. The vinyl chloride resins include semi-rigid and soft vinyl chloride resins plasticized with phthalate esters, adipate esters, phosphate esters, polyester plasticizers, and the like. These vinyl chloride resins also contain fillers, polymer modifiers, and pigments.

Compounding agents that are generally added during molding of vinyl chloride resins, such as a heat stabilizer and a one-component stabilizer, can be blended as necessary.

In addition, in the present invention, as an adhesive layer, 0.01-t to 0.0-t to an unsaturated carboxylic acid or its anhydride is added to the polyolefin.
An adhesive polyolefin resin composition is used, which is prepared by blending a specific amount of a vinyl chloride resin into a modified polyolefin obtained by graft polymerization.

The above-mentioned modified polyolefin is a polyolefin in which an unsaturated carboxylic acid, its anhydride, or a polymer is chemically bonded, and the amount of the bond is calculated in terms of unsaturated carboxylic acid or its anhydride monomer. , 0.01~ for polyolefin! , Q weight t%. If the bonding amount is less than O0θ1 weight fleas, the adhesive strength will be low, and if it is more than t, 0% by weight, the smelly gel-like substance will increase, which is not preferable. Within this range, preferably 0.01 to 0.3% by weight, most preferably 0.03 to 0.
．． It is 3% by weight.

Examples of the polyolefins include high-density polyethylene, low-density polyethylene, medium-density polyethylene, ethylene-propylene/copolymer, ethylene-butene-7 copolymer, polypropylene, propylene-butene-7 copolymer, polybutene-! , polybutsu-methylpentene-1, and the like. Preferred polyolefins differ somewhat depending on the base material used in the present invention.For example, for a crushing layer between a vinyl chloride resin and a metal, polyolefins with densities o, qio
Low density polyethylene or elastomeric ethylene-propylene copolymers with a density of ˜0.9.3 are preferred.

Examples of the unsaturated carboxylic acid or anhydride thereof to be graft-polymerized include acrylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, and anhydrides thereof. In particular, it is preferable to use maleic anhydride.

The above-mentioned modified polyolefin is produced by adding an unsaturated carboxylic acid or its anhydride to a polyolefin.

It can be produced by causing a graft polymerization reaction according to a known method. The reaction method for causing the graft polymerization reaction may be a solution method or a slurry method, but
From an economic point of view, the melt intermixing method is preferable. In the case of the melt mixing method, the polyolefin has θ, Q/~1. Q% by weight of unsaturated carboxylic acid or its anhydride and up to 0.07% by weight, preferably from o,ooi to 0.00% by weight. O! If 5% by weight of organic peroxide is blended and melt-kneaded at -300℃, the grafting efficiency is high and a modified polyolefin with good color and no odor can be obtained. It is advantageous because it can be obtained.

To further explain the above melt-kneading method, the amount of unsaturated carboxylic acid or its anhydride blended into the polyolefin is as follows:
If it is less than 0.0/X food %, the adhesive strength is low, and if it is more than 117% by weight, it is not preferable because the smelly gel-like substance increases. Among the above ranges, θ, Ql-σ, 5 weight ratio is preferable.

Most preferred is 0.03-0.3% by weight. If the amount of organic peroxide used is more than Q,/weight fit%, gel-like substances and fisheyes in the film will increase.

This is not preferable because it causes a significant decrease in molecular weight.

The lower limit is not particularly limited, but if it is less than 0.00/
/wt% or more is desirable.

Examples of organic peroxides include benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide, and t-
Butyl peroxylaurate, dicumyl peroxide,
α,α′-bis(1-butylperoxyJ-1)-diisopropylbenzene, 2,3-dimethyl,! -bis(t-butylperoxy)hexane, t-butylpero dibenzoate% n-butyl-q, q-bis(t-butylperoxy)valerate, octanoyl peroxide, co, 3-dimethylruco, j-bis(pensoyl) Examples include peroxynohexane, vinyltris(1-butylperoxy)silane, and methylvinyl(cumylperoxy)silane.

In the melt-kneading method, polyolefin powder or pellets are triblended with an unsaturated carboxylic acid or its anhydride and, if necessary, an organic peroxide in a predetermined mixing ratio using a Henschel mixer, or an unsaturated carboxylic acid is added to an organic solvent. The acid father is a solution of its anhydride and, if necessary, an organic peroxide, which is sprayed onto polyolefin powder or pellets, and further blended using a Henschelmigisser or the like. In the present invention, the unsaturated carboxylic acid or its anhydride used as the graft monomer is used in a smaller amount than in the conventional method, so when kneading it with the polyolefin, an organic solvent is used to mix it uniformly as described above. It is preferable to measure Such organic solvents include acetone.

Examples include methyl ethyl ketone and cyclohexanone. The blended polyolefin powder or pellets is put into a kneading machine 1, such as a Banbury mill, a double screw mixer, an extruder, etc., which is purged with nitrogen gas, at a temperature of 120 to 00C, for a time of Q, / ~30
Melt and knead in minutes. If the crosstalk temperature is less than 120°C, the graft reaction described below will be difficult to occur, and if it exceeds 300°C, thermal deterioration of the polyolefin will become significant, which is not preferable.

However, by the above melt-kneading method, unsaturated carboxylic acid was added to polyolefin! ! ! ! When a graft reaction is performed with an unsaturated carboxylic acid or its anhydride, the organic peroxide used as an initiator for the graft reaction is completely decomposed in the resulting modified polyolefin, and the unsaturated carboxylic acid or its anhydride is dissolved in the polyolefin resin. Most of them are chemically bonded.

Next, the vinyl chloride resin blended into the modified polyolefin generally has a polymerization degree of aOO to a, ooo obtained by polymerizing vinyl chloride monomers.

Preferably a homopolymer of 6!0 to 1, JOθ.

Polymerization degree of 300 made by copolymerizing vinyl chloride and vinyl vinegar
~3,000 copolymers, copolymers in which vinyl chloride is grafted onto ethylene-vinyl acetate copolymers, small amounts of monomers copolymerizable with vinyl chloride such as ethylene, propylene, acrylic esters, vinylidene chloride, and chloride. Examples include copolymers with vinyl. The above-mentioned vinyl chloride resins include semi-hard and soft vinyl chloride resins plasticized with phthalic acid esters, adipine esters, phosphorus esters, polyester plasticizing agents, and the like. In addition, these vinyl chloride resins are blended with fillers, polymer modifiers, pigments, heat stabilizers, light stabilizers, and other additives that are commonly added during the molding process of vinyl chloride resins. can do.

The blending ratio of each of the above components is modified polyolefin 95 to 2.
0 parts by weight, preferably 90 to 0 parts by weight, and 3 to 3 parts of vinyl chloride resin.

Preferably it is in the range of 70 to 60 parts by weight. If the amount of vinyl chloride resin is less than 3 parts by weight, the adhesion will not improve and -
If the amount is more than 1,000,000 parts by weight, the adhesive strength will be significantly lowered, which is not preferable.

In addition, as a method for preparing an adhesive polyolefin resin composition by blending each of the above components, a modified polyolefin and a vinyl chloride resin are mixed using a Henschel mixer, a V-shaped blender, etc., and then an extruder, a double screw mixer, etc. A method of pelletizing under cover, or a method of pelletizing modified polyolefin and vinyl chloride resin using a Banbury mixer.
For example, the mixture may be loaded into a single twin-roll mixer, blended, and passed through a sheet cutter to form pellets using a direction pressure method.

As a method for producing a vinyl chloride resin laminate comprising a vinyl chloride resin layer, an adhesive layer, and a base material according to the present invention, a vinyl chloride resin and the above-mentioned adhesive polyolefin resin composition are coextruded onto a base material in advance. A method of extrusion laminating the adhesive layer side of a composite, in which a film or sheet of the above-mentioned adhesive polyolefin resin composition extruded uniaxially is extrusion laminated onto a base material, and the adhesive layer side is extruded onto the adhesive layer side using a separate extruder. A method of extrusion laminating a film or sheet of vinyl chloride resin, a film or sheet of the above-mentioned adhesive polio or reflex resin composition extruded in advance on a base material, and a film or sheet of vinyl chloride resin are laminated and thermocompression bonded using a press. how to.

A method of three-layer extrusion lamination of a film or sheet of the adhesive polyolefin resin composition previously extruded onto a base material and a film or sheet of vinyl chloride resin, a film of the adhesive polyolefin resin composition extruded from an extruder. or after laminating the sheet to the base material or PVC resin board or pipe.

Examples include a method in which a film or sheet of the above-mentioned adhesive polyolefin resin composition is interposed between a base material and a plate or pipe made of a vinyl chloride resin, and the adhesive is bonded under heat. In addition, the vinyl chloride resin laminate of the present invention has a vinyl chloride resin layer C below which is abbreviated as A, and an adhesive layer C below B.
3 consisting of abbreviated as C and a base material (hereinafter abbreviated as C)
), 7B10/B/k.

0/B/A, /B10. A/B/○/B/A/B/C
It may also be a multilayer laminate such as. The conditions for the above thermocompression bonding method are a temperature of 100-20°C.

Preferably 30-270°C, pressure 0. ~50 Yu/d
, preferably 1-30'Q/cut, time Q, l-2
It is within the range of 0 minutes.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the following Examples unless the gist of the present invention is exceeded.

Note that the melt index in Examples is C or lower.

(abbreviated as M)) ASTM D-/2.3g-j
7T, and the shear adhesive strength was measured in accordance with J Engineering S Y, ArN2. For film blocking tests, lj
- When the film wound up on a roll was peeled off by hand, a film that could be easily peeled off was marked with ○, a film with a little resistance was marked with Δ, and a film with considerable resistance that caused the film to tear when peeled off was marked with ×.

Examples 7 to 3 and Comparative Example 1 (1) Production of resin composition High pressure low density polyethylene C4aK: 0.9 JOy 1
M: 3. λi/10 minutes] ioo parts by weight.

3 parts by weight of 0.0U of α,α'-bis(1-butylperoxyJ-I)-diinoprobylbenzene dissolved in a small amount of acetone and 1 part by weight of anhydrous maleic acid O,3O are blended in a blender. . This mixed pellet has an inner diameter of ao
It was extruded into pellets at 30° C. using an extruder with %yf, T, +/D=2. When maleic anhydride was quantified using an infrared absorption spectrum in a part of this pellet, it was found that 13% by weight of maleic anhydride had been graft-polymerized with O. The thus obtained maleic anhydride-modified low-density polyethylene pellets (M process; 1.5 g, 710 minutes) were combined with vinyl chloride resin [Nica Vinyl 5G-700 (trademark; Ryoichi Co., Ltd.; Vinyl chloride heptapolymer, Polymerization degree too) ioo parts by weight, tin stabilizer y, 0 parts by weight side lubricant 1. 2 parts of plasticizer, Q''i parts]
were blended in a blender in the proportions shown in Table 1.

(2) f[manufactured diameter of layer J O%1. L/D = The above blend was charged into a compact Koda extruder equipped with a downward T-die, and a T-die film with a thickness of 0.7% was produced at -00-2-0°C. Using this film as an adhesive, a galvanized steel plate (2 x width, 1 door thickness) and a hard vinyl chloride resin plate [
Nikavinyl EIG-too (trademark; manufactured by Ryoichi Co., Ltd.; vinyl chloride homopolymer, degree of polymerization goθ) ioo heavy weight part, lead stabilizer 3.3 parts by weight, metal soap O, S weight parts and lubricant O0 double i It was prepared by kneading parts;
Insert between m width, thickness 3 yrrz 1, 20
After preheating for 5 minutes at 0°C.

Thermocompression bonding was carried out by holding at 200° C. for 3 minutes in a pressure chamber Okg/a/IG. Next to the obtained laminate.

The shear adhesive strength was measured using the method described above. The results are shown in Table 7.

Comparative Examples C and 3 In Example 1, ethylene-vinyl acetate copolymer (vinyl acetate content:
, 2g weight %, M engineering: 1. g//Q min) or a modified ethylene-vinyl acetate copolymer obtained by graft polymerizing maleic anhydride (maleic anhydride graft amount: 20.7.
The same procedure was carried out except that 7-fold fi%) was used and no vinyl chloride resin was added. The results are shown in Table 1.

〔Effect of the invention〕

According to the present invention, an adhesive polyolefin resin composition obtained by blending a specific amount of a vinyl chloride resin into a polyolefin modified by graft polymerization of an unsaturated carboxylic acid or its anhydride is used. By using it as an interlayer adhesive between a substrate and a substrate, a laminate with excellent adhesion can be obtained. The laminate of the present invention, particularly the laminate in which metals such as steel plates, steel pipes, iron wires, and aluminum plates are coated with vinyl chloride resin, is suitably used for industrial materials, building materials, and the like.

Claims (1)

[Claims] (1) In a vinyl chloride resin laminate composed of a vinyl chloride resin layer, an adhesive layer, and a base material, the adhesive layer is
5 parts by weight of a vinyl chloride resin to 95 to 20 parts by weight of a modified polyolefin obtained by graft polymerizing 0.01 to 1.0% by weight of an unsaturated carboxylic acid or its anhydride to a polyolefin.
A vinyl chloride resin laminate, characterized in that it is an adhesive polyolefin resin composition containing ~80 parts by weight.