JPS61104846A - 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 with the use of plasticizers such as dioctyl phthalate, it can be made into a wide range of properties, from highly rigid hard products to flexible soft products. It is used in an extremely wide range of applications such as films, sheets, and molded products.

However, the cyclized vinyl resin having the above-mentioned excellent % properties has the disadvantage of extremely poor adhesion to base materials such as synthetic resins, metals, or wood.

In order to improve this adhesiveness, several attempts have been made to interpose an adhesive layer between the vinyl chloride resin layer and the base material. 1 For example, ■ A method of applying an acrylic or epoxy adhesive, ■ A method of applying an ethylene-vinyl acetate copolymer or a compound containing a tackifier such as renirosine, indene, coumaron, modified rosin, or aromatic petroleum resin. Method of using as a layer, (1) A method of using a modified product obtained by graft polymerizing an ethylene-vinyl acetate copolymer with an unsaturated carboxylic acid and its anhydride as an adhesive layer (*Kaisho r7-/47
(Refer to No. 326), ■ Method of using a mixture of carboxylated ethylene-vinyl acetate copolymer with petroleum resin as an adhesive layer (Refer to JP-A-11613), ■ Ethylene-vinyl acetate copolymer and polyethylene A method in which a modified mixture of unsaturated carboxylic acid or its anhydride is used as an adhesive layer by graft polymerization of a mixture consisting of A method has been proposed in which an anhydride-modified material is blended with an ethylene-vinyl acetate copolymer and an aliphatic petroleum resin as an adhesive layer (see %Kaisho J-3-127 No. 4). ing.

[Problem that the invention seeks to solve]

The above method (2) has insufficient interlayer adhesion, requires complicated steps such as coating and drying, is complicated to operate, and has the problem of deteriorating the working environment due to the use of organic solvents.

In addition, the above methods (■ to ■) are somewhat insufficient in terms of interlayer adhesion, and when the adhesive layer is formed into a film,
There is a problem that the film comrades are prone to pronking and workability is poor.

Furthermore, in methods (2) and (2) above, when the adhesive layer is formed into a film, it has the advantage of no blocking property and good workability, but there is a problem that the interlayer adhesion is somewhat insufficient. .

[Means for solving problems]

In view of the above-mentioned prior art, the inventors of the present invention have conducted intensive studies on improving the interlayer adhesion when laminating vinyl chloride resin and base material by an adhesive layer intervening method, and found that the vinyl chloride resin layer An adhesive resin composition that is made by blending a specific amount of vinyl chloride resin with an ethylene-vinyl acetate copolymer modified by graft polymerization of an unsaturated carboxylic acid or its anhydride as an adhesive layer between the base material and the base material. The present invention was completed based on the discovery that the interlayer adhesion was significantly improved by using the adhesive layer, and that when the adhesive layer was formed into a film, there was no blocking property and the workability was good.

That is, the gist of the present invention is that, in a vinyl chloride resin laminate composed of a vinyl chloride resin layer, an adhesive layer, and a base material, the adhesive layer contains vinyl acetate in an amount of ts to 70% by weight.
Modified ethylene-vinyl acetate copolymer 95-2, which is obtained by graft-polymerizing 0.0/-/,0% by weight of an unsaturated carboxylic acid or its anhydride to the ethylene-vinyl acetate copolymer.
The present invention relates to an adhesive resin in which 5 to 10 parts by weight of a vinyl chloride resin is blended to 0 parts by weight, and a vinyl chloride resin laminate characterized by being parabolic.

The present invention will be explained in more detail below.

As the vinyl chloride resin used in the present invention,
Generally, when vinyl chloride monomer is polymerized, the degree of polymerization is 9≠00S.
−≠,000, preferably Otsu! Homopolymer with a degree of polymerization of 300 to J, 000 obtained by copolymerization of vinyl chloride and vinyl acetate, ethylene-
Copolymers made by grafting vinyl chloride onto vinyl acetate copolymers, copolymers of vinyl chloride and small amounts of heptamers that can be copolymerized with vinyl chloride, such as ethylene, propylene, acrylic esters, and vinylidene chloride, etc. can be mentioned. 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. In addition, these vinyl chloride resins may be supplemented 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 be blended.

In addition, in the present invention, as an adhesive layer, an unsaturated carboxylic acid or its anhydride is graft-polymerized to an ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 70% by weight at 0.07 to 0% by weight. An adhesive resin composition is used, which is a modified ethylene-vinyl acetate copolymer mixed with a specific amount of a vinyl chloride resin.

The above-mentioned modified ethylene-vinyl acetate copolymer is an ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 70%, and a monomer-like polymer of an unsaturated carboxylic acid or anhydride thereof chemically bonded to the ethylene-vinyl acetate copolymer. The amount of bonding is 0.0 /
~/, It's like a weight with 0 layers. The amount of binding is 0,
If the amount is less than 0.07% by weight, the adhesive strength will be low, and if it is more than 0% by weight, the smelly gel will increase, which is not preferable. Within this range, preferably 0.0/-0.6% by weight
, most preferably 0.03 to 0.3% by weight.

The above ethylene-vinyl acetate copolymer (hereinafter abbreviated as KVA) is produced by a high-pressure polymerization method under /, 000-j, θQθ atmospheric pressure, or a solution or emulsion polymerization method under 1oo-≠00 atmospheric pressure, etc. Vinyl acetate content j~70
Heavy weight, preferably IO−≠θ heavy′! ks and has a melt index (according to A8TM D-/2Jt-!l; 7T) of 0.1 to 1001710 minutes. When using ETA with a vinyl acetate content of less than 5% by weight,
The compatibility with vinyl chloride deteriorates, the adhesion of the resulting blend composition decreases, and the vinyl acetate content decreases to 70% by weight.
It is not preferable to use a very high ETA because the resulting blend composition will have poor film formability.

On the other hand, as the unsaturated carboxylic acid or anhydride thereof to be graft-polymerized, acrylic acid, maleic acid, itaconic acid, hexamaric acid, ctraconic acid, or anhydride thereof is used. In particular, it is preferable to use maleic anhydride.

Therefore, the modified ethylene-vinyl acetate copolymer of the present invention is obtained by adding an unsaturated carboxylic acid or its anhydride to EVA,
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 economically the melt-kneading method is preferable. When using the melt kneading method, KVA is 0.0 /~/,
0 weight group carboxylic acid or its anhydride and 011
% by weight or less, preferably 0.00/-0.0! heavy i
If the organic peroxide of
Advantageously, a vinyl acetate copolymer is obtained.

To further explain the above-mentioned melt mixing method, the bone of unsaturated carboxylic acid or its anhydride mixed in KVA is 0.07
If it is less than 1.0% by weight, the adhesive strength is low, and if it is more than 1.0% by weight, it is not preferable because it increases the smelly gel-like substance. Among the above ranges, 0.0/~O,S weight % is preferable, and 0.03 to 0.3 weight % is most preferable. When the organic peroxide is used in an amount exceeding 0.1% by weight, it is not preferable because gel-like substances and fish eyes in the film increase and the molecular weight decreases significantly. There is no particular lower limit, but if it is less than 0,007% by weight, the grafting efficiency will decrease, and problems such as a decrease in adhesive strength or the odor of unreacted monomers will likely occur, so if it is 0,00/ili% or more, It is desirable that there be.

Examples of organic peroxides include benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide, and t-
Butyl peroxylaurate, dicumyl peroxide,
α,α′-bis(1-butylperoxy)-p-diisopropylbenzene, λ,! -dimethylruco, j-bis(
1-Butylperoxy)hexane, t-butylperoxydipenzoate, n-butyl-≠-bis(t-butylperoxy)valerate, octanoylperoxide,
λ,j-dimethyl-2. ! -Bis(benzoylperoxy)hexane, vinyltris(t-butylperoxy)
Examples include silane, methylvinyl(cumylperoxy)silane, and the like.

In the melt-kneading method, EVA powder or pellets are triblended with an unsaturated carboxylic acid or its anhydride and, if necessary, an organic peroxide at a predetermined mixing ratio using a Henschel mixer, or an unsaturated carboxylic acid is added to an organic solvent. A solution of the acid or its anhydride and, if necessary, an organic peroxide is sprayed onto the Fi'VA powder or pellets, and further blended using a Henschel mixer or the like. In the present invention, the unsaturated carboxylic acid or its anhydride as a graft monomer is used in a smaller amount than in the conventional method, so when kneading it with EVA, an organic solvent is used to ensure uniform mixing as described above. Preferably measured. Such organic solvents include acetone, methyl ethyl ketone, cyclohexanone, and the like. The blended l1lvA powder or pellets were mixed with nitrogen gas in the system. machine,
For example, the mixture is put into a Banbury mixer, a double screw mixer, an extruder, etc., and melt-kneaded at a temperature of /jO-2IO'r and a time of o and i for 30 minutes. Kneading temperature is 110℃
If the temperature is less than 0°C, the graft reaction described below will hardly occur, and if it exceeds 0°C, thermal deterioration of KVAQ will become significant, which is not preferable.

Therefore, in the modified ethylene-vinyl acetate copolymer obtained by the above-mentioned melt-kneading method, the organic peroxide used as an initiator for the above-mentioned grafting reaction is completely decomposed, and the unsaturated carboxylic acid or its anhydride is completely decomposed. The material is chemically bonded to EVA by more than fk% of the charged amount.

Next, the vinyl chloride resin to be blended into the above-mentioned modified ethylene-vinyl acetate copolymer generally has a polymerization degree of 0 to 0, preferably t.
Polymerization degree of 300 ~ obtained by copolymerization of so-i, 3oo homopolymer, vinyl chloride, and vinyl acetate! ,000
Copolymers of ethylene-vinyl acetate copolymers grafted with vinyl chloride, copolymers of vinyl chloride with small amounts of monomers that can be copolymerized with vinyl chloride, such as ethylene, propylene, acrylic esters, and vinylidene chloride. Examples include polymers. The vinyl chloride resins include semi-hard and soft vinyl chloride resins plasticized with phthalate esters, adipate esters A, phosphate esters, polyester plasticizers, and the like. Also,
These vinyl chloride resins are blended with fillers, polymer modifiers, fillers, heat stabilizers, light stabilizers, and other additives that are commonly added during the molding process of vinyl chloride resins, as necessary. be able to.

The blending ratio of each component in the adhesive resin composition is 25 to 202 parts by weight of the modified ethylene-vinyl acetate copolymer, preferably 5 to 10 parts by weight of the vinyl chloride resin to 0-1-HiroO. parts, preferably in the range of 0-10 parts by weight. If the amount of the vinyl chloride resin is less than the above-mentioned SZ amount, the adhesive performance will not be improved, while if it is more than 10 parts by weight, the adhesive strength of the modified ethylene-vinyl acetate copolymer will be significantly lowered, which is not preferable.

In addition, the method for blending each of the above components is modified ethylene-
Vinyl acetate copolymer and vinyl chloride resin are mixed using a Henschel mixer, a V-shaped blender, etc., and an extruder is used.
Examples include a method of pelletizing by using a double screw mixer, or a method of blending the modified ethylene-vinyl acetate copolymer and vinyl chloride resin in a Banbury mixer-1 two-wheel roll mixer, and pelletizing by using a sheet cutter. It will be done.

Next, in the present invention, as the base material to be laminated with the vinyl chloride resin, in addition to the vinyl chloride resin, polystyrene,
A wide range of materials can be selected, including synthetic resins such as polyethylene and polyamide, metals such as iron and aluminum, and cellulosic natural materials such as wood, cotton, and hemp.

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 resin composition are coextruded onto the base material in advance. A method of extrusion laminating the adhesive layer surface of the composite, in which a film or sheet of the adhesive resin composition extruded uniaxially is extrusion laminated onto a base material, and the adhesive layer surface L/C is extruded with a separate extruder. A method of extruding and laminating a film or sheet of vinyl chloride resin, which is a method of laminating a film or sheet of the above-mentioned adhesive resin composition extruded in advance on a base material and a vinyl chloride resin film or sheet, and heat-compression bonding with a press. A method of three-layer extrusion lamination of a film or sheet of the adhesive resin composition previously extruded onto a base material and a film or sheet of vinyl chloride resin, the adhesive resin composition extruded through an extruder. A method in which a film or sheet of the above adhesive resin composition is laminated to a base material or a plate or pipe made of vinyl chloride resin, and then bonded by thermocompression. Examples include a method of thermocompression bonding by interposing the material with the material. Furthermore, the vinyl chloride resin laminate of the present invention is a three-layer laminate consisting of a vinyl chloride resin layer (hereinafter abbreviated as A), an adhesive layer (hereinafter abbreviated as B), and a base material (hereinafter abbreviated as C). Not limited to the body, A / B / O / B /
A, C/B/A/B/ C%A/B/C/B/A/B/
A multilayer laminate such as C may also be used. The conditions for the above thermocompression bonding method are a temperature of 100-220°C, preferably 73°C.
0~. 270℃, pressure 0. / -j Okf / ca
, preferably within the range of /~30 hours/-1 hour, i~20 minutes.

〔Example〕

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

In addition, the melt index (hereinafter abbreviated as M-work) in the examples was measured in accordance with ASTM D-/231-j7T, and the shear adhesive strength was measured in accordance with JIs.
It was measured in accordance with KtrsO. Also,
Regarding the film bronking test, when a film wound on a roll is peeled off by hand, a film that peels off easily is O1, a film that has a little resistance is marked Δ, and a film that has a slight resistance is marked X. expressed.

Examples/-3 and Comparative Examples/ (1) Production of resin composition Ethylene-vinyl acetate copolymer [Evaflex P-2
1or (trademark) i manufactured by Mikata Petrochemical Industry Co., Ltd.; vinyl acetate content 2g weight %, M work: tt/10 minutes] 1001! and 0.0 of α, α′-bis(1-butylperoxy)-p-diinpropylbenzene dissolved in a small amount of a7ton.
2 parts by weight of maleic anhydride and 0.30 parts by weight of maleic anhydride are blended in a premix. This mixed pellet has an inner diameter of p
It was extruded into pellets at 220° C. using an extrusion mode of ozφ, L/D ==2t. When maleic anhydride was quantified using an infrared absorption spectrum for a part of this pellet, it was found that 0. / 3% by weight of maleic anhydride was graft polymerized. The maleic anhydride-modified ethylene-vinyl acetate copolymer pellet thus obtained and the vinyl chloride resin [dicavyl 5a-yoo (trademark; manufactured by Ryoichi Co., Ltd.; vinyl chloride homopolymer, degree of polymerization 700) 100 A mixture of Chokei Chokei tin stabilizer λ, parts of OX, 7.2 parts by weight of oxidation part and 2.0 parts by weight of plasticizer] were blended in a blender in the proportions shown in Table 1.

(2) Manufacture of laminate with downward T for small extrusion with diameter 301φ and L/D=24c
Charge the above blend into a molding machine equipped with a die, and
A T-die film with a thickness of O0l\;I was produced at a temperature of 00 to λλθ°C. Using this film as an adhesive, a galvanized steel plate (mm width, 2 cm thickness) and a hard vinyl chloride resin plate [NICA VINYL 5A-ROO (trademark: manufactured by Ryoichi Co., Ltd.; vinyl homopolymer, polymerization degree roo) 100 It was prepared by kneading 3.5 parts by weight of lead stabilizer, 015 parts by weight of metal soap, and 002 parts by weight of lubricant: 2Jrrrm width, 3wn thickness], and preheated at -00°C for 5 minutes. , 200° C. and a pressure of 20 k/, fe for 5 minutes to perform thermocompression bonding. The shear adhesive strength of the obtained laminate was measured using the method described above. The results are shown in Table 1.

Example 1If The same procedure as in Example 1 was carried out except that the modification rate and blending amount of the modified ethylene-vinyl acetate copolymer were changed as shown in Table 1. The results are shown in Table/.

Comparative example 2~! The same procedure as in Example 1 was carried out except that the ethylene-vinyl acetate copolymer was used without any modification and the amount of vinyl chloride resin was changed as shown in Table 1. The results are shown in Table 1.

Comparative Example 6 In Example/, low density polyethylene/(density O0 λ7?/-1M engineering x, orlt
The same procedure was performed except that the amount of modified ethylene-vinyl acetate copolymer was determined as shown in Table 7. The results are shown in Table 1.

〔Effect of the invention〕

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

Patent applicant: Mitsubishi Chemical Industries, Ltd. Representative: Patent Attorney Hase - 1 other person

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 immobilized with an ethylene-vinyl acetate copolymer having a vinyl acetate content of 5 to 70% by weight. 0 saturated carboxylic acids or their anhydrides
．． An adhesive resin composition comprising 95 to 20 parts by weight of a graft-polymerized modified ethylene-vinyl acetate copolymer of 01 to 1.0% by weight and 5 to 80 parts by weight of a vinyl chloride resin. A vinyl chloride resin laminate.