JPS61108550A - Polyolefin group resin composite body - 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 Field of Application] The present invention relates to a polyolefin resin composite. Specifically, the present invention relates to a composite of a polyolefin resin and a base material with improved adhesiveness using a specific adhesive resin composition.

[Conventional technology]

Polyolefin resin has chemical resistance, weather resistance, mechanical properties,
It has excellent properties such as formability, and has been widely used for lining υ steel plates, steel pipes, drum pipes, etc., coating electric wires, machinery and equipment, and protecting glass. Particularly, metal surfaces such as iron and aluminum are frequently coated, and various processing methods have been proposed.

However, polyolefins such as polyethylene, polypropylene, and polybutene have polar parts in their molecules.
For example, since it has no functional groups and is highly crystalline, it has the disadvantage of extremely poor adhesion to other base materials, such as synthetic resins, metals, or wood.

Various attempts have been made to improve this adhesiveness. For example, ■ A method of surface treatment such as solvent treatment, flame treatment, heated air treatment, or oxidation treatment on the adhesive surface of polyolefin; ■ A method of mechanically roughening or surface oxidation treatment of the metal surface to be bonded; ■ A method in which a modified polyolefin modified with an anhydride and an unmodified polyolefin are sequentially laminated on metal by extrusion coating (Tokuko Sho ≠ 2-
107! (2) A method in which a primer such as an epoxy resin adhesive is applied to the metal, and then a modified polyolefin modified with an unsaturated carboxylic acid or its anhydride and an unmodified polyolefin are sequentially laminated by extrusion lamination (
Tokukai Akira! T4-141; Za6co, etc.), ■ A mixture of polyethylene and ethylene-vinyl acetate copolymer is modified by graft polymerization of an unsaturated carboxylic acid or its anhydride, and then a mixture of metal and vinyl chloride resin is used. A method of interposing an adhesive between
(Refer to No. 1Io), ■ A polyolefin modified by graft polymerization of an unsaturated carboxylic acid or its anhydride, blended with an ethylene-vinyl acetate copolymer and an aliphatic petroleum resin, is used as a base material, such as vinyl chloride. A method of interposing it as an adhesive between the metal and the metal (see Japanese Patent Application Laid-Open No. 1983-1999/Ko-jlIA),
etc. have been proposed.

[Problem that the invention seeks to solve]

However, both of the above methods (1) and (2) involve complicated processing operations and cannot provide sufficient adhesive strength. In method (2) above, in order to obtain sufficient adhesion by coating the unmodified polyolefin on the modified polyolefin once solidified on the metal surface, it is necessary to extrude coat the unmodified polyolefin at a temperature of about SOO℃. undergoes high thermal history and deteriorates, resulting in a decline in physical properties such as weather resistance and stress crack resistance. In addition, in method (1) above, since a primer is used, a coating and drying process is required, and in order to obtain sufficient adhesion between each layer, it is necessary to melt and extrude the resin at about 300°C. The layer undergoes high thermal history and deteriorates,
Physical properties such as weather resistance and stress crack resistance deteriorate.

Furthermore, in methods (1) and (2) above, when the adhesive is in the form of a film, it has the advantage of no blocking property and good workability, but it has the problem that interlayer adhesion is somewhat insufficient. have

[Means for solving problems]

In view of the above-mentioned conventional technology, the present inventors have conducted intensive studies to improve the adhesion between polyolefin resin and base material, and as a result, they have graft-polymerized unsaturated carboxylic acid or its anhydride to polyolefin resin. To something that has degenerated,
Use a product containing a specific amount of vinyl chloride resin.
Therefore, the present invention was completed based on the discovery that when the composition is made into a film, there is no blocking property, the workability is good, and the adhesion to the substrate is significantly improved.

That is, the gist of the present invention is to provide a polyolefin resin composite composed of a polyolefin resin layer and a base material, in which the polyolefin resin layer contains an unsaturated carboxylic acid or its anhydride of 0.07 to 1.
．． 3 to 20 parts by weight of a vinyl chloride resin based on 5 to 20 parts by weight of a 0% by weight graft polymerized modified polyolefin resin.

There is a polyolefin resin composite characterized by being an adhesive polyolefin resin composition containing parts by weight of K.

The present invention will be explained in more detail below.

The modified polyolefin resin used in the preparation of the adhesive polyolefin resin composition in the present invention is one in which a monomer or polymer of an unsaturated carboxylic acid or anhydride thereof is chemically bonded to a polyolefin resin,
The bond amount is O1θl~i relative to the polyolefin resin in terms of monomer of unsaturated carboxylic acid or its anhydride.
, o% by weight. Binding amount is 0.0
If it is less than /wt%, the adhesive strength is low; /,0 wt%
If the amount is more than 1, the smelly gel-like substance will increase, which is not preferable. Within this range, preferably 0.0/~O,! weight%,
Most preferably 0.03 to θ. It is 3% by weight.

Polyolefin resins used as raw materials for the above modified polyolefin resin include high density polyethylene, low density polyethylene, medium density polyethylene, ethylene-propylene copolymer, ethylene-butene-l copolymer, polyfurohile/, propylene-butene-l Examples include copolymers, polybutene-/, and polyhiro-methylpentene-t'4. Preferred polyolefin resins vary somewhat depending on the base material used in the present invention; for example, when metal is used as the base material, the density is 0.910-0.93!
low-density polyethylene or elastomeric ethylene
Propylene copolymers are preferred.

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

The above-mentioned modified polyolefin resin can be produced by adding an unsaturated carboxylic acid or its anhydride to a polyolefin resin and 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 the melt mixing method is economically preferable. When using the melt mixing method, the polyolefin resin contains 0.
0/~/, 0% by weight of unsaturated carboxylic acid or its anhydride and o, i% by weight or less, preferably 0.00/-0,
0! % by weight of organic peroxide, /20℃～,30
Melt-kneading at 0°C is advantageous because it provides a modified polyolefin with high grafting efficiency, no fish eyes or gel-like substances, good color, and no odor.0 To further explain the above-mentioned melt-kneading method, If the amount of the unsaturated carboxylic acid or its anhydride to be blended is less than 0.0% by weight, the adhesive strength will be low, and if it is more than 0% by weight, the amount of smelly gel will increase, which is undesirable. Within the above range, 0.0/~o
, r% by weight are preferred, and 0.03-0.3% by weight is most preferred. When the amount of organic peroxide used is more than 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.

The lower limit is not particularly limited, but if it is less than 0.0 θ% by weight, the grafting efficiency decreases and problems such as a decrease in adhesive strength or the odor of unreacted monomers occur.

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, co,5-dimethylruco, 3-bis(
1-butylperoxy)hexane, t-7” tylperoxyhenzoate, n-butyl-≠, t-bis(t=nibutylperoxyvalerate, octanoylperoxide, co, S-dimethylruco, !-bis(benzoylperoxy) ) hexane, vinyltris(t-butylperoxy)silane, methylvinyl(cumylperoxy)silane, etc.

In the melt mixing method, polyolefin resin 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 organic solvent is mixed with an unsaturated carboxylic acid or an organic peroxide. A solution of carboxylic acid or its anhydride and, if necessary, an organic peroxide is added to polyolefin resin powder or pellets at 9XN, and further blended using a Henschel mixer 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 resin, an organic solvent is used as described above to mix it uniformly. It is preferable to measure Such organic solvents include acetone, methyl ethyl ketone, cyclohexanone, and the like. The blended polyolefin resin powder or pellets is put into a mixing machine whose interior is purged with nitrogen gas, such as a Banbury mixer, double screw mixer, extruder, etc., at a temperature of 20 to 300°C for a period of 0. 1-30
Melt and knead in minutes. If the crosstalk temperature is less than 720°C, the graft reaction described below will be difficult to occur, and if it exceeds 300°C, thermal deterioration of the polyolefin resin will become significant, which is not preferable.

Therefore, when a polyolefin resin is subjected to a graft reaction with an unsaturated carboxylic acid or its anhydride by the above-mentioned melt mixing method, the organic peroxide used as an initiator for the above-mentioned graft reaction is completely removed in the resulting modified polyolefin resin. Most of the unsaturated carboxylic acids or their anhydrides are chemically bonded to polio and reflex resins.

Next, the modified polyolefin resin is blended with the above-mentioned modified polyolefin resin.
A homopolymer of 0 to 300, a polymerization degree of 300 to 300, which is a copolymer of vinyl chloride and vinyl acetate. ? , 000 copolymers, copolymers obtained by grafting vinyl chloride onto ethylene-vinyl acetate copolymers, ethylene, propylene, acrylic esters, small amounts of heptamers copolymerizable with vinyl chloride such as vinylidene chloride, and chloride. Examples include copolymers with vinyl. The above-mentioned vinyl chloride resins also include semi-hard and soft vinyl chloride resins plasticized with phthalate esters, adipate esters, phosphate esters g4, ho'J ester plasticizers, and the like. In addition, these vinyl chloride resins are blended with pigments, heat stabilizers, light stabilizers, fillers, polymer modifiers, and other additives that are commonly added during the molding process of vinyl chloride resins. can do.

The blending ratio of each component above is modified polyolefin resin 95%
~aOji parts, preferably ? The amount of vinyl chloride resin is in the range of 0 parts by weight, preferably 70 to 60 parts by weight, based on θ to lIo parts by weight. If the amount of vinyl chloride resin is less than 5 parts by weight, the adhesion will not improve;
If the amount is more than 0 parts by weight, the adhesive strength will be significantly lowered, which is not preferable.

In addition, the method for blending each of the above components is to mix a modified polyolefin resin layer and a vinyl chloride resin using a Henschel mixer.
A method of mixing in a V-shaped blender, etc., and pelletizing by using an extruder, double screw mixer, etc., or a method of blending the modified polyolefin resin and vinyl chloride resin in a Banbury mixer (1 twin-roll mixer), and then using a sheet cutter. Examples include a method of making it into a pellet shape.

In the present invention, the base material to be bonded to the polyolefin resin layer includes vinyl chloride resin, polyethylene,
A wide range of materials can be selected, including synthetic resins such as polystyrene and polyamide, metals such as iron and aluminum, and cellulosic natural materials such as wood, cotton, and hemp.

As a method for manufacturing the composite consisting of the polyolefin resin layer and the base material of the present invention, the adhesive polyolefin resin composition is applied to the base material by applying an electrostatic coating method, a fluidized dipping method, a spray coating method, etc. Examples include a method of powder coating, a method of fusing the resin composition in the form of a film or sheet to a substrate, and a method of extruding the resin composition.

Particularly suitable is a method in which the resin composition is fused to a base material in the form of a film or sheet.

Examples of this method include a method of extrusion laminating a film or sheet extruded from an extruder onto a base material, and a method of laminating a film or sheet of the resin composition extruded in advance on a base material and thermocompression bonding with a press. The conditions for thermocompression bonding are usually a temperature of 100-. 230°C, preferably 130-210°C, pressure 0. /~50 Ryo'ff
l, preferably /~30 Kg/ct/i, time 0.
It is within the range of 1 to 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") in the examples is ASTM D-/λ3g-! It was measured in accordance with T, and the T peel strength was 61
141, Examples/- and Comparative Examples/High Pressure Process Low Density Polyethylene [Density: 0.9 J 09
/d sM Engineering: 3. ．． 21//0 minutes] 100 parts by weight and 0.0 of α,α'-bis(t-butylperoxy)-p-diisopropylbenzene dissolved in a small amount of a7ton.
23 parts by weight and 0.30 parts by weight of maleic anhydride are blended in a blender. This mixed pellet has an inner diameter of a
OXφ, L/D = , SSO℃ using 2g extruder
It was extruded into pellets. When maleic anhydride was quantified using an infrared absorption spectrum in a part of this pellet, it was found that 0.23% by weight of maleic anhydride had been graft-polymerized. The thus obtained maleic anhydride-modified low-density polyethylene
(trademark; manufactured by Ryoichi Co., Ltd.; vinyl chloride homopolymer, polymerization degree too > ioo parts by weight, tin stabilizer a, OX part,
(parts by weight of the detergent and 0 parts by weight of the softening agent λ) were blended in a blender in the proportions shown in Table 1.

This blend was formed into a sheet with a thickness of /IIm using a mixing roll, and three of these sheets were stacked on top of each other for 30 minutes at -00℃.
Laminate them into sheets with a thickness of J+m by hot-pressing them for 1 minute, stack them on galvanized steel sheets (-!wa width, thickness, 1+a+), preheat at 200℃ for 5 minutes, and then
A composite was formed by thermocompression bonding with Wa for 5 minutes.

The T-temperature peel strength of this composite was measured. [Effects of the Invention] According to the present invention, a polyolefin resin obtained by blending a specific amount of a vinyl chloride resin into a polyolefin resin modified by graft polymerization with an unsaturated carboxylic acid or its anhydride. The composition has excellent adhesion to the substrate. Therefore, the composite of the adhesive polyolefin resin composition of the present invention and a base material can be widely used in industrial materials, construction materials, packaging materials, and the like.

Claims (1)

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