JPS6064845A - Denatured oelfin group polymer and laminate thereof - 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 The present invention relates to a modified olefin polymer with excellent adhesive properties and a laminate thereof.

Polyolefin resins are generally used for injection molded products, films, etc. because of their high strength, good heat resistance, and low cost.
Used in a wide range of applications such as blow bottles.

However, since this polyolefin resin does not have polar groups in its molecules, it has excellent chemical resistance, but it has the disadvantage of extremely poor adhesion to exotic materials such as synthetic resins, metals, and wood. .

Therefore, various attempts have been made to provide adhesive at to polyolefin resins. For example, there are methods of subjecting the adhesive surface of polyolefin resin to surface treatments such as flame treatment, corona discharge treatment, and solvent treatment, but all of these methods require complicated treatment operations and are difficult to achieve sufficient adhesiveness. cannot be granted.

In addition, various attempts have been made to impart adhesive properties to polyolefin resins by adding unsaturated carboxylic acids, etc. to polyolefin resins in the presence of organic peroxides, etc., and introducing functional groups. Although these results have been achieved, the above-mentioned conventional methods cannot satisfy the requirements under severe usage conditions and molding conditions. The first object of the present invention is to provide a modified olefin polymer having strong adhesive strength, and the second object is to provide a laminate using the modified olefin polymer.

As a result of intensive research by the present inventors to achieve the above object,
Modified olefin obtained by heating and mixing a reaction product of rubber with an unsaturated carboxylic acid or its derivative of 0.05 to 5 weight (based on rubber) and an olefin polymer in the presence of an organic peroxide. The first invention was achieved by discovering that the polymer has extremely strong adhesive strength with various base materials.

The rubber of the present invention includes polyimbutylene, butyl rubber, ethylene-propylene rubber, ethylene-propylene rubber,
Diene rubber, styrene-butadiene rubber, polybutadiene rubber, polypropylene rubber, urethane rubber, ethylene-
Examples include solid rubber such as vinyl acetate copolymer rubber and natural rubber, synthetic rubber such as liquid rubber such as liquid polybutadiene, and natural rubber. These may be used alone or in combination, but solid rubbers such as polyisobutylene and butyl rubber are particularly preferred because they have excellent compatibility with olefin polymers.

As an unsaturated carboxylic acid! Examples include monobasic acids and dibasic acids such as lylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, and the like.

Examples of derivatives of unsaturated carboxylic acids include metal salts, amides, imides, and ester anhydrides of the unsaturated carboxylic acids, among which maleic anhydride is most preferred.

The olefin polymers of the present invention include olefin homopolymers such as polyethylene, polypropylene, polybutene-1, poly-4-methyl-pentene, ethylene, propylene, butene-1,4-methyl-pentene-1, and hexene. -1, octene-1, copolymers of ethylene and vinyl esters, unsaturated carboxylic acids, unsaturated carboxylic acid esters, etc. are used, but particularly preferred are polyethylene, polypropylene, and ethylene-butene. Copolymers of ethylene and other α-olefins such as -1 copolymers are used.

The reaction product of rubber and an unsaturated carboxylic acid or a derivative thereof (hereinafter simply referred to as unsaturated carboxylic acid) has an amount of unsaturated carboxylic acid of 0.05 to 5% by weight, preferably 0.
．． 1 to 3% by weight is added and heated, preferably in the presence of an organic peroxide, to form a reaction. The above reaction can be carried out in an extruder or in a Banbury mixer. The reaction can be carried out by melt-mixing in a machine without a solvent, or by heating and mixing in a solvent such as aromatic hydrocarbons such as benzene, xylene, and toluene, and aliphatic hydrocarbons such as hexane, heptane, and octane. The reaction method is not particularly limited, but it is preferable to carry out the reaction in an extruder for reasons such as ease of operation, excellent economic efficiency, and continuity with subsequent steps.

When the amount of unsaturated carboxylic acid exceeds 5% by weight, decomposition and crosslinking reactions may occur in addition to addition reactions, and when it is less than 0.05% by weight, the purpose of the present invention is to improve the adhesiveness. cannot be achieved.

The modified olefin polymer of the present invention is obtained by further heating and mixing the reaction product of the rubber and unsaturated carboxylic acid with the olefin polymer in the presence of an organic peroxide. The mixing ratio of the reaction product and the olefin polymer is arbitrary, but the weight ratio is preferably 1:99 to 50:50. More preferably, the ratio is 10:90 to 45:55.

If the ratio of the reaction product is less than 1, the adhesion will not be improved, while if it exceeds 50, the modified olefin polymer may have problems in flexibility, processability, etc.

Contains 181-crystalline vinegar, liquid vinegar, penzoyl chloride, lauryl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-
Butyl hydroperoxide, α,α'-bis(t-butylperoxydiisoglobil)benzene, di-t-butylperoxide, 2,5-di(t-butylperoxy)hexyne, etc. are preferably used. It is used in an amount of 0.005 to 2.0 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the reaction product of the rubber and unsaturated carboxylic acid and the olefin polymer. If the amount of organic peroxide added is less than 0.005 parts by weight, the modification effect will not be substantially exhibited, and even if it is added in excess of 2 parts by weight, it will be difficult to obtain any further effect, and it will be excessive. This may cause decomposition or crosslinking reactions.

In addition, similar to the reaction between rubber and unsaturated carboxylic acid, the above reaction can be carried out in a solvent-free environment such as in an extruder or a mixer such as a Banbury mixer, or in an aromatic environment such as be/zene, toluene, or xylene. Although heating reactions can be carried out in a solvent such as group hydrocarbons, it is preferable to use an extruder to react the rubber with the unsaturated carboxylic acid in the first stage and the reaction product with the olefin polymer in the second stage. It is desirable to carry out the reaction continuously as a series of steps.

The reaction temperatures in the first and second stages are selected as appropriate, taking into account the usual temperature conditions, such as deterioration of rubber, decomposition of unsaturated carboxylic acids, decomposition temperature of organic peroxide, etc., but generally 150'C Reaction temperatures in the range ˜300° C. are used.

The modified olefin polymer of the present invention may be further mixed with an unmodified olefin polymer, unmodified rubber, or the like, and then used.

As mentioned above, the modified olefin polymer of the present invention has good adhesion to various base materials, and can be laminated with each base material and formed into a film, sheet, tube, hollow container, etc., and used for food packaging. Effectively used in the fields of materials, medicine, cosmetics, etc.

It is also effectively used as a compatible dispersant for thermoplastic resins and inorganic/organic fillers such as glass fiber, carbon black, wood flour, and pigments.

The second aspect of the present invention provides a laminate of the modified olefin polymer and various base materials, and specifically, the base material (
4), a reaction product of rubber and 0.05 to 5% by weight (based on the rubber) of an unsaturated carboxylic acid or its derivative, and an olefinic polymer, obtained by heating and mixing in the presence of an organic peroxide. The present invention provides a laminate comprising at least two modified olefin polymer layers or an olefin polymer layer containing the modified olefin polymer.

As the base material (2), saponified ethylene-vinyl acetate copolymer (EVM), polyethylene terephthalate (
PET), polyester polymers such as polybutylene terephthalate (PBT), nylon-6, -66, -12
, -11, etc., polyamide polymers (PA), polyvinylidene chloride polymers (FVDCl), polycarbonate polymers, acrylonitrile polymers, polyvinyl alcohol polymers, fluorine polymers such as polytetrafluoroethylene, etc. Synthetic resins, metals such as aluminum, iron, zinc, and copper, wood such as veneer and plywood, glass and ceramics, concrete, plaster, asbestos, FRP, woven fabrics, and paper. These include synthetic resins used in food packaging materials, etc.
Pgl', PA, etc. are preferred.

The laminate of the present invention is based on a laminate including at least two layers of the above-mentioned base material layer (4)/modified olefin polymer layer (2),
A/B/A.

B/A/B, A/E/C (here, C is an unmodified polyolefin layer), A/B/C/B, B/A/B/C,
It includes a laminate of multiple layers, such as 3 layers, 4 layers, or 5 layers, such as A/B/A/B or C/B/A/B/C.

The form of the laminate of the present invention is film-like, plate-like, tube-like, foil-like,
It may be in the form of a woven fabric, a bottle, a container, an injection molded product, etc., and is not particularly limited.

The modified olefin polymer layer or the olefin polymer layer containing the modified olefin polymer is a reaction product of rubber and 0.05 to 5% by weight (based on the rubber) of an unsaturated carboxylic acid or a derivative thereof. This is a modified olefin polymer layer obtained by heating and mixing a product and an olefin polymer in the presence of an organic peroxide, and the mixing ratio of the reaction product and the olefin polymer is arbitrary. Preferably 1:9
9-50:50 range, more preferably 10:9
A range of 0 to 45:55 is preferable.

When the amount of the reaction product between the rubber and the unsaturated carboxylic acid or its derivative is less than 1, the adhesion to various substrates (4) is not improved, while when it exceeds 50, the main component of layer B is rubber. If the main component is a reaction product of 1 and an unsaturated carboxylic acid, the layer 1 may be too flexible, which may cause problems in processability, etc.

On the other hand, the olefin polymer layer containing the modified olefin polymer is one in which any amount of the same or different olefin polymer is added to the modified olefin polymer, but preferably It is preferable to mix the modified olefin polymer and the olefin polymer at a mixing ratio (weight ratio) of 100:0 to 2:98. In addition to these components, unmodified rubber and the like may be added as appropriate.

Methods for producing the laminate of the present invention include co-extrusion methods such as the inflation method, which uses a multilayer die and joins resins melted in an extruder at the die tip to form a laminate structure, and the multilayer T-die method. Conventional molding methods such as multilayer blow molding and injection molding can be applied, and are not particularly limited.

The laminate of the present invention exhibits remarkable effects particularly when the base material is a synthetic resin. It has superior adhesive strength compared to conventional layers made of olefin polymers graft-modified with unsaturated carboxylic acids, or layers made of mixtures of graft-modified products and olefin polymers. It is characterized by its excellent ability to maintain adhesive strength during deformation such as stretching. This property cannot be achieved by reacting an olefin polymer mixed with rubber and unsaturated carboxylic acids, or by mixing rubber with an olefin polymer modified with unsaturated carboxylic acids.

Due to these characteristics of the material constituting the layer (1) of the present invention,
It can also be suitably used for multilayer stretch blow molding, which is difficult to achieve with conventional laminated structures.

Of course, the laminate of the present invention has excellent heat sealability and can be used as an excellent packaging material for foods, drugs, cosmetics, etc. by using materials with low gas permeability such as EVAL, PET, and FVDCI as the base material (2). Effectively used in many fields.

The sound effects of the present invention will be explained in more detail below using Examples and Comparative Examples.

Example 1゜Polyinbutylene (viscosity average molecular weight 140,000, trade name: Vistanex +140, manufactured by Esso Chemical Co., Ltd.) 10
0.25 parts by weight of maleic anhydride and organic peroxide (2,5-dimethyl-2,5-di(tertiary)
0.02 part by weight of butylperoxy)hexyne-3) was added and kneaded in a Banbury mixer at 200°C for 15 minutes to obtain a reaction product. 20 parts by weight of the reaction product and linear low density polyethylene (ethylene-butene-1 copolymer,
Density Q, 928, melt index 2/1()0)
80]i part and 0.025 part by weight of the same organic peroxide as above were added and mixed by heating at 230°C in an extruder to obtain a pellet of modified olefin polymer.

A saponified ethylene-vinyl acetate copolymer (product name: EVAL ED-F, C stock) is prepared using a blown film molding machine with the modified olefin polymer as an intermediate layer.
(manufactured by Kuraray Co., Ltd.) (hereinafter abbreviated as EVAL) and high-density polyethylene (density 0.948, melt index 0.03)
F/10 minutes, product name: Nisseki Stafrene E903, manufactured by Nippon Petrochemical Co., Ltd.) was supplied to the multilayer die, and the die temperature was 2.
They were combined and laminated at 20° C. in front of the die lip to form a three-layer blown film. The thickness of the laminated film at that time was 30P of EVAL layer/70μ of modified olefin polymer layer/500μ of high-density polyethylene layer.

A test piece with a width of 25 wI was prepared from the above laminated film, and the adhesive strength was defined as the delamination strength when it was pulled using a Tensilon tensile tester at an angle of 180 degrees and a take-up speed of 50 s/min. It is shown in Table 1. Table 1 also shows the peel strength (adhesive strength) measured after stretching the test piece 4.5 times as a severe air test method.

Examples 2 to 3゜In place of the polyisobutylene in Example 1, ethylene-propylene rubber [trade name: EP-02P, Japan Synthetic Rubber Co., Ltd. # (Example 2) and polybutadiene rubber (trade name: BR) were used.
-02, manufactured by Japan Synthetic Rubber Co., Ltd.) (Example 3), a laminated film was obtained in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Examples 4-7. Comparative Examples 1 and 2゜The entire laminated film was obtained and evaluated in the same manner as in Example 1, except that the amount of maleic anhydride, the type of olefin polymer, and the amount of mixture with the olefin polymer were changed. The results are shown in Table 1.

Comparative Example 3 The polyisobutylene of Example 1 was replaced with the linear low-density polyethylene of Example 1. The results are shown in Table 1.

Examples 8 to 11゜The modified olefin polymer prepared in Example 1 and EVAL as a base material, aluminum plate (hereinafter abbreviated as At), nylon-6 (trade name: Toshi Amilan 1046) C below F
A), polyethylene terephthalate (product name:
kodar PgI'G 6763, manufactured by Eastman Chemical Products, -0) (hereinafter abbreviated as PET)
The modified olefin polymer was superimposed on a substrate preheated to 220°C using a 220°C oven, and then pressurized at 100 Ky/crIt for 5 minutes in an oven at 220°C. After cooling slowly, a test piece (25 width) was prepared. was created and machined into a tensile tester at a tensile speed of 50
Table 2 shows the value of 180° peeling in m/Ms as the adhesive strength.

Comparative Example 4-7° Testing was carried out in the same manner as in Examples 8-11 except that the resin of Comparative Example 2 was used, and the results are shown in Table 2.

Examples 12-13. and Comparative Example 8-9° base material was polyvinylidene chloride resin (manufactured by Guigen Kagaku Co., Ltd.) (hereinafter referred to as WOC).
l) and polyvinyl chloride resin (trade name: Nearon Compound BL, 2.IV-11VI-P, manufactured by Toagosei Co., Ltd.) (hereinafter abbreviated as PVC), and the test piece molding temperature e was 160°C. The results are shown in Table 2. In addition, as a comparative example, Comparative Example 2
The same procedure as in Examples 12 to 13 was carried out except that the following resin was used, and the results are shown in Table 2.

Examples 14-18゜A blown film was produced in the same manner as in Example 1 using various blended compositions of the modified olefin polymer prepared in Example 1 and the linear low density polyethylene used in Example 1. The adhesive strength was measured and the results are shown in Table 3.

Claims (9)

[Claims] (1) A reaction product of rubber and an unsaturated carboxylic acid or its derivative in an amount of 0.05% to 5% by weight (based on the rubber) and an olefinic polymer are heated and mixed in the presence of an organic peroxide. A modified olefin polymer obtained by (2) Mixing ratio of the reaction product of the rubber with the unsaturated carboxylic acid or its derivative and the olefin polymer (
The modified olefin polymer according to claim 1, wherein the weight ratio is 1=99 to 50:50. (3) The rubber is a solid rubber selected from the group consisting of polyisobutylene, butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, polybutadiene rubber, and styrene-butadiene rubber. The modified olefin polymer according to item 2. (4) The olefin polymer is polyethylene, polypropylene, polybutene-1, poly-4-methyl-pentene-1, and ethylene, propylene, butene-1,4
- selected from the group consisting of mutual copolymers of two or more of methyl-pentene-1, hexene-1, or octene-1, and copolymers of ethylene with vinyl esters, unsaturated carboxylic acids, or unsaturated carboxylic acid esters. The modified olefin polymer according to claim 1 or 2, which is a modified olefin polymer according to claim 1 or 2. (5) The modified olefin-based heavy body according to claim 1 or 2, wherein the unsaturated carboxylic acid or its derivative is maleic anhydride. (6) The amount of the organic peroxide is o. The modified olefin polymer according to any one of the ranges 4 to 5. (7) The base material layer (to), the reaction product of the rubber and the unsaturated carboxylic acid or its derivative (0.05 to 5% C to rubber), and the olefinic polymer are combined into an organic peroxide. A laminate comprising at least two layers of a modified olefin polymer layer obtained by heating and mixing in the presence of a modified olefin polymer or an olefin polymer layer containing the modified olefin polymer. (8) The mixing ratio (weight ratio) of the reaction product of the rubber of the modified olefin polymer and the unsaturated carboxylic acid and the olefin polymer is 1:99 to 50:50. The laminate according to item 7. (9) The laminate according to claim 7, wherein the mixing ratio (weight ratio) of the modified olefin polymer and the olefin polymer is 100:0 to 2:98. αQ The base material (to) is saponified ethylene-vinyl acetate copolymer, polyester polymer, polyamide polymer, polyvinyl chloride polymer, polyvinylidene chloride polymer, polycarbonate polymer, acrylonitrile The laminate according to any one of claims 7 to 9, which is a synthetic resin selected from the group consisting of polyvinyl alcohol-based polymers, polyvinyl alcohol-based polymers, and fluorine-based polymers. at+ The laminate according to any one of claims 7 to 9, wherein the base material (4) is selected from the group consisting of metal, wood, glass, ceramic, concrete, plaster, and FRP board. body.