JPS585384A - Adherent resin composition - Google Patents

Abstract

PURPOSE:A resin composition with excellent adhesion to a wide variety of materials such as an olefinic polymer, a halogen-contg. polymer, metal, glass and paper, comprising an epoxy group-contg. ethylene copolymer, a rubbery material and an ethylenic copolymer. CONSTITUTION:An epoxy group-contg. ethylene copolymer (A) of an epoxy group content about 0.01-20mol% and melt index about 0.1-300g/10min, a rubbery material (B) such as an ethylene/propylene copolymer rubber or styrene/ butadiene block copolymer rubber, and an ethylenic polymer (C) such as an ethylene/unsaturated ester copolymer of melt index about 0.1-300g/10min are compounded in a proportion of the total of the compounded A and C contg. about 20-100wt% component A to the component B of about 40-97 to about 60-30 in wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel & adhesive 11N@composition. More particularly, the present invention relates to a modified adhesive resin composition having high adhesiveness to olefin polymers, halogen-containing polymers, metals, glass, ceramics, wood paper, etc.

Generally, it is widely used for metal-metal laminates, olefin polymer-metal laminates, olefin polymer-halogen-containing polymer laminates, or halogen-containing polymerization needles. If only this is done, a satisfactory adhesive effect cannot be obtained, and a laminate that can be used practically cannot be obtained.

Therefore, already olefin polymers and metals.

As an adhesive resin for glass, ceramics, wood, and paper, epoxy group-containing ethylene copolymer (Tokukai Shoq!-J?
j,? 7), nine polyolefins graft-modified with unsaturated carboxylic acids or acid anhydrides (Special Publication No. 32-
/? λ31 Publication), Ethylene-unsaturated carboxylic acid copolymer (Special Publication No. 44.2-Bite), Part of the carboxylic acid group of the Ethylene-unsaturated carboxylic acid copolymer is cross-linked with metal ions to produce nine ionomer C special Kimiakijj-? /#?
A number of proposals have been made, including the following: However, with these adhesive resins, it is difficult to obtain adhesion properties that are sufficiently satisfactory for practical use, and in particular, they exhibit only low adhesion properties to halogen-containing polymers.

Therefore, when manufacturing the above-mentioned laminate, it is desired to develop an adhesive resin that has well-balanced and high adhesion performance to different types of base materials.

As a result of intensive studies aimed at improving one aspect of the adhesive resin with reverse electricity, the inventors of the present invention discovered that epoxy group-containing ethylene copolymer (containing ethylene copolymer) and rubber-like material (2) or further ethylene polymer (0) A composition consisting of.

We have now discovered that this material exhibits excellent adhesion to a variety of substrates.

That is, the present invention provides an adhesive resin composition characterized by comprising an epoxy group-containing ethylene copolymer (0) and a rubber-like material (0) or an ethylene polymer (0).

The characteristics of the adhesive resin composition according to the present invention are that compared to the case where the epoxy group-containing ethylene copolymer (4) is used alone, the adhesive resin composition contains an olefin polymer, a halogen-containing polymer, a metal,
glass, ceramic, wood.

When manufacturing a laminate using a base material selected from paper types, the point #c4 is that it has a high adhesive cost with no variation even under adhesive processing conditions at a relatively low temperature.

The present invention will be explained in detail below. 1. The epoxy group-containing ethylene copolymer (4) used in the present invention is:
An epoxy group-containing unsaturated hazy polymer 1 that can be copolymerized with ethylene by a known method such as high-pressure radical polymerization, S'tub polymerization, emulsion polymerization, etc. For example, α, β-unsaturated glycidyl ester, α, β - Obtained by copolymerizing with an unsaturated monomer such as unsaturated glycidyl ether. Examples of odorants of unsaturated monomers include glycidyl methacrylate, glycidyl 7'acrylate, allyl glycidyl ether, -monomethylallyl glycidyl ether, etc.
It will be done.

The amount of the epoxy group-containing unsaturated monomer in the copolymer is generally θ, θ/~-θ mol, preferably 0.7~
It is 70 moles.

Furthermore, the ethylene copolymer (4) can also be produced by graft-modifying polyethylene or a copolymer with ethylene with the aforementioned unsaturated monomer.

The epoxy group-containing ethylene copolymer used in the present invention is not a copolymer with the above-mentioned components.
That is, the @J acid component is an unsaturated ester monomer, such as methyl acrylate, ethyl acrylate, and methyl methacrylate.

Copolymers made by copolymerizing nine or more selected from unsaturated carboxylic acid esters such as butyl acrylate and unsaturated vinyl esters such as vinyl acetate and vinyl pro-sulfate can also be used.

The melt index of the epoxy group-containing ethylene copolymer (4) should generally be within a range that is easy to process.
, 1-4soσ1//ρ, preferably θ, t-j
ρf/10 minutes.

Next, the rubbery substances used in the present invention include ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, poly-norbutene copolymer rubber, ethylene-isobutyne, styrene-butadiene Random copolymer rubber, green styrene-butadiene block copolymer rubber, hydrogenated styrene-butadiene block copolymer rubber, natural rubber, attack polypropylene, and mixtures thereof. Among others.

Particularly preferred are ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene polymer rubber, and styrene-butadiene block copolymer rubber.

As the ethylene polymer (0) used in the present invention,
Examples include at least four polymers selected from polyethylene and ethylenically unsaturated ester copolymers. The method for producing these polymers is not limited to *, and a high-pressure radical polymerization method, solvent polymerization method, f111111 polymerization method, and other methods are applicable, and monoethylenically unsaturated ester copolymers are popular.

Ethylene-vinyl ester copolymers such as ethylene-vinyl acetate copolymers and ethylene-vinyl propionate copolymers, and ethylene-methyl methacrylate copolymers;
Ethylene-unsaturated carboxylic acid, such as ethylene-acrylic methyl copolymer, ethylene-1 ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer. Since acid ester copolymers can be mentioned, this ethylene polymer (
When 0) is a copolymer, its ethylene content is 50 mol or more, preferably 7a~! It is 9 moles. The melt index of the ethylene polymer backbone is θ, θ/~Jθθ
f//θ minutes, preferably θ, 03 to 101//θ minutes.

The proportion of each component in the adhesive resin composition of the present invention is not particularly limited, but the total amount of the epoxy group-containing ethylene copolymer (4) and the ethylene polymer (0) is U, O to 97% by weight, Good luck jθ~9ρ weight section.

The rubbery substance (S) has a weight of 3-ru θ weight q4. Preferably /θ
~50% by weight, and the ratio of the epoxy group-containing ethylene copolymer (4) in the total amount of the epoxy group-containing ethylene copolymer (4) and the ethylene polymer (0) is 1θ~/
θ0 weight - 1 is preferably 30 to /θ0 weight. If the weight of the rubbery substance is less than 3, no improvement in adhesion is observed.

Because the weight exceeds 6θ, not only is there no significant adhesion improvement effect, but the epoxy group-containing ethylene copolymer (4) or even the ethylene polymer (0) has poor processability. 1. Advantages such as mechanical strength are lost. The total amount of the epoxy group-containing ethylene copolymer (4) and the ethylene polymer (0) is less than 40% by weight, and the epoxy group-containing ethylene copolymer (4) and the ethylene polymer (
0) in the total amount of epoxy group-containing ethylene copolymer (4
) If the ratio is less than 10% by weight, the ethylene content will be too low and sufficient adhesion will not be obtained.

The adhesive resin composition of the present invention can be produced using a -screw extruder.

It can be produced using a method of melt-kneading using a twin-screw extruder, a Banbury mixer, two heated rolls, or the like. The components may be mixed simultaneously.

Alternatively, it may be carried out by scavenging. For example, epoxy group-containing ethylene copolymer (4) and a high concentration of rubbery substance)
Alternatively, an adhesive resin composition is prepared by adding the epoxy group-containing ethylene copolymer (4) and the ethylene polymer (0) to a master batch of the ethylene polymer (0) and a highly concentrated rubber-like substance. You can also get Temperature Fi/θθ~-jθ℃ required for melt-kneading, preferably /θθ~-
〇θ℃, and 30 seconds to 70 minutes is sufficient for one hour.

For the adhesive resin composition of the present invention, if necessary.

Antioxidants, stabilizers such as ultraviolet absorbers, and lubricants.

Inorganic filled Tsuru, surfactant Tsuru, antistatic agent, copper damage inhibitor, -
It is advisable to add and mix colored steel such as a foamed fuel with a fuel.

The base material to which the adhesive # of the present invention is adhered with the pus composition may be olefinic heavy ester phosphors such as polyethylene, ethylene-unbonded ester copolymer, polypropylene, ethylene-α-olefin copolymer, etc. vinyl chloride grafted ethylene-ms vinyl copolymer,
Halogen-containing polymers such as chlorinated polyolefins, chlorosulfuranated polyolefins, i-ethylene-tetrofluoroethylene copolymers, ethylene-hemofluoropropylene copolymers, polyesters, boria tjlF, ethylene-acetic acid vinyl copolymers Saponide, aluminum, iron, Nisokeru.

Metals such as zinc, steel, chrome, glass,! l#porcelain.

Paper, wood, etc. can be used. Among them, polyethylene, ethylene-unsaturated ester copolymer, ethylene-propylene copolymer, vinyl chloride-grafted vinylidene chloride resin N, vinyl chloride-grafted ethylene-vinyl acetate copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-hexane Fluoropropylene copolymers, metals such as aluminum, iron, and metals, olefin polymers and metals, olefin polymers and halogen-containing polymers, or halogen-containing polymers can be used. for example,
A method in which the adhesive resin composition of the present invention is interposed between base materials in the form of a film, sheet, powder, pellet, etc., and the adhesive resin composition is heated to a temperature higher than the welding temperature and bonded by pressure. , directly on one substrate surface.

The adhesive resin composition of the present invention is coated by extrusion coating method, dry lamination method, coextrusion molding method, or by heating after electric cloth with powder or solution, and the adhesive resin composition of the present invention is laminated with the other base material and heated to a temperature higher than the melting temperature. There are methods such as heating and crimping. i
*Temperature is generally 70 to -50°C.

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these examples.

In addition, in the examples, the adhesion test with various base materials was measured by the following method.

(1) Ml/Ml is <9 strength soft aluminum (M1) and soft aluminum (A1)
An adhesive resin composition film (/θθμ) was interposed in between, and the upper 2nd lever was heated to /6θ”CK using a heat seal tester.

After bonding for 3 seconds at 3kl/c+1', 710°
It was measured at an angle of C and a tensile rate of /θθ/min.

(, 2) 8-pvo/5-PVO peeling strength An adhesive IIt resin composition film (700 μm) was interposed between the soft vinyl chloride resin film ts-pva+ and the soft vinyl chloride resin film (B-PVOI, and heat-sealed. Using a tester, heat the 2nd upper i-bar to 71θ℃ and heat for 5 seconds.
After bonding under the conditions of /#/d, the angle of /lO#jJ, -
It was measured at a tensile rate of θθ & i/min.

(J) H-P VO/Al foil 9-strength soft aluminum (Mu1) and hard vinyl chloride resin sheet (H-
Adhesive resin composition film (/θθμ) between PVOI
After heating the upper seal bar to IBO''C using a heat seal tester and bonding at 2H/cd for 3 minutes, bend the aluminum at an angle of 1tro@ and apply 1.2θθ/min. It was determined by tensile speed.

(+1) M-F/HD P Iff barrier strength ethylene-tetrafluoroethylene copolymer film (Ill-41
'lCI Seki Km adhesive resin composition film (/θOμ)
After heating the upper seal bar to -7θ℃ using a heat seal tester and adhering it for 3 seconds under the conditions of /#/-, the high-density polyethylene film was bent at an angle of igo' and pulled at /ρθB/min. Measured by speed.

(a) 5-pVo/mu15! A laminated tape was prepared by laminating a soft aluminum (mul) K laminated with a paper-strength adhesive resin composition film (700 μm) and heat-treating it in an oven at 70°C for 7 minutes after death. Layer the vinyl resin film (8-PVOI) and the above laminated tape, heat the upper seal bar to /λ0~itθ゛C using a heat seal tester, and heat for 5 seconds.
After adhering under the conditions of /#/ζ, fold the soft vinyl chloride resin film at an angle of /10" and bend 10θam/
It was measured at a tensile speed of 10 min.

Moreover, the base materials used in the above adhesiveness test are as follows.

0 Soft aluminum J engineering 5-HtIθθθ, mu/θSθR-0, (/jθμ
Tape) 0 Soft vinyl chloride resin manufactured by Kokoku Kagaku (manufactured by Kokoku Kagaku Co., Ltd.) % IPWNAJfoJ, (de θμ film) 0 Hard vinyl chloride resin cylinder plastic (manufactured by 1.mu 7θθ, gray.

l, (,-Parrot Sheet 10 Ethylene and Tetrafluoroethylene Copolymer Layered Glass (manufactured by 1.Afflex [F]-L', Film, Product Number #3
0M, (jθμ film, no surface anchor coating treatment 1 0 High density polyethylene Sumitomo Chemical (manufactured by Sumitomo Chemical Co., Ltd. 1. Sumirikisen 8-do 342/T-die film (7008m Examples/~q and Comparative Examples/, - Epoxy group As a containing ethylene copolymer.

Melt index f//θ min, glycidyl methacrylate J, - mol qb and vinyl acetate/, 1 mol ethylene copolymer (Mo-7) as a rubbery substance at /-0°C. Viscosity If7θ2 Ethylene content 4
Ethylene-propylene copolymer rubber (B
-/I was kneaded with a hot roll at a temperature of /6θ°C for 5 minutes. A heat press film (7) of the obtained adhesive resin composition
Table 47 shows the results of adhesion tests with various substrates using 008m.

Ethylene-propylene copolymer rubber (
The results when 0 and 70 weight percentages of B-/l were added are shown in Table 47 as comparative examples. Example j-2 and Comparative Example 3, melt index j, / f / / θ as geepoxy group-containing ethylene copolymer. Ethylene copolymer (A-, 2) containing glycidyl methacrylate mg molti and vinyl acetate t molti It was carried out in the same manner as in Examples/--d, except that the combination (A-J) was used. The results are shown in Table 1.

Used as a rubbery substance, tyrene-propylene copolymer (B
-/) is shown in Table 1 as a comparative example.

JP-A-58-5384 ttj) Examples/θ~/- As epoxy group-containing ethylene copolymers, Examples/~y
Ethylene copolymer (mu-/) ffθ weight% used for the rubber-like substance, Mooney viscosity qj at 100°C, ethylene content guar weight% ethylene-propylene copolymer rubber (B-, 2), Mooney viscosity 6θ at /θθ℃
, ethylene content 30% by weight, iodine value // ethylene-propylene-ethylidene norbornene copolymer rubber (B-J) or styrene-gx amount H, molecular weight 7!
, 000 styrene-butadiene block copolymer rubber (B-tt)-0% by weight was kneaded for S minutes at a temperature of 760° C. using a hot roll. Table 3 shows the results of adhesion tests with various substrates using the hot press film (/θθμ) of the obtained adhesive resin composition. In addition, rubber-like substance (B)
In the case of not adding ethylene-propylene copolymer rubber (B-, 2), in Comparative Examples J and 6 Examples/θ, crystalline large melt index, l f / / 0 min (ko3θ
°C), a propylene-ethylene block copolymer (D-/) with an ethylene content of 73% by weight in the resin
Ihayl & Toindex 7f//θ min (230℃)
, propylene with an ethylene content of 3% by weight in the resin.
Ethylene random co-monomerization<D-2) The same procedure was carried out except that it was edible. The results are shown in Example 3/j~/6 and Comparative Examples 7 and l. Melt index λ゛θf/10 as a system copolymer
ethylene-vinyl acetate copolymer (0-/) with a vinyl acetate content of -0 weight% or an ethylene-vinyl acetate copolymer (C-/) with a melt index of -01710 minutes and a vinyl acetate content of 30% by weight. C) was kneaded for S minutes at a temperature of 76θ°C using a hot roll. Adhesion tests with various substrates were conducted using a heat-press film (10θμ) of the obtained adhesive resin composition. The results are shown in Table 1. The results when no rubbery substance (B-/) was added were also the same as Comparative Example 7,
It is shown in Table DA as t.

Example 77-co/and Comparative Examples 9-/3-engineered poxy group-containing ethylene copolymer with a melt index of 79//
An ethylene copolymer containing θ, 2 mol of glycidyl methacrylate and 61 mol of vinyl acetate.
7), melt index t/10 min, ethylene copolymer (MU-4I) containing 2.6 mol of glycidyl methacrylate and 3.9 mol of vinyl acetate or melt index/4f//θ min, glycidyl methacrylate fJ mol - containing ethylene copolymer (mu-3
) and Mooney viscosity 7θ at 7.2θ℃ as a rubbery substance.
, an ethylene-propylene copolymer rubber (B-/) with an ethylene content of 69% by weight, or even an ethylene-based polymer with a melt index of −θP / / 0 min,
Ethylene-vinyl acetate copolymer (0-2) having a vinyl acetate content of 30% by weight was heated at 76θ in a Banbury mixer.
The mixture was kneaded for 6 minutes at a temperature of .degree. An adhesion test was conducted using a T-die film (/θOμ) of the obtained adhesive resin composition.

The results are shown in Table 5.

The results when epoxy group-containing ethylene copolymers (A-/, Mu-3, Mu-4t) and ethylene polymers (0-/) were used alone were compared with Examples 2.2 to 2j of S. Example/Glue/As an ethylene copolymer containing 6 epoxy groups, melt index JP//θmin, glycidylme,
Ethylene copolymer (A-3) containing talyl acid copolymer, 3 molti, vinyl acetate 7.7 molti, and rubbery copolymer, Mooney viscosity 7θ at 720°C, ethylene content 69
Ethylene-propylene copolymer rubber (B-
/) Alternatively, the ethylene polymer (0) was further kneaded in a Banbury mixer at a temperature of /lθ°C for 7 minutes. Table 6 shows the results of an adhesion test using the T-die film (/θθμ) of the obtained adhesive resin composition. 6th Procedural Amendment (Method) using the results when no rubbery substance (B-/) is added as a comparative example 1975/- Month, Japan Patent Office Commissioner Shima 1) Haruki Tono1, Display of the case 1962 Year Patent Application No. 10 da J/1 No. 2 Name of the invention Adhesive resin composition 3 Relationship to the case of the person making the amendment Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative Sat
Takeshi 4, agent dated 1925/1977, 6, subject to amendment

Claims (2)

[Claims] (1) An adhesive resin composition comprising an epoxy group-containing ethylene copolymer (4) and a rubber-like material (elongated rubber) or an ethylene polymer (0). (2) The total amount of the epoxy group-containing ethylene copolymer (4) and the ethylene polymer (0) is qO~97 weight, the rubber-like material is 3~10 weight, and the epoxy group-containing The ratio of the epoxy group-containing ethylene copolymer (in the total amount of the ethylene copolymer (4) and the ethylene polymer (0)) is 10 to /θσ, so the scope of claims (/) The adhesive resin composition described in . (j Ethylene copolymer (4) has epoxy groups θ, θl
--The adhesive** fat composition according to claim 1, which contains tatami roux. (to) Claims jlE (1 ) The adhesive resin composition described in item 1. [5] Adhesive 11N@composition according to claim 1, wherein the ethylene polymer (0) is at least /II polymer selected from polyethylene and ethylene-unsaturated ester copolymers. .