JPH066650B2 - Ethylene-ethyl acrylate copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is a modified ethylene-ethyl acrylate copolymer composition, which has excellent mechanical properties and improved adhesiveness, Molded products, adhesives and adhesive sheets,
It is preferably used as a solution or the like.

[Conventional technology and its problems]

Ethylene-ethyl acrylate copolymer (hereinafter referred to as "EE
A) is a thermoplastic resin excellent in flexibility, rubber elasticity, and low temperature characteristics, and blended with wax.
It is widely used as a base resin for hot melt adhesives and molded products. Hot melt adhesives prepared by mixing EEA with adhesives such as rosins, turpentine oil, polyisobutylene, patifin and waxes do not always have sufficient adhesive strength, and also have a weak adhesive strength at high temperatures. .

The present invention has found an EEA composition having high strength and excellent adhesive strength.

[Means for solving problems]

The present invention has variously studied the utilization of the unique property of the cyanato group of the compound having a cyanato group (—O—C≡N). As a result, the mechanical properties of EEA can be obtained by adding the compound having a cyanato group to EEA. It was completed by finding that the adhesiveness can be greatly improved.

That is, the present invention has an ethyl acrylate content of 8 to
Modified by mixing 0.1 to 20% by weight of a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato group in the molecule with 36% by weight of ethylene-ethyl acrylate copolymer. And a cross-linking catalyst of the ethylene-ethyl acrylate copolymer or a monofunctional or polyfunctional maleimide compound as an ethylene-ethyl acrylate copolymer composition. It is a modified ethylene-ethyl acrylate copolymer obtained by mixing together 0.1 to 5% by weight based on the acrylate copolymer.

The present invention will be described below.

The EEA of the present invention has an ethyl acrylate content of 8 to 36.
It is an ethylene-ethyl acrylate copolymer which is a weight%. Further, as a mixture of EEA and a polyolefin such as polyethylene and polypropylene, a mixture of EEA and EVA, EPR, etc., a mixture of EEA and rosin, paraffin, rosin ester, neoprene, nitrile rubber, etc., a wax, and carbonic acid. Inorganic fillers such as calcium, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, talc, clay, mica, wollastonite, copper, iron, cobalt, nickel, chromium, manganese, aluminum, manganese or alloys of these metals, etc. Powder, fiber, flakes and other metals, copper oxide, iron oxide, antimony trioxide, lead oxide and other powders, fibers, flakes and other metal oxides, copper phthalocyanine (= phthalocyanine blue) and other organometallic compounds, yellow lead , Mineral violet, carbon black, red iron oxide Ultramarine blue, cobalt blue, cobalt violet, titanium white and other pigments, other plasticizers, flame retardants, UV absorbers, stabilizers, etc. as a composition added, as a composition further added with a thermosetting resin such as an epoxy resin Also has an effect, and these are also included.

Suitable monofunctional or polyfunctional cyanate compounds having one or more cyanato group in the molecule of the present invention, which are added to the EEA composition comprising the above components as a modifier, are represented by the following general formula ( 1) R (OCN) _m (1) (where m is an integer of 1 or more and usually 5 or less, R is an aromatic organic group, and the cyanato group is an aromatic ring of the organic group. A compound bound to. Specific examples include monocyanatobenzene, alkylcyanatobenzene such as P-tert-butylcyanatobenzene, monocyanatonaphthalene, 1,3- or 1,4-dicyanatobenzene, 1,3,5- Tricyanatobenzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene 1,3,6-tricyanatonaphthalene, 4,4 '
-Dicyanatobiphenyl, bis (4-dicyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (3,5-dichloro-4-cyanatophenyl)
Propane, 2,2-bis (3,5-dibromo-4-cyanatophenyl) propane, bis (4-cyanatophenyl) ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) Sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and cyanate ester (USP-4026913) obtained by the reaction of a terminal-OH group-containing polycarbonate oligomer with a cyanogen halide, Examples thereof include cyanate ester (USP-4022755, US-3448079) obtained by the reaction of novolac and cyanogen halide.
In addition to these, Japanese Examined Sho 41-1928, 43-18468, 44-47
91, ibid. 45-11712, ibid. 46-41112, ibid. 47-26853, JP-A-51-6
3149, USP-3553244, 3755402, 3740348, 359590
The cyanate esters described in 0, 364410 and 4116946 can also be used.

Further, the above-mentioned polyfunctional cyanate ester as it is, or in the presence of mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, phosphoric acid esters such as tributylphosphine, organometallic salts or the like, or absent. It can be used as a prepolymer having a cyanato group in the molecule obtained by polymerization below, and is a premixture or prereactant (= prepolymer with a monofunctional or polyfunctional maleimide compound, which is a modifying aid described later). ) Can be used as
Further, it can be used as a prepolymer with an amine which is a raw material of a maleimide compound described later.

EEA of the cyanate compound of the present invention described above
The amount to be blended with is not particularly limited, but it is 0 from the point of effect.
It is appropriately selected from the range of 1 to 20% by weight. If the added amount is less than 0.1%, the effect of improving the properties is insufficient, and if it is used in excess of 20% by weight, it shows a remarkable effect in preventing deterioration of stability and the like, but decreases adhesive strength and elongation of EEA. Is not preferable because other properties such as deterioration of Further, as described above, since a cyanato group is necessary for the effect of the present invention, additives that react with this functional group-for example, -OH,
-COOH, -NH _2, -COOM, -SH, etc. (M = metal atom) - when it is necessary to add a compound having, including adding by previously mixing the cyanate ester compound and these compounds Should be avoided.

The cross-linking catalyst for cross-linking EEA used as the reforming auxiliary agent of the present invention includes, for example, known organic peroxides such as dicumyl peroxide and sulfur, and these known catalysts and their promoters such as acetylacetone iron and Examples thereof include a combination with a known metal chelate such as zinc octylate or an organic metal salt, and the amount used is usually 0.1 to 5% by weight based on the EEA composition.

Further, based on the EEA composition of the present invention, 0.1 to 5% by weight of a monofunctional or polyfunctional maleimide compound can also be preferably used alone or in combination with the above-mentioned crosslinking catalyst as a modifying aid. .

Preferred compounds as such monofunctional or polyfunctional maleimide compounds are represented by the following general formula (2) and general formula (2): (In the formula, R ₁ is a monovalent or more and usually pentavalent or less aromatic or alicyclic organic group, X ¹ and X ² are hydrogen, halogen, or an alkyl group, and n is an integer of 1 to 5. The maleimides represented by the above formula are, as maleic anhydrides, reacted with polyamines containing 1 to 5 amino groups to prepare maleamic acid and then dehydrate and cyclize the maleamic acid. It can be produced by a known method. The polyamines used are preferably aromatic polyamines from the viewpoint of heat resistance of the final resin, but when flexibility or flexibility of the resin is desired, alicyclic amines may be used alone or in combination. Good. Further, the polyamines are preferably primary amines from the viewpoint of reactivity, but secondary amines can also be used. Suitable amines include aniline, meta or paraphenylenediamine, meta or paraxylylenediamine, 1,4- or 1,3-cyclohexanediamine, hexahydroxylylene diane, 4,4′-diaminobiphenyl, bis ( 4-aminophenyl) methane,
Bis (4-aminophenyl) ether, bis (4-aminophenyl) sulfone, bis (4-amino-3-methylphenyl) methane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4- Aminophenyl) cyclohexane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-amino-3-methylphenyl) propane, 2,2-bis (4-amino-3-chlorophenyl) propane , Bis (4-amino-3-chlorophenyl) methane, 2,2-bis (4-amino-3,5-dibromophenyl) propane, bis (4-aminophenyl) phenylmethane, 3,4-diaminophenyl-4 -Aminophenylmethane, 1,1-bis (4-aminophenyl) -1-phenylmethane, melamines having an s-triazine ring,
Examples thereof include polyamines in which aniline and formalin are reacted to bond a benzene ring with a methylene bond. In addition, it is also a preferable method to use these maleimides as a preliminary reaction product with a cyanate ester.

The method of mixing the cyanate ester compound, or the crosslinking catalyst or the monofunctional or polyfunctional maleimide compound, which is the modifying aid, with the EEA composition of the present invention may be a method in which these components are uniformly dispersed. There is no particular limitation,
Ordinary method, a method of mixing the above components by a blender or other means and using an extruder; a method of mixing with EEA as a solution and drying; a method of mixing as it is with a kneader, a Henschel mixer, or the like and used as it is; inorganic The fillers, metals, metal oxides or pigments and other additives are premixed with the additives of the invention and this is mixed with EEA.
And a method of mixing and extruding; a masterbatch method of producing a high-concentration masterbatch and mixing it, and a method of forming a solution are also suitable, and mixing conditions are extrusion conditions of EEA in the case of an extruder. Can be used as is. Mixing is performed at room temperature with heating or with heating.

The EEA composition of the present invention prepared by the above method is pressed,
Plates, sheets, films, etc. by extrusion, injection molding, etc.
As rods and other shaped bodies, toluene, xylene,
A slightly emulsified solution is prepared by dissolving and mixing in another organic solvent that dissolves EEA and cyanate ester compound at room temperature or under heating, and is used as a liquid adhesive or for forming an adhesive layer or for adhesion. It is used for the production of the film.

Further, the EEA composition of the present invention is more suitable for practical use in a state in which the EEA component is crosslinked, from the viewpoint of adhesive strength, the crosslinking conditions, the crosslinking agent to be used, the type of crosslinking aid, It depends on the amount used, the type and amount of inorganic fillers, pigments, and other additive components not used or in the case of use, but it is usually in the range of 30 seconds to 3 hours at 80 to 300 ° C. . However, depending on the temperature of melt-adhesion or molding, a cross-linking reaction is not necessary because the cross-linking reaction occurs under such conditions as molding.

〔Example〕

Hereinafter, the present invention will be described with reference to examples. In the examples and the like, parts and% are based on weight.

Example-1 EEA (manufactured by Mitsui DuPont Polychemical Co., Ltd., trade name; EVAFLEX-EEA, 709A, ethyl acrylate content 35
%, Random copolymer, hereinafter referred to as "EEA709") at 80 ° C
100 parts of EEA709 as shown in Table 1, 2,2-bis (4-cyanatophenyl) propane (hereinafter referred to as "BPCN") and BPCN at 140 ° C for 8 hours. Pre-reacted prepolymer having a weight average molecular weight of 2000 (hereinafter referred to as "PBP2"), 90 parts of BPCN and 10 parts of bis (4-maleimidophenylmethane (hereinafter referred to as BMI)) at 140 ° C
Pre-reacted weight average molecular weight, 1500 prepolymer (hereinafter referred to as "BT15") rosin, or dicumyl peroxide (hereinafter referred to as "DCPO") was added, and the mixture was kneaded with a roll at 80 ° C for 10 minutes. Roll the mixture on a roll at 80 ° C for 20
The film was 0 μm.

This film was sandwiched between polyethylene terephthalate films having a thickness of 100 μm, and press-molded at 5 kg / cm ² , 180 ° C. for 3 minutes to bond the films.

Table 1 shows the results of measuring the peeling strength (σ _{s, 180} , unit: kg / 25 mm) of the bonded surface of the bonded film in the 180 ° direction.

Example-2 Using the components described in Table 2, the thickness was the same as in Example-1.
A film of 200 μm is produced, and the film is sandwiched between an aluminum foil having a thickness of 100 μm, a copper foil having a thickness of 50 μm, a polysulfone film, a polyetherimide film and a polyetheretherketone film, respectively, 20 kg / cm ₂ , 190 ° C. Press molding was carried out for 1 minute to bond the films.

The results of measuring the peeling strength in the same manner as in Example-1 are shown in Table 2.

Example-3 After mixing the same EEA resin as in Example-1 with a roll at 80 ° C, 100 parts of EEA were mixed with the components shown in Table 3 at 100 ° C for 10 parts.
Kneaded with a roll for a minute.

This mixture was press-molded at 170 ° C. for 30 minutes to prepare a flat plate having a thickness of 3 mm, and a test piece was produced from this.

The test results are shown in Table 3.

[Operations and Effects of the Invention] As is apparent from the above detailed description and Examples, the composition of the present invention has other mechanical properties and thermal properties, and particularly when used as an adhesive film, It can be seen that the composition is extremely excellent in practical use such as showing extremely excellent adhesive strength.

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Claims (2)

[Claims] 1. The content of ethyl acrylate is 8 to 36% by weight.
Modified ethylene-ethyl acrylate copolymer obtained by mixing 0.1 to 20% by weight of a monofunctional or polyfunctional cyanate ester compound containing at least one cyanato group in the molecule. Ethyl acrylate copolymer composition. 2. A cross-linking catalyst of the ethylene-ethyl acrylate copolymer or a monofunctional or polyfunctional maleimide compound is used as a modifying aid in an amount of 0.1 to 0.1 each based on the ethylene-ethyl acrylate copolymer composition. Composition according to claim 1, wherein 5% by weight is used.