JPS62190240A - Ethylene-ethyl acrylate copolymer composition - Google Patents

Abstract

PURPOSE:The titled composition suitable as a film for adhesion, etc., having improve mechanical characteristics and adhesiveness, obtained by blending an ethylene-ethyl acrylate copolymer with a specific amount of a cyanic acid ester compound containing a cyanato group in the molecule. CONSTITUTION:An ethylene-ethyl acrylate copolymer containing 8-36wt% ethyl acrylate is blended with 0.1-20wt% monofunctional or polyfunctional cyanic acid ester compound (e.g., monocyanotobenzene, etc.,) shown by formula I (m is 1-5; R is aromatic organic group and cyanato group is bonded to aromatic ring of the organic group) containing one or more cyanato groups in the molecule. The blend is preferably mixed with 0.1-5wt% crosslinking catalyst (e.g., dicumyl peroxide, etc.,) for the copolymer as a modification auxiliary or a mono- or polyfunctional maleimide compound [e.g., formula II (R1 is 1-5 functional organic group; X<1> and X<2> are H, etc.,; n is 1-5)].

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is a modified ethylene-dityl acrylate copolymer composition, which has excellent mechanical properties and improved adhesiveness, and which is suitable for molding. It is suitably used as a body, an adhesive, an adhesive sheet, a solution, etc.

[Conventional technology and its problems]

Ethylene-ethyl acrylate copolymer (rEEA)
J) is a thermoplastic resin with excellent flexibility, rubber elasticity, and low-temperature properties, and is widely used as a blend into wax, a base resin for hot melt adhesives, and molded products. Hot melt adhesives made by mixing EEA with adhesives and waxes such as rosin, turpentine, polyisobutylene, and batifine do not necessarily have sufficient adhesive strength, and also have the disadvantage of weak adhesive strength at high temperatures. .

The present invention is based on the discovery of an EEA composition that has high strength and extremely excellent adhesive strength.

[Means for solving problems]

As a result of various studies on the use of the unique properties of cyanato groups in compounds having a cyanato group (-0-CEN), the present invention has revealed that by adding a compound having a cyanato group to EEA, the mechanical properties and adhesive properties of EEA can be improved. This product was developed after discovering that it can significantly improve sexual performance.

That is, in the present invention, 0.1 of a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule is added to an ethylene-ethyl acrylate copolymer.
This is a modified ethylene-ethyl acrylate copolymer composition formed by mixing ~20% by weight of the ethylene-ethyl acrylate copolymer. This is a modified ethylene-ethyl acrylate copolymer obtained by co-mixing a functional or polyfunctional maleimide compound in an amount of 0.1 to 5% by weight based on the ethylene-ethyl acrylate copolymer.

The present invention will be explained below.

The EEA of the present invention is a combination of known ethylene and ethyl acrylate, usually with an ethyl acrylate content of 8 to 36
These are random copolymers formed by polymerizing using % by weight. In addition, mixtures of ordinary EEA and polyolefins such as polyethylene and polypropylene, EEA and EVA, EPR, etc., mixtures of EEA and adhesives such as rosin, paraffin, rosin ester, neorene, nitrile rubber, and waxes, Inorganic fillers such as calcium carbonate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, talc, clay, mica, wollastonite, copper, iron, cobalt, nickel, chromium, manganese,
Metals such as powders, fibers and flakes such as aluminum, manganese or alloys of these metals, metal oxides such as powders, fibers and flakes such as copper oxide, iron oxide, antimony dioxide and lead oxide, copper phthalocyanine (=phthalocyanine blue) Organometallic compounds such as yellow lead, mineral violet, carbon black, red iron, ultramarine blue, cobalt blue, cobalt violet, titanium white and other pigments;
It is effective not only as a composition to which a flame retardant, an ultraviolet absorber, a stabilizer, etc. are added, but also as a composition to which a thermosetting resin such as an epoxy resin is added, and these are also included.

Suitable monofunctional or polyfunctional cyanate ester compounds containing one or more cyanato groups in the molecule of the present invention to be added as a modifier to the EEA composition consisting of the above components are represented by the following general formula: (1) % Formula % (1) (In the formula, m is an integer of 1 or more and usually 5 or less, R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group. It is a compound represented by Specific examples include monocyanatobenzene, alkylcyanatobenzene such as p-tert-butylcyanatobenzene, monocyanatonaphthalene, 1,3- or 1,4-dicyanatobenzene, 1.
3.5-) lycyanatobenzene, 1.3-, 1.4-
.

1,6-, 1.8-, 2.6- or 2,7-dicyanatonaphthalene, 1,3.6-) dicyanatonaphthalene,
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 a cyane [
tlsP-4,026,913, / cyanic acid ester obtained by reaction of borac with cyanogen halide (USP-4,022,755, same 3.
448.079) etc. In addition to these, Tokuko Sho 4
1-1928, 43-18468, 44-479
1, 45-11712, 46-41112, 4
7-26853, JP-A-51-63149, tlsP-
3,553,244, 3,755.402, 3.7
40.348, 3.595.900, 3, 694.
Cyanic acid esters described in 410 and 4.116.946 may also be used.

In addition, the above-mentioned polyfunctional cyanate ester may be used as it is, or in the presence or absence of mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, phosphate esters such as tributylphosphine, organic metal salts, etc. It can be used as a prepolymer having a cyanato group in the molecule obtained by polymerization, and can be used as a premix or prereactant (= prepolymer) with a monofunctional or polyfunctional maleimide compound that is a modification aid described later ), and can also be used as a prepolymer with amine, which is a raw material for the maleimide compound described later.

EEA of the cyanate ester compound of the present invention explained above
There is no particular limitation on the amount of the compound, but from the viewpoint of effectiveness it is
．． It is appropriately selected from the range of 1 to 20% by weight. Added amount is 0
．． If it is less than 1%, the effect of improving properties is insufficient, and if it is used in excess of 20% by weight, it shows a remarkable effect in preventing deterioration such as stability, but there are problems such as a decrease in adhesive strength and a decrease in EEA elongation. This is not preferable because other properties of the material are impaired.

Furthermore, as explained above, since a cyanato group is necessary for the effect of the present invention, additives that react with this functional group such as -Ko, -COKo, -Nl2, -COOM, -3
When it is necessary to add a compound having - such as l1 (M=metal atom), it is preferable to avoid mixing the cyanate ester compound and these compounds in advance before adding them.

The crosslinking catalyst for crosslinking EEA used as a reforming aid in the present invention includes, for example, known organic peroxides such as dicumyl peroxide, sulfur, these known catalysts, and their cocatalysts such as acetylacetonate iron, Examples include combinations with known metal chelates and organic metal salts such as zinc octylate, and the amount used is usually 0.1 to
5% by weight is preferred.

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

Preferred compounds as such monofunctional or polyfunctional maleimide compounds are the following general formula (2) and general formula (2).
: (wherein, R8 is a monovalent or more, usually pentavalent or less, aromatic or alicyclic organic group, x', x2 are hydrogen, halogen, or an alkyl group, and n is usually an integer of 1 to 5. ). Maleimides represented by the above formula are produced by a method known per se, in which maleic anhydride and polyamines containing 1 to 5 amino groups are reacted to prepare maleamic acid, and then maleamic acid is cyclodehydrated. be able to. The polyamines used are preferably aromatic polyamines in terms of the heat resistance of the final resin, but if flexibility and flexibility of the resin are desired, alicyclic amines may be used alone or in combination. good. Further, it is desirable that the polyamines be 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, hexahydroxylylenediamine, 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)furopane, 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-
These include (aminophenyl)-1-phenylethane, melamines with S-triazine rings, and polyamines with benzene rings linked with methylene bonds by reacting aniline with formalin. It is also preferable to use these maleimides as a preliminary reaction product with cyanate ester.

The method of mixing a cyanate ester compound, a crosslinking catalyst as a stiffness modifying aid, or a monofunctional or polyfunctional maleimide compound with the EEA composition of the present invention may be any method in which these components are uniformly dispersed. There are no particular restrictions,
Ordinary method, method of mixing the above components using a blender or other means and using an extruder; method of mixing with EEA as a solution and drying; method of mixing with a Niegoo, Henschel mixer, etc. and using as it is or by extrusion; inorganic Fillers, metals, metal oxides, or pigments and other additives are mixed in advance with the additives of the present invention, and EEA
A method of mixing and extruding; a masterbatch method in which a high-concentration masterbatch is manufactured and mixed, and a method of making a solution are also suitable, and the mixing conditions are the extrusion conditions of EEA in the case of an extruder. can be used as is. The mixture may be mixed at room temperature, heated, or under heating.

The EEA composition of the present invention prepared by the above method is pressed,
Plate, sheet, film, etc. by extrusion, injection molding, etc.
Toluene, xylene, as rods and other shaped bodies.
A slightly emulsified solution is prepared by dissolving and mixing other EEA and cyanate ester compounds in an organic solvent at room temperature or under heating, and is used as a liquid adhesive or for forming an adhesive layer or an adhesive film. It is used for manufacturing.

In addition, it is more suitable for the EEA composition of the present invention to be put to practical use in a state in which the EEΔ component is crosslinked, from the viewpoint of adhesive strength, and the crosslinking conditions are determined by the type of crosslinking agent and crosslinking aid used, Although it varies depending on the amount used and the types and amounts of inorganic fillers, pigments, and other additive components, whether they are not used or used, it is usually heated at 80 to 300°C for 30 seconds to 30 seconds.
It is a range of time. However, depending on the temperature of melt adhesion or molding, a crosslinking reaction occurs under these molding conditions, so no particular crosslinking treatment is required.

〔Example〕

The present invention will be explained below with reference to Examples. Note that parts and percentages in Examples and the like are based on weight.

Example-1 EEA (manufactured by Mitsui DuPont Polychemicals, trade name;
BVAFLHX-BEA, 709A, : r-thyl acrylate content 35%, random copolymer, hereinafter rE
EA709J) was mixed with a roll at 80°C,
As shown in Table 1 for 100 parts of EEA709, 2
, 2-bis(4-cyanatophenyl)propane (r
[1PcNJ], a prepolymer with a weight average molecular weight of 2.000 obtained by pre-reacting BPCN at 140°C for 8 hours (hereinafter referred to as "rPBP2"), BPCN 90
and bis(4-maleimidophenylmethane (hereinafter referred to as BM)
A prepolymer with a weight average molecular weight ff of 11.500 (hereinafter referred to as r
BT15J), rosin, or dicumyl peroxide (hereinafter referred to as rDCPOJ) were added and heated at 80°C for 1
The mixture was kneaded with a roll for 0 minutes, and the mixture was made into a film having a thickness of 200ρ with a roll at 80°C.

Sandwiched between 100 thick polyethylene terephthalate films, 5kg/cnf, 180℃,
Press molding was performed for 3 minutes to bond the films together.

Table 1 shows the results of measuring the peel strength (σ5IIlIO% unit: kg/25mm) of the adhesive surface of the adhered film in the 180° direction.

Table 1 Example-2 Using the components listed in Table 2, a 200-thick film was produced in the same manner as in Example-1, and each of these films was 100-thick. It was sandwiched between a ca aluminum foil, a 50 m thick copper foil, a polysulfone film, a polyether imide film, and a polyether ether ketone film, and press-molded at 20 kg/cnf at 190°C for 1 minute to adhere the films.

Table 2 shows the results of measuring the peel strength in the same manner as in Example-1.

Table 2 Example-3 The same EEA resin as in Example-1 was mixed with a roll at 80°C, and then the components listed in Table 3 were kneaded with a roll at 100°C for 10 minutes with respect to 100 parts of EIEA.

This mixture was press-molded at 170° C. for 30 minutes to create a flat plate with a thickness of 3 mm, from which test pieces were manufactured.

The test results are shown in Table 3.

Table 3 [Operations and Effects of the Invention] As is clear from the above detailed description and Examples, the composition of the present invention can be used as an adhesive film in addition to improving mechanical properties and thermal properties. In this case, it can be seen that the composition is extremely excellent in practical use, such as exhibiting extremely excellent adhesive strength.

Claims (1)

[Claims] 1. 0.1 to 20% by weight of a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule is mixed into an ethylene-ethyl acrylate copolymer. A modified ethylene-ethyl acrylate copolymer composition. 2. As a modification aid, a crosslinking catalyst for the ethylene-ethyl acrylate copolymer or a monofunctional or polyfunctional maleimide compound is used in an amount of 0.1 to 5% by weight, respectively, based on the ethylene-ethyl acrylate copolymer composition. The composition according to claim 1 for use.