JPH0623280B2 - Modified ethylene-propylene rubber composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a modified ethylene-propylene rubber composition, which has excellent mechanical properties, improved heat aging properties, and further improved contact properties. It is an improved composition and is preferably used as a molded product, an adhesive, an adhesive sheet, a solution and the like.

[Conventional technology and its problems]

Ethylene / propylene rubber is widely used in the industry as a rubber having relatively excellent resistance to ultraviolet rays, but it has poor adhesiveness, and if it is mixed with an inorganic filler, metal, metal oxide or pigment, it will be heated and oxidized. There are drawbacks such as accelerated deterioration.

The present invention prevents these defects and improves elongation, strength and elastic modulus, and further has a modified ethylene having excellent adhesion to metals, plastics, inorganic substances, wood, fibers, pulp and the like. -A propylene rubber composition has been found.

[Means for solving problems]

The present invention has made various investigations on the utilization of the unique property of the cyanato group of the compound having a cyanato group (—O—C≡N). As a result, by adding a compound having a cyanato group to ethylene / propylene rubber, ethylene. It was found that the mechanical properties, thermal stability, and adhesiveness of propylene rubber can be greatly improved, and it has been completed.

That is, the present invention provides a monofunctional or polyfunctional cyanate ester compound containing one or more cyanato groups in the molecule as an additive for modification to ethylene / propylene rubber, based on the ethylene / propylene rubber. , 0.1 ~ 20
Modified ethylene prepared by mixing wt% and a crosslinking catalyst
A propylene rubber composition, and in a more preferred embodiment, 0.1 to 5% by weight of a polyfunctional maleimide compound is mixed and mixed as a modifying aid for promoting the modification by the cyanate ester compound and the crosslinking catalyst. It is a modified ethylene-propylene rubber composition.

The present invention will be described below.

The ethylene / propylene rubber (hereinafter referred to as EPR) of the present invention is ethylene, propylene rubber, or a copolymer of these with ethylidene, norbornene, dicyclopentadiene or the like as a raw material.
It is a rubbery copolymer such as a propylene copolymer or an ethylene / propylene / diene-based monomer copolymer, but calcium carbonate, magnesium hydroxide as a mixture with a known plastic such as polyethylene, polypropylene, nylon or polycarbonate. Inorganic fillers such as aluminum hydroxide, calcium hydroxide, talc, clay, mica and wollastonite, powders and fibers of copper, iron, cobalt, nickel, chromium, manganese, aluminum, manganese or alloys of these metals , Flakes such as metal,
Powders such as copper oxide, iron oxide, antimony trioxide and lead oxide, fibers, metal oxides such as flakes, 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,
It is effective as a composition to which a stabilizer or the like is added, and also to a composition to which a thermosetting resin such as an epoxy resin is added, and these compositions are also included.

Suitable monofunctional or polyfunctional cyanate ester compounds containing at least one cyanato group in the molecule of the present invention added to the EPR composition comprising the above components as a modifier are those represented by the following general formula ( 1) General formula (1): R (OCN) _m (1) (wherein m is an integer of 1 or more and usually 5 or less, R ₂ is an aromatic organic group, and is the above cyanato group. Is a compound bonded to the aromatic ring of the organic group). Specific examples are 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,
Reaction of bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, tris (4-cyanatophenyl) phosphite, tris (4-cyanatophenyl) phosphate, and novolacs with cyanogen halides And a cyanate ester obtained by. In addition to these, Japanese Examined Sho 41-1928, 43-18468, 44-4791, 45
-11712, 46-41112, 47-26853 and JP-A-51-63149
Cyanate esters described in etc. can also be used.

In addition, the above-mentioned polyfunctional cyanate ester,
Alternatively, it can be used as a prepolymer having a cyanato group in the molecule obtained by polymerization in the presence of a mineral acid, a Lewis acid, a salt such as sodium carbonate or lithium chloride, a phosphate ester such as tributylphosphine, an organometallic salt or the like. However, it can be used as a pre-mixture or a pre-reactant (= prepolymer) with a polyfunctional maleimide compound described later, and can also be used as a prepolymer with an amine.

EPR of the cyanate ester 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 used in an amount of more than 20% by weight, it shows a remarkable effect in preventing deterioration of stability, etc. This is not preferable because the properties of (3) are impaired. Also, as explained above,
Since the effects of the present invention is required cyanato group, additive agents to react with the functional groups - for example, -OH, -COOH, -NH _2, -CO
When it is necessary to add a compound having OM, —SH or the like (M = metal atom), it is preferable to avoid mixing the cyanate ester compound with these compounds in advance.

The crosslinking catalyst of the present invention is for crosslinking EPR, and includes, for example, known organic peroxides such as dicumyl peroxide and sulfur, and these known catalysts and cocatalysts thereof such as acetylacetone iron and octyl acid. Examples thereof include known metal chelates such as zinc and combinations with organic metal salts. The amount of the catalyst used is usually 0.1 to 5% by weight based on the EPR.

Further, in a preferred embodiment of the present invention, as a modifying aid,
Based on the composition, 0.1-5% by weight of polyfunctional maleimide compound is used.

A preferred compound as such a polyfunctional maleimide compound is the following general formula (2): (In the formula, R ₁ is a divalent 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 usually an integer of 2 to 5. The maleimides represented by the above formula are prepared by reacting maleic anhydrides with polyamines containing 2 to 5 amino groups to prepare maleamic acid and then dehydrating and cyclizing with maleamic acid. Can be manufactured by a 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 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) 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-phenylethane, s
-Melamines having a triazine ring, polyamines in which aniline and formalin are reacted to bond a benzene ring with a methylene bond, and the like.

The EPR composition of the present invention may be mixed with a cyanate ester compound, a cross-linking catalyst or a polyfunctional maleimide compound as a co-catalyst and a co-catalyst and a reforming aid, so long as these components are uniformly dispersed. There is no particular limitation as long as it is a conventional method, a method of mixing the above components by a blender or other means and using an extruder; a method of mixing with an EPR as a solution and drying; To use;
Inorganic fillers, metals, metal oxides or pigments and other additives are pre-mixed with the additives of the invention and this is mixed with E
A method of mixing with PR and extruding; a method such as a masterbatch method of producing a high-concentration masterbatch and mixing them is also suitable, and the mixing condition is EPR in the case of an extruder.
The extrusion conditions of can be used as they are. Mixing is performed at room temperature, while heating or heating.

The EPR 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 an organic solvent that dissolves other EPR and cyanate ester compound at room temperature or under heating, and used as a liquid adhesive or a film for forming an adhesive layer or an adhesive film. Is used for manufacturing.

Further, the EPR composition of the present invention is put to practical use in a state where the EPR component is crosslinked.

That is, when it is used as a molded product in the form of a plate, sheet, film, rod, or other, or when it is used for manufacturing a molded product, it is usually crosslinked at the time of manufacturing these or at the time of manufacturing a molded product or an adhesive from the molded product. Also, a film for adhesion,
When it is used for adhesion as an adhesive layer or the like, it is usually cross-linked during the production of an adhesive structure (laminate, etc.).

The cross-linking conditions include the cross-linking agent used, the type of cross-linking aid, the amount used,
Further, the inorganic filler, the pigment, and other additive components are not used or are different depending on the type and amount when used, etc., but are usually at 80 to 300 ° C. for 30 seconds to 3 hours.

〔Example〕

Hereinafter, the present invention will be described with reference to examples. In addition, the addition amount in the examples and the like is based on weight.

Example-1 EPR (manufactured by Japan Synthetic Rubber Co., Ltd., trade name; EP-11) 10
0 parts to 50 parts calcium carbonate, 10 parts process oil (made by Idemitsu Petrochemical Co., Ltd., trade name; NS-24), 5 parts zinc oxide
Parts, 0.3 part of sulfur as a cross-linking agent and 2.7 parts of dicumyl peroxide and stearic acid (hereinafter referred to as SA) or calcium stearate (hereinafter referred to as CaSA) described in Table 1.
Or a lubricant such as 2,2-bis (4-cyanatophenyl) propane (hereinafter referred to as BPA-CN) or mercaptobenzothiazole (hereinafter referred to as BSH) is added, and the mixture is rolled at room temperature, 2
The mixture obtained by kneading for 0 minutes was molded by a press at a temperature of 160 ° C. for 30 minutes to produce a sheet having a thickness of 1 mm.

Tensile rupture strength (σ _T , unit: kg / mm ² , about normal state (= A) of this sheet and after heating at 100 ° C. for 50 hours (= D),
The results of measuring the elongation at break (= ε, unit%) are shown in Table 1.

Example-2 A copper foil having a thickness of 70 μm was contact-fixed on both sides of the sheet produced in Example-1, and after heating in an oven at 150 ° C. for 24 hours,
The state of the copper foil contact surface was visually observed. The results are shown in Table 2.

Example-3 100 parts of EPR as in Example-1, 50 parts of clay, 10 parts of process oil, 5 parts of zinc oxide, 0.3 part of sulfur as a cross-linking agent, 2.7 parts of dicumyl peroxide and 0.3 part of SA and a third part. 1,4-dicyanatobenzene listed in the table (hereinafter HQ-CN
Or 2,6-di-tert-butyl-P-methylphenol (hereinafter referred to as BHT) is added, and the mixture obtained by kneading for 20 minutes with a roll at room temperature is pressed with a press at a temperature of 160 ° C. for 30 minutes. A sheet having a thickness of 1 mm was manufactured by molding under the condition of 1 minute. Table 3 shows the tensile strength and elongation at normal state of this sheet, and the results of the measurement of the rate of increase in weight (%) after being immersed in xylene at 23 ° C. for 2 days (xylene resistance).

Example-4 100 parts of the same EPR as in Example-1 was added with calcium carbonate 5
0 part, process oil 10 parts, zinc oxide 5 parts, sulfur as a cross-linking agent 0.3 part and dicumyl peroxide 2.7 parts, zinc stearate 0.25 part and BPA-CN, BPA-CN shown in Table 4.
Weight average molecular weight of 2,800
BPA-CN prepolymer (hereinafter referred to as PrB-CN) or BP
Weight average molecular weight 3,000 obtained by heating and stirring 90 parts of A-CN and 10 parts of bis (4-maleimidophenyl) methane at 140 ° C for 5 hours.
Prepolymer (hereinafter referred to as BT-10) was added in the amount shown in Table 4, and the mixture was kneaded with a roll at 80 ° C for 5 minutes, and then the mixture was molded by a press at a temperature of 160 ° C for 30 minutes. A sheet having a thickness of 1 mm was manufactured.

Normal tensile strength, elongation and elongation 100 of this sheet
Table 4 shows the results of measuring the tensile strength at the time of 100% and at the time of 300%.

Example-5 In the same EPR100 parts as in Example-1, 1.0 parts of dicumyl peroxide and BPA-CN, acetylacetone iron (hereinafter referred to as ACFe) shown in Table 5 or bisphenol A having an epoxy equivalent of 450 to 500 are used. Type epoxy resin (hereinafter referred to as EPO)
Was added, and the mixture obtained by kneading with a roll at room temperature for 10 minutes was sandwiched between fluororesin films and pressed to produce a film having a thickness of 35 μm.

This film is sandwiched between polyethylene terephthalate films with a thickness of 50 μm, and the temperature is 170 ° C and the pressure is 20 kg / cm ^2.
After press molding for 10 minutes or 60 minutes (PET / 10 minutes, PET /
60 minutes), and 35 μm thick copper foil sandwiched between the glossy side and temperature
160 ° C., after press molding at a pressure 20 kg / cm ² 30 min (Cu / 3
Peeling strength in 90 ° direction (= σ _S ⁹⁰ unit kg / cm)
Was measured. The results are shown in Table 5.

100 parts of EPR similar to that of Example-1 (Test Nos. 6 to 6)
Or 100 parts of low-density polyethylene (test No. 6-),
1.0 part of dicumyl peroxide and BPA-CN listed in Table 5,
Add PrB-CN, BT-10, bis (4-maleimidophenyl) methane (hereinafter referred to as BM) or rosin and roll to 80
After kneading at 10 ° C for 10 minutes, a thickness of 10 was obtained in the same manner as in Example-5.
A 0 μm film was produced.

This film is sandwiched between 100 μm thick polyethylene terephthalate film (PET /) or the glossy side (Al /) of 50 μm thick aluminum foil, temperature 160 ° C., pressure 20 kg / cm ²
After press molding for 30 minutes, the peel strength in the 180 ° direction was measured and the results are shown in Table 6.

Example-7 Xylene was added to the composition of 6-of Example-6, and the temperature was 70 ° C.
The mixture was stirred and mixed for 6 hours to prepare a light brown emulsion having a solid content of 9% by weight.

This emulsion was applied to a copper foil having a thickness of 35 μm, and then dried in an oven at 130 ° C. for 15 minutes to prepare a copper foil with an adhesive layer having an average coating film thickness of 30 μm.

The coating film side of this copper foil was overlaid with a polyethylene terephthalate film having a thickness of 50 μm and press-molded at 170 ° C. for 30 minutes at 20 kg / cm ² to obtain a copper-clad polyethylene terephthalate film. Copper foil peeling strength of this film is 2.8kg / cm, 2
It floated in a solder bath at 25 ° C for 2 minutes, but there was no blister.

[Operation and effect of the invention]

As is clear from the above detailed description and Examples-1 to 6, the composition of the present invention has the effect of preventing thermal decomposition, the effect of improving the elongation, strength and the effect of preventing thermal decomposition seen in the additive-containing composition. The appearance and heat deterioration are greatly improved, and when it is used as an adhesive film, it shows extremely excellent adhesive strength even on the surface that was not adhered until conventionally without surface treatment for adhesion. It can be seen that the composition is extremely excellent in practical use.

Claims (2)

[Claims] 1. A cross-linking catalyst containing 0.1 to 20% by weight of a monofunctional or polyfunctional cyanate ester compound containing at least one cyanato group in the molecule in ethylene / propylene rubber. A modified ethylene-propylene rubber composition obtained by mixing 2. An ethylene-propylene rubber composition based on the ethylene-propylene rubber composition as an auxiliary agent for modifying the ethylene-propylene rubber with the cyanate ester compound and the crosslinking catalyst.
The ethylene-propylene rubber composition according to claim 1, further comprising 1 to 5% by weight of a polyfunctional maleimide compound.