JPH02150441A - Moldable resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition, having a high mechanical strength, readily forming films and excellent in moldability by blending an ethylenic polymer with an organopolysiloxane, hydrocarbon compound and organic peroxide. CONSTITUTION:A composition obtained by blending 100 pts.wt. ethylenic polymer with (A) 0.01-300 pts.wt. organopolysiloxane expressed by the formula (R<1> is aliphatic unsaturated group; R<2> is monofunctional hydrocarbon group without containing aliphatic unsaturated group; 0<a<1; 0.5<b<3; 1<a+b<3), (B) 0.01-30 pts.wt. hydrocarbon compound expressed by the formula CH2=CH (CH2)cCH=CH2 (c is 1-30) and (C) 0.001-3 pts.wt. organic peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition that can be molded into a film or a tube. More specifically, the present invention relates to a moldable resin composition comprising a polyethylene resin polysiloxane polymer, a compound containing unsaturated groups at both ends, and an organic peroxide.

(Prior art) Silicone has been widely used due to its excellent properties such as slipperiness, mold releasability, easy oxygen permeability, water repellency, and electrical insulation, but it has low mechanical strength and It has the disadvantage that it is difficult to form a film and has poor moldability.

(Problems to be Solved by the Invention) The present invention aims to obtain a resin that is improved from the disadvantages of silicone, such as low mechanical strength, low acid film resistance, and low moldability. .

(Means for Solving the Problems) The present inventors have conducted extensive research in order to obtain a resin that has improved disadvantages of silicone, such as low mechanical strength, low film-forming properties, and low moldability. As a result, the present invention was completed.

That is, in the present invention, 0.01 parts of organopolysiloxane represented by formula A1 is added to 100 parts by weight of the ethylene polymer.
~300 parts by weight, R', R"ゎSIO<-a-b (A
l (in the formula, R' is an aliphatic unsaturated group, R2 is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group, O<a<
1, 0.5<b<3. l<alb<3) (0.01 to 30 parts of a hydrocarbon compound represented by the formula B1, CH2''CH(CHa)CCH:CH2(al (in the formula,
C is an integer of 1 to 30), and 0.001 to 3 parts of an organic peroxide.

The resin composition of the present invention can be molded into films, tubes, etc., and from this it is possible to obtain a molded product in which the ethylene polymer and the organic silicone compound are uniformly mixed without macroscopically poor dispersion.

Even if an ethylene polymer and an organopolysiloxane represented by the formula A1 are kneaded in a Banbury mixer, for example, slipping occurs and kneading is difficult, and even if mixing occurs, reaction is difficult to occur. When a compound is added to the system, the torque increases in a short period of time, a reaction begins, and the ethylene polymer and organopolysiloxane compound bond together.However, in this system, many lumps of silicone crosslinked products are generated, It is difficult to form a uniform resin.

Therefore, as a result of intensive studies, the present inventors found that by adding a hydrocarbon compound represented by the formula B1 to this system, a uniform resin in which almost no lumps of silicone crosslinks are generated is created. I found out what I can get.

The resin obtained from the composition of the present invention can be processed into films and tubes using general molding machines such as polyethylene.

Further, the film or tube becomes a uniform molded product with almost no lumps of silicone crosslinked material.

The processability and impact resistance of the resin obtained from the composition of the present invention can be improved by mixing it with other resins such as polystyrene, nylon, polyester, polycarbonate, etc.

The ethylene polymer used in the present invention is a polymer whose main component is ethylene, such as high-pressure polyethylene, linear low-density polyethylene (LLDPEI), ethylene-α olefin copolymer, ethylene-vinyl acetate copolymer, etc. , ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl methacrylate copolymer Examples include polymers, ethylene-vinyl alcohol copolymers, ethylene-propylene-diene terpolymers, and others.

In the organopolysiloxane represented by the formula fAj used in the present invention, examples of the R' group include a vinyl group, an allyl group, an acrylic group, a methacryl group, and R2
Examples of groups include alkyl groups such as methyl, ethyl, and propyl; aryl groups such as phenyl and tolyl;
Examples include cycloalkyl groups such as cyclohexyl and cyclobutyl groups, and groups in which the hydrogen group bonded to the carbon atom of these hydrocarbon groups is partially substituted with a halogen atom, cyan group, mercapto group, etc. It may be a combination of the same or different types.

Further, a is 0 or more and 1 or less; if it is 0, it will not react with the ethylene polymer or the hydrocarbon compound represented by formula (B), which is undesirable; if it is 1 or more, the composition of the present invention will not react. The molded product made becomes too hard, which is undesirable.

a is preferably 0.0004 to 0.06. b is 0.
If it is 5 or more and 3 or less, and if it is 0.5 or less, the cross-wire of the composition of the present invention will be difficult and the processability will be poor, and if it is 3 or more, the molded product made from the composition of the present invention will be hard. Too undesirable, b is preferably 1-2.

The molecular structure of the organopolysiloxane of the present invention is (A
) may be in the form of a chain, a 45°41 shape, a ring shape, a net shape, a three-dimensional network shape, or any other shape.

Although the degree of polymerization of the organopolysiloxane of the present invention is not particularly limited, it is necessary to have an appropriate degree of polymerization that does not interfere with crosstalk with the ethylene polymer used in the present invention, and is preferably 250 or more.

Examples of the hydrocarbon compound represented by the formula B1 used in the present invention include 1,4-pentadiene, 1,5-
Hexadiene, 1.6-hebutadiene, 1.7-octadiene, 1.8-nonadiene, 1.9-decadiene, 1, 10-undecadiene, 1,11-dodecadiene, 1.12-tridecadiene, 1.13- Tetradecadiene, 1, 14-pentadecadiene, 1,15-hexadecadiene, 1.16-'hebutadecadiene, 1,
Examples include 17-octadecadiene, 1,18-nonadecadiene, and others.

The organic peroxide used in the present invention has a decomposition temperature of 100 to 220° C. with a half-life of 10 minutes, and examples thereof include the following. However, the value in parentheses is the decomposition temperature (°C).

Succinic acid peroxide (1101, benzoyl peroxide (1101, t-butylperoxy-2-ethylhexanoate (113)) p-chlorobenzoyl peroxide (1151, t-butylperoxyisobutyrate (115), t-butylperoxyisopropyl carbonate (1351, t-butylperoxylaurate f140), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (1401, t-butylperoxyacetate (140), di-t-butylperoxyphthalate (140) ), t-butylperoxymaleic acid + 1401 cyclohexanone peroxide (145), t-butylperoxybenzoate (145), cycumylheroxide (15)
0) 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (1551 t-butylcumyl peroxide (1551, t-butyl hydroperoxide (
1581, di-t-butylheroxide (160)2.
5-dimethyl-2,5-di(t-butylperoxy)hexyne 3 (1701, di-isopropylbenzene hydroperoxide (170), p-menthane hydroperoxide (180), 2,5-dimethylhexane-
2,5-dihydroperoxide The organopolysiloxane represented by formula (A) used in the present invention is required in an amount of 0.01 part or more, preferably 0.05 to 300 parts by weight, per 100 parts by weight of the ethylene polymer. Part is necessary. If the amount is less than 0.01 part, the characteristics of silicone will not be exhibited (and if it is more than 300 parts, film formation etc. may become difficult).

The amount of the hydrocarbon compound represented by the formula B1 used in the present invention is required to be 0.01 part or more. 0
．． If the amount is less than 0.01 parts, many lumps of silicone crosslinked products will be formed in the molded product.

The organic peroxide used in the present invention is required in an amount of 0.001 to 3 parts, preferably 0.01 to 0.05 parts, per 100 parts by weight of the ethylene polymer.

If the amount is less than o or ooi parts, the reaction will hardly proceed, and if it is more than 3 parts, the moldability of the resin may be impaired.

In the present invention, the composition may contain oxidation stabilizers, ultraviolet stabilizers, inorganic fillers, pigments, flame retardants, rubbers, etc., if necessary.

By heating and kneading the composition of the present invention, it is homogenized,
Extrusion molding becomes possible. The heating and mixing can be carried out using a Banbury mixer, a 12-screw extruder, and other conventional mixing devices. The heating temperature is preferably about 100°C to 300°C.

(Example) Example 1 Melt index (190°C, 2160g12.5
g/10111in + ethylene-vinyl acetate copolymer with a vinyl acetate content of 18 wt% (manufactured by Nippon Unicar) 100
100 parts of silicone gum stock (manufactured by Nippon Unicar) with a viscosity of 300.0 OOC3 at 23°C and a methyl vinyl silicone content of 1.0%, 1 part of 1.9 depot diene, 0.05 part of dicumyl peroxide, and Irganox 1010 (antioxidant manufactured by Ciba Geigy) 0.1
10% at 100°C using a Boulavender plastograph.
After mixing for a minute, the mixture was kneaded at 200° C. for 10 minutes, and then compressed into a sheet with a thickness of 1 mm.

This sheet had no non-uniform areas. The melt index of this mixed wire was 0.5 g, 710 m1n, and the sheet had a tensile strength of 60 kg/crn', an elongation of 300%, and no silicone bleeding on the surface. A pelletized version of this sheet could be extruded into a tape at 160° C. using a Brabender Plastograph extruder.

Comparative Example 1 In the same manner as in Example 1, it was formed into a sheet and pelletized without adding dicumyl peroxide. The resulting sheet had a lot of smudges and the pellets were difficult to extrude.

Comparative Example 2 When kneading was carried out in the same manner as in Example 1 without adding 1.9 decadiene, the silicone crosslinked product formed a film on the inner surface of the plastograph, and when the mixed material was taken out after the reaction, The contents could not be completely removed. The mixed material is made into a sheet with a diameter of about 0.1 to 0.5 mm.
There were areas where crosslinked organic silicone compounds aggregated, and a uniform sheet could not be obtained.

Example 2 100 parts of ethylene-vinyl acetate copolymer (manufactured by Nippon Unicar) with a melt index of 1.5 g, 710 m1n and a vinyl acetate content of 15 wt%, and a viscosity of 300 at 23°C.
．． 0OOC3, methylvinyl silicone content 5.0%
100 parts of silicone gum stock (manufactured by Nippon Unicar), 2 parts of 1,9-diene, 0.0 parts of dicumyl peroxide.
03 parts and 0.1 part of Irganox 1010 (antioxidant manufactured by Ciba Geigy) were mixed in a Prabender Plastograph at 100°C for 10 minutes, then kneaded at 200°C for 10 minutes, and then compression molded into 1mm thick pieces. I made it into a sheet.

This sheet had no non-uniform areas. The melt index of this mixed wire is 0.2 g/10 m1n, and the tensile strength is 70 kg/err? The sheet had an elongation of 300% and had almost no silicone bleeding on its surface.

This sheet was pelletized and could be extruded into tape at 160°C using a Brabender Blastgraph extruder.

(manufactured by Nion Carbide) 100 parts, viscosity at 23°C is 300.0OOC3, methylvinyl silicone content 5
, 0% silicone gum stock (manufactured by Nippon Unicar) 1
00 parts, 2 parts of 1.9 DEG diene, 0.03 parts of dicumyl peroxide, and 0.1 part of Irganox 1O1O (oxidation inhibitor manufactured by Ciba Geigy) were mixed in a Brabender Plastograph at 100°C for 10 minutes. After that, the mixture was kneaded at 200°C for 10 minutes, and then compressed into a sheet with a thickness of 1 mm. The melt index of this kneaded product is 0.4g7
10m1n, and tensile strength 90kg/Ctrl
'The sheet had an elongation of 600% and had almost no silicone bleeding on its surface. A pelletized version of this sheet could be extruded into a tape at 160° C. using a Brabender Plastograph extruder.

Example 3 Melt index 4.7g710m1n, density 0.
900, ethylene-butene-1 copolymer (U Example 4 Melt flow index (200°C, 5.000 g
10.0g/10m1n, Izot impact strength (notched) 1.3kg -am7cm polystyrene 1
00 parts, the lo part of the pellet obtained in Example 1 was mixed with a Brabender plastograph at 200°C for 10 minutes, taken out and formed into a sheet, and the Izot impact strength was measured, and it was found to be 3.3 kg - cm / It was am.

(Effects of the Invention) Since the composition of the present invention can be molded into films, sheets, tubes, etc., molded products that retain the properties of silicone can be obtained, and can be applied to medical parts, industrial parts, electrical material parts, etc. It can also be used as a material to improve the processability and impact resistance of engineering plastics.

Patent applicant: Nippon Unicar Co., Ltd. (2 idiots)

Claims (2)

[Claims] (1) For 100 parts by weight of ethylene polymer, (A)
Organopolysiloxane represented by the formula 0.01-30
0 parts by weight, R^1_aR^2_bSiO_4_-_a_-_b_/
_2(A) (in the formula, R^1 is an aliphatic unsaturated group, R^2 is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group, 0<a<1, 0.5<b <3, 1<a+b<3) (B) 0.01 to 30 parts of a hydrocarbon compound represented by the formula, CH_2=CH(CH_2)cCH=CH_2(B)(
(where c is an integer of 1 to 30); and 0.001 to 3 parts of an organic peroxide. (2) A sheet made from the resin composition of claim (1).