JPH0321641A - Composition for stain-resistant crosslinked ethylene resin foam containing fine open cells - Google Patents

Abstract

PURPOSE:To obtain the subject composition resistant to staining, giving a foamed material resistant to the deterioration of appearance and suitable as a cushioning material for building. etc., by compounding a crosslinkable and foamable composition with a reaction product of an ethylenic resin, a silicone having vinyl group and a hydrocarbon containing diene. CONSTITUTION:The objective composition is produced by compounding (A) a crosslinkable and foamable composition satisfying the formula I (Tp is 10min half-life temperature of organic peroxide; Tf is foaming temperature) and com posed of 100 pts.wt. of an ethylenic resin, 1-30 pts.wt. of a foaming agent and 0.2-10 pts. of an organic peroxide as a crosslinking agent with (B) >=0.1 pts.wt. of a reaction product derived from 100 pts.wt. of an ethylenic resin, 0.01-300 pts.wt. of an organopolysiloxane of formula II (R<1> is aliphatic unsaturated group; R2 is univalent hydrocarbon group free from aliphatic unsaturated group; 0<x<1; 0.5<y<3, 1<x+y<3), a hydrocarbon compound of formula III (n is 1-30) and 0.001-3 pts.wt. of an organic peroxide.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a low-staining, open-cell, cross-linked ethylene resin foam assembly. More specifically, the present invention relates to a non-bleeding, low-contamination, open-cell, cross-linked ethylene resin foam assembly that can be applied to cushions for building materials, interior wall cushions for automobiles, packaging sheets, etc. It is.

Conventional technology Open-cell crosslinked ethylene resin foam composites containing silicone compounds have good air permeability, water absorption,
It is known that it has excellent weather resistance (Special Publication Act 1986
- 49657, Japanese Patent Application Laid-Open No. 63-113034), when open-cell foams produced from these assemblies are used as cushions for building materials, interior wall cushions for automobiles, packaging sheets, etc., the foams often Silicone compounds and the like oozed out onto the surface, causing problems such as adsorption of dust, adhesion to the human body or clothing, and deterioration of appearance.

Problems to be Solved by the Invention The present invention has the same excellent properties as the open-cell foam produced from such a conventional open-cell foam crosslinked ethylene resin foam composition, We have created a low-contamination, open-cell, cross-linked ethylene resin foam with excellent properties that does not cause the problem of silicone compounds bleeding onto the surface of the foam, which is a drawback when using conventional silicone compounds. The purpose of this invention is to provide a foam assembly that can be manufactured.

Means for Solving the Problems In order to develop a foam composition having the above-mentioned favorable properties, the present inventors have conducted various studies on many compounds in order to find substitutes for silicone compounds. This objective can be achieved by using an ethylene resin-vinyl group-containing silicone-diene-containing hydrocarbon reactant instead of a silicone compound, and by selecting a predetermined value to satisfy a predetermined relational expression. Based on this finding, the present invention was completed.

That is, the present invention includes 100 parts by weight of an ethylene resin, 1 to 30 parts by weight of a blowing agent, and 0.2 to 0.2 to 30 parts by weight of an organic peroxide as a crosslinking agent.
10 parts by weight of a cross-linked foamable composition containing at least 0.1 part by weight of an ethylene resin-vinyl group-containing silicone-diene-containing hydrocarbon reactant, and which has a 10-minute half-life temperature ( A low-contamination, open-cell, cross-linked ethylene system characterized in that the foaming temperature (Tf) of the foaming agent and the foaming agent are selected such that the foaming temperature (Tf) of the foaming agent satisfies the following formula: -IO ℃≦Tp-Tf≦50°C The present invention provides a composite for resin foam.

The present invention will be explained in detail below.

The ethylene resin used in the present invention is an ethylene homopolymer, or ethylene and propylene, butene-11 foamed
Methyl-pentene-11 hexene-1, octene-11
σ- of nonene-11 decene-l1 dodecene-l, etc.
A copolymer of ole7ine, vinyl ester, unsaturated carboxylic acid, unsaturated carboxylic acid ester, etc., such as high pressure low density polyethylene, medium low pressure high density polyethylene, medium density polyethylene, Gas-phase polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer,
Examples include ethylene-ethyl acrylate copolymer.

The organic peroxide used in the present invention has a decomposition temperature with a half-life of 10
It is preferable to have a temperature of 100 to 220°C per minute, that is, a half-life temperature of 100 to 220°C in 10 minutes. Examples of such a material include the following. However, the value in parentheses is the decomposition temperature (°C).

Succinic acid peroxide (110), pensoyl peroxide (110), t-butylperoxy-2-ethylhexanoate} (113), p-chloropenzoyl peroxide (115), t-butylperoxyisobutyrate ( 115), t-butylperoxyisogropyl carbonate (135), t-butylperoxylaurate (140), 2,5-dimethyl-2,5-di(penzoylperoxy)hexane (140), t-butylperoxy Acetate-I- (140), di-t-butyl diperoxyphthalate (140), t-butynorepenoleoxymaleic acid (140), cyclohexanone peroxide (145), t-butylperoxybenzoate (145), dicumyl Peroxide (150), 2.5
-dimethyl-2,5-di(L-butylperoxy)hexane (155), t-butylcumylperoxide (15)
5), t-butyl hydroperoxide (158), di-L-butyl peroxide (160), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 (
170), diisobrobylbenzenehydrobenoleoxide (170), p-menthanehydroberoxide (1
80), 2,5-dimethylhexane-2,5-dihydroperoxide (213).

The foaming agent used in the present invention has a foaming temperature of 90 to 220'c.
Preferred are azobisisobutyronitrile, diazocarbonamide, p-toluenesulfonyl hydrazide, 4.4' to xybis(benzenesulfonylhydrazide), n-hebutane, n-hebutane,
-octane, n-nonane, n-decane and the like. This also includes those in which the decomposition temperature is controlled within the above range by using a promoter or an auxiliary agent.

Next, in the present invention, when the 10 minute half-life temperature of the organic peroxide is Tp and the foaming temperature of the blowing agent is Tf,
It is necessary to select and combine the organic peroxide and the blowing agent so as to satisfy the following formula -10°C≦Tp-Tf≦50°C. That is, by using such a combination, by heating the composite and then cooling it, a foam with open cells or open cells containing some closed cells can be obtained.

The amount of organic peroxide added is 0.2 to 10! It is necessary that the amount is t parts. If the amount is less than 0.2 parts by weight, the viscosity of the resin layer will hardly increase when the composite is heated, and the resin layer will become flattened. If it is more than 10 parts by weight, the crosslinking efficiency will not improve. This is inevitable.

It is necessary that the amount of the blowing agent is 1 to 30 parts by weight. If the amount is less than 1 part by weight, there will be almost no foaming effect, and if it is more than 30 parts by weight, the amount of decomposed foaming agent that wastefully escapes into the atmosphere during foaming will increase, resulting in a decrease in efficiency. do not have.

The ethylene resin-vinyl group-containing silicone-diene-containing hydrocarbon reactant used in the present invention is usually prepared by the following formula (A) per 100 parts by weight of the ethylene resin. ',R2,S
iO. ,■ (A)1■71 (in the formula, R1 is an aliphatic unsaturated group, R2 is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group, 0<x<1
, 0.5<y<3, l<x+y<3). oi~300 parts by weight,
The following formula (B) CHz-CI(CJ), CH-CHz (B
) (n in the formula is an integer of 1 to 30) A hydrocarbon compound represented by 0. It is made by heating and kneading a moldable resin composition containing 1 to 30 parts by weight of O and 0.001 to 3 parts by weight of organic peroxide.

This is disclosed in detail in Japanese Patent Application No. Sho 63-305185, for which the present inventors previously filed a patent application.

In the organopolysiloxane represented by the above formula (A), examples of the Rl group include a vinyl group, allyl group, acrylic group, and methacryl group, and examples of the R2 group include:
Alkyl groups such as methyl group, ethyl group, proyl group, 7
Aryl groups such as enyl and tolyl groups, cycloalkyl groups such as cyclohexyl and cyclobutyl groups, and groups in which the hydrogen bonded to the carbon atom of these hydrocarbon groups is partially substituted with a halogen atom, cyano group, mercapto group, etc. etc., and these may be the same type or a combination of different types.

Further, X needs to be greater than 0 and less than ■, preferably from 0.0004 to 0.06. X is O
If it is more than 1, the reaction with the ethylene resin will not occur, and if it is more than 1, the foam produced from the composite of the present invention will become too hard, which is not desirable.

y needs to be greater than 0.5 and less than 3, and preferably l7< is J~2. If y is less than 0.5, it will be difficult to knead the composition of the present invention and the workability will decrease;
If this is the case, the foam produced from the assembly of the present invention will become too hard, which is not desirable.

The molecular structure of the surganopolysiloxane of the present invention may be linear, branched, cyclic, network, three-dimensional network, etc., as long as it is within the range of formula (A), but it may be linear, branched, cyclic, network, three-dimensional network, etc. Preferably.

The degree of polymerization of this organopolysiloxane is not particularly limited, but it is necessary to have a degree of polymerization that does not interfere with kneading with the ethylene resin, and a degree of polymerization of 250 or more is desirable.

Examples of the hydrocarbon compound represented by formula (B) include 1,4-pentadiene, 1,5-hexadiene, 1
．． 6-heptadiene, 1.7-year-old cutadiene, 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, l,17-octadecadiene, 1.
Examples include 18-nonadecadiene.

The blending amount of the ethylene resin-vinyl group-containing silicone-diene-containing hydrocarbon reactant must be at least 0.1 part by weight. If this amount is less than 0.1 part by weight, the open cell ratio of the foam will tend to decrease.

In addition to the above-mentioned essential precepts, the composition of the present invention may optionally contain various additive components that are conventionally used in molds for resin foams, as long as they do not impair the purpose of the present invention. For example, oxidation stabilizers, ultraviolet stabilizers, inorganic fillers, pigments, flame retardants, rubbers, etc. can be optionally added.

The temperature at which the composition of the present invention is heated is at least the temperature necessary for foaming and crosslinking, and is usually 120 to 3
Selected within the range of 00°C. In addition, heating depends on the purpose.
This can be carried out either under normal pressure or under increased pressure. Moreover, since the decomposition temperature of the organic peroxide in the present invention is indicated by the temperature at which the half-life of the pure product is 10 minutes, crosslinking proceeds even below this temperature.

Effects of the Invention Since the composite of the present invention uses an ethylene resin-vinyl group-containing silicone-diene-containing hydrocarbon reactant, it provides a low-contamination, open-cell, cross-linked ethylene resin foam. The obtained foam does not have the phenomenon of silicone compounds bleeding onto the foam surface, which is a drawback when conventional silicone compounds are used, and therefore there is no adsorption of dust, dirt, etc. to the foam surface. It has advantages such as no adhesion of silicone compounds to the human body or clothing, and no deterioration of the appearance of the foam surface.

Therefore, the assembly of the present invention is suitable for use as a foam with lower pollution properties in cushions for building materials, interior wall cushions for automobiles, packaging sheets, and the like.

Example Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Ethylene-vinyl acetate copolymer with a melt index of 15 and a vinyl acetate content of 20% by weight (manufactured by Nihon Yunika Ichi Co., Ltd.) 1
00 parts by weight, viscosity at 23°C is 300. 00
0 cs, 100 parts by weight of silicone gum stock (manufactured by Nippon Unica Ichi) with a methyl vinyl silicone content of 1.0% by weight, 1 part by weight of 1.13-tetradecadiene, 0.05 part by weight of dicumyl peroxide, and Irganox 101.
A reaction product was obtained by kneading 0.05 parts by weight of 0.0 (manufactured by Ciba Geigy, antioxidant) at 100° C. for 10 minutes using a Brabender blastograph, and then kneading at 170° C. for 20 minutes.

Ethylene-vinyl acetate copolymer with a melt index of 20 and a vinyl acetate content of 28% by weight (manufactured by Nippon Unicar Co., Ltd.) 1
00 parts by weight, 4 parts by weight of the azodicarbonamide foaming agent "Celmic CAPJ (foaming temperature: 130°C, manufactured by Nisankyo Kasho Co., Ltd.), 1 weight of dicumyl peroxide (decomposition temperature: 150°C, manufactured by NOF Corporation) 5 parts by weight of ethylene resin, vinyl group-containing silicone, and diene-containing hydrocarbon reactant were kneaded for 40 minutes in a roll mill at 70°C to form pellets. A sheet with a thickness of 2 mm was prepared.The pressure and time were 100h9/cm'' and 5 minutes, respectively. When this sheet was placed on a polyester sheet and placed in an oven at 180°C, it foamed uniformly in 5 minutes. When this foam was taken out and allowed to cool to room temperature, a foam with a thickness of 0.7 mm, a bubble size of 0.09 mm and a bubble size of 0.02 mm, and a pleasant texture and no oozing was obtained.

Comparative Example 1 Same as Example 1 except that the ethylene resin-vinyl group-containing silicone-diene-containing hydrocarbon reactant was replaced with a viscosity of 1.
When a combination of 5 parts by weight of 000cs silicone oil and 1 part by weight of triallyl cyanurate was used, a foam with oozing on the surface was obtained.

Example 2 100 parts by weight of an ethylene-ethyl acrylate copolymer (manufactured by Nippon Unica Co., Ltd.) with a melt index of 20 and an ethyl acrylate content of 35% by weight, a viscosity of 30 at 23°C
0,000 cs, methyl vinyl silicone content 1
．． 100 parts by weight of 0% silicone gum stock (manufactured by Nihon Unica Co., Ltd.), 1 part by weight of 1.13-tetradecadiene, 0.05 parts by weight of dicumyl peroxide, and Irgano 7X 1010 (manufactured by Ciba Geigy, antioxidant). )0
．． 05 parts by weight with Brabender blast graph, 120
After kneading at 180°C for 10 minutes, the mixture was kneaded at 180°C for 15 minutes to obtain a reaction product.

Melt Indesox 20 and 100 parts by weight of ethylene-ethyl acrylate copolymer (manufactured by Nippon Unicar Co., Ltd.) containing 20% by weight of ethyl acrylate were mixed with azodicarbonamide foaming agent "Celmic CAPJ (foaming temperature: 130°C). (manufactured by Kyokai Co., Ltd.) 4M parts, dicumyl peroxide (decomposition temperature 150'C, manufactured by NOF Corporation) ■ parts by weight, 5 parts by weight of ethylene resin-vinyl group-containing silicone-diene-containing hydrocarbon reactant to 70 parts by weight The pellets were kneaded for 40 minutes in a roll mill at 80°C and made into a sheet with a thickness of 0.2 mm by compression method at 80°C.The pressure and time were IOO&g/cm', respectively, for 5 minutes. Place this sheet on top of the polyester sheet, and
When placed in the open air at 0°C, it foamed uniformly in 5 minutes.

When this foam was taken out and allowed to cool to room temperature, a foam without oozing was obtained.

Claims (1)

[Scope of Claims] 1 A crosslinkable foaming composition consisting of 100 parts by weight of an ethylene resin, 1 to 30 parts by weight of a blowing agent, and 0.2 to 10 parts by weight of an organic peroxide as a crosslinking agent is added with an ethylene resin-vinyl Group-containing silicone-diene-containing hydrocarbon reactant at least 0.
1 part by weight, and the 10-minute half-life temperature (Tp) of the organic peroxide and the foaming temperature (Tf) of the blowing agent satisfy the following formula -10°C≦Tp-Tf≦50°C. A composition for use in a low-contamination, open-cell, cross-linked ethylene-based resin foam, characterized in that 2 Ethylene resin - vinyl group-containing silicone - diene-containing hydrocarbon reactant is the following formula (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^1 in the formula is Aliphatic unsaturated group, R^2 is an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated group, 0<x
<1, 0.5<y<3, 1<x+y<3), 0.01 to 300 parts by weight of an organopolysiloxane represented by the following formula (B) CH_2=CH(CH_2)nCH=CH_2(B )(
A moldable resin composition consisting of 0.01 to 30 parts by weight of a hydrocarbon compound represented by the formula (n is an integer of 1 to 30) and 0.001 to 3 parts by weight of an organic peroxide is heated and kneaded. 2. The composition for a low-staining, open-cell, cross-linked ethylene resin foam according to claim 1, which is produced by the following steps. 3 The 10-minute half-life temperature (Tp) of organic peroxide is 100
〜220℃, and the foaming temperature (Tf) of the blowing agent is 90〜220℃.
3. The composition for a low-contamination, open-cell, crosslinked ethylene resin foam according to claim 1 or 2, wherein the temperature is 220°C.