JPH0321642A - Composition for crosslinked ethylene resin foam containing continual multiple open cells - Google Patents

Abstract

PURPOSE:To obtain the subject composition for cushioning material for buildings, and the like usable as a substitute for silicone compound and free from migration to the surface of foamed material and the deterioration of appearance by compounding a crosslinkable and foamable composition having a specific foaming temperature with a fluorine-based surfactant. CONSTITUTION:The objective composition can be produced by compounding (A) a crosslinkable and foamable composition composed of 100 pts.wt. of an ethylenic resin, 1-30 pts.wt. of a foaming agent and 0.2-10 pts.wt. of an organic peroxide and satisfying the formula (Tp is 10min half-life temperature of the organic peroxide; Tf is foaming temperature of the foaming agent) with (B) 0.1-5 pts.wt. of a fluorine-base surfactant (preferably a compound having perfluoroalkyl group and a surface tension of <=30 dyne/cm as 0.1% aqueous solution).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a composition for use in open-cell, crosslinked ethylene resin foam. More specifically, the present invention relates to a non-bleeding, open-cell crosslinked ethylene resin foam composition that can be applied to cushions for building materials, interior cushions for automobiles, packaging sheets, and the like.

Conventional technology Compositions for open-cell crosslinked ethylene resin foams containing silicone compounds have good air permeability, water absorption,
It is known that it has excellent weather resistance (Special Publication Act 1986
- No. 49657, Japanese Patent Application Laid-Open No. 63-113034), when open-cell foams produced from these composites are used as cushions for building materials, interior wall cushions for automobiles, packaging sheets, etc. Silicone compounds and the like often bleed onto the surface of the foam, 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 properties as the open-cell foam produced using such a conventional open-cell foam composition for cross-linked ethylene resin foam, but has the same characteristics as the conventional open-cell foam. Foaming that allows the production of open-cell crosslinked ethylene resin foams with excellent properties without the phenomenon of silicone compounds bleeding onto the foam surface, which is a disadvantage when using silicone compounds. It was created for the purpose of providing a body mask.

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 a number of compounds to find substitutes for silicone compounds. As a result, we found that the purpose could be achieved by using a fluorine-based surfactant instead of a silicone-based compound and by selecting a predetermined precept to satisfy a predetermined relational expression, and based on this knowledge, we The present invention has now been 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.
It is made by blending 0.1 to 5 parts by weight of a heptadium-based surfactant into a cross-linked foaming compound consisting of parts by weight of IO, and the 10-minute half-life temperature (Tp) of the organic peroxide and the blowing agent. Foaming temperature (
Tf) is the following formula - i o 'c≦Tp-Tf≦50
The object of the present invention is to provide a composite for an open-cell crosslinked ethylene resin foam, characterized in that these components are selected so as to satisfy the temperature.

The present invention will be explained in detail below.

The ethylene resin used in the present invention is an ethylene homopolymer, or ethylene and σ-olefins such as propylene, butene-L foamed monomethyl-pentene-1, hexene-1, octene-11 nonene-11 decene-11 tothecene-1, and vinyl esters. , unsaturated carboxylic acids, unsaturated carboxylic acid esters, etc., such as high-pressure low-density polyethylene, medium-low-pressure high-density, medium-density polyethylene, vapor-phase polyethylene, and ethylene. -propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and the like.

The organic peroxide used in the present invention has a decomposition temperature with a half-life of 10
100~220'C in minutes! The following are preferred, and examples of such materials include the following. However, the value in parentheses is the decomposition temperature (°C).

Succinic acid peroxide (110), penzoyl peroxide (110), t-butylperoxy-2-ethylhexanoate (113), p-chloropenzoyl peroxide (115), t-butylperoxyisobutyrate (115), t-Butyl peroquine isobutyl carbonate (135), t-butyl peroxylaurate (140), 2,5-dimethyl-2,5-di(penzoylberoxy)hexane (140), t-butyl peroxyacetate-1-(140), di-L-butyldiberoxy-7-thale} (140), t-butynoleperoxymaleic acid (140), cyclohexanone peroxide (
145), t-butylberoxybenzoate (l45)
), dicumyl peroxide (150), 2,5-dimethyl-2,5-di(L-butylberoxy)hexane (1
55), t-butylcumyl peroxide (155), t
-butyl hydroperoxide (158), di-t-butyl peroxide (160), 2.5-dimethyl-2.5
-di(L-butylberoxy)hexyne-3 (170)
, diisopropylbenzene hydroperoxide (17
0), p-menthane hydroperoxide (180), 2
．． 5-dimethylhexane-2,5-dihydroberoxide (213).

The foaming agent used in the present invention preferably has a foaming temperature of 90 to 220°C, examples of which include azobisisobutyronitrile, diazocarbonamide, p-
+-Luenesulfonylhydrazide, 4.4'-oxybis(benzenesulfonylhydrazide), n-hebutane,
Examples include n-octane, n-nonene, and n-decane. 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 ip, 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 -lO℃≦'rp-''rr≦50℃.In other words, by using such a combination, the combination By heating the material 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 must be 0.2 to 10 parts by weight. If this amount is less than 0.2 parts by weight, the viscosity of the resin layer will hardly increase when the composition is heated, and the resin layer will become flattened, and if it is more than 10 parts by weight, the improvement in crosslinking efficiency will be small. I can't escape it.

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 fluorine-based surfactant used in the present invention usually has both a perfluoroalkyl group and a parent group, and preferably has a surface tension of 30 dyne/cm or less. General formula RfOH,
RfO(CnH2nO). H, Rf(CHz)-
08, Rf(CHt) 0RfOH, Rf-O). H
, Rf(CHz). COOH, RfAN(R'XC
J40). H. RfCOOM, RfAN(R')CH
, COOM. RfAN(R')C,H40SO,M,
RfSOJ, RfAN(R'XCHz). OP(OH)
)z, ■ 0 RfANH(C2Ha)N O (CH3)!・I
o, RfANH(CzH4)NO(R')zcJ4c
Oo O (Rf in the formula is a fluorinated aliphatic group or fluorinated aromatic group having 5 to 20 carbon atoms, A is a divalent linking group, R' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, M is a hydrogen atom or an alkali metal, and 4, m, and n are integers of 1 to 50.

Specific examples of the fluorosurfactant of the present invention include CyF
+s(CH2)scOONa, CaF+y(CHz)
scOOK, CaF+ySOz-N(C2H5)C2
H40PO(OH)2, C8F l 7SO2N(C2
s)CHzCOOK1CaF+ySOzN(CzHs
)CzH<OSOsH, CaFrrSOzN(CJs
)-(C2HaO)++H, CaFryCONHCJ
a position CH3)!・Ho,C,F+s-COONa,
CaF+, COOLi%C*F+, CONH(C2H.
O), H1C, F. , CONI {C Yamahachi CHI) 2
C Mountain CooO, CsF r scOONH CJ I
7CONH (CH2) scOONH+, CsF +
scONH(CHs)C2Ha-COONa, etc. can be mentioned.

Commercially available fluorosurfactants having a barfluoroalkyl group as described above include, for example, Unidyne DS401 (surface tension 17.4) manufactured by Daikin Industries, Ltd. and Unidyne DS4 manufactured by Daikin Industries, Ltd.
03 (surface tension 17.2), DS451 (surface tension 2
6.4) is desirable; other examples include Surflon S-Ill S-113, S-121, and S-Ill manufactured by Asahi Glass Co., Ltd.
-13L S-132, S-141, S-145
, Asahi Guard AG7 10, Dainippon Ink & Chemicals Megafac F-141, F-142, F-142
- D, F-143, F-144, F-1440
, F-528, F-170, F-171 F-1
72, F-173, F-177, F-183, F-184, Florado FC-43 manufactured by Sumitomo 3M
0, FC-431 F-top EF30 manufactured by Shin-Akita Kabosha
1, EF-303, EF-352, B. M-Che
mie BM-1000, 1100% Schwe
Examples include Schwego-Fluor manufactured by Gmann.

If the surface tension of the 1% aqueous solution of the fluorosurfactant of the present invention is 3 Q dyne/Cal+ or more, bubbles with a uniform fine structure cannot be obtained, which is not desirable.

The amount of the fluorosurfactant used in the present invention needs to be 0.1 to 5 parts by weight. If the amount is less than 0.1, it will not be possible to obtain bubbles with a uniform fine structure, and if it is more than 5 parts by weight, little improvement in the effect can be expected, and the surface may develop stickiness, which is undesirable. .

The fluorosurfactant of the present invention may be used alone, or
Two or more types may be used in combination.

In the present invention, an open-cell foam can be obtained even when silicone oil or a silicone block copolymer is used in combination.

In addition to the above-mentioned essential components, the composite of the present invention may optionally contain various additives conventionally used in composites for resin foams, as long as the purpose of the present invention is not impaired. For example, oxidation stabilizers, ultraviolet stabilizers, inorganic fillers, pigments, flame retardants, rubbers, etc. can be blended as optional ingredients.

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 pure product has a half-life of 10 minutes, crosslinking proceeds even below this temperature.

Effects of the Invention The composite of the present invention provides an open-cell crosslinked ethylene resin foam, and the resulting foam has no disadvantages when using conventional silicone compounds. There is no oozing phenomenon of silicone-based compounds onto the foam surface, and therefore there is no adsorption of dust, dirt, etc. to the foam surface, and there is no adhesion of silicone-based compounds to the human body or clothing, and the appearance of the foam surface. It has advantages such as no deterioration.

Therefore, the composite 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 A blowing agent "Celmic CA" was added to 100 parts by weight of ultra-low density polyethylene DFDA-1 137 (manufactured by Union Carbide) having a melt index of 1 and a density of 0.906.
10 parts by weight of P500J (foaming temperature: 150°C, manufactured by Nisankyo Kasho Co., Ltd.), 1 part by weight of crosslinking agent "Percumil P" (50% product of diisoglopylbenzene hydroperoxide: manufactured by NOF Corporation)
Parts by weight, Unidyne DS-401 (manufactured by Daikin Industries)
3 parts by weight and 0.02 parts by weight of Irganox 1076 (manufactured by Ciba Geigy, antioxidant) were kneaded in a Banbury mixer at 120°C for 20 minutes, and the mixture was pelletized. The pellets were molded into 0.2 m by compression molding method at 130℃.
It was made into a sheet with a thickness of m. Pressure and time are each 10
0k97 cm2 for 5 minutes. This sheet was placed on a polyester sheet and placed in an oven at 210'C, whereupon it foamed uniformly in 5 minutes.

When this foam was taken out and allowed to cool to room temperature, a non-oozing foam with a thickness of 1.5 mm was obtained. A
The open cell ratio of this foam was measured using STM D-2856 and was found to be 88%.

Comparative Example 1 In the same manner as in Example 1, silicone oil with a viscosity of 100 cs was used instead of Unidyne DS-401, and a foam with oozing on the surface was obtained.

Example 2 High-pressure polyethylene DFD-0405 (manufactured by Nippon Unicar Co., Ltd.) with a melt index of 20 and a density of 0.924 10
0 parts by weight, foaming agent "Celmic CAP500J (
Sankyo Kaoru Co., Ltd.) 10 parts by weight, crosslinking agent "Perc Mill P" (
1 part by weight of Unidyne DS-401 (manufactured by Daikin Industries, Ltd.) and Irganox 1076
(manufactured by Ciba Geigy, antioxidant) 0.02 parts by weight was kneaded at 120'C for 20 minutes using a Banparee mixer and pelletized. This pellet was made into a sheet with a thickness of 0.2 mm by a compression molding method at 130°C. The pressure and time were 100#g/cm'' and 5 minutes, respectively.

Place this sheet on top of the polyester sheet and
When placed in oven 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 1.5 mrn and no oozing was obtained. The open cell rate of this foam was measured according to ASTM D-2856 and was found to be 81%.

Example 3 Fluorosurfactant of Example 1 (Unidyne DS401
) instead of Surflon S-145 (manufactured by Asahi Glass Co., Ltd.).
The open cell rate was 83% in the same manner as in Example 1, except that a nonionic, per7-fluoroalkyl EO adduct was used.
A foam with no oozing was obtained. Example 4 The seven elemental surfactant of Example 2 (Unidyne DS40
The same procedure as in Example 2 was used except that Surflon S-121 (manufactured by Asahi Glass Co., Ltd., cationic, barfluoroalkyltrimethylammonium salt) was used in place of 1), with an open cell rate of 85% and no oozing. A foam was obtained.

Example 5 Surflon S was used in place of the 77 element surfactant in Example 1.
A non-bleeding foam with an open cell ratio of 86% was obtained in the same manner as in Example 1, except that -113 (manufactured by Asahi Glass Co., Ltd., anionic, perfluoroalkyl carginate) was used.

Example 6 Sur7ron S was used instead of the fluorosurfactant of Example 2.
A non-bleeding foam with an open cell ratio of 82% was obtained in the same manner as in Example 2, except that - 131 (manufactured by Asahi Glass Co., Ltd., amphoteric, barfluoroalkyl betaine) was used.

Claims (1)

[Scope of Claims] 1. A crosslinking and 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, and a fluorosurfactant 0.1~5
parts 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 open-cell crosslinked ethylene resin foam, characterized by comprising selected components. 2 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℃.
2. The composition for open-cell crosslinked ethylene resin foam according to claim 1, wherein the temperature is 220°C. 3. The fluorine-based surfactant has a perfluoroalkyl group, and the surface tension of its 0.1% aqueous solution is 30 dyne.
3. The composition for an open-cell crosslinked ethylene resin foam according to claim 1 or 2, wherein the composition has a particle size of 1 cm or less. 4 Fluorine surfactants have the general formula RfOH, Rf-O(CnH_2nO)mH, Rf(C
H_2)nOH, Rf(CH_2)O(CnH_2nO
)mH, Rf(CH_2)nCOOH, RfAN(R'
)(C_2H_4O)nH, RfCOOM, RfAN(
R')CH_2COOM, RfAN(R')C_2H_
4OSO_3M, RfSO_3M, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ RfANH(C_2H_4)N■(CH_3)_3・I
■、RfANH(C_2H_4)N■(R')_2C_
2H_4COO■ (Rf in the formula is a fluorinated aliphatic group or fluorinated aromatic group having 5 to 20 carbon atoms, A is a divalent linking group, R' is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, M is a hydrogen atom or an alkali metal, and l, m, and n are integers of 1 to 50. The composition for an open-cell crosslinked ethylene resin foam according to claim 1, 2, or 3.