JPH0535736B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing an ethylene resin open-cell foam sheet. More specifically, after irradiating a foamable composition sheet consisting of an ethylene resin, a blowing agent, and a silicone block copolymer with ionizing radiation, the ethylene resin open-cell foam sheet is heated to a temperature higher than the decomposition temperature of the blowing agent. Relating to a method of manufacturing. The ethylene resin foam produced by the method of the present invention has air permeability, water absorption, and weather resistance, and since it is an open cell type, it is softer than a closed cell type, and has a good texture.
It is a foam with an excellent texture, and its production method is characterized by the fact that an open-cell foam can be obtained by irradiation with ionizing radiation and subsequent heating, and the foam can be ruptured by applying pressure. No process required. This foam is used for cushions, pillows, mats, winter clothing,
Used as a cushioning material, heat insulating material, sound absorbing material, or material for carpet lining, balls, toys, supporters, filters, etc. Currently, foams made of ethylene resin are used as insulation materials,
Although they are used in large quantities for packaging materials, cushioning materials, etc., most of them are closed-cell foams and are not used for applications that require water absorption, breathability, etc. Although some open-cell foams with air permeability can be found, they are limited to those with large cell diameters, rough texture, poor texture, and low commercial value. On the other hand, rubber or polyurethane open-cell foams are rapidly degraded by ultraviolet rays or ozone. Conventional open-cell foams made of ethylene resin are produced by first manufacturing closed-cell foams and then heating and expanding them. Causes "sagging",
There is no elasticity, it is difficult to break the bubbles uniformly, and the bubble diameter is large. In order to solve this problem, a method was developed in which closed cells were first molded and then broken by pressure, but the process was two-step, the resulting foam was thinner, and the cells became open. However, the bubble membranes overlap and cannot be said to have good water absorption or air permeability. In order to improve this problem, Japanese Patent Publication No. 47-31695 proposes a method in which the closed-cell foam is first cooled to a temperature near or below the glass transition temperature, and then compressed to destroy the cell membrane. Although this method has been proposed, in the case of polyethylene, it is necessary to cool it with an expensive refrigerant such as liquid nitrogen, and the equipment becomes expensive. On the other hand, Japanese Patent Publication No. 55-42100 proposed a one-step pressurizing and hot-pressing method in which polyethylene is mixed with a crosslinking agent in a considerable amount of amorphous polypropylene as a method for obtaining open-cell polyethylene foam in a one-step process. However, in this method, it is said that it is preferable to mix 30 to 50% by weight of amorphous polypropylene, and if it is less than 20% by weight, the open cell ratio will be low. Amorphous polypropylene is a by-product during the production of crystalline polypropylene, and it has no use value and has been discarded, so it makes sense to utilize it, but on the other hand, amorphous polypropylene is sticky even at room temperature. It is a clay-like substance that uses the properties of clay, and it is difficult to make molded products by itself, and it has traditionally been added in small amounts as an extender to low-cost foams, as disclosed in this patent. Mixing in large quantities will adversely affect the mechanical properties and feel of the foam. The technical content of Japanese Patent Publication No. 54-63172 is to disperse and mix 30 to 300 parts by weight of inorganic powder with 100 parts by weight of polyolefin resin, foam it to form a closed-cell foam, and then deform it to break the foam. It is characterized by Moreover, in this method, it is said that the communication of air bubbles is made even more effective by subjecting the inorganic powder to a surface treatment that actively reduces the adhesive force between the inorganic material interface and the polymer. In other words, this foam requires mixing a large amount of inorganic material simply to break the foam. It is easy to imagine that the presence of the inorganic substance causes the mechanical properties and tactile sensation of the foam to be different from those of the original polyethylene foam. More importantly, it shows how difficult it is to produce open-cell foams from polyolefins. The inventors of the present application have made extensive studies to solve the many problems contained in these prior art technologies, and have found that (a) there is no need to use a separate process to break the bubbles, and (b) a large amount of additives can be used. Therefore, a method for producing an open-cell ethylene resin foam that does not lose the characteristics of the ethylene resin itself and has excellent water absorption, weather resistance, and texture (c) by adding a small amount of silicone block copolymer, This was made possible by the ionizing radiation irradiation method. Conventionally, as a manufacturing method for thermoplastic resin foam sheets, a thermoplastic resin sheet mixed with a blowing agent is irradiated with ionizing radiation to crosslink the resin sheet, and then the resin is heated to a temperature higher than the decomposition temperature of the blowing agent. Methods of foaming sheets are known. However, most of the resin foam sheets obtained by the above method have a closed cell ratio of 95%.
The above is a so-called closed cell foam sheet,
Due to its properties such as almost no water absorption, low air permeability, high elastic modulus, and poor flexibility, its uses have sometimes been limited. The present inventors irradiated a foamable composition sheet consisting of an ethylene resin, a foaming agent, and a silicone block copolymer with ionizing radiation, and then heated the foaming agent to a temperature higher than its decomposition temperature to foam the foamable sheet. A method for producing a foam sheet with an open cell ratio of 5 to 85%, characterized in that the sheet is irradiated with ionizing radiation so that the gel content of the substantially crosslinked portions of the sheet is 40 to 70%. I found a way. According to the present invention, it is possible to obtain an open-cell foam that is water-absorbent, breathable, and highly flexible. That is, by irradiating an ethylene resin foamable composition sheet with ionizing radiation and crosslinking the sheet to a gel content of 70% or less, the fluidity of the foamable sheet during heating can be moderately suppressed. ,and,
Due to the effect of the appropriate lipophilic balance of the silicone block copolymer, when the blowing agent is decomposed by heating and foaming occurs, some of the cells burst and the cells become open-celled. However, if an ethylene resin foamable composition sheet is irradiated with ionizing radiation and the gel content of the crosslinked portion of the sheet exceeds 70%, the expansion ratio will decrease when the sheet is heated and foamed. This results in a low foam structure, almost no open-cell foam, little water absorption, and reduced flexibility. On the other hand, when the gel content is low, it becomes an open cell foam. However, if the gel content is less than 40%, when the sheet is heated and foamed, the sheet may be greatly deformed due to resin flow, and the heat resistance of the foam may be reduced. There are some things that may be undesirable. The ethylene resin used in the present invention is a polymer whose main component is ethylene, such as high-pressure polyethylene, low-pressure low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer,
Refers to ethylene-alkyl acrylate copolymer, ethylene-α-olefin copolymer, and others. The foaming agent used in the present invention preferably has a foaming temperature of 90°C or higher. The decomposition temperature can also be adjusted by using a promoter or an auxiliary agent.
Examples include: Azobisisobutyronitrile, cyazocarbonamide (with auxiliary agent), P-toluenesulfonyl hydrazide (with auxiliary agent), 4,4'-oxybis(benzenesulfonyl hydrazide) (with auxiliary agent), m-heptane, n -Octane, n-nonane, n-decane. The silicone block copolymer used in the present invention has the general formula or ₍ In _the above _formula , _R is a monovalent hydrocarbon group, , P is 0 or 1 Y is (C _o H _2o O) _t -R' m is 0 to 300 n is 2 to 10 s is 1 to 30 q is 1 to 300 t is 1 to 100 Here, (C _o H _2o O) is an oxyalkylene group or a mixture of such groups. The ratio of each component of the foamable composition of the present invention is shown below. The blowing agent is based on 100 parts by weight of ethylene resin.
1 to 30 parts by weight are required. If it is less than 1 part by weight, there is almost no foaming effect.
If the amount is more than 30 parts by weight, the amount of foaming agent decomposition products wastefully escaping into the atmosphere during foaming increases, resulting in poor efficiency. The amount of silicone block copolymer ranges from 0.1 to
5 parts by weight are required. If it is less than 0.1 parts by weight, it will not be effective in providing cells with a uniform fine structure, and if it is more than 5 parts by weight, it will bleed out significantly, adversely affecting the physical properties of the foam, and will not work effectively. In the present invention, the composition may optionally include oxidation stabilizers, ultraviolet stabilizers, inorganic fillers, pigments, flame retardants, plasticizers, other additives, or other resins,
Rubbers and the like can be added. In the present invention, the method of irradiating the foamable sheet with ionizing radiation is a known method. In the present invention, the temperature at which the crosslinked foamable sheet is heated is at least the temperature necessary for foaming, and specifically is between about 120 and 250°C. In the present invention, the structure is fixed by cooling the foam after heating. The cooling temperature is preferably 50℃ or less. Heating methods include heating gas such as electricity, direct or indirect contact with heated metals such as iron or aluminum, external heating using infrared rays, burners, electric heat, etc., as well as internal heating such as high frequency heating. . Furthermore, depending on the purpose, it may be heated under normal pressure.
Heating under pressure is also possible. The present invention will be explained below with reference to Examples.
The physical properties of the foam were measured as follows. Gel content: The foam (weight Wa grams) was covered with a 325 mesh wire mesh (weight Wb grams) and subjected to Soxhlet extraction with toluene for 3 hours. (Weight Wc grams). The gel content x was calculated using the following formula. x (wt.%) = 100 (Wc - Wb) / Wa Apparent density; according to JISK6767. Average bubble diameter: According to JISK6402. Open cell rate: Based on ASTMD-2856. Maximum water absorption: After vacuum drying a 50 mm x 50 mm square foam at 50° C. for 5 hours, its dimensions (volume V) and weight (Wd) were measured. This foam is immersed in water, compressed and decompressed repeatedly with fingers until the gas in the foam is replaced with water as much as possible, then taken out of the water, wiped the surface with gauze, and then Weighed (Weight We grams). The maximum water absorption amount Qmax was calculated using the following formula. Qmax (g/cm ³ )=(We-Wd)/V Example 1 Auxiliary agent is added to 100 parts of ethylene-vinyl acetate copolymer (manufactured by Nippon Unicar) with a melt index of 20 and a vinyl acetate component of 28% by weight. 10 parts of azodicarbonamide “Cellmic CAP149” (foaming temperature 125°C; manufactured by Sankyo Kasei), silicone block copolymer represented by formula (a) (manufactured by Nippon Unicar; 1300CS)
One part was kneaded in a Banbury mixer at 80°C for 5 minutes and then pelletized. (CH ₃ )Si[O{(CH ₃ ) ₂ SiO} ₃ (C ₂ H ₄ O) ₂₀ (C ₃ H ₆ O) _2
5 C ₄ H ₉ 〕 ₃ (a) This pellet was compression molded into a sheet with a thickness of 1 mm and then subjected to electron beam irradiation equipment manufactured by Nissin High Voltage.
Electron beams of 2, 4, 6, and 10 Mrad were irradiated in air using ESP-750 (acceleration voltage 750 kV), respectively. Cut this irradiation sheet into 5 cm x 5 cm squares, secure the top with a clip, and hang it in a heated oven.
After heating for 4 minutes, it was taken out and allowed to cool, and the following foam was obtained.

[Table] Example 2 Melt index 20, ethyl acrylate component
For 100 parts of 20% by weight ethylene-ethyl acrylate copolymer (manufactured by Nippon Unicar), 10 parts of azodicarbonamide foaming agent "Cellmic CAP124" (foaming temperature 130°C; manufactured by Sankyo Kasei), (b) 1.5 parts of silicone block copolymer (manufactured by Nippon Unicar; 500CS) represented by the formula was heated at 80°C in a Banbury mixer.
After kneading for 5 minutes, the mixture was pelletized. (CH ₃ )Si[O{(CH ₃ ) ₂ SiO} ₄ (C ₂ H ₄ O) ₁₅ C ₄ H ₉ ] ₃
(b) This pellet was compression molded into a 1 mm thick sheet and then placed in an electron beam irradiation device manufactured by Nissin High Voltage.
Electron beams of 2, 4, 6, and 10 Mrad were irradiated in air using ESP-750 (acceleration voltage 750 kV), respectively. This irradiated sheet was cut into 5 cm x 5 cm squares, placed on an aluminum plate, heated in a heating oven for 5 minutes, then taken out and allowed to cool, yielding the following foam.

[Table] Comparative Example 1 A sheet was formed in the same manner as in Example 1 without adding silicone block copolymer, and irradiated with an electron beam of 6 Mrad. This irradiated sheet was cut into 5 cm x 5 cm squares, the upper part was fixed with a clip, and the sheets were hung in a heating oven. After heating for 4 minutes, they were taken out and allowed to stand. As a result, closed-cell foaming with a maximum water absorption of <0.01 g/cm ³ was found. I got a body.

Claims (1)

[Claims] 1. 100 parts by weight of ethylene resin, 1 to 30 parts by weight of blowing agent, and general formula or ₍ In _the above _formula , R _is a monovalent hydrocarbon group, group, P is 0 or 1 Y is (C _o H _2o O) _t −R' m is 0 to 300 n is 2 to 10 s is 1 to 30 q is 1 to 300 t is 1 to 100 In addition, here ( C _o H _2o O) is an oxyalkylene radical or a mixture of such radicals).
A foamable composition sheet consisting of 0.1 to 5 parts by weight,
In the method of foaming the foamable sheet by irradiating it with ionizing radiation and then heating it to a temperature higher than the decomposition temperature of the foaming agent, the gel content of the substantially crosslinked portions of the sheet is adjusted to be 40 to 70%. Open cell ratio 5 to 85 characterized by irradiating ionizing radiation to
% foam sheet manufacturing method.