KR20040016454A - Composition and uses thereof - Google Patents

Abstract

PURPOSE: A composition, a foam obtained by using the composition, a laminate containing the foam, its preparation method, and shoes and shoes part prepared from the foam or the laminate are provided, to obtain a foam or a laminate having Asker C hardness of 20-80, low specific viscosity, low compression set, and excellent tear strength, impact resilience and formability. CONSTITUTION: The composition comprises an ethylene-α-olefin copolymer which comprises 5-95 wt% of an ethylene-α-olefin copolymer having a density of 0.880-0.900 g/cm¬3 and a melt flow index of 0.1-50 g/10 min (ASTM D 1238, 190 deg.C, load of 2.16 kg) and 5-95 wt% of an ethylene-α-olefin copolymer having a density of 0.900-0.930 g/cm¬3, a melt flow index of 0.1-50 g/10 min (ASTM D 1238, 190 deg.C, load of 2.16 kg) and a main melting point peak at a position of 110 deg.C or less; and a foaming agent. Preferably both the ethylene-α-olefin copolymers are an ethylene-1-butene copolymer. The laminate comprises a foam formed by heating the composition; and a layer formed by using at least one material selected from the group consisting of polyolefin, polyurethane, rubber, leather and artificial leather.

Description

Composition and Uses thereof {COMPOSITION AND USES THEREOF}

The present invention relates to a composition and its use. More specifically, the present invention has an Asker C hardness of 20 to 80, low specific gravity, low compression set (CS), excellent tear strength A composition and foams thereof which can provide foams (uncrosslinked or crosslinked foams) with properties, good resilience and good moldability.

Techniques using crosslinked foamed products to obtain resins with low specific gravity, i.e. light weight, softness and high mechanical strength, include automotive interiors such as architectural interior or exterior materials, automotive interiors, door glass run channels, It is widely used for packaging materials and daily necessities. This is because only foaming the resin in order to obtain light weight results in a decrease in the mechanical strength of the resin, but molecular chain bonding through the crosslinking reaction of the resin can obtain the light weight of the resin by foaming while preventing a decrease in the mechanical strength. Because it is.

In addition, for footwear and footwear parts such as soles of sneakers (primarily midsoles), cross-linked foams of resins are used, which are lightweight, prevent deformation by long-term use, and withstand harsh use conditions. This is because a material having mechanical strength and resilience is required.

For shoe soles, crosslinked foams of ethylene / vinylacetate copolymers have conventionally been used, which is well known. The crosslinked foams obtained by the use of ethylene / vinylacetate copolymers have high specific gravity and high compression set so that the soles are heavy when they are used as soles, and the soles are compressed when used for long periods of time, thus losing mechanical strength such as resilience. There is a problem.

International Patent Publication No. 501147/1997 and Japanese Patent Publication No. 206406/1999 disclose inventions relating to crosslinked foams using ethylene / α-olefin copolymers and mixtures of ethylene / vinylacetate copolymers and ethylene / α-olefin copolymers. An invention relating to a crosslinked foam using is described. However, in the case of the above invention, low specific gravity and compression set are improved, but satisfactory performance is not obtained.

Japanese Patent Laid-Open No. 344924/2000 filed by the present inventors has a high expansion ratio, no surface roughness caused by defoaming, soft feel, low compression set, excellent tear strength characteristics, and excellent An olefin elastomer crosslinked foam having heat resistance and an elastomer composition for the crosslinked foam are disclosed. In other words, the crosslinked foam is an ethylene / α-olefin copolymer (A) and an organic peroxide (B) having a density of 0.88 to 0.92 g / cm 3 and a melt flow rate (190 ° C.) of 0.1 to 10 g / 10 minutes. And an olefin elastomer composition comprising a crosslinking aid (C) and a blowing agent (D). The ethylene / α-olefin copolymer (A) is an ethylene / α-olefin copolymer (A1 ′) having a density of 0.88 g / cm 3 or more and 0.90 g / cm 3 or less and a melt flow rate (190 ° C.) of 0.1 to 50 g / 10 minutes. 5 to 95 parts by weight, an ethylene / α-olefin copolymer (A2 ') having a density of 0.90 to 0.93 g / cm 3 and a melt flow rate (190 ° C.) of 0.1 to 50 g / 10 min. The sum of (A1 ') and (A2') is 100 parts by weight, and the mixture of the ethylene / α-olefin copolymer (A1 ') and (A2') has a melt flow rate of 190 to 10 g / 10 minutes (190 DEG C). Has In this invention, ethylene / a-olefin copolymers (A2 ') having a relatively high density are blended to ensure the hardness required for the resulting crosslinked foam, for example the hardness required for footwear. The hardness required for footwear can not be ensured alone with a relatively low density of ethylene / α-olefin copolymer (A1 ′) alone, and the resulting crosslinked foams are not satisfactory for footwear.

However, the ethylene / α-olefin copolymer (A2 ') also has a problem. That is, the copolymer (A2 ') for increasing the surface hardness of the resulting crosslinked foam is likely to have a higher melting point compared with the ethylene / α-olefin copolymer (A1'), and the kneading operation becomes difficult. More specifically, the copolymer (A2 ') does not require high energy or mixing well in the kneading process, and in extreme cases, the kneading apparatus is destroyed. In the case of containing a high melting point component in a conventional composition, the above kneading problem is solved by raising the kneading temperature, but in the case of a foamable composition, the kneading operation is performed because the elevated kneading temperature decomposes the blowing agent and / or the crosslinking agent. It is necessary to carry out at temperature lower than predetermined temperature (usually 100 degrees C or less).

The present inventors have diligently studied to solve the above-mentioned problems of kneading. As a result, instead of the above ethylene / α-olefin copolymer (A2 '), the density is 0.900 to 0.930 g / cm 3, and the melt flow rate (ASTM D 1238 , 190 ° C., 2.16 kg load) of 0.1 to 50 g / 10 minutes, and the main melting point peak adopts an ethylene / α-olefin copolymer (A2) of 110 ° C. or less, which makes kneading easier and more footwear. It has been found that a crosslinked foam having a sufficient hardness for the foam can be obtained, and in particular when both of the above-mentioned ethylene / α-olefin copolymers (A1) and (A2) are contained in the composition of the foam, It has been found that good interlayer adhesion strength of layers and laminates of layers of one or more materials selected from the group consisting of polyolefins, polyurethanes, rubbers, leathers and artificial leathers can be obtained. Based on the above findings, the present invention has been completed.

The present invention is to solve the above problems associated with the prior art described above, the object of the present invention is 20 to 80 asker C hardness, low specific gravity, low compression set (CS), excellent tear strength properties, excellent repulsion It is to provide a composition capable of providing a foam (uncrosslinked or crosslinked foam) having elasticity and good moldability, a foam thereof and a laminate having excellent interlayer adhesive strength using the foam.

It is a further object of the present invention to provide parts of footwear such as shoe soles, midsoles of shoes, inner soles of shoes and sandals made of the foams or laminates.

1 is a graph showing a change in torque (torque) according to the kneading time of the composition of Example 1 and Comparative Example 1, respectively.

2 is a schematic perspective view showing a secondary compression mold having an engraved side used in Example 1 and Comparative Example 1 to evaluate the formability of the foam.

The composition according to the invention is a composition comprising an ethylene / α-olefin copolymer (A) and a blowing agent (B), wherein the ethylene / α-olefin copolymer (A) is

Ethylene / α-olefin copolymer (A1) 5 to 95 having a density of 0.880 g / cm 3 or more and 0.900 g / cm 3 or less and a melt flow rate (ASTM D 1238, 190 ° C., load 2.16 kg) of 0.1 to 50 g / 10 min. Parts by weight; And,

Ethylene / density of 0.900 g / cm 3 to 0.930 g / cm 3, melt flow rate (ASTM D 1238, 190 ° C., 2.16 kg load) of 0.1 to 50 g / 10 min, and main melting point peak of 110 ° C. or less 5 to 95 parts by weight of the α-olefin copolymer (A2) (in this case, the sum of the components (A1) and (A2) is 100 parts by weight).

The foam obtained from the composition has sufficient hardness for foam for footwear.

In the present invention, it is particularly preferable that both the ethylene / α-olefin copolymers (A1) and (A2) are ethylene / 1-butene copolymers.

In the present invention, at least one of the ethylene / α-olefin copolymers (A1) and (A2) preferably has the following properties:

Melt flow rate measured according to ASTM D 1238 at a temperature of 190 ° C. and a load condition of 10 kg, for a melt flow rate measured according to ASTM D 1238 under a temperature of 190 ° C. and a load of _2.16 kg. The ratio of MFR ₁₀ ) (MFR ₁₀ / MFR _2.16 )

Satisfies the relationship of MFR ₁₀ / MFR _2.16 ≧ 5.63; And,

The molecular weight distribution (M _w / M _n ) and the melt flow rate ratio

It satisfies the relationship M _w / M _n ≤ (MFR ₁₀ / MFR _2.16 )-4.63.

In addition, at least one of the ethylene / α-olefin copolymers (A1) and (A2) preferably has the following properties;

Melt flow rate measured according to ASTM D 1238 at a temperature of 190 ° C. and a load condition of 10 kg, for a melt flow rate measured according to ASTM D 1238 under a temperature of 190 ° C. and a load of _2.16 kg. The ratio of MFR ₁₀ ) (MFR ₁₀ / MFR _2.16 )

Satisfies the relationship of MFR ₁₀ / MFR _2.16 ≧ 5.63; And,

The molecular weight distribution (M _w / M _n ) and the melt flow rate ratio

M _w / M _n + 4.63 ≤ MFR ₁₀ / MFR _2.16 ≤ ₁₄ -2.9 Log (MER _2.16 ) Satisfied.

The ethylene / α-olefin copolymer (A) preferably has a density of 0.880 to 0.920 g / cm 3 and a melt flow rate (ASTM D 1238, 190 ° C., load of 2.16 kg) of 0.1 to 10 g / 10 minutes. .

In the composition of the present invention, the blowing agent (B) is usually selected from organic pyrolytic blowing agents, inorganic pyrolytic blowing agents, organic physical blowing agents and inorganic physical blowing agents.

The foam according to the invention is obtained by heat treatment of the above-mentioned composition of the invention.

The foam of the present invention may be a foam obtained by secondary compression of the foam.

The laminate according to the invention has a layer of the foam of the invention and a layer of at least one material selected from the group consisting of polyolefins, polyurethanes, rubbers, leathers and artificial leathers.

The method for producing a laminate according to the present invention comprises the steps of foaming the composition of the present invention and laminating the foam obtained by the above process with at least one material selected from the group consisting of polyolefin, polyurethane, rubber, leather and artificial leather. Is done.

Footwear and footwear parts according to the invention consist of the foam of the invention or the laminate of the invention.

The footwear part is for example a midsole, an inner sole or a shoe sole.

The composition according to the invention and its use are described in detail below.

The composition according to the invention comprises a specific ethylene / α-olefin copolymer (A), blowing agent (B) and, if necessary, an organic peroxide (C) and a crosslinking aid (D).

The foam according to the invention is obtained by foaming or crosslinking the composition. Examples of the crosslinking method include heat crosslinking and ionizing radiationcrosslinking. In the case of heat crosslinking, addition of an organic peroxide (C) and a crosslinking adjuvant (D) is necessary in a composition, and in the case of ionizing radiation crosslinking, you may add a crosslinking adjuvant (D).

Ethylene / α-olefin Copolymers (A)

The ethylene / α-olefin copolymer (A) used in the present invention includes the following ethylene / α-olefin copolymers (A1) and (A2).

The ethylene / α-olefin copolymer (A1) is an amorphous or low crystalline random or block copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, preferably 0.880 g / cm 3 or more and 0.900 g / cm 3 or less Soft ethylene with a density (ASTM D 1505), melt flow rate (MFR, ASTM D 1238, 190 ° C., 2.16 kg load) of 0.1 to 50 g / 10 minutes, preferably 0.5 to 20 g / 10 minutes / α-olefin copolymer.

Α-olefins copolymerized with ethylene are α-olefins having 3 to 20 carbon atoms, and examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1- Decene, 1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-nonadecene, 1-eicosene and 4-methyl-1-pentene. Among these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene and 1-octene are particularly preferable. These alpha -olefins are used individually or in combination of 2 or more types.

The ethylene / α-olefin copolymer (A1) preferably contains 85 to 95 mole percent of units derived from ethylene and 5 to 15 mole percent of units derived from α-olefins having 3 to 20 carbon atoms. It contains.

As will be described later, the composition of the ethylene / α-olefin copolymer (A1) or ethylene / α-olefin copolymer (A2) is usually ethylene / α-olefin air in 1 ml of hexachlorobutadiene in a 10 mm diameter test tube. The ¹³ C-NMR spectrum of the sample obtained by homogeneously dissolving about 200 mg of the coalesce was measured under the measurement conditions of 120 ° C measurement temperature, 25.05 MHz measurement frequency, 1500 kHz spectral width, 4.2 sec pulse repetition time and 6 μ sec pulse width. Determined by measuring.

The ethylene / α-olefin copolymer (A1) may contain units derived from other polymerizable monomers in addition to the above units within a range that is not detrimental to the object of the present invention.

Examples of ethylene / α-olefin copolymers (A1) include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / 1-butene copolymers, ethylene / propylene / ethylidenenorbornene copolymers, ethylene / 1-hexene copolymers and ethylene / 1-octene copolymers. Among these, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer and ethylene / 1-octene copolymer are preferably used, and ethylene / 1-butene copolymer is particularly preferably used. . Although these copolymers may be random or a block copolymer, a random copolymer is especially preferable.

Ethylene / α-copolymer (A1) is measured by an X-ray diffractometer and usually has a crystallinity of 40% or less, preferably 10 to 30%.

The ethylene / α-olefin copolymer (A1) can be produced by a conventionally known method using a vanadium catalyst, a titanium catalyst, a metallocene catalyst and the like.

Ethylene / α-olefin copolymers (A2) are usually low-crystalline random or block copolymers of ethylene and α-olefins having 3 to 20 carbon atoms, having a density of 0.900 to 0.930 g / cm 3, preferably 0.910 to 0.920 g / Cm 3, melt flow rate (MFR, ASTM D 1238, 190 ° C., load of 2.16 kg) is 0.1 to 50 g / 10 minutes, preferably 0.5 to 20 g / 10 minutes, and the main melting point peak is 110 It is a soft ethylene / alpha -olefin copolymer of not more than ℃.

Α-olefins copolymerized with ethylene are α-olefins having 3 to 20 carbon atoms, and examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1- Decene, 1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-nonadecene, 1-eicosene and 4-methyl-1-pentene. Among these, α-olefins having 3 to 10 carbon atoms are preferable, and propylene, 1-butene, 1-hexene, and 1-octene are preferable among them. Especially preferred is 1-butene. These alpha -olefins are used individually or in combination of 2 or more types.

The ethylene / α-olefin copolymer (A2) preferably contains 90 to 99 mole percent of units derived from ethylene and 1 to 10 mole percent of units derived from α-olefins having 3 to 20 carbon atoms. It contains.

The ethylene / α-olefin copolymer (A2) may contain units derived from other polymerizable monomers in addition to the above units within the scope of not detrimental to the object of the present invention.

Examples of ethylene / α-olefin copolymers (A2) include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / propylene / 1-butene copolymers, ethylene / propylene / ethylidene norbornene air Copolymer, ethylene / 1-hexene copolymer and ethylene / 1-octene copolymer. Among them, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer and ethylene / 1-octene copolymer are preferably used, and ethylene / 1-butene copolymer is particularly preferably used. do. Although these copolymers may be random or a block copolymer, a random copolymer is especially preferable.

The “melting point peak” is a differential scanning calorimeter (DSC) used to heat a sample placed on an aluminum pan to 200 ° C. at a rate of 50 ° C./min, then hold at 200 ° C. for 5 minutes and at a rate of 10 ° C./min. It refers to the largest peak among the endothermic peaks which appear in the endothermic curve of the copolymer when it cools to 40 degreeC and then heats to 150 degreeC at the speed of 10 degreeC / min again. When there are a plurality of endothermic peaks, the absolute values on the vertical axis expressed in unit W (energy / time) are compared, not the area of the peak, and the peak having the maximum value is the main melting point peak.

The surface hardness of the ethylene / α-olefin copolymer (A2) preferably has a range of 30 to 70 in Shore D hardness (ASTM D 2240). When using an ethylene / α-olefin copolymer (A2) having a Shore D hardness in the above range, it is possible to obtain a crosslinked foam having a preferred hardness for footwear.

The ethylene / α-olefin copolymer (A2) is measured by an X-ray diffractometer and usually has a crystallinity of 50% or less, preferably 15 to 40%.

The ethylene / α-olefin copolymer (A2) can be produced by a conventionally known method using a Ziegler catalyst, a metallocene catalyst and the like.

The ethylene / α-olefin copolymer (A2) is preferably an ethylene / α-olefin copolymer obtained by solution polymerization. By solution polymerization, the ethylene / α-olefin copolymer (A2) having a preferable melting point can be easily obtained. On the other hand, since the ethylene / α-olefin copolymer obtained by gas phase polymerization tends to have a plurality of melting point peaks, a part of the melting point peaks are likely to occur in a temperature range of 110 ° C or higher.

It is desired that at least one of the ethylene / α-olefin copolymers (A1) and (A2) have the following properties:

As measured in accordance with ASTM D 1238 under a load of 10kg and a temperature of 190 ℃ for a temperature and a melt flow rate (MFR _2.16) as measured according to ASTM D 1238 under a load of 2.16kg conditions of 190 ℃ melt flow rate (MFR ₁₀ ) Ratio (MFR ₁₀ / MFR _2.16 )

Satisfies the relationship of MFR ₁₀ / MFR _2.16 ≧ 5.63;

The molecular weight distribution (M _w / M _n ) and the melt flow rate ratio

M _w / M _n ≤ (MFR ₁₀ / MFR _2.16 )-4.63,

Preferably, the relationship of M _w / M _n +4.63 <MFR ₁₀ / MFR _2.16 ≤ 14-2.9 Log (MFR _2.16 ) is satisfied.

When the above relationship is satisfied, a composition capable of producing a foam (uncrosslinked foam, crosslinked foam) having a high foaming ratio, that is, a low specific gravity, a high elastic body property, excellent compression set resistance and excellent moldability can be obtained. have.

Molecular weight distribution (M _w / M _n ) is measured by the following method using Millipore GPC-150C.

A separation column of TSK GNH HT having a diameter of 72 mm and a length of 600 mm was used, and the column temperature was set at 140 ° C. The sample (concentration: 0.1% by weight, injection amount: 500 µl) uses ο-dichlorobenzene (manufactured by Wako Junyaku Kogyo Co., Ltd.) as a mobile phase and 0.025% by weight of BHT (manufactured by Takeda Chemical Co., Ltd.) as an antioxidant. Moving at a rate of 1.0 ml / min. As a detector, a differential refractometer was used. Standard polystyrene is, Mw <1,000 and Mw> was used Tosoh (week) for the first, the 1000≤Mw≤4 × 10 ⁶ Pressure Chemical (weeks) for the 4 × 10 ^6.

Under the condition that the sum of the components (A1) and (A2) is 100 parts by weight, the ethylene / α-olefin copolymer (A1) is used at 5 to 95 parts by weight, preferably 50 to 90 parts by weight, and ethylene / α- The olefin copolymer (A2) is used in 5 to 95 parts by weight, preferably 10 to 50 parts by weight.

The ethylene / α-olefin copolymer (A) used in the present invention, that is, a mixture of ethylene / α-olefin copolymer (A1) and ethylene / α-olefin copolymer (A2) is preferably 0.880 to 0.920 g / Soft ethylene / α with a density of cm 3 (ASTM D 1505), melt flow rate (MFR, ASTM D 1238, 190 ° C., 2.16 kg load) of 0.1 to 10 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes It is preferable that it is a -olefin copolymer.

The ethylene / α-olefin copolymer (A) preferably has a molecular weight distribution (Mw / Mn) of 2.3 to 4.0 as measured by gel permeation chromatography (GPC). When the ethylene / α-olefin copolymer (A) having a molecular weight distribution in the above range is used, a composition capable of producing a foam having excellent compression set resistance and moldability is obtained.

The ethylene / α-olefin copolymer (A) usually exhibits the properties of the elastomer.

Foaming Agent (B)

The blowing agent (B) used in the present invention is, for example, a chemical blowing agent. Examples of chemical blowing agents include organic pyrolytic blowing agents and inorganic pyrolytic blowing agents. Specific examples of the organic pyrolytic blowing agent include azodicarbonamide (ADCA), 1,1′-azobis (1-acetoxy-1-phenylethane), dimethyl-2,2′-azobisbutyrate, dimethyl-2, 2′-azobisisobutyrate, 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis (cyclohexane-1-carbonitrile) and 2,2′-azobis Azo compounds such as [N- (2-carboxyethyl) -2-methyl-propionamidine]; Nitroso compounds such as N, N'-dinitrosopentamethylenetetramine (DPT); Hydrazine derivatives such as 4,4'-oxybis (benzenesulfonylhydrazide) and diphenylsulfone-3,3'-disulfonylhydrazide; semicarbazide compounds such as p-toluenesulfonyl semicarbazide; And trihydrazinotriazines. Specific examples of the inorganic pyrolytic blowing agent include bicarbonates such as sodium bicarbonate and ammonium bicarbonate; Carbonates such as sodium carbonate and ammonium carbonate; Nitrites such as ammonium nitrite; And hydrogen compounds. Among the above compounds, azodicarbonamide (ADCA) and sodium bicarbonate are particularly preferable.

In the present invention, a physical blowing agent such as an organic physical blowing agent or an inorganic physical blowing agent (a blowing agent that does not necessarily accompany a chemical reaction during the foaming step) can also be used as the blowing agent (B). Examples of the organic physical blowing agent include methanol; ethanol; Various aliphatic hydrocarbons such as propane, butane, pentane and hexane; Various chlorinated hydrocarbons such as dichloroethane, dichloromethane and carbon tetrachloride; And various fluorinated hydrocarbons such as freon. Examples of the inorganic physical blowing agent include air, carbon dioxide, nitrogen, argon and water. Of these, carbon dioxide, nitrogen, and argon are most preferred in view of the need for evaporation, cost, environmental pollution and the possibility of combustion.

The physical blowing agent used as the blowing agent (B) in the present invention is completely decomposed without residues, thereby preventing contamination of the mold in the crosslinking foaming process of the composition. In addition, since the physical blowing agent is not a powder, the kneading property is excellent. In addition, by using such a physical blowing agent, it is possible to prevent the smell of the crosslinked foaming agent obtained (ammonia smell in the decomposition of ADCA, etc.).

In the present invention, the above-described chemical blowing agent can be used in combination with the above physical blowing agent within a range that does not harm the occurrence of odor and mold contamination.

With regard to the storage of the physical blowing agent, when used in small quantities, a gas such as carbon dioxide or nitrogen in a bomb can be fed to an injection molding machine or an extruder via a regulator. In addition, after the physical blowing agent is compressed by a pump or the like, it may be supplied to an injection molding machine or an extrusion molding machine.

In mass production equipment of crosslinked foam, the physical blowing agent can be fed to an injection molding machine or an extruder by pipeline from a liquid carbon dioxide or liquid nitrogen storage tank after evaporation through an evaporator and decompression by a pressure reducing valve.

When the physical blowing agent is in a liquid state, the storage pressure is preferably in the range of 0.13 to 100 MPa. If the storage pressure is too low, it cannot be fed to the injection molding machine or the extrusion machine through the pressure reducing valve. In addition, if the storage pressure is too high, it is not preferable because the design pressure of the storage equipment must be increased and the size becomes large or complicated. The specified storage pressure in the present invention is the pressure after evaporation and before the pressure reducing valve supply.

When a chemical blowing agent is used as the blowing agent (B), the chemical blowing agent is usually used in an amount of 3 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the ethylene / α-olefin copolymer (A). However, the amount of chemical blowing agent can be increased or decreased as appropriate to achieve a desired foaming ratio, since the gas released varies depending on the type or grade of chemical blowing agent used.

When the physical blowing agent is used as the blowing agent (B), the amount of the physical blowing agent is appropriately determined according to the desired foaming ratio.

In the present invention, a foaming aid may be used together with the blowing agent (B) if necessary. The foaming aid lowers the decomposition temperature of the blowing agent (B), promotes decomposition and functions to produce uniform bubbles.

Examples of the foaming aid include organic acids such as zinc oxide (ZnO), zinc stearate, salicylic acid, phthalic acid, stearic acid and oxalic acid, and urea or derivatives thereof.

Organic Peroxides (C)

Examples of the organic peroxide (C) used as needed in the present invention include dicumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2 , 5-dimethyl-2,5-di- (t-butylperoxy) hexyn-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperbenzoate, t-butylperoxybenzoisopropylcarbonate, diacetylperoxide, lauroylperoxide and t-butylcumylperoxide.

In the present invention, the organic peroxide (C) is usually 0.1 to 1.5 parts by weight, preferably 0.2 to 1 part by weight based on 100 parts by weight of the ethylene / α-olefin copolymer (A) (a mixture of component (A1) and component (A2)). It is used in the amount of 1.0 weight part. When the organic peroxide (C) is used in the above amount, it is possible to obtain a crosslinked foam having a suitable crosslinked structure. When the organic peroxide (C) is used in the above amount with the crosslinking aid (D), a crosslinked foam having a more suitable crosslinked structure can be obtained.

Crosslinking Aid (D)

Preferred examples of the crosslinking aid (D) used as necessary in the present invention include sulfur, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitro Peroxy crosslinking aids such as sobenzene, diphenylguanidine and trimethylolpropane-N, N'-m-phenylenedimaleimide; Divinylbenzene, triallyl cyanurate (TAC), and triallyl isocyanurate (TAIC). In addition, polyfunctional methacrylate monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate; And polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate. Among these, triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC) are preferable.

In the present invention, the crosslinking aid (D) has a weight ratio (D) / (C) of the crosslinking aid (D) to the organic peroxide (C) of 1/30 to 5/1, preferably 1/20 to 3 / 1, more preferably from 1/15 to 2/1.

Preparation of the composition

The composition according to the invention is a composition which is not crosslinked and not foamed, and may be in the form of pellets or sheets which are molten or cooled and cured.

Pellets of the composition of the present invention, for example

Ethylene / α-olefin copolymer (A) (mixture of components (A1) and (A2)), blowing agent (B) and, if necessary, organic peroxide (C), crosslinking aid (D) and blowing aid Blend by a Henschel mixer or the like,

Kneading, such as a Banbury mixer, roll or extruder, melt-plastifying the blend at a temperature at which the blowing agent (B) and / or organic peroxide (C) does not decompose,

The mixture can then be prepared by mixing and dispersing the mixture uniformly.

In addition to the above components, various additives such as fillers, heat stabilizers, weather stabilizers, flame retardants, hydrochloric acid absorbers and pigments and the like may be added to the composition as necessary without departing from the object of the present invention.

The composition sheet of this invention can be manufactured from the pellet of the composition obtained as mentioned above using an extruder or a calender molding machine. The foamed sheet which is not crosslinked and not foamed is kneaded with the components of the composition by a brabender mill or the like and then the mixture is molded into a sheet by a calender roll or a press molding machine, or by kneading the components with an extruder and then T By kneading the mixture through a die or a circular die.

Foam

The foams according to the invention can be obtained by foaming or crosslinking foaming the composition of the invention under conditions of a temperature of generally 130 ° C. to 200 ° C., a pressure of 30 to 300 kgf / cm 2 and a period of 10 to 90 minutes. However, since the (crosslinking) foaming time depends on the thickness of the mold, the time in the above range can be appropriately increased or decreased.

The foam of the present invention is obtained by foaming or crosslinked foamed molded article under the above conditions under a temperature of 130 ° C to 200 ° C, a period of 30 to 300kgf / cm 2, 5 to 60 minutes and a compression ratio of 1.1 to 3, preferably 1.3 to 2 The foam obtained by compression molding may be used.

The foam has a specific gravity of 0.05 to 0.25 (JIS K 7222) and a surface hardness of 20 to 80 (Asker C hardness). The crosslinked foams preferably have a gel fraction of at least 70% and usually have a gel fraction of 70 to 90%.

Foams of the invention, in particular crosslinked foams, having the above characteristics have low compression set, high tear strength and high resilience.

Gel fraction (gel content, xylene-insoluble content) is measured by the following method.

A sample of the crosslinked foam is weighed and cut into fine pieces. Subsequently, the fine pieces are put in a sealed container together with xylene and refluxed for 3 hours.

The sample is then taken out on filter paper and completely dried. The value obtained by subtracting the weight of the xylene-insoluble component (eg filler, filler, pigment) other than the polymer component from the weight of the dry residue is referred to as the "corrected final weight (Y)".

Meanwhile, the weight of the sample is subtracted from the weight of the xylene-soluble component (e.g., stabilizer) other than the polymer component and the weight of the xylene-insoluble component (e.g. filler, filler, pigment) other than the polymer component. The obtained value is referred to as "corrected initial weight (X)".

Gel content (xylene-insoluble content) is calculated from the following formula:

Gel content (% weight) = (corrected final weight (Y)) ÷ (corrected initial weight (X)) x 100.

Preparation of the foam

The foam according to the invention (uncrosslinked or crosslinked foam) can be produced, for example, by the following method.

The composition sheet of the present invention can be produced by, for example, molding the mixture described above in the preparation of the composition using a calender molding machine, a press molding machine or a T-die extruder. Sheet molding needs to be performed at the temperature below the decomposition temperature of a blowing agent (B) and an organic peroxide (C). More specifically, sheet molding needs to be carried out under the condition that the temperature of the molten composition is from 100 to 130 ° C.

The obtained sheet-like composition is cut into a volume of 1.0 to 1.2 times the volume of the mold, and placed in a mold maintained at 130 to 200 ° C., and a holding time of 10 to 90 minutes at a clamping force of 30 to 300 kgf / cm 2 ( Holding time) in the mold to produce a primary foam (uncrosslinked or crosslinked foam). However, since the (crosslinking) time depends on the thickness of the mold, it is preferable to increase or decrease the time in the above range as appropriate.

The shape of the mold for (crosslinking) foaming is not particularly limited, but usually a mold having a shape from which a sheet can be obtained is used. The mold needs to have a completely sealed structure so that the melted resin and the gas generated during decomposition of the blowing agent do not escape. The mold is preferably an inside-tapered frame in terms of releasability of the resin.

The primary foam obtained above becomes a desired shape by compression molding. Compression molding is carried out under conditions of a mold temperature of 130 to 200 ° C., a tightening force of 30 to 300 kgf / cm 2, a compression time of 5 to 60 minutes, and a compression ratio of 1.1 to 3.0.

In order to obtain a crosslinked foam by crosslinking by irradiation of ionizing radiation, first, an organic pyrolytic foaming agent and other additives as ethylene / α-olefin copolymer (A) and a foaming agent (B) are used at temperatures below the decomposition temperature of the organic pyrolytic foaming agent. After melt kneading at a temperature, the resulting kneaded product is molded into a sheet to obtain a foamable sheet.

Then, the obtained expandable sheet is irradiated with a predetermined amount of ionizing radiation to crosslink the ethylene / α-olefin copolymer (A), and then the obtained expandable crosslinked sheet is heated to a temperature equal to or higher than the decomposition temperature of the organic pyrolytic blowing agent. By foaming, a crosslinked foam sheet can be obtained.

Examples of ionizing radiation that can be used here include α rays, β rays, γ rays, electron beams, neutron rays and X rays. Of these, gamma rays and electron beams of cobalt-60 are preferably used.

Examples of the shape of the foam include sheets, thick boards, nets and shaped bodies.

From the crosslinked foams obtained as described above, secondary crosslinked foams having the above-described characteristics can be produced in a manner similar to the method for producing primary foams.

Laminate

The laminate according to the invention is a laminate having a layer of the foam (uncrosslinked or crosslinked foam) of the invention and a layer of one or more materials selected from the group consisting of polyolefins, polyurethanes, rubber, leather and artificial leather. It is a sieve.

There is no restriction | limiting in particular in polyolefin, polyurethane, rubber, leather, and artificial leather, A conventionally well-known polyolefin, polyurethane, rubber, leather, and artificial leather can be used.

The laminate of the present invention can be suitably used as footwear and footwear parts.

Footwear and Footwear Parts

Footwear and footwear parts according to the invention consist of the foam of the invention (uncrosslinked or crosslinked foam) or the laminate of the invention.

Examples of footwear parts include soles, midsoles, inner soles, and shoe soles and sandals.

<Example>

The present invention is further described with reference to the following examples, but the present invention is not limited to these examples.

The foams obtained in Examples and Comparative Examples were measured or evaluated for specific gravity, Asker C hardness, tensile strength, tear strength, compression set, rebound elasticity and formability by the following method, and softness was evaluated by the following method. In addition, the adhesive strength of the laminated body which consists of the obtained foam and a polyurethane sheet was measured by the method demonstrated below.

(1) specific gravity of foam

While measuring the specific gravity of the foamed body (hereinafter abbreviated as skin _oil) with a foamed skin according to JIS K 7222, the proportion of foam (also abbreviated as _non-skin) does not have a foam skin is Mirage Trading Co., Ltd (Model It measured using the electronic hydrometer made from MD-200S).

(2) Asker C Hardness

Asker C hardness was calculated | required according to the "Spring Hardness Test C Test Method" described in Appendix 2 of JIS K 7312-1996.

(3) tensile strength

In order to measure the tensile strength at break of the crosslinked foam sheet, a tensile test was conducted under the conditions of a measuring temperature of 23 ° C. and a stress rate of 500 mm / min according to JIS K 6301.

(4) tear strength

To find the tear strength, a tear strength test was conducted under conditions of a stress rate of 100 mm / min in accordance with BS5131-2.6.

(5) compression set

In order to determine the compression set, the compression set was subjected to a compression set under a compression condition of 50 ° C. for 6 hours and a compression condition of 50% according to JIS K 6301 to compress the foam, and the thickness thereof was measured after standing for 30 minutes.

(6) Feel of softness

The surface of the foam was touched to evaluate the softness in the following 5 grades.

[Rating of 5]

5: The surface is flat and flexible.

4: The surface is slightly gritty but flexible.

3: evaluated between 2 and 4

2: The surface is gritty and slightly hard.

1: Rough surface and hard like resin.

(7) resilience

The resilience was measured according to JIS K 6255.

(8) adhesive strength of laminate

[Treatment of Secondary Crosslinked Foam]

The surface of the secondary crosslinked foam was washed with water containing the surface active agent and then dried at room temperature for 1 hour.

The secondary crosslinked foam was then soaked in methylcyclohexane for 3 minutes and dried in an oven at 60 ° C. for 3 minutes.

Subsequently, an ultraviolet curable primer (trade name: GE258H1, manufactured by Daito Jyushi K.K.) was thinly coated with a brush, and then dried in an oven at 60 ° C. for 3 minutes. Then, using three high-pressure mercury lamps (made by Japan Storage Battery Co., Ltd., a UV irradiation device of type EPSH-600-3S) of 80 W / cm each, 10 m / at a distance of 15 cm from the light installed perpendicular to the direction of travel. Ultraviolet light was irradiated while moving at the conveyor speed of minutes.

Subsequently, 5 wt% of the auxiliary primer (trade name GE366S (trade name) was added to the primer GE6001L (trade name), both manufactured by Daito Jyushi K.K) were thinly coated with a brush, and then dried in an oven at 60 ° C. for 3 minutes.

Subsequently, 4 weight% of the adhesive (curing agent GE348 ™) was added to the adhesive 98H (trade name), both manufactured by Daito Jyushi K.K., thinly coated with a brush, and then dried in an oven at 60 ° C. for 5 minutes.

Finally, the secondary crosslinked foam coated with the adhesive described above and the polyurethane artificial leather sheet produced by the following method were laminated by bonding at a pressure of 20 kg / cm 2 for 10 seconds.

[Treatment of Polyurethane Artificial Leather Sheet]

The surface of the polyurethane artificial leather sheet was washed with methyl ethyl ketone and then dried at room temperature for 1 hour.

Subsequently, 5 wt% of the auxiliary primer (trade name GE366S (trade name) was added to the primer GE6001L (trade name), both manufactured by Daito Jyushi K.K) were thinly coated with a brush, and then dried in an oven at 60 ° C. for 3 minutes.

Subsequently, 4 weight% of the adhesive (curing agent GE348 ™) was added to the adhesive 98H (trade name), both manufactured by Daito Jyushi K.K., thinly coated with a brush, and then dried in an oven at 60 ° C. for 5 minutes.

[Peel experiment]

After 24 hours, the adhesive strength of the sheets laminated by the above coating bonding was evaluated in the following manner:

That is, the sheet | seat laminated | stacked by the coating bonding is cut out to 1 cm width. After peeling the end of the sheet, the peel strength was measured by pulling the end of the sheet in a 180 degree direction at a rate of 200 mm / min.

After measuring the five samples, the average value of the adhesive strength is shown in Table 1. Peeling state was visually observed.

(9) formability

After stamping on the surface of the secondary compression mold in a pattern as shown in Fig. 2, the moldability was evaluated using these. For example, when the moldability was good at a site having a depth of 2 mm and a width of 2 mm, the evaluation result was described as t2-w2.

Preparation Example 1:

Preparation of Catalyst Solution

Toluene solution having a concentration of 0.004 mmol / ml was prepared by weighing 18.4 mg of triphenylcarbenium (tetrakispentafluorophenyl) borate and dissolving it in 5 ml of toluene. Separately, 1.8 mg of [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride was weighed, and 5 ml of toluene was added thereto to dissolve it, and thus 0.001 mmol Toluene solution with a concentration of / ml was prepared.

Next, 0.38 ml of toluene solution of triphenylcarbenium (tetrakispentafluorophenyl) borate was weighed, and [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride 0.38 ml of toluene solution was weighed, and then 4.24 ml of toluene was added and diluted, and triphenylcarbenium (tetrakispentafluorophenyl) borate concentration was 0.002 mmol / L in terms of boron (B), and [dimethyl (t -Butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium dichloride concentration was converted into Ti to prepare 5 ml of toluene solution having 0.0005 mmol / L. The toluene solution was used as a catalyst solution for polymerization.

Preparation of Ethylene / 1-butene Copolymer (A-1)

750 ml of heptane was supplied at 23 ° C to a thoroughly nitrogen-substituted 1.5 liter SUS autoclave equipped with a stirring blade. The autoclave was fed 8 g of 1-butene and 250 ml of hydrogen while the stirring blade was rotated and ice cooled.

The autoclave was then heated to 100 ° C. and then pressurized with ethylene so that the total pressure was 6 kg / cm 2. When the internal pressure of the autoclave reached 6 kg / cm 2, 1.0 ml of a hexane solution of triisobutylaluminum (TIBA) having a concentration of 1.0 mmol / ml was injected into the autoclave with nitrogen. Subsequently, 5 ml of the catalyst solution was pressed into the autoclave with nitrogen to initiate polymerization of ethylene and 1-butene. Subsequently, temperature control and direct ethylene feeding were performed for 5 minutes so that the internal temperature of the autoclave was 100 ° C. and the pressure was 6 kg / cm 2. 5 minutes after the start of the polymerization, 5 ml of methanol was injected into the autoclave by a pump to stop the polymerization, and the autoclave was depressurized to normal pressure. It stirred, pouring 3 liters of methanol into the obtained reaction solution. The resulting polymer containing solvent was dried at 600 Torr for 13 hours at 130 ° C. to obtain 10 g of ethylene / 1-butene copolymer (A-1).

The obtained ethylene / 1-butene copolymer (A-1) had 91 mol% of ethylene content, 9 mol% of 1-butene content, 0.893 g / cm3 of density (ASTM D 1505), melt flow rate (ASTM D 1238, 190 ° C, 2.16 kg load) 3.8 g / 10 min, melt flow rate (ASTM D 1238, 190 ° C., 10 kg load) 31 g / 10 min, molecular weight distribution measured by GPC (M _w / M _n ) 2.0 and MFR ₁₀ / MFR _2.16 has 8.2. The Shore A hardness (ASTM D 2240) of the ethylene / 1-butene copolymer (A-1) was 92, and the temperature of the endothermic curve melting point peak of the copolymer (A-1) measured by DSC was 82 ° C.

In the endothermic curve, no other peak was observed, so the position of the main melting peak was 82 ° C.

The molded body of the ethylene / 1-butene copolymer (A-1) used for the measurement of Shore A hardness was prepared in the following manner.

The ethylene / 1-butene copolymer (A-1) was placed in a mold having a size of 200 mm × 200 mm × 2 mm (thickness), and then heat-pressed at a press temperature of 200 ° C. and a press pressure of 160 kg / cm 2. It hot-pressed and cooled at 20 degreeC for 5 minutes, and obtained the molded object.

Preparation Example 2:

Preparation of Ethylene / 1-butene Copolymer (A-2)

12 g of ethylene / 1-butene copolymer (A-2) was obtained in the same manner as in Production Example 1, except that the amount of 1-butene was changed to 6 g and the amount of hydrogen was changed to 150 mL.

The obtained ethylene / 1-butene copolymer (A-2) had 94 mol% of ethylene content, 6 mol% of 1-butene content, 0.905 g / cm3 of density (ASTM D 1505), melt flow rate (ASTM D 1238, 190 ° C, 2.16 kg load) 1.2 g / 10 min, melt flow rate (ASTM D 1238, 190 ° C., 10 kg load) 11.5 g / 10 min, molecular weight distribution measured by GPC (M _w / M _n ) 2.0 and MFR ₁₀ / MFR _2.16 9.6. The Shore D hardness (ASTM D 2240) of the ethylene / 1-butene copolymer (A-2) was 43, and the temperature of the endothermic curve melting point peak of the copolymer (A-2) measured by DSC was 94 ° C. In the endothermic curve, no other peak was observed, so the position of the main melting peak was 94 ° C.

The molded article of the ethylene / 1-butene copolymer (A-2) used for the measurement of Shore D hardness was prepared in the same manner as in Preparation Example 1.

Preparation Example 3:

Preparation of Ethylene / 1-butene Copolymer (A-3)

10 g of ethylene / 1-butene copolymer (A-3) was obtained in the same manner as in Preparation Example 1, except that the amount of 1-butene was changed to 10 g and the amount of hydrogen was changed to 100 mL.

The obtained ethylene / 1-butene copolymer (A-3) had 89 mol% of ethylene content, 11 mol% of 1-butene content, 0.885 g / cm3 of density (ASTM D 1505), melt flow rate (ASTM D 1238, 190 ° C, 2.16 kg load) 0.5 g / 10 min, melt flow rate (ASTM D 1238, 190 ° C., 10 kg load) 5.0 g / 10 min, molecular weight distribution measured by GPC (M _w / M _n ) 2.1 and MFR ₁₀ / MFR _2.16 10. The Shore A hardness (ASTM D 2240) of the ethylene / 1-butene copolymer (A-3) was 87, and the temperature of the endothermic curve melting point peak of the copolymer (A-3) measured by DSC was 66 ° C. In the endothermic curve, no other peak was observed, so the position of the main melting peak was 66 ° C.

The molded body of the ethylene / 1-butene copolymer (A-3) used for the measurement of Shore A hardness was prepared in the same manner as in Preparation Example 1.

Preparation Example 4:

Preparation of the catalyst

In 154 liters of toluene, 10 kg of silica dried at 250 ° C. for 10 hours was suspended and the suspension cooled to 0 ° C. Next, 57.5 liters of toluene solution of methylaluminoxane (Al concentration: 1.33 mol / L) was added dropwise to the suspension over 1 hour. During the dropping, the temperature of the system was maintained at 0 ° C. The reaction of silica and methylaluminoxane was continued for 30 minutes at 0 ° C. The system was then heated to 95 ° C. over a period of 1.5 hours, at which temperature the reaction was carried out for 20 hours. The temperature was then lowered to 60 ° C. and the supernatant was removed along. The obtained solid component was washed twice with toluene and then resuspended in 100 liters of toluene. 16.8 liters of a toluene solution of bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride (Zr concentration: 27.0 mmol / L) was added dropwise to the system at 80 DEG C over 30 minutes, and then 80 The reaction was further performed for 2 hours at &lt; RTI ID = 0.0 &gt; The supernatant was then removed and the residue was washed twice with hexane to give a solid catalyst containing 3.5 mg zirconium based on 1 g of catalyst.

Preparation of Prepolymerized Catalyst

870 g of the solid catalyst and 260 g of 1-hexene were added to 87 liters of hexane containing 2.5 mol of triisobutylaluminum, and prepolymerization of ethylene was carried out at 35 DEG C for 5 hours, based on 1 g of solid catalyst. A prepolymerized catalyst containing 10 g of polyethylene prepared by prepolymerization was obtained.

Copolymerization

In a continuous fluidized bed gas phase polymerization apparatus, copolymerization of ethylene and 1-hexene was carried out at a total pressure of 18 kg / cm 2 -G and a polymerization temperature of 75 ° C. The prepolymerized catalyst to the polymerizer was continuously fed triisobutylaluminum at a rate of 0.15 mmol / hour and 10 mmol / hour in terms of zirconium atoms. During the polymerization, the gas composition was kept constant by continuously supplying ethylene, 1-hexene, hydrogen and nitrogen (gas composition: 1-hexene / ethylene = 0.034, hydrogen / ethylene = 1.7 × 10 ⁻⁴ , ethylene concentration = 20% ).

The yield of the ethylene / 1-hexene copolymer (A-4) obtained above was 5.8 kg / hour.

The obtained ethylene / 1-hexene copolymer (A-4) had 94 mol% of ethylene content, 6 mol% of 1-hexene content, 0.908 g / cm3 of density (ASTM D 1505), melt flow rate (ASTM D 1238, 190 ° C, 2.16 kg load) 0.8 g / 10 min, melt flow rate (ASTM D 1238, 190 ° C., 10 kg load) 4.4 g / 10 min, molecular weight distribution measured by GPC (M _w / M _n ) 2.1 and MFR ₁₀ / MFR _2.16 5.5. The Shore D hardness (ASTM D 2240) of the ethylene / 1-hexene copolymer (A-4) was 46, and the temperatures of the endothermic melting point peaks of the copolymer (A-4) measured by DSC were 85 ° C and 113 ° C. And 120 ° C. Among these, since the maximum peak was 120 degreeC, the position of the main melting point peak was 120 degreeC.

A molded article of the ethylene / 1-hexene copolymer (A-4) used for the measurement of the Shore D strength was prepared in the same manner as in Preparation Example 1.

Example 1

50 parts by weight of the ethylene / 1-butene copolymer (A-1) obtained in Production Example 1, 50 parts by weight of the ethylene / 1-butene copolymer (A-2) obtained in Production Example 2, 3.0 parts by weight of zinc oxide, 1.0 of stearic acid Parts by weight, titanium parts by weight 4.0 parts by weight, dicumyl peroxide (DCP) 0.6 parts by weight, triallyl isocyanurate (TAIC, trade name: M-60 (TAIC content: 60%), manufactured by Nippon Kasei Co., Ltd.) 0.15 parts by weight Parts (in terms of TAIC content), and 7.0 parts by weight of azodicarbonamide (trade name: CELLCOM-JTR, manufactured by Kum Yang Chemical Co., Ltd., Korea) at 110 ° C by laboplastomill (manufactured by Toyo Seiki Seisakusho, type 100MR2). The mixture was kneaded at the set temperature of 5 minutes, and then molded into a sheet.

1, the change of the torque according to kneading time is shown. As shown in FIG. 1, after 60 seconds of kneading start, the torque of Example 1 is always smaller than that of Comparative Example 1, which will be described later, and it can be seen that kneadablity of Example 1 is superior to Comparative Example 1. .

In the kneading step, the maximum temperature of the composition was measured, and the state of the composition after kneading was visually observed to evaluate dispersibility. The results are shown in Table 1.

Then, the obtained sheet was placed in a press die and pressed under heating under conditions of 150 kg / cm 2, 155 ° C. and 30 minutes to obtain a primary crosslinked foam. The press mold had a size of 15 mm thick, 200 mm long and 150 mm wide.

The specific gravity, compression set and tear strength of the obtained primary crosslinked foam were measured in accordance with the above-described method. In addition, the softness was evaluated according to the above-described method.

The results are shown in Table 1.

After the cuticle was cut out, the primary crosslinked foam was heat compressed under conditions of 150 kg / cm 2, 155 ° C. and 10 minutes, and then immediately cooled to 20 ° C. for 10 minutes to obtain a secondary crosslinked foam. The secondary crosslinked foam had a size of 15 mm thick, 250 mm long and 160 mm wide.

Specific gravity, Asker C hardness, tensile strength, tear strength, compression set, rebound elasticity and formability of the secondary crosslinked foams were measured or evaluated in accordance with the above-described methods.

The adhesive strength of the laminate obtained from the obtained foam and the polyurethane sheet was measured by the above-described method, and the peeling state was visually observed.

The results are shown in Table 1.

Example 2

A primary crosslinked foam and then a secondary crosslinked foam were prepared in the same manner as in Example 1, except that 0.8 parts by weight of DCP was used instead of 0.6 parts by weight of dicumyl peroxide (DCP).

Subsequently, the specific gravity, compression set and tear strength of the obtained primary crosslinked foam were measured in accordance with the above-described method, and the softness was also evaluated in accordance with the above-described method.

The results are shown in Table 1.

In addition, specific gravity, Asker C hardness, tensile strength, tear strength, compression set, rebound elasticity, and moldability of the obtained secondary crosslinked foam were measured or evaluated in accordance with the above-described method.

The adhesive strength of the obtained foamed product and the laminate made of a polyurethane artificial leather sheet was measured according to the method described above, and the peeling state was visually observed.

The results are shown in Table 1.

Example 3

Primary in the same manner as in Example 1 except that 50 parts by weight of the ethylene / 1 butene copolymer (A-3) obtained in Preparation Example 3 was used instead of 50 parts by weight of the ethylene / 1-butene copolymer (A-1). Crosslinked foams and then secondary crosslinked foams were prepared.

Subsequently, the specific gravity, compression set and tear strength of the obtained primary crosslinked foam were measured in accordance with the above-described method, and the softness was also evaluated in accordance with the above-described method.

The results are shown in Table 1.

In addition, specific gravity, Asker C hardness, tensile strength, tear strength, compression set, rebound elasticity, and moldability of the obtained secondary crosslinked foam were measured or evaluated in accordance with the above-described method.

The adhesive strength of the obtained foamed product and the laminate made of a polyurethane artificial leather sheet was measured according to the method described above, and the peeling state was visually observed.

The results are shown in Table 1.

Example 4

50 weight part of ethylene / 1-butene copolymers (A-1) and 50 weight part of ethylene / 1-butene copolymers (A-5) mentioned later instead of 50 weight part of ethylene / 1-butene copolymers (A-1) and 50 weight part of ethylene / 1-butene copolymers (A-2). Primary crosslinked foam and then secondary crosslinked foam were prepared in the same manner as in Example 1, except that 50 parts by weight of ethylene and 50 parts by weight of the ethylene / 1-octene copolymer (A-6) were used.

Subsequently, the specific gravity, compression set and tear strength of the obtained primary crosslinked foam were measured in accordance with the above-described method, and the softness was also evaluated in accordance with the above-described method.

The results are shown in Table 1.

In addition, specific gravity, Asker C hardness, tensile strength, tear strength, compression set, rebound elasticity, and moldability of the obtained secondary crosslinked foam were measured or evaluated in accordance with the above-described method.

The adhesive strength of the obtained foamed product and the laminate made of a polyurethane artificial leather sheet was measured according to the method described above, and the peeling state was visually observed.

The results are shown in Table 1.

The ethylene / 1-octene copolymer (A-5) is a commercially available trade name "Engage" manufactured by DuPont Dow Elastomers LLC. Cm 3, melt flow rate (ASTM D 1238, 190 ° C., 2.16 kg load) 2.67 g / 10 min, melt flow rate (ASTM D 1238, 190 ° C., 10 kg load) 21.9 g / 10 min, molecular weight measured by GPC Distribution (Mw / Mn) 2.1, and MFR ₁₀ / MFR _2.16 8.2. The Shore A hardness (ASTM D 2240) of the ethylene / 1-octene copolymer (A-5) was 88, and the temperature of the endothermic curve melting point peak of the copolymer (A-5) measured by DSC was 83 ° C. In the melting point curve, no other peak was observed, so the position of the main melting peak was 83 ° C.

A molded article of the ethylene / 1-octene copolymer (A-5) used for the measurement of Shore A hardness was prepared in the same manner as in Preparation Example 1.

The ethylene / 1-octene copolymer (A-6) is a commercial trade name "Exact" manufactured by Exxon-Mobil Chemical Co., which has an ethylene content of 94 mol%, a 1-octene content of 6 mol%, and a density (ASTM D 1505) 0.903 g / cm 3, melt flow rate (ASTM D 1238, 190 ° C., 2.16 kg load) 1.1 g / 10 min, melt flow rate (ASTM D 1238, 190 ° C., 10 kg load) 8.7 g / 10 min, measured by GPC One molecular weight distribution (Mw / Mn) 2.1, and MFR ₁₀ / MFR _2.16 7.9. The Shore D hardness (ASTM D 2240) of the ethylene / 1-octene copolymer (A-6) was 41, and the temperature of the endothermic curve melting point peak of the copolymer (A-6) measured by DSC was 98 ° C. In the melting point curve, no other peak was observed, so the position of the main melting peak was 98 ° C.

A molded article of the ethylene / 1-octene copolymer (A-6) used for the measurement of Shore D hardness was prepared in the same manner as in Preparation Example 1.

Comparative Example 1

In the same manner as in Example 1, except that 50 parts by weight of the ethylene / 1-hexene copolymer (A-4) obtained in Production Example 4 was used instead of 50 parts by weight of the ethylene / 1-butene copolymer (A-2). The primary crosslinked foam and then the secondary crosslinked foam were prepared.

1, the torque change of the composition with the kneading time is shown. In addition, the highest temperature of the composition was measured in the kneading step, and the state of the composition was visually observed after kneading to evaluate dispersibility.

The results are shown in Table 1.

Specific gravity, compressive permanent deformation and tear strength of the primary crosslinked foam were measured according to the above-described method, and softness was also evaluated according to the above-described method.

The results are shown in Table 1.

Then, specific gravity, Asker C hardness, tensile strength, tear strength, compression set, rebound elasticity and moldability of the secondary crosslinked foam were measured or evaluated in accordance with the above-described method.

The adhesive strength of the obtained foamed product and the laminate made of a polyurethane artificial leather sheet was measured according to the method described above, and the peeling state was visually observed.

The results are shown in Table 1.

Comparative Example 2

50 parts by weight of ethylene / 1-butene copolymer (A-4) instead of 50 parts by weight of ethylene / 1-butene copolymer (A-1) and 50 parts by weight of ethylene / 1-butene copolymer (A-2) and A primary crosslinked foam and then a secondary crosslinked foam were prepared in the same manner as in Example 1 except that 50 parts by weight of ethylene / 1-octene (A-5) was used.

Subsequently, specific gravity, compressive permanent deformation and tear strength of the primary crosslinked foam were measured according to the above-described method, and softness was also evaluated according to the above-described method.

The results are shown in Table 1.

In addition, specific gravity, Asker C hardness, tensile strength, tear strength, compression set, rebound elasticity and moldability of the secondary crosslinked foam were measured or evaluated according to the above-described method.

The adhesive strength of the obtained foamed product and the laminate made of a polyurethane artificial leather sheet was measured according to the method described above, and the peeling state was visually observed.

The results are shown in Table 1.

TABLE 1

According to the present invention, foams having an Asker C hardness of 20 to 80, low specific gravity, low compression set (CS), good tear strength properties, good rebound elasticity and good formability (uncrosslinked or Alternatively, a composition capable of providing a crosslinked foam), a foam of the composition (including a secondary compression foam), and a laminate using the foam can be provided. In particular, when ethylene / α-olefin copolymers (A1) and (A2) are used as the ethylene / 1-butene copolymer contained in the composition of the foam, a laminate having better interlayer adhesion strength can be obtained.

According to the invention, it is also possible to provide footwear and footwear parts made of the uncrosslinked or crosslinked foam or the laminate.

Claims (17)

A composition consisting of an ethylene / α-olefin copolymer (A) and a blowing agent (B), The ethylene / α-olefin copolymer (A) Ethylene / α-olefin copolymer (A1) having a density of 0.880 g / cm 3 or more and 0.900 g / cm 3 or less and a melt flow rate (ASTM D 1238, 190 ° C., 2.16 kg load) of 0.1 to 50 g / 10 min. To 95 parts by weight; And, Ethylene / density of 0.900 g / cm 3 to 0.930 g / cm 3, melt flow rate (ASTM D 1238, 190 ° C., 2.16 kg load) of 0.1 to 50 g / 10 min, and main melting point peak of 110 ° C. or less 5 to 95 parts by weight of an α-olefin copolymer (A2), The sum total of said component (A1) and (A2) is 100 weight part. The method of claim 1, Ethylene / α-olefin copolymer (A1) and (A2) are both ethylene / 1-butene copolymers. The method according to claim 1 or 2, At least one of the ethylene / α-olefin copolymers (A1) and (A2) has the following properties: Melt flow rate (MFR) measured according to ASTM D 1238 under a temperature of 190 ° C. and a load of 10 kg, for a melt flow rate measured according to ASTM D 1238 under a temperature of 190 ° C. and a load of _2.16 kg. ₁₀ ) is the ratio (MFR ₁₀ / MFR _2.16 ) Satisfies the relationship of MFR ₁₀ / MFR _2.16 ≧ 5.63; The molecular weight distribution (M _w / M _n ) and the melt flow rate ratio It satisfies the relationship M _w / M _n ≤ (MFR ₁₀ / MFR _2.16 )-4.63. The method of claim 3, At least one of the ethylene / α-olefin copolymers (A1) and (A2) has the following properties: Melt flow rate measured according to ASTM D 1238 at a temperature of 190 ° C. and a load condition of 10 kg, for a melt flow rate measured according to ASTM D 1238 under a temperature of 190 ° C. and a load of _2.16 kg. The ratio of MFR ₁₀ ) (MFR ₁₀ / MFR _2.16 ) Satisfies the relationship of MFR ₁₀ / MFR _2.16 ≧ 5.63; And, The molecular weight distribution (M _w / M _n ) and the melt flow rate ratio M _w / M _n + 4.63 ≤ MFR ₁₀ / MFR _2.16 ≤ ₁₄ -2.9 Log (MER _2.16 ) Satisfied. The method according to any one of claims 1 to 4, The ethylene / α-olefin copolymer (A2) has a surface hardness of 30 to 70 in terms of Shore D hardness (ASTM D 2240). The method according to any one of claims 1 to 5, The ethylene / α-olefin copolymer (A2) is a composition obtained by solution polymerization. The method according to any one of claims 1 to 6, The ethylene / α-olefin copolymer (A2) is an ethylene / 1-butene random copolymer. The method according to any one of claims 1 to 7, The ethylene / α-olefin copolymer (A) has a density of 0.880 to 0.920 g / cm 3 and a melt flow rate (ASTM D 1238, 190 ° C., load of 2.16 kg) of 0.1 to 10 g / 10 min. The method according to any one of claims 1 to 8, The blowing agent (B) is a composition selected from organic pyrolytic blowing agents, inorganic pyrolytic blowing agents, organic physical blowing agents and inorganic physical blowing agents. The foam obtained by heat-treating the composition of any one of Claims 1-9. The method of claim 10, A foam obtained by secondary compression of the foam of claim 10. The method according to claim 10 or 11, wherein Foam having a specific gravity (JIS K 7222) of 0.05 to 0.25 and a surface hardness (asker C hardness) of 20 to 80. A layer of foam according to any one of claims 10 to 12; And A laminate having a layer of at least one material selected from the group consisting of polyolefins, polyurethanes, rubbers, leathers and artificial leathers. Foaming the composition according to any one of claims 1 to 9, and A process of laminating the foam obtained in the above process with at least one material selected from the group consisting of polyolefin, polyurethane, rubber, leather and artificial leather The manufacturing method of the laminated body of Claim 13 which becomes. Footwear comprising the foam according to any one of claims 10 to 12 or the laminate according to claim 13. A footwear component comprising the foam according to any one of claims 10 to 12 or the laminate according to claim 13. The method of claim 16, Footwear parts, characterized in that the footwear parts are midsole, inner sole or sole.