CN1235966C - composition and its use - Google Patents
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- CN1235966C CN1235966C CN 02130217 CN02130217A CN1235966C CN 1235966 C CN1235966 C CN 1235966C CN 02130217 CN02130217 CN 02130217 CN 02130217 A CN02130217 A CN 02130217A CN 1235966 C CN1235966 C CN 1235966C
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Abstract
The present invention relates to a composition comprising an ethylene/alpha-olefin copolymer (A), a foaming agent (B), an optional organic peroxide and an optional crosslinking auxiliary agent. The ethylene/alpha-olefin copolymer (A) according to specific proportion comprises an ethylene/alpha-olefin copolymer (A1) and an ethylene/alpha-olefin copolymer (A2), wherein the density of the ethylene/alpha-olefin copolymer (A1) is not lower than 0.880 g/cm<3> and lower than 0.900 g/cm<3>, and the melt flow rate (190DEG C) is from 0.1 to 50g/10 minutes; the density of the ethylene/alpha-olefin copolymer (A2) is from 0.900 to 0.930 g/cm<3>, the melt flow rate (190DEG C) is from 0.1 to 50 g/10 minutes, and the ethylene/alpha-olefin copolymer (A2) comprises a main melting point peak at the temperature of 110DEG C. The foaming product of the present invention, which is obtained by thermally treating the composition, can also be secondarily compressed. The laminated substance of the present invention comprises a first layer and a second layer, wherein the first layer contains the foaming product, and the second layer contains at least one material, such as polyolefin. The footwear or the footwear component of the present invention comprises the foaming product or the laminated substance. A composition which can be obtained according to the present invention can provide a crosslinked foaming product, the foaming product and the laminated substance obtained by using the foaming product, and the crosslinked foaming product with the Asker hardness of 20 to 80 has the advantages of low specific gravity, small compressive deformation, superior tearing strength, superior impact elasticity and superior mould ability. Additionally, the composition can provide the footwear and the footwear component for containing the foaming product and the laminated substance.
Description
Invention field
The present invention relates to a kind of composition and application thereof.Particularly, the present invention relates to a kind of composition and this foamed products that foamed products (uncrosslinked or crosslinked foamed products) can be provided, described foamed products has the Asker C hardness of 20-80, low proportion, low compression deformation (CS), good tear strength, bounce impact elasticity and mouldability.
Background of invention
The technology of using the crosslinked foaming product to obtain low-gravity (promptly in light weight), softness and high mechanical strength resin is widely used in interior of building or external decorative material, trolley part (as interior trim and glass run channel), wrapping material, daily necessities etc.Reason is the crosslinking reaction bonding molecular chain by resin, and the feasible lightweight performance that may obtain resin by foaming, and the decline of inhibition physical strength are although only obtain the reduction that the lightweight performance can cause the resin physical strength by foamex.
The crosslinked foaming product of resin also is used for the parts of footwear and footwear such as the sole of sports shoes (mainly being the end), reason be need in light weight, can suppress the distortion that life-time service causes, have high mechanical strength and bounce impact elasticity, can bear the material of abominable working conditions.
The crosslinked foaming product that always used ethylene in the past is as sole, and is known.The problem that exists by the crosslinked foaming product that uses ethylene to obtain be its than great, compressive set is big, therefore, when when the sole, sole is heavier, and if during the sole life-time service, they can be compressed, and lose physical strength such as bounce impact elasticity.
In the national bulletin and the open communique 206406/1999 of Japanese Patent of international monopoly 501447/1997, the invention of having described the invention that relates to the crosslinked foaming product that uses ethylene/alpha-olefin copolymer and having related to the crosslinked foaming product of the mixture that uses ethylene and ethylene/alpha-olefin copolymer.Yet,, still can not obtain satisfied performance although these inventions have improved low-gravity and compression set resistant.
In the open communique 344924/2000 of the Japanese Patent of inventor's application, a kind of olefin elastomer crosslinked foaming product with high expansion ratio is disclosed, this product is not because froth breaking has surface roughening, have flexible touch, low compression deformation, good tear strength and thermotolerance, also disclose the elastic composition that is used for this crosslinked foaming product.Promptly, the olefin elastomer composition that comprises ethylene/alpha-olefin copolymer (A), organo-peroxide (B), crosslinking coagent (C) and whipping agent (D) by thermal treatment obtains this crosslinked foaming product, and described ethylene/alpha-olefin copolymer (A) density is the 0.88-0.92 gram per centimeter
3, melt flow rate (MFR) (190 ℃) restrains/10 minutes for 0.1-10.Ethylene/alpha-olefin copolymer (A) comprises 5-95 weight part density and is not less than 0.88 gram per centimeter
3But less than 0.90 gram per centimeter
3, melt flow rate (MFR) (190 ℃) is the 0.90-0.93 gram per centimeter for/10 minutes ethylene/alpha-olefin copolymer of 0.1-50 gram (A1 ') and 5-95 weight part density
3And melt flow rate (MFR) (190 ℃) is/10 minutes ethylene/alpha-olefin copolymer of 0.1-50 gram (A2 '), described component (A1 ') and (A2 ') total amount are 100 weight parts, and the melt flow rate (MFR) (190 ℃) of the mixture of ethylene/alpha-olefin copolymer (A1 ') and (A2 ') is 0.5-10 gram/10 minutes.In this invention, add and to have highdensity relatively ethylene/alpha-olefin copolymer (A2 '), with the required hardness of guaranteeing to make of crosslinked foaming product, for example required hardness of footwear.Only add the low relatively ethylene/alpha-olefin copolymer of a kind of density (A1 ') and can not guarantee the hardness of footwear needs, the crosslinked foaming product of making can not satisfy the needs of footwear.
Yet, ethylene/alpha-olefin copolymer (A2 ') also have problems.That is, the surface hardness of the crosslinked foaming product of making for raising, multipolymer (A2 ') and ethylene/alpha-olefin copolymer (A1 ') are compared has high melt point, so the kneading operation difficulty.Particularly, and multipolymer (A2 ') in kneading process, have problems, need high-energy or mixing not good, kneader device breaks down under extreme case.Comprising under the common composition situation of high melting point component, mediating temperature by raising and solved above-mentioned kneading problem.Yet for the foaming composition situation, kneading operation need carry out being lower than under the temperature of regulation (not being higher than 100 ℃ usually), mediates temperature can reduce foaming agent and/or linking agent because raise.
The inventor is devoted to research and solve above-mentioned kneading problem, and the result finds that by adopting density be the 0.900-0.930 gram per centimeter
3Melt flow rate (MFR) (ASTM D 1238,190 ℃, 2.16 kilogram load) restrain/10 minutes for 0.1-50, and be not higher than the ethylene/alpha-olefin copolymer (A2) that 110 ℃ of positions have main fusing point peak, replace above-mentioned ethylene/alpha-olefin copolymer (A2 '), can be so that the crosslinked foaming product that kneading and acquisition have the required enough hardness of footwear foaming product, when especially and (A2) being ethene/butene-1 copolymer when the above-mentioned ethylene/alpha-olefin copolymer (A1) that comprises in the foamed products composition, can make sandwich obtain good plunger bond strength, this sandwich comprises that a foamed products layer and at least one are selected from the layer of following material: polyolefine, urethane, rubber, leather and imitation leather.According to this discovery, finish the present invention.
Goal of the invention
The present invention is with solving the problem relevant with above-mentioned prior art, the purpose of this invention is to provide a kind ofly can provide foamed products (uncrosslinked or crosslinked foamed products) composition, foamed products and have good plunger bond strength and use the sandwich of this foamed products, described foamed products have the Asker C hardness, low-gravity, low compression deformation (CS) of 20-80, good tear strength, bounce impact elasticity and mouldability.
Another object of the present invention provides the parts of the footwear that comprise foamed products or sandwich, for example the middle end of sole, footwear, the interior end and sandals.
Summary of the invention
The present composition is a kind of composition that comprises ethylene/alpha-olefin copolymer (A) and whipping agent (B), and therein ethylene/alpha-olefin copolymer (A) comprises:
5-95 weight part density is not less than 0.880 gram per centimeter
3And less than 0.900 gram per centimeter
3, melt flow rate (MFR) (1238,190 ℃ of ASTM D, 2.16 kilogram load) is/10 minutes ethylene/alpha-olefin copolymer (A1) of 0.1-50 gram,
5-95 weight part density is the 0.900-0.930 gram per centimeter
3, melt flow rate (MFR) (1238,190 ℃ of ASTM D, load are 2.16 kilograms) was for 0.1-50 gram/10 minutes and be not higher than 110 ℃ of ethylene/alpha-olefin copolymers (A2) that main fusing point peak is arranged,
Described component (A1) and (A2) total amount be 100 weight parts.
The foamed products that is obtained by this composition has the hardness that enough is used for footwear.
Among the present invention, best ethylene/alpha-olefin copolymer (A1) and (A2) all be ethene/butene-1 copolymer.
Among the present invention, ethylene/alpha-olefin copolymer (A1) and (A2) at least aly better have a following performance:
Melt flow rate (MFR) (the MFR that under 190 ℃ and 10 kilogram load conditions, measures according to ASTM D 1238
10) with the melt flow rate (MFR) (MFR that under 190 ℃ and 2.16 kilogram load conditions, measures according to ASTM D 1238
2.16) ratio (MFR
10/ MFR
2.16) satisfy following the relation:
MFR
10/MFR
2.16≥5.63
And molecular weight distribution (Mw/Mn) and the satisfied following relation of above-mentioned melt flow rate (MFR) ratio:
Mw/Mn≤(MFR
10/MFR
2.16)-4.63。
And, ethylene/alpha-olefin copolymer (A1) and (A2) at least a to have following performance better:
Melt flow rate (MFR) (the MFR that under 190 ℃ and 10 kilogram load conditions, measures according to ASTM D 1238
10) with the melt flow rate (MFR) (MFR that under 190 ℃ and 2.16 kilogram load conditions, measures according to ASTM D 1238
2.16) ratio (MFR
10/ MFR
2.16) satisfy following the relation:
MFR
10/MFR
2.16≥5.63
And molecular weight distribution (Mw/Mn) and the satisfied following relation of above-mentioned melt flow rate (MFR) ratio:
Mw/Mn+4.63≤MFR
10/MFR
2.16≤14-2.9Log(MFR
2.16)。
Ethylene/alpha-olefin copolymer (A) better has the 0.880-0.920 gram per centimeter
3Density and/10 minutes melt flow rate (MFR) (1238,190 ℃ of ASTM D, 2.16 kilogram load) of 0.1-10 gram.
In the present composition, whipping agent (B) generally is selected from organic thermolysis type whipping agent, inorganic thermolysis type whipping agent, organic pneumatogen and inorganic pneumatogen.
Foamed products of the present invention can obtain by the composition of thermal treatment the invention described above.
Foamed products of the present invention can be the foamed products that above-mentioned foamed products obtains through second-compressed.
Sandwich of the present invention has the layer that comprises foamed products of the present invention and comprises at least a layer that is selected from polyolefine, urethane, rubber, leather and imitation leather material.
The method of making sandwich of the present invention comprises the following steps: to make the step of present composition foaming and makes rapid foamed products and at least a synergetic step of material that is selected from polyolefine, urethane, rubber, leather and imitation leather that obtains of previous step.
The parts of footwear of the present invention and footwear comprise foamed products of the present invention or sandwich of the present invention.
The parts of footwear for example are the middle end, the interior end or sole.
The accompanying drawing summary
The moment of torsion of each composition that Figure 1 shows that embodiment 1 and comparative example 1 is with the variation of mediating the time.
Fig. 2 is the synoptic diagram of second-compressed mould, and this mould has the sculptured surface that uses in embodiment 1 and comparative example 1, to estimate the mouldability of foamed products.
Detailed description of the Invention
The below describes the present composition and application thereof in detail.
Composition of the present invention comprises specific ethylene/alpha-olefin copolymer (A), blowing agent (B), optional organic peroxide (C) and crosslinking coagent (D).
Foamed products of the present invention is by obtaining described composition foaming or crosslinked foaming. The example of cross-linking method comprises heat cross-linking and crosslinking by ionizing radiation. For the heat cross-linking situation, need in composition, add organic peroxide (C) and crosslinking coagent (D). For the situation of crosslinking by ionizing radiation, can add crosslinking coagent (D).
Ethylene/alpha-olefin copolymer (A)
The ethylene/alpha-olefin copolymer (A) that the present invention uses comprises following ethylene/alpha-olefin copolymer (A1) and ethylene/alpha-olefin copolymer (A2).
Ethylene/alpha-olefin copolymer (A1) is ethene and the random or block copolymer of noncrystalline or low crystallization that the alpha-olefin of 3-20 carbon atom is arranged, and requires the density (ASTM D 1505) of soft ethylene/alpha-olefin copolymer to be not less than 0.880 gram per centimeter3And less than 0.900 gram per centimeter3, melt flow rate (MFR) (MFR, 1238,190 ℃ of ASTM D, load are 2.16 kilograms) restrains/10 minutes for 0.1-50, and preferably the 0.5-20 gram is/10 minutes.
With the alpha-olefin of ethylene copolymer be the alpha-olefin that 3-20 carbon atom arranged, example comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-endecatylene, 1-dodecylene, 1-hexadecene, 1-vaccenic acid, 1-19 carbenes, 1-eicosylene and 4-methyl-1-pentene. Wherein, alpha-olefin is the alpha-olefin of 3-10 carbon atom preferably, preferably propylene, 1-butylene, 1-hexene and 1-octene. These alpha-olefins can use separately, or make up two or more uses.
Require ethylene/alpha-olefin copolymer (A1) to contain 85%-95% (mole) from the unit of ethene and 5%-15% (mole) unit from the alpha-olefin of 3-20 carbon atom.
The assay method of the composition of the ethylene/alpha-olefin copolymer that the following describes (A1) or ethylene/alpha-olefin copolymer (A2) is, by in the sample cell of 10 millimeters of diameters, about 200 milligrams of ethylene/alpha-olefin copolymer uniform dissolution being made sample in 1 milliliter of hexachlorobutadiene, it is 120 ℃ measuring temperature, the mensuration frequency is 25.05MHz, and 1500Hz spectrum width, pulse-recurrence time are that 4.2 seconds and pulse width are working sample under the 6 microsecond conditions13The C-NMR spectrogram is determined to form.
Ethylene/alpha-olefin copolymer (A1) also comprises the unit from other polymerisable monomers except said units, only otherwise depart from purpose of the present invention.
The example of ethylene/alpha-olefin copolymer (A1) comprises ethylene/propene copolymer, Ethylene/1-butene copolymer, ethylene/propene/butene-1 copolymer, ethylene/propylene/ethylidene norbornene copolymer, ethene/1-hexene copolymer and ethene/1-octene copolymer. Wherein, better use ethylene/propene copolymer, Ethylene/1-butene copolymer, ethene/1-hexene copolymer and ethene/1-octene copolymer. Preferably use the Ethylene/1-butene copolymer. These copolymers can be random copolymer or block copolymer, but random copolymer preferably.
Measure by the X-ray diffraction method, the degree of crystallinity of ethylene/alpha-olefin copolymer (A1) generally is not more than 40%, preferably 10%-30%.
Ethylene/alpha-olefin copolymer (A1) can adopt hitherto known method, uses the preparations such as phosphorus/vanadium catalyst, titanium catalyst, metallocene catalyst.
Ethylene/alpha-olefin copolymer (A2) generally is low-crystallinity random copolymer or the block copolymer of the alpha-olefin of ethene and 3-20 carbon atom, requires soft ethylene/alpha-olefin copolymer density (ASTM D 1505) to be the 0.900-0.930 gram per centimeter3, 0.900-0.920 gram per centimeter preferably3, melt flow rate (MFR) (MFR, 1238,190 ℃ of ASTM D, load are 2.16 kilograms) is 0.1-50 gram/10 minutes, preferably the 0.5-20 gram is/10 minutes, main fusing point peak is arranged not being higher than 110 ℃.
With the alpha-olefin of ethylene copolymer be the alpha-olefin that 3-20 carbon atom arranged, example comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-endecatylene, 1-dodecylene, 1-hexadecene, 1-vaccenic acid, 1-19 carbenes, 1-eicosylene and 4-methyl-1-pentene. Wherein, alpha-olefin is the alpha-olefin of 3-10 carbon atom preferably, preferred propylene, 1-butylene, 1-hexene and 1-octene. 1-butylene preferably. These alpha-olefins can use separately, or make up two or more uses.
Require ethylene/alpha-olefin copolymer (A2) to contain 90%-99% (mole) from the unit of ethene and 1%-10% (mole) unit from the alpha-olefin of 3-20 carbon atom.
Ethylene/alpha-olefin copolymer (A2) also can comprise the unit from other polymerisable monomers except said units, only otherwise depart from purpose of the present invention.
The example of ethylene/alpha-olefin copolymer (A2) comprises ethylene/propene copolymer, Ethylene/1-butene copolymer, ethylene/propene/butene-1 copolymer, ethylene/propylene/ethylidene norbornene copolymer, ethene/1-hexene copolymer and ethene/1-octene copolymer. Wherein, better use ethylene/propene copolymer, Ethylene/1-butene copolymer, ethene/1-hexene copolymer and ethene/1-octene copolymer. Ethylene/1-butene copolymer preferably. These copolymers can be random copolymer or block copolymer, but random copolymer preferably.
" main fusing point peak " is the top in the endothermic peak shown in the copolymer endothermic curve, by using poor formula scanning calorimeter (DSC), place the sample of aluminium dish to be heated to 200 ℃ with 50 ℃ of/minute speed, then kept 5 minutes at 200 ℃, be cooled to-40 ℃ with 10 ℃ of/minute speed, obtain described endothermic curve when being heated to 150 ℃ with 10 ℃ of/minute speed again. When having a plurality of endothermic peak, relatively by the absolute value on the longitudinal axis of the W of unit (energy/time) representative, rather than peak area, peaked peak is got and is made main fusing point peak.
The case hardness of ethylene/alpha-olefin copolymer (A2) is according in the Shore D hardness (ASTM D 2240) more fortunately 30-70 scope. When use has the ethylene/alpha-olefin copolymer (A2) of such Shore D hardness, the crosslinked foaming product that can obtain to have the required hardness of footwear.
Measure by the X-ray diffraction method, the degree of crystallinity of ethylene/alpha-olefin copolymer (A2) generally is not more than 50%, is 15-40% preferably.
Ethylene/alpha-olefin copolymer (A2) can adopt hitherto known method, uses the preparations such as Ziegler catalyst, metallocene catalyst.
Requiring ethylene/alpha-olefin copolymer (A2) is the ethylene/alpha-olefin copolymer that obtains by polymerisation in solution. Utilize polymerisation in solution, can obtain easily to have the ethylene/alpha-olefin copolymer (A2) of better fusing point. On the other hand, the ethylene/alpha-olefin copolymer for preparing by gas-phase polymerization can have a plurality of fusing points peak, therefore can part fusing point peak occur in the temperature range that is not less than 110 ℃.
Require ethylene/alpha-olefin copolymer (A1) and (A2) in have a kind of following performance that has at least:
Melt flow rate (MFR) (the MFR that under 190 ℃ and 10 kilogram load conditions, measures according to ASTM D 123810) with the melt flow rate (MFR) (MFR that under 190 ℃ and 2.16 kilogram load conditions, measures according to ASTM D 12382.16) ratio (MFR10/MFR
2.16) satisfy following the relation:
MFR
10/MFR
2.16≥5.63
And molecular weight distribution (Mw/Mn) and the satisfied following relation of above-mentioned melt flow rate (MFR) ratio:
Mw/Mn≤(MFR
10/MFR
2.16)-4.63，
Better satisfy: Mw/Mn+4.63≤MFR
10/ MFR
2.16≤ 14-2.9Log (MFR
2.16).
If satisfy above-mentioned relation, can obtain to make and have the composition that high expansion ratio is the foamed products (uncrosslinked foamed products, crosslinked foaming product) of low-gravity, snappiness, good compression set resistant and mouldability.
According to following mode, use Millipore GPC-150C determining molecular weight distribution (Mw/Mn).
Use the TSK GNH HT separator column of 72 millimeters of diameters, 600 millimeters of length, column temperature is set in 140 ℃.Use orthodichlorobenzene (buying) as moving phase from Wako Junyaku Kog yo K.K., 0.025% (weight) BHT is (from Takeda Chemical Industries, Ltd. buy) as oxidation inhibitor, sample [concentration: 0.1% (weight), injection: 500 microlitres] is flowed with the speed of 1.0 ml/min.Use differential refractometer as detector.Use is available from Mw＜1000 and Mw＞4 * 10 of Tosoh K.K.
6Polystyrene and 1000≤Mw≤4 of buying from Pressure Chemical Co. * 10
6Polystyrene as polystyrene standards.
Component (A1) and (A2) total amount be under the condition of 100 weight, ethylene/alpha-olefin copolymer (A1) consumption is the 5-95 weight part, is preferably the 50-90 weight part, ethylene/alpha-olefin copolymer (A2) consumption is the 5-95 weight part, is preferably the 10-50 weight part.
The ethylene/alpha-olefin copolymer (A) that uses among requirement the present invention, promptly the density (ASTM D 1505) of the soft ethylene/alpha-olefin copolymer of the mixture of ethylene/alpha-olefin copolymer (A1) and ethylene/alpha-olefin copolymer (A2) is the 0.880-0.920 gram per centimeter
3, melt flow rate (MFR) (MFR, 1238,190 ℃ of ASTM D, load are 2.16 kilograms) is preferably 0.5-10 gram/10 minutes for 0.1-10 restrains/10 minutes.
The molecular weight distribution (Mw/Mn) of ethylene/alpha-olefin copolymer (A) is measured according to gel permeation chromatography (GPC), is preferably 2.3-4.0.When the ethylene/alpha-olefin copolymer (A) that uses molecular weight distribution in above-mentioned scope, obtain to prepare the composition of foamed products with good compression set resistant and mouldability.
Ethylene/alpha-olefin copolymer (A) generally has elastomeric properties.
Whipping agent (B)
The whipping agent (B) that the present invention uses for instance, can be a kind of chemical foaming agent.The example of chemical foaming agent comprises organic thermolysis type whipping agent and inorganic thermolysis type whipping agent.The object lesson of organic thermolysis type whipping agent comprises azo-compound, as Cellmic C 121 (ADCA), 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane), 2,2 '-azo, two butyric acid dimethyl esters, 2,2 '-azo-bis-iso-dimethyl, 2,2 '-azo two (2,4, the 4-trimethylpentane), 1,1 '-azo two (hexanaphthene-1-nitrile) and 2,2 '-azo two [N-(2-propyloic)-2-methyl-propionyl amidine) (2,2 '-azobis[N-(2-carboxyethyl)-2-methyl-propionamidine]); Nitroso compound, as N, N '-dinitrosopentamethylene tetramine (DPT); Hydrazine derivative, as 4,4 '-oxygen two (benzol sulfohydrazide) and sulfobenzide-3,3 '-disulfonyl hydrazide; Semicarbazide compound is as p-toluenesulfonyl Urea,amino-and trihydrazinotriazine.The object lesson of inorganic thermolysis type whipping agent comprises supercarbonate such as sodium bicarbonate and bicarbonate of ammonia; Carbonate such as yellow soda ash and volatile salt; Nitrite such as ammonium nitrite; And hydrogen compound.Wherein, preferably Cellmic C 121 (ADCA) and sodium bicarbonate.
Among the present invention, also use pneumatogen (in foaming process not always with the whipping agent of chemical reaction) as organic pneumatogen and inorganic pneumatogen as whipping agent (B).The example of organic pneumatogen comprises methyl alcohol; Ethanol; Various aliphatic hydrocrbons are as propane, butane, pentane and hexane; Various hydrochloric ethers are as ethylene dichloride, methylene dichloride and tetrahydro-carbon; With various fluorochlorohydrocarbons, as freonll-11 (Freon).The example of inorganic pneumatogen comprises air, carbonic acid gas, nitrogen, argon G﹠W.From vaporability, cost, environmental pollution and flammable consideration, wherein best is carbonic acid gas, nitrogen and argon gas.
Do not have residue owing to the pneumatogen as whipping agent of the present invention (B) can decompose fully, therefore can prevent from composition crosslinked foaming process, to stain mould.And because pneumatogen is not a powdery, so it mediates excellent property.When using pneumatogen, can avoid the smell (smell of the ammonia when ADCA decomposes etc.) of the crosslinked foaming product that makes.
Among the present invention, above-mentioned chemical foaming agent can use together with pneumatogen, only otherwise produce smell and stain mould etc.
To the storage of pneumatogen, when less throughput rate uses pneumatogen, gas such as carbonic acid gas or nitrogen are supplied with injector or extrusion shaper by setter.A kind of situation is, by after the pressurization of equipment such as pump it being supplied with injector or extrusion shaper.
In the larger factory of crosslinked foaming products production, can pneumatogen be supplied with injector or extrusion shaper by pipeline from Liquid carbon dioxide or liquid nitrogen holder by evaporator evaporation with by after the reducing valve decompression.
When pneumatogen was liquid state, pressure store was advisable in the 0.13-100MPa scope.If pressure store is too low, can not supply with injector or extrusion shaper by reducing valve.If but pressure store is too high, because the design pressure of storage facilities must raise, its size can be excessive or complicated.Pressure store among the present invention is defined as the evaporation back and supplies with reducing valve pressure before.
When using chemical foaming agent as whipping agent (B), the chemical foaming agent consumption is the whipping agent that generally contains the 3-20 weight part in the ethylene/alpha-olefin copolymer (A) of per 100 weight parts, is preferably the 5-15 weight part.Yet the amount of chemical foaming agent can suitably increase or reduce to desired ratio of expansion, because the gas that produces is according to the kind of the chemical foaming agent that uses or rank and difference.
When using pneumatogen as whipping agent (B), the suitable consumption of ratio of expansion decision pneumatogen as requested.
Among the present invention, if desired, frothing aid can and whipping agent (B) use together.The effect of frothing aid is the decomposition temperature that reduces whipping agent (B), quickens its decomposition and produces uniform bubble.
The example of frothing aid comprises zinc oxide (ZnO), Zinic stearas, organic acid such as Whitfield's ointment, phthalic acid, stearic acid and oxalic acid and urea or derivatives thereof.
Organo-peroxide (C)
The example of the optional organo-peroxide (C) that uses comprises dicumyl peroxide among the present invention, di-t-butyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-two-(t-butyl peroxy) hexin-3,1,3-two (t-butyl peroxy sec.-propyl) benzene, 1,1-two (t-butyl peroxy)-3,3, the 5-trimethyl-cyclohexane, 4,4-two (t-butyl peroxy) n-butyl pentanoate, benzoyl peroxide, chloro benzoyl peroxide, peroxidation 2,4 dichloro benzene formyl, t-butylperoxyl benzoate, t-butylperoxy isobutyl carbonate propyl ester, diacetyl peroxide, the peroxide lauroyl, the tert-butyl peroxide cumyl.
Among the present invention, organo-peroxide (C) consumption is generally ethylene/alpha-olefin copolymer (A) (mixture of ethylene/alpha-olefin copolymer (A1) and ethylene/alpha-olefin copolymer (A2)) the 0.1-1.5 weight part of per 100 weight parts, is preferably the organo-peroxide (C) of 0.2-1.0 weight part.When using the organo-peroxide (C) of above-mentioned amount, the crosslinked foaming product that can obtain to have appropriately crosslinked structure.When the organo-peroxide (C) of above-mentioned amount and crosslinking coagent (D) when using together, can obtain to have the crosslinked foaming product of more suitable crosslinking structure.
Crosslinking coagent (D)
The better example of the optional crosslinking coagent (D) that uses comprises the peroxide crosslinking auxiliary agent among the present invention, as sulphur, paraquinonedioxime, p, p '-dibenzoyl quininie dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, vulkacit D and TriMethylolPropane(TMP)-N, N '-meta-phenylene bismaleimide; Vinylstyrene, triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC).Can also use multifunctional methacrylate monomer such as Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and allyl methacrylate(AMA); With polyfunctional vinyl monomer such as vinyl butyrate and stearic acid vinyl ester.Wherein, be preferably triallyl cyanurate (TAC) and triallyl isocyanurate (TAIC).
Among the present invention, it is 1/30 to 5/1 that the crosslinking coagent consumption should make the weight ratio ((D)/(C)) of crosslinking coagent (D) and organo-peroxide (C), is preferably 1/20 to 3/1, preferably 1/15 to 2/1.
Preparation of compositions
Composition of the present invention is a composition uncrosslinked and that do not foam, can be the consolidation state, or cooling and hardened particle or sheet-form.
The particle of the present composition can be by following method preparation, for example, with Henschel mixing tank etc., according to aforementioned proportion mixed ethylene/alpha-olefin copolymer (A) (mixture of A1 and A2), whipping agent (B) and optional organo-peroxide (C), crosslinking coagent (D) and frothing aid, under whipping agent (B) and/or the not resolvent temperature of organo-peroxide (C), melt this mixture of plasticating by kneader device such as Banbury mixing tank, roller or forcing machine, uniform mixing and disperse this mixture, and granulation then.
Except that said components, if desired, can add various additives in the composition, as filler, thermo-stabilizer, the stablizer of anti-weather the, fire retardant, hydrochloric acid absorbent and pigment, as long as the object of the invention is not had detrimentally affect.
The sheet material of composition of the present invention can use the composition pellet preparation by above-mentioned acquisition of forcing machine or rolling press.Can be by the component of kneading compositions such as Brabender mill; with stack or compression mold device kneaded material is configured as sheet material then; or mediate component with forcing machine and make this kneaded material then, but preparation foam sheet uncrosslinked and that do not foam by T-mould or circular die.
Foamed products
Foamed products of the present invention can pass through at 130-200 ℃, the 30-300 kilogram force/centimetre
2Pressure is experience 10-90 minute down, makes present composition foaming or crosslinked foaming and makes.Yet (crosslinked) foamed time depends on the thickness of molding, and therefore, above-mentioned time range can suitably increase or reduce.
Foamed products of the present invention can be foamed under these conditions or the shaping prod of crosslinked foaming at 130-200 ℃, the 30-300 kilogram force/centimetre
2The following time of pressure is that 5-60 minute and compression ratio are 1.1-3, is preferably the foamed products that the condition lower compression of 1.3-2 is shaped and obtains.
The proportion (JIS K 7222) of foaming back product is 0.05-0.25, and surface hardness (Asker C hardness) is 20-80.Require crosslinked foamed products gel fraction to be not less than 70%, general gel fraction is 70-90%.
Foamed products of the present invention has above-mentioned performance, and especially the crosslinked foaming product has low compressive set, high-tear strength and HI high impact rebound resilience.
Measure gel fraction (gel content is insoluble to the content of dimethylbenzene) according to following mode:
Take by weighing the sample of crosslinked foaming product, and cut into pieces.Then, these fragments and dimethylbenzene are placed an encloses container together, refluxed 3 hours.
Afterwards, sample is taken out complete drying on filter paper.Deduct the weight that is insoluble to toluene component (as filler, packing material and pigment) except that polymeric constituent from dried residue weight, the value of obtaining get work " final weight after the correction (Y) ".
On the other hand, deduct weight that is dissolved in toluene component (as stablizer) except that polymeric constituent and the weight that is insoluble to dimethylbenzene component (as filler, packing material and pigment) except that polymeric constituent from example weight, the value of obtaining get work " initial weight after the correction (X) ".
By following formula calculated for gel content (being insoluble to the content of dimethylbenzene):
Gel content (% (weight))=(proofreading and correct back final weight (Y))/(proofreading and correct back initial weight (X)) * 100
The preparation of foamed products
Foamed products of the present invention (uncrosslinked or crosslinked foamed products) can be by following method manufacturing.
Sheet material of the present invention for example can use rolling press, compression mold device or T shape mould forcing machine, makes the front prepare the mixture forming described in the composition and obtains.Sheet forming need be carried out under the decomposition temperature that is not higher than whipping agent (B) and organo-peroxide (C).More specifically, sheet forming need be carried out under the melt composition temperature reaches 100-130 ℃ temperature.
The sheet shape composition of above-mentioned acquisition is cut into volume 1.0-1.2 times for this mould volume, then, places to maintain the temperature at 130-200 ℃ mould, maintenance 30-300 kilogram force in this mould/centimetre
2Locking force, kept 10-90 minute, make elementary foamed products (uncrosslinked or crosslinked foamed products).Yet (crosslinked) time is depended on mold thickness, and therefore above-mentioned time range can suitably increase or shorten.
The mold shape that is used for (crosslinked) foaming is had no particular limits, but general use can obtain the mould of sheet form.Mould must have the structure of complete closure, and the gas of molten resin and generation during whipping agent decomposes can not escaped.Consider that from the resin rippability mould bases better is the mould bases that there is tapering inside.
Provide the elementary foamed products that obtains above predetermined shape by compressed moulding.In die temperature is 130-200 ℃, locking force be the 30-300 kilogram force/centimetre
2, compression time is that 5-60 minute and compression ratio are to carry out compressed moulding under the condition of 1.1-3.0.
For passing through to obtain crosslinked foamed products by crosslinking by ionizing radiation, at first, ethylene/alpha-olefin copolymer (A), be lower than melt kneading under organic thermolysis type foaming agent decomposition temperature as organic thermolysis type whipping agent of whipping agent (B) and other additives, the kneaded material that makes is shaped to sheet material, obtains foamable sheet material.
Then, but thus obtained foam sheet is by ionizing rays, come cross-linked ethylene/alpha-olefin copolymer (A) with the doses radiation, then, the foamable crosslinked sheet material that makes is heated to the decomposition temperature that is not less than organic thermolysis type whipping agent, this sheet material that foams, thus crosslinked foam sheet obtained.
Example in this spendable ionizing rays comprises alpha-ray, β ray, gamma-rays, electron rays, neutron ray and X ray.Wherein, should use the gamma-rays and the electron rays of cobalt-60.
The example of the shape of foamed products comprises the goods of sheet shape, slab, net material and moulding.
By the crosslinked foaming product that obtains above, according to preparation elementary foamed products identical mode, make the foamed products of secondary crosslinking with above-mentioned performance.
Sandwich
Sandwich of the present invention is to have the layer that comprises foamed products of the present invention (uncrosslinked or crosslinked foaming product) and comprise at least a sandwich that is selected from the layer of polyolefine, urethane, rubber, leather and imitation leather material.
Polyolefine, urethane, rubber, leather and imitation leather are had no particular limits, can use any hitherto known polyolefine, urethane, rubber, leather and imitation leather.
Sandwich of the present invention is preferably used in the parts of footwear and footwear.
The parts of footwear and footwear
The parts of footwear of the present invention and footwear comprise foamed products of the present invention (uncrosslinked or crosslinked foaming product) or sandwich.
The examples of members of footwear comprises the sole of sole, the middle end, the interior end and footwear and sandals.
Effect of the present invention
The invention provides a kind of foamed products (foamed products that comprises second-compressed) of the composition said composition that foamed products (uncrosslinked or crosslinked foamed products) can be provided and the sandwich that uses this foamed products, described foamed products has the Asker C hardness, low-gravity, low compression deformation (CS) of 20-80, good tear strength, bounce impact elasticity and mouldability.Especially and (A2) time, sandwich has better plunger bond strength at the ethylene/alpha-olefin copolymer (A1) that uses ethylene/alpha-olefin copolymer to comprise in as the foamed products composition.
The present invention also provides the footwear that comprise above-mentioned uncrosslinked or crosslinked foamed products and the parts of footwear.
Embodiment
Further describe the present invention with reference to the following examples, but these embodiment are construed as limiting the invention never.
Measure proportion, Asker C hardness, tensile strength, tear strength, compressive set, bounce impact elasticity and the mouldability of the foamed products that makes in embodiment and the comparative example according to the methods below.Estimate sensation of softness in the following method.And measure the bond strength of the sandwich that comprises prepared foamed products and polyurethane artificial leather sheet material by method described below.
(1) proportion of foamed products
According to JIS K 7222, mensuration has the foaming surface and (is abbreviated as skin
On) the proportion of foamed products, use Mirgae Trading Co., the electronics proportion instrument (model MD-200S) that Ltd makes is measured foaming surface (skin
Off) foamed products proportion.
(2) Asker C hardness
Measure Asker C hardness according to " test method of spring hardness test C " described in JIS K 7312-1996 Annex 2 annexes.
(3) tensile strength
According to JIS K 6301, under the stress rate condition of 23 ℃ mensuration temperature and 500 mm/min, carry out tension test, the tensile strength when being determined at the fracture of crosslinked foaming sheet material.
(4) tear strength
According to BS5131-2.6, under the stress rate condition of 100 mm/min, carry out tear strength test, measure tear strength.
(5) compressive set
According to JIS K 6301, under 50 ℃ * 6 hours and 50% contractive condition, carry out compression deformation test, measure compressive set.
(6) pliability sensation
By touching the surface of foamed products, estimate the pliability sensation, be divided into 5 grades.
[evaluations of 5 grades]
5: sensory surface is smooth and soft.
4: sensory surface is soft but grit is arranged.
3: estimate between 2 and 4.
2: sensory surface has sand grains, and is a bit hard.
1: sensory surface is coarse and hard as resin.
(7) bounce impact elasticity
Measure bounce impact elasticity according to JIS K 6255.
(8) plunger bond strength of sandwich
[processing of secondary crosslinking foamed products]
With the surface of the water cleaning secondary crosslinking foamed products that contains tensio-active agent, and at room temperature dry 1 hour.
Then, the secondary crosslinking foamed products was immersed in the methylcyclohexane 3 minutes, in 60 ℃ of baking ovens dry 3 minutes.
Subsequently, coat very thin one deck ultraviolet curing type priming paint (trade(brand)name: GE258H1 obtains from DaitoJyushi K.K.) with brush, drying is 3 minutes in 60 ℃ of baking ovens.Use 3 power respectively to be high voltage mercury lamp (the UV irradiator of 80W/cm, Japan Storage Battery Co., Ltd makes, the EPSH-600-35 type) the irradiation UV-light, forwarder speed with 10m/min moves foamed products, is being 15 centimetres perpendicular to travel direction apart from the lamp distance of installing.
Afterwards, coat the auxiliary priming paint of thin one deck (for adding the stiffening agent of 5% (weight) among the priming paint GE6001L (trade(brand)name), GE366S (trade(brand)name), priming paint and stiffening agent are all available from Daito JyushiK.K.) with brush, drying is 3 minutes in 60 ℃ of baking ovens.
Subsequently, coat thin layer of adhesive (for adding the stiffening agent of 5% (weight) among the tackiness agent 98H (trade(brand)name), GE348 (trade(brand)name), tackiness agent and stiffening agent are all available from Daito JyushiK.K.) with brush, drying is 5 minutes in 60 ℃ of baking ovens.
At last, by at 20kg/cm
2Down bonding 10 seconds of contact of pressure, the secondary crosslinking foamed products that will scribble above-mentioned tackiness agent is stacked with the polyurethane artificial leather sheet material of making according to following method.
[processing of polyurethane artificial leather sheet material]
With methyl ethyl ketone clean polyurethane imitation leather sheet surface, at room temperature dry 1 hour.
Afterwards, coat the auxiliary priming paint of thin one deck (for adding the stiffening agent of 5% (weight) among the priming paint GE6001L (trade(brand)name), GE366S (trade(brand)name), priming paint and stiffening agent are all available from Daito JyushiK.K.) with brush, drying is 3 minutes in 60 ℃ of baking ovens.
Subsequently, coat thin layer of adhesive (for adding the stiffening agent of 5% (weight) among the tackiness agent 98H (trade(brand)name), GE348 (trade(brand)name), tackiness agent and stiffening agent are all available from Daito JyushiK.K.) with brush, drying is 5 minutes in 60 ℃ of baking ovens.
[stripping test]
Estimate above-mentioned bond strength after 24 hours according to following mode by the stacked sheet material of coat binding:
Cut out 1 centimetre wide by the stacked sheet material of coat binding.Peel off after the end of this sheet material,, measure stripping strength with 200mm/min speed and 180 ° of these sheet material ends of direction tractive.
Estimate 5 samples, the mean value of bond strength is listed in table 1.State is peeled off in visual inspection this moment.
(9) mouldability
In the one side of second-compressed mould, carve figure as shown in Figure 2, and use the average mouldability of this mould.For example, if be that the mouldability of 2mm part is good in the degree of depth for the 2mm width, evaluation result is described as t2-w2.
Preparation embodiment 1
The preparation catalyst solution
Take by weighing 18.4 milligram of four (pentafluorophenyl group) boric acid triphenylcarbenium, add 5 milliliters of toluene and dissolve, thereby make the toluene solution that concentration is 0.004 mmole/milliliter.In addition, take by weighing 1.8 milligrams of dichloride [dimethyl (tert-butylamides) (tetramethyl--η
5-cyclopentadienyl) silane] titanium, add 5 milliliters of toluene and dissolve, thereby make the toluene solution that concentration is 0.001 mmole/milliliter.
Then, take out toluene solution and 0.38 milliliter of dichloride [dimethyl (tert-butylamides) (tetramethyl--η of 0.38 milliliter of four (pentafluorophenyl group) boric acid triphenylcarbenium
5-cyclopentadienyl) silane] toluene solution of titanium, adding 4.24 milliliters of toluene subsequently dilutes, make 5 milliliters of toluene solutions, four (pentafluorophenyl group) boric acid triphenylcarbenium concentration of this solution is counted 0.002 mmole/milliliter by B, dichloride [dimethyl (tert-butylamides) (tetramethyl--η
5-cyclopentadienyl) silane] titanium concentration counts 0.0005 mmole/milliliter by Ti.This toluene solution is as the catalyst solution of polyreaction.
Preparation ethene/butene-1 copolymer (A-1)
1.5 rise the SUS autoclave that is equipped with stirring rake, thoroughly purge with nitrogen.At 23 ℃, in this autoclave, drop into 750 milliliters of heptane.Rotate stirring rake and, drop into 8 gram 1-butylene and 250 milliliters of hydrogen with under ice-cooled.
Then, this autoclave is heated to 100 ℃,, makes stagnation pressure reach 6kg/cm with the ethene pressurization
2When the autoclave internal pressure reaches 6kg/cm
2The time, be that the hexane solution of the triisobutyl aluminium (TIBA) of 1.0 mmole/milliliters is pressed into this autoclave with nitrogen with 1.0 ml concns.Be pressed into 5 milliliters of catalyst solutions with nitrogen subsequently, cause the polyreaction of ethene and 1-butylene.After 5 minutes, controlled temperature and directly send into ethene makes this high pressure temperature in the kettle reach 100 ℃, and pressure reaches 6kg/cm
2Behind the initiated polymerization 5 minutes, feed 5 ml methanol with pump and stop polyreaction, relief pressure is to normal atmosphere subsequently.Stir down, in the reaction soln that obtains, pour 3 liters of methyl alcohol into.The solvent-laden polymkeric substance that makes in 130 ℃ of dryings 13 hours, obtains 10 gram ethene/butene-1 copolymers (A-1) under 600 torrs.
The ethylene content of the ethene/butene-1 copolymer (A-1) that obtains is 91% (mole), and 1-butylene content is 9% (mole), and density (ASTM D 1505) is 0.893 gram per centimeter
3, melt flow rate (MFR) (1238,190 ℃ of ASTM D, 2.16 kilogram load) is 3.8 grams/10 minutes, and melt flow rate (MFR) (1238,190 ℃ of ASTM D, 10 kilogram load) is 31 grams/10 minutes, and the molecular weight distribution of being measured by GPC (Mw/Mn) is 2.0, MFR
10/ MFR
2.16Be 8.2.The Xiao A hardness of ethene/butene-1 copolymer (A-1) (ASTM D 2240) is 92, is 82 ℃ by fusing point peak temperature on multipolymer (A-1) endothermic curve of DSC mensuration.Do not observe other peaks on endothermic curve, therefore main fusing point peak position is changed to 82 ℃.
Shaping prod according to the ethene/butene-1 copolymer (A-1) that uses in the following mode formation determination Xiao A hardness.
In 200 millimeters * 200 millimeters * mould of 2 millimeters (thickness), drop into ethene/butene-1 copolymer (A-1), at 200 ℃ and 160kg/cm
2Hot pressing is 10 minutes under the pressure, and 20 ℃ of coolings 5 minutes, obtains shaping prod.
Preparation embodiment 2
Preparation ethene/butene-1 copolymer (A-2)
According to obtaining 12 gram ethene/butene-1 copolymers (A-2) with preparation embodiment 1 identical mode, difference is, the 1-butylene amount changes 6 grams into, and the hydrogen amount changes 150 milliliters into.
Ethylene content is 94% (mole) in the ethene/butene-1 copolymer (A-2) that obtains, and 1-butylene content is 6% (mole), and density (ASTM D 1505) is 0.905 gram per centimeter
3, melt flow rate (MFR) (1238,190 ℃ of ASTM D, 2.16 kilogram load) is 1.2 grams/10 minutes, and melt flow rate (MFR) (1238,190 ℃ of ASTM D, 10 kilogram load) is 11.5 grams/10 minutes, and the molecular weight distribution of being measured by GPC (Mw/Mn) is 2.0, MFR
10/ MFR
2.16Be 9.6.The Xiao A hardness of ethene/butene-1 copolymer (A-2) (ASTM D 2240) is 43, is 94 ℃ by fusing point peak temperature on multipolymer (A-2) endothermic curve of DSC mensuration.Do not observe other peaks on endothermic curve, therefore main fusing point peak position is changed to 94 ℃.
According to preparing the shaping prod of the ethene/butene-1 copolymer (A-2) that in measuring Shore D hardness, uses with preparation embodiment 1 identical mode.
Preparation embodiment 3
Preparation ethene/butene-1 copolymer (A-2)
According to obtaining 10 gram ethene/butene-1 copolymers (A-3) with preparation embodiment 1 identical mode, difference is, the 1-butylene amount changes 10 grams into, and the hydrogen amount changes 100 milliliters into.
Ethylene content is 89% (mole) in the ethene/butene-1 copolymer (A-3) that obtains, and 1-butylene content is 11% (mole), and density (ASTM D 1505) is 0.885 gram per centimeter
3, melt flow rate (MFR) (1238,190 ℃ of ASTM D, 2.16 kilogram load) is 0.5 gram/10 minutes, and melt flow rate (MFR) (1238,190 ℃ of ASTM D, 10 kilogram load) is 5.0 grams/10 minutes, and the molecular weight distribution of being measured by GPC (Mw/Mn) is 2.1, MFR
10/ MFR
2.16Be 10.The Xiao A hardness of ethene/butene-1 copolymer (A-3) (ASTM D 2240) is 87, is 66 ℃ by fusing point peak temperature on multipolymer (A-3) endothermic curve of DSC mensuration.Do not observe other peaks on endothermic curve, therefore main fusing point peak position is changed to 66 ℃.
According to preparing the shaping prod of the ethene/butene-1 copolymer (A-3) that in measuring Xiao A hardness, uses with preparation embodiment 1 identical mode.
Preparation embodiment 4
The preparation catalyzer
10 kilograms have been suspended in 154 liters of toluene at 10 hours silicon-dioxide of 250 ℃ of dryings, and this suspension is cooled to 0 ℃.Afterwards, toluene solution (the Al concentration: 1.33 mol) of 7.5 liters of methylaluminoxane of Dropwise 5 in 1 hour inherent this suspension.During the dropping, this system temperature remains on 0 ℃.Being reflected at 0 ℃ and continuing 30 minutes of silicon-dioxide and methylaluminoxane.Then, in 1.5 hours, this system is heated to 95 ℃, under this temperature, reaction was carried out 20 hours.Afterwards, temperature is reduced to 60 ℃, takes by weighing the liquid of suspension by decantation.The solid that obtains toluene wash twice, and then be suspended in 100 liters of toluene.In 30 minutes, in 80 ℃, the toluene solution of dropping 16.8 liters of dichloride two (1-methyl-3-n-butyl cyclopentadienyl) zirconium in this system (Zr concentration: 27.0 mmoles/liter), be reflected at 80 ℃ and carried out again 2 hours.Then, remove supernatant liquor, resistates obtains solid catalyst with hexane wash twice, is benchmark with 1 gram catalyzer, and this catalyzer contains 3.5 milligrams of zirconiums.
The preparation pre-polymerized catalyst
Heating 870 above-mentioned solid catalysts of gram and 260 gram 1-hexenes in 87 liters of hexanes that contain 2.5 moles of triisobutyl aluminiums, 35 ℃ of ethene prepolymerizations of carrying out 5 hours, with 1 gram solid catalyst is benchmark, obtains to contain the poly pre-polymerized catalyst that 10 grams produce by prepolymerization.
Copolymerization
In successive type fluidized bed gas-phase polymerization reaction unit, be 18kg/cm at stagnation pressure
2-G and polymerization temperature are the copolymerization of carrying out ethene and 1-hexene under 75 ℃.This device in, in the speed of 0.15 mmole/hour (according to zirconium atom) import continuously pre-polymerized catalyst and with 10 mmoles/hour speed import triisobutyl aluminium continuously.During the polyreaction, import ethene, 1-hexene, hydrogen and nitrogen continuously, to keep the constant (gas composition: 1-hexene/ethene=0.034, hydrogen/ethene=1.7 * 10 of gas composition
-4, ethylene concentration=20%).
The productive rate of the above-mentioned ethene that obtains/1-hexene copolymer (A-4) is 5.84 Grams Per Hours.
Ethylene content is 94% (mole) in ethene/1-hexene copolymer (A-4), and 1-hexene content is 6% (mole), and density (ASTM D 1505) is 0.908 gram per centimeter
3, melt flow rate (MFR) (1238,190 ℃ of ASTM D, 2.16 kilogram load) is 0.8 gram/10 minutes, and melt flow rate (MFR) (1238,190 ℃ of ASTM D, 10 kilogram load) is 4.4 grams/10 minutes, and the molecular weight distribution of being measured by GPC (Mw/Mn) is 2.1, MFR
10/ MFR
2.16Be 5.5.The Shore D hardness (ASTM D 2240) of ethene/1-hexene copolymer (A-4) is 46, is 85 ℃, 113 ℃ and 120 ℃ by fusing point peak temperature on multipolymer (A-4) endothermic curve of DSC mensuration.Wherein, the maximum peak temperature is 120 ℃, and therefore main fusing point peak position is changed to 120 ℃.
According to preparing the shaping prod of the ethene/1-hexene copolymer (A-4) that in measuring Shore D hardness, uses with preparation embodiment 1 identical mode.
Embodiment 1
Ethene/butene-1 copolymer (A-1) by the acquisition in preparation embodiment 1 of 50 weight parts, ethene/butene-1 copolymer (A-2) that 50 weight parts obtain in preparation embodiment 2,3.0 the zinc oxide of weight part, 1.0 weight part stearic acid, 4.0 the titanium white of weight part, 0.6 the dicumyl peroxide of weight part (DCP), 0.15 isocyanic ester triallyl (TAIC: trade(brand)name: M-60 (the TAIC content: 60%) of weight part (according to TAIC content meter), available from Nippon KaseiK.K.) and the azodicarboamide (trade(brand)name: CELLCOM-JTR of 7.0 weight parts, from Kum Yang ChemicalCo., Ltd (Korea) buys) mixture formed, under 110 ℃ of preset temperatures, (Toyo Seiki Seisakusho makes with plastics runner millings (lapoplastomill) with the laboratory, model is 100MR2) mediated 5 minutes, be configured as sheet shape then.
Figure 1 shows that the variation of moment of torsion with the time of kneading.After beginning to mediate 60 seconds, by shown in Figure 1, the moment of torsion of embodiment 1 can find out thus that all the time less than the moment of torsion of comparative example 1 described later the kneading of embodiment 1 is better than comparative example 1.
Measure the top temperature of composition in the kneading process, the state of composition after visual inspection is mediated is to estimate dispersiveness.These the results are shown in table 1.
Then, the sheet material that obtains above is placed in the compacting tool set, at 150kg/cm
2, 155 ℃ and added hot pressing under the condition in 30 minutes, obtain elementary crosslinked foamed products.Compacting tool set is of a size of: thick 15 millimeters, long 200 millimeters, wide 150 millimeters.
Measure proportion, compressive set and the tear strength of the elementary crosslinked foaming product that makes according to the method described above.Also estimate the pliability sensation.
The results are shown in table.
Cut epidermis, at 150kg/cm
2, under 155 ℃, 10 minutes and the 1.5 compression ratio conditions, add the elementary crosslinked foaming product of hot pressing, at once 20 ℃ of coolings 10 minutes, obtain the product of secondary crosslinking foaming then.The secondary crosslinking foamed products is of a size of: thick 15 millimeters, long 250 millimeters, wide 160 millimeters.
Measure proportion, Asker C hardness, tensile strength, tear strength, compressive set, bounce impact elasticity and the mouldability of postevaluation secondary crosslinking foamed products according to the method described above.
Measure the kneading intensity of the sandwich comprise institute's foamed products that obtains and polyurethane artificial leather sheet material according to the method described above, state is peeled off in the while visual inspection.
The results are shown in table 1.
Embodiment 2
According to preparing elementary crosslinked foaming product with embodiment 1 described identical method, prepare the secondary crosslinking foamed products then, difference is that the dicumyl peroxide (DCP) that adds 0.8 weight part replaces the DCP of 0.6 weight part.
Subsequently, measure proportion, compressive set and the tear strength of elementary crosslinked foaming product according to the method described above, also estimate the pliability sensation.
The results are shown in table 1.
Measure or estimate proportion, Asker C hardness, tensile strength, tear strength, compressive set, bounce impact elasticity and the mouldability of secondary crosslinking foamed products according to the method described above.
Measure the kneading intensity of the sandwich comprise institute's foamed products that obtains and polyurethane artificial leather sheet material according to the method described above, state is peeled off in the while visual inspection.
The results are shown in table 1.
Embodiment 3
According to preparing elementary crosslinked foaming product with embodiment 1 described identical method, prepare the secondary crosslinking foamed products then, difference is to use the ethene/butene-1 copolymer (A-3) of 50 weight parts preparation in preparation embodiment 3 to replace 50 parts by weight of ethylene/butene-1 copolymer (A-1).
Subsequently, measure proportion, compression set and the tear strength of elementary crosslinked foaming product according to the method described above, also estimate the pliability sensation.
The results are shown in table 1.
Measure or estimate proportion, Asker C hardness, tensile strength, tear strength, compressive set, bounce impact elasticity and the mouldability of secondary crosslinking foamed products according to the method described above.
Measure the kneading intensity of the sandwich comprise institute's foamed products that obtains and polyurethane artificial leather sheet material according to the method described above, state is peeled off in the while visual inspection.
The results are shown in table 1.
Embodiment 4
According to preparing elementary crosslinked foaming product with embodiment 1 described identical method, prepare the secondary crosslinking foamed products then, difference is to use the ethene/1-octene copolymer (A-5) of 50 weight parts that below will describe and the ethene of 50 weight parts/1-octene copolymer (A-6) to replace the ethene/butene-1 copolymer (A-1) of 50 weight parts and the ethene/butene-1 copolymer (A-2) of 50 weight parts.
Subsequently, measure proportion, compressive set and the tear strength of elementary crosslinked foaming product according to the method described above, also estimate the pliability sensation.
The results are shown in table 1.
Measure or estimate proportion, Asker C hardness, tensile strength, tear strength, compression set, bounce impact elasticity and the mouldability of secondary crosslinking foamed products according to the method described above.
Measure the kneading intensity of the sandwich comprise institute's foamed products that obtains and polyurethane artificial leather sheet material according to the method described above, state is peeled off in the while visual inspection.
The results are shown in table 1.
Above-mentioned ethene/1-octene copolymer (A-5) is prepared by DuPont Dow Elastomers L.L.C., can " Engage " trade(brand)name buy, its ethylene content is 90% (mole), and the 1-octene content is 10% (mole), and density (ASTM D 1238) is 0.886 gram per centimeter
3, melt flow rate (MFR) (1238,190 ℃ of ASTM D, 2.16 kilogram load) is 2.67 grams/10 minutes, and melt flow rate (MFR) (1238,190 ℃ of ASTM D, 10 kilogram load) is 21.9 grams/10 minutes, and the molecular weight distribution of being measured by GPC (Mw/Mn) is 2.1, MFR
10/ MFR
2.06Be 8.2.The Xiao A hardness (ASTM D 2240) of ethene/1-octene copolymer (A-5) is 88, is 83 ℃ by fusing point peak temperature on multipolymer (A-5) endothermic curve of DSC mensuration.Do not observe other peaks on endothermic curve, therefore main fusing point peak position is changed to 83 ℃.
According to preparing the shaping prod of the ethene/1-octene copolymer (A-5) that in measuring Xiao A hardness, uses with preparation embodiment 1 identical mode.
Above-mentioned ethene/1-octene copolymer (A-6) is produced by Exxon-Mobil Chemical Co., can " Exact " trade(brand)name buy, its ethylene content is 94% (mole), and the 1-octene content is 6% (mole), and density (ASTM D 1505) is 0.903 gram per centimeter
3, melt flow rate (MFR) (1238,190 ℃ of ASTM D, 2.16 kilogram load) is 1.1 grams/10 minutes, and melt flow rate (MFR) (1238,190 ℃ of ASTM D, 10 kilogram load) is 8.7 grams/10 minutes, and the molecular weight distribution of being measured by GPC (Mw/Mn) is 2.1, MFR
10/ MFR
2.16Be 7.9.The Shore D hardness (ASTM D 2240) of ethene/1-octene copolymer (A-6) is 41, is 98 ℃ by fusing point peak temperature on multipolymer (A-6) endothermic curve of DSC mensuration.Do not observe other peaks on endothermic curve, therefore main fusing point peak position is changed to 98 ℃.
Shaping prod according to the ethene/1-octene copolymer (A-6) that uses in the mode formation determination Shore D hardness identical with preparation embodiment 1.
Comparative example 1
According to preparing elementary crosslinked foaming product with embodiment 1 described identical method, prepare the secondary crosslinking foamed products then, difference is that the ethene/1-hexene copolymer (A-4) that uses 50 weight parts to obtain in preparation embodiment 4 replaces the ethene/butene-1 copolymer (A-2) of 50 weight parts.
Figure 1 shows that the variation of moment of torsion with the time of kneading.Also measured the top temperature of composition in the kneading process, and visual inspection mediate after the state of composition, to estimate dispersiveness.
The results are shown in table 1.
Measure proportion, compression set and the tear strength of elementary crosslinked foaming product according to the method described above, also estimate the pliability sensation.
The results are shown in table 1.
Subsequently, measure or estimate proportion, Asker C hardness, tensile strength, tear strength, compressive set, bounce impact elasticity and the mouldability of secondary crosslinking foamed products according to the method described above.
Measure the kneading intensity of the sandwich comprise institute's foamed products that obtains and polyurethane artificial leather sheet material according to the method described above, state is peeled off in the while visual inspection.
The results are shown in table 1.
Comparative example 2
According to preparing elementary crosslinked foaming product with embodiment 1 described identical method, prepare the secondary crosslinking foamed products then, difference is to use the ethene/1-hexene copolymer (A-4) of 50 weight parts and the ethene of 50 weight parts/1-octene copolymer (A-5) to replace the ethene/butene-1 copolymer (A-1) of 50 weight parts and the ethene/butene-1 copolymer (A-2) of 50 weight parts.
Subsequently, measure proportion, compressive set and the tear strength of elementary crosslinked foaming product according to the method described above, also estimate the pliability sensation.
The results are shown in table 1.
Measure or estimate proportion, Asker C hardness, tensile strength, tear strength, compressive set, bounce impact elasticity and the mouldability of secondary crosslinking foamed products according to the method described above.
Measure the kneading intensity of the sandwich comprise institute's foamed products that obtains and polyurethane artificial leather sheet material according to the method described above, state is peeled off in the while visual inspection.
The results are shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| The kneading composition top temperature of composition (℃) | 118 | 119 | 130 | 121 | 132 | 133 |
| Mediate back composition state | Soft and fine dispersion | Soft and fine dispersion | Soft and fine dispersion | Soft and fine dispersion | Unfairness, it is slightly poor to disperse | Unfairness, it is slightly poor to disperse |
| Elementary crosslinked foaming product performance proportion (Skin off) | 0.090 | 0.101 | 0.098 | 0.092 | 0.093 | 0.095 |
| Compressive set (%) | 62 | 60 | 58 | 60 | 65 | 62 |
| Tear strength (N/cm) | 19 | 21 | 20 | 21 | 19 | 20 |
| The pliability sensation | 5 | 5 | 5 | 5 | 4 | 4 |
| Secondary crosslinking foamed products performance compression ratio | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Proportion (Skin on) | 0.138 | 0.162 | 0.153 | 0.143 | 0.144 | 0.144 |
| Asker C hardness | 53 | 56 | 53 | 52 | 54 | 53 |
| Tensile strength (MPa) | 2.6 | 2.9 | 3.0 | 2.7 | 2.7 | 2.7 |
| Compressive set (%) | 41 | 38 | 36 | 40 | 42 | 40 |
| Tear strength (N/cm) | 30 | 31 | 31 | 31 | 30 | 30 |
| Bounce impact elasticity (%) | 59 | 62 | 63 | 61 | 58 | 59 |
| Mouldability | t2-w2 | t2-w3 | t2-w2 | t2-w2 | t1-w2 | t1-w2 |
| Sandwich is bond strength (N/cm) after 24 hours | 36 | 33 | 38 | 18 | 28 | 22 |
| Peel off state | The material of foamed products is damaged | The material of foamed products is damaged | The material of foamed products is damaged | About 50% interface peel ( *) | Interface portion peel off ( *) | About 50% interface peel ( *) |
(
*): the interface peel that comprises the sandwich of one deck foamed products and one deck polyurethane artificial leather sheet material.
Claims (17)
1. a composition comprises the ethylene/alpha-olefin copolymer (A) of 100 weight parts and the whipping agent (B) of 3-20 weight part, and therein ethylene/alpha-olefin copolymer (A) comprising:
5-95 weight part density is not less than 0.880 gram per centimeter
3And less than 0.900 gram per centimeter
3, melt flow rate (MFR), press 1238,190 ℃ of ASTM D, 2.16 under the kilogram load, be/10 minutes ethylene/alpha-olefin copolymer (A1) of 0.1-50 gram, it contains the 85-95% mole from the unit of ethene and the 5%-15% mole unit from the alpha-olefin of 3-20 carbon atom
5-95 weight part density is the 0.900-0.930 gram per centimeter
3, melt flow rate (MFR), press ASTM D 1238,190 ℃, load is under 2.16 kilograms, for 0.1-50 restrains/10 minutes and be not higher than 110 ℃ of ethylene/alpha-olefin copolymers (A2) that main fusing point peak is arranged, it contains the 90%-99% mole from the unit of ethene and the 1%-10% mole unit from the alpha-olefin of 3-20 carbon atom
Described component (A1) and (A2) total amount be 100 weight parts.
2. composition as claimed in claim 1 is characterized in that ethylene/alpha-olefin copolymer (A1) and ethylene/alpha-olefin copolymer (A2) are ethene/butene-1 copolymers.
3. composition as claimed in claim 1 or 2 is characterized in that at least aly in ethylene/alpha-olefin copolymer (A1) and the ethylene/alpha-olefin copolymer (A2) having a following performance:
The melt flow rate (MFR) MFR that under 190 ℃ and 10 kilogram load conditions, measures according to ASTM D 1238
10With the melt flow rate (MFR) MFR that under 190 ℃ and 2.16 kilogram load conditions, measures according to ASTM D 1238
2.16Ratio MFR
10/ MFR
2.16Relation below satisfying:
MFR
10/MFR
2.16≥5.63
And relation below molecular weight distribution mw/mn and above-mentioned melt flow rate (MFR) ratio satisfy:
Mw/Mn≤(MFR
10/MFR
2.16)-4.63。
4. composition as claimed in claim 3 is characterized in that at least aly in ethylene/alpha-olefin copolymer (A1) and the ethylene/alpha-olefin copolymer (A2) having a following performance:
The melt flow rate (MFR) MFR that under 190 ℃ and 10 kilogram load conditions, measures according to ASTM D 1238
10With the melt flow rate (MFR) MFR that under 190 ℃ and 2.16 kilogram load conditions, measures according to ASTM D 1238
2.16Ratio MFR
10/ MFR
2.16Relation below satisfying:
MFR
10/MFR
2.16≥5.63
And relation below molecular weight distribution mw/mn and above-mentioned melt flow rate (MFR) ratio satisfy:
Mw/Mn+4.63≤MFR
10/MFR
2.16≤14-2.9Log(MFR
2.16)。
5. composition as claimed in claim 1 or 2, the surface hardness that it is characterized in that ethylene/alpha-olefin copolymer (A2) is pressed ASTM D 2240 according to Shore D hardness, is 30-70.
6. composition as claimed in claim 1 or 2 is characterized in that ethylene/alpha-olefin copolymer (A2) is the multipolymer that obtains by solution polymerization.
7. composition as claimed in claim 1 or 2 is characterized in that ethylene/alpha-olefin copolymer (A2) is ethene/butene-1 copolymer.
8. composition as claimed in claim 1 or 2, the density that it is characterized in that ethylene/alpha-olefin copolymer (A) is the 0.880-0.920 gram per centimeter
3, melt flow rate (MFR) is pressed 1238,190 ℃ of ASTM D, under 2.16 kilogram load, for 0.1-10 restrains/10 minutes.
9. composition as claimed in claim 1 or 2 is characterized in that described whipping agent (B) is selected from organic thermolysis type whipping agent, inorganic thermolysis type whipping agent, organic pneumatogen and inorganic pneumatogen.
10. a foamed products obtains by the described composition of arbitrary claim among thermal treatment such as the claim 1-9.
11. foamed products as claimed in claim 10 is characterized in that described product obtains by second-compressed foamed products as claimed in claim 10.
12. as claim 10 or 11 described foamed products, it is characterized in that described foamed products proportion, JI K7222 is 0.05-0.25, surface hardness, and Asker C hardness is 20-80.
13. a sandwich comprises:
Comprise layer as the described foamed products of arbitrary claim among the claim 10-12,
Comprise at least a layer that is selected from following material: polyolefine, urethane, rubber, leather and imitation leather.
14. the manufacture method of sandwich as claimed in claim 13, this method comprises:
Make the step of the described composition foaming of arbitrary claim among the claim 1-9,
The foamed products and at least a synergetic step of following material that is selected from that will obtain by a last foaming step: polyolefine, urethane, rubber, leather and imitation leather.
15. comprise footwear as described foamed products of arbitrary claim or the described sandwich of claim 13 among the claim 10-12.
16. comprise parts as the footwear of described foamed products of arbitrary claim or the described sandwich of claim 13 among the claim 10-12.
17. the parts of footwear as claimed in claim 16, the parts that it is characterized in that described footwear are the middle end, the interior end or sole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02130217 CN1235966C (en) | 2002-08-15 | 2002-08-15 | composition and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02130217 CN1235966C (en) | 2002-08-15 | 2002-08-15 | composition and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1475523A CN1475523A (en) | 2004-02-18 |
| CN1235966C true CN1235966C (en) | 2006-01-11 |
Family
ID=34144421
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|---|---|---|---|
| CN 02130217 Expired - Lifetime CN1235966C (en) | 2002-08-15 | 2002-08-15 | composition and its use |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020200999A1 (en) | 2019-03-29 | 2020-10-08 | Covestro Intellectual Property Gmbh & Co. Kg | Method for preparing a bonded article by conducting single-sided gluing |
| EP3730563A1 (en) | 2019-04-24 | 2020-10-28 | Covestro Deutschland AG | Method for preparing a bonded article by conducting single-sided gluing |
| WO2022200199A1 (en) | 2021-03-22 | 2022-09-29 | Covestro Deutschland Ag | Method for preparing an adhered article by conducting single-sided gluing |
| EP4071221A1 (en) | 2021-04-06 | 2022-10-12 | Covestro Deutschland AG | Method for preparing an adhered article by conducting single-sided gluing |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181066B (en) * | 2018-08-20 | 2021-04-06 | 湖北祥源新材科技股份有限公司 | High-resilience polyethylene filling particle, application and processing method thereof |
-
2002
- 2002-08-15 CN CN 02130217 patent/CN1235966C/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020200999A1 (en) | 2019-03-29 | 2020-10-08 | Covestro Intellectual Property Gmbh & Co. Kg | Method for preparing a bonded article by conducting single-sided gluing |
| EP3730563A1 (en) | 2019-04-24 | 2020-10-28 | Covestro Deutschland AG | Method for preparing a bonded article by conducting single-sided gluing |
| WO2022200199A1 (en) | 2021-03-22 | 2022-09-29 | Covestro Deutschland Ag | Method for preparing an adhered article by conducting single-sided gluing |
| EP4071221A1 (en) | 2021-04-06 | 2022-10-12 | Covestro Deutschland AG | Method for preparing an adhered article by conducting single-sided gluing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1475523A (en) | 2004-02-18 |
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