CN1676538A - Ethene copolymer, resin composition, foaming formed body and making method thereof - Google Patents
Ethene copolymer, resin composition, foaming formed body and making method thereof Download PDFInfo
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- CN1676538A CN1676538A CNA2005100625579A CN200510062557A CN1676538A CN 1676538 A CN1676538 A CN 1676538A CN A2005100625579 A CNA2005100625579 A CN A2005100625579A CN 200510062557 A CN200510062557 A CN 200510062557A CN 1676538 A CN1676538 A CN 1676538A
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/02—Flooring or floor layers composed of a number of similar elements
- E04F15/02038—Flooring or floor layers composed of a number of similar elements characterised by tongue and groove connections between neighbouring flooring elements
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F15/00—Flooring
- E04F15/22—Resiliently-mounted floors, e.g. sprung floors
- E04F15/225—Shock absorber members therefor
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F2203/00—Specially structured or shaped covering, lining or flooring elements not otherwise provided for
- E04F2203/02—Specially structured or shaped covering, lining or flooring elements not otherwise provided for having particular shapes, other than square or rectangular, e.g. triangular, hexagonal, circular, irregular
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Abstract
To provide an ethylene copolymer for foam molding under pressure imparting a foam molded article excellent in dimensional stability and foam properties, to provide a resin composition for foam molding under pressure comprising the copolymer and a foaming agent, to provide a foam molded article comprising the copolymer and to provide a method for manufacturing the same.The invention relates to the ethylene copolymer for foam molding under pressure comprising a monomer unit based on ethylene and a monomer unit based on a 3-20 C [alpha]-olefin, wherein the copolymer has >=5 of a molecular weight distribution (Mw/Mn) and >= 40 kJ/mol of an activation energy (Ea).
Description
Technical field
The present invention relates to foaming and use the manufacture method of resin combination, expanded moldings and expanded moldings with ethene copolymer, foaming.
Background technology
The expanded moldings that constitutes by polythylene resin, be widely used as sundry goods, flooring material, sound-proof material, thermal insulation material, all the time, propose the polythylene resin that utilizes the manufacturing of high-pressure free radical polymerization, the formed body (for example, with reference to patent documentation 1) that for example ethylene-vinyl acetate copolymer has carried out pressure expansion mostly.Recently, as the outstanding expanded moldings of intensity, the pressure expansion formed body that is made of ethene-1-hexene copolymer is also proposed, wherein, described ethene-1-hexene copolymer is to use and metallocene, methylaluminoxane and silicon-dioxide such as two (dimethyl cyclopentadienyl) zirconium dichloride are carried out the solid catalyst that combination treatment obtains makes (for example, with reference to patent documentation 2).
Patent documentation 1: special fair 3-2657 communique;
Patent documentation 2: the spy opens flat 10-182866 communique.
But the pressure expansion formed body by ethylene-vinyl acetate copolymer constitutes can shrink under heated condition, is not the formed body that fully satisfies dimensional stability.In addition, in the pressure expansion formed body that is made of above-mentioned ethene-1-hexene copolymer, the bubble proterties in the expanded moldings is inhomogeneous, in addition, because of broken bubble causes cracking in the pressure expansion formed body, is not the formed body that fully satisfies the bubble proterties.
Summary of the invention
In view of the foregoing, the problem to be solved in the present invention is, provide the pressure expansion moulding that can obtain the outstanding pressure expansion formed body of dimensional stability and bubble proterties with ethene copolymer, contain this multipolymer and whipping agent the pressure expansion molding resin composition, contain the manufacture method of the pressure expansion formed body and the pressure expansion formed body of this multipolymer.
Promptly, one of the present invention relates to a kind of pressure expansion moulding ethene copolymer, it is the ethene copolymer that has based on the monomeric unit of ethene with based on carbonatoms the monomeric unit that is 3～20 alpha-olefin, molecular weight distribution (Mw/Mn) is more than 5, and mobile activation energy (Ea) is the above pressure expansion moulding ethene copolymer of 40kJ/mol.
The present invention's two relates to the pressure expansion molding resin composition that contains above-mentioned ethene copolymer and whipping agent.
The present invention's three relates to contain the pressure expansion formed body of above-mentioned ethene copolymer.
The present invention's four relates to the manufacture method of the pressure expansion formed body that uses above-mentioned ethene copolymer.
According to the present invention, can provide can obtain the pressure expansion moulding of pressure expansion formed body outstanding aspect bubble proterties and the dimensional stability with ethene copolymer, contain this multipolymer and whipping agent the pressure expansion molding resin composition, contain the manufacture method of the pressure expansion formed body and the pressure expansion formed body of this multipolymer.
Embodiment
Pressure expansion moulding ethene copolymer of the present invention is the ethene copolymer that has based on the monomeric unit of ethene with based on carbonatoms the monomeric unit that is 3～20 alpha-olefin.As this alpha-olefin, can enumerate propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene etc., preferably 1-butylene, 1-hexene.
As ethene copolymer of the present invention, can list ethene-butene-1 copolymer, ethene-4 methyl 1 pentene copolymer, ethene-1-hexene copolymer, ethene-1-octene copolymer, ethene-1-decene multipolymer, ethene-1-butylene-4 methyl 1 pentene copolymer, ethene-1-butylene-1-hexene copolymer, ethene-1-butylene-1-octene copolymer etc., from the dimensional stability angle, ethene-butene-1 copolymer preferably, ethene-1-hexene copolymer, ethene-1-butylene-1-hexene copolymer, more preferably ethene-1-butylene-1-hexene copolymer, ethene-1-hexene copolymer.
The content of the whole monomeric units in this multipolymer is made as 100 weight %, and ethene copolymer of the present invention preferably contains more than the monomeric unit 50 weight % based on ethene.
From the angle that improves the bubble proterties, the angle that improves expansion ratio, the molecular weight distribution of ethene copolymer of the present invention is more than 5, and is preferred more than 5.5, more preferably more than 6.Wherein, this molecular weight distribution is the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn), measures as the molecular weight standard material by gel permeation chromatography (GPC) and with polystyrene standard.
Ethene copolymer of the present invention is that mobile activation energy (Ea) is the above multipolymer of 40kJ/mol.The Ea of known ethene-alpha-olefin copolymer was lower than 40KJ/mol in the past, and the expanded moldings that is made of this multipolymer is being inferior aspect the bubble proterties.From improving bubble proterties angle, as Ea, preferably more than 50kJ/mol, more preferably more than 55kJ/mol.In addition, from the more slick angle in the surface that makes expanded moldings, preferably below 100kJ/mol, more preferably below 90kJ/mol.
Mobile activation energy (Ea) is by A Leiniesi (Arrhenius) equation, from make the fusing complex viscosity of expression under 190 ℃ (the unit: (unit: rad/sec) shift factor during dependent master curve and the value that calculates of radian frequency Pasec) based on temperature-time superposition principle.Promptly, based on temperature-time superposition principle, for the fusing complex viscosity-radian frequency curve (unit of fusing complex viscosity is that the unit of Pasec, radian frequency is rad/sec) of the ethene-alpha-olefin copolymer under each temperature of 130 ℃, 150 ℃, 170 ℃ and 190 ℃ (T, unit: ℃), the shifter factor (a under each temperature (T) that obtains when obtaining the fusing complex viscosity of the ethene copolymer under fusing complex viscosity-radian frequency curve under each temperature (T) and 190 ℃-radian frequency curve superposition
T) from each temperature (T) and the shifter factor (a under each temperature (T)
T), calculate [ln (a with method of least squares
T)] and the first-order approximation formula (following (I) formula) of [1/ (T+273.16)].Then, try to achieve the Ea value with the slope m and the following formula (II) of this expression of first degree.
ln(a
T)＝m(1/(T+273.16))+n
(I)
Ea＝|0.008314×m|
(II)
a
T: shifter factor
Ea: mobile activation energy (Ea) (unit: kJ/mol)
T: temperature (unit: ℃)
Aforementioned calculation also can be used commercially available software for calculation, and as this software for calculation, V.4.4.4 the Rhios that can be exemplified as the Rheometrics system waits.Wherein, shifter factor (a
T) be instigate each temperature (T) fusing complex viscosity-radian frequency two logarithmic curves along log (Y)=-log (X) direction of principal axis moves (wherein, the fusing complex viscosity is made as Y-axis, radian frequency is made as X-axis), and with 190 ℃ under the amount of movement of fusing complex viscosity-when the angular frequency number is superimposed, in this is superimposed, for two logarithmic curves of the fusing complex viscosity-radian frequency under each temperature (T), the radian frequency that makes each curve is with a
TDoubly, the fusing complex viscosity is with 1/a
TDoubly move.In addition, with the relation conefficient of method of least squares when 130 ℃, 150 ℃, 170 ℃ and 190 ℃ 4 s' value is asked (1) formula, usually more than 0.99.
The mensuration of fusing complex viscosity-radian frequency curve, use determination of viscoelasticity device (for example the rheology spectrometer of Rheometrics system (Rheometrics MechanicalSpectrometer) RMS-800 etc.), normally at geometry: parallel plate, board diameter: 25mm, plate at interval: 1.5～2mm, distortion: radian frequency 5%: carry out under the condition of 0.1～100rad/ second.Wherein, mensuration is carried out in nitrogen environment, in addition, preferably cooperates oxidation inhibitor (for example 1000ppm) in advance in right amount in measuring sample.
From the secondary workability angle of the cutting that improves expanded moldings etc., the density of ethene copolymer of the present invention is 890kg/m preferably
3More than, be more preferably 900kg/m
3More than.In addition, from the angle of the flexibility that improves formed body, this density is 930kg/m preferably
3Below, be more preferably 925kg/m
3Below.Wherein, this density is measured with substitution method in the water described in the JIS K7112 after the annealing of having carried out described in JIS K6760.
The melt flow rate (MFR) of ethene copolymer of the present invention (MFR) normally 0.01～5g/10 minute.This MFR is described and determined under the condition of 190 ℃ of temperature and load 21.18N according to JIS K7210.
From the angle of the broken bubble of further minimizing, the cold xylene of ethene copolymer of the present invention is fusible, and an amount (CXS) is preferably more than the 1 weight %, more preferably more than the 1.5 weight %, further more than the preferred 3 weight %.Wherein, this CXS is generally below the 15 weight %, from preventing to adhere mutually, improve between the particle (pellet) angle of the property handled, is preferably below 10% weight.This CXS is measured by following method.
(1) about 1g ethene copolymer is put into flask, make it be dissolved in the boiling xylene of 200ml.
(2) at room temperature make flask be cooled to 50 ℃, then, on one side the stirred flask content, be cooled to 20 ℃ with ice-water bath on one side.
(3) flask was left standstill 3 hours under 20 ℃.
(4) solution in the filtration flask, and reclaim filtrate, making dimethylbenzene evaporation and dry from this filtrate, taking-up is dissolved in the polymkeric substance in the filtrate.
(5) measure the weight that is dissolved in the polymkeric substance in the filtrate, calculate with respect to part by weight ethene copolymer 100 weight %, that be dissolved in the polymkeric substance in the filtrate that uses.
Manufacture method as ethene copolymer of the present invention, can enumerate method as described below, promptly the catalyzer that obtains in that two indenyl zirconium complexs (B) of following promotor carrier (A), cross-linking type and organo-aluminium compound (C) are contacted in the presence of, making ethene and carbonatoms is the method for 3～20 alpha-olefin copolymer.
Above-mentioned promotor carrier (A) is to make (a) zinc ethyl, (b) fluoridize phenol, (c) water, (d) silicon-dioxide and (e) trimethylammonium disilazane (((CH
3)
3Si)
2NH) contact and the carrier that obtains.
Usage quantity to above-mentioned (a) and (b), (c) each composition has no particular limits, if but the molar ratio of each composition usage quantity is made as composition (a): composition (b): composition (c)=1: y: z, so preferred y and z satisfy following formula.
|2-y-2z|≤1
As the y in the above-mentioned formula, preferred numerical value is 0.01～1.99, and preferred numerical value is 0.10～1.80, and further preferred numerical value is 0.20～1.50, and most preferred numerical value is 0.30～1.00.
In addition, amount as the relative composition (a) of the composition (d) that uses, for by the mole number that contact the zinc atom that in the particle that obtain contain of composition (a), preferably in this particle of every 1g, contain the amount more than the 0.1mmol, more preferably the amount of 0.5～20mmol with composition (d).As the composition (e) that the uses amount of composition (d) relatively, preferably composition (e) is a amount more than the 0.1mmol in every 1g composition (d), more preferably the amount of 0.5～20mmol.
As the two indenyl zirconium complexs (B) of cross-linking type, two (1-indenyl) the zirconium dichloride of preferred racemization ethene, two (1-indenyl) zirconium two phenates of racemization ethene.
In addition, as organo-aluminium compound (C), preferred triisobutyl aluminium, tri-n-octylaluminium.
Usage quantity for the two indenyl zirconium complexs (B) of cross-linking type preferably has 5 * 10 in every 1g promotor carrier (A)
-6～5 * 10
-4Mol.In addition, as the usage quantity of organo-aluminium compound (C), the every 1mol zirconium atom in the two indenyl zirconium complexs (B) of preferred cross-linking type relatively, the aluminium atom of organo-aluminium compound (C) is 1～2000mol.
As polymerization process, the preferred continuous polymerization method that forms with the particle of ethene copolymer, for example, continuous gas-phase polymerization, continuous slurry polymerization, continuous bulk polymerization, preferably continuous gas-phase polymerization.As the gas phase polymerization device, normally have the device of mobile stratotype reactive tank, preferably have the device of the mobile stratotype reactive tank that the expansion section is arranged.Also agitating wing can be set in reactive tank.
As the method that each composition of the class of metallocenes catalyst for olefines polymerizing that uses in the manufacturing of polyvinyls of the present invention is offered in the reactive tank, can use usually: with rare gas elementes such as nitrogen, argon gas, hydrogen, ethene etc. in the method that does not have to supply with under the state of water; The dissolving or the method for diluting each composition and supplying with at solution or slurry state in solvent.Can supply with each composition of catalyzer respectively, also can make the contact of any composition in advance and supply with according to random order.
In addition, before implementing this polymerization, implement prepolymerization, preferably being used by the catalyst component or the catalyzer of prepolymerized pre-polymerized catalyst composition as this polyreaction.
As polymerization temperature, common temperature, preferred 0～150 ℃, more preferably 30～100 ℃ less than the ethene copolymer fusing.
In addition, in order to regulate the melt fluidity of multipolymer, also can add hydrogen as molecular weight regulator.Then, the rare gas element that also can in mixed gas, coexist.
Ethene copolymer of the present invention be used to the to pressurize manufacturing of bubble formed body.Manufacture method as the pressurization bubble formed body that uses this multipolymer, for example, under the Undec temperature of whipping agent, for the composition that obtains by melt-blended these ethene copolymers such as mixing roll, kneading machine, extrusion machine and whipping agent, fill it in the metal die by injection moulding machine, under pressurization (pressurize), heated condition, make it foaming, then cooling, the method for taking out expanded moldings; This melt-blended composition that obtains is put in the metal die, makes it under pressurization (pressurize), heating condition, to foam, then cooling, the method for taking out expanded moldings with moulding pressure machine etc.
As the whipping agent that can use in the present invention, can enumerate the pyrolysis-type whipping agent of the decomposition temperature more than the temperature of fusion with this multipolymer.For example, can be exemplified as azoformamide, barium azodicarboxylate, the two butyronitrile of azo, nitro biguanides, N, N-dinitrosopentamethylene tetramine, N, N '-dimethyl-N, N '-dinitroso Ursol D, P-toluene sulfonyl hydrazide, P, two (benzol sulfohydrazide) azobis isobutyronitriles of P '-hydroxyl, P, the two phenylsulfonamido ureas of P '-hydroxyl, 5-phenyltetrazole, trihydrazinotriazine, hydrazo-dicarbonamide etc., can use wherein a kind of, or make up two or more uses.Wherein, preferred azoformamide or sodium bicarbonate.In addition, with respect to ethene copolymer 100 weight parts, the cooperation ratio of whipping agent is generally 1～50 weight part, preferred 1～15 weight part.
Above-mentioned melt-blended and in the composition that obtains, also can cooperate frothing aid as required.As this frothing aid, can be exemplified as with urea is the compound of principal constituent; Metal oxide such as zinc oxide, plumbous oxide; Senior lipid acid such as Whitfield's ointment, stearic acid; The metallic compound of this higher fatty acid etc.The total of whipping agent and frothing aid is made as 100 weight %, preferred 0.1～30 weight % of the usage quantity of frothing aid, more preferably 1～20 weight %.
In addition,, can carry out the heat cross-linking foaming, produce crosslinked pressure expansion formed body the composition that cooperates this linking agent above-mentioned melt-blended and in the composition that obtains, also can cooperate linking agent as required.As this linking agent, suitable use has the organo-peroxide of the above decomposition temperature of the flow starting temperature of this multipolymer.Can be exemplified as dicumyl peroxide, 1, the peroxidation-3 of 1-di-tert-butyl, 3,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane, 2,5-dimethyl-2,5-di-tert-butyl peroxide hexin, α, α-di-tert-butyl peroxy isopropyl base benzene, tertiary butyl peroxide ketone, tertiary butyl peroxy benzoate etc.
And then, above-mentioned melt-blended and in the composition that obtains, also can cooperate crosslinking coagent, heat-resisting stabilizing agent, weather agent, lubricant, antistatic agent, packing material or pigment (metal oxides such as zinc oxide, titanium oxide, calcium oxide, magnesium oxide, silicon oxide as required; Carbonate such as magnesiumcarbonate, lime carbonate; Fibrous matters such as paper pulp etc.) etc. various additives also can cooperate resin, rubber constituents such as high-pressure process new LDPE (film grade), high density polyethylene(HDPE), polypropylene, polyvinyl acetate (PVA), polybutene as required.
Expanded moldings of the present invention has advantage aspect the bubble proterties.In addition, also have advantage aspect dimensional stability, the expansion ratio of expanded moldings and the balance of dimensional stability become good.
Bubble formed body of the present invention is used to structure materials such as cushioning material, core, thermal insulation material, also can be used to material for sole of shoe such as midsole, footwear outer bottom in addition.
Embodiment
Below, the present invention will be described in further detail to use embodiment and comparative example.
[1] physical property measurement method
(1) fusing flow rate (MFR)
According to JIS K6760-1995, under 190 ℃ of temperature, load 21.18N, measure.
(2) density
After carrying out the annealing described in the JIS K6760-1995, measure with substitution method in the water described in the JIS K7112-1980.
(3) molecular weight distribution
Use gel permeation chromatography (GPC),, try to achieve molecular weight distribution (Mw/Mn) by measuring weight-average molecular weight (Mw) and number-average molecular weight (Mn) in the following condition.
Condition determination
Device: Water system 150CV ALC/GPC
Post (column): clear and electrician makes Shodex GPC AT-806MS
Temperature: 140 ℃
Solvent: orthodichlorobenzene
Eluting solvent flow velocity: 1.0ml/ branch
Sample solution concentration: 1mg/ml
Measure injection rate: 400 μ l
Molecular weight standard material: polystyrene standard (East ソ ウ system; Molecular weight=6000000～500) detector: differential refraction
(4) mobile activation energy (Ea, unit: kJ/mol)
Use determination of viscoelasticity device (the rheology spectrometer RMS-800 of Rheometrics system), dissolve complex viscosity-radian frequency curve when under following condition determination, measuring 130 ℃, 150 ℃, 170 ℃ and 190 ℃, then, V.4.4.4, the software for calculation Rhios of use Rheometrics system tries to achieve activation energy (Ea) from the complex viscosity-radian frequency curve that dissolves that obtains.
＜condition determination 〉
Geometry: parallel plate
Board diameter: 25mm
Plate interval: 1.5～2mm
Distortion: 5%
Radian frequency: 0.1～100rad/ second
Measure environment: in the nitrogen
(5) cold xylene soluble portions amount (CXS, unit: weight %)
Measure in the following method.
(1) about 1g ethene copolymer is put into flask, make it be dissolved in the boiling xylene of 200ml.
(2) at room temperature make flask be cooled to 50 ℃, then, on one side the stirred flask content, be cooled to 20 ℃ with ice-water bath on one side.
(3) flask was left standstill 3 hours under 20 ℃.
(4) solution in the filtration flask, and reclaim filtrate, making dimethylbenzene evaporation and dry from this filtrate, taking-up is dissolved in the polymkeric substance in the filtrate.
(5) measure the weight of the polymkeric substance obtain, making employed ethene copolymer is 100 weight %, calculates the polymer phase that the obtains part by weight for the ethene copolymer that uses.
(6) the bubble proterties of expanded moldings
Bubble to expanded moldings under visual carries out evaluation as follows.
Zero: bubble shape is even.
△: bubble shape is inhomogeneous a little.
*: bubble shape is inhomogeneous.Perhaps, broken bubble cracks because causing in expanded moldings.
(7) dimensional stability of expanded moldings
From expanded moldings, cut out the test film of long 2cm * wide 2cm * thick 2cm, these test films are put into the baking oven heat treated 4 hours that is set in 80 ℃.Measure the preceding test film volume V of heating
0With the test film volume V after the heating
1, calculate heat shrink rate Q (%) by following formula.This value is big more, and dimensional stability runs off look.
Q＝V
1/V
0×100
(8) expansion ratio
Measure the volume of the preceding resin combination of foaming and the volume of the expanded moldings behind the foaming, calculating volume increases multiplying power, as expansion ratio.
Embodiment 1
(1) modulation of promotor carrier
By opening the synthetic the same method of the embodiment 10 (1) and the composition (A) described in (2) of 2003-171415 communique, obtain solid product (following, be called promotor carrier (A)) with the spy.
(2) prepolymerization
In the internal volume that carries out nitrogen replacement in advance is 210 liters the autoclave pan that has stirrer, 12 liters of the hydrogen under above-mentioned promotor carrier (A) 0.7kg, 100 liters of butane, 1-butylene 0.02kg, the normal temperature and pressure be contained in the inside after, make autoclave pan be warming up to 42 ℃.And then, the ethene of packing under the gaseous pressure in autoclave pan and only for 0.1MPa part, during being stable after, drop into triisobutyl aluminium 225mmol, two (1-indenyl) zirconium two phenates 75mmol of racemization ethene, begin polymerization.In 50 ℃ of intensifications, continuously supply with ethene and hydrogen on one side, implement to amount to 6 hours prepolymerization down at 50 ℃ on one side.After polymerization finishes, remove ethene, butane, hydrogen etc. and at room temperature residual solid is carried out vacuum-drying, the above-mentioned promotor carrier of every 1g (A), the ethene-butene-1 copolymer that obtains 13g is by prepolymerized pre-polymerized catalyst composition.
(3) continuous gas-phase polymerization
Use continous way fluidised bed gas phase polymerization apparatus, making polymerization temperature is 85 ℃, polymerization pressure is 2MPa, in reactor, supply with above-mentioned pre-polymerized catalyst composition, triisobutyl aluminium, ethene, 1-butylene and hydrogen continuously, hydrogen with respect to the mol ratio of the ethene in the reactant gases be 1.12%, 1-butylene with respect to the mol ratio of ethene be 2.4%, the 1-hexene is 0.3% with respect to the mol ratio of ethene, be under 5 hours the condition, to implement the copolymerization of ethene, 1-butylene, 1-hexene in the average polymerization time.By polymerization, obtain the powder of ethene-1-butylene-1-hexene copolymer (below, be called PE (1)).
(4) granulation of ethene-1-butylene-1-hexene copolymer powder
Use made LCM 50 extrusion machines of Kobe Steel, in input speed is under the condition of 200～215 ℃ of 50kg/hr, water screw rotation number 450rpm, door aperture 50%, suction pressure 0.1MPa, resin temperatures, powder to the above-mentioned PE that obtains (1) carries out granulation, obtains PE (1) particle.The MFR of PE (1) is that 0.5g/10 minute, density are 923kg/m
3, molecular weight distribution is 16.8, mobile activation energy is 74.2kJ/mol.
(5) foaming and molding
Use the roll stirrer, under 120 ℃ of roller temperatures, to PE (1) 100 weight part, water-ground limestone 50 weight parts, stearic acid 1 weight part, zinc oxide 0.9 weight part, chemical foaming agent (three associations change into Co., Ltd.'s system " セ Le マ イ Network CE ") 6.4 weight parts, dicumyl peroxide 1.2 weight parts mixed 5 minutes, obtained resin combination.This resin combination is put into the metal die of 10cm * 10cm * 1cm, and pressure expansion under the condition of 150 ℃ of temperature, 10 minutes time, pressure 1MPa obtains expanded moldings thus.Table 1 shows the evaluation of physical property result of the expanded moldings that obtains.
Embodiment 2
In embodiment 1 (3) continuous gas-phase polymerization, change the composition of reactant gases, in addition, carry out according to embodiment 1.Table 1 shows the evaluation of physical property result of the expanded moldings that obtains.
Comparative example 1
Replace PE (1), use commercially available ethylene-vinyl acetate copolymer [エ パ テ-ト H2020 (MFR=1.3g/10 minute, the density=936kg/m of Sumitomo Chemical Company Ltd's system
3, molecular weight distribution=7.2, mobile activation energy=63.2kJ/mol); Below, be called EVA], dicumyl peroxide is 1.0 weight parts, in addition, carries out foaming according to embodiment 1.Table 1 shows the evaluation of physical property result of the expanded moldings that obtains.
Comparative example 2
Replace PE (1), use commercially available ethylene-vinyl acetate copolymer [the system ス ミ カ セ of Sumitomo Chemical Company Ltd Application E FV401 (MFR=4g/10 minute, density=905kg/m
3, molecular weight distribution=4.0, mobile activation energy=33.2kJ/mol); Below, be called PE (2)], in addition, carry out foaming according to embodiment 1, because of causing in expanded moldings, broken bubble cracks.
Table 1
| Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | |
| Multipolymer | ||||
| MFR (g/10 minute) | 0.5 | ?1.3 | ?1.3 | ?4 |
| Density (kg/m 3) | 923 | ?923 | ?936 | ?905 |
| Molecular weight distribution (-) | 16.8 | ?13.0 | ?7.2 | ?4.0 |
| Mobile activation energy (kJ/mol) | 74.2 | ?71.0 | ?63.2 | ?33.2 |
| CXS (weight %) | 3.1 | ?3.3 | ?- | ?4.0 |
| Expanded moldings | ||||
| The bubble proterties | ○ | ?○ | ?○ | ?× |
| Dimensional stability Q (%) | 36.5 | ?35.9 | ?17.4 | ?- |
| Expansion ratio (doubly) | 12.2 | ?12.5 | ?10.5 | ?- |
Claims (5)
1. pressure expansion moulding ethene copolymer is the ethene copolymer that has based on the monomeric unit of ethene with based on carbonatoms the monomeric unit that is 3～20 alpha-olefin, it is characterized in that,
Molecular weight distribution (Mw/Mn) is more than 5, and activation energy (Ea) is more than the 40kJ/mol.
2. a pressure expansion molding resin composition is characterized in that,
Contain described ethene copolymer of claim 1 and whipping agent.
3. pressure expansion molding resin composition according to claim 2 is characterized in that, the ethene copolymer of per 100 weight parts contains whipping agent 1～50 weight part.
4. a pressure expansion formed body is characterized in that,
Constitute by the described ethene copolymer of claim 1.
5. the manufacture method of a pressure expansion formed body is characterized in that,
Use the described ethene copolymer of claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004104347 | 2004-03-31 | ||
| JP2004104347 | 2004-03-31 | ||
| JP2004286823A JP2005314638A (en) | 2004-03-31 | 2004-09-30 | Ethylene copolymer, resin composition, foam molded article, and method for producing the same |
| JP2004286823 | 2004-09-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1676538A true CN1676538A (en) | 2005-10-05 |
| CN100593026C CN100593026C (en) | 2010-03-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510062557A Expired - Fee Related CN100593026C (en) | 2004-03-31 | 2005-03-29 | Ethene copolymer, resin composition, foaming formed body and making method thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2005314638A (en) |
| KR (1) | KR101144689B1 (en) |
| CN (1) | CN100593026C (en) |
| TW (1) | TWI370141B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102459436A (en) * | 2009-05-29 | 2012-05-16 | 住友化学株式会社 | Resin composition for crosslinking/foam molding, crosslinked molded foam, member for footwear, and footwear |
| CN101910266B (en) * | 2007-10-31 | 2012-09-05 | 住友化学株式会社 | Thermoplastic resin for expansion molding, thermoplastic resin composition for expansion molding, expansion molded body, and footwear |
| CN101157775B (en) * | 2006-09-29 | 2012-09-05 | 住友化学株式会社 | Resin composition for press foaming, foam and process for producing the foam |
| CN102131848B (en) * | 2008-08-29 | 2013-02-06 | 住友化学株式会社 | Resin composition for cross-linked foam molding, cross-linked foam molded article, and method for production of cross-linked foam molded article |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4830661B2 (en) * | 2006-06-22 | 2011-12-07 | 住友化学株式会社 | Method for producing foam |
| JP5167742B2 (en) * | 2006-09-29 | 2013-03-21 | 住友化学株式会社 | PRESSURE FOAM MOLDING RESIN COMPOSITION, PRESSURE FOAM MOLDED BODY, PROCESS FOR PRODUCING PRESSURE FOAM MOLDED BODY, FOOTHER MEMBER AND FOOD |
| KR20110085982A (en) | 2008-10-22 | 2011-07-27 | 스미또모 가가꾸 가부시끼가이샤 | Process for producing crosslinked molded foam and crosslinked molded foam |
| JP2011132401A (en) * | 2009-12-25 | 2011-07-07 | Sumitomo Chemical Co Ltd | ETHYLENE-alpha-OLEFIN COPOLYMER FOR FOAMING, RESIN COMPOSITION FOR FOAMING, AND FOAM |
| WO2011132790A1 (en) | 2010-04-20 | 2011-10-27 | 住友化学株式会社 | ETHYLENE/α-OLEFIN COPOLYMER FOR FOAM PRODUCTION, RESIN COMPOSITION FOR FOAM PRODUCTION, AND METHOD FOR PRODUCING FOAM |
| KR101248421B1 (en) * | 2010-07-15 | 2013-03-28 | 에스케이이노베이션 주식회사 | Ethylene copolymer with improved elasticity and processibility |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3344015B2 (en) * | 1993-08-23 | 2002-11-11 | 住友化学工業株式会社 | Ethylene-α-olefin copolymer and molded article molded from the copolymer |
| KR20000036047A (en) * | 1999-03-11 | 2000-06-26 | 고토 기치 | Method of injection molding expandable plastic composition |
-
2004
- 2004-09-30 JP JP2004286823A patent/JP2005314638A/en active Pending
-
2005
- 2005-03-15 TW TW094107790A patent/TWI370141B/en not_active IP Right Cessation
- 2005-03-29 KR KR1020050026186A patent/KR101144689B1/en not_active IP Right Cessation
- 2005-03-29 CN CN200510062557A patent/CN100593026C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157775B (en) * | 2006-09-29 | 2012-09-05 | 住友化学株式会社 | Resin composition for press foaming, foam and process for producing the foam |
| CN101910266B (en) * | 2007-10-31 | 2012-09-05 | 住友化学株式会社 | Thermoplastic resin for expansion molding, thermoplastic resin composition for expansion molding, expansion molded body, and footwear |
| CN102131848B (en) * | 2008-08-29 | 2013-02-06 | 住友化学株式会社 | Resin composition for cross-linked foam molding, cross-linked foam molded article, and method for production of cross-linked foam molded article |
| CN102459436A (en) * | 2009-05-29 | 2012-05-16 | 住友化学株式会社 | Resin composition for crosslinking/foam molding, crosslinked molded foam, member for footwear, and footwear |
| CN102459436B (en) * | 2009-05-29 | 2013-07-31 | 住友化学株式会社 | Resin composition for crosslinking/foam molding, crosslinked molded foam, member for footwear, and footwear |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101144689B1 (en) | 2012-05-24 |
| TW200604214A (en) | 2006-02-01 |
| CN100593026C (en) | 2010-03-03 |
| JP2005314638A (en) | 2005-11-10 |
| TWI370141B (en) | 2012-08-11 |
| KR20060045130A (en) | 2006-05-16 |
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