CN1765967A - Resin composition, foaming forming body and laminate - Google Patents
Resin composition, foaming forming body and laminate Download PDFInfo
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- CN1765967A CN1765967A CN 200510114176 CN200510114176A CN1765967A CN 1765967 A CN1765967 A CN 1765967A CN 200510114176 CN200510114176 CN 200510114176 CN 200510114176 A CN200510114176 A CN 200510114176A CN 1765967 A CN1765967 A CN 1765967A
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Abstract
A resin composition wherein the content of the following component (i) is 99 to 30 wt % and the content of the following component (ii) is 1 to 70 wt %, a pressurized foaming molded body of the resin composition, and a laminate obtained by laminating a layer composed of the pressure-foamed molding and a layer composed of another material: (i) an ethylene-a-olefin-based copolymer comprising an ethylene monomer unit and an a-olefin monomer unit having 3 to 20 carbon atoms wherein the melt flow rate is 0.01 to 5 g/10 minutes and the activation energy for flow is 30 kJ/mol or more, (ii) an ethylene-unsaturated ester-based copolymer comprising an unsaturated ester monomer unit and an ethylene monomer unit.
Description
Technical field
The duplexer that the present invention relates to resin combination, its pressure expansion molding and have the layer of this foam.
Background technology
To the foam molding that constitutes by polythylene resin, the duplexer that this foam molding and the molding that is made of non-polythylene resin are laminated, be widely used as sundry goods, flooring material, sound-proof material, thermal insulation material, for example, known have following such sole etc., promptly, ethene-vinyl acetate copolymer is carried out pressure expansion to be shaped, be formed into body, then this molding is cut into the parts that need shape, with the parts pressure expansion shaping once more that obtains, thereby (for example, the opening flat 11-151101 communique) such as soles that forms (midsole) at the bottom of the top and be laminated with reference to the spy by the lower bottom (footwear outer bottom) of formations such as vinylbenzene-divinyl rubber.
But above-mentioned foam molding can't be fully satisfied aspect light weight and inflexible balance, and then the duplexer that itself and the molding that is made of non-polythylene resin are laminated also can't satisfy.
Summary of the invention
In view of the foregoing, the objective of the invention is to, provide the resin combination, this pressure expansion molding of the pressure expansion molding that gives light weight and inflexible balance excellence, the layer of this pressure expansion molding and the duplexer that is laminated by the layer that the material that is different from this foaming layer constitutes.
And then, as other purposes, except above-mentioned, resin combination, this foam molding that gives high-intensity pressure expansion molding also be provided and comprise the duplexer of interlayer tackiness excellence of the layer of this pressure expansion molding.
That is, the present invention relates to contain following compositions (i) and (ii) and when making composition (i) and total amount (ii) be 100 weight % the content of composition (i) be that 99～30 weight %, composition content (ii) are the resin combination of 1～70 weight %.
(i) having based on the monomeric unit of ethene with based on carbonatoms is that monomeric unit, the melt flow rate (MFR) of 3～20 alpha-olefin is that 0.01～5g/10 minute and mobile activation energy are the ethene-alpha-olefin analog copolymer more than the 30kJ/mol
(ii) have based on the monomeric unit of at least a unsaturated ester from vinyl carboxylates and unsaturated carboxylic acid alkyl ester, selected with based on the ethene-unsaturated ester analog copolymer of the monomeric unit of ethene
In addition, the present invention relates to above-mentioned resin combination is carried out the pressure expansion molding that pressure expansion is shaped and forms.
And then, the present invention relates to layer that constitutes by above-mentioned pressure expansion molding and the duplexer that is laminated by the layer that the material of non-vinyl resins constitutes.
By the present invention, can provide resin combination, this pressure expansion molding of the pressure expansion molding that gives light weight and inflexible balance excellence and the duplexer that contains the foaming layer of this pressure expansion molding.And then, according to the present invention, and then can provide resin combination, this pressure expansion molding of the pressure expansion molding that gives excellent strength and the duplexer that contains this pressure expansion molding.
Embodiment
The ethene-alpha-olefin analog copolymer of composition (i) is to have based on the monomeric unit of ethene and is the ethene copolymer of 3～20 alpha-olefin (below, be called alpha-olefin) for the monomeric unit on basis with carbonatoms.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.
Ethene-alpha-olefin analog copolymer as composition (i), 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., angle from intensity, 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.
With regard to the ethene-alpha-olefin analog copolymer of composition (i), the content of the whole monomeric units in this multipolymer is made as 100, the monomeric unit that preferably contains based on ethene is more than the 50 weight %.In addition, when the content of ethene increased, the density of multipolymer increased, and is 930kg/m so preferably make its density as described later
3Below.
The melt flow rate (MFR) (MFR) of the ethene-alpha-olefin analog copolymer of composition (i) normally 0.01～5g/10 minute.As this MFR during less than 0.01g/10 minute, expansion ratio reduces sometimes, and is preferred more than 0.05g/10 minute, more preferably more than 0.1g/10 minute.In addition, when this MFR surpassed 5g/10 minute, the interlayer tackiness of multilevel shaping body reduced, and is preferred below 2g/10 minute, more preferably below 0.8g/10 minute, further preferred below 0.6g/10 minute.Wherein, this MFR be according to JIS K7210-1995 under the condition of 190 ℃ of temperature and load 21.18N, measure with the A method.
The ethene-alpha-olefin analog copolymer of composition (i) is that mobile activation energy (Ea) is the above multipolymer of 30kJ/mol.When this Ea crosses when low, the inhomogeneous and appearance degradation of bubble proterties sometimes.From improving the angle of bubble proterties, be preferably more than the 40kJ/mol as Ea, more preferably more than the 50kJ/mol, more preferably more than the 55kJ/mol.In addition, from the more slick angle in the surface that makes foam molding, preferably this Ea is below the 100kJ/mol, more preferably below the 90kJ/mol.
Mobile activation energy (Ea) is by make the melt complex viscosity of expression under 190 ℃ (the unit: (unit: the rad/sec) shifted divisor (a during dependent principal curve (master curve) of radian frequency Pasec) according to temperature-time superposition principle
T), by the value that A Leiniesi (Arrhenius) type equation calculates, be the value of obtaining with method as follows.Promptly, based on temperature-time superposition principle, for the melt complex viscosity-radian frequency curve (unit of melt 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 shifted divisor (a under each temperature (T) that obtains when obtaining the melt complex viscosity of the ethene copolymer under melt complex viscosity-radian frequency curve under each temperature (T) and 190 ℃-radian frequency curve superposition
T), from each temperature (T) and the shifted divisor (a under each temperature (T)
T), calculate [1n (a with method of least squares
T)] and the first-order approximation formula (following (I) formula) of [1/ (T+273.16)].Then, by the slope m and the following formula (II) of this expression of first degree, try to achieve the Ea value.
1n(a
T)＝m(1/(T+273.16))+n (I)
Ea＝|0.008314×m| (II)
a
T: shifted divisor
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 corporate system waits.Wherein, shifted divisor (a
T) be instigate each temperature (T) melt complex viscosity-radian frequency two logarithmic curves along log (Y)=-log (X) direction of principal axis moves (wherein, the melt complex viscosity is made as Y-axis, radian frequency is made as X-axis), and with 190 ℃ under the amount of movement of melt complex viscosity-when the angular frequency number is superimposed, in this is superimposed, for two logarithmic curves of the melt complex viscosity-radian frequency under each temperature (T), the radian frequency that makes each curve is with a
TDoubly, the melt 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 melt complex viscosity-radian frequency curve, be to use determination of viscoelasticity device (for example the rheology spectrometer of Rheometrics system (Rheometrics Mechanical Spectrometer) RMS-800 etc.), usually 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.In addition, mensuration is carried out in nitrogen environment, in addition, preferably cooperates antioxidant (for example 1000wt-ppm) in advance in right amount in measuring sample.
From the angle of the secondary workabilities such as cutting of the rigidity that improves the pressure expansion molding, pressure expansion molding, the density of the ethene-alpha-olefin analog copolymer of composition (i) is 890kg/m preferably
3More than, be more preferably 900kg/m
3More than, further 905kg/m preferably
3More than.In addition, from the angle of the light weight that improves the pressure expansion molding, this density is 930kg/m preferably
3Below, be more preferably 925kg/m
3Below.Wherein, for this density, be after the annealing of having carried out described in JIS K6760-1995, measure with substitution method in the water described in the JIS K7112-1980.
Manufacture method as the ethene-alpha-olefin analog copolymer of composition (i), can enumerate method as described below, promptly the catalyzer that obtains in that two indenyl zirconium coordination compoundes (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} contacts 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, preferred component (a) contacts with composition (d) and the mole number of the zinc atom that contains in the particle that obtains reaches the amount more than the 0.1mmol in this particle of every 1g, more preferably reaches the amount of 0.5～20mmol.As the composition (e) that the uses amount of composition (d) relatively, preferably composition (e) reaches amount more than the 0.1mmol in every 1g composition (d), more preferably reaches the amount of 0.5～20mmol.
As the two indenyl zirconium coordination compoundes (B) of cross-linking type, two (1-indenyl) zirconium dichlorides of preferred racemize ethene, two (1-indenyl) the diphenol zirconiums of racemize ethene.
In addition, as organo-aluminium compound (C), preferred triisobutyl aluminium, tri-n-octylaluminium.
Usage quantity for the two indenyl zirconium coordination compoundes (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 coordination compoundes (B) of preferred cross-linking type relatively, the aluminium atom of organo-aluminium compound (C) reaches the amount of 1～2000mol.
As polymerization process, preferably with the continuous polymerization method of the formation of the particle of ethene-alpha-olefin analog 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 comprise the device of mobile stratotype reactive tank with expansion section.Also stirring rake 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 the ethene-alpha-olefin analog copolymer of composition (i) 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; In solvent, dissolve or dilute each composition, with the method for solution or slurry state supply.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 formal polymerization, preferably implement prepolymerization, being used by the catalyst component or the catalyzer of prepolymerized pre-polymerized catalyst composition as formal polyreaction.
As polymerization temperature, usually less than ethylene-alpha-olefin analog copolymer fused temperature, preferred 0～150 ℃, more preferably 30～100 ℃.
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.
Composition ethene-unsaturated ester analog copolymer (ii) is to have based on the monomeric unit of at least a unsaturated ester selected from vinyl carboxylates and unsaturated carboxylic acid alkyl ester with based on the multipolymer of the monomeric unit of ethene.As this vinyl carboxylates, can enumerate vinyl acetate, propionate etc., in addition, as this unsaturated carboxylic acid alkyl ester, can enumerate alkyl acrylates such as methyl acrylate, ethyl propenoate, vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, alkyl methacrylates such as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, methacrylic tert-butyl acrylate, Propenoic acid, 2-methyl, isobutyl ester etc.
As composition ethene-unsaturated ester analog copolymer (ii), preferably use ethene-vinyl acetate copolymer, ethene-methylmethacrylate copolymer, ethene-methyl acrylate copolymer, ethene-ethyl acrylate copolymer.
The melt flow rate (MFR) (MFR) of composition ethene-unsaturated ester analog copolymer (ii) 0.1～1000g/10 minute scope, can suitably be selected according to purpose usually.The viewpoint of the intensity of the pressure expansion molding that obtains from raising, this MFR was preferably below 100g/10 minute, more preferably below 50g/10 minute, more preferably below 20g/10 minute, most preferably was below 10g/10 minute.In addition, from improving the viewpoint of rebound elasticity, be preferably below 20g/10 minute, more preferably below 5g/10 minute, more preferably below 4g/10 minute, so can suitably select as required.
In addition, the viewpoint of the interlayer tackiness of the pressure expansion molding that obtains from raising is preferably more than 0.2g/10 minute, more preferably more than 0.7g/10 minute.And then, when obtaining the foam molding of high foamability, more than the preferred 4g/10 of this MFR minute, more preferably more than 5g/10 minute, more preferably more than 6g/10 minute.
Therefore, in order to obtain the pressure expansion molding of foam intensity height, high foamability, the MFR of composition ethene-unsaturated ester analog copolymer (ii) is preferably 4～100g/10 minute scope.
In addition, in order to obtain foam intensity height, pressure expansion molding that rebound elasticity is high, MFR is preferably 0.2～20g/10 minute scope.Therefore, can suitably select from above-mentioned scope as required.Wherein, this MFR is to be that 190 ℃ and load are under the condition of 21.18N according to JIS K7210-1995 and in temperature, the value that adopts the A method to measure.
In composition ethene-unsaturated ester analog copolymer (ii), based on the monomeric unit of vinyl carboxylates with based on the total content of the monomeric unit of unsaturated carboxylic acid alkyl ester be, when the content of the total monomer units in this multipolymer is made as 100 weight %, common 2～50 weight %, preferred 5～45 weight %.From improving the viewpoint of interlayer tackiness, this content is preferably more than the 5 weight %, more preferably more than the 10 weight %, more preferably more than the 15 weight %.When content surpassed 50 weight %, the intensity of pressure expansion molding reduced sometimes.More preferably below the 40 weight %, more preferably below the 35 weight %.This content adopts known method to measure.Content based on the monomeric unit of vinyl acetate is measured according to JIS K6730-1995.
Composition ethene-unsaturated ester analog copolymer (ii) is to make by the known polymerization process that has used known catalyst for olefines polymerizing.For example, can enumerate the mass polymerization of having used radical initiator, solution polymerization process etc.
Resin combination of the present invention is to contain composition (i) and composition resin combination (ii), and when composition (i) and composition total amount (ii) were made as 100 weight %, the content of composition (i) was 99～30 weight %, and composition content (ii) is 1～70 weight %.When the content of composition (i) during less than 30 weight %, the light weight of pressure expansion molding and inflexible balance reduce sometimes.The content of preferred component (i) is more than the 40 weight %, more preferably more than the 50 weight %, more preferably more than the 60 weight %, most preferably is more than the 70 weight %.On the other hand, when the content of composition (i) surpassed 99 weight %, the interlayer tackiness of duplexer reduced sometimes.The content of preferred component (i) is below the 98 weight %, and more preferably the content of composition (i) is below the 95 weight %, and composition content (ii) is more than the 5 weight %, and more preferably the content of composition (i) is below the 90 weight %.In addition, from the viewpoint of the rebound elasticity that improves the pressure expansion molding, the content of preferred component (i) is below the 70 weight %, more preferably below the 65 weight %.
In resin combination of the present invention, composition (ii) based on the monomeric unit of vinyl carboxylates with based on the total content of the monomeric unit of unsaturated carboxylic acid alkyl ester be, when (ii) total content is made as 100 weight % with composition (i) and composition, viewpoint from the interlayer tackiness that improves duplexer, preferred 1～15 weight %, viewpoint from the intensity of further raising pressure expansion molding, more preferably below the 10 weight %, in addition, from the viewpoint of the interlayer tackiness of further raising duplexer, more preferably more than the 2 weight %.
The viewpoint of the interlayer tackiness of the pressure expansion molding that obtains from further raising, the composition of use MFR (ii) composition use level (ii) hour, the composition use level (ii) when big with composition MFR is (ii) compared, and preferably they are more.That is, composition MFR and the content (wherein, making composition (i) and composition total amount (ii) is 100 weight %) (ii) of the composition in the resin combination (ii) preferably satisfies following formula (1), more preferably satisfies following formula (2).Preferred especially
log(M)≥-0.02×W+0.48 (1)
log(M)≥-0.02×W+0.85 (1)
M: composition MFR (unit: g/10 minute) (ii)
W: composition content (unit: weight %) (ii).
In the present invention, in order to obtain special light weight and intensity height, to give the pressure expansion molding of high foamability, the other good duplexer of adhesiveness between layers in addition, preferred resin combination is as follows.
The content that is composition (i) when containing following compositions (i) and composition and being made as 100 weight % (ii) and with composition (i) and total amount (ii) is that 98～50 weight %, composition content (ii) are the resin combination of 2～50 weight %.
(i) having based on the monomeric unit of ethene with based on carbonatoms is that monomeric unit, the melt flow rate (MFR) of 3～20 alpha-olefin is that 0.01～5g/10 minute and mobile activation energy are the ethene-alpha-olefin analog copolymer more than the 40kJ/mol
(ii) have based on the monomeric unit of at least a unsaturated ester from vinyl carboxylates and unsaturated carboxylic acid alkyl ester, selected and be that 5～45 weight %, melt flow rate (MFR) are ethene-unsaturated ester analog copolymer of 4～100g/10 minute based on the monomeric unit of ethene and based on the content of the monomeric unit of this unsaturated ester
In resin combination of the present invention, also can cooperate crosslinking coagent, heat-resisting stabilizing agent, weather agent, lubricant, antistatic agent, packing material, 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, polybutene as required.
Resin combination of the present invention is preferred for making the pressure expansion molding.Manufacture method as the pressure expansion molding that uses this resin combination can adopt known pressure expansion moulding method.For example, under the Undec temperature of whipping agent, utilize mixing roll, kneader, extrusion machine etc. that composition (i) and composition are (ii) carried out melting mixing and obtain composition with whipping agent, by injection molding machine etc. composition is filled in the mould, under pressurization (pressurize), heated condition, make its foaming, then cool off the method for taking out the pressure expansion molding; The composition that this melting mixing is obtained puts in the mould and utilizes pressurization stamping machine etc. to make its foaming under pressurization (pressurize), heated condition, then cools off the method for taking out the pressure expansion molding etc.
In the manufacturing of pressure expansion molding, the pressure expansion molding severing that utilizes above-mentioned method to obtain can be become desirable shape, can and then the parts that severing obtains be heated figuration, in addition, can polish processing.
As the whipping agent that can use in the present invention, can enumerate the thermolysis type whipping agent of the decomposition temperature more than the melt temperature with corresponding copolymers.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 pentamethylene tetramine, 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 diformamide etc., can use wherein a kind of, or make up two or more uses.Wherein, preferred azoformamide or sodium bicarbonate.In addition, composition (i) and composition total amount (ii) are made as 100 weight parts, the cooperation ratio of whipping agent is generally 1～50 weight part, preferred 1～15 weight part.
Can cooperate frothing aid above-mentioned passing through as required in the composition that melting mixing obtains.As this frothing aid, can enumerate with urea is the compound of principal constituent, metal oxides 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, in the composition that obtains in above-mentioned melting mixing, also can cooperate linking agent as required, can carry out the heat cross-linking foaming, form crosslinked pressure expansion molding the composition that cooperates this linking agent.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.In addition, when pressure expansion molding of the present invention is used for sole or shoe sole component, preferably with the pressure expansion molding as crosslinked pressure expansion molding.
In the present invention, can adopt above-mentioned method to obtain the pressure expansion body, expansion ratio is not particularly limited, be preferably about 3～16 times, more preferably about 5～13 times.
Duplexer of the present invention is to foaming layer that forms and the duplexer that is laminated by the layer that the material beyond the vinyl resins constitutes that resin combination pressure expansion of the present invention is shaped.
As stacked material in pressure expansion is shaped, can enumerate leathers such as material, natural leather material, artificial leather material and cloth material beyond the polyvinyl chloride (PVC) RESINS material, styrene copolymer elastomeric material, olefinic copolymer elastomeric material vinyl resins such as (ethene copolymer elastomeric material, propylene copolymers elastomeric materials etc.), cloth material etc., these materials can be used at least a material.
Manufacture method as duplexer of the present invention, for example can enumerate method as follows, promptly utilize above-mentioned method to make resin combination of the present invention is carried out the pressure expansion molding shaping that pressure expansion is shaped and forms, then, this pressure expansion molding and the molding that constitutes by non-vinyl resins material that is shaped in addition, with heat posted is closed or chemical adhesive etc. is fitted method etc.As this chemical adhesive, can use known chemical adhesive.Wherein, preferred especially amino formate chemical adhesive and chloroprene class chemical adhesive etc.In addition, when the applying carried out by these chemical adhesives, can be called the finish paint of priming paint in coating in advance.
Pressure expansion molding of the present invention is excellence aspect light weight and inflexible balance.For example, pressure expansion molding of the present invention is compared by the pressure expansion molding that in the past ethylene vinyl acetate copolymer constitutes with the inflexible with equal extent, and light weight is more excellent; Compared by the pressure expansion molding that in the past ethylene vinyl acetate copolymer constitutes with the inflexible with equal extent, rigidity is more excellent.In addition, the rebound elasticity of pressure expansion molding of the present invention is good, and intensity is also excellent in above-mentioned preferred compositing range.For this reason, for example, pressure expansion molding of the present invention is fit to be used to sole or shoe sole component.In addition, the tackiness of pressure expansion molding of the present invention and non-vinyl resins material is also good, thus can with the above-mentioned stacked use of various materials.For example, pressure expansion molding of the present invention is suitable is used as (midsole) at the bottom of the top.By to carrying out stackedly with the lower bottom (outsole) that constitutes by non-vinyl resins material at the bottom of this top, can be used as sole or shoe sole component.In addition, duplexer of the present invention can also be used for the various uses such as material of construction of thermal insulation material, cushioning material etc. except being used for sole.
Embodiment
Below, the present invention will be described in further detail to use embodiment and comparative example.
[1] physical property measurement method
(1) melt flow rate (MFR) (MFR, unit: g/10 minute)
According to JIS K7210-1995, under 190 ℃ of temperature, load 21.18N and adopt the A method to measure.
(2) density (unit: kg/m
3)
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) mobile activation energy (Ea, unit: kJ/mol)
Use determination of viscoelasticity device (the rheology spectrometer RMS-800 of Rheometrics corporate system), dynamic 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 dynamic viscosity-radian frequency curve 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
(4) vinyl acetate unit vol (unit: weight %)
Measure according to JIS K6730-1995.
(5) density of foam molding (unit: kg/m
3)
Measure according to ASTM-D297.The more little light weight of this value is excellent more.
(6) hardness of foam molding (unit: do not have)
According to ASTM-D2240, measure with C method sclerometer.The big more rigidity of this value is excellent more.
(7) the rebound elasticity modulus (unit: %) of foam molding
From height (L apart from the surperficial 15cm of 2 moldinies
0), iron spheroid is freely fallen to the surperficial of 2 moldinies, measure the height (L) of iron spheroid from the surface knock-on of 2 moldinies, calculate rebound elasticity modulus (unit: %) according to following formula.Carry out judgement as follows for rebound elasticity by the value of rebound elasticity modulus.
Rebound elasticity modulus=L/L
0* 100
L: iron spheroid is from the height L of the surface knock-on of 2 moldinies
L
0: the height (unit: cm) that iron spheroid falls
[judgement]
Zero: the rebound elasticity modulus is more than 40%.
△: the rebound elasticity modulus is less than 40%.
(8) intensity (unit: kg/cm) of foam molding
According to ASTM-D642, measure the tearing strength of foam molding.Specifically, foam molding is cut into the thickness of 10mm, then its stamping-out is become the shape of No. 3 dumbbells, make test film.With 500mm/ minute speed this test film is stretched, the ultimate load when test film is ruptured (kg) is removed with the thickness 1cm of sample strip and is obtained tearing strength.
(9) the interlayer tackiness of duplexer
Downcut the test film of long 10cm * wide 2mm * thick 1cm and make the surface of 2 moldinies become the face of a long 10cm * wide 2mm of test film from 2 moldinies, end 3cm at the long side direction of this long 10cm * wide 2mm face partly locates, coating priming paint (Taiwan, big eastern resin system " GE-320A "), following dry 5 minutes at 60 ℃.Then, the mixed solution of adhesive coating (same corporate system " GE-420 ") and solidifying agent (4wt% of same corporate system " 348 " tackiness agent), coating sheet rubber (priming paint (Taiwan, big eastern resin system " GE-310A ") and make it after the drying, applying, crimping apply the mixed solution of tackiness agent (same corporate system " GE-420 ") and solidifying agent (same corporate system " 348 ") and the thin slice of formation, drying is 5 minutes under 60 ℃, obtains having the duplexer of foaming layer and rubber layer thus.Use 180 degree electronic stripping testers, under 50mm/ minute peeling rate, peel off the foaming layer and the rubber layer of this multi-layer laminate, measure the adhesive strength of foaming layer and rubber layer thus.Estimate the interlayer tackiness according to adhesive strength and according to following judgment standard 1 or 2.
Judgment standard 1
◎: adhesive strength is more than the 2.5kg/cm width.
Zero: adhesive strength is more than the 2kg/cm width, less than the 2.5kg/cm width.
*: adhesive strength is less than the 2kg/cm width.
Judgment standard 2
◎: adhesive strength is more than the 3kg/cm width.
Zero: adhesive strength is more than the 2kg/cm width, less than the 3kg/cm width.
*: adhesive strength is less than the 2kg/cm width.
Embodiment 1
(1) modulation of promotor carrier
Embodiment 10 (1) and the composition (A) in (2) of opening the 2003-171415 communique with the spy are the same, modulate solid product (following, be called promotor carrier (A1)).
(2) prepolymerization
In the internal volume that carries out nitrogen replacement in advance is 210 liters the pressure kettle that has stirrer, 80 liters of above-mentioned promotor carrier (A) 0.7kg, butane are contained in the inside after, make pressure kettle be warming up to 30 ℃.And then the ethene of packing under the gaseous pressure in pressure kettle 0.21MPa part after stablizing, is dropped into two (1-indenyl) the diphenol zirconium 70mmol of racemize ethene, the beginning polymerization in system.In 45 ℃ of intensifications, continuously supply with ethene and hydrogen on one side, implement to amount to 4 hours prepolymerization down at 49 ℃ on one side.After polymerization finishes,, at room temperature residual solid is carried out vacuum-drying, obtain the prepolymerized pre-polymerized catalyst composition of Alathon that the above-mentioned promotor carrier of corresponding every 1g (A) has 14g with flushings such as ethene, butane, hydrogen.
(3) continuous gas-phase polymerization
Use above-mentioned pre-polymerized catalyst composition, in continous way thermopnore gas phase polymerization apparatus, implement the copolymerization of ethene and 1-hexene.Polymerizing condition is, 75 ℃ of temperature, and total pressure is 2MPa, is 0.31%, is 1.2% with respect to the mol ratio of the 1-hexene of ethene with respect to the mol ratio of the hydrogen of ethene, in order to keep the constant gas composition, supplies with ethene, 1-hexene and hydrogen continuously in the polymerization.And then for the total powder weight thermopnore maintains 80kg, making the average polymerization time is 4hr, supplies with above-mentioned pre-polymerized catalyst composition and triisobutyl aluminium according to a certain percentage continuously.By polymerization, under the production efficiency of 22kg/hr, obtain the powder of ethene-1-hexene copolymer (below, be called PE (1)).
(4) granulation of ethene-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 the particle of PE (1).The MFR of PE (1) is that 0.5g/10 minute, density are 912kg/m
3, mobile activation energy is 72.9kJ/mol.
(5) pressure expansion is shaped
Use the single shaft mixing roll, under the condition of 150 ℃ of temperature, water screw rotation number 80rpm, to PE (1) 60 weight part and ethene-vinyl acetate copolymer (Sumitomo Chemical Company Ltd's system, エ バ テ one ト K2010[MFR=3g/10 minute, density=940kg/m
3, vinyl acetate quantity of units=25 weight %]; Hereinafter referred to as EVA (1).) 40 weight parts carry out melting mixing, obtain resin combination thus.Use the roller mixing roll, under 120 ℃ of roll temperatures, 5 minutes condition of mixing time, these resin combination 100 weight parts, water-ground limestone 10 weight parts, stearic acid 0.5 weight part, zinc oxide 1.5 weight parts, chemical foaming agent 3.5 weight parts, dicumyl peroxide 1.0 weight parts are carried out mixing, obtain resin combination.This resin combination is put into the mould of 22.8cm * 15cm * 1.2cm, at 160 ℃ of temperature, 11 minutes time, pressure 150kg/cm
2Condition under pressure expansion, obtain foam molding thus 1 time.Then, the thin slice that 1 foam that obtains is cut into thick 1.0cm is put into the mould of 26cm * 18cm * 1.0cm, at 150 ℃ of temperature, pressure 150kg/cm
2Condition under added hot stamping 210 seconds, cooled off then 600 seconds, obtain molding 2 times.The evaluation of physical property of 2 moldinies obtaining be the results are shown in table 1.In addition, adopt the method for in the interlayer tackiness of (9) duplexer, putting down in writing to make duplexer, measure the interlayer tackiness.Evaluation result is shown in table 1.
Embodiment 2
(1) modulation of promotor carrier
Embodiment 10 (1) and the composition (A) in (2) of opening the 2003-171415 communique with the spy are the same, modulate solid product (following, be called promotor carrier (A)).
(2) prepolymerization
In the internal volume that carries out nitrogen replacement in advance is 210 liters the pressure kettle that has stirrer, 3 liters of the hydrogen under above-mentioned promotor carrier (A) 0.68kg, 80 liters of butane, 1-butylene 0.02kg, the normal temperature and pressure be contained in the inside after, make pressure kettle be warming up to 30 ℃.And then the ethene of packing under the gaseous pressure in pressure kettle 0.03MPa part after stablizing, is dropped into triisobutyl aluminium 216mmol, two (1-indenyl) the diphenol zirconium 70mmol of racemize ethene, the beginning polymerization in system.In 50 ℃ of intensifications, continuously supply with ethene and hydrogen on one side, implement to amount to 4 hours prepolymerization down at 50 ℃ on one side.After polymerization finishes, with flushings such as ethene, butane, hydrogen, at room temperature residual solid is carried out vacuum-drying, obtaining the above-mentioned promotor carrier of corresponding every 1g (A) has ethene-butene-1 copolymer of 14g by prepolymerized pre-polymerized catalyst composition.
(3) continuous gas-phase polymerization
Use above-mentioned pre-polymerized catalyst composition, in continous way thermopnore gas phase polymerization apparatus, implement the copolymerization of ethene and 1-butylene.Polymerizing condition is, 75 ℃ of temperature, total pressure are 2MPa, is 0.77%, is 1.98% with respect to the mol ratio of the 1-hexene of ethene with respect to the mol ratio of the hydrogen of ethene, in order to keep the constant gas composition, supplies with ethene, 1-hexene and hydrogen continuously in the polymerization.And then for the total powder weight with thermopnore maintains 80kg, making the average polymerization time is 4hr, supplies with above-mentioned pre-polymerized catalyst composition and triisobutyl aluminium according to a certain percentage continuously.By polymerization, under the production efficiency of 22kg/hr, obtain the powder of ethene-1-hexene copolymer (below, be called PE (1)).
(4) granulation of ethene-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 the particle of PE (1).The MFR of PE (1) is that 0.5g/10 minute, density are 912kg/m
3, activation energy is 73kJ/mol.
(5) pressure expansion is shaped
Use the single shaft mixing roll, under the condition of 150 ℃ of temperature, water screw rotation number 80rpm, to PE (1) 80 weight part and ethene-vinyl acetate copolymer (Sumitomo Chemical Company Ltd's system, ス ミ テ one ト KA-31[MFR=7g/10 minute, density=940kg/m
3, vinyl acetate quantity of units=28 weight %]; Hereinafter referred to as EVA (1).) 20 weight parts carry out melting mixing, obtain resin combination.Then, use the roller mixing roll, under 120 ℃ of roll temperatures, 5 minutes condition of mixing time, to these resin combination 100 weight parts, water-ground limestone 10 weight parts, stearic acid 0.5 weight part, zinc oxide 1.5 weight parts, chemical foaming agent 3.5 weight parts, dicumyl peroxide 1.0 weight parts carry out mixing, obtain resin combination.This resin combination is put into the metal pattern of 22.8cm * 15cm * 1.2cm, at 160 ℃ of temperature, 11 minutes time, pressure 150kg/cm
2Condition under pressure expansion, obtain foam molding thus 1 time.Then, the molding that 1 foam that will obtain is cut into thick 1.0cm is put into the metal pattern of 26cm * 18cm * 1.0cm, at 150 ℃ of temperature, pressure 150kg/cm
2Condition under added hot stamping 210 seconds, obtained molding in 600 seconds 2 times by cooling off then.The evaluation of physical property of 2 moldinies obtaining be the results are shown in table 1.The method that employing is put down in writing in the interlayer tackiness of (9) duplexer makes duplexer, measures the interlayer tackiness.Evaluation result is shown in table 1.
Embodiment 3
Use the single shaft stirrer, under the condition of 150 ℃ of temperature, water screw rotation number 80rpm, to PE (1) 80 weight part, ethene-vinyl acetate copolymer (ザ Port リ オ レ Off イ Application カ Application パ ニ one corporate system, コ ス モ セ Application H2181[MFR=2g/10 minute, density=940kg/m
3, vinyl acetate quantity of units=18 weight %]; Hereinafter referred to as EVA (2).) 20 weight parts carry out melting mixing, obtain resin combination thus.Use the roller mixing roll, under 120 ℃ of roll temperatures, 5 minutes condition of mixing time, to these resin combination 100 weight parts, water-ground limestone 10 weight parts, stearic acid 0.5 weight part, zinc oxide 1.5 weight parts, chemical foaming agent 3.5 weight parts, dicumyl peroxide 1.0 weight parts carry out mixing, obtain resin combination.This resin combination is put into the mould of 22.8cm * 15cm * 1.2cm, at 160 ℃ of temperature, 11 minutes time, pressure 150kg/cm
2Condition under pressure expansion, obtain foam molding thus 1 time.Then, the thin slice that 1 foam that obtains is cut into thick 1.0cm is put into the mould of 26cm * 18cm * 1.0cm, at 150 ℃ of temperature, pressure 150kg/cm
2Condition under added hot stamping 210 seconds, cool off then and obtained molding in 600 seconds 2 times.The evaluation of physical property of 2 moldinies obtaining be the results are shown in table 1.In addition, adopt the method for in the interlayer tackiness of (9) duplexer, putting down in writing to make duplexer, measure the interlayer tackiness.Evaluation result is shown in table 1.
Comparative example 1
Use the roller mixing roll, under 120 ℃ of roll temperatures, 5 minutes condition of mixing time, to ethene-vinyl acetate copolymer (ザ Port リ オ レ Off イ Application カ Application パ ニ one corporate system, コ ス モ セ Application H2181[MFR=2g/10 minute, density=940kg/m
3, vinyl acetate quantity of units=18 weight %]; Hereinafter referred to as EVA (3).) 100 weight parts, water-ground limestone 10 weight parts, stearic acid 0.5 weight part, zinc oxide 1.5 weight parts, chemical foaming agent 3.0 weight parts, dicumyl peroxide 0.7 weight part carry out mixingly, obtain resin combination.This resin combination is put into the mould of 22.8cm * 15cm * 1.2cm, at 160 ℃ of temperature, 11 minutes time, pressure 150kg/cm
2Condition under pressure expansion, obtain foam molding thus 1 time.Then, the thin slice that 1 foam that obtains is cut into thick 1.0cm is put into the mould of 26cm * 18cm * 1.0cm, at 150 ℃ of temperature, pressure 150kg/cm
2Condition under added hot stamping 210 seconds, cool off then and obtained molding in 600 seconds 2 times.The evaluation of physical property of 2 moldinies obtaining be the results are shown in table 1.The method that employing is put down in writing in the interlayer tackiness of (9) duplexer makes duplexer, measures the interlayer tackiness.Evaluation result is shown in table 1.
Table 1
| Project | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Ethene-alpha-olefin copolymer | PE(1) | PE(2) | PE(1) | - | |
| Content | Weight % | 60 | 80 | 80 | - |
| MFR | G/10 minute | 0.5 | 0.5 | 0.5 | - |
| Density | kg/m 3 | 912 | 912 | 912 | - |
| Mobile activation energy | kJ/mol | 73 | 73 | 73 | - |
| Ethene-vinyl acetate copolymer | EVA(1) | EVA(2) | EVA(3) | EVA(3) | |
| Content | Weight % | 40 | 20 | 20 | 100 |
| MFR | G/10 minute | 3 | 7 | 2 | 2 |
| Density | kg/m 3 | 940 | 940 | 940 | 940 |
| Foam molding | |||||
| Density | kg/m 3 | 193 | 190 | 160 | 211 |
| Hardness | - | 55 | 55 | 55 | 55 |
| Intensity | kg/cm | 16.3 | 18.9 | - | 14.2 |
| The interlayer tackiness of duplexer | - | ◎ *1 ○ *2 | ◎ *1 ◎ *2 | ○ *1 ○ *2 | ◎ *1 ○ *2 |
| Rebound elasticity | - | ○ | ○ | △ | ○ |
Annotate:
*1: judgment standard 1,
*2: judgment standard 2.
Claims (9)
1. resin combination contain following compositions (i) and (ii), and when making composition (i) and total amount (ii) be 100 weight %, the content of composition (i) is 99～30 weight %, and composition content (ii) is 1～70 weight %, wherein,
(i) be that to have based on the monomeric unit of ethene with based on carbonatoms be that monomeric unit, the melt flow rate (MFR) of 3～20 alpha-olefin is that 0.01～5g/10 minute and mobile activation energy are the ethene-alpha-olefin analog copolymer more than the 30kJ/mol;
(ii) be to have based on the monomeric unit of at least a unsaturated ester from vinyl carboxylates and unsaturated carboxylic acid alkyl ester, selected and based on the ethene-unsaturated ester analog copolymer of the monomeric unit of ethene.
2. resin combination according to claim 1 is characterized in that,
The mobile activation energy of ethene-alpha-olefin analog copolymer (i) is more than the 40kJ/mol.
3. resin combination according to claim 1 is characterized in that,
The composition content based on the monomeric unit of this unsaturated ester class (ii) is 5～45 weight %.
4. resin combination, when containing following compositions (i) and composition and being made as 100 weight % (ii) and with composition (i) and total amount (ii), the content of composition (i) is 98～50 weight %, composition content (ii) is 2～50 weight %, wherein,
(i) be that to have based on the monomeric unit of ethene with based on carbonatoms be that monomeric unit, the melt flow rate (MFR) of 3～20 alpha-olefin is that 0.01～5g/10 minute and mobile activation energy are the ethene-alpha-olefin analog copolymer more than the 40kJ/mol;
(ii) be to have, and be that 5～45 weight %, melt flow rate (MFR) are ethene-unsaturated ester analog copolymer of 4～100g/10 minute based on the content of the monomeric unit of this unsaturated ester based on the monomeric unit of at least a unsaturated ester from vinyl carboxylates and unsaturated carboxylic acid alkyl ester, selected and based on the monomeric unit of ethene.
5. pressure expansion molding is any described resin combination in the claim 1～4 to be carried out pressure expansion be shaped and obtain.
6. sole that contains the described pressure expansion molding of claim 5.
7. a duplexer is to be laminated to the foaming layer of the described pressure expansion molding of claim 5 with by the layer that the material outside the vinyl resins constitutes.
8. sole that contains the described duplexer of claim 7.
9. duplexer according to claim 5, wherein,
By the layer that the material beyond the vinyl resins constitutes, be contain from polyvinyl chloride (PVC) RESINS material, styrene copolymer elastomeric material, olefinic copolymer elastomeric material, natural leather material, artificial leather material, and cloth material etc. at least a kind of material selecting layer.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004313535 | 2004-10-28 | ||
| JP2004313536 | 2004-10-28 | ||
| JP2004313535 | 2004-10-28 | ||
| JP2005063453 | 2005-03-08 |
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| CN1765967A true CN1765967A (en) | 2006-05-03 |
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Cited By (4)
| 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 |
| WO2015042820A1 (en) * | 2013-09-26 | 2015-04-02 | Dow Global Technologies Llc | A polymeric blend composition |
| CN104844917A (en) * | 2015-05-11 | 2015-08-19 | 湖州福泽鞋业有限公司 | Non-gumming wear-resistant sole and preparation method thereof |
| CN105518073A (en) * | 2013-09-26 | 2016-04-20 | 陶氏环球技术有限责任公司 | A polymeric blend composition |
-
2005
- 2005-10-26 CN CN 200510114176 patent/CN1765967A/en active Pending
Cited By (6)
| 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 |
| WO2015042820A1 (en) * | 2013-09-26 | 2015-04-02 | Dow Global Technologies Llc | A polymeric blend composition |
| CN105518073A (en) * | 2013-09-26 | 2016-04-20 | 陶氏环球技术有限责任公司 | A polymeric blend composition |
| CN105518073B (en) * | 2013-09-26 | 2017-11-24 | 陶氏环球技术有限责任公司 | Polymer blend composition |
| CN104844917A (en) * | 2015-05-11 | 2015-08-19 | 湖州福泽鞋业有限公司 | Non-gumming wear-resistant sole and preparation method thereof |
| CN104844917B (en) * | 2015-05-11 | 2017-05-10 | 宾度投资股份有限公司 | Non-gumming wear-resistant sole and preparation method thereof |
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