CN101469077A - Process for producing thermoplastic elastomer composition foam body, and thermoplastic elastomer composition for foam injection molding - Google Patents
Process for producing thermoplastic elastomer composition foam body, and thermoplastic elastomer composition for foam injection molding Download PDFInfo
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- CN101469077A CN101469077A CNA2008101855209A CN200810185520A CN101469077A CN 101469077 A CN101469077 A CN 101469077A CN A2008101855209 A CNA2008101855209 A CN A2008101855209A CN 200810185520 A CN200810185520 A CN 200810185520A CN 101469077 A CN101469077 A CN 101469077A
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Abstract
A process for producing a thermoplastic elastomer composition foam body is provided that includes, in sequence, a step of injecting by an injection molding machine into a cavity of a mold for injection molding a foaming agent and a thermoplastic elastomer composition comprising component (A), component (B), and component (C) below, component (B) having a content of 5 to 150 parts by weight relative to 100 parts by weight of component (A) and component (C) having a content of 5 to 300 parts by weight relative to 100 parts by weight of component (A), a step of holding for not less than 4 seconds after completion of the injection, and a step of enlarging the volume of the cavity by moving a wall face of the cavity to a predetermined position. (A): A hydrogenated product of a block copolymer comprising a block composed of an aromatic vinyl compound-based monomer unit and a block composed of a conjugated diene compound-based monomer unit, (B): a propylene resin, and (C): a mineral oil.
Description
Technical field
The present invention relates to the manufacture method and the thermoplastic elastomer composition for foam injection molding of composition for thermoplastic elastomer foam.
Background technology
At present, the foam that the foam unit that requirements such as automotive interior material, household electrical appliances parts have flexibility, a thermotolerance etc. adopts the styrene analog thermoplastic elastomer composition by hydride that contains following segmented copolymer and polypropylene-based resin to form, this segmented copolymer contains block that is made of the monomeric unit based on aromatic ethenyl compound and the block that is made of the monomeric unit based on conjugated diene compound.
Manufacture method as described foam, from the viewpoint of boosting productivity, adopt the foam injection molding method, for example in Japanese patent laid-open 6-218741 communique, put down in writing following manufacture of foamed body, it is characterized in that: will be that the hydride of the vinylbenzene conjugated diene block copolymer below 150000 is raw material with molecular-weight average by (a), the JIS-A hardness that obtains according to JIS-K6301 is after 40～95 styrene analog thermoplastic elastomer composition 100 weight parts and the expandable styrene analog thermoplastic elastomer that (b) formed by the blowing agent component of 0.01～10 weight part are injected in the mould cavity, enlarge this die cavity volume and make its foaming and moulding.In addition, the Japanese Patent spy open put down in writing by configuration in shaping mould or the polyolefins compound resin layer that obtains of injection molding in the 2006-175825 communique on foaming layer with the composition foam injection molding with the one-body molded composite shaped body that obtains of foaming layer, the weight-average molecular weight that (a) that above-mentioned foaming layer contains 30～70 weight % with composition has aromatic ethenyl compound block and a conjugated diene compound block is the hydride of the segmented copolymer below 200,000 and (b) acronal, (c) rubber softener material, (d) crystallinity propene polymer, the acronal mixture that all the other non-crystalline copolymers of including propylene and ethene of serving as reasons form, above-mentioned foaming layer has following character with composition or above-mentioned foaming layer: (A) the above-mentioned foaming layer of measuring according to JIS-K6253 is below 80 with the type A hardness of composition, and the surface hardness of the above-mentioned foaming layer that records according to ASKER C is below 75; (B) foam expansion of above-mentioned foaming layer is more than 1.2 times; (C) above-mentioned foaming layer is down more than 80m/ minute with the fusion ductility of composition at 170～190 ℃; (D) the above-mentioned foaming layer of measuring according to JIS-K 7196 is with in the TMA measured value of composition, and the temperature during the 0.1mm distortion is more than 100 ℃, and the temperature during the 0.5m distortion is more than 120 ℃.
But, in the foam of the aromatic ethenyl compound analog thermoplastic elastomer composition, particularly the styrene analog thermoplastic elastomer composition that utilize existing foam injection molding method, because foamed cell is big, or because the size and the shape inequality of foamed cell, cause flexibility to descend, the fine property of foamed cell and the homogeneity of foamed cell do not make us very satisfied.
Summary of the invention
In view of the foregoing, the technical problem to be solved in the present invention is to provide a kind of method of aromatic ethenyl compound analog thermoplastic elastomer composition foam that can make the homogeneity excellence of the fine property of foamed cell and foamed cell by foam injection molding.
In addition, the present invention's other technologies problem that will solve be can by foam injection molding obtain the fine property of foamed cell and foamed cell the homogeneity excellence foam aromatic ethenyl compound class thermoplastic elastomer composition for foam injection molding, the foam that this composition for thermoplastic elastomer foam injection molding is obtained and with the manufacture method of the foam of this composition for thermoplastic elastomer foam injection molding.
＜1〉a kind of manufacture method of composition for thermoplastic elastomer foam is characterized in that, comprises following operation successively:
Following composition for thermoplastic elastomer and whipping agent are injected to the operation of the die cavity of die for injection molding by injection moulding machine, described composition for thermoplastic elastomer contains following compositions (A), composition (B) and composition (C), and with respect to composition (A) 100 weight parts, the content of composition (B) is that the content of 5～150 weight parts, composition (C) is 5～300 weight parts; Injection finishes the operation of back maintenance more than 4 seconds; And enlarge die cavity volumetrical operation by the die cavity wall being moved to default position, wherein,
(A): the hydride of segmented copolymer, the hydride of this segmented copolymer contain block that is made of the monomeric unit based on aromatic ethenyl compound and the block that is made of the monomeric unit based on conjugated diene compound,
(B): propylene resin,
(C): mineral oil.
＜2〉manufacture method of basis＜1〉described composition for thermoplastic elastomer foam, wherein, above-mentioned expansion die cavity volumetrical operation enlarges the volume of die cavity with 700%/second above die cavity volume expansion speed.
3. according to＜1〉or＜2〉described composition for thermoplastic elastomer foam manufacture method, wherein, the total amount 100 weight % of block that constitutes with respect to the monomeric unit by based on aromatic ethenyl compound of above-mentioned (A) composition and the block that is made of the monomeric unit based on conjugated diene compound, the content of the block that is made of the monomeric unit based on aromatic ethenyl compound are more than the 5 weight % below the 50 weight %.
＜4〉according to＜1 〉～＜3 in the manufacture method of each described composition for thermoplastic elastomer foam, wherein, the hydrogenation ratio of composition (A) is more than 50%.
5. according to＜1 〉～＜4 in the manufacture method of each described composition for thermoplastic elastomer foam, wherein, the weight-average molecular weight of composition (A) is more than 50,000 below 500,000.
6. according to＜1 〉～＜5 in the manufacture method of each described composition for thermoplastic elastomer foam, wherein, the melt flow rate (MFR) of composition (B) (230 ℃ of load 21.18N, temperature) is more than 0.1g/10 minute below 300g/10 minute.
7. according to＜1 〉～＜6 in the manufacture method of each described composition for thermoplastic elastomer foam, wherein, the molecular-weight average of composition (C) is more than 300 below 1500, yield point is below 0 ℃.
8. a foam injection molding (foam injection molding) is used composition for thermoplastic elastomer, it contains following compositions (A '), composition (B ') and composition (C), it is with respect to composition (A ') 100 weight parts, the content of composition (B ') is 5～150 weight parts, the content of composition (C) is 5～300 weight parts
(A '): contain the block that constitutes by monomeric unit and the hydride of the segmented copolymer of the block that constitutes by monomeric unit, and weight-average molecular weight is more than 200,000 based on conjugated diene compound based on aromatic ethenyl compound,
(B '): melt flow rate (MFR) is that 2～300g/10 minute, melt tension (melt tension) are the above propylene resin of 3cN,
(C): mineral oil.
9. according to＜8〉described composition for thermoplastic elastomer, it also contains following compositions (B "), and with respect to composition (A ') 100 weight parts, and the content of mentioned component (B ') and following compositions (B ") adds up to 5～150 weight parts,
(B "): the propylene resin of not enough 2g/10 minute of melt flow rate (MFR) or the not enough 3cN of melt tension.
10. foam, it is by will＜8〉or＜9〉described composition for thermoplastic elastomer foam injection molding obtain.
＜11〉a kind of manufacture method of foam is characterized in that, comprises preparation＜8〉or＜9〉described composition for thermoplastic elastomer operation and with the operation of above-mentioned composition for thermoplastic elastomer foam injection molding.
＜12〉a kind of general＜8〉or＜9〉described composition for thermoplastic elastomer application as foam injection molding usefulness composition.
The present invention can provide a kind of method of aromatic ethenyl compound analog thermoplastic elastomer composition foam of the homogeneity excellence of making the fine property of foamed cell and foamed cell by foam injection molding.
The present invention also provide a kind of can by foam injection molding obtain the fine property of foamed cell and foamed cell the homogeneity excellence foam aromatic ethenyl compound class thermoplastic elastomer composition for foam injection molding, the foam that this composition for thermoplastic elastomer foam injection molding is formed and with the manufacture method of the foam of this composition for thermoplastic elastomer foam injection molding.
Embodiment
The composition for thermoplastic elastomer that the present invention uses contains following compositions (A), composition (B) and composition (C), and with respect to composition (A) 100 weight parts, the content of composition (B) is 5～150 weight parts, and the content of composition (C) is 5～300 weight parts.
(A): the hydride of segmented copolymer, the hydride of this segmented copolymer contain block that is made of the monomeric unit based on aromatic ethenyl compound and the block that is made of the monomeric unit based on conjugated diene compound,
(B): propylene resin
(C): mineral oil
The hydride of composition (A) is the compound that obtains by with following segmented copolymer hydrogenation, and described segmented copolymer contains block (aromatic ethenyl compound block) that is made of the monomeric unit based on aromatic ethenyl compound and the block (conjugated diene compound block) that is made of the monomeric unit based on conjugated diene compound.As this aromatic ethenyl compound, can enumerate vinylbenzene, alpha-methyl styrene, o-methyl styrene, a vinyl toluene, p-methylstyrene, 1,3-dimethyl styrene, vinyl naphthalene, vinyl anthracene etc., optimization styrene.These aromatic ethenyl compounds can use more than 2 kinds.As this conjugated diene compound, can enumerate divinyl, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene etc., preferred divinyl, isoprene.These conjugated diene compounds can use more than 2 kinds.
Content about aromatic ethenyl compound block and conjugated diene compound block, from improving the physical strength and the stable on heating viewpoint of foam, the content of optimization aromatic vinyl compound block is more than the 5 weight %, the content of conjugated diene compound section chain is below the 95 weight %, further the content of optimization aromatic vinyl compound block is more than the 10 weight %, and the content of conjugated diene compound section chain is below the 90 weight %.In addition, viewpoint from the flexibility that improves foam, the content of optimization aromatic vinyl compound block is below the 50 weight %, the content of conjugated diene compound section chain is more than the 50 weight %, further the content of optimization aromatic vinyl compound block is below the 40 weight %, and the content of conjugated diene compound section chain is more than the 60 weight %.But the total amount of aromatic ethenyl compound block and conjugated diene compound block is 100 weight %.In addition, the content of above-mentioned aromatic ethenyl compound block is meant the total amount of aromatic ethenyl compound block, for example when above-mentioned segmented copolymer is aromatic ethenyl compound block-conjugated diene compound block-this triblock copolymer of aromatic ethenyl compound block, as the total amount of aromatic ethenyl compound block, be preferably above-mentioned content.
In addition, the content of above-mentioned each block is the content after the hydrogenation.
Above-mentioned segmented copolymer can be the Synthetic rubber, isoprene-styrene, hydrogenated, block, diblock of aromatic ethenyl compound block-conjugated diene compound block structure, also can be aromatic ethenyl compound block-conjugated diene compound block-triblock copolymers such as aromatic ethenyl compound block structure.
The hydride of segmented copolymer is the material that the part or all of hydrogenation of two keys based on the monomeric unit of conjugated diene compound that will constitute above-mentioned conjugated diene compound block obtains.For hydrogenation ratio, being with the two key amounts based on the monomeric unit of conjugated diene compound in the segmented copolymer before the hydrogenation is 100%, the amount of two keys that the hydrogenation by segmented copolymer in this pair key is hydrogenated, from improving the weathering resistance and the stable on heating viewpoint of foam, preferred more than 50% below 100%, further preferred more than 80% below 100%.
About the weight-average molecular weight of hydride, the viewpoint from the physical strength of the homogeneity of the fine property that improves foamed cell and foamed cell, foam is preferably more than 50,000, more preferably is more than 100,000.From improving the viewpoint of oil-proofness, homogeneity and physical strength, the weight-average molecular weight of hydride is preferably more than 200,000, is preferably more than 250,000 especially.In addition, from improving the viewpoint of formability, be preferably below 500,000, more preferably below 400,000.Weight-average molecular weight is the weight-average molecular weight that polyethylene converts, and measures with gel permeation chromatography (GPC) method.
Manufacture method as hydride, can be listed below method: make segmented copolymer with the method for for example in the special public clear 40-23798 communique of Japanese Patent, putting down in writing, open the method put down in writing in the clear 60-79005 communique with this segmented copolymer hydrogenation with for example opening clear 59-133203 communique or Japanese Patent spy then the special public clear 42-8704 communique of Japanese Patent, the special public clear 43-6636 communique of Japanese Patent, Japanese Patent spy.
In addition, as hydride, also can use commercially available product.For example, can the section of enumerating rise Polymer Company's system " KRATON-G " (trade(brand)name), Kuraray Co., Ltd.'s system " SEPTON " (trade(brand)name), Asahi Kasei Corporation's system " Tuftec " (trade(brand)name) etc.
As the propylene resin of composition (B), can enumerate alfon, be selected from by ethene and carbonatoms is at least a kind of comonomer in the comonomer group formed of 4～10 alpha-olefin and the multipolymer of propylene.This multipolymer can be a random copolymers, also can be segmented copolymer.As this multipolymer, more specifically, but illustration propylene-ethylene copolymers, propylene-butene-1 copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-butene-1 copolymer, propylene-ethylene-1-hexene copolymer.As propylene resin, preferred alfon, propylene-ethylene copolymers, propylene-butene-1 copolymer.They can use more than a kind or 2 kinds and be used in combination.
The content of the monomeric unit based on propylene of the polymkeric substance that uses in the propylene resin (propylene units) is preferably more than the 50 weight %, below the 100 weight %, further preferably surpass 60 weight %, below the 100 weight %, more preferably 80 weight % above, below the 100 weight %.Wherein, be 100 weight % with this polymkeric substance.
The melt flow rate (MFR) of propylene resin is preferably 0.1～300g/10 minute, and more preferably 0.5～200g/10 minute, more preferably 1～150g/10 minute.This melt flow rate (MFR) is measured down for 230 ℃ in load 21.18N, temperature according to JISK7210.
It is that the known polymerization process of polymerizing catalyst is made that propylene resin can adopt with Ziegler-Natta catalyst, metallocene catalyst etc.As this polymerization process, can enumerate solution polymerization process, mass polymerization, slurry polymerization process, gaseous polymerization etc., they can be the combination more than 2 kinds.
Composition (C) is a mineral oil, it has been the composition of tenderizer effect, but illustration aromatics mineral oil (aromatic mineral oil), naphthenic mineral oil (naphthenic mineral oil), paraffin class mineral oil (paraffinic mineral oil), preferred paraffin class mineral oil.In addition, preferred molecular-weight average is 300～1500, and also the preferred flow point is below 0 ℃.
In the present invention, as composition for thermoplastic elastomer, the also preferred composition for thermoplastic elastomer that contains following compositions (A '), composition (B ') and composition (C) that uses.
(A ') contains the block that is made of the monomeric unit based on aromatic ethenyl compound and the hydride of the segmented copolymer of the block that is made of the monomeric unit based on conjugated diene compound, and weight-average molecular weight is more than 200,000,
(B '): melt flow rate (MFR) is that 2～300g/10 minute, melt tension are the above propylene resin of 3cN,
(C): mineral oil.
That is, as (A) composition, using weight-average molecular weight is hydride (composition (A ') more than 200,000), as (B) composition, to use melt flow rate (MFR) be 2～300g/10 minute, melt tension is the propylene resin more than the 3cN (composition (B ')).
As (A ') composition,, use preferably that weight-average molecular weight is the hydride of the segmented copolymer more than 200,000 in above-mentioned (A) composition from the viewpoint of the physical strength of the homogeneity that improves foamed cell, foam.At this moment, more preferably more than 220,000, more preferably more than 250,000.In addition, from improving the viewpoint of forming process, weight-average molecular weight is preferably below 500,000.Weight-average molecular weight is the weight-average molecular weight of polystyrene conversion, measures with gel permeation chromatography (GPC) method.
As (B ') composition, preferably using in above-mentioned (B) composition melt flow rate (MFR) is that 2～300g/10 minute, melt tension are the above acrylic resin of 3cN.
Above-mentioned melt flow rate (MFR) is preferably more than 2g/10 minute from the viewpoint that improves forming process, more preferably more than 3g/10 minute.In addition, from improving the viewpoint of physical strength,, preferred below 200g/10 minute for below 300g/10 minute.This melt flow rate (MFR) is measured down for 230 ℃ in load 21.18N, temperature according to JISK7210.
Above-mentioned melt tension is preferably more than the 3cN, more preferably more than the 4cN from the viewpoint of the homogeneity of the fine property that improves foamed cell and foamed cell.In addition, from improving the viewpoint of forming process, below 500cN, more preferably below the 300cN.This melt tension is, be under 5.7mm/ minute the condition at 190 ℃ of temperature, piston rotation perdurability, utilize piston will be filled in barrel dliameter and extrude the tension force the when sample that will melt extrude batched with 15.7m/ minute for the sample in the cylinder of 9.55mm with molten state from the jet pipe of being located at the vertical long 8mm of cylinder, diameter 2mm.
As above-mentioned melt flow rate (MFR) is that 2～300g/10 minute, melt tension are the manufacture method of the propylene resin more than the 3cN, the method that can be listed below, to with the propylene monomer polymerization of main component for example in the 1st stage, manufacturing limit viscosity number (intrinsic viscosity) is the above crystallinity acronal composition (composition (b1)) of 5dl/g, to be the monomer polymerization of main component with the propylene after the 2nd stage then, the manufacturing limit viscosity number be the following crystallinity acronal composition (composition (b2)) of 3dl/g continuously.
As composition (b1) and composition (b2), preferred isotactic acronal, wherein, preferred alfon, to be selected from by ethene and carbonatoms be at least a kind of comonomer in the comonomer group formed of 4～10 alpha-olefin and the multipolymer of propylene.As this alpha-olefin, for example can enumerate 1-butylene, 4-methylpentene-1,1-octene, 1-hexene etc.When comonomer is ethene, be preferably below the 10 weight % based on the content of the monomeric unit of ethene, in addition, when comonomer is a carbonatoms when being 4～10 alpha-olefin, be preferably below the 30 weight % based on the content of the monomeric unit of this alpha-olefin.
The limit viscosity number of composition (b1) is preferably more than the 6dl/g, more preferably more than the 7dl/g.In addition, the limit viscosity number of composition (b1) is preferably below the 100dl/g, more preferably below the 50dl/g.
The limit viscosity number of composition (b2) is preferably below the 2dl/g.In addition, the limit viscosity number of composition (b2) is more than the 0.1dl/g, to be preferably more than the 0.5dl/g.
The limit viscosity number [η] of composition (b2)
B2Can calculate by following formula.
[η]
b2＝([η]
T×100-[η]
b1×W
b1)/W
b2
[η]
T: the limit viscosity number (unit: dl/g) of propylene resin
[η]
B1: the limit viscosity number (unit: dl/g) of composition (b1)
W
B1: the content (unit: weight %) of composition (b1)
W
B2: the content (unit: weight %) of composition (b2)
(wherein, with W
B1And W
B2Add up to 100 weight %.)
About the polymerization ratio of composition (b1), when being 100 weight %, be preferably 0.05～25 weight %, more preferably 0.3～20 weight % with the total amount of composition (b1) and composition (b2).
As the olefin polymerization catalysis that in the manufacturing of composition (b1) and composition (b2), uses, can enumerate with Ti, Mg, halogen is the olefin polymerization catalysis of necessary composition, particularly, can preferably use the catalyzer of putting down in writing in the Japanese patent laid-open 7-216017 communique.
Method as continuous manufacturing composition (b1) and composition (b2), can be set forth in and make the polymerization tank that the batchwise polymerization method of then making composition (b2) in composition (b1) back in same polymerization tank or series connection setting are made up of 2 grooves at least, behind the polymerization tank manufacturing composition (b1) of previous stage, composition (b1) is transferred to the polymerization tank of the latter half and in the polymerization of the polymerization tank manufacturing composition (b2) of the latter half etc.
As the manufacture method of composition (b1) and composition (b2), can enumerate with the solvent polymerization method of hydrocarbon such as hexane, heptane, octane, decane, hexanaphthene, methylcyclohexane, benzene,toluene,xylene as solvent; With the mass polymerization of liquid monomer as solvent; In the monomer of gas, carry out polymeric gaseous polymerization etc.Preferred mass polymerization, gaseous polymerization.
In the manufacturing of composition (b1) and composition (b2), polymerization temperature is preferably 20～150 ℃, more preferably 35～95 ℃.
To use melt flow rate (MFR) be 2～300g/10 minute, melt tension is the propylene resin more than the 3cN (composition (B ') as (B) propylene resin) time, can also with the propylene resin of not enough 2g/10 minute of melt flow rate (MFR) or the not enough 3cN of melt tension (composition (B ")) share.
As mentioned component (B ") propylene resin, can enumerate alfon, be selected from by ethene and carbonatoms is at least a kind the comonomer in the comonomer group formed of 4～10 alpha-olefin and the multipolymer of propylene.This multipolymer can be a random copolymers, also can be segmented copolymer.As this multipolymer, more specifically, but illustration propylene-ethylene copolymers, propylene-butene-1 copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-butene-1 copolymer, propylene-ethylene-1-hexene copolymer.As the propylene resin of not enough 2g/10 minute of melt flow rate (MFR) or the not enough 3cN of melt tension (composition (B ")), preferred alfon, propylene-ethylene copolymers, propylene-butene-1 copolymer.
Melt flow rate (MFR) is not enough 2g/10 minute or the propylene resin of the not enough 3cN of melt tension (composition (B ")) in the content of the monomeric unit based on propylene (propylene units) of the polymkeric substance that uses be preferably more than the 50 weight %, more preferably more than the 80 weight %.Wherein, be 100 weight % with this polymkeric substance.
Melt flow rate (MFR) is not enough 2g/10 minute or the propylene resin of the not enough 3cN of melt tension (composition (B ")) melt tension, from improving the viewpoint of forming process, be preferably below the 2cN.In addition, from improving the viewpoint of mechanical properties, be preferably more than the 0.01cN, more preferably more than the 0.05cN.This melt tension is, be under 5.7mm/ minute the condition at 190 ℃ of temperature, piston rotation perdurability, utilize piston will be filled in barrel dliameter and extrude the tension force the when sample that will melt extrude batched with 15.7m/ minute for the sample in the cylinder of 9.55mm with molten state from the jet pipe of being located at the vertical long 8mm of cylinder, diameter 2mm.
The melt flow rate (MFR) of the propylene resin of not enough 2g/10 minute of melt flow rate (MFR) or the not enough 3cN of melt tension from improving the viewpoint of forming process, is preferably more than 0.1g/10 minute, more preferably more than 0.3g/10 minute.In addition, from improving the viewpoint of mechanical properties, be preferably below 300g/10 minute, more preferably below 200g/10 minute.This melt flow rate (MFR) is measured down for 230 ℃ in load 21.18N, temperature according to JIS K7210.
The propylene resin of not enough 2g/10 minute of melt flow rate (MFR) or the not enough 3cN of melt tension can adopt with Ziegler-Natta catalyst, metallocene catalyst etc. to be made as the known polymerization process of polymerizing catalyst.As this polymerization process, can enumerate solution polymerization process, mass polymerization, slurry polymerization process, gaseous polymerization etc., they can make up more than 2 kinds.
In the present invention, as (B) propylene resin, with melt flow rate (MFR) is that 2～300g/10 minute, melt tension are the propylene resin (composition (B ") more than the 3cN) and the propylene resin of not enough 2g/10 minute of melt flow rate (MFR) or the not enough 3cN of melt tension (composition (B ")) when share, the total amount of propylene resin is that the content of above-mentioned (B) composition gets final product.
In addition, above-mentioned containing (A ') composition, (B ') composition and (C) composition for thermoplastic elastomer of composition be preferred for the injection molding foaming, form foam.At this moment, injection moulding is not limited to injection moulding described later, so long as following method can not be subjected to any restriction, that is: in the die cavity of the mould of Coinjection molding apparatus, fill the molten thermoplastic elastic composition that is dissolved with whipping agent, the molten thermoplastic elastic composition is foamed in mould, with the cooling of molten thermoplastic elastic composition, curing, obtain foam then.
As the injecting method in the foam injection molding, can enumerate single shaft injection, multiaxis injection, high-pressure injection method, low head injection method, use the injecting method of plunger etc.In addition, as injecting method, preferably the rare gas element that will use as pneumatogen injects the method for carrying out in the machine barrel of Coinjection molding apparatus under supercritical state.
As the foaming method in the foam injection molding, for example can enumerate the method for following (1), (2), (3).
(1) the molten thermoplastic elastic composition that contains whipping agent of the amount that will lack than the mould cavity volume is injected in the mould cavity, utilizes the expansion of the gas of whipping agent, makes the molten thermoplastic elastic composition be filled in mould cavity and the method that makes it to foam.
(2) the molten thermoplastic elastic composition that contains whipping agent that can fill up the amount of mould cavity is injected in the mould cavity, utilizes the gas of whipping agent to make composition for thermoplastic elastomer be accompanied by the volume demi-inflation that cooling shrinks and the method that foams.
(3) the molten thermoplastic elastic composition that contains whipping agent that can fill up the amount of mould cavity is injected in the mould cavity, and the die cavity wall of mould is retreated, and increases the die cavity volume, makes the gas expansion of whipping agent and the method that foams.
As the foaming method in the foam injection molding, the molten thermoplastic elastic composition that contains whipping agent that preferably can fill up the amount of mould cavity is injected to the method (completely filled method) in the mould cavity.
Composition for thermoplastic elastomer can contain various additives in the scope of not damaging the object of the invention.As the object lesson of additive, can enumerate various oxidation inhibitor such as phenol oxidation inhibitor, Phosphorus oxidation inhibitor, sulfur type antioxidant; Various thermo-stabilizers such as hindered amines thermo-stabilizer; Various UV light absorber such as Benzophenones UV light absorber, benzotriazole category UV light absorber, benzoate UV light absorber; Various static inhibitor such as non-ionic antistatic agent, cationic static inhibitor, anionic antistatic agent; Various dispersion agents such as bisamide class dispersion agent, paraffin class dispersion agent, organo-metallic salt dispersion agent; Various chlorine scavenger such as the metal carboxylate chlorine scavenger of alkaline earth salt; Various lubricants such as amides lubricant, paraffin class lubricant, organic metal salt series lubricant agent, ester series lubricant agent; Various decomposition agents such as oxide-based decomposition agent, hydrotalcite decomposition agent; Various metal passivators such as hydrazine metalloid passivator, amine metal passivator; Various fire retardants such as brominated organic based flame retardant, phosphoric acid based flame retardant, ANTIMONY TRIOXIDE SB 203 99.8 PCT, magnesium hydroxide, red phosphorus; Various inorganic fillers such as talcum powder, mica, clay, lime carbonate, aluminium hydroxide, magnesium hydroxide, barium sulfate, glass fibre, carbon fiber, silicon-dioxide, Calucium Silicate powder, potassium titanate, wollastonite; Organic filler; Pigment dyestuff; Mineral dye; Inorganic antiseptic; Organic antibacterial agent etc.
From improving the stable on heating viewpoint of foam, blending amount as composition (B) propylene resin of composition for thermoplastic elastomer, with respect to composition (A) 100 weight parts, be more than 5 weight parts, be preferably more than 10 weight parts, more preferably be more than 20 weight parts, to be preferably especially more than 40 weight parts.In addition, from the viewpoint of the flexibility that improves foam, be below 150 weight parts, be preferably below 120 weight parts, more preferably below 100 weight parts, be preferably especially below 80 weight parts.
From the flexibility that improves foam, the viewpoint of forming process, as the blending amount of composition (C) mineral oil of composition for thermoplastic elastomer,, be more than 5 weight parts with respect to composition (A) 100 weight parts, be preferably more than 30 weight parts, more preferably more than 50 weight parts.In addition, from improving impermeability (bleed resistance), the stable on heating viewpoint of foam, be below 300 weight parts, be preferably below 250 weight parts, more preferably below 200 weight parts.
Composition for thermoplastic elastomer can by other compositions that the mineral oil of the propylene resin of the hydride of composition (A), composition (B), composition (C) and additive etc. are used as required with mixing roller, kneader, Banbury mixer, extrude known melting mixing machine melting mixings such as mixing roll and obtain.
As the whipping agent that uses among the present invention, can use known whipping agents such as chemical foaming agent, pneumatogen.Chemical foaming agent and pneumatogen can share more than 2 kinds respectively.In addition, also chemical foaming agent and pneumatogen can be share.
As chemical foaming agent, can enumerate mineral compound and organic compound, they can be used in combination more than 2 kinds.As mineral compound, can enumerate supercarbonate, volatile salts etc. such as sodium bicarbonate.
As organic compound, can enumerate poly carboxylic acid, azo-compound, sulfonyl hydrazide compound, nitroso compound, p-toluene sulfonylsemicarbazide, isocyanate compound etc.As poly carboxylic acid, can enumerate citric acid, oxalic acid, fumaric acid, phthalic acid etc.As azo-compound, can enumerate Cellmic C 121 (ADCA) etc.As the sulfonyl hydrazide compound, can enumerate to methylene dicarbamate benzol sulfohydrazide, 2 4-toluene disulfonyl hydrazide, 4,4 '-oxo, two benzol sulfohydrazides etc.As nitroso compound, can enumerate dinitrosopentamethylene tetramine (DPT) etc.
As pneumatogen, can enumerate rare gas element; Volatile organic compounds such as butane, pentane etc.As pneumatogen, preferred rare gas element as rare gas element, can be enumerated carbonic acid gas, nitrogen, argon, neon, helium etc.Further preferably carbon dioxide, nitrogen.
About the consumption of whipping agent, with respect to composition for thermoplastic elastomer 100 weight parts, be preferably 0.1～20 weight part, further preferred 0.2～8 weight part.In addition, when chemical foaming agent and pneumatogen share, the consumption of chemical foaming agent was preferably 0.05～5 weight part with respect to composition for thermoplastic elastomer 100 weight parts.
Manufacture method of the present invention is as follows: utilize injection moulding machine composition for thermoplastic elastomer and whipping agent to be injected to the die cavity of die for injection molding, keep more than 4 seconds after injection is finished, then, the die cavity wall is moved to default position, thereby the volume of die cavity is enlarged, carry out the moulding of foam.
As the method that chemical foaming agent is provided to injection moulding machine; can adopt the method for the material that obtains to the injection moulding machine chemical foaming agent that has been provided in the composition for thermoplastic elastomer melting mixing in advance, adopt usually to provide by the masterbatch pellet that contains chemical foaming agent and mix the particulate method that obtains with the composition for thermoplastic elastomer particle to injection moulding machine.
As the method that pneumatogen is provided to injection moulding machine, can enumerate and inject in the nozzle of injection moulding machine pneumatogen or the method for the molten composition for thermoplastic elastomer in the machine barrel.From improving the viewpoint of foamed cell homogeneity, preferably pneumatogen is injected the method for the molten composition for thermoplastic elastomer in the machine barrel.
As injecting method, can enumerate single shaft injection, multiaxis injection, high-pressure injection method, low head injection method, use the method for plunger etc.
Before injection composition for thermoplastic elastomer and the whipping agent, making the pressure in the die cavity usually is below the normal atmosphere in the die cavity of mould.Making the pressure in the die cavity is the outward appearance that can improve foam below the normal atmosphere.
As making pressure in the die cavity is method below the normal atmosphere, can adopt known method, can enumerate (1) adopt can vacuum take-off mould, in advance to carrying out the method for vacuum take-off in the die cavity; (2) adopt the mould with air-releasing mechanism, the pressure that will produce to cavity injection molten composition for thermoplastic elastomer and whipping agent the time utilizes above-mentioned air-releasing mechanism to discharge outside die cavity, thereby makes method that pressure in the die cavity and normal atmosphere be equal to etc.
Can equate with the volume of die cavity to the composition for thermoplastic elastomer of cavity injection and the volume of whipping agent, also can be less than the volume of die cavity.When less than the volume of die cavity, can after injection, reduce the volume of die cavity immediately, composition for thermoplastic elastomer is equated with the volume of die cavity with the volume of whipping agent.The composition for thermoplastic elastomer of injection and the volume of whipping agent preferably equate with the volume of die cavity.
Temperature during injection (mold temperature) is preferably 180～250 ℃.Be preferably inject time in 10 seconds.In addition, the temperature of mould is preferably 5～80 ℃.
In the present invention, with composition for thermoplastic elastomer and foam in die cavity, inject finish after, keep then the die cavity wall being moved to default position more than 4 seconds, the volume of die cavity is enlarged.From injection finish to the time that mobile die cavity wall makes the die cavity volume begin to enlarge be time of lag, from the fine property that improves foamed cell and the viewpoint of homogeneity, be preferably more than 5 seconds.In addition, be preferably below 30 seconds from the fine property of raising foamed cell and the viewpoint of homogeneity this time of lag.
Enlarge die cavity volumetrical method as the die cavity wall that moves moulds, can adopt known method, the core of mould is retreated, and (the so-called core that moves back) enlarges the method for whole die cavity, comes the method for expansion section s and/or whole die cavity etc. with slide core.
Die cavity volume when the die cavity volume enlarges enlarges speed more than preferred 700%/second, more preferably more than 2000%/second.This die cavity volume enlarges speed and considers to be preferably below 25000%/second from the aspect of performance of device.In addition, the die cavity volume with end-of-fill the time is 100%, reduce the die cavity volume immediately after the injection when filling, and die cavity volume expansion speed is the volume of the die cavity after reducing.
After the die cavity wall moved to default position, the composition for thermoplastic elastomer in the die cavity is fully cooled off.After the cooling, take out foam from mould.
Manufacture method of the present invention can be with gas assisted molding, melt core moulding (metl core molding), insert moulding, move back forming methods such as core moulding, dual-color forming makes up and implements.
In addition, can be at foam sticky table leather material.As this skin material, can enumerate and spin cloth; Non-woven fabrics; Looped fabric; The film, the thin slice that form by thermoplastic resin or thermoplastic elastomer; Urethane film; Sheet rubber; Polyurethane foaming body; The co-polymer foamed body of ethene vinyl-acetic ester; Polypropylene expanded body; Foam polyethylene etc.
The expanded moldings that utilizes expanded moldings that the manufacture method of composition for thermoplastic elastomer foam of the present invention obtains and obtain with thermoplastic elastomer composition for foam injection molding is excellence aspect the homogeneity of the fine property of foamed cell and foamed cell.Therefore, the flexibility of foam is good, and also very excellent aspect lightweight, rigidity, shock-resistance.
Utilize expanded moldings that the manufacture method of composition for thermoplastic elastomer foam of the present invention obtains and be applicable to automotive interior material, household appliances, furniture etc. with the expanded moldings that thermoplastic elastomer composition for foam injection molding of the present invention obtains.
[embodiment]
Below, illustrate in greater detail the present invention with embodiment and comparative example.
[I] physical property measurement method
1, weight-average molecular weight
With gel permeation chromatography (GPC) method, mensuration is tried to achieve down in following condition (1)～(8).
(1) device: Water system Waters 150C
(2) separator column: eastern Cao TSK gel GMH6-HT
(3) measure temperature: 140 ℃
(4) carrier gas: orthodichlorobenzene
(5) flow: 1.0mL/ minute
(6) injection rate: 500 μ L
(7) detector: differential refractometer
(8) molecular weight standard material: polystyrene standard
2, melt flow rate (MFR) (MFR)
According to JIS K7210, measure down for 230 ℃ in load 21.18N, temperature.
3, melt tension
Use the smart mechanism of Japan to make made melt tension determinator (MT-501D3 type, barrel dliameter 9.55mm), sample 5g jet pipe from diameter 2mm, long 8mm under the condition of 190 ℃ of temperature and piston rotation perdurability 5.7mm/ minute is melt extruded, is to batch in 15.7m/ minute this sample of extruding with the coiling speed with roller, measures the tension force when batching.
4, the fine property and the homogeneity of foamed cell
Foam is cut off, observe its cross section, the fine property and the homogeneity of following evaluation foamed cell down at microscope (Scalar Co., Ltd. system, digital visual field microscope DG-3).
The fine property of foamed cell
Zero: unitary number average diameter is below the 500 μ m.
*: unitary number average diameter surpasses 500 μ m.
The homogeneity of foamed cell
Zero: unitary size and shape homogeneous.
△: find continuous unit, unitary size and shape heterogeneity.
*: find to have continuous unit, unitary size and shape heterogeneity.
5, oil-proofness
Under 230 ℃ temperature with sample (thermoplastic elastic composition) preheating 5 minutes, and pressurize and obtained fusing sample in 5 minutes, this sample was cooled under pressure 5 minutes to 30 ℃, pressing mold is the compressed tablet of 1mm to obtain thickness, the cylindrical drum of a hollow is set on this compressed tablet, and the cylindrical drum of this hollow is made of fluorine resin that (trade(brand)name: Teflon), its internal diameter is 38mm, external diameter is 42mm, and height is 15mm.The load of 500g is arranged on the cylindrical circular top of hollow, to apply constant load to compressed tablet.Constant load is applied to compressed tablet 24 hours under 80 ℃ temperature, compressed tablet is cooled to room temperature (25 ℃), following then the evaluation.
Zero: do not have and observe expansion;
*: do not observe expansion.
[II] raw material
(1) hydride of vinylbenzene-conjugated diolefine-styrene block copolymer
A-1: the hydride of styrene-butadiene-styrene block copolymer
(weight-average molecular weight 320,000, styrene units content 33 weight %, hydrogenation ratio 100%)
A-2: the hydride of styrene isoprene styrene block copolymer (SIS)
(weight-average molecular weight 120,000 9 thousand, styrene units content 13 weight %, hydrogenation ratio 100%)
A-3: the hydride of styrene isoprene styrene block copolymer (SIS)
(weight-average molecular weight 120,000 6 thousand, styrene units content 18 weight %, hydrogenation ratio 99%)
A-4: the hydride of styrene-butadiene-styrene block copolymer
(weight-average molecular weight 100,000 1 thousand, styrene units content 30 weight %, hydrogenation ratio 99%)
(2) propylene resin
B-1: the system NOBRENEHR100EG (trade(brand)name) of Sumitomo Chemical Co
(MFR=19g/10 minute, melt tension=0.33cN)
(3) mineral oil
C-1: the system Diana Process Oil PW-100 (trade(brand)name) of Idemitsu Kosen Co., Ltd.
(yield point=-15 ℃)
[embodiment 1]
(preparation of composition for thermoplastic elastomer)
Hydride 100 weight parts with vinylbenzene-conjugated diolefine-styrene block copolymer of A-1, with respect to the A-1100 weight part is the B-1 propylene resin of 70 weight parts, with respect to the A-1100 weight part is the C-1 mineral oil of 180 weight parts, with respect to A-1, total 100 weight parts of B-1 and C-1 are the erucicamide (Japan refines and makes NEUTRON S (trade(brand)name)) of 0.05 weight part, 0.05 the antioxidant of the calcium stearate of weight part and 0.15 weight part (the system IRGANOX 1010 (trade(brand)name) of Ciba Co., Ltd. 0.1 weight part, GE Specialty Chemicals corporate system Ultranox 626 (trade(brand)names) 0.05 weight part) melting mixing in Banbury mixer, be molded into particulate state then, obtain the particle of composition for thermoplastic elastomer.
(manufacturing of foam injection molding body)
Injection moulding machine adopts ENGEL corporate system ES2550/400HL-Mu Cell (clamp force 400t), mould adopts moulding product portion to be of a size of the mould of the box shape (pouring gate structure: valve gate, formed body middle body) of 290mm * 370mm, high 45mm, thick 1.5mm, implements foam injection molding.In particle 100 weight parts of composition for thermoplastic elastomer, mix organic acid salt whipping agent master batch (masterbatch) (three associations change into system MB3083 (trade(brand)name)) 1 weight part as chemical foaming agent, the admixture that obtains is offered injection moulding machine, make its fusion in the machine barrel of injection moulding machine, offer in this machine barrel (with respect to particulate molten resin 100 weight parts of composition for thermoplastic elastomer, carbonic acid gas injection rate: 0.6 weight part) after carbonic acid gas is forced into 6MPa.Then, under 210 ℃ of mold temperatures, 20 ℃ of die temperatures, the condition of 2.6 seconds inject time,,, fill the back and keep 8 seconds (8 seconds time of lag) in the die cavity completely filled of mould with composition for thermoplastic elastomer and whipping agent injection.Then, with 7000%/the die cavity volume expansion speed of second (the die cavity volume when finishing with injection is 100%) makes the die cavity wall retreat 3mm, make die cavity volume gain and foam thus, cool off then, solidify, obtain expanded moldings.Evaluation result is as shown in table 1.Evaluation result to compressed tablet is as shown in table 2.
[embodiment 2]
The hydride that replaces vinylbenzene-conjugated diolefine-styrene block copolymer of A-1 with the hydride of vinylbenzene-conjugated diolefine-styrene block copolymer of the A-2 of 100 weight parts, the propylene resin of B-1 is 56 weight parts with respect to the A-2100 weight part, the mineral oil of C-1 is 67 weight parts with respect to the A-2100 weight part, in addition all operations similarly to Example 1.Evaluation result as shown in Table 1 and Table 2.
[embodiment 3]
The hydride that replaces vinylbenzene-conjugated diolefine-styrene block copolymer of A-1 with the hydride of vinylbenzene-conjugated diolefine-styrene block copolymer of the A-3 of 100 weight parts, the propylene resin of B-1 is 56 weight parts with respect to the A-3100 weight part, the mineral oil of C-1 is 67 weight parts with respect to the A-3100 weight part, in addition all operations similarly to Example 1.Evaluation result as shown in Table 1 and Table 2.
[embodiment 4]
The hydride that replaces vinylbenzene-conjugated diolefine-styrene block copolymer of A-1 with the hydride of vinylbenzene-conjugated diolefine-styrene block copolymer of the A-4 of 100 weight parts, the propylene resin of B-1 is 50 weight parts with respect to the A-4100 weight part, the mineral oil of C-1 is 100 weight parts with respect to the A-4100 weight part, in addition all operations similarly to Example 1.Evaluation result as shown in Table 1 and Table 2.
[comparative example 1]
Except will changing into time of lag 2 seconds, all the other are operation similarly to Example 1 all.Evaluation result is as shown in table 3.
[comparative example 2]
Except will changing into time of lag 2 seconds, all the other are operation similarly to Example 2 all.Evaluation result is as shown in table 3.
[comparative example 3]
Except will changing into time of lag 2 seconds, all the other are operation similarly to Example 3 all.Evaluation result is as shown in table 3.
[comparative example 4]
Except will changing into time of lag 2 seconds, all the other are operation similarly to Example 4 all.Evaluation result is as shown in table 3.
[comparative example 5]
Except will change 2 seconds time of lag into, die cavity volume expansion speed changes 70% into/second, all the other are operation similarly to Example 1 all.Evaluation result is as shown in table 3.
[table 1]
[table 2]
[table 3]
Claims (12)
1. the manufacture method of a composition for thermoplastic elastomer foam is characterized in that, comprises following operation successively:
Utilize injection moulding machine following composition for thermoplastic elastomer and whipping agent to be injected to the operation of the die cavity of die for injection molding, described composition for thermoplastic elastomer contains following compositions (A), composition (B) and composition (C), and with respect to composition (A) 100 weight parts, the content of composition (B) is that the content of 5～150 weight parts, composition (C) is 5～300 weight parts;
Injection finishes the operation of back maintenance more than 4 seconds; And
Enlarge die cavity volumetrical operation by the die cavity wall being moved to default position, wherein,
(A): the hydride of segmented copolymer, the hydride of this segmented copolymer contain block that is made of the monomeric unit based on aromatic ethenyl compound and the block that is made of the monomeric unit based on conjugated diene compound,
(B): propylene resin,
(C): mineral oil.
2. the manufacture method of composition for thermoplastic elastomer foam according to claim 1, wherein, described expansion die cavity volumetrical operation enlarges the volume of die cavity with 700%/second above die cavity volume expansion speed.
3. the manufacture method of composition for thermoplastic elastomer foam according to claim 1, wherein, the total amount 100 weight % of block that constitutes with respect to the monomeric unit by based on aromatic ethenyl compound of described (A) composition and the block that is made of the monomeric unit based on conjugated diene compound, the content of the block that is made of the monomeric unit based on aromatic ethenyl compound are more than the 5 weight % below the 50 weight %.
4. the manufacture method of composition for thermoplastic elastomer foam according to claim 1, wherein, the hydrogenation ratio of composition (A) is more than 50%.
5. the manufacture method of composition for thermoplastic elastomer foam according to claim 1, wherein, the weight-average molecular weight of composition (A) is more than 50,000 below 500,000.
6. the manufacture method of composition for thermoplastic elastomer foam according to claim 1, wherein, the melt flow rate (MFR) of composition (B) (230 ℃ of load 21.18N, temperature) is more than 0.1g/10 minute below 300g/10 minute.
7. the manufacture method of composition for thermoplastic elastomer foam according to claim 1, wherein, the molecular-weight average of composition (C) is more than 300 below 1500, yield point is below 0 ℃.
8. thermoplastic elastomer composition for foam injection molding, it contains following compositions (A '), composition (B ') and composition (C), and with respect to composition (A ') 100 weight parts, and the content of composition (B ') is 5～150 weight parts, the content of composition (C) is 5～300 weight parts
(A '): contain the block that constitutes by monomeric unit and the hydride of the segmented copolymer of the block that constitutes by monomeric unit, and weight-average molecular weight is more than 200,000 based on conjugated diene compound based on aromatic ethenyl compound,
(B '): melt flow rate (MFR) is that 2～300g/10 minute, melt tension are the above propylene resin of 3cN,
(C): mineral oil.
9. composition for thermoplastic elastomer according to claim 8, it also contains following compositions (B "), and with respect to composition (A ') 100 weight parts, and the content of described composition (B ') and following compositions (B ") adds up to 5～150 weight parts,
(B "): the propylene resin of not enough 2g/10 minute of melt flow rate (MFR) or the not enough 3cN of melt tension.
10. foam, it is by obtaining the described composition for thermoplastic elastomer foam injection molding of claim 8.
11. the manufacture method of a foam is characterized in that, comprises the operation of preparing the described composition for thermoplastic elastomer of claim 8 and with the operation of described composition for thermoplastic elastomer foam injection molding.
12. the described composition for thermoplastic elastomer of claim 8 is as the application of foam injection molding with composition.
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| JP2007320560 | 2007-12-12 | ||
| JP2007320559 | 2007-12-12 | ||
| JP2007320559A JP2009143996A (en) | 2007-12-12 | 2007-12-12 | Thermoplastic elastomer composition for foam injection molding, foam body, and method for producing it |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190851A (en) * | 2010-03-05 | 2011-09-21 | 住友化学株式会社 | Thermoplastic elastomer composition, foam body and laminated body |
| CN115403891A (en) * | 2021-05-28 | 2022-11-29 | 李长荣化学工业股份有限公司 | Crosslinkable foam composition, foam obtained using same, foaming composition, and use thereof |
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2007
- 2007-12-12 JP JP2007320559A patent/JP2009143996A/en active Pending
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2008
- 2008-12-12 CN CNA2008101855209A patent/CN101469077A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190851A (en) * | 2010-03-05 | 2011-09-21 | 住友化学株式会社 | Thermoplastic elastomer composition, foam body and laminated body |
| CN115403891A (en) * | 2021-05-28 | 2022-11-29 | 李长荣化学工业股份有限公司 | Crosslinkable foam composition, foam obtained using same, foaming composition, and use thereof |
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