WO1988005799A1 - Sheet-like molding material and laminate for molding containing the material as one layer - Google Patents
Sheet-like molding material and laminate for molding containing the material as one layer Download PDFInfo
- Publication number
- WO1988005799A1 WO1988005799A1 PCT/JP1988/000120 JP8800120W WO8805799A1 WO 1988005799 A1 WO1988005799 A1 WO 1988005799A1 JP 8800120 W JP8800120 W JP 8800120W WO 8805799 A1 WO8805799 A1 WO 8805799A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- sheet
- propylene polymer
- parts
- molding
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000000465 moulding Methods 0.000 title claims abstract description 24
- 239000012778 molding material Substances 0.000 title claims abstract description 22
- 229920001155 polypropylene Polymers 0.000 claims abstract description 42
- 239000000945 filler Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 21
- 238000004898 kneading Methods 0.000 claims description 14
- 239000006260 foam Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 239000012792 core layer Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 2
- 239000002649 leather substitute Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920005992 thermoplastic resin Polymers 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 claims 1
- 235000021189 garnishes Nutrition 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- -1 1-hexisene Chemical compound 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 239000011162 core material Substances 0.000 description 8
- 238000003856 thermoforming Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 238000007666 vacuum forming Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960003624 creatine Drugs 0.000 description 2
- 239000006046 creatine Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- OPBFFNZNNJKRCS-UHFFFAOYSA-N 2-hydroxy-4,4-dimethylpentanoic acid Chemical compound CC(C)(C)CC(O)C(O)=O OPBFFNZNNJKRCS-UHFFFAOYSA-N 0.000 description 1
- DRWYRROCDFQZQF-UHFFFAOYSA-N 2-methylpenta-1,4-diene Chemical compound CC(=C)CC=C DRWYRROCDFQZQF-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- NPOJQCVWMSKXDN-UHFFFAOYSA-N Dacthal Chemical compound COC(=O)C1=C(Cl)C(Cl)=C(C(=O)OC)C(Cl)=C1Cl NPOJQCVWMSKXDN-UHFFFAOYSA-N 0.000 description 1
- 235000010650 Hyssopus officinalis Nutrition 0.000 description 1
- 240000001812 Hyssopus officinalis Species 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 206010030113 Oedema Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XRLSGYQIHTVOMC-UHFFFAOYSA-N aminomethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCN XRLSGYQIHTVOMC-UHFFFAOYSA-N 0.000 description 1
- QHOTVLWYQNKORC-UHFFFAOYSA-N aminomethyl prop-2-enoate Chemical compound NCOC(=O)C=C QHOTVLWYQNKORC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000000378 dietary effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000000400 lauroyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 210000002445 nipple Anatomy 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C51/00—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor
- B29C51/002—Shaping by thermoforming, i.e. shaping sheets or sheet like preforms after heating, e.g. shaping sheets in matched moulds or by deep-drawing; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
Definitions
- the present invention relates to a sheet-like molding material composed of a propylene polymer at least partially crosslinked, and a sheet-like molding laminate using the molding material as a core layer.
- plastic materials for manufacturing large molded products such as doors for vehicles, instrument panels, molded ceilings, and trunk materials.
- a sheet manufactured from a composition in which a filler is blended or a laminate using the sheet as a core is used.
- thermoforming such as vacuum forming or pressure forming to form the material as described above.
- the drawback is that when the material is formed into a product, concentrated stress is generated depending on the shape of the product, for example, at a corner, the material is specially stretched, resulting in a thinner wall, which tends to result in uneven thickness of the product. is there.
- the giant aspect of the present invention is that when a large molded product is manufactured from a sheet-like material by thermoforming such as vacuum forming or pressure forming, only the stress concentration portion is not thinned, and the thickness of the entire molded product is reduced.
- An object of the present invention is to provide a sheet-shaped plastic material for thermoforming which enables the production of a molded article having a substantially uniform surface.
- a material is provided in the case of a sheet-like molding composed of a composition of a ⁇ -pyrene polymer (A) and a filler which are at least partially bridged.
- a sheet-shaped molding laminate comprising a skin material layer having the sheet-shaped molding material as a core material and a core material layer.
- FIG. 1 is a stress-elongation curve diagram showing sheet-like tensile properties obtained in Example 1 and Comparative Example described later.
- the sheet-shaped molding material of the invention is a propylene polymer at least partially cross-linked (hereinafter sometimes abbreviated as “Kachibana propylene polymer (A)”) and a filler.
- a composition comprising:
- the crosslinked propylene polymer (A) is
- the uncrosslinked propylene polymer (a) can be obtained by treating the uncrosslinked propylene polymer in the presence of a radical generator and a crosslinked vinegar auxiliaries. There are a method of melting and kneading the ren polymerization (a) and a method of irradiating the unpolymerized propylene polymer (a) with radiation. The former method is preferred.
- Examples of the uncrosslinked propylene polymer (a) include a crystalline propylene homopolymer and a crystalline random copolymer of propylene and another ⁇ -olefin. And crystalline block copolymerization of provylene with other ⁇ -olefins.
- ⁇ -olefins having 2 to 20 carbon atoms other than propylene are preferable, and examples thereof include ethylene, 1-butene, and 1-olefin.
- ethylene 1-butene
- 1-olefin One pentene, 4-methylene, 1-pentene, 1-hexisene, 1-decene and the like can be exemplified as preferred, and especially ethylene is preferred.
- the total amount of such ⁇ -olefin is usually 10 mol% or less, preferably 5 mol% or less.
- the crystalline propylene block copolymer is usually subjected to a polymerization operation such that it comprises the following ( ⁇ and (ii), (i) and ( ⁇ i) or (i), ( ⁇ i) and (iii). Was carried out and manufactured.
- a rubber-like propylenno ⁇ -olefin copolymer component obtained by copolymerizing a small amount of cc-olefin.
- the content of ⁇ -olebuin other than propylene in the block copolymer is preferably from 10 to 30 mol%.
- a particularly preferred block copolymer is a propylene / ethylene block copolymer having a polyethylene content of 100,000 to 30 mol%.
- the melt flow rate (ASTM D1238 condition L) of such a pre-D-pyrene polymer (a) is preferably 0.1 to 10 g Z 10 minutes. is there.
- unpigmented pi-pyrene polymer ( a ) is preferably kneaded by melt-kneading in the presence of a radical citrus agent (c) and a crosslinking aid (d). be able to.
- the radical generator (c) that can be used is preferably a radical generator such as an organic peroxide, an organic hydroperoxide or an analog thereof, for example, dicumyl perogide, benzimimeperi. Leogicide, Lauroyl peroxyside, t-butyl perebenzoate, g-butyl peroxyside, cumene hydroperoxide, 2,5—dimethyl-2,5—di (t-butylperoxygide) C) 1 hegisan (per hege 2,5 B), 2,5-dimethyl-2,5—di (t-butyl perogishi) one 3—hegi Ginsin 2, 5B), t-butyl hydroperoxide, isop ⁇ -pillper carbonate, azobisisobutyrate, and the like.
- the amount of the radical generator is usually 0.01 to 0.5 part by weight, preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the propylene polymer. It is.
- crosslinking auxiliary for example, polymerizable monomers having one or more ethylenic unsaturated bonds.
- Acid methacrylic acid, maleic anhydride, vinylpyridin, aminomethyl acrylate, aminomethyl methacrylate, dimethyl methacrylate Luminoethyl, t-butylyl methacrylate, N-vinylpyrrolidone, methacrylamide, vinyltris (/ 3 G) Silane, vinyl trimethoxysilane, vinyl trichlorsilane, butylene glycol, metal create, butylene glycol, Ethylene glycol recharge rate, ethylene glycol Recall, dietary recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, recall, Polyethylene Grace Recall, Trimethylol Prono, Trimetary Recreate, Trimethylolup D Pantry
- a polymerizable monomer having two or more ethylenically unsaturated bonds is preferred, and divinylbenzene is particularly preferred.
- the mixing amount of the Tachibana auxiliaries is usually 0.5 to 2 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the uncrosslinked propylene polymer (a).
- melt-kneading is performed at a melting temperature of the uncrosslinked propylene polymer (a) or higher. It is preferably carried out at a temperature not lower than the decomposition temperature of the radical generator (c), and it is generally recommended that the melt-mixing be carried out near the degree of the humid so that the radigal ripener has a half-life of 1 minute. However, of course, higher temperatures can be used. It is generally performed at 180 to 250, preferably at a degree of 200 to 230 degrees.
- This operation can be carried out in batches 7 with a kneading machine such as a Banbury mixer, or it can be carried out continuously using an extruder, preferably a twin-roll extruder.
- a kneading machine such as a Banbury mixer
- an extruder preferably a twin-roll extruder.
- the kneading time is usually about 1 to 10 minutes. When kneading with an extruder, this time is the residence time in the extruder.
- Kachibana propylene polymer (A) is mixed with an inorganic filler, once pelletized, and then formed into a sheet molding machine. Can be formed into a sheet.
- the inorganic filler can be coexistent during the above-mentioned melt-kneading operation, and this is preferred.
- Fillers are added to improve the dimensional stability and rigidity of the molded product.
- Inorganic fillers such as talc, calcium carbonate, and my strength, and organic cells such as thick flour, paper, and pulp ⁇ - Examples of such fillers can be given as examples.
- the amount of the filler is usually from 10 to 50 parts by weight, based on 100 parts by weight of the unpolymerized propylene polymer (a) or the crosslinked propylene polymer (A). It is preferably 20 to 40 parts by weight.
- ethylene-propylene rubber ethylene-propylene rubber
- polybutene-1 polyethylene and the like
- ethylene-propylene rubber ethylene-propylene rubber
- polybutene-1 polyethylene and the like
- ethylene-propylene rubber ethylene-propylene rubber
- polybutene-1 polyethylene and the like
- ethylene-propylene rubber ethylene-propylene rubber
- polybutene-1 polyethylene and the like
- the extent of the cross-linked propylene polymer (A) can be known as the amount of the insoluble part of boiling garlicene.
- Amount of edema insoluble in xylene (Weight is measured by the following method: # 100 (measured with stainless steel screen made of mesh) (Zg)
- # 100 measured with stainless steel screen made of mesh
- Zg After about 0.3 g of the accurately weighed cross-linked propylene polymer (Y g) has been placed in the tank, about 200 m Put into a tray extractor, perform oil removal under boiling water for 3 hours, then remove ⁇ , dry under reduced pressure (50 mmHg) at 100 ° C for 1 hour,
- the amount (X g) is measured and determined by the following equation.
- X is the weight of the hermitage after drying under reduced pressure
- Y is the weight of the sample placed in the hermitage before extraction
- Z is the weight of itself.
- the thus-measured amount of the gisylene-insoluble content of the crosslinked propylene polymer (A) is usually at least 5% by weight, preferably from 10 to 60% by weight. It is suitable.
- a method of molding the pellet-like composition with a sheet molding machine but the most preferable method is used.
- a new technique is to provide a sheet die at the exit of the extruder used for melt-kneading and to perform direct sheet molding. Naturally, in this case, the filler is present at the time of melt-kneading.
- the unpolymerized propylene polymer (a) is in powder form for the purpose of uniformly mixing the propylene polymer and the filler. It is better to use
- the thickness of the sheet is usually between 0.5 and 5 ⁇ , a force which is chosen according to the object to be produced by thermoforming.
- a sheet-like material is manufactured by one-stage molding, and then the sheet-like material is subjected to vacuum forming, pressure forming, etc. under heating to form a molded product of a desired shape in the second stage of forming. Can be manufactured.
- Such a sheet-shaped molding material of the invention has a feature of high strength at a high temperature.
- the sheet-shaped molding material has a concentrated stress.
- the tendency to reduce the wall thickness is reduced at a portion where the angle is reduced, for example, at a corner where the angle of the deep drawing portion is small, and it is possible to manufacture a molded product having a substantially uniform wall thickness as a whole.
- a molding laminate comprising a sheet in which the above-mentioned sheet-like molding material is used as a core material layer and combined with a skin material is obtained.
- thermoplastic elastomer As the material of the skin material layer, thermoplastic elastomer, fabric, polyvinyl chloride (PVC), non-woven fabric, synthetic leather, and the like can be used. As these materials, those known per se can be used.
- thermoplastic elastomer polyethylene butyl rubber is used.
- Photo-copolymer, ethylene-propylene-non-conjugated gem, peroxide, Tachibana-type olefin-based copolymer rubber and peroxyside non-tachibana-type hydrocarbon-based rubber-like substance For example, a composition obtained by dynamically heat-treating a composition as a main component in the presence of an organic peroxyside can be used.
- This skin material layer can be mixed with additives known per se, for example, a heat stabilizer, an antioxidant, a flame retardant, a colorant, etc., as long as the properties of the laminate are not impaired. .
- Such laminate but it may also be provided click Tsu sheet 3 down material layer made of Netsuka plastic resin foam between the core material layer and the skin layer o
- Thermoplastic caustic foams include polyolefin, polypropylene, polyolefin, polystyrene, polyurethane, and polyamide.
- a foam produced by a method known per se from a thermoplastic resin such as an acrylic tributary-butadiene-styrene-based street fat can be used. It is preferable that the foam ratio of the foam is 10 to 30 times.
- each layer of the laminate is 0.5 to 5 mm for the core material layer, 0.1 to 1.5 mm for the skin material layer, and 2 to 5 mm for the cushion material layer. It is preferably mm.
- This laminate is formed by laminating a sheet-like material composed of the above-described layers and heat-sealing the laminate with or without providing an adhesive between the respective layers. Can be manufactured. Further, this laminate can be produced by a process known per se, which comprises simultaneously extruding a skin layer and a core material layer using a two-layer extruder.
- the sheet molding material and the sheet molding laminate of the present invention have high strength at a high temperature, a molded product having a substantially uniform wall thickness can be manufactured as a whole.
- the molding material and the laminate of the present invention are particularly suitable for producing large-sized molded products.
- doors for automobiles, instrument panels, and the like It can be advantageously used for manufacturing vehicle interior materials such as nails, molded ceilings, dashboards, and trunk rooms, or core materials thereof.
- the mixture was extruded with an extruder of 11 ⁇ ⁇ (extruder operating conditions: screw rotation speed of 40 rpm, throughput of 150 kg / hr) and a die width of 150 mm.
- a sheet having a thickness of 2. Omm was produced at an extruder temperature of 220 ° C.
- the estimated residence time in the extruder is about 3 minutes.
- the xylene insoluble content of this sheet was about 40% by weight. 170 of this sheet.
- Fig. 11 shows the tensile properties of C.
- the above sheets with a size of 130 mm x 800 mm are heated for 2 to 3 minutes using a far-infrared heater to bring the sheet temperature to about 170 ° G, and the car door
- the automobile door was manufactured by air pressure molding using a single die. At this time, the heat-softened sheet did not drop down at all.
- the minimum thickness of this door was as shown in Table 1 and corresponded to 3 .. Oma of the raw material thickness in the following comparative example.
- Example 1 Each sheet manufactured in Example 1 was coated with a ripple elastomer (Mitsui Petrochemicals Co., Ltd., trade name: Mirastoma 1) with a thickness of 0.8 mm using Nipple. And a 3.0 mm thick sheet of polypropylene foam (trade name: PPAM 1503, manufactured by Toray Industries, Inc.), a thermoplastic elastomer, polypropylene foam, The propylene polymer composition was laminated in this order, and the layers were heat-sealed to produce a laminate of a propylene polymer molding material.
- a ripple elastomer Mitsubishi Chemicals Co., Ltd., trade name: Mirastoma 1
- PPAM 1503 manufactured by Toray Industries, Inc.
- the propylene polymer composition was laminated in this order, and the layers were heat-sealed to produce a laminate of a propylene polymer molding material.
- Each of the above stacks with a size of 1300 mm X 800 mm is heated for 2 to 3 minutes using a far-infrared heater to reduce the temperature of the stack to about 170, and
- the automobile door was manufactured by air pressure molding using a metal mold. The appearance was good, and the thinnest part of the handle of the door was thick and flexible enough to use in use.
- composition obtained by uniformly mixing 70 parts by weight of the propylene powder of Example 1 and 30 parts by weight of talc with a helical mixer was subjected to the same sheet molding conditions as in Example 1.
- the gicillen-insoluble content of these sheets was 0 and 170.
- the tensile properties in C were as shown in Fig. 11.
- An automobile door was formed by the same thermoforming as in Example 1, and the minimum thickness was as shown in Table 1.
- Example 1 the amount of the polypropylene powder used was 80 parts by weight, the amount of dicumylperogide as a radical keratotic agent was 0.05 parts by weight, and the amount of divinylbenzene used was 0. The procedure was the same except that the amount was 7 parts by weight.
- the minimum thickness of the door was as good as 0.7 iDffl.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019880701250A KR890700635A (ko) | 1987-02-09 | 1988-10-08 | 시트상 성형재료와 그 성형재료릍 1층으로 포함하는 적층판 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2639887 | 1987-02-09 | ||
JP62/26398 | 1987-02-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1988005799A1 true WO1988005799A1 (en) | 1988-08-11 |
Family
ID=12192449
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1988/000120 WO1988005799A1 (en) | 1987-02-09 | 1988-02-09 | Sheet-like molding material and laminate for molding containing the material as one layer |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0301103A4 (ja) |
KR (1) | KR890700635A (ja) |
CN (1) | CN88101343A (ja) |
WO (1) | WO1988005799A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009529439A (ja) * | 2006-03-10 | 2009-08-20 | ベネツケ−カリコ・アーゲー | 熱可塑性フィルムの製造方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2113280B1 (es) * | 1994-11-10 | 1999-04-01 | Repsol Quimica Sa | Modificaciones polimericas para aplicaciones de termoconformado. |
CN104369492B (zh) * | 2013-08-16 | 2016-11-16 | 神华集团有限责任公司 | 一种多层板材及其制备方法和应用 |
CN104861300B (zh) * | 2015-05-27 | 2016-03-02 | 惠州市峄董塑胶科技有限公司 | 一种改性板材及其制备方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS55177422U (ja) * | 1979-06-05 | 1980-12-19 | ||
JPS568256A (en) * | 1979-07-03 | 1981-01-28 | Mitsubishi Petrochemical Co | Surface protective film |
JPS56108524U (ja) * | 1980-01-21 | 1981-08-22 | ||
JPS56118434A (en) * | 1980-02-22 | 1981-09-17 | Nippon Petrochem Co Ltd | Preparation of polyolefin resin composition |
JPS56118433A (en) * | 1980-02-22 | 1981-09-17 | Nippon Petrochem Co Ltd | Production of polyolefin resin composition |
JPS61215044A (ja) * | 1985-03-20 | 1986-09-24 | Sekisui Plastics Co Ltd | 架橋された表皮層を有する積層体および容器の製造方法 |
JPH0422865B2 (ja) * | 1982-08-20 | 1992-04-20 | Morgan Refractories Ltd | |
JPH0649045A (ja) * | 1992-03-31 | 1994-02-22 | Bayer Ag | 3−アミノ置換イソキサゾール誘導体の内部寄生虫防除用の使用、新規な3−アミノ置換イソキサゾール誘導体、およびその製造方法 |
JPH0649046A (ja) * | 1992-05-06 | 1994-02-22 | E R Squibb & Sons Inc | フェニルスルホンアミドエンドセリンアンタゴニスト |
JPH0647043A (ja) * | 1992-08-03 | 1994-02-22 | Olympus Optical Co Ltd | 超音波診断装置 |
JPH0655012A (ja) * | 1992-08-10 | 1994-03-01 | Yamamoto Kogyo Kk | 回転ドラム式脱水装置 |
JPH0655014A (ja) * | 1992-08-04 | 1994-03-01 | Aisin Aw Co Ltd | ストレーナの装着構造 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4087485A (en) * | 1976-08-16 | 1978-05-02 | Exxon Research & Engineering Co. | Polypropylene blends having high impact strength and improved optical properties |
JPS5825340A (ja) * | 1981-08-07 | 1983-02-15 | Mitsui Petrochem Ind Ltd | 部分架橋ゴム−樹脂組成物の製造法 |
DE3133183A1 (de) * | 1981-08-21 | 1983-03-10 | Luperox GmbH, 8870 Günzburg | Verfahren zur vernetzung und gegebenenfalls verschaeumung von polypropylen |
US4489034A (en) * | 1982-08-25 | 1984-12-18 | Shell Oil Company | Thermoforming process using modified polymer blend |
JPS62288645A (ja) * | 1986-06-06 | 1987-12-15 | Japan Synthetic Rubber Co Ltd | 熱可塑性樹脂組成物 |
-
1988
- 1988-02-09 WO PCT/JP1988/000120 patent/WO1988005799A1/ja not_active Application Discontinuation
- 1988-02-09 EP EP19880901468 patent/EP0301103A4/en not_active Ceased
- 1988-02-09 CN CN198888101343A patent/CN88101343A/zh active Pending
- 1988-10-08 KR KR1019880701250A patent/KR890700635A/ko not_active Abandoned
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55177422U (ja) * | 1979-06-05 | 1980-12-19 | ||
JPS568256A (en) * | 1979-07-03 | 1981-01-28 | Mitsubishi Petrochemical Co | Surface protective film |
JPS56108524U (ja) * | 1980-01-21 | 1981-08-22 | ||
JPS56118434A (en) * | 1980-02-22 | 1981-09-17 | Nippon Petrochem Co Ltd | Preparation of polyolefin resin composition |
JPS56118433A (en) * | 1980-02-22 | 1981-09-17 | Nippon Petrochem Co Ltd | Production of polyolefin resin composition |
JPH0422865B2 (ja) * | 1982-08-20 | 1992-04-20 | Morgan Refractories Ltd | |
JPS61215044A (ja) * | 1985-03-20 | 1986-09-24 | Sekisui Plastics Co Ltd | 架橋された表皮層を有する積層体および容器の製造方法 |
JPH0649045A (ja) * | 1992-03-31 | 1994-02-22 | Bayer Ag | 3−アミノ置換イソキサゾール誘導体の内部寄生虫防除用の使用、新規な3−アミノ置換イソキサゾール誘導体、およびその製造方法 |
JPH0649046A (ja) * | 1992-05-06 | 1994-02-22 | E R Squibb & Sons Inc | フェニルスルホンアミドエンドセリンアンタゴニスト |
JPH0647043A (ja) * | 1992-08-03 | 1994-02-22 | Olympus Optical Co Ltd | 超音波診断装置 |
JPH0655014A (ja) * | 1992-08-04 | 1994-03-01 | Aisin Aw Co Ltd | ストレーナの装着構造 |
JPH0655012A (ja) * | 1992-08-10 | 1994-03-01 | Yamamoto Kogyo Kk | 回転ドラム式脱水装置 |
Non-Patent Citations (1)
Title |
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See also references of EP0301103A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009529439A (ja) * | 2006-03-10 | 2009-08-20 | ベネツケ−カリコ・アーゲー | 熱可塑性フィルムの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR890700635A (ko) | 1989-04-26 |
EP0301103A4 (en) | 1989-07-20 |
CN88101343A (zh) | 1988-09-14 |
EP0301103A1 (en) | 1989-02-01 |
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