CN1860026A - Biodegradable layered sheet - Google Patents
Biodegradable layered sheet Download PDFInfo
- Publication number
- CN1860026A CN1860026A CN 200480028109 CN200480028109A CN1860026A CN 1860026 A CN1860026 A CN 1860026A CN 200480028109 CN200480028109 CN 200480028109 CN 200480028109 A CN200480028109 A CN 200480028109A CN 1860026 A CN1860026 A CN 1860026A
- Authority
- CN
- China
- Prior art keywords
- layer
- polylactic resin
- resin
- laminated plate
- quality
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 claims abstract description 184
- 239000011347 resin Substances 0.000 claims abstract description 184
- 229930182843 D-Lactic acid Natural products 0.000 claims abstract description 38
- 229940022769 d- lactic acid Drugs 0.000 claims abstract description 38
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims abstract description 37
- 238000002425 crystallisation Methods 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 32
- 230000009477 glass transition Effects 0.000 claims abstract description 26
- 229920002799 BoPET Polymers 0.000 claims description 40
- 239000005041 Mylar™ Substances 0.000 claims description 40
- 238000000465 moulding Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 45
- 239000004626 polylactic acid Substances 0.000 abstract description 40
- 230000037303 wrinkles Effects 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 229920001225 polyester resin Polymers 0.000 abstract 2
- 239000004645 polyester resin Substances 0.000 abstract 2
- 239000011342 resin composition Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 87
- 229920003232 aliphatic polyester Polymers 0.000 description 74
- 229910052623 talc Inorganic materials 0.000 description 29
- 239000011256 inorganic filler Substances 0.000 description 28
- 229910003475 inorganic filler Inorganic materials 0.000 description 28
- 235000012222 talc Nutrition 0.000 description 28
- 239000000454 talc Substances 0.000 description 28
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 23
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000463 material Substances 0.000 description 19
- 229960000448 lactic acid Drugs 0.000 description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 239000004310 lactic acid Substances 0.000 description 13
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 13
- 125000001931 aliphatic group Chemical group 0.000 description 12
- 238000007599 discharging Methods 0.000 description 12
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 150000005690 diesters Chemical class 0.000 description 10
- 235000014655 lactic acid Nutrition 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 8
- 229960005137 succinic acid Drugs 0.000 description 8
- NGEWQZIDQIYUNV-UHFFFAOYSA-N 2-hydroxy-3-methylbutyric acid Chemical compound CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 description 6
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 6
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 238000007666 vacuum forming Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 4
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000001851 biosynthetic effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- UVCJGUGAGLDPAA-UHFFFAOYSA-N ensulizole Chemical compound N1C2=CC(S(=O)(=O)O)=CC=C2N=C1C1=CC=CC=C1 UVCJGUGAGLDPAA-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 description 2
- NDPLAKGOSZHTPH-UHFFFAOYSA-N 3-hydroxyoctanoic acid Chemical compound CCCCCC(O)CC(O)=O NDPLAKGOSZHTPH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000252867 Cupriavidus metallidurans Species 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- ZSLZBFCDCINBPY-ZSJPKINUSA-N acetyl-CoA Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCSC(=O)C)O[C@H]1N1C2=NC=NC(N)=C2N=C1 ZSLZBFCDCINBPY-ZSJPKINUSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 229940100228 acetyl coenzyme a Drugs 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000013527 bean curd Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MIPAOONFKSZNDF-UHFFFAOYSA-N butanedioic acid carbonic acid Chemical compound C(CCC(=O)O)(=O)O.C(O)(O)=O.C(CCC(=O)O)(=O)O MIPAOONFKSZNDF-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 235000019503 curry powder Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000021185 dessert Nutrition 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920005839 ecoflex® Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019688 fish Nutrition 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000008446 instant noodles Nutrition 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000118 poly(D-lactic acid) Polymers 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
It is an object to provide a biodegradable laminated sheet which is high in heat resistance, impact resistance and strength when subjected to loads at high temperature, does not develop wrinkles called 'bridges', which can be easily deep-drawn or formed into blister articles, which are typically complicated in shape. The biodegradable sheet is a laminated sheet comprising at least two layers. Each of the layers forming the laminated sheet is a resin composition comprising 75 to 25% by mass of a polylactic acid resin, and 25 to 75% by mass of a polyester resin having a glass transition temperature not exceeding 0 degrees C and a melting point higher than the glass transition temperature of the polylactic acid resin, and not exceeding the melting point of the polylactic acid resin, based on 100 mass percent of the total amount of the polylactic acid resin and the polyester resin. The D-lactic acid content of the polylactic acid resin contained in one layer, and the D-lactic acid content of the polylactic acid resin in the other layer are determined to satisfy a predetermined relationship. The laminated sheet is subjected to crystallization treatment.
Description
Technical field
The present invention relates to biodegradable laminated plate,, reach the method for these goods of moulding by the goods that this laminated plate is made.
Background technology
Used plastics such as polyethylene, polypropylene, polyvinyl chloride, polystyrene and PET material as the dish of food containers (if any cup and dish), blister package thing (blister pack), hot filling containers, conveying electronic parts, conveyer belt (carrier tape) etc.
These plastic products usually with after promptly be dropped soon, and how to dispose them and nowadays become important problem as burning or landfill.In particular, these resins such as polyethylene, polypropylene and polystyrene have high heating value when burning, so often damage incinerator when it burns in incinerator.Produce pernicious gas during the polyvinyl chloride burning.If these plastic products of landfill, they often promptly fill up the landfill place in a short time, and this is because they decompose in natural environment hardly because of its chemical stability, thus semipermanent be kept in the soil.If be poured in the natural environment, they can damage view or destroy the growing environment of marine animal.
Therefore, in order to protect environment, researching and developing biodegradable material at present energetically.One of this biodegradable material is a polylactic resin.Because polylactic resin is biodegradable, thus its hydrolysis naturally in soil or water, and resolved into harmless material by microorganism.In addition, because its combustion heat is low, so even also do not damage incinerator when burning.And, because polylactic resin derives from plant, so it does not rely on one of natural resources that crude oil-expection will exhaustion.
But, because the polylactic resin hear resistance is low, the material of its container that is considered to be not suitable for use at high temperature using (as deposit the food that will heat or the container of boiling water).In addition, if polylactic resin plate or be stored in the warehouse or transported in truck or steamer by the goods that this plate is made, because the inside of these warehouses, truck or steamer for example generates heat to high temperature in summer, they often are out of shape or fusion each other.
Patent document 1 discloses the stable on heating technology of a kind of improvement polylactic resin, promptly by polylactic resin being remained in the mould of temperature near polylactic resin crystallization temperature (80～130 ℃), and then makes the polylactic resin highly crystalline.
From patent document 2, as can be known,, can improve hear resistance, impact resistance and the formability of the goods that form by this lamina by the lamina that pre-crystallization is made by the resin combination that comprises polylactic resin and polyester.
Patent document 1:JP 8-193165A
Patent document 2:JP 2003-147177A
Summary of the invention
The problem to be solved in the present invention
But in the method in front, because molded PLA crystallization in mould so molded polylactic resin must remain in the mould when crystallization, makes the molded period ratio cycle generally speaking to grow, this has increased production cost.Moreover, also additionally need the firing equipment of heating mould.
For the lamina of patent document 2,, then on goods, produce the wrinkle of so-called " bridge joint phenomenon " according to its shape if utilize combination die to form a plurality of goods by this lamina.Utilize vacuum forming machine by the goods of this plate formation of deep-draw or the bubble goods (blisterarticle) with complicated shape that formed by above-mentioned plate, the mouldability of this mechanograph worsens slightly.
The purpose of this invention is to provide a kind of biodegradable laminated plate, and the goods that utilize this biodegradable laminated plate to form, this laminated plate does not cause environmental problem, under high temperature load, still has high hear resistance, impact resistance and intensity, do not produce the wrinkle that is called " bridge joint phenomenon ", and easily deep-draw or be shaped to the bubble goods that have complicated shape usually.
Solve the method for described problem
According to the present invention, to achieve these goals, a kind of biodegradable laminated plate is provided, it comprises two-layer at least, described each two-layer at least layer comprises resin combination, this resin combination comprises the polylactic resin of 75～25% quality and the mylar of 25～75% quality, this mylar has and is no more than 0 ℃ glass transition temperature, and be higher than the glass transition temperature of polylactic resin but be no more than the fusing point of polylactic resin fusing point, the total amount of described polylactic resin and mylar is by 100% quality, wherein said two-layer at least in the polylactic resin that comprised of one deck D-lactic acid content Da (%) with described two-layer at least in the D-lactic acid content Db (%) of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
This laminated plate lives through crystallization and handles.
Advantage of the present invention
Because laminated plate of the present invention comprises polylactic resin and mylar, so it can not cause any environmental problem.
Because laminated plate of the present invention comprises that the D-lactic acid content is not more than 7% ground floor, and the D-lactic acid content is greater than the ground floor D-lactic acid content 3% or the higher second layer, so when this laminated plate crystallization, the ground floor that the D-lactic acid content is low is easier to crystallization than the second layer.Thereby laminated plate of the present invention not only is included in the layer of the preceding crystallization of moulding, and comprises the seldom layer of possibility crystallization.This has eliminated and has kept mold temperature to form laminated plate near the crystallization temperature (80～130 ℃) of polylactic resin to promote the needs of laminated plate crystallization, to make to utilize the mould that remains normal temperature in the normal moulding circulation.So the goods of moulding have enough hear resistances.
Because laminated plate of the present invention comprises the layer that is difficult to crystallization, so, the gentle brewage of the shell that has complicated shape usually can be formed by laminated plate of the present invention.
Laminated plate according to the present invention comprises the mylar with particular glass transition temperature (Tg) and fusing point, and has high hear resistance, impact resistance, formability and the intensity under high temperature load by the goods that this laminated plate forms.They also seldom produce the wrinkle of so-called " bridge joint phenomenon ".
Description of drawings
Fig. 1 is according to the typical relation figure between the dynamic viscoelastic of biodegradable laminated plate of the present invention and its temperature.
The specific embodiment
Biodegradable laminated plate according to the present invention comprises two-layer at least, and each layer comprises resin combination, and this resin combination comprises the mylar of polylactic resin and regulation.
Polylactic resin is the polymer that obtains for the monomer of its main component with lactic acid by polycondensation.There are two kinds of lactic acid, i.e. L-lactic acid and D-lactic acid, it is an optical isomer.Polylactic resin has different degree of crystallinity according to the ratio of these two kinds of lactic acid contents.Comprising ratio is 80: 20 to 20: 80 the L-lactic acid and the randomcopolymer of D-lactic acid, is the complete unbodied transparent polymer that does not have degree of crystallinity.Near its glass transition temperature 60 ℃ is softening.
Comprise ratio and be 100: 0 to 80: 20 or 20: 80 to 0: 100 L-lactic acid and the randomcopolymer of D-lactic acid have degree of crystallinity.Although its degree of crystallinity depends on the content ratio of L-lactic acid and D-lactic acid, the copolymer of its glass transition temperature and front is roughly the same, promptly about 60 ℃.Extrude this copolymer and cooling rapidly soon after melt is extruded by melt, it is transformed into the amorphous materials of highly transparent.Then, if cooling lentamente, then it is transformed into crystalline material.Homopolymers promptly only contains the polymer of L-lactic acid or D-lactic acid, is not less than 180 ℃ semi-crystalline polymer for fusing point.
Be used for polylactic resin of the present invention and can be containing L-lactic acid or D-lactic acid homopolymers, i.e. poly-(L-lactic acid) or poly-(D-lactic acid) for its construction unit; Contain L-lactic acid and D-lactic acid copolymer, i.e. poly-(DL-lactic acid) for its construction unit; Perhaps their mixture.It also can be the copolymer of aforementioned polymer and other hydroxycarboxylic acid or glycol/dicarboxylic acids.It can also comprise a spot of chain extender residue.
Polylactic resin can carry out polymerization by known method such as polycondensation or ring-opening polymerisation.In polycondensation, the PLA with required composition can obtain by directly making the polycondensation that stands to dewater of L-lactic acid, D-lactic acid or its mixture.
In ring-opening polymerisation (lactide method), PLA can be obtained by lactide, the cyclic dimer of lactic acid, can add the catalysts selective with polymerization regulating action when needing.
Aforementioned will can be the optical isomer (for example, the D-lactic acid when this lactic acid is L-lactic acid, and the L-lactic acid of this lactic acid when being D-lactic acid) of lactic acid with other hydroxycarboxylic acid of PLA copolymerization; The aliphatic hydroxyl carboxylic acid such as the glycolic acid of two functional groups, 3-hydroxybutyric acid, 4 hydroxybutyric acid, 2-hydroxyl n-butyric acie, 2-hydroxyl-3,3-acid dimethyl, 2-hydroxy-3-methyl butyric acid, 2-methyllactic acid and 2-hydroxycaproic acid; And lactone such as caprolactone, butyrolactone and valerolactone.
Above-mentionedly to can be ethylene glycol, 1,4-butanediol or 1,4-cyclohexanedimethanol with the aliphatic diol of polylactic acid polymer copolymerization.Aforementioned aliphatic dicarboxylic acid can be butanedioic acid, adipic acid, suberic acid, decanedioic acid or dodecanedioic acid.
In addition, as a spot of copolymerization component, can use the ethylene oxide adduct of non-aliphatic dicarboxylic acid such as terephthalic acid (TPA) and/or non-aliphatic diol such as bisphenol-A as required.
The weight average molecular weight that is used for polylactic resin of the present invention is preferably 60000～700000, and more preferably 80000～400000, be preferably 100000～300000 especially.If molecular weight is too little, then actual physical character such as mechanical strength and hear resistance almost do not improve.If too big, then melt viscosity raises in so much, to such an extent as to infringement formability and machinability.
The mylar of afore mentioned rules is meant the mylar with particular glass transition temperature (Tg) and fusing point.Preferred this mylar has and is no more than 0 ℃, more preferably no more than-20 ℃ glass transition temperatures (Tg).If it is glass transition temperature is higher than 0 ℃, then often insufficient to the improvement of impact resistance.
Preferred this mylar has the fusing point of the glass transition temperature (Tg) that is higher than the polylactic resin that is added, and more preferably has to be not less than 80 ℃ fusing point.If be lower than this scope, then the hear resistance of the goods that formed by this laminated plate may be insufficient.The upper limit of the fusing point of mylar is the fusing point of the polylactic resin that added.If be higher than the fusing point of the PLA that is added, the PLA crystallization that then made in the laminated plate before forming laminated plate to be comprised is meaningless, and the appearance problem relevant with rigidity and formability.Polylactic resin has 135～180 ℃ fusing point usually, although it is along with construction unit is the mixing ratio of L-lactic acid and D-lactic acid and changing.
Have the glass transition temperature of above-mentioned particular range and the mylar of fusing point by employing, resulting laminated plate and the goods that formed by this laminated plate will have improved hear resistance, impact resistance and formability.
This mylar also comprises biodegradable aliphatic polyester except polylactic resin.This biodegradable aliphatic polyester comprises, the aliphatic polyester that obtains by condensation polyhydroxycarboxyliacid acid, aliphatic diol and aliphatic dicarboxylic acid, the aliphatic-aromatic polyester that obtains by condensation aliphatic diol, aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the aliphatic polyester copolymer that obtains by aliphatic diol, aliphatic dicarboxylic acid and hydroxycarboxylic acid, the aliphatic polyester that ring-opening polymerisation by annular lactone obtains, synthetic aliphatic polyester, and biosynthetic aliphatic polyester in the bacterium.
Aforementioned polyhydroxycarboxyliacid acid comprises hydroxycarboxylic acid such as 3-hydroxybutyric acid, 4 hydroxybutyric acid, 2-hydroxyl n-butyric acie, 2-hydroxyl-3,3-acid dimethyl, 2-hydroxy-3-methyl butyric acid, 2-methyllactic acid, and the homopolymers and the copolymer of 2-hydroxycaproic acid.
Aforementioned aliphatic diol comprises ethylene glycol, 1, and the 4-butanediol, and 1, the 4-cyclohexanedimethanol.Aforementioned aliphatic dicarboxylic acid comprises butanedioic acid, adipic acid, suberic acid, decanedioic acid, and dodecanedioic acid.Aforementioned aromatic dicarboxylic acid comprises terephthalic acid (TPA) and M-phthalic acid.
The aliphatic polyester that obtains by this condensation aliphatic diol and aliphatic dicarboxylic acid, and, obtain by making at least a aforesaid compound carry out polycondensation by the aliphatic-aromatic polyester that condensation aliphatic diol, aliphatic dicarboxylic acid and aromatic dicarboxylic acid obtain.Then, by with for example isocyanate compound chain extension, obtain required polymer.
Aforementioned aliphatic polyester comprises poly-butanedioic acid second diester, poly-butanedioic acid fourth diester, poly-butanedioic acid-adipic acid fourth diester, and poly-butanedioic acid-carbonic acid fourth diester.Aforementioned aliphatic-aromatic polyester comprises poly-adipic acid-butylene terephthalate, and poly-butanedioic acid-adipic acid-butylene terephthalate.
The aliphatic diol and the aliphatic carboxylic acid that are used for the aliphatic polyester copolymer that obtains by aliphatic diol, aliphatic dicarboxylic acid and hydroxycarboxylic acid, can be above-mentioned those.And hydroxycarboxylic acid can also be a L-lactic acid, D-lactic acid, DL-lactic acid, glycolic acid, 3-hydroxybutyric acid, 4 hydroxybutyric acid, 2-hydroxyl-n-butyric acie, 2-hydroxyl-3,3-acid dimethyl, 2-hydroxy-3-methyl-butyric acid, 2-methyllactic acid, 2-hydroxycaproic acid etc.
Aforementioned aliphatic polyester copolymer comprises poly-butanedioic acid-lactic acid fourth diester and poly-butanedioic acid-adipic acid-lactic acid fourth diester.For its composition, aliphatic diol and aliphatic dicarboxylic acid are its key component but in this case.In other words, preferred aliphat glycol: aliphatic dicarboxylic acid: the ratio of hydroxycarboxylic acid is 30～49.99: 35～49.99: 30～0.02.
The above-mentioned aliphatic polyester that obtains by the annular lactone ring-opening polymerisation obtains by one or more cyclic monomers of polymerization such as 6-caprolactone, δ-Wu Neizhi, Beta-methyl-δ-Wu Neizhi.
Aforementioned synthetic aliphatic polyester comprises the copolymer of cyclic acid anhydride and ethylene oxide, as the copolymer of succinyl oxide and oxirane or expoxy propane.
Biosynthetic aliphatic polyester comprises such as the biosynthetic aliphatic polyester of effect that passes through acetyl coenzyme A in the alcaligenes eutrophus bacteriums such as (Alcaligeneseutrophus) in the aforementioned bacterium.Although this class aliphatic polyester mainly comprise Poly-(poly--3HB), but industrially can advantageously they and hydroxypentanoic acid (HV) be copolymerized into the copolymer (copolymer of hydroxybutyric acid and hydroxypentanoic acid) of poly-(3HB-CO-3HV), thereby improve its practicality in plastics.HV copolymerization ratio is preferably 0～40mol%.Replace hydroxypentanoic acid, they can with alkanoic acid such as 3-hydroxycaproic acid, 3-Hydroxyoctanoic acid or the copolymerization of 3-hydroxyl octadecanoid acid of long-chain.The copolymer of 3HB and 3-hydroxycaproic acid comprises the copolymer of hydroxybutyric acid and hydroxycaproic acid.
In above-mentioned resin combination, the mixing ratio (quality) of preferred polylactic resin and mylar is 75～25: 25～75, more preferably 65: 35 to 35: 65.If the content of polylactic resin is higher than 75% quality, then formability is poor, so general moulding such as vacuum forming or air-pressure forming difficulty.If less than 25% quality, then resulting sheet material and the goods that formed by this sheet material are poor rigidity often.
Only constitute according to resin combination of the present invention by polylactic resin and mylar.In other words, in fact polylactic resin content and mylar content sum are 100% quality.
Utilize this resin combination, preparation is according to biodegradable laminated plate of the present invention.This laminated plate should comprise multilayer such as two-layer, three layers or four layers.
If it is two-layer that biodegradable laminated plate according to the present invention comprises, then D-lactic acid content Da (%) and the Db (%) in the polylactic resin that comprised of each layer (ground floor and the second layer) should satisfy following relational expression (1):
Da≤7 and Db-Da＞3 (1)
Particularly, the D-lactic acid content (Da) in the polylactic acid polymer of formation ground floor should be not more than 7%, preferably is not more than 5%.If be higher than 7%, even then also often reduction of degree of crystallinity after crystallization is handled, this situation will be illustrated in the back.This can cause laminated plate rigidity deficiency when standing high temperature (for example 60～80 ℃) loading.In other words, as the polylactic resin that is comprised in the ground floor, preferably in handling, following crystallization can be easy to the material of crystallization.Preferred the following of Da value is limited to 0.5%.If be lower than 0.5%, then gained sheet material may be frangible.
D-lactic acid content (Db) the ratio content Da that is preferably formed in the polylactic acid polymer of the second layer is high more than 3%.If the difference of Db and Da is 3% or littler, the polylactic acid polymer that then forms the second layer has no practical significance at the polylactic acid polymer that all approaches to form ground floor aspect degree of crystallinity and the fusing point so form the sheet material of multilayer.
Biodegradable laminated plate according to the present invention stands crystallization to be handled.Crystallization is handled the crystallization that promotes specific polylactic resin.There is not concrete restriction to being used for crystallization processing of the present invention, as long as it promotes the crystallization of specific polylactic resin.For example, can adopt via the crystallization that heats.In handling via the crystallization of heating, sheet material can be heated to about 60～120 ℃ hot-rolling and contact several seconds to a few minutes, sheet material can heat preset time continuously by infrared heater or by hot-air, sheet material also can be in being heated to about 60～120 ℃ hot-air rolling and heating 0.5～72 hour.
After the crystallization, the polylactic resin that is comprised in the preferred ground floor has and is not less than 20% and be not more than 100% degree of crystallinity, more preferably has to be not less than 25% and be not more than 99% degree of crystallinity.If less than 20%, then can cause laminated plate rigidity deficiency when standing high temperature (for example 60～80 ℃) loading.The degree of crystallinity of the polylactic resin in the ground floor can be 100%.
After the crystallization, the polylactic resin that is comprised in the preferred second layer has and is not less than 0% and be not more than 20% degree of crystallinity, more preferably has to be not less than 1% and less than 15% degree of crystallinity.If greater than 20%, then formability is often insufficient, and often produces the wrinkle of so-called " bridge joint phenomenon ".The degree of crystallinity of the polylactic resin in the second layer can be 0%.
The polylactic resin that is contained in the ground floor or the second layer all can be the mixture of two or more dissimilar polylactic resin.In this case, no matter be content Da or content Db, it is the average D-lactic acid content in two or more polylactic resin.
Biodegradable laminated plate can be for double-layer structure, i.e. ground floor/second layer structure; For three-decker, i.e. ground floor/second layer/ground floor structure; Perhaps be structure more than four layers or four layers, as ground floor/second layer/ground floor ... / second layer structure, or ground floor/second layer/ground floor ... / ground floor structure.Preferred two skins are made of ground floor, and at least one internal layer is the second layer.If two skins constitute by ground floor, then two skins are high-crystallinity, so this biodegradable laminated plate has high-fire resistance and impact resistance, and have improved formability during moulding when it in vacuum forming machine or air-pressure forming machine.Between any ground floor and the second layer, can arrange and reclaim resin bed or the layer of performance between the ground floor and the second layer.
The gross thickness of preferred ground floor is 3～300 microns, more preferably 10～200 microns, and more preferably 30～100 microns.If less than 3 microns, can cause laminated plate rigidity deficiency when standing high temperature (for example 60～80 ℃) loading.If surpass 300 microns, formability may be insufficient.
Preparation method according to biodegradable laminated plate of the present invention now will be described.Each of plate layer can be formed by common forming method sheet material by above-mentioned resin combination.For example, each of plate layer can be by the formation of extruding in the T-die casting.But because polylactic resin has high-hygroscopicity and water-disintegrable, so need in preparation process, control moisture.Thereby if each layer is to utilize common single screw extrusion machine by extruding formation, then material should be used for example vacuum desiccator dehumidifying (drying).If use the discharge type double screw extruder to extrude, then can more effectively form each layer of plate, because this extruder can more effectively make material dehydration.
For each layer of laminated preparation thus without limits, as long as its not loss purpose of the present invention with the method that forms laminated plate.For example, this laminating method can be by choosing in four kinds of following methods.
(1) adopt two or more extruders, by each layer of branch manifold (multi-manifold) or feed sleeve pipe (feed block) type extruder head laminate, and the form of fusion sheet material is extruded.
(2) one of each layer of plate launched, and use resin as other layer by coating.
(3) after each layer with plate is heated to proper temperature, by hot pressing each layer combined by means of roller or press.
(4) by means of adhesive each is lumped together layer by layer.
The biodegradable laminate of Xing Chenging has excellent formability thus, does not have cross-over connection in the reality, and can form in the short period under the temperature that heating mould can not reach.
Particularly, can be shaped to required goods by any method in several different methods such as vacuum forming, air-pressure forming, vacuum pressure moulding and the compacting according to biodegradable laminated plate of the present invention.The forming temperature of preferred biodegradable laminated plate is not less than the fusing point of aforementioned mylar, but less than the fusing point that comprises polylactic resin in the ground floor.If forming temperature is less than the fusing point of mylar, then hear resistance and/or formability can be insufficient.If the fusing point of the polylactic resin that forming temperature is equal to or higher than in the ground floor to be comprised then can the appearance problem relevant with rigidity and formability.
Thereby, can under the temperature that is significantly less than the polylactic resin crystallization temperature, in short molding cycle, be shaped to required goods according to biodegradable laminated plate of the present invention.So, do not need mold heated to the crystallization temperature that approaches polylactic resin (as 80～130 ℃).The goods of Xing Chenging have high-fire resistance and impact resistance thus.The chances are for this because being contained in polylactic resin in the ground floor of the biodegradable laminated plate according to the present invention is partially crystallizable at least, but also may be because polylactic resin mix with other mylar, so have the viscoplasticity of uniqueness.
Fig. 1 shows the relation between dynamic viscoelastic according to biodegradable laminated plate of the present invention (E ') and its temperature.In Fig. 1, numeral＜1〉glass transition temperature (Tg) of expression polylactic resin, numeral＜2〉fusing point of expression mylar, and numeral＜3 expression is contained in the fusing point of the polylactic resin in the ground floor.
Biodegradable laminated plate can be＜1〉and＜3 between the temperature compacted under, but preferably＜2 and＜3 between the temperature compacted under.Because the polylactic resin that is comprised in the ground floor is handled partially crystallizable at least by crystallization, so resulting product has good hear resistance.
Biodegradable laminated plate according to the present invention can be shaped to following goods: lunch box, the dish of splendid attire food such as fish, meat, fruits and vegetables, bean curd, prepared food, dessert and the instant noodles and cup, the packing container of toothbrush, battery, medicine and cosmetics, the heat of pudding, jam and curry powder is filled (hot-fill) container, and transmits the dish and the carrier band (carrier tape) of electronic unit such as IC (integrated circuit), transistor and diode.
Can in forming, add additive to improve its performance according to the resin combination of biodegradable laminated plate of the present invention.This additive comprises stabilizing agent, antioxidant, and the UV absorbent, pigment, antistatic additive, conductive agent, releasing agent (release agent), plasticizer, flavor enhancement, antiseptic, nucleator reaches similar additive with it.
Embodiment
Now embodiments of the invention and Comparative Examples will be described.These examples do not limit the present invention in any way.The physical property of embodiments of the invention and Comparative Examples is measured and is estimated as follows.
[measure and estimate]
(1) hear resistance estimates 1
To utilize the goods of the punch moulding of diameter 75mm, degree of depth 50mm, draw ratio 0.67, by the hot air circulate baking oven 80 ℃ of following heat treatments 20 minutes.The volume slip is calculated as follows:
Volume slip (%)={ 1-(volume before the volume/moulded products heat treatment after the moulded products heat treatment) } * 100
The volume slip is good less than 3% goods, and the volume slip is not more than 6% goods and can uses in practice, and the volume slip can not use greater than 6% goods.
(2) hear resistance estimates 2
Utilize four goods of punch moulding of diameter 75mm, degree of depth 50mm, draw ratio 0.67, and water is filled.Then, seal its opening, it stacked mutually, and in the hot air circulate baking oven in 65 ℃ of following heat treatments 60 minutes.After the heat treatment, the observation goods see whether it is out of shape.
(3) impact resistance estimates 1
The water bullet shock machine that utilizes Toyo Seiki to make clashes into the water bullet of 0.5 inch of diameter against each biodegradable laminated plate sample with the speed of 3m/ second, and calculates and break up the required energy of laminated plate.
(4) impact resistance estimates 2
To fill water by the goods that each biodegradable laminated plate sample obtains, and, make its height fall on the concrete floor from 1m with its opening sealing.Observe then to determine whether it breaks.
(5) measurement of glass transition temperature (Tg)
According to JIS-K-7121, measure the glass transition temperature of polyester with 10 ℃/minute firing rate by differential scanning calorimetry (DSC).
(6) measurement of crystallized temperature
According to JIS-K-7121, measure and to result from the melting heat (Δ Hm) and the crystallization heat (Δ Hc) of the polylactic resin in the biodegradable plate, and as follows according to the degree of crystallinity of these numerical computations polylactic resin:
Degree of crystallinity: χ c%=(Δ Hm-Δ Hc)/(content of polylactic resin in 92.8 * plate) * 100
(7) evaluation of formability
Utilize the punch (25 ℃ of mould temperature) of diameter 75mm, degree of depth 50mm, draw ratio 0.67, make the sheet material sample carry out vacuum forming (vacuum :-70cmHg).Observe the goods of moulding like this, to check its how moulding, whether to produce bridge joint and any other forming defect.The meaning of symbol is as follows in the table.
Zero: good moulding
△: in fact can accept
*: bad moulding
(8) overall assessment
In the table, hear resistance 1, hear resistance 2, impact resistance 1 and impact resistance 2 all with any sample of symbol zero, are all represented with symbol zero; Simultaneously to above-mentioned every all with symbol * any sample, all with symbol * expression.
(composition of polylactic resin in the laminated plate)
For the polylactic resin that forms each laminated plate sample, use Cargill Dow makes one of Nature Works level D-lactic acid of (seeing Table 1) or mixture, and is as shown in table 2.If the use mixture, then the D-lactic acid content in each rank D-lactic acid by the mean value of the D-lactic acid content of its mass fraction.
Table 1
| Nature Works level | |||
| 4031 | 4050 | 4060 | |
| D-lactic acid (quality %) | 1.2 | 5 | 12 |
| Tg(Tg) | 58 | 58 | 56 |
| Weight average molecular weight | 200000 | 190000 | 190000 |
Table 2
| The resin numbering | |||||
| 1 | 2 | 3 | 4 | ||
| Nature Works level | 4031 (quality %) | 100 | 0 | 0 | |
| 4050 (quality %) | 0 | 100 | 70 | 0 | |
| 4060 (quality %) | 0 | 0 | 30 | 100 | |
| Average D-lactic acid content (quality %) | 1.2 | 5 | 7.1 | 12 | |
(embodiments of the invention 1)
Will as the resin in the table 2 of PLA 1 with as the PBS of biodegradable aliphatic polyester (poly-butanedioic acid fourth diester, Showa Highpolymer Co., Ltd makes: Bionolle 1001, fusing point: 111 ℃; Glass transition temperature :-40 ℃), the ratio in polylactic resin/biodegradable aliphatic polyester=50/50 (% quality) mixes.In this mixture of 100% quality, add of talcum (the Nippon Talc Co., Ltd manufacturing: Micro Ace L1) of 10% quality as inorganic filler, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 2)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=25/75 (% quality).In this mixture of 100% quality, add the talcum of 20% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=25/75 (% quality).In this mixture of 100% quality, add the talcum of 20% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 3)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=75/25 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=75/25 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 100: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 4)
Except using PBAT (poly-adipic acid-butylene terephthalate, BASF makes, Ecoflex, fusing point: 109 ℃, glass transition temperature :-30 ℃) as outside the biodegradable aliphatic polyester, obtaining thickness by the mode identical with embodiment 1 is 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 5)
Except using PBSL (poly-butanedioic acid-lactic acid fourth diester, Mitsubishi Chemical Corporation makes: AZ81T, the copolymer of 94% mole of butanedioic acid and 6% molar lactic acid, as acid constituents, fusing point: 110 ℃, glass transition temperature :-40 ℃) as outside the biodegradable aliphatic polyester, obtaining thickness by the mode identical with embodiment 1 is 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 6)
Except using PBSLA (poly-butanedioic acid-adipic acid-lactic acid fourth diester, Mitsubishi ChemicalCorporation makes: AD82W, the copolymer of 74% mole of butanedioic acid, 20% mole of adipic acid and 6% molar lactic acid, as acid constituents, fusing point: 87 ℃, glass transition temperature :-40 ℃) as outside the biodegradable aliphatic polyester, obtaining thickness by the mode identical with embodiment 1 is 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 7)
Except using PBSA (poly-butanedioic acid-adipic acid fourth diester, Showa Highpolymer Co., Ltd makes: Bionolle 3001, the copolymer of 85% mole of butanedioic acid and 15% mole of adipic acid, as acid constituents, fusing point: 93 ℃, glass transition temperature :-40 ℃) as outside the biodegradable aliphatic polyester, obtaining thickness by the mode identical with embodiment 1 is 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 3.
(embodiments of the invention 8)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=25/75 (% quality).In this mixture of 100% quality, add the talcum of 20% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=25/75 (% quality).In this mixture of 100% quality, add the talcum of 20% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 1: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 400 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 9)
Will be as resin in the table 2 of PLA 2 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 115 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 10)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 3 (Db=7.1) and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 100 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 11)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and descend this mixture from the two-layer branch manifold extruder head of the parallel double-screw extruder of diameter 25mm at 220 ℃ as the aforementioned model of inorganic filler, extrude in the mode of anterior layer.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Because the biodegradable laminated plate of this embodiment has double-layer structure, so the back layer of this laminated plate is also served as in the intermediate layer.Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer and back layer is 2: 5.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 12)
Will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality as the aforementioned model of inorganic filler, and with this mixture under 220 ℃ from the branch manifold extruder head of the parallel double-screw extruder of diameter 40mm, extrude with the form of anterior layer and back layer.
In addition, will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and be the branch manifold extruder head of parallel double-screw extruder of 25mm from diameter this mixture as the aforementioned model of inorganic filler, extrude with the form in intermediate layer.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 3: 1: 3.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 13)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=50/50 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 40 ℃, obtain thickness and be 300 microns biodegradable laminated plate.The laminated plate of so preparation is rolled into the about 300 meters scroll of length.This scroll was heated 24 hours down in 75 ℃ in air oven.After the heat treatment, estimate this laminated plate in a manner described.Evaluation result is shown in Table 4.
(embodiments of the invention 14)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=40/60 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form of anterior layer and back layer with this mixture branch manifold extruder head from the parallel double-screw extruder of diameter 25mm under 220 ℃ as the aforementioned model of inorganic filler.
In addition, will press polylactic resin/biodegradable aliphatic polyester=40/60 (% quality) as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester.In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 40 ℃, obtain thickness and be 300 microns biodegradable laminated plate.The laminated plate of so preparation is rolled into the about 300 meters scroll of length.This scroll was heated 24 hours down in 75 ℃ in air oven.After the heat treatment, estimate this laminated plate in a manner described.Evaluation result is shown in Table 4.
(Comparative Examples 1)
To 100% quality as the resin in the table 2 of PLA 1 in, add the talcum of 10% quality, and this mixture extruded from diameter is the individual layer extruder head of parallel double-screw extruder of 25mm under 220 ℃ as the aforementioned model of inorganic filler.The plate of so preparation is contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable plate.Estimate resulting plate in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 2)
To 100% quality as the resin in the table 2 of PLA 1 in, add the talcum of 10% quality, and this mixture extruded from diameter is the individual layer extruder head of parallel double-screw extruder of 25mm under 220 ℃ as the aforementioned model of inorganic filler.The plate of so preparation is contacted with the stack that remains 40 ℃, obtain thickness and be 300 microns biodegradable plate.Estimate resulting plate in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 3)
Will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=80/20 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and this mixture is extruded from diameter is the individual layer extruder head of parallel double-screw extruder of 25mm under 220 ℃ as the aforementioned model of inorganic filler.The plate of so preparation is contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable plate.Estimate resulting plate in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 4)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=80/20 (% quality).In this mixture of 100% quality, add the talcum of 10% quality as the aforementioned model of inorganic filler, and with this mixture under 220 ℃ from the branch manifold extruder head of the parallel double-screw extruder of diameter 20mm, extrude with the form of anterior layer and back layer.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=80/20 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 2: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 5)
Will be as resin in the table 2 of PLA 1 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=60/40 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and be to extrude the individual layer extruder head of parallel double-screw extruder of 25mm from diameter at 220 ℃ this mixture as the aforementioned model of inorganic filler.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate resulting plate in a manner described.Evaluation result is shown in Table 5.
(Comparative Examples 6)
Will be as resin in the table 2 of PLA 3 (Da=7.1) and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=60/40 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and under 220 ℃, be the branch manifold extruder head of parallel double-screw extruder of 25mm from diameter with this mixture as the aforementioned model of inorganic filler, extrude with the form of anterior layer and back layer.
In addition, will be as resin in the table 2 of PLA 4 and PBS as the aforementioned model of biodegradable aliphatic polyester, mix in the ratio of polylactic resin/biodegradable aliphatic polyester=60/40 (% quality).In this mixture of 100% quality, add the talcum of 10% quality, and, extrude with the form in intermediate layer with the branch manifold extruder head of this mixture from the parallel double-screw extruder of diameter 40mm as the aforementioned model of inorganic filler.
Regulate the discharging speed of molten resin, make that the thickness ratio of anterior layer, intermediate layer and back layer is 1: 5: 1.Each layer of so extruding contacted with the stack that remains 110 ℃, obtain thickness and be 300 microns biodegradable laminated plate.Estimate the laminated plate that so obtains in a manner described.Evaluation result is shown in Table 5.
Table 3
| Embodiments of the invention | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||||
| Biodegradable laminated plate | Full plate | Plate thickness (μ m) | 300 | |||||||
| Layer structure | Three layers | |||||||||
| Layer is arranged *1) | 1/2/1 | |||||||||
| The thickness ratio | 1/5/1 | 1/100/1 | 1/5/1 | |||||||
| Db-Da (quality %) | 10.8 | |||||||||
| Ground floor | Da (quality %) | 1.2 | ||||||||
| Thickness (μ m) | 86 | 6 | 86 | |||||||
| Degree of crystallinity *2) (％) | 44 | 45 | 44 | 47 | 46 | 40 | 39 | |||
| Mylar | Model | PBS | PBTA | PBSL | PBSLA | PBSA | ||||
| Content (quality %) | 50 | 75 | 25 | 50 | ||||||
| The second layer | Db ％ | 12 | ||||||||
| Thickness (μ m) | 214 | 294 | 214 | |||||||
| Degree of crystallinity *2) (％) | 1 | 1.2 | 1 | 1.3 | 2 | 1 | 1.3 | |||
| Mylar | Model | PBS | PBTA | PBSL | PBSLA | PBSA | ||||
| Content (quality %) | 50 | 75 | 25 | 50 | ||||||
| Estimate | Hear resistance 1 (%) | 0.9 | 0.7 | 2.2 | 1.3 | 0.8 | 1.5 | 1.4 | ||
| Hear resistance 2 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
| Impact resistance 1 (Kgfmm) | 215 | 416 | 125 | 325 | 200 | 285 | 312 | |||
| Impact resistance 2 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
| Formability | ○ | ○ | △ | ○ | ○ | ○ | ○ | |||
| Overall assessment | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
* 1: ground floor; 2: the second layer
* the degree of crystallinity of the polylactic resin that is wherein comprised
Table 4
| Embodiments of the invention | ||||||||||
| 8 | 9 | 10 | 11 | 12 | 13 | 14 | ||||
| Biodegradable laminated plate | Full plate | Plate thickness (μ m) | 300 | |||||||
| Layer structure | Three layers | Two-layer | Three layers | |||||||
| Layer is arranged *1) | 1/2/1 | 1/2 | 2/1/2 | 1/2/1 | ||||||
| The thickness ratio | 1/1/1 | 1/5/1 | 2/5 | 3/1/3 | 1/5/1 | |||||
| Db-Da (quality %) | 10.8 | 7 | 5.9 | 10.8 | ||||||
| Ground floor | Da (quality %) | 1.2 | 5 | 1.2 | ||||||
| Thickness (μ m) | 267 | 86 | 43 | 86 | ||||||
| Degree of crystallinity *2)(％) | 42 | 30 | 43 | 46 | 42 | 42 | 43 | |||
| Mylar | Model | PBS | ||||||||
| Content (quality %) | 75 | 50 | 60 | |||||||
| The second layer | Db ％ | 12 | 7.1 | 12 | ||||||
| Thickness (μ m) | 34 | 214 | 257 | 214 | ||||||
| Degree of crystallinity *2)(％) | 1.8 | 2.4 | 9.2 | 1.1 | 3.4 | 1 | 1.1 | |||
| Mylar | Model | PBS | ||||||||
| Content (quality %) | 75 | 50 | 60 | |||||||
| Estimate | Hear resistance 1 (%) | 0.7 | 1 | 0.9 | 1.2 | 1.4 | 0.9 | 0.8 | ||
| Hear resistance 2 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
| Impact resistance 1 (Kgfmm) | 398 | 270 | 198 | 203 | 222 | 220 | 302 | |||
| Impact resistance 2 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
| Formability | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
| Overall assessment | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |||
* 1: ground floor; 2: the second layer
* the degree of crystallinity of the polylactic resin that is wherein comprised
Table 5
| Comparative Examples | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | ||||
| Biodegradable laminated plate | Full plate | Plate thickness (μ m) | 300 | ||||||
| Layer structure | Individual layer | Three layers | Individual layer | Three layers | |||||
| Layer is arranged *1) | 1 | 1/2/1 | 1 | 1/2/1 | |||||
| The thickness ratio | - | 1/2/1 | - | 1/5/1 | |||||
| Db-Da (quality %) | - | 10.8 | - | 4.8 | |||||
| Ground floor | Da (quality %) | 1.2 | - | 1.2 | 7.1 | ||||
| Thickness (μ m) | 300 | - | 150 | 300 | 86 | ||||
| Degree of crystallinity *2)(％) | 46 | 5.2 | - | 45 | 43 | 10.1 | |||
| Mylar | Model | Do not have | PBS | ||||||
| Content (quality %) | 0 | 20 | 40 | ||||||
| The second layer | Db ％ | - | 12 | - | 12 | ||||
| Thickness (μ m) | - | 300 | 150 | - | 214 | ||||
| Degree of crystallinity *2)(％) | - | 3.4 | 1.1 | - | 1.2 | ||||
| Mylar | Model | Do not have | PBS | Do not have | PBS | ||||
| Content (quality %) | 0 | 20 | 0 | 40 | |||||
| Estimate | Hear resistance 1 (%) | 82.3 | 84.1 | 8.1 | 6.5 | 1.2 | 1.5 | ||
| Hear resistance 2 | × | × | × | ○ | ○ | × | |||
| Impact resistance 1 (Kgfmm) | 11 | 10 | 78 | 85 | 156 | 202 | |||
| Impact resistance 2 | × | × | ○ | ○ | ○ | ○ | |||
| Formability | × | ○ | ○ | × | × | ○ | |||
| Overall assessment | × | × | × | × | × | × | |||
* 1: ground floor; 2: the second layer
* the degree of crystallinity of the polylactic resin that is wherein comprised
[result]
From table 3 to table 5 as can be seen, the hear resistance of embodiments of the invention 1～14, impact resistance and formability all are excellent, and required goods can be formed by common moulding circulation by the laminated plate among any of these embodiment.
On the other hand, it is all poor aspect impact resistance and hear resistance not comprise the Comparative Examples 1 of any biodegradable aliphatic polyester.In addition, the formability extreme difference of goods in vacuum forming.The same with Comparative Examples 1, Comparative Examples 2 is also poor aspect hear resistance and impact resistance.Particularly about hear resistance 2, by the container generation shrinkage (buckling) of the sheet metal forming of Comparative Examples 2.
Poor heat resistance with Comparative Examples 3 of the biodegradable aliphatic polyester of low content.The same with Comparative Examples 2, about hear resistance 2, by the container generation shrinkage of the sheet metal forming of Comparative Examples 3.The hear resistance and the formability of Comparative Examples 4 are poor.Formability is also bad.
Comparative Examples 5 bridging occurs during the formability evaluation.The container that is formed by the plate of Comparative Examples 6 shrinkage occurs during hear resistance evaluation 2.
Claims (8)
1. the biodegradable laminated plate of a Zhong; It comprises that Zhi is few two-layer; Every one deck of the few two-layer Zhong of described Zhi all comprises resin combination; This resin combination comprises the polylactic resin of 75～25% Zhi amount and the mylar of 25～75% Zhi amount; Described mylar has and is no more than 0 ℃ glass transition temperature; And be higher than the glass transition temperature of described polylactic resin but be no more than the fusing point of described polylactic resin fusing point; The Zong amount of described polylactic resin and described mylar is measured by 100% Zhi
Wherein said two-layer at least in the D-lactic acid content Da (%) of the polylactic resin that comprised of one deck, with described two-layer at least in the D-lactic acid content Db (%) of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
Described laminated plate lives through crystallization and handles.
2. biodegradable laminated plate, it comprises two-layer at least, described each layer in two-layer at least all comprises resin combination, this resin combination comprises the polylactic resin of 75～25% quality and the mylar of 25～75% quality, described mylar has and is no more than 0 ℃ glass transition temperature, and being not less than 80 ℃ but be no more than the fusing point of described polylactic resin fusing point, the total amount of described polylactic resin and described mylar is by 100% quality
Wherein said two-layer at least in the D-lactic acid content Da (%) of the polylactic resin that comprised of one deck, with described two-layer at least in the D-lactic acid content Db (%) of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
Described laminated plate lives through crystallization and handles.
3. the biodegradable laminated plate of a Zhong; It comprises that Zhi is few two-layer; Every one deck of the few two-layer Zhong of described Zhi all comprises resin combination; This resin combination comprises the polylactic resin of 75～25% Zhi amount and the mylar of 25～75% Zhi amount; Described mylar has and is no more than 0 ℃ glass transition temperature; And be higher than the glass transition temperature of described polylactic resin but be no more than the fusing point of described polylactic resin fusing point; The Zong amount of described polylactic resin and described mylar is measured by 100% Zhi
Wherein said two-layer at least in the D-lactic acid content Da (%) of the polylactic resin that comprised of one deck, with described two-layer at least in the D-lactic acid content Db (%) of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
Described two-layer at least in the degree of crystallinity of the polylactic resin that comprised of one deck be not less than 20% but be not more than 100%, described two-layer at least in the degree of crystallinity of the polylactic resin that another layer comprised be not less than 0% but less than 20%.
4. biodegradable laminated plate, it comprises two-layer at least, described each layer in two-layer at least all comprises resin combination, this resin combination comprises the polylactic resin of 75～25% quality and the mylar of 25～75% quality, described mylar has and is no more than 0 ℃ glass transition temperature, and being not less than 80 ℃ but be no more than the fusing point of described polylactic resin fusing point, the total amount of described polylactic resin and described mylar is by 100% quality
Wherein said two-layer at least in the D-lactic acid content Da (%) of the polylactic resin that comprised of one deck, with described two-layer at least in the D-lactic acid content Db (%) of the polylactic resin that another layer the comprised relational expression (1) below satisfying:
Da≤7 and Db-Da＞3 (1)
Described two-layer at least in the degree of crystallinity of the polylactic resin that comprised of one deck be not less than 20% but be not more than 100%, described two-layer at least in the degree of crystallinity of the polylactic resin that another layer comprised be not less than 0% but less than 20%.
5. according to each biodegradable laminated plate in the claim 1～4, wherein said one deck in two-layer at least has 3～300 microns thickness.
6. according to each biodegradable laminated plate in the claim 1～5, wherein said one deck in two-layer at least comprises two skins, and described another layer in two-layer at least is for being arranged in the one deck at least between described two skins.
7. goods, it is to obtain by each biodegradable laminated plate in the moulding claim 1～6, forming temperature be not less than mylar fusing point but less than described two-layer at least in the fusing point of the polylactic resin that comprised of one deck.
8. method by each biodegradable laminated plate moulded products in the claim 1～6, this method comprise make described laminated plate at the fusing point that is not less than mylar but less than described two-layer at least in the temperature compacted under of fusing point of the polylactic resin that one deck comprised.
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| CN101618565B (en) * | 2009-04-28 | 2011-02-02 | 王勇 | Manufacture method of environment-friendly wood substrate composite material |
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| JP2000141955A (en) * | 1998-06-03 | 2000-05-23 | Mitsubishi Plastics Ind Ltd | Biodegradable card |
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Effective date of registration: 20170901 Address after: Tokyo, Japan Patentee after: MITSUBISHI RAYON Co.,Ltd. Address before: Tokyo, Japan Patentee before: MITSUBISHI PLASTICS, Inc. |
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| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20081203 |