JP2008248419A - Surface member for interior automotive trim - Google Patents
Surface member for interior automotive trim Download PDFInfo
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- JP2008248419A JP2008248419A JP2007089983A JP2007089983A JP2008248419A JP 2008248419 A JP2008248419 A JP 2008248419A JP 2007089983 A JP2007089983 A JP 2007089983A JP 2007089983 A JP2007089983 A JP 2007089983A JP 2008248419 A JP2008248419 A JP 2008248419A
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- polylactic acid
- acid
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- surface member
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- 239000000835 fiber Substances 0.000 claims abstract description 104
- 239000004626 polylactic acid Substances 0.000 claims abstract description 77
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 76
- 239000010410 layer Substances 0.000 claims abstract description 47
- 125000003118 aryl group Chemical group 0.000 claims abstract description 42
- 229920000728 polyester Polymers 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000002344 surface layer Substances 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 18
- 229930182843 D-Lactic acid Natural products 0.000 claims description 14
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 14
- 229940022769 d- lactic acid Drugs 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 239000004745 nonwoven fabric Substances 0.000 abstract description 8
- 238000005299 abrasion Methods 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 3
- 238000010030 laminating Methods 0.000 abstract description 2
- 238000004080 punching Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 description 12
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001432 poly(L-lactide) Polymers 0.000 description 5
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- RGMMREBHCYXQMA-UHFFFAOYSA-N 2-hydroxyheptanoic acid Chemical compound CCCCCC(O)C(O)=O RGMMREBHCYXQMA-UHFFFAOYSA-N 0.000 description 2
- JKRDADVRIYVCCY-UHFFFAOYSA-N 2-hydroxyoctanoic acid Chemical compound CCCCCCC(O)C(O)=O JKRDADVRIYVCCY-UHFFFAOYSA-N 0.000 description 2
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 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
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- XGIAHMUOCFHQTI-UHFFFAOYSA-N Cl.Cl.Cl.Cl.CC Chemical compound Cl.Cl.Cl.Cl.CC XGIAHMUOCFHQTI-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 240000001980 Cucurbita pepo Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Laminated Bodies (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
本発明は自動車内装材のための表面部材に関する。 The present invention relates to a surface member for an automobile interior material.
自動車の内装を構成する天井、カーペット、トリム類、シートカバー等の自動車内装材には、石油系プラスチック短繊維を使用したニードルパンチ不織布がよく使用されている。しかし、石油系プラスチックは難分解性であるため、ゴミ処理問題等、循環型社会を実践する上で大きな障害となっている。また、焼却時に発生する二酸化炭素は地球温暖化の原因となっている。加えて、原料が石油由来であるため、化石資源の枯渇の問題が懸念されている。そのような状況の中、安全上、強度や耐久性を必要とするために自動車内装材に使用されている石油系プラスチック短繊維ニードルパンチ不織布においても、その代替、使用量低減が検討されている。代替短繊維ニードルパンチ不織布に使用する繊維として、具体的には、トウモロコシなどの植物資源を原料とするポリ乳酸繊維の使用が検討されている。しかし、ポリ乳酸繊維は、従来の合成繊維よりも強度、耐久性が劣っている。また、染色等の湿熱処理による重合度の低下が大きく、これによっても強度の低下が生じるという問題がある。このため、従来のポリ乳酸繊維は、強度、耐久性、耐磨耗性、モールド加工時の耐熱性が要求される自動車内装材として使用することには制限があるのが現状である。 Needle punch nonwoven fabrics using petroleum-based plastic short fibers are often used for automobile interior materials such as ceilings, carpets, trims, seat covers and the like that constitute the interior of automobiles. However, since petroleum-based plastics are hardly decomposable, they are a major obstacle to practicing a recycling society, such as waste disposal problems. Carbon dioxide generated during incineration is a cause of global warming. In addition, since the raw material is derived from petroleum, there is a concern about the problem of depletion of fossil resources. Under such circumstances, in the case of petroleum-based plastic short fiber needle punched nonwoven fabrics that are used for automobile interior materials in order to require strength and durability for safety, alternatives and reduction of the amount of use are being studied. . Specifically, the use of polylactic acid fibers made from plant resources such as corn as a raw material has been studied as a fiber used in the alternative short fiber needle punched nonwoven fabric. However, polylactic acid fibers are inferior in strength and durability to conventional synthetic fibers. In addition, there is a problem that the degree of polymerization is greatly reduced by wet heat treatment such as dyeing, and this also causes a reduction in strength. For this reason, the present condition is that there is a restriction | limiting in using the conventional polylactic acid fiber as a vehicle interior material by which intensity | strength, durability, abrasion resistance, and the heat resistance at the time of a mold process are requested | required.
特許文献１では、ポリ乳酸の耐久性を上げるためにカルボジイミドなどの末端封鎖剤によりポリマーの末端を封鎖し耐加水分解性を向上させることが提案されている。しかしながら、このポリ乳酸を使用した繊維では、加水分解を促進する末端基の数を減らすことはできるが、ポリ乳酸のみを使用する繊維であるため、耐久性（耐湿熱分解性）の向上効果は不十分である。また、モールド加工時の熱処理でポリ乳酸繊維が溶融し加工できない事態が発生している。 In Patent Document 1, in order to increase the durability of polylactic acid, it has been proposed to improve the hydrolysis resistance by blocking the ends of the polymer with a terminal blocking agent such as carbodiimide. However, in this fiber using polylactic acid, the number of end groups that promote hydrolysis can be reduced, but because it is a fiber that uses only polylactic acid, the effect of improving durability (moisture and thermal decomposition resistance) It is insufficient. Moreover, the situation where the polylactic acid fiber melts and cannot be processed by the heat treatment at the time of molding is occurring.
特許文献２には、ポリ乳酸と他の成分とからなる複合繊維として、ポリ乳酸が単繊維の表面の全部又は一部を形成し、他の成分としてのポリエチレンテレフタレート等のポリエステルを芯部に用いた複合繊維が提案されている。しかしながら、この繊維は、ポリ乳酸成分が繊維の外周部を占めポリ乳酸成分を接着成分するバインダー繊維であるため、強度、耐久性が要求される自動車内装材の用途で好適に使用可能なものではない。 In Patent Document 2, as a composite fiber composed of polylactic acid and other components, polylactic acid forms all or part of the surface of a single fiber, and polyester such as polyethylene terephthalate as another component is used for the core. The proposed composite fiber has been proposed. However, since this fiber is a binder fiber in which the polylactic acid component occupies the outer periphery of the fiber and the polylactic acid component is an adhesive component, it cannot be suitably used for automotive interior materials that require strength and durability. Absent.
特許文献３に記載されているところの、芯部がポリ乳酸、鞘部がポリエステルで構成されているポリエステル芯鞘複合繊維を、自動車内装材のためのニードルパンチ不織布に使用することも検討されている。このものについては、強度、耐久性、モールド加工時の耐熱性においては実用に足るレベルの製品が得られることが確認されている。しかし、耐磨耗性については、芯鞘型複合構造であるために耐磨耗試験で芯鞘割れが発生し、自動車内装材としては実用に足るレベルではないことが確認されている。
本発明は、上記の問題点を解決し、ポリ乳酸を使用した繊維を構成繊維とする不織布を使用しながらも、強度、耐久性（耐湿熱分解性）、耐磨耗性、及び特にモールド加工時の耐熱性に優れ、自動車の内装材として好適に使用することが可能な、自動車内装材のための表面部材を提供しようとするものである。 The present invention solves the above-mentioned problems and uses strength, durability (moisture and thermal decomposition resistance), wear resistance, and particularly mold processing while using a nonwoven fabric composed of fibers using polylactic acid. An object of the present invention is to provide a surface member for an automobile interior material that is excellent in heat resistance at the time and can be suitably used as an interior material for an automobile.
本発明者は、上記の課題を解決するために鋭意検討の結果、本発明に到達した。すなわち本発明は、次の（１）〜（４）を要旨とするものである。 The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above-described problems. That is, the gist of the present invention is the following (1) to (4).
（１） 自動車の内装材のための表面部材であって、複数の不織ウェブが積層されてニードルパンチにより一体化されており、前記内装材において自動車内に露出する表層は、この表層を構成する繊維を形成する重合体として芳香族ポリエステルを含みかつポリ乳酸を含まないものであり、前記内装材において自動車内に露出する表層以外の少なくとも１層の不織ウェブ層は、この不織ウェブ層を構成する繊維を形成する重合体としてポリ乳酸を含むものであることを特徴とする自動車内装材のための表面部材。 (1) A surface member for an automobile interior material, in which a plurality of nonwoven webs are laminated and integrated by a needle punch, and the surface layer exposed in the automobile in the interior material constitutes this surface layer The non-woven web layer is a non-woven web layer that contains aromatic polyester and does not contain polylactic acid as the polymer that forms the fibers to be used, and that is not the surface layer exposed in the automobile in the interior material. A surface member for an automobile interior material characterized in that it contains polylactic acid as a polymer that forms the fibers constituting the glass.
（２）第１の表層と、この第１の表層とは反対側の第２の表層とを有し、これら第１及び第２の表層は、これら第１及び第２の表層の不織ウェブを構成する繊維を形成する重合体として芳香族ポリエステルを含みかつポリ乳酸を含まないものであり、第１の表層と第２の表層との間に単数または複数の中間不織ウェブが積層されており、この中間不織ウェブの少なくとも１つは、この中間不織ウェブを構成する繊維を形成する重合体としてポリ乳酸を含むものであることを特徴とする（１）の自動車内装材のための表面部材。 (2) It has a first surface layer and a second surface layer opposite to the first surface layer, and the first and second surface layers are nonwoven webs of the first and second surface layers. The polymer that forms the fibers constituting the fiber contains aromatic polyester and does not contain polylactic acid, and one or more intermediate nonwoven webs are laminated between the first surface layer and the second surface layer. And at least one of the intermediate nonwoven webs contains polylactic acid as a polymer for forming fibers constituting the intermediate nonwoven web, (1) A surface member for an automobile interior material .
（３）ポリ乳酸は、Ｌ−乳酸および／又はＤ−乳酸を含むものであり、融点が１２０℃以上であり、融解熱が１０Ｊ／ｇ以上であることを特徴とする（１）又は（２）の自動車内装材のための表面部材。 (3) Polylactic acid contains L-lactic acid and / or D-lactic acid, has a melting point of 120 ° C. or higher, and a heat of fusion of 10 J / g or higher (1) or (2 Surface members for automotive interior materials.
（４）芳香族ポリエステルの全酸成分の７０モル％以上が芳香族ジカルボン酸成分であることを特徴とする（１）から（３）までのいずれかの自動車内装材のための表面部材。 (4) The surface member for an automobile interior material according to any one of (1) to (3), wherein 70 mol% or more of the total acid component of the aromatic polyester is an aromatic dicarboxylic acid component.
本発明の自動車内装材のための表面部材は、ポリ乳酸を含んだ繊維を使用しながらも、芳香族ポリエステルを含みかつポリ乳酸を含まない繊維を特定の位置に配置したものであることにより、すなわち、自動車内に露出する表層がこの表層を構成する繊維を形成する重合体として芳香族ポリエステルを含みかつポリ乳酸を含まないものであることにより、強度、耐久性（耐湿熱分解性）、耐磨耗性に優れたものとすることができる。 The surface member for the automobile interior material of the present invention is a fiber that contains polylactic acid, and includes an aromatic polyester and a fiber that does not contain polylactic acid at a specific position. That is, the surface layer exposed in the automobile contains an aromatic polyester as a polymer that forms the fiber constituting the surface layer and does not contain polylactic acid, so that strength, durability (moisture and thermal decomposition resistance), It can be excellent in abrasion.
以下、本発明を詳細に説明する。
本発明の自動車内装材のための表面部材は、ニードルパンチ不織布にて構成されており、複数の不織ウェブによる積層構造を呈している。この表面部材において、自動車内に露出する表層は、この表層を構成する繊維を形成する重合体として芳香族ポリエステルを含みかつポリ乳酸を含まないものである。また自動車内に露出する表層以外の少なくとも１層の不織ウェブは、この不織ウェブを構成する繊維を形成する重合体としてポリ乳酸を含むものである。このような構成であるのは、ポリ乳酸にて形成された繊維は脆いため、表面部材における自動車内に露出する表層にポリ乳酸繊維が存在する場合は、実用に足るレベルの表面部材が得られないためである。
Hereinafter, the present invention will be described in detail.
The surface member for the automobile interior material of the present invention is composed of a needle punched nonwoven fabric and has a laminated structure of a plurality of nonwoven webs. In this surface member, the surface layer exposed in the automobile contains an aromatic polyester and does not contain polylactic acid as a polymer forming the fibers constituting the surface layer. In addition, the nonwoven web of at least one layer other than the surface layer exposed in the automobile contains polylactic acid as a polymer for forming fibers constituting the nonwoven web. This is because the fibers formed of polylactic acid are brittle, so if polylactic acid fibers are present in the surface layer exposed in the automobile of the surface member, a surface member having a practical level can be obtained. This is because there is not.
加えて、表面部材における自動車内に露出する表層にポリ乳酸繊維が存在する場合は、この表面部材を得るためのモールド加工時の熱処理でポリ乳酸繊維が溶融して、加工が不可能になることがある。このため、モールド加工に供する場合は、両側の表層において、この表層の構成繊維を形成する重合体として芳香族ポリエステルを含みかつポリ乳酸を含まないものであることが好適である。この場合は、構成繊維を形成する重合体としてポリ乳酸を含む不織ウェブは、両側の表層を形成する不織ウェブどうしの間に挟みこまれた状態で配置されることになる。 In addition, when polylactic acid fibers are present in the surface layer exposed in the automobile of the surface member, the polylactic acid fibers melt by heat treatment during molding to obtain this surface member, making the processing impossible. There is. For this reason, when it uses for a mold process, it is suitable for the surface layer of both sides to contain aromatic polyester as a polymer which forms the constituent fiber of this surface layer, and not to contain polylactic acid. In this case, the nonwoven web containing polylactic acid as a polymer forming the constituent fibers is arranged in a state of being sandwiched between the nonwoven webs forming the surface layers on both sides.
本発明の自動車内装材のための表面部材は、重合体としてポリ乳酸を含む繊維を用いたものでありながら、芳香族ポリエステルを含みかつポリ乳酸を含まない繊維を表層に配したものであるため、表面部材全体の強度、耐久性（耐湿熱分解性）、耐磨耗性、および特にモールド加工時の耐熱性に優れたものとなる。よって、これらの諸特性を備えた、自動車内装材のための表面部材とすることができる。 Since the surface member for the automobile interior material of the present invention uses fibers containing polylactic acid as a polymer, fibers containing aromatic polyester and not containing polylactic acid are arranged on the surface layer. The surface member as a whole has excellent strength, durability (moisture and thermal decomposition resistance), wear resistance, and particularly heat resistance during molding. Therefore, it can be set as the surface member for automobile interior materials provided with these various characteristics.
本発明の表面部材に含まれる繊維に使用されるポリ乳酸（ＰＬＡ）は、ポリＤ−乳酸、ポリＬ−乳酸、ポリＤ−乳酸とポリＬ−乳酸との共重合体であるポリＤＬ−乳酸、ポリＤ−乳酸とポリＬ−乳酸との混合物（ステレオコンプレックス）、ポリＤ−乳酸とヒドロキシカルボン酸との共重合体、ポリＬ−乳酸とヒドロキシカルボン酸との共重合体、ポリＤ−乳酸又はポリＬ−乳酸と脂肪族ジカルボン酸及び脂肪族ジオールとの共重合体、あるいはこれらのブレンド体であることが好ましい。そして、ポリ乳酸は、上記のようにＬ−乳酸とＤ−乳酸が単独で用いられているもの、もしくは併用されているものであるが、中でも融点が１２０℃以上、融解熱が１０Ｊ／ｇ以上であるものが耐熱性の点で好ましい。 The polylactic acid (PLA) used for the fibers contained in the surface member of the present invention is poly D-lactic acid, poly L-lactic acid, poly DL-lactic acid which is a copolymer of poly D-lactic acid and poly L-lactic acid. , Poly D-lactic acid and poly L-lactic acid mixture (stereo complex), poly D-lactic acid and hydroxycarboxylic acid copolymer, poly L-lactic acid and hydroxycarboxylic acid copolymer, poly D-lactic acid Alternatively, a copolymer of poly L-lactic acid, an aliphatic dicarboxylic acid and an aliphatic diol, or a blend thereof is preferable. The polylactic acid is one in which L-lactic acid and D-lactic acid are used alone or in combination as described above. Among them, the melting point is 120 ° C. or more, and the heat of fusion is 10 J / g or more. Is preferable from the viewpoint of heat resistance.
ポリ乳酸のホモポリマーであるＬ−乳酸やＤ−乳酸の融点は約１８０℃であるが、Ｄ−乳酸とＬ−乳酸との共重合体の場合は、いずれかの成分の割合を１０モル％程度とすると、融点はおよそ１３０℃程度となる。さらにいずれかの成分の割合を１８モル％以上とすると、融点が１２０℃未満、融解熱が１０Ｊ／ｇ未満となって、ほぼ完全に非晶性の性質となる。このような非晶性のポリマーとなると、製造工程において特に熱延伸し難くなり、高強度の繊維が得られ難くなるという問題が生じたり、繊維が得られたとしても耐熱性に劣ったものとなったりする。 The melting point of L-lactic acid and D-lactic acid, which are homopolymers of polylactic acid, is about 180 ° C., but in the case of a copolymer of D-lactic acid and L-lactic acid, the proportion of any component is 10 mol%. If it is about, melting | fusing point will be about 130 degreeC. Further, when the proportion of any of the components is 18 mol% or more, the melting point is less than 120 ° C., the heat of fusion is less than 10 J / g, and almost completely amorphous properties are obtained. When such an amorphous polymer is used, it becomes difficult to heat-stretch particularly in the production process, and it becomes difficult to obtain high-strength fibers, or even if fibers are obtained, heat resistance is inferior. It becomes.
そこで、ポリ乳酸としては、ラクチドを原料として重合する時のＬ−乳酸やＤ−乳酸の含有割合で示されるＬ−乳酸とＤ−乳酸の含有比（モル比）であるＬ／Ｄ又はＤ／Ｌが、８２以上／１８以下であるのものが好ましく、９０以上／１０以下であるものがより好ましく上、９５以上／５以下であるものがいっそう好ましい。ポリ乳酸とヒドロキシカルボン酸との共重合体である場合において、ヒドロキシカルボン酸の具体例としては、グリコール酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシカプロン酸、ヒドロキシペンタン酸、ヒドロキシヘプタン酸、ヒドロキシオクタン酸等が挙げられる。中でもヒドロキシカプロン酸又はグリコール酸を用いることがコスト面から好ましい。 Therefore, as polylactic acid, L / D or D / which is the content ratio (molar ratio) of L-lactic acid and D-lactic acid indicated by the content ratio of L-lactic acid or D-lactic acid when polymerizing using lactide as a raw material. L is preferably 82 or more / 18 or less, more preferably 90 or more and 10 or less, and further preferably 95 or more and 5 or less. In the case of a copolymer of polylactic acid and hydroxycarboxylic acid, specific examples of hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxypentanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid Etc. Of these, use of hydroxycaproic acid or glycolic acid is preferable from the viewpoint of cost.
ポリ乳酸と脂肪族ジカルボン酸及び脂肪族ジオールとの共重合体の場合において、脂肪族ジカルボン酸及び脂肪族ジオールとしては、セバシン酸、アジピン酸、ドデカン二酸、トリメチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール等が挙げられる。 In the case of a copolymer of polylactic acid, aliphatic dicarboxylic acid and aliphatic diol, examples of the aliphatic dicarboxylic acid and aliphatic diol include sebacic acid, adipic acid, dodecanedioic acid, trimethylene glycol, and 1,4-butane. Diol, 1,6-hexanediol, etc. are mentioned.
このようにポリ乳酸に他の成分を共重合させる場合は、ポリ乳酸を８０モル％以上とすることが好ましい。８０モル％未満であると、共重合ポリ乳酸の結晶性が低くなって、融点１２０℃未満、融解熱１０Ｊ／ｇ未満となりやすい。 Thus, when making polylactic acid copolymerize another component, it is preferable that polylactic acid shall be 80 mol% or more. When it is less than 80 mol%, the crystallinity of the copolymerized polylactic acid tends to be low, and the melting point is less than 120 ° C. and the heat of fusion is less than 10 J / g.
ポリ乳酸の分子量に関しては、分子量の指標として用いられる、ＡＳＴＭ Ｄ−１２３８法に準じ、温度２１０℃、荷重２１．２Ｎ（２１６０ｇ）で測定したメルトフローレートが、１〜１００ｇ／１０分であることが好ましく、より好ましくは５〜５０ｇ／１０分である。メルトフローレートをこの範囲とすることにより、強度、湿熱分解性が向上する。 Regarding the molecular weight of polylactic acid, the melt flow rate measured at a temperature of 210 ° C. and a load of 21.2 N (2160 g) is 1 to 100 g / 10 min in accordance with the ASTM D-1238 method used as an index of molecular weight. Is more preferable, and 5 to 50 g / 10 min is more preferable. By setting the melt flow rate within this range, strength and wet heat decomposability are improved.
ポリ乳酸の耐久性を高める目的で、ポリ乳酸に、脂肪族アルコール、カルボジイミド化合物、オキサゾリン化合物、オキサジン化合物、エポキシ化合物などの末端封鎖剤を添加してもよい。 For the purpose of improving the durability of polylactic acid, endblockers such as aliphatic alcohols, carbodiimide compounds, oxazoline compounds, oxazine compounds, and epoxy compounds may be added to polylactic acid.
本発明の目的を損なわない範囲であれば、必要に応じて、ポリ乳酸に、熱安定剤、結晶核剤、艶消剤、顔料、耐光剤、耐候剤、滑剤、酸化防止剤、抗菌剤、香料、可塑剤、染料、界面活性剤、難燃剤、表面改質剤、各種無機及び有機電解質、その他類似の添加剤を添加してもよい。 As long as it does not impair the purpose of the present invention, if necessary, polylactic acid, heat stabilizer, crystal nucleating agent, matting agent, pigment, light-proofing agent, weathering agent, lubricant, antioxidant, antibacterial agent, A fragrance, a plasticizer, a dye, a surfactant, a flame retardant, a surface modifier, various inorganic and organic electrolytes, and other similar additives may be added.
本発明の表面部材に含まれる繊維に使用される芳香族ポリエステルとしては、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート、ポリトリメチレンテレフタレートなどのポリアルキレンテレフタレートを主体としたポリエステルが挙げられる。このポリエステルは、イソフタル酸、５−スルホイソフタル酸などの芳香族ジカルボン酸や、アジピン酸、コハク酸、スベリン酸、セバシン酸、ドデカン二酸などの脂肪族ジカルボン酸や、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノールなどの脂肪族ジオールや、グリコール酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシカプロン酸、ヒドロキシペンタン酸、ヒドロキシヘプタン酸、ヒドロキシオクタン酸などのヒドロキシカルボン酸や、ε−カプロラクトンなどの脂肪族ラクトン等を共重合していてもよい。 Examples of the aromatic polyester used for the fibers contained in the surface member of the present invention include polyesters mainly composed of polyalkylene terephthalates such as polyethylene terephthalate (PET), polybutylene terephthalate, and polytrimethylene terephthalate. This polyester includes aromatic dicarboxylic acids such as isophthalic acid and 5-sulfoisophthalic acid, aliphatic dicarboxylic acids such as adipic acid, succinic acid, suberic acid, sebacic acid and dodecanedioic acid, ethylene glycol, propylene glycol, 1 Aliphatic diols such as 1,4-butanediol and 1,4-cyclohexanedimethanol, and hydroxycarboxylic acids such as glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxypentanoic acid, hydroxyheptanoic acid and hydroxyoctanoic acid Alternatively, an aliphatic lactone such as ε-caprolactone may be copolymerized.
芳香族ポリエステルは、芳香族ジカルボン酸成分が全酸成分の７０モル％以上であることが好ましい。芳香族ジカルボン酸成分が全酸成分に対して７０モル％未満であると、芳香族ポリエステルの耐湿熱分解性、耐候性などが低下しやすくなる。 In the aromatic polyester, the aromatic dicarboxylic acid component is preferably 70 mol% or more of the total acid component. When the aromatic dicarboxylic acid component is less than 70 mol% with respect to the total acid component, the wet heat decomposition resistance and weather resistance of the aromatic polyester are likely to be lowered.
ポリ乳酸の場合と同様に、芳香族ポリエステルには、本発明の目的を損なわない範囲であれば、必要に応じて、熱安定剤、結晶核剤、艶消剤、顔料、耐光剤、耐候剤、滑剤、酸化防止剤、抗菌剤、香料、可塑剤、染料、界面活性剤、難燃剤、表面改質剤、各種無機及び有機電解質、その他類似の添加剤を添加することができる。 As in the case of polylactic acid, the aromatic polyester has a heat stabilizer, a crystal nucleating agent, a matting agent, a pigment, a light-proofing agent, and a weathering agent as necessary, as long as the object of the present invention is not impaired. , Lubricants, antioxidants, antibacterial agents, fragrances, plasticizers, dyes, surfactants, flame retardants, surface modifiers, various inorganic and organic electrolytes, and other similar additives.
次に、本発明の自動車内装材のための表面部材を構成する繊維の形態について説明する。本発明においては、たとえば一種類のポリ乳酸と一種類の芳香族ポリエステルとをそれぞれ単独で使用して単相形態のポリ乳酸繊維、芳香族ポリエステル繊維を形成し、これらの繊維を単独で使用したり混繊状態で使用したりすることによって、不織ウェブを構成することができる。 Next, the form of the fibers constituting the surface member for the automobile interior material of the present invention will be described. In the present invention, for example, one type of polylactic acid and one type of aromatic polyester are each used alone to form single-phase polylactic acid fibers and aromatic polyester fibers, and these fibers are used alone. A nonwoven web can be constituted by using it in a mixed fiber state.
あるいは、同種もしくは異種のポリ乳酸を複合した複合繊維や、同種もしくは異種の芳香族ポリエステルを複合した複合繊維によって、不織ウェブを構成することもできる。この場合は、上述したモールド成形時に熱処理を行い、複合繊維における低融点成分を溶融させて使用することもできる。 Alternatively, the nonwoven web can be constituted by a composite fiber composited with the same or different polylactic acid or a composite fiber composited with the same or different aromatic polyester. In this case, heat treatment can be performed at the time of molding described above, and the low melting point component in the composite fiber can be melted and used.
本発明において使用する繊維の断面形状は、任意である。すなわち、丸断面に限定されるものではなく、扁平断面、多角形断面、多葉形断面、ひょうたん形断面、アルファベット形（Ｔ形、Ｙ形等）断面、井形断面等の各種の異形のものであってもよい。また、これらの形状において中空部を有するものでもよい。 The cross-sectional shape of the fiber used in the present invention is arbitrary. In other words, it is not limited to a round cross section, but has various shapes such as a flat cross section, a polygon cross section, a multilobal cross section, a gourd cross section, an alphabetic (T-shaped, Y-shaped, etc.) cross section, and a well-shaped cross section. There may be. Moreover, you may have a hollow part in these shapes.
その他の糸質として、捲縮数は５個／２５ｍｍ〜２５個／２５ｍｍであることが好ましく、捲縮率は５〜３０％であることが好ましい。繊度（単糸繊度）は１〜１００ｄｔｅｘであることが好ましく、繊維長は５〜１５０ｍｍ程度であることが好ましい。ただし、これらに限定されるものではない。 As other yarn quality, the number of crimps is preferably 5/25 mm to 25/25 mm, and the crimp rate is preferably 5 to 30%. The fineness (single yarn fineness) is preferably 1 to 100 dtex, and the fiber length is preferably about 5 to 150 mm. However, it is not limited to these.
本発明の自動車内装材のための表面部材は、ポリ乳酸繊維と芳香族ポリエステル繊維のみの使用でもよいが、本発明の目的を損なわない範囲で他の繊維を混用してもよい。混用する他の繊維としては、ナイロン、アクリル、アラミド等の合成繊維や、ビスコース、キュプラ、ポリノジック等のレーヨン系繊維や、リヨセル等の溶剤紡糸セルロース繊維や、絹、綿、麻、羊毛その他の獣毛繊維等の天然繊維などが挙げられる。 The surface member for the automobile interior material of the present invention may be a polylactic acid fiber and an aromatic polyester fiber alone, but other fibers may be mixed within a range not impairing the object of the present invention. Other mixed fibers include synthetic fibers such as nylon, acrylic and aramid, rayon fibers such as viscose, cupra and polynosic, solvent-spun cellulose fibers such as lyocell, silk, cotton, hemp, wool and other Examples thereof include natural fibers such as animal hair fibers.
以下、実施例により本発明を具体的に説明する。なお、下記の実施例、比較例における各物性値の測定方法及び評価方法は、次のとおりである。 Hereinafter, the present invention will be described specifically by way of examples. In addition, the measuring method and evaluation method of each physical property value in the following Examples and Comparative Examples are as follows.
（１）ポリ乳酸のメルトフローレート値（ｇ／１０分）：前記のように、ＡＳＴＭ Ｄ−１２３８法に準じ、温度２１０℃、荷重２１．２Ｎ（２１６０ｇ）で測定した。 (1) Melt flow rate value of polylactic acid (g / 10 min): As described above, it was measured at a temperature of 210 ° C. and a load of 21.2 N (2160 g) according to the ASTM D-1238 method.
（２）芳香族ポリエステル及びポリ乳酸の相対粘度：フェノールと四塩化エタンの等質量混合物を溶媒とし、ウベローデ粘度計を使用して、試料濃度０．５ｇ／１００ｃｃ、温度２０℃の条件で測定した。 (2) Relative viscosity of aromatic polyester and polylactic acid: Measured under the conditions of a sample concentration of 0.5 g / 100 cc and a temperature of 20 ° C. using an Ubbelohde viscometer with an equal mass mixture of phenol and ethane tetrachloride as a solvent. .
（３）芳香族ポリエステル及びポリ乳酸の融点（℃）、ポリ乳酸の融解熱（Ｊ／ｇ）：パーキンエルマー社製の示差走査熱量計ＤＳＣ−２型を使用し、昇温速度２０℃／分の条件で測定した。 (3) Melting point (° C.) of aromatic polyester and polylactic acid, heat of fusion of polylactic acid (J / g): using differential scanning calorimeter DSC-2 manufactured by Perkin Elmer, temperature increase rate 20 ° C./min It measured on condition of this.
（４）ポリ乳酸のＬ−乳酸とＤ−乳酸の含有比（モル比）：超純水と１Ｎの水酸化ナトリウムのメタノール溶液との等質量混合溶液を溶媒とし、高速液体クロマトグラフィー（ＨＰＬＣ）法により測定した。カラムにはｓｕｍｉｃｈｉｒａｌ ＯＡ６１００を使用し、ＵＶ吸収測定装置により検出した。 (4) Content ratio (molar ratio) of L-lactic acid and D-lactic acid in polylactic acid: high-performance liquid chromatography (HPLC) using an equimass mixed solution of ultrapure water and 1N sodium hydroxide in methanol as a solvent. Measured by the method. The column used was sumichiral OA6100, and was detected by a UV absorption measuring device.
（５）単繊維繊度（ｄｔｅｘ）：ＪＩＳ Ｌ−１０１５ 正量繊度Ａ法に準じて測定した。 (5) Single fiber fineness (dtex): measured according to JIS L-1015 positive fineness A method.
（６）単繊維強度（ｃＮ／ｄｔｅｘ）：ＪＩＳ Ｌ−１０１５に規定される引張強さの標準時試験法に従って測定した。 (6) Single fiber strength (cN / dtex): Measured according to the standard test method for tensile strength specified in JIS L-1015.
（７）単繊維捲縮数（個／２５ｍｍ）、捲縮率（％）：ＪＩＳ Ｌ−１０１５ 捲縮の捲縮数及び捲縮率に準じて測定した。なお、１５０℃乾熱処理後の捲縮数は、複合繊維を２ｍｇ／ｄｔｅｘの荷重下で１５０℃、１５分間熱処理した後に測定した。 (7) Number of crimps of single fibers (pieces / 25 mm), crimp rate (%): Measured according to the number of crimps and crimp rate of JIS L-1015 crimp. The number of crimps after 150 ° C. dry heat treatment was measured after heat treating the composite fiber at 150 ° C. for 15 minutes under a load of 2 mg / dtex.
（８）表面部材の強力（Ｎ／５０ｍｍ幅）：ＪＩＳ Ｌ−１９０６ 一般長繊維不織布の標準時試験に準じて測定した。
強力が５００Ｎ／５０ｍｍ幅以上のものを、実用に足るレベルであると評価した。
(8) Strength of surface member (N / 50 mm width): Measured according to a standard time test of JIS L-1906 non-woven fabric.
Those having a strength of 500 N / 50 mm width or more were evaluated as being practically sufficient.
（９）表面部材の耐湿熱分解性（％）：試料を５０℃、９５％相対湿度の条件下で１０００時間保持し、処理前の強力に対する処理後の強力の比を次式にて算出することにより耐湿熱分解性を求めた。なお、これらの強力は、前記の(８)にしたがって測定した。 (9) Moisture and thermal decomposition resistance (%) of surface member: A sample is held for 1000 hours under conditions of 50 ° C. and 95% relative humidity, and the ratio of strength after treatment to strength before treatment is calculated by the following equation. Thus, the resistance to wet thermal decomposition was determined. These strengths were measured according to the above (8).
耐湿熱分解性＝（処理後強力／処理前強力）×１００
耐湿熱分解性が７０％以上のものを、実用に足るレベルであると評価した。
Resistance to heat and moisture decomposition = (Strength after treatment / Strength before treatment) x 100
Those having a heat and heat resistance of 70% or more were evaluated as being practically satisfactory.
（１０）表面部材の耐磨耗性：ＪＩＳ Ｌ−１０９６ 磨耗強さＣ法（テーバ形法）に準じて、荷重を５００ｇ、回転の数を３００回として磨耗試験を実施した。実施後の試料の表面状態を目視で確認して、ＪＩＳ Ｌ−１９０６に規定される限度写真と比較して等級付けを行い、下記の基準で評価した。 (10) Abrasion resistance of surface member: According to JIS L-1096 abrasion strength C method (Taber method), a wear test was performed with a load of 500 g and a rotation number of 300 times. The surface condition of the sample after the implementation was visually confirmed, graded in comparison with a limit photograph defined in JIS L-1906, and evaluated according to the following criteria.
◎：５級以上
○：４級を超え５級未満
×：４級以下
◎: 5th grade or higher ○: Over 4th grade and under 5th grade ×: 4th grade or less
（１１）表面部材のモールド加工時の耐熱性：円錐形で先端が丸く形成されたピストンと、これに対応する凹部（径１２０ｍｍ、深さ８０ｍｍ）とからなる金型を準備した。また５０ｃｍ×２５ｃｍの大きさの試料を準備し、これを保持枠の内部に固定した。 (11) Heat resistance during molding of surface member: A mold having a conical piston with a rounded tip and a corresponding recess (diameter 120 mm, depth 80 mm) was prepared. A sample having a size of 50 cm × 25 cm was prepared, and this was fixed inside the holding frame.
そして保持枠の内部に固定された試料を保持枠とともに１９０℃の高温雰囲気のもとに６０秒間おき、その後ただちに試料を保持枠とともに金型の凹部を覆うように固定し、この状態で常温のピストンを常温の凹部に向けて加圧することで成形を行った。 Then, the sample fixed inside the holding frame is placed together with the holding frame in a high-temperature atmosphere of 190 ° C. for 60 seconds, and immediately after that, the sample is fixed together with the holding frame so as to cover the concave portion of the mold. Molding was performed by pressurizing the piston toward the concave portion at room temperature.
ピストンによる加圧を行った後、１０秒間放置し、その後に成形試料を保持枠とともに金型から取り出した。そして、成形試料が十分に冷却したことを確認したうえで、これを保持枠から取り外した。 After pressurizing with a piston, it was left for 10 seconds, and then the molded sample was taken out of the mold together with the holding frame. Then, after confirming that the molded sample was sufficiently cooled, it was removed from the holding frame.
この状態の成形試料の外観を目視により観察して、そのモールド加工時の耐熱性を次の３段階で評価した。
◎：試料が均等に伸び、きれいに成形されており、耐熱性は良好
○：試料に破れはないものの、一部均等に伸びていない部分があり、先端が若干薄くなっているが、耐熱性は良好
×：試料に破れが生じている、もしくは加熱により繊維が溶融し成形が不可能であり、耐熱性は劣る
The appearance of the molded sample in this state was visually observed, and the heat resistance during the molding was evaluated in the following three stages.
◎: The sample is evenly stretched and neatly shaped, and heat resistance is good. ○: Although the sample is not torn, there is a part that is not evenly stretched and the tip is slightly thin, but the heat resistance is Good x: The sample is torn or the fiber is melted by heating and cannot be molded, and the heat resistance is poor.
実施例１
融点が２００℃、融解熱が３８Ｊ／ｇ、Ｌ−乳酸とＤ−乳酸の含有比であるＬ／Ｄが９８．５／１．５（モル比）、メルトフローレート値が２３ｇ／１０分、相対粘度が１．８５のポリ乳酸を用い、紡糸温度２２０℃で溶融紡糸を行った。紡出糸条を冷却した後、引取速度１０００ｍ／分で引き取って未延伸糸条を得た。得られた糸条を集束して３３万ｄｅｔｅｘのトウにし、延伸倍率３．２倍、温度６０℃で延伸し、温度１１０℃のヒートドラムで熱処理してから押し込み式クリンパーを使用して機械捲縮を付与した後、繊維長５１ｍｍに切断して、ポリ乳酸短繊維を得た。得られたポリ乳酸短繊維は、繊度（単繊維繊度）が３．３ｄｔｅｘの丸断面形状のものであり、捲縮数１１．２個／２５ｍｍ、捲縮率１１．１％、強度３．３１ｃＮ／ｄｔｅｘであった。
Example 1
The melting point is 200 ° C., the heat of fusion is 38 J / g, the content ratio of L-lactic acid and D-lactic acid is 98.5 / 1.5 (molar ratio), the melt flow rate value is 23 g / 10 minutes, Using polylactic acid having a relative viscosity of 1.85, melt spinning was performed at a spinning temperature of 220 ° C. After cooling the spun yarn, it was drawn at a take-up speed of 1000 m / min to obtain an undrawn yarn. The obtained yarn is converged into a tow of 330,000 detex, drawn at a draw ratio of 3.2 times and at a temperature of 60 ° C., heat-treated with a heat drum at a temperature of 110 ° C. After the crimping, the fiber length was cut to 51 mm to obtain polylactic acid short fibers. The obtained polylactic acid short fibers have a round cross-sectional shape with a fineness (single fiber fineness) of 3.3 dtex, a number of crimps of 11.2 pieces / 25 mm, a crimping rate of 11.1%, and a strength of 3.31 cN. / Dtex.
相対粘度が１．３０５、融点が２５５℃の芳香族ポリエステルであるＰＥＴ（全酸成分が芳香族ジカルボン酸成分）を用い、紡糸温度２７０℃で溶融紡糸を行った。紡出糸条を冷却した後、引取速度１０００ｍ／分で引き取って未延伸糸条を得た。得られた糸条を集束して３３万ｄｅｔｅｘのトウにし、延伸倍率３．２倍、温度６０℃で延伸し、温度１６０℃のヒートドラムで熱処理してから押し込み式クリンパーを使用して機械捲縮を付与した後、繊維長５１ｍｍに切断し、芳香族ポリエステル短繊維を得た。得られた芳香族ポリエステル短繊維は、繊度（単繊維繊度）が３．３ｄｔｅｘの丸断面形状のものであり、捲縮数1２.２個／２５ｍｍ、捲縮１２．２％、強度４．３８ｃＮ／ｄｔｅｘであった。 PET, which is an aromatic polyester having a relative viscosity of 1.305 and a melting point of 255 ° C. (all acid components are aromatic dicarboxylic acid components), was melt-spun at a spinning temperature of 270 ° C. After cooling the spun yarn, it was drawn at a take-up speed of 1000 m / min to obtain an undrawn yarn. The resulting yarn is converged into a tow of 330,000 detex, drawn at a draw ratio of 3.2 times, at a temperature of 60 ° C., heat treated with a heat drum at a temperature of 160 ° C., and then subjected to a mechanical crimp using a push-in crimper. After the shrinkage was imparted, the fiber was cut into a fiber length of 51 mm to obtain an aromatic polyester short fiber. The obtained aromatic polyester short fibers have a round cross-sectional shape with a fineness (single fiber fineness) of 3.3 dtex, a crimp number of 12.2 pieces / 25 mm, a crimp of 12.2%, and a strength of 4.38 cN. / Dtex.
これらのポリ乳酸短繊維と芳香族ポリエステル短繊維とをカード機にかけウェブとした後、第１の芳香族ポリエステルの短繊維ウェブと、ポリ乳酸の短繊維ウェブと、第２の芳香族ポリエステルの短繊維ウェブとを積層したうえでニードルパンチ加工を行い、目付け４００ｇ／ｍ２、ニードルパンチ数２５０回／ｃｍ２の、本発明の自動車内装材のための表面部材を得た。この表面部材は、上層が芳香族ポリエステル短繊維のみから構成され、中層がポリ乳酸短繊維のみから構成され、下層が芳香族ポリエステル短繊維のみから構成された３層の積層構造を呈したものであり、上層、中層、下層の目付は、それぞれ、１５０ｇ／ｍ２、１００ｇ／ｍ２、１５０ｇ／ｍ２であった。 After these polylactic acid short fibers and aromatic polyester short fibers are put on a card machine to form a web, the first aromatic polyester short fiber web, the polylactic acid short fiber web, and the second aromatic polyester short fiber After laminating the fiber web, needle punching was performed to obtain a surface member for an automobile interior material of the present invention having a basis weight of 400 g / m 2 and a needle punch number of 250 times / cm 2 . This surface member has a three-layer laminated structure in which the upper layer is composed only of aromatic polyester staple fibers, the middle layer is composed only of polylactic acid staple fibers, and the lower layer is composed only of aromatic polyester staple fibers. Yes, the basis weights of the upper layer, middle layer, and lower layer were 150 g / m 2 , 100 g / m 2 , and 150 g / m 2 , respectively.
実施例２
目付を、上層、中層、下層の順に、１００ｇ／ｍ２、２００ｇ／ｍ２、１００ｇ／ｍ２とした。それ以外は実施例１と同様にして、実施例２の、本発明の自動車の内装材のための表面部材を得た。
Example 2
The basis weight, the upper layer, middle layer, in the order of the lower layer, and a 100g / m 2, 200g / m 2, 100g / m 2. Other than that was carried out similarly to Example 1, and obtained the surface member for the interior material of the motor vehicle of Example 2 of Example 2. FIG.
実施例３
目付を、上層、中層、下層の順に、５０ｇ／ｍ２、３００ｇ／ｍ２、５０ｇ／ｍ２とした。それ以外は実施例１と同様にして、実施例３の、本発明の自動車の内装材のための表面部材を得た。
Example 3
The basis weight, the upper layer, middle layer, in the order of the lower layer was a 50g / m 2, 300g / m 2, 50g / m 2. Other than that was carried out similarly to Example 1, and obtained the surface member for the interior material of the motor vehicle of Example 3 of Example 3. FIG.
実施例４
上層が芳香族ポリエステル短繊維のみから構成され、中層が芳香族ポリエステル短繊維のみから構成され、下層がポリ乳酸短繊維のみから構成された３層の積層構造とし、目付を、上層、中層、下層の順に、１００ｇ／ｍ２、１００ｇ／ｍ２、２００ｇ／ｍ２とした。それ以外は実施例１と同様にして、実施例４の、本発明の自動車の内装材のための表面部材を得た。
Example 4
The upper layer is composed only of aromatic polyester short fibers, the middle layer is composed only of aromatic polyester short fibers, and the lower layer is composed of only polylactic acid short fibers, and the basis weight is the upper layer, middle layer, lower layer In this order, they were 100 g / m 2 , 100 g / m 2 , and 200 g / m 2 . Other than that was carried out similarly to Example 1, and obtained the surface member for the interior material of the motor vehicle of Example 4 of Example 4. FIG.
実施例５
上層が芳香族ポリエステル短繊維のみから構成され、中層がポリ乳酸短繊維のみから構成され、下層がポリ乳酸短繊維のみから構成された３層の積層構造とし、目付を、上層、中層、下層の順に、１００ｇ／ｍ２、１００ｇ／ｍ２、２００ｇ／ｍ２とした。それ以外は実施例１と同様にして、実施例５の、本発明の自動車の内装材のための表面部材を得た。
Example 5
The upper layer is composed of only aromatic polyester short fibers, the middle layer is composed only of polylactic acid short fibers, and the lower layer is composed of only polylactic acid short fibers, and the basis weight is the upper layer, middle layer, lower layer In order, they were set to 100 g / m 2 , 100 g / m 2 , and 200 g / m 2 . Other than that was carried out similarly to Example 1, and obtained the surface member for the interior material of the motor vehicle of Example 5 of Example 5. FIG.
実施例６
上層が芳香族ポリエステル短繊維のみから構成され、中層が芳香族ポリエステル短繊維のみから構成され、下層がポリ乳酸短繊維のみから構成された３層の積層構造とし、目付を、上層、中層、下層の順に、１５０ｇ／ｍ２、１５０ｇ／ｍ２、１００ｇ／ｍ２とした。それ以外は実施例１と同様にして、実施例６の、本発明の自動車の内装材のための表面部材を得た。
Example 6
The upper layer is composed of only aromatic polyester short fibers, the middle layer is composed only of aromatic polyester short fibers, and the lower layer is composed of only polylactic acid short fibers, and the basis weight is the upper layer, middle layer, lower layer In this order, they were 150 g / m 2 , 150 g / m 2 , and 100 g / m 2 . Other than that was carried out similarly to Example 1, and obtained the surface member for the interior material of the motor vehicle of Example 6 of Example 6. FIG.
比較例１
上層がポリ乳酸短繊維のみから構成され、中層が芳香族ポリエステル短繊維のみから構成され、下層が芳香族ポリエステル短繊維のみから構成された３層の積層構造とし、目付を、上層、中層、下層の順に、１００ｇ／ｍ２、１５０ｇ／ｍ２、１５０ｇ／ｍ２とした。それ以外は実施例１と同様にして、比較例１の表面部材を得た。
Comparative Example 1
The upper layer is composed of only polylactic acid short fibers, the middle layer is composed only of aromatic polyester staple fibers, and the lower layer is composed of only aromatic polyester staple fibers, and the basis weight is the upper layer, middle layer, lower layer in the order of, was 100g / m 2, 150g / m 2, 150g / m 2. Other than that was carried out similarly to Example 1, and obtained the surface member of the comparative example 1.
実施例１〜６、比較例１の表面部材についての評価結果は、表１に示すとおりであった。
表１から明らかなように、実施例１〜３の表面部材は、強力、耐久性（耐湿熱分解性）、耐磨耗性、モールド加工時の耐熱性とも実用に足るレベルであった。
The evaluation results for the surface members of Examples 1 to 6 and Comparative Example 1 were as shown in Table 1.
As is apparent from Table 1, the surface members of Examples 1 to 3 were at levels sufficient for practical use in terms of strength, durability (moisture and thermal decomposition resistance), wear resistance, and heat resistance during molding.
実施例４〜６の表面部材は、強力、耐久性（耐湿熱分解性）、耐磨耗性とも実用に足るレベルであった。しかし、ポリ乳酸繊維の一部が下層に露出していたため、熱成形時にポリ乳酸繊維が溶融してしまい、モールド加工時の耐熱性は良好とはいえないものであった。このため、モールド加工を施さない自動車内装材のための表面部材として使用できるものであった。 The surface members of Examples 4 to 6 were at levels sufficient for practical use in terms of strength, durability (moisture and heat decomposition resistance), and wear resistance. However, since a part of the polylactic acid fiber was exposed in the lower layer, the polylactic acid fiber melted during thermoforming, and the heat resistance during molding was not good. For this reason, it can be used as a surface member for an automobile interior material not subjected to molding.
比較例１の表面部材は、ポリ乳酸繊維の一部が上層に露出していたため、熱成形時にポリ乳酸繊維が溶融してしまってモールド加工時の耐熱性が良好とはいえないものであるうえに、耐磨耗性も劣っており、自動車内装材のための表面部材として使用できるものではなかった。 In the surface member of Comparative Example 1, since a part of the polylactic acid fiber is exposed in the upper layer, the polylactic acid fiber is melted at the time of thermoforming and the heat resistance at the time of molding cannot be said to be good. In addition, the wear resistance is also inferior, and it cannot be used as a surface member for automobile interior materials.
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| JP2010270425A (en) * | 2009-05-25 | 2010-12-02 | Toyota Motor Corp | Needle punch nonwoven fabric |
| JP2011152684A (en) * | 2010-01-27 | 2011-08-11 | Suminoe Textile Co Ltd | Car carpet made of component derived from vegetable |
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|---|---|---|---|---|
| JPH08300533A (en) * | 1995-05-11 | 1996-11-19 | Bridgestone Corp | Fiber formed article and automobile interior material |
| JP2001055653A (en) * | 1999-06-07 | 2001-02-27 | Kureha Ltd | Interior material made of nonwoven fabric |
| JP2006057197A (en) * | 2004-08-19 | 2006-03-02 | Unitika Ltd | Polylactic acid nonwoven fabric |
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| JP2010270425A (en) * | 2009-05-25 | 2010-12-02 | Toyota Motor Corp | Needle punch nonwoven fabric |
| WO2010137514A1 (en) * | 2009-05-25 | 2010-12-02 | 東レ株式会社 | Needle-punched nonwoven fabric |
| CN102395719A (en) * | 2009-05-25 | 2012-03-28 | 东丽株式会社 | Needle-punched nonwoven fabric |
| CN102395719B (en) * | 2009-05-25 | 2014-08-13 | 东丽株式会社 | Needle-punched nonwoven fabric |
| US9279202B2 (en) | 2009-05-25 | 2016-03-08 | Toray Industries, Inc. | Needle-punched nonwoven fabric |
| JP2011152684A (en) * | 2010-01-27 | 2011-08-11 | Suminoe Textile Co Ltd | Car carpet made of component derived from vegetable |
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