JP5560576B2 - Resin composition and resin molded product - Google Patents
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- 239000011342 resin composition Substances 0.000 title claims description 31
- 229920005989 resin Polymers 0.000 title claims description 20
- 239000011347 resin Substances 0.000 title claims description 20
- 239000003963 antioxidant agent Substances 0.000 claims description 42
- 230000003078 antioxidant effect Effects 0.000 claims description 40
- 239000000835 fiber Substances 0.000 claims description 29
- 239000003112 inhibitor Substances 0.000 claims description 27
- 229920006167 biodegradable resin Polymers 0.000 claims description 24
- 230000007062 hydrolysis Effects 0.000 claims description 24
- 238000006460 hydrolysis reaction Methods 0.000 claims description 24
- -1 polybutylene succinate Polymers 0.000 claims description 17
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 239000004626 polylactic acid Substances 0.000 claims description 8
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 5
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 5
- 240000000797 Hibiscus cannabinus Species 0.000 claims description 5
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 5
- 239000011425 bamboo Substances 0.000 claims description 5
- 229920002961 polybutylene succinate Polymers 0.000 claims description 5
- 239000004631 polybutylene succinate Substances 0.000 claims description 5
- 240000008564 Boehmeria nivea Species 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000000465 moulding Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 241001330002 Bambuseae Species 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004071 soot Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 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 2
- 241000196324 Embryophyta Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- IUPHTVOTTBREAV-UHFFFAOYSA-N 3-hydroxybutanoic acid;3-hydroxypentanoic acid Chemical compound CC(O)CC(O)=O.CCC(O)CC(O)=O IUPHTVOTTBREAV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 235000011624 Agave sisalana Nutrition 0.000 description 1
- 229920013642 Biopol™ Polymers 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- JEQPWXGHMRFTRF-UHFFFAOYSA-N n,n'-bis(2-methylpropyl)methanediimine Chemical compound CC(C)CN=C=NCC(C)C JEQPWXGHMRFTRF-UHFFFAOYSA-N 0.000 description 1
- NASVTBDJHWPMOO-UHFFFAOYSA-N n,n'-dimethylmethanediimine Chemical compound CN=C=NC NASVTBDJHWPMOO-UHFFFAOYSA-N 0.000 description 1
- NWBVGPKHJHHPTA-UHFFFAOYSA-N n,n'-dioctylmethanediimine Chemical compound CCCCCCCCN=C=NCCCCCCCC NWBVGPKHJHHPTA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Description
本発明は、樹脂組成物及び樹脂成形品に関するものである。 The present invention relates to a resin composition and a resin molded product.
生分解性樹脂を含有する樹脂組成物、及び該樹脂組成物を用いた成形品としては、分解性樹脂からなるバインダー繊維と、天然繊維とを混合してなる繊維複合材において、天然繊維表面上に加水分解防止剤、望ましくはカルボジイミドを被覆し、耐加水分解性を効果的に高めた生分解性樹脂繊維と天然繊維の複合材が提案されている（例えば、特許文献１参照）。また、生分解性を有する有機高分子化合物と、植物繊維と、生分解性を有する有機高分子化合物の加水分解抑制剤とを含有する複合組成物、及びこれを用いた成形品が提案されている（例えば、特許文献２参照）。 As a resin composition containing a biodegradable resin, and a molded product using the resin composition, a fiber composite material obtained by mixing a binder fiber made of a degradable resin and a natural fiber is used. A composite material of a biodegradable resin fiber and a natural fiber, which is coated with a hydrolysis inhibitor, preferably carbodiimide, and has effectively improved hydrolysis resistance, has been proposed (for example, see Patent Document 1). In addition, a composite composition containing a biodegradable organic polymer compound, plant fibers, and a biodegradable organic polymer compound hydrolysis inhibitor, and a molded article using the same are proposed. (For example, refer to Patent Document 2).
更に、優れた機械的強度と耐熱性とを有し、成形性と成形品の色相とが優れたポリ乳酸樹脂組成物が提案されている（例えば、特許文献３参照）。 Furthermore, a polylactic acid resin composition having excellent mechanical strength and heat resistance and excellent moldability and hue of a molded product has been proposed (see, for example, Patent Document 3).
本発明は、機械的強度を維持しつつ、難燃性を向上させた樹脂組成物を提供することを課題とする。 This invention makes it a subject to provide the resin composition which improved the flame retardance, maintaining mechanical strength.
上記課題は、以下の手段により解決された。
即ち、請求項１に係る発明は、
（Ａ）生分解性樹脂、（Ｂ）天然繊維、（Ｃ）加水分解抑制剤、及び（Ｄ）酸化防止剤を含有し、
前記（Ａ）生分解性樹脂の含有量は、６５．２５質量％以上７６．５５質量％以下であり、
前記（Ｂ）天然繊維の含有量は、２０質量％以上３０質量％以下であり、
前記（Ｃ）加水分解抑制剤の含有量は、２質量％以上４質量％以下であり、
前記（Ｄ）酸化防止剤は、ヒンダードフェノール系酸化防止剤及びリン系酸化防止剤を含み、かつ前記（Ｄ）酸化防止剤の含有量は、０．４５質量％以上１．５質量％以下であることを特徴とする樹脂組成物である。
The above problems have been solved by the following means.
That is, the invention according to claim 1
(A) a biodegradable resin, (B) a natural fiber, (C) a hydrolysis inhibitor, and (D) an antioxidant,
Content of said (A) biodegradable resin is 65.25 mass% or more and 76.55 mass% or less,
The content of the (B) natural fiber is 20% by mass or more and 30% by mass or less,
The content of the (C) hydrolysis inhibitor is 2% by mass or more and 4% by mass or less,
The (D) antioxidant contains a hindered phenol antioxidant and a phosphorus antioxidant, and the content of the (D) antioxidant is 0.45 mass% or more and 1.5 mass% or less. It is a resin composition characterized by being.
請求項２に係る発明は、
前記（Ａ）生分解性樹脂が、少なくとも、ポリ乳酸、３−ヒドロキシ酪酸と３−ヒドロキシ吉草酸との共重合体、ポリブチレンサクシネートから選択される１種であることを特徴とする請求項１に記載の樹脂組成物である。
The invention according to claim 2
The biodegradable resin (A) is at least one selected from polylactic acid, a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid, and polybutylene succinate. 1. The resin composition according to 1.
請求項３に係る発明は、
前記（Ｃ）加水分解抑制剤が、カルボジイミド化合物、及びイソシアネート系化合物から選択される少なくとも一種であることを特徴とする請求項１又は請求項２に記載の樹脂組成物である。
The invention according to claim 3
The resin composition according to claim 1 or 2, wherein the (C) hydrolysis inhibitor is at least one selected from a carbodiimide compound and an isocyanate compound.
請求項４に係る発明は、
前記（Ｂ）天然繊維が、ケナフ、ラミー、及び竹から選択される少なくとも一種であることを特徴とする請求項１乃至請求項３の何れか１項に記載の樹脂組成物である。
The invention according to claim 4
The resin composition according to any one of claims 1 to 3 , wherein the natural fiber (B) is at least one selected from kenaf, ramie, and bamboo.
請求項５に係る発明は、
（Ａ）生分解性樹脂、（Ｂ）天然繊維、（Ｃ）加水分解抑制剤、及び（Ｄ）酸化防止剤を含有し、
前記（Ａ）生分解性樹脂の含有量は、６５．２５質量％以上７６．５５質量％以下であり、
前記（Ｂ）天然繊維の含有量は、２０質量％以上３０質量％以下であり、
前記（Ｃ）加水分解抑制剤の含有量は、２質量％以上４質量％以下であり、
前記（Ｄ）酸化防止剤は、ヒンダードフェノール系酸化防止剤及びリン系酸化防止剤を含み、かつ前記（Ｄ）酸化防止剤の含有量は、０．４５質量％以上１．５質量％以下であることを特徴とする樹脂成形品である。
The invention according to claim 5
(A) a biodegradable resin, (B) a natural fiber, (C) a hydrolysis inhibitor, and (D) an antioxidant,
Content of said (A) biodegradable resin is 65.25 mass% or more and 76.55 mass% or less,
The content of the (B) natural fiber is 20% by mass or more and 30% by mass or less,
The content of the (C) hydrolysis inhibitor is 2% by mass or more and 4% by mass or less,
The (D) antioxidant contains a hindered phenol antioxidant and a phosphorus antioxidant, and the content of the (D) antioxidant is 0.45 mass% or more and 1.5 mass% or less. It is a resin molded product characterized by being.
請求項１、２、３及び４に係る発明によれば、本構成を有さない場合に比べて、機械的強度を維持しつつ、難燃性を向上させた樹脂組成物が提供される。
請求項５に係る発明によれば、本構成を有さない場合に比べて、機械的強度を維持しつつ、難燃性を向上させた樹脂成形品が提供される。
According to the invention which concerns on Claim 1, 2, 3 and 4 , compared with the case where it does not have this structure, the resin composition which improved the flame retardance is maintained, maintaining mechanical strength.
According to the invention which concerns on Claim 5 , compared with the case where it does not have this structure, the resin molded product which improved the flame retardance is provided, maintaining mechanical strength.
＜樹脂組成物＞
本実施形態に係る樹脂組成物は、（Ａ）生分解性樹脂、（Ｂ）天然繊維、（Ｃ）加水分解抑制剤、及び（Ｄ）酸化防止剤を含有することを特徴とする。
樹脂材料の難燃化のためには、従来、ハロゲン系、リン系、無機金属系の難燃材などを混合する必要があったが、この場合機械物性が低下する。特に生分解性樹脂は、分解温度が低く、難燃化の要求が高かった。前記特許文献１乃至３の提案は、機械物性の向上を目的としたものであるが、難燃性については改善の余地がある（特に事務機器部品などに使用する場合には）。
但し、本実施形態に係る樹脂組成物は、（Ａ）生分解性樹脂の含有量が６５．２５質量％以上７６．５５質量％以下、（Ｂ）天然繊維の含有量が２０質量％以上３０質量％以下、（Ｃ）加水分解抑制剤の含有量が２質量％以上４質量％以下、（Ｄ）酸化防止剤がヒンダードフェノール系酸化防止剤及びリン系酸化防止剤を含み、かつ酸化防止剤の含有量が０．４５質量％以上１．５質量％以下であるものが適用される。
<Resin composition>
The resin composition according to this embodiment contains (A) a biodegradable resin, (B) natural fiber, (C) a hydrolysis inhibitor, and (D) an antioxidant.
Conventionally, in order to make a resin material flame-retardant, it has been necessary to mix a halogen-based, phosphorus-based, inorganic metal-based flame retardant, etc., but in this case, the mechanical properties are lowered. In particular, biodegradable resins have a low decomposition temperature and a high demand for flame retardancy. The proposals in Patent Documents 1 to 3 are intended to improve mechanical properties, but there is room for improvement in flame retardancy (especially when used for office equipment parts).
However, in the resin composition according to the present embodiment , the content of (A) the biodegradable resin is 65.25% by mass or more and 76.55% by mass or less, and (B) the content of natural fiber is 20% by mass or more and 30%. Mass% or less, (C) hydrolysis inhibitor content is 2 mass% or more and 4 mass% or less, (D) antioxidant contains hindered phenol antioxidant and phosphorus antioxidant, and antioxidant the content of the agent is applied not more than 1.5 mass% to 0.45 mass%.
本実施形態に係る樹脂組成物は、（Ａ）生分解性樹脂、（Ｂ）天然繊維、（Ｃ）加水分解抑制剤、及び（Ｄ）酸化防止剤を含有することにより、生分解性、及び機械的強度を維持しつつ、難燃性を向上させた樹脂組成物が提供される。これは（Ｄ）酸化防止剤を含有させることで、本実施形態に係る樹脂組成物が燃焼しても、熱分解により発生したラジカルを捕捉することで分解速度が抑制され、（Ｃ）加水分解抑制剤を含有させることで、分解した樹脂が再結合し、分解による可燃ガスの発生を抑え、（Ｂ）天然繊維を含有させることで、高いチャー形成及び熱吸収を行うことで、機械的強度を維持しつつ、難燃性を向上させた。（Ｂ）天然繊維は、燃焼した場合、効率よくすす（チャー）を生成し、発生する可燃性ガスの拡散を防ぎ、さらに断熱するという機能があり、難燃性の向上に寄与する。 The resin composition according to the present embodiment contains (A) a biodegradable resin, (B) a natural fiber, (C) a hydrolysis inhibitor, and (D) an antioxidant, A resin composition having improved flame retardancy while maintaining mechanical strength is provided. This is because (D) an antioxidant is contained, and even when the resin composition according to this embodiment burns, the decomposition rate is suppressed by capturing radicals generated by thermal decomposition, and (C) hydrolysis By containing an inhibitor, the decomposed resin recombines, suppresses the generation of flammable gas due to decomposition, and (B) contains natural fiber, thereby forming high char and absorbing heat, resulting in mechanical strength. While maintaining the above, flame retardancy was improved. (B) When natural fiber burns, it has a function of efficiently generating soot (char), preventing diffusion of the generated combustible gas, and further insulating it, thereby contributing to improvement of flame retardancy.
以下、本実施形態に係る樹脂組成物の構成等について説明する。
（Ａ）生分解性樹脂
（Ａ）生分解性樹脂は、生分解性を有している樹脂であればよく、ポリ乳酸、ポリヒドロキシブチレート、ポリカプロラクトン、ポリブチレンサクシネート、ポリ（ブチレンサクシネート／アジペート）、ポリ（ブチレンサクシネート／カーボネート）、ポリエチレンサクシネート、ポリビニルアルコール、酢酸セルロース、デンプン変性樹脂、セルロース変性樹脂等が用いられ、少なくとも、ポリ乳酸、３−ヒドロキシ酪酸と３−ヒドロキシ吉草酸との共重合体、ポリブチレンサクシネートから選択される１種であることが好ましく、この中でも入手が容易で成形性に優れるポリ乳酸がより好ましい。
Hereinafter, the configuration of the resin composition according to the present embodiment will be described.
(A) Biodegradable resin (A) The biodegradable resin may be any resin having biodegradability, such as polylactic acid, polyhydroxybutyrate, polycaprolactone, polybutylene succinate, poly (butylene succinate). Acrylate / adipate), poly (butylene succinate / carbonate), polyethylene succinate, polyvinyl alcohol, cellulose acetate, starch-modified resin, cellulose-modified resin, and the like, and at least polylactic acid, 3-hydroxybutyric acid and 3-hydroxyyoshi One selected from a copolymer with herbic acid and polybutylene succinate is preferred, and among them, polylactic acid that is easily available and excellent in moldability is more preferred.
（Ａ）生分解性樹脂は、本実施形態に係る樹脂組成物のマトリックス樹脂であり、樹脂組成物における含有量は、６０質量％以上９０質量％以下であることが好ましく、６５質量％以上８５質量％以下であることがより好ましく、７０質量％以上８０質量％以下であることが更に好ましい。前記（Ａ）生分解性樹脂の含有量が６０質量％未満であると、混練や成形時の加工性が悪化するとともに、燃焼時のすすの発生が速くなり難燃性を低下させる場合があり、９０質量％を超えると、機械的物性が低下し、難燃性も悪化する場合がある。 (A) The biodegradable resin is a matrix resin of the resin composition according to the present embodiment, and the content in the resin composition is preferably 60% by mass or more and 90% by mass or less, and 65% by mass or more and 85%. More preferably, it is 70 mass% or less, and more preferably 70 mass% or less. When the content of the (A) biodegradable resin is less than 60% by mass, the workability during kneading and molding deteriorates, and the generation of soot at the time of combustion may increase and flame retardancy may be reduced. If it exceeds 90% by mass, the mechanical properties may decrease and the flame retardancy may also deteriorate.
（Ｂ）天然繊維は、天然由来（植物由来等）の繊維であれば限定されず、麻（亜麻、ラミー、マニラ麻、サイザル麻、ケナフ、ジュート）、竹、綿、パルプ等が挙げられ、この中でも、引張強度などの機械的物性が高い点で、ラミー、ケナフ、竹が好ましい。 (B) Natural fibers are not limited as long as they are naturally derived (plant derived, etc.) fibers, and include hemp (flax, ramie, manila hemp, sisal hemp, kenaf, jute), bamboo, cotton, pulp, etc. Among these, ramie, kenaf, and bamboo are preferable because they have high mechanical properties such as tensile strength.
前記（Ｂ）天然繊維の樹脂組成物における含有量は、１０質量％以上４０質量％以下であることが好ましく、１５質量％以上３５質量％以下であることがより好ましく、２０質量％以上３０質量％以下であることが更に好ましい。前記（Ｂ）天然繊維の含有量が１０質量％未満であると、荷重たわみ温度や曲げ特性等の機械的物性が低下し、難燃性も悪化する場合があり、４０質量％を超えると、混練や成形時の加工性が悪化するとともに、燃焼時のすすの発生が速すぎて難燃性を低下させる場合がある。 The content of the (B) natural fiber in the resin composition is preferably 10% by mass to 40% by mass, more preferably 15% by mass to 35% by mass, and more preferably 20% by mass to 30% by mass. % Or less is more preferable. When the content of the (B) natural fiber is less than 10% by mass, mechanical properties such as deflection temperature under load and bending characteristics may be lowered, and flame retardancy may be deteriorated. While workability at the time of kneading and molding deteriorates, soot generation at the time of combustion may be too fast and flame retardancy may be reduced.
（Ｃ）加水分解抑制剤は、カルボキシル末端、または水酸基をもつ末端と反応する材料であれば限定されず、カルボジイミド化合物、イソシアネート化合物が好ましく挙げられる。カルボジイミド化合物としては、例えば２，２，６，６−テトライソプロピルジフェニルカルボジイミド、ジシクロヘキシルカルボジイミド、ジイソプロピルカルボジイミド、ジメチルカルボジイミド、ジオクチルカルボジイミド、ジイソブチルカルボジイミド等が挙げられる。 (C) A hydrolysis inhibitor will not be limited if it is a material which reacts with the terminal which has a carboxyl terminal or a hydroxyl group, A carbodiimide compound and an isocyanate compound are mentioned preferably. Examples of the carbodiimide compound include 2,2,6,6-tetraisopropyldiphenylcarbodiimide, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, dioctylcarbodiimide, diisobutylcarbodiimide and the like.
また、イソシアネート化合物としては、例えば芳香族ジイソシアネート、脂肪族ジイソシアネート、脂環族ジイソシアネートやこれらの混合物等が挙げられる。 Examples of the isocyanate compound include aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and mixtures thereof.
前記（Ｃ）加水分解抑制剤の樹脂組成物における含有量は、０．５質量％以上５質量％以下であることが好ましく、１質量％以上４質量％以下であることがより好ましく、２質量％以上３質量％以下であることが更に好ましい。前記（Ｃ）加水分解抑制剤の含有量が０．５質量％未満であると、耐久性が悪化し、さらに燃焼時の難燃性を低下させる場合があり、５質量％を超えると、機械的物性と難燃性が低下する場合がある。 The content of the (C) hydrolysis inhibitor in the resin composition is preferably 0.5% by mass or more and 5% by mass or less, more preferably 1% by mass or more and 4% by mass or less, and 2% by mass. % To 3% by mass is more preferable. When the content of the (C) hydrolysis inhibitor is less than 0.5% by mass, the durability deteriorates and the flame retardancy during combustion may be further reduced. The physical properties and flame retardancy may be reduced.
前記（Ｄ）酸化防止剤としては、ヒンダードフェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤を単独、或いはヒンダードフェノール系酸化防止剤とリン系酸化防止剤もしくはイオウ系酸化防止剤が挙げられ、ヒンダードフェノール系酸化防止剤、及びリン系酸化防止剤が好ましく、これらのうちの複数を混合して用いることがより好ましい。また、前記（Ｄ）酸化防止剤としては、高分子量タイプのものが好ましく、分子量が５００以上２０００以下のものが好ましい。 As the (D) antioxidant, a hindered phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant alone, or a hindered phenol antioxidant and a phosphorus antioxidant or a sulfur antioxidant. An hindered phenolic antioxidant and a phosphorus antioxidant are preferable, and it is more preferable to use a mixture of a plurality of these. Moreover, as said (D) antioxidant, a high molecular weight type is preferable and a molecular weight is 500 or more and 2000 or less.
前記（Ｄ）酸化防止剤の樹脂組成物における含有量は、０．０１質量％以上５質量％以下であることが好ましく、０．０５質量％以上３質量％以下であることがより好ましく、０．１質量％以上１質量％以下であることが更に好ましい。前記（Ｄ）酸化防止剤の含有量が０．０１質量％未満であると、加工中の材料の劣化による機械的物性の低下、燃焼時の難燃性の低下を引き起こす場合があり、５質量％を超えると、燃焼時の難燃性の低下を引き起こす場合がある。 The content of the (D) antioxidant in the resin composition is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.05% by mass or more and 3% by mass or less. More preferably, the content is 1% by mass or more and 1% by mass or less. If the content of the antioxidant (D) is less than 0.01% by mass, it may cause a decrease in mechanical properties due to deterioration of the material during processing and a decrease in flame retardancy during combustion. If it exceeds 50%, the flame retardancy during combustion may be reduced.
本実施形態に係る樹脂組成物には、通常配合される安定剤などを配合させてもよい。これらは特に限定されるものではないが、例えば、橋掛け剤、橋掛け促進剤、橋掛け促進助剤、活性剤、橋掛け抑制剤、老化防止剤、酸化防止剤、オゾン劣化防止剤、紫外線吸収剤、光安定剤、粘着付与剤、可塑剤、軟化剤、補強剤、強化剤、発砲剤、発泡助剤、安定剤、滑剤、離型剤、帯電防止剤、変性剤、着色剤、カップリング剤、防腐剤、防カビ剤、改質剤、接着剤、付香剤、重合触媒、重合開始剤、重合禁止剤、重合抑制剤、重合調整剤、結晶核剤、相溶化剤、分散剤、消泡剤などが挙げられる。
これらは、単独もしくは２つ以上で複合して使用してもよい。
You may mix | blend the stabilizer etc. which are normally mix | blended with the resin composition which concerns on this embodiment. These are not particularly limited, for example, crosslinking agents, crosslinking accelerators, crosslinking accelerators, activators, crosslinking inhibitors, anti-aging agents, antioxidants, ozone degradation inhibitors, ultraviolet rays Absorber, light stabilizer, tackifier, plasticizer, softener, reinforcing agent, reinforcing agent, foaming agent, foaming aid, stabilizer, lubricant, mold release agent, antistatic agent, modifier, colorant, cup Ring agent, preservative, antifungal agent, modifier, adhesive, flavoring agent, polymerization catalyst, polymerization initiator, polymerization inhibitor, polymerization inhibitor, polymerization regulator, crystal nucleating agent, compatibilizing agent, dispersant And antifoaming agents.
These may be used alone or in combination of two or more.
本実施形態に係る樹脂組成物は、以上述べた（Ａ）生分解性樹脂、（Ｂ）天然繊維、（Ｃ）加水分解抑制剤、及び（Ｄ）酸化防止剤、及び必要に応じて安定剤などを混合し、これを混練機で混練することにより得られる。
上記混練機としては、特に制限されないが、３本ロールや２本ロールを用い、せん断応力と位置交換の繰り返しによって、（Ｂ）天然繊維、（Ｃ）加水分解抑制剤、及び（Ｄ）酸化防止剤を分散させる方法、及びニーダー、バンバリーミキサー、インターミックス、１軸押出機、２軸押出機を用い、分散機壁面の衝突力やせん断力によって分散させる方法が、高い分散性を得る観点から好ましく用いられる。
The resin composition according to the present embodiment includes the (A) biodegradable resin, (B) natural fiber, (C) hydrolysis inhibitor, (D) antioxidant, and stabilizer as necessary. Etc. are mixed and kneaded with a kneader.
Although it does not restrict | limit especially as said kneading machine, (B) natural fiber, (C) hydrolysis inhibitor, and (D) oxidation prevention by repeating a shear stress and position exchange using 3 rolls or 2 rolls. From the viewpoint of obtaining high dispersibility, a method of dispersing the agent and a method of dispersing by a collision force or shearing force of the disperser wall surface using a kneader, a Banbury mixer, an intermix, a single screw extruder, or a twin screw extruder are preferable. Used.
＜樹脂成形品＞
本実施形態に係る樹脂成形品は、（Ａ）生分解性樹脂、（Ｂ）天然繊維、（Ｃ）加水分解抑制剤、及び（Ｄ）酸化防止剤を含有することを特徴とする。
本実施形態に係る樹脂成形品は、既述した本実施形態に係る樹脂組成物を成形機により成形することで得られる。
<Resin molded product>
The resin molded product according to this embodiment is characterized by containing (A) a biodegradable resin, (B) natural fiber, (C) a hydrolysis inhibitor, and (D) an antioxidant.
The resin molded product according to the present embodiment can be obtained by molding the resin composition according to the present embodiment described above with a molding machine.
本実施形態に係る樹脂成形品を成形する成形機としては、プレス成形機、射出成形機、モールド成形機、ブロー成形機、押出成形機、及び紡糸成形機のうちから選択される１以上の成形機が用いられる。したがって、これらの１つにより成形を行ってもよいし、１つの成形機により成形を行った後、他の成形機により続けて成形を行ってもよい。本実施形態においては、射出成形機を用いることが、生分解性及び機械的強度を維持しつつ、難燃性を向上させたという効果が発揮される成形品が得られる点で好ましい。 As a molding machine for molding the resin molded product according to the present embodiment, one or more moldings selected from a press molding machine, an injection molding machine, a molding machine, a blow molding machine, an extrusion molding machine, and a spinning molding machine Machine is used. Therefore, molding may be performed by one of these, or molding may be performed by one molding machine and then performed by another molding machine. In the present embodiment, it is preferable to use an injection molding machine from the viewpoint of obtaining a molded product that exhibits the effect of improving flame retardancy while maintaining biodegradability and mechanical strength.
射出成形機を用いて本実施形態に係る樹脂成形品を成形する場合の成形条件（シリンダー温度、金型温度等）は、マトリックス樹脂である（Ａ）生分解性樹脂の一般的な条件で構わない。 Molding conditions (cylinder temperature, mold temperature, etc.) when molding a resin molded product according to the present embodiment using an injection molding machine may be the general conditions of (A) biodegradable resin which is a matrix resin. Absent.
成形された本実施形態に係る樹脂成形品の形状は、シート状、棒状、糸状など特に限定されるものではなく、また、その大きさも制限されるものではない。 The shape of the molded resin molded product according to the present embodiment is not particularly limited, such as a sheet shape, a rod shape, or a thread shape, and the size is not limited.
本実施形態に係る樹脂成形品は、例えばシート状成形物として包装材及び建材などに、また構造物状の成形物として複写機及びプリンターなどの筐体、内部部品等のＯＡ機器部品などに用いてもよい。 The resin molded product according to the present embodiment is used for, for example, a packaging material and a building material as a sheet-shaped molded product, and as a structural molded product for OA equipment parts such as a casing of a copying machine and a printer, an internal part, and the like. May be.
以下、本実施形態について実施例により具体的に説明する。但し、本実施形態は以下の実施例に限定されるものではない。
＜実施例１乃至７、比較例１乃至７＞
表１に示す組成（単位は質量部）の化合物を２軸混練装置（東洋精機、ラボプラストミル）にて、表１に示すシリンダ温度で混練して、それをペレタイザー（東洋精機、ＰＥＴＥ−Ｃ型）によりカットすることにより、樹脂組成物ペレットを得た。
得られたペレットを射出成形機（日精樹脂工業製、ＮＥＸ５０）にて、表１に示すシリンダ温度、金型温度で、ＩＳＯ多目的ダンベル試験片、ＵＬ試験片（厚み２ｍｍ）を成形した。得られた試験片を用いて以下の評価を実施した。その結果を表２に示す。
Hereinafter, the present embodiment will be specifically described with reference to examples. However, this embodiment is not limited to the following examples.
<Examples 1 to 7, Comparative Examples 1 to 7>
A compound having a composition shown in Table 1 (unit: parts by mass) is kneaded with a biaxial kneader (Toyo Seiki, Labo Plast Mill) at the cylinder temperature shown in Table 1, and then pelletized (Toyo Seiki, PETE-C). The resin composition pellets were obtained by cutting with a mold.
The obtained pellets were molded into ISO multipurpose dumbbell test pieces and UL test pieces (thickness 2 mm) with an injection molding machine (NEX50, manufactured by Nissei Plastic Industry Co., Ltd.) at the cylinder temperature and mold temperature shown in Table 1. The following evaluation was implemented using the obtained test piece. The results are shown in Table 2.
尚、表１に示す組成に記載の化合物の詳細は以下の通りである。
（Ａ）生分解性樹脂
・ＰＬＡ−Ａ
ポリ乳酸、テラマックＴＥ２０００（ユニチカ社製）
・ＰＬＡ−Ｂ
ポリ乳酸、テラマックＴＥ７０００（ユニチカ社製）
・ＰＨＢＶ
３−ヒドロキシ酪酸（ＨＢ）と３−ヒドロキシ吉草酸（ＨＶ）との共重合体、バイオポール（日本モンサント社製）
・ＰＢＳ
ポリブチレンサクシネート、ＧＳＰｌａ（三菱化学社製）
In addition, the detail of the compound as described in the composition shown in Table 1 is as follows.
(A) Biodegradable resin / PLA-A
Polylactic acid, Terramac TE2000 (manufactured by Unitika)
・ PLA-B
Polylactic acid, Terramac TE7000 (manufactured by Unitika)
・ PHBV
Copolymer of 3-hydroxybutyric acid (HB) and 3-hydroxyvaleric acid (HV), Biopol (manufactured by Monsanto Japan)
・ PBS
Polybutylene succinate, GSPla (Mitsubishi Chemical Corporation)
（Ｂ）天然繊維
・ケナフ（自社作製）
・ラミー（自社作製）
・竹（自社作製）
(B) Natural fiber / kenaf (manufactured in-house)
・ Lamy (manufactured in-house)
・ Bamboo (manufactured in-house)
（Ｃ）加水分解抑制剤
・カルボジライト
カルボジライトＬＡ−１（日清紡社製）
・カルボジイミド変性ジイソシアネート
ミリオネートＭＴＬ（日本ポリウレタン社製）
(C) Hydrolysis inhibitor, carbodilite carbodilite LA-1 (Nisshinbo Co., Ltd.)
・ Carbodiimide-modified diisocyanate millionate MTL (manufactured by Nippon Polyurethane Co., Ltd.)
（Ｄ）酸化防止剤
・フェノール系Ａ
ｉｒｇａｎｏｘ２４５（チバジャパン社製）
・フェノール系Ｂ
ｉｒｇａｎｏｘ１０１０（チバジャパン社製）
・リン系
ｉｒｇａｎｏｘ１６８（チバジャパン社製）
(D) Antioxidants and phenolic A
Irganox 245 (Ciba Japan)
・ Phenolic B
irganox1010 (Ciba Japan)
・ Phosphorus irganox 168 (Ciba Japan)
（評価）
［難燃性評価］
ＵＬ試験片を用いて、ＵＬ９４規定に従いＶ試験を実施した。その結果を表２に示す。
(Evaluation)
[Flame retardance evaluation]
Using a UL test piece, a V test was performed in accordance with UL94 regulations. The results are shown in Table 2.
［耐熱性評価］
ＩＳＯ多目的ダンベル試験片を用いて、ＩＳＯ７５に従い、ＤＴＵＬ測定装置（東洋精機製、ＨＤＴ−３）にて１．８０ＭＰａ荷重時の荷重たわみ温度（ＤＴＵＬ）を測定した。その結果を表２に示す。
[Heat resistance evaluation]
Using an ISO multipurpose dumbbell test piece, the deflection temperature under load (DTUL) at 1.80 MPa load was measured with a DTUL measuring device (manufactured by Toyo Seiki Co., Ltd., HDT-3) according to ISO75. The results are shown in Table 2.
［曲げ弾性率評価］
ＩＳＯ多目的ダンベル試験片を用いて、ＩＳＯ１７８に従い、曲げ特性評価装置（島津製作所製、精密万能試験機オートグラフＡＧ−ＩＳ ５ｋＮ）にて、ＩＳＯ多目的ダンベル試験片が破壊又は１０％以上のたわみに達するまで２ｍｍ／ｍｉｎ．の速度でたわませ、その間の試験片に負荷される荷重を測定した。その結果を表２に示す。
[Evaluation of flexural modulus]
Using ISO multi-purpose dumbbell test piece, in accordance with ISO 178, the ISO multi-purpose dumbbell test piece breaks or reaches a deflection of 10% or more with a bending property evaluation apparatus (manufactured by Shimadzu Corporation, precision universal testing machine Autograph AG-IS 5kN) Up to 2 mm / min. The load applied to the test piece during that time was measured. The results are shown in Table 2.
Claims (5)
前記（Ａ）生分解性樹脂の含有量は、６５．２５質量％以上７６．５５質量％以下であり、
前記（Ｂ）天然繊維の含有量は、２０質量％以上３０質量％以下であり、
前記（Ｃ）加水分解抑制剤の含有量は、２質量％以上４質量％以下であり、
前記（Ｄ）酸化防止剤は、ヒンダードフェノール系酸化防止剤及びリン系酸化防止剤を含み、かつ前記（Ｄ）酸化防止剤の含有量は、０．４５質量％以上１．５質量％以下であることを特徴とする樹脂組成物。 (A) a biodegradable resin, (B) a natural fiber, (C) a hydrolysis inhibitor, and (D) an antioxidant,
Content of said (A) biodegradable resin is 65.25 mass% or more and 76.55 mass% or less,
The content of the (B) natural fiber is 20% by mass or more and 30% by mass or less,
The content of the (C) hydrolysis inhibitor is 2% by mass or more and 4% by mass or less,
The (D) antioxidant contains a hindered phenol antioxidant and a phosphorus antioxidant, and the content of the (D) antioxidant is 0.45 mass% or more and 1.5 mass% or less. A resin composition characterized by the above.
前記（Ａ）生分解性樹脂の含有量は、６５．２５質量％以上７６．５５質量％以下であり、
前記（Ｂ）天然繊維の含有量は、２０質量％以上３０質量％以下であり、
前記（Ｃ）加水分解抑制剤の含有量は、２質量％以上４質量％以下であり、
前記（Ｄ）酸化防止剤は、ヒンダードフェノール系酸化防止剤及びリン系酸化防止剤を含み、かつ前記（Ｄ）酸化防止剤の含有量は、０．４５質量％以上１．５質量％以下であることを特徴とする樹脂成形品。 (A) a biodegradable resin, (B) a natural fiber, (C) a hydrolysis inhibitor, and (D) an antioxidant,
Content of said (A) biodegradable resin is 65.25 mass% or more and 76.55 mass% or less,
The content of the (B) natural fiber is 20% by mass or more and 30% by mass or less,
The content of the (C) hydrolysis inhibitor is 2% by mass or more and 4% by mass or less,
The (D) antioxidant contains a hindered phenol antioxidant and a phosphorus antioxidant, and the content of the (D) antioxidant is 0.45 mass% or more and 1.5 mass% or less. A resin molded product characterized by
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