JP2017024407A - Polylactic acid resin composition laminated sheet - Google Patents
Polylactic acid resin composition laminated sheet Download PDFInfo
- Publication number
- JP2017024407A JP2017024407A JP2016135178A JP2016135178A JP2017024407A JP 2017024407 A JP2017024407 A JP 2017024407A JP 2016135178 A JP2016135178 A JP 2016135178A JP 2016135178 A JP2016135178 A JP 2016135178A JP 2017024407 A JP2017024407 A JP 2017024407A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- polylactic acid
- acid resin
- mass
- resin composition
- 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
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 179
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 178
- 239000011342 resin composition Substances 0.000 title claims abstract description 112
- 239000004014 plasticizer Substances 0.000 claims abstract description 102
- 229920005989 resin Polymers 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 74
- 239000003484 crystal nucleating agent Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- -1 ester compound Chemical class 0.000 claims description 45
- 238000004898 kneading Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 193
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000001816 cooling Methods 0.000 description 15
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 15
- 239000003112 inhibitor Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
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- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 150000005690 diesters Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 239000001384 succinic acid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- ALDZNWBBPCZXGH-UHFFFAOYSA-N 12-hydroxyoctadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(N)=O ALDZNWBBPCZXGH-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000004609 Impact Modifier Substances 0.000 description 4
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical class OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
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- TUEYHEWXYWCDHA-UHFFFAOYSA-N ethyl 5-methylthiadiazole-4-carboxylate Chemical compound CCOC(=O)C=1N=NSC=1C TUEYHEWXYWCDHA-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- FHHGCKHKTAJLOM-UHFFFAOYSA-N hexaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCO FHHGCKHKTAJLOM-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
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- 239000008188 pellet Substances 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
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- 239000003463 adsorbent Substances 0.000 description 3
- 229920001222 biopolymer Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
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- 235000013305 food Nutrition 0.000 description 3
- 239000004790 ingeo Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920002601 oligoester Polymers 0.000 description 3
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- 229920001432 poly(L-lactide) Polymers 0.000 description 3
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- 238000007127 saponification reaction Methods 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940121375 antifungal agent Drugs 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
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- 229920006038 crystalline resin Polymers 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
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- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CLZOHDKRJJFTSA-UHFFFAOYSA-N n'-[2,3-di(propan-2-yl)phenyl]methanediimine Chemical compound CC(C)C1=CC=CC(N=C=N)=C1C(C)C CLZOHDKRJJFTSA-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RJRRZABNCURWAM-UHFFFAOYSA-N (2-butylphenyl)phosphonic acid Chemical compound CCCCC1=CC=CC=C1P(O)(O)=O RJRRZABNCURWAM-UHFFFAOYSA-N 0.000 description 1
- YXTSJMYYIRPSDF-UHFFFAOYSA-N (2-methylphenyl)phosphonic acid Chemical compound CC1=CC=CC=C1P(O)(O)=O YXTSJMYYIRPSDF-UHFFFAOYSA-N 0.000 description 1
- GDKNDQBTIVRVAV-UHFFFAOYSA-N (2-propylphenyl)phosphonic acid Chemical compound CCCC1=CC=CC=C1P(O)(O)=O GDKNDQBTIVRVAV-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BOSWPVRACYJBSJ-UHFFFAOYSA-N 1,3-di(p-tolyl)carbodiimide Chemical compound C1=CC(C)=CC=C1N=C=NC1=CC=C(C)C=C1 BOSWPVRACYJBSJ-UHFFFAOYSA-N 0.000 description 1
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical group C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
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- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical group C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ポリ乳酸樹脂組成物積層シートに関する。更に詳しくは、日用品、化粧品、家電製品等のパックやトレイ等の成形体に好適に使用し得るポリ乳酸樹脂組成物積層シート、及び該シートの製造方法に関する。 The present invention relates to a polylactic acid resin composition laminated sheet. More specifically, the present invention relates to a polylactic acid resin composition laminated sheet that can be suitably used for molded articles such as packs and trays of daily necessities, cosmetics, home appliances, and the like, and a method for producing the sheet.
ポリ乳酸樹脂は、原料が植物由来であるために二酸化炭素排出量が極めて少ないこと等からその利用が期待されているが、樹脂の特性として剛性が強く透明性が高いこと等の特徴により、積層化により機能性を付与する技術が検討されている。 Polylactic acid resin is expected to be used because the raw material is plant-derived and therefore emits very little carbon dioxide. However, due to the characteristics of the resin being rigid and highly transparent, it is laminated. A technology for imparting functionality through conversion is being studied.
例えば、特許文献1には、ポリ乳酸樹脂等の脂肪族ポリエステル系樹脂を主体とする樹脂(A)100重量部に対し、液状添加剤(B)を1重量部〜20重量部を含む樹脂組成物(C)からなる層を表層に少なくとも1層と、上記脂肪族ポリエステル系樹脂の内、結晶融点が120℃〜250℃の脂肪族ポリエステル系樹脂を主体とする樹脂(D)100重量部に対し、上記液状添加剤(B)を1重量部未満含有する若しくは含有しない層を少なくとも1層有する、少なくとも2層からなる延伸フィルムが、引張弾性率が高く、耐熱性や密着性にも優れると開示されている。 For example, Patent Document 1 discloses a resin composition containing 1 to 20 parts by weight of a liquid additive (B) with respect to 100 parts by weight of a resin (A) mainly composed of an aliphatic polyester resin such as a polylactic acid resin. At least one layer comprising the product (C) as a surface layer, and 100 parts by weight of a resin (D) mainly composed of an aliphatic polyester resin having a crystal melting point of 120 ° C. to 250 ° C. of the aliphatic polyester resin. On the other hand, when the stretched film comprising at least two layers containing at least one layer containing or not containing the liquid additive (B) is less than 1 part by weight, the tensile elastic modulus is high, and the heat resistance and adhesion are excellent. It is disclosed.
特許文献2では、結晶核剤を含有するポリ乳酸系樹脂組成物からなる層Aを、結晶核剤を実質的に含有しない樹脂組成物からなる層Bで挟み込むように積層したところ、耐熱性、透明性、光沢性が共に優れた成形体を得ることができる成形性の良好なポリ乳酸系樹脂シートが得られている。 In Patent Document 2, when layer A made of a polylactic acid-based resin composition containing a crystal nucleating agent is laminated so as to be sandwiched between layers B made of a resin composition containing substantially no crystal nucleating agent, heat resistance, A polylactic acid-based resin sheet with good moldability that can obtain a molded article excellent in both transparency and gloss has been obtained.
特許文献3には、ガラス転移温度Tg(A)、融点Tm(A)である結晶性ポリ乳酸系重合体Aを主成分とするA層と、ガラス転移温度Tg(B)、結晶化温度Tc(B)である結晶性樹脂組成物Bを主成分とするB層からなる積層フィルムであって、Tg(A)、Tm(A)、Tg(B)およびTc(B)の関係が、Tg(A)≧Tg(B)かつTm(A)≧Tc(B)であり、DSC昇温測定における該フィルムの結晶融解熱量(ΔHm)が15J/g以上かつ、層の構成がA/B/A、あるいはB/A/Bの構成を含む3層以上であることを特徴とする積層フィルムが開示されている。かかる積層フィルムは、結晶性ポリ乳酸の製膜条件を大きく変化させることなく、積層させる結晶性樹脂を変更するのみで各種特性が付与でき、例えば、充分な易引裂き性あるいは耐溶剤性が付与されると報告されている。 Patent Document 3 discloses a glass transition temperature Tg (A), an A layer mainly composed of a crystalline polylactic acid polymer A having a melting point Tm (A), a glass transition temperature Tg (B), and a crystallization temperature Tc. (B) is a laminated film composed of a B layer composed mainly of the crystalline resin composition B, wherein the relationship between Tg (A), Tm (A), Tg (B) and Tc (B) is Tg (A) ≧ Tg (B) and Tm (A) ≧ Tc (B), the heat of crystal fusion (ΔHm) of the film in the DSC temperature rise measurement is 15 J / g or more, and the layer structure is A / B / A laminated film characterized by having three or more layers including the configuration of A or B / A / B is disclosed. Such a laminated film can be imparted with various properties only by changing the crystalline resin to be laminated without greatly changing the film formation conditions of crystalline polylactic acid.For example, sufficient tearability or solvent resistance is imparted. It has been reported.
一方、中央層の表裏に表面層を積層して三層構造にした樹脂シートまたはフィルムであって、前記中央層を100%のポリ乳酸で構成するとともに、全体の厚さに対して60%〜90%の厚さを有するものとし、前記各表面層を70%〜95%のポリ乳酸と5%〜30%の乳酸系共重合ポリエステルとを成分として、全体の厚さに対して5%〜20%の厚さを有するものとした樹脂シートまたはフィルムが、生分解性を高めることができ、包装用容器の破損や、これに伴う破損片を飛散させないものであると開示されている(特許文献4参照)。 On the other hand, a resin sheet or film in which a surface layer is laminated on the front and back of the central layer to form a three-layer structure, and the central layer is made of 100% polylactic acid and has a thickness of 60% to The surface layer is composed of 70% to 95% polylactic acid and 5% to 30% lactic acid copolymer polyester as components, and the surface layer is 5% to the total thickness. It is disclosed that a resin sheet or film having a thickness of 20% can improve biodegradability and does not cause damage to packaging containers and scattered pieces associated therewith (patent) Reference 4).
また、特許文献5には、ポリ乳酸系樹脂組成物からなる層Aと層Bとを含む積層シートであって、該層Aと該層Bがポリ(メタ)アクリレートをそれぞれ特定の含有量で含有することで、透明性、耐熱性に優れ、さらには植物度の高い成形体を得ることができるポリ乳酸系樹脂積層シートを提供することができると開示されている。 Patent Document 5 discloses a laminated sheet including a layer A and a layer B made of a polylactic acid-based resin composition, and each of the layer A and the layer B contains poly (meth) acrylate with a specific content. It is disclosed that the inclusion of a polylactic acid-based resin laminate sheet that is excellent in transparency and heat resistance and that can provide a molded product having a high plant degree can be provided.
特許文献6には、層Aを少なくとも一方の最外層に有し、層Bを内層に有する、少なくとも3層からなる積層シートであり、層Aが、ポリ乳酸とポリブチレンサクシネート系樹脂とを含有し、さらに層Aの全成分100質量%においてポリ乳酸が60質量%以上97.5質量%以下であり、かつ、層Aの厚みの割合が、積層シートの全体厚さ100%に対して10〜40%であり、層Bが、ポリ乳酸とポリブチレンサクシネート系樹脂とを含有し、さらに層Bの全成分100質量%においてポリ乳酸が90質量%以上100質量%未満であり、面配向度ΔPが0以上0.002以下であることを特徴とする、積層シートが開示されている。この積層シートは、耐衝撃性、透明性、耐ブロッキング性に優れ、特に成形品用途にも印刷用途にも適すると記載されている。 Patent Document 6 is a laminated sheet consisting of at least three layers having layer A as at least one outermost layer and layer B as an inner layer, wherein layer A comprises polylactic acid and polybutylene succinate resin. In addition, in 100% by mass of all components of layer A, polylactic acid is 60% by mass or more and 97.5% by mass or less, and the ratio of the thickness of layer A is 100% of the total thickness of the laminated sheet. 10 to 40%, layer B contains polylactic acid and polybutylene succinate resin, and polylactic acid is 90% by mass or more and less than 100% by mass in 100% by mass of all components of layer B, A laminated sheet having an orientation degree ΔP of 0 or more and 0.002 or less is disclosed. It is described that this laminated sheet is excellent in impact resistance, transparency and blocking resistance, and is particularly suitable for use in molded products and printing.
しかしながら、ポリ乳酸樹脂の透明性に優れる積層シートを調製しようとしたところ、耐衝撃性を向上しようとすると透明性が低下することが判明し、更なる改良が必要であることが分かった。 However, when an attempt was made to prepare a laminated sheet excellent in the transparency of the polylactic acid resin, it was found that if the impact resistance was improved, the transparency was lowered, and further improvement was necessary.
本発明は、高い耐衝撃性と透明性を両立するポリ乳酸樹脂組成物積層シート、及び該積層シートの製造方法に関する。 The present invention relates to a polylactic acid resin composition laminated sheet having both high impact resistance and transparency, and a method for producing the laminated sheet.
本発明は、下記〔1〕〜〔2〕に関する。
〔1〕 複数のポリ乳酸樹脂組成物の層を含むポリ乳酸樹脂組成物積層シートであり、少なくとも次の層Pと層Qを含むポリ乳酸樹脂組成物積層シートであって、
層Pが、(P−A)ポリ乳酸樹脂、(P−B)可塑剤、及び(P−C)有機結晶核剤を含有するポリ乳酸樹脂組成物の層であり、層中の(P−B)可塑剤の含有量が4質量%以上18質量%以下であり、(P−C)有機結晶核剤の含有量が0.05質量%以上1.0質量%以下であり、
層Qが、(Q−A)ポリ乳酸樹脂、(Q−B)可塑剤、及び(Q−C)有機結晶核剤を含有するポリ乳酸樹脂組成物の層であり、層中の(Q−B)可塑剤の含有量が0質量%以上6質量%以下であり、(Q−C)有機結晶核剤の含有量が0質量%以上0.3質量%以下であり、
ここで、層P中の(P−B)可塑剤の含有量の方が層Q中の(Q−B)可塑剤の含有量より多く、シートの表面側と裏面側の少なくとも一方の最外層が層Pであるポリ乳酸樹脂組成物積層シート。
〔2〕 複数のポリ乳酸樹脂組成物の層を含むポリ乳酸樹脂組成物積層シートの製造方法であり、下記工程(1)、(2)及び(3)を含むポリ乳酸樹脂組成物積層シートの製造方法。
工程(1):(P−A)ポリ乳酸樹脂、(P−B)可塑剤、及び(P−C)有機結晶核剤を含有する原料を溶融混練して、層Pを構成するポリ乳酸樹脂組成物を調製する工程であって、層中の(P−B)可塑剤の含有量が4質量%以上18質量%以下であり、(P−C)有機結晶核剤の含有量が0.05質量%以上1.0質量%以下である工程
工程(2):(Q−A)ポリ乳酸樹脂、(Q−B)可塑剤、及び(Q−C)有機結晶核剤を含有する原料を溶融混練して、層Qを構成するポリ乳酸樹脂組成物を調製する工程であって、層中の(Q−B)可塑剤の含有量が0質量%以上6質量%以下であり、(Q−C)有機結晶核剤の含有量が0質量%以上0.3質量%以下であり、
ここで、層P中の(P−B)可塑剤の含有量の方が層Q中の(Q−B)可塑剤の含有量より多い工程
工程(3):工程(1)で得られた層Pのポリ乳酸樹脂組成物と、工程(2)で得られた層Qのポリ乳酸樹脂組成物とを層Pがシートの表面側と裏面側の少なくとも一方の最外層になるように溶融共押出成形する工程
The present invention relates to the following [1] to [2].
[1] A polylactic acid resin composition laminated sheet including a plurality of polylactic acid resin composition layers, and a polylactic acid resin composition laminated sheet including at least the following layers P and Q,
Layer P is a layer of a polylactic acid resin composition containing (P-A) polylactic acid resin, (P-B) plasticizer, and (P-C) organic crystal nucleating agent, and (P- B) The content of the plasticizer is 4% by mass or more and 18% by mass or less, and the content of the (PC) organic crystal nucleating agent is 0.05% by mass or more and 1.0% by mass or less,
Layer Q is a layer of a polylactic acid resin composition containing (QA) polylactic acid resin, (QB) plasticizer, and (QC) organic crystal nucleating agent, and (Q- B) The content of the plasticizer is 0% by mass or more and 6% by mass or less, and the content of the (QC) organic crystal nucleating agent is 0% by mass or more and 0.3% by mass or less.
Here, the content of the (P-B) plasticizer in the layer P is greater than the content of the (Q-B) plasticizer in the layer Q, and at least one of the outermost layers on the front and back sides of the sheet Is a polylactic acid resin composition laminate sheet in which layer P is.
[2] A method for producing a polylactic acid resin composition laminate sheet comprising a plurality of polylactic acid resin composition layers, comprising the following steps (1), (2) and (3): Production method.
Step (1): Polylactic acid resin constituting layer P by melting and kneading raw materials containing (PA) polylactic acid resin, (PB) plasticizer, and (PC) organic crystal nucleating agent In the step of preparing the composition, the content of the (P-B) plasticizer in the layer is 4% by mass or more and 18% by mass or less, and the content of the (PC) organic crystal nucleating agent is 0.00. Process step (2) which is not less than 05% by mass and not more than 1.0% by mass: A raw material containing (QA) polylactic acid resin, (QB) plasticizer, and (QC) organic crystal nucleating agent A step of preparing a polylactic acid resin composition constituting the layer Q by melt-kneading, wherein the content of the (Q-B) plasticizer in the layer is 0% by mass to 6% by mass, (Q -C) The content of the organic crystal nucleating agent is 0% by mass or more and 0.3% by mass or less,
Here, the content of the (P-B) plasticizer in the layer P is larger than the content of the (Q-B) plasticizer in the layer Q. The process step (3): obtained in the step (1). The polylactic acid resin composition of layer P and the polylactic acid resin composition of layer Q obtained in step (2) are melt-coagulated so that layer P is at least one of the outermost layers on the front side and the back side of the sheet. Extrusion process
本発明のポリ乳酸樹脂組成物積層シートは、高い耐衝撃性と透明性を両立するという優れた効果を奏する。 The polylactic acid resin composition laminate sheet of the present invention has an excellent effect of achieving both high impact resistance and transparency.
本発明のポリ乳酸樹脂組成物積層シートは、ポリ乳酸樹脂、可塑剤、及び有機結晶核剤を含有するポリ乳酸樹脂組成物の層が少なくとも2種類積層されたものであり、一方の層が他方の層より可塑剤の含有量が多いことを特徴とする。一般に、外部から衝撃が加わると緩和作用を奏するために、衝撃を吸収するシートの体積に応じて可塑剤が必要となるところ、可塑剤が均一に分散された系では全体体積に応じた可塑剤量が必要となる。すると、シート全体に亘って透明性が低下することになる。一方、可塑剤含有量が多い層と少ない層とが存在する本願発明においては、外部からの衝撃緩和は可塑剤含有量が多い層が担うため、当該層に均一分散系で必要とされる可塑剤量と同じ量を含有させることになると可塑剤の分布割合が高くなり結果として耐衝撃性が向上すると考えられる。また、可塑剤が少ない層はポリ乳酸樹脂が元来有する高い透明性を維持することが可能になるから、シート全体の透明性も向上し、耐衝撃性と透明性の両立が達成されると考えられる。ただし、これらの推測は、本発明を限定するものではない。なお、本発明のポリ乳酸樹脂組成物積層シートのことを、単に、本発明の積層シートと記載することもある。 The polylactic acid resin composition laminate sheet of the present invention is obtained by laminating at least two layers of a polylactic acid resin composition containing a polylactic acid resin, a plasticizer, and an organic crystal nucleating agent, and one layer is the other. The plasticizer content is higher than that of the layer. Generally, a plasticizer is required according to the volume of the sheet that absorbs the impact in order to exert a relaxing action when an impact is applied from the outside. In a system in which the plasticizer is uniformly dispersed, the plasticizer according to the entire volume. A quantity is required. Then, transparency will fall over the whole sheet | seat. On the other hand, in the present invention in which there are a layer having a high plasticizer content and a layer having a low plasticizer content, a layer having a high plasticizer content is responsible for impact reduction from the outside. If the same amount as the amount of the agent is contained, the distribution ratio of the plasticizer is increased, and as a result, the impact resistance is considered to be improved. In addition, since the layer with less plasticizer can maintain the high transparency inherent in the polylactic acid resin, the transparency of the entire sheet is improved, and both impact resistance and transparency are achieved. Conceivable. However, these assumptions do not limit the present invention. In addition, the polylactic acid resin composition laminated sheet of the present invention may be simply referred to as the laminated sheet of the present invention.
<ポリ乳酸樹脂組成物積層シート>
本発明のポリ乳酸樹脂組成物積層シートは、少なくとも後述の層Pと層Qを含み、ポリ乳酸樹脂組成物の層を複数含む。また、層Pはシートの表面側と裏面側の少なくとも一方の最外層に、好ましくは表面側と裏面側の各最外層に配置されるのに対し、層Qは内側の層であればよく、層Pの間に層Qが存在することが好ましい。例えば、3層構造であれば中心に層Qが位置し、5層構造であれば最外層以外のいずれかに層Qを配置することができる。積層シートの積層数は特に限定されないが、耐衝撃性と成形性の観点から、好ましくは3層以上8層以下、より好ましくは3層以上5層以下であり、例えば、層P/層Q/層P/層Q/層Pの順、層P/層Q/層Pの順に積層された積層シートである。
<Polylactic acid resin composition laminated sheet>
The polylactic acid resin composition laminate sheet of the present invention includes at least a layer P and a layer Q described later, and includes a plurality of layers of the polylactic acid resin composition. Further, the layer P is disposed on at least one outermost layer on the front surface side and the back surface side of the sheet, preferably on each outermost layer on the front surface side and the back surface side, whereas the layer Q may be an inner layer, It is preferred that a layer Q exists between the layers P. For example, in the case of a three-layer structure, the layer Q is located at the center, and in the case of a five-layer structure, the layer Q can be arranged in any one other than the outermost layer. The number of laminated sheets is not particularly limited, but from the viewpoint of impact resistance and moldability, it is preferably 3 or more and 8 or less, more preferably 3 or more and 5 or less. For example, layer P / layer Q / It is a laminated sheet laminated in the order of layer P / layer Q / layer P and layer P / layer Q / layer P.
なお、本発明のポリ乳酸樹脂組成物積層シートは、層Pと層Q以外の層を含むものであってもよく、例えば、本発明のポリ乳酸樹脂組成物積層シート自体を対象に載置する際に剥離が可能な剥離シート、あるいは、本発明のポリ乳酸樹脂組成物積層シートにガスバリア性あるいはヒートシール性を付与するシート等、各種機能性シートを含む態様が挙げられる。具体的には、PET、PBT、あるいはPTT等のポリエステル樹脂組成物、PE、PP等のポリオレフィン系樹脂組成物、あるいはナイロン樹脂組成物を構成成分とするシートである。これらの機能性シートは公知のものを用いることができ、その機能に応じて本発明のポリ乳酸樹脂組成物積層シートの適切な位置に積層させることができる。例えば、剥離シートは、本発明のポリ乳酸樹脂組成物積層シートの外側に貼り付けることができる。 In addition, the polylactic acid resin composition laminate sheet of the present invention may include a layer other than the layer P and the layer Q. For example, the polylactic acid resin composition laminate sheet of the present invention is placed on the subject. Examples include various release sheets such as a release sheet that can be peeled off or a sheet that imparts gas barrier properties or heat sealability to the polylactic acid resin composition laminate sheet of the present invention. Specifically, it is a sheet comprising a polyester resin composition such as PET, PBT or PTT, a polyolefin resin composition such as PE or PP, or a nylon resin composition as a constituent component. A well-known thing can be used for these functional sheets, According to the function, it can be laminated | stacked on the suitable position of the polylactic acid resin composition laminated sheet of this invention. For example, the release sheet can be attached to the outside of the polylactic acid resin composition laminate sheet of the present invention.
〔層P〕
本発明における層Pは、(P−A)ポリ乳酸樹脂、(P−B)可塑剤、及び(P−C)有機結晶核剤を含有するポリ乳酸樹脂組成物の層であって、可塑剤の含有量と有機結晶核剤の含有量が以下の含有量であることを特徴とする。
[Layer P]
The layer P in the present invention is a layer of a polylactic acid resin composition containing (PA) polylactic acid resin, (PB) plasticizer, and (PC) organic crystal nucleating agent, and is a plasticizer. The content of and the content of the organic crystal nucleating agent are the following contents.
[(P−A)ポリ乳酸樹脂]
層Pにおけるポリ乳酸樹脂としては、市販されているポリ乳酸樹脂、例えば、Nature Works社製:Nature Works PLA/NW2003D、NW3001D、NW4032D、NW4060Dや、トヨタ自動車社製:エコプラスチックU'z S−09、S−12、S−17等の他、乳酸やラクチドから合成したポリ乳酸樹脂が挙げられる。なかでも、層Pのポリ乳酸樹脂組成物の耐衝撃性と成形性を向上する観点から、光学純度が好ましくは90%以上、より好ましくは95%以上のポリ乳酸樹脂が好ましく、例えば、Nature Works社製ポリ乳酸樹脂(NW4032D等)を用いることができる。なお、本発明におけるポリ乳酸の光学純度は、「ポリオレフィン等合成樹脂製食品容器包装等に関する自主基準 第3版改訂版 2004年6月追補 第3部 衛生試験法 P12-13」記載のD体含有量の測定方法に従って求めることができる。
[(PA) polylactic acid resin]
Examples of the polylactic acid resin in the layer P include commercially available polylactic acid resins such as those manufactured by Nature Works: Nature Works PLA / NW2003D, NW3001D, NW4032D, NW4060D, and Toyota Motor Corporation: Eco Plastic U'z S-09. In addition to S-12, S-17, and the like, polylactic acid resin synthesized from lactic acid or lactide can be used. Among them, from the viewpoint of improving the impact resistance and moldability of the polylactic acid resin composition of the layer P, a polylactic acid resin having an optical purity of preferably 90% or more, more preferably 95% or more is preferable. For example, Nature Works A polylactic acid resin (NW4032D or the like) manufactured by KK can be used. The optical purity of the polylactic acid in the present invention is D-containing as described in “Voluntary Standards for Food Containers and Packaging Made of Synthetic Resins such as Polyolefins, Third Edition, Revised June 2004, Part 3 Sanitation Test Method P12-13”. It can be determined according to the method of measuring the quantity.
また、本発明において、ポリ乳酸樹脂として、ポリ乳酸樹脂組成物の強度や透明性の観点から、異なる異性体を主成分とする乳酸成分を用いて得られた2種類のポリ乳酸からなるステレオコンプレックスポリ乳酸樹脂を用いてもよい。 In the present invention, from the viewpoint of the strength and transparency of the polylactic acid resin composition, as the polylactic acid resin, a stereocomplex comprising two types of polylactic acid obtained by using lactic acid components mainly composed of different isomers. Polylactic acid resin may be used.
また、本発明におけるポリ乳酸樹脂は、ポリ乳酸樹脂以外の生分解性ポリエステル樹脂やポリプロピレン等の非生分解性樹脂がポリ乳酸樹脂とのブレンドによるポリマーアロイとして含有されていてもよい。なお、本明細書において「生分解性」とは、自然界において微生物によって低分子化合物に分解され得る性質のことであり、具体的には、JIS K6953(ISO14855)「制御された好気的コンポスト条件の好気的かつ究極的な生分解度及び崩壊度試験」に基づいた生分解性のことを意味する。 In addition, the polylactic acid resin in the present invention may contain a biodegradable polyester resin other than the polylactic acid resin or a non-biodegradable resin such as polypropylene as a polymer alloy by blending with the polylactic acid resin. In the present specification, “biodegradable” means a property that can be decomposed into a low molecular weight compound by a microorganism in nature. Specifically, JIS K6953 (ISO 14855) “controlled aerobic composting conditions”. This means biodegradability based on the “Aerobic and Ultimate Biodegradation and Disintegration Test”.
ポリ乳酸樹脂の含有量は、耐衝撃性と透明性の観点から、層Pのポリ乳酸樹脂組成物中、80質量%以上が好ましく、85質量%以上がより好ましく、98質量%以下が好ましく、90質量%以下がより好ましい。 The content of the polylactic acid resin is preferably 80% by mass or more, more preferably 85% by mass or more, and preferably 98% by mass or less in the polylactic acid resin composition of the layer P from the viewpoint of impact resistance and transparency. 90 mass% or less is more preferable.
[(P−B)可塑剤]
層Pで用いられる可塑剤としては、耐衝撃性と透明性を向上させ、成形性も向上させる観点から、以下の(i)及び(ii)からなる群より選ばれる1種又は2種以上のエステル化合物を含むことが好ましい。
(i)分子中に2個以上のエステル基を有するエステル化合物であって、該エステル化合物を構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2〜3のアルキレンオキサイドを平均0.5〜8モル付加したアルコールであるエステル化合物、及び
(ii)式(I):
R1O−CO−R2−CO−〔(OR3)mO−CO−R2−CO−〕nOR1 (I)
(式中、R1は炭素数が1〜4のアルキル基、R2は炭素数が2〜4のアルキレン基、R3は炭素数が2又は3のアルキレン基であり、mは1〜6の数、nは1〜12の数を示し、但し、全てのR2は同一でも異なっていてもよく、全てのR3は同一でも異なっていてもよい)
で表される化合物
[(P-B) Plasticizer]
The plasticizer used in the layer P is one or more selected from the group consisting of the following (i) and (ii) from the viewpoint of improving impact resistance and transparency and improving moldability. It is preferable that an ester compound is included.
(I) An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound has an average of 0.5 to 3 alkylene oxides per hydroxyl group. Ester compound which is an alcohol added to ˜8 mol, and (ii) Formula (I):
R 1 O—CO—R 2 —CO — [(OR 3 ) m O—CO—R 2 —CO—] n OR 1 (I)
(Wherein R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is an alkylene group having 2 to 4 carbon atoms, R 3 is an alkylene group having 2 or 3 carbon atoms, and m is 1 to 6) And n represents a number from 1 to 12, provided that all R 2 may be the same or different, and all R 3 may be the same or different.
Compound represented by
(i)のエステル化合物としては、耐衝撃性、透明性、及び成形性の観点から、分子中に2個以上、好ましくは2個以上5個以下、より好ましくは2個以上3個以下のエステル基を有するエステル化合物であって、該エステル化合物を構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2又は3のアルキレンオキサイドを平均0.5モル以上8モル以下、好ましくは1モル以上6モル以下、より好ましくは1モル以上3モル以下付加したアルコールであるエステル化合物を用いることができる。なかでも、好ましくは、分子中に2個以上、好ましくは2個以上5個以下、より好ましくは2個以上3個以下のエステル基を有する多価アルコールエステル又は多価カルボン酸エステルであって、該エステル化合物を構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2又は3のアルキレンオキサイドを平均0.5モル以上8モル以下、好ましくは1モル以上6モル以下、より好ましくは1モル以上3モル以下付加したアルコールであるエステル化合物を用いることができる。 The ester compound (i) is an ester having 2 or more, preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less in the molecule from the viewpoint of impact resistance, transparency, and moldability. An ester compound having a group, wherein at least one alcohol component constituting the ester compound is an average of 0.5 to 8 moles, preferably 1 mole or more of an alkylene oxide having 2 or 3 carbon atoms per hydroxyl group An ester compound which is an alcohol added with 6 mol or less, more preferably 1 mol or more and 3 mol or less can be used. Among them, preferably a polyhydric alcohol ester or a polycarboxylic acid ester having an ester group of 2 or more, preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less in the molecule, At least one alcohol component constituting the ester compound is an average of 0.5 to 8 mol, preferably 1 to 6 mol, more preferably 1 mol of an alkylene oxide having 2 or 3 carbon atoms per hydroxyl group. An ester compound which is an alcohol added in an amount of 3 mol or less can be used.
具体的には、例えば、特開2008−174718号公報及び特開2008−115372号公報に記載の可塑剤が挙げられる。なかでも、酢酸とグリセリンのエチレンオキサイド平均3モル以上6モル以下付加物(水酸基1個あたりエチレンオキサイドを1モル以上2モル以下付加)とのエステル、酢酸とエチレンオキサイドの平均付加モル数が4以上6以下のポリエチレングリコールとのエステル、コハク酸とエチレンオキサイドの平均付加モル数が2以上6以下のポリエチレングリコールモノメチルエーテル(水酸基1個あたりエチレンオキサイドを2モル以上6モル以下付加)とのエステル、アジピン酸とジエチレングリコールモノメチルエーテルとのエステル、1,3,6−ヘキサントリカルボン酸とジエチレングリコールモノメチルエーテルとのエステルが好適に用いられる。 Specifically, for example, plasticizers described in JP 2008-174718 A and JP 2008-115372 A can be given. Of these, an average of 3 to 6 moles of an adduct of acetic acid and glycerin with an average of 3 to 6 moles of adduct (addition of 1 to 2 moles of ethylene oxide per hydroxyl group), an average number of moles of acetic acid and ethylene oxide added to 4 or more. Esters with 6 or less polyethylene glycol, esters with succinic acid and ethylene oxide having an average addition mole number of 2 to 6 polyethylene glycol monomethyl ether (addition of 2 to 6 moles of ethylene oxide per hydroxyl group), adipine An ester of an acid and diethylene glycol monomethyl ether and an ester of 1,3,6-hexanetricarboxylic acid and diethylene glycol monomethyl ether are preferably used.
(ii)のエステル化合物は、耐衝撃性、透明性、及び耐ブリード性の観点から、好ましい。 The ester compound (ii) is preferable from the viewpoint of impact resistance, transparency, and bleed resistance.
式(I)におけるR1は、炭素数が1以上4以下、好ましくは1又は2のアルキル基を示し、1分子中に2個存在して、分子の両末端に存在する。R1は炭素数が1以上4以下であれば、直鎖であっても分岐鎖であってもよい。具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、sec−ブチル基、tert−ブチル基が挙げられ、なかでも、ポリ乳酸樹脂との相溶性を向上させ可塑剤のブリードアウトを抑制する観点、及び耐衝撃性と透明性の観点から、メチル基が好ましい。 R 1 in formula (I) represents an alkyl group having 1 to 4 carbon atoms, preferably 1 or 2, and is present in two molecules in one molecule and is present at both ends of the molecule. R 1 may be linear or branched as long as it has 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and a tert-butyl group. A methyl group is preferable from the viewpoint of suppressing the out and from the viewpoint of impact resistance and transparency.
式(I)におけるR2は、炭素数が2以上4以下のアルキレン基を示し、直鎖のアルキレン基が好適例として挙げられる。具体的には、エチレン基、1,3−プロピレン基、1,4−ブチレン基が挙げられ、なかでも、ポリ乳酸樹脂との相溶性を向上させ可塑剤のブリードアウトを抑制する観点、及び耐衝撃性と透明性の観点から、エチレン基、1,3−プロピレン基が好ましく、エチレン基がより好ましい。但し、全てのR2は同一でも異なっていてもよい。 R 2 in the formula (I) represents an alkylene group having 2 to 4 carbon atoms, and a linear alkylene group is a preferred example. Specific examples include an ethylene group, a 1,3-propylene group, and a 1,4-butylene group. Among them, the viewpoint of improving the compatibility with the polylactic acid resin and suppressing the bleed-out of the plasticizer, and the resistance to resistance. From the viewpoint of impact and transparency, an ethylene group and a 1,3-propylene group are preferable, and an ethylene group is more preferable. However, all R 2 may be the same or different.
式(I)におけるR3は、炭素数が2又は3のアルキレン基を示し、OR3はオキシアルキレン基を示す。具体的には、エチレン基、1,2−プロピレン基、1,3−プロピレン基が挙げられる。但し、全てのR3は同一でも異なっていてもよい。 R 3 in formula (I) represents an alkylene group having 2 or 3 carbon atoms, and OR 3 represents an oxyalkylene group. Specific examples include an ethylene group, a 1,2-propylene group, and a 1,3-propylene group. However, all R 3 may be the same or different.
mはオキシアルキレン基の平均の繰り返し数を示し、1以上6以下の数である。mが大きくなると、式(I)で表されるエステル化合物のエーテル基価が上がり、酸化されやすくなり安定性が低下する傾向がある。ポリ乳酸樹脂との相溶性を向上させる観点から、1以上4以下の数が好ましく、1以上3以下の数がより好ましく、1以上2以下の数が更に好ましい。 m represents the average number of repeating oxyalkylene groups and is a number of 1 or more and 6 or less. When m increases, the ether group value of the ester compound represented by the formula (I) increases, which tends to be oxidized and the stability tends to decrease. From the viewpoint of improving the compatibility with the polylactic acid resin, the number is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and still more preferably 1 or more and 2 or less.
nは平均重合度を示し、1以上12以下の数である。ポリ乳酸樹脂との相溶性を向上させ可塑剤のブリードアウトを抑制する観点、及び耐衝撃性と透明性の観点から、1以上4以下の数が好ましく、1以上3以下の数がより好ましく、1以上2以下の数が更に好ましい。 n represents an average degree of polymerization and is a number of 1 or more and 12 or less. From the viewpoint of improving the compatibility with the polylactic acid resin and suppressing the bleeding out of the plasticizer, and from the viewpoint of impact resistance and transparency, the number of 1 or more and 4 or less is preferable, and the number of 1 or more and 3 or less is more preferable. A number of 1 or more and 2 or less is more preferable.
かかる構造のうちでも、透明性の観点から、コハク酸、グルタル酸、及びアジピン酸から選ばれる少なくとも1つの二塩基酸と、ジエチレングリコール、トリエチレングリコール、1,2−プロパンジオール、及び1,3−プロパンンジオールから選ばれる少なくとも1つの2価アルコールのオリゴエステル〔式(I)中、n=1〜3〕が好ましい。 Among such structures, from the viewpoint of transparency, at least one dibasic acid selected from succinic acid, glutaric acid, and adipic acid, diethylene glycol, triethylene glycol, 1,2-propanediol, and 1,3- At least one dihydric alcohol oligoester selected from propandiol (in formula (I), n = 1 to 3) is preferred.
式(I)で表される化合物は、市販品であっても公知の製造方法に従って合成したものを用いてもよく、例えば特開2012−62467号公報に開示されているような方法に従って製造することができる。 The compound represented by the formula (I) may be a commercially available product or may be synthesized according to a known production method, for example, produced according to a method disclosed in JP2012-62467A. be able to.
本発明においては、本発明の効果を損なわない範囲内で、前記(i)及び(ii)以外の他の可塑剤を用いることができる。他の可塑剤としては、例えば、前記(i)及び(ii)以外の、ポリエステル系可塑剤、グリセリン系可塑剤、多価カルボン酸エステル系可塑剤、ポリアルキレングリコール系可塑剤、及びエポキシ系可塑剤等を用いることができる。本発明で用いられる全可塑剤における前記(i)及び(ii)からなる群より選ばれる1種又は2種以上のエステル化合物の含有量は、耐衝撃性と透明性の観点から、50質量%以上が好ましく、70質量%以上がより好ましく、90質量%以上が更に好ましく、95質量%以上が更により好ましく、100質量%が更により好ましい。なお、本明細書において、(i)及び(ii)からなる群より選ばれる1種又は2種以上のエステル化合物の含有量とは、複数の化合物を用いている場合は合計含有量を意味する。 In the present invention, plasticizers other than the above (i) and (ii) can be used within a range not impairing the effects of the present invention. Examples of the other plasticizers include polyester plasticizers, glycerin plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, and epoxy plasticizers other than the above (i) and (ii). An agent or the like can be used. The content of one or more ester compounds selected from the group consisting of (i) and (ii) in the total plasticizer used in the present invention is 50% by mass from the viewpoint of impact resistance and transparency. The above is preferable, 70% by mass or more is more preferable, 90% by mass or more is further preferable, 95% by mass or more is further more preferable, and 100% by mass is even more preferable. In the present specification, the content of one or more ester compounds selected from the group consisting of (i) and (ii) means the total content when a plurality of compounds are used. .
層P中の可塑剤の含有量は、層Pのポリ乳酸樹脂100質量部に対して、耐衝撃性の観点から、5質量部以上が好ましく、7質量部以上がより好ましく、9質量部以上が更に好ましく、13質量部以上が更に好ましく、相溶性、成形性の観点から、20質量部以下が好ましく、18質量部以下がより好ましく、17質量部以下が更に好ましい。 From the viewpoint of impact resistance, the content of the plasticizer in the layer P is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and 9 parts by mass or more with respect to 100 parts by mass of the polylactic acid resin of the layer P. Is more preferably 13 parts by mass or more, and preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and still more preferably 17 parts by mass or less from the viewpoints of compatibility and moldability.
また、層Pのポリ乳酸樹脂組成物中の可塑剤の含有量は、4質量%以上18質量%以下であるが、耐衝撃性の観点から、6質量%以上が好ましく、8質量%以上がより好ましく、10質量%以上が更に好ましく、透明性の観点から、15質量%以下が好ましく、14質量%以下がより好ましい。 Further, the content of the plasticizer in the polylactic acid resin composition of the layer P is 4% by mass or more and 18% by mass or less, but from the viewpoint of impact resistance, 6% by mass or more is preferable, and 8% by mass or more is preferable. More preferably, 10% by mass or more is further preferable, and from the viewpoint of transparency, 15% by mass or less is preferable, and 14% by mass or less is more preferable.
[(P−C)有機結晶核剤]
層Pで用いられる有機結晶核剤としては、透明性の観点から、以下の(a)〜(d)からなる群より選ばれる少なくとも1種の有機結晶核剤を用いることが好ましい。
(a)イソインドリノン骨格を有する化合物、ジケトピロロピロール骨格を有する化合物、ベンズイミダゾロン骨格を有する化合物、インジゴ骨格を有する化合物、フタロシアニン骨格を有する化合物、及びポルフィリン骨格を有する化合物からなる群より選ばれる少なくとも1種の有機化合物〔有機結晶核剤(a)という〕
(b)カルボヒドラジド類、ウラシル類、及びN−置換尿素類からなる群より選ばれる少なくとも1種の有機化合物〔有機結晶核剤(b)という〕
(c)芳香族スルホン酸ジアルキルの金属塩、リン酸エステルの金属塩、フェニルホスホン酸の金属塩、ロジン酸類の金属塩、芳香族カルボン酸アミド、及びロジン酸アミドからなる群より選ばれる少なくとも1種の有機化合物〔有機結晶核剤(c)という〕
(d)分子中に水酸基とアミド基を有する化合物及びヒドロキシ脂肪酸エステルからなる群より選ばれる少なくとも1種の有機化合物〔有機結晶核剤(d)という〕
[(PC) Organic Crystal Nucleating Agent]
As the organic crystal nucleating agent used in the layer P, it is preferable to use at least one organic crystal nucleating agent selected from the group consisting of the following (a) to (d) from the viewpoint of transparency.
(A) From the group consisting of a compound having an isoindolinone skeleton, a compound having a diketopyrrolopyrrole skeleton, a compound having a benzimidazolone skeleton, a compound having an indigo skeleton, a compound having a phthalocyanine skeleton, and a compound having a porphyrin skeleton At least one organic compound selected [referred to as organic crystal nucleating agent (a)]
(B) At least one organic compound selected from the group consisting of carbohydrazides, uracils, and N-substituted ureas (referred to as organic crystal nucleating agent (b))
(C) at least one selected from the group consisting of metal salts of dialkyl aromatic sulfonates, metal salts of phosphoric acid esters, metal salts of phenylphosphonic acids, metal salts of rosin acids, aromatic carboxylic acid amides, and rosin acid amides Species of organic compound [referred to as organic crystal nucleating agent (c)]
(D) At least one organic compound selected from the group consisting of a compound having a hydroxyl group and an amide group in the molecule and a hydroxy fatty acid ester [referred to as organic crystal nucleating agent (d)]
これらの中では、透明性向上の観点から、有機結晶核剤(c)、有機結晶核剤(d)が好ましく、有機結晶核剤(d)がより好ましい。 Among these, from the viewpoint of improving transparency, the organic crystal nucleating agent (c) and the organic crystal nucleating agent (d) are preferable, and the organic crystal nucleating agent (d) is more preferable.
有機結晶核剤(c)としては、上記の観点から、置換基を有しても良いフェニル基とホスホン基(−PO(OH)2)を有するフェニルホスホン酸の金属塩が好ましく、フェニルホスホン酸の具体例としては、無置換のフェニルホスホン酸、メチルフェニルホスホン酸、エチルフェニルホスホン酸、プロピルフェニルホスホン酸、ブチルフェニルホスホン酸、ジメトキシカルボニルフェニルホスホン酸、ジエトキシカルボニルフェニルホスホン酸等が挙げられ、無置換のフェニルホスホン酸が好ましい。 From the above viewpoint, the organic crystal nucleating agent (c) is preferably a phenylphosphonic acid metal salt having an optionally substituted phenyl group and a phosphonic group (—PO (OH) 2). Specific examples of these include unsubstituted phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, dimethoxycarbonylphenylphosphonic acid, diethoxycarbonylphenylphosphonic acid, and the like. Unsubstituted phenylphosphonic acid is preferred.
有機結晶核剤(d)の分子中に水酸基とアミド基を有する化合物としては、水酸基を有する脂肪族アミドが好ましく、具体例としては、12−ヒドロキシステアリン酸モノエタノールアミド等のヒドロキシ脂肪酸モノアミド、メチレンビス12−ヒドロキシステアリン酸アミド、エチレンビス12−ヒドロキシステアリン酸アミド、ヘキサメチレンビス12−ヒドロキシステアリン酸アミド等のヒドロキシ脂肪酸ビスアミド等が挙げられる。 The compound having a hydroxyl group and an amide group in the molecule of the organic crystal nucleating agent (d) is preferably an aliphatic amide having a hydroxyl group. Specific examples thereof include hydroxy fatty acid monoamides such as 12-hydroxystearic acid monoethanolamide, methylenebis. Examples thereof include hydroxy fatty acid bisamides such as 12-hydroxystearic acid amide, ethylene bis 12-hydroxystearic acid amide, and hexamethylene bis 12-hydroxystearic acid amide.
層P中の有機結晶核剤の含有量は、層Pのポリ乳酸樹脂100質量部に対して、シートの結晶化度を向上させる観点から、0.1質量部以上が好ましく、0.3質量部以上がより好ましく、透明性の観点から、1.0質量部以下が好ましく、0.8質量部以下がより好ましく、0.75質量部以下が更に好ましく、0.5質量部以下が更に好ましい。 The content of the organic crystal nucleating agent in the layer P is preferably 0.1 parts by mass or more, from the viewpoint of improving the crystallinity of the sheet with respect to 100 parts by mass of the polylactic acid resin of the layer P, and is 0.3 mass. Part or more is more preferable, and from the viewpoint of transparency, 1.0 part by mass or less is preferable, 0.8 part by mass or less is more preferable, 0.75 part by mass or less is further preferable, and 0.5 part by mass or less is still more preferable. .
また、層Pのポリ乳酸樹脂組成物中の有機結晶核剤の含有量は、0.05質量%以上1.0質量%以下であるが、結晶化度を向上させる観点から、0.1質量%以上が好ましく、0.2質量%以上がより好ましく、透明性の観点から、0.9質量%以下が好ましく、0.5質量%以下がより好ましい。 The content of the organic crystal nucleating agent in the polylactic acid resin composition of the layer P is 0.05% by mass or more and 1.0% by mass or less, but from the viewpoint of improving the crystallinity, 0.1% by mass. % Or more, more preferably 0.2% by mass or more, and from the viewpoint of transparency, 0.9% by mass or less is preferable, and 0.5% by mass or less is more preferable.
[(P−D)加水分解抑制剤]
本発明のポリ乳酸樹脂組成物積層シートは、耐衝撃性を向上させる観点から、前記成分以外に、更に、加水分解抑制剤を用いることができる。
[(PD) hydrolysis inhibitor]
From the viewpoint of improving impact resistance, the polylactic acid resin composition laminated sheet of the present invention can further contain a hydrolysis inhibitor in addition to the above components.
加水分解抑制剤としては、ポリカルボジイミド化合物やモノカルボジイミド化合物等のカルボジイミド化合物が挙げられる。 Examples of the hydrolysis inhibitor include carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds.
モノカルボジイミド化合物としては、ジフェニルカルボジイミド、ジ−2,6−ジメチルフェニルカルボジイミド、ジ−2,6−ジエチルフェニルカルボジイミド、ジ−2,6−ジイソプロピルフェニルカルボジイミド、ジ−2,6−ジ−tert−ブチルフェニルカルボジイミド、ジ−o−トリルカルボジイミド、ジ−p−トリルカルボジイミド、ジ−2,4,6−トリメチルフェニルカルボジイミド、ジ−2,4,6−トリイソプロピルフェニルカルボジイミド、ジ−2,4,6−トリイソブチルフェニルカルボジイミド等の芳香族モノカルボジイミド化合物;ジ−シクロヘキシルカルボジイミド、ジ−シクロヘキシルメタンカルボジイミド等の脂環族モノカルボジイミド化合物;ジ−イソプロピルカルボジイミド、ジ−オクタデシルカルボジイミド等の脂肪族モノカルボジイミド化合物等が挙げられる。 Examples of monocarbodiimide compounds include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, di-2,6-diethylphenylcarbodiimide, di-2,6-diisopropylphenylcarbodiimide, di-2,6-di-tert-butyl. Phenylcarbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, di-2,4,6-trimethylphenylcarbodiimide, di-2,4,6-triisopropylphenylcarbodiimide, di-2,4,6- Aromatic monocarbodiimide compounds such as triisobutylphenylcarbodiimide; Alicyclic monocarbodiimide compounds such as di-cyclohexylcarbodiimide, di-cyclohexylmethanecarbodiimide; Di-isopropylcarbodiimide, di-octadecylca Aliphatic mono carbodiimide compounds such as Bojiimido like.
ポリカルボジイミドとしては、具体的には、ポリ(4,4’−ジフェニルメタンカルボジイミド)、ポリ(p−フェニレンカルボジイミド)、ポリ(m−フェニレンカルボジイミド)、ポリ(ジイソプロピルフェニルカルボジイミド)、ポリ(トリイソプロピルフェニルカルボジイミド)等の芳香族ポリカルボジイミド;ポリ(ジシクロヘキシルメタンカルボジイミド)等の脂環族ポリカルボジイミドが挙げられる。 Specific examples of the polycarbodiimide include poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (diisopropylphenylcarbodiimide), and poly (triisopropylphenylcarbodiimide). ) And other alicyclic polycarbodiimides such as poly (dicyclohexylmethanecarbodiimide).
前記カルボジイミド化合物は、単独で又は2種以上組み合わせて用いてもよい。これらの中では、耐衝撃性の観点から、ジ−2,6−ジイソプロピルフェニルカルボジイミド、ポリ(ジシクロヘキシルメタンカルボジイミド)が好ましく、ジ−2,6−ジイソプロピルフェニルカルボジイミドがより好ましい。 You may use the said carbodiimide compound individually or in combination of 2 or more types. Among these, from the viewpoint of impact resistance, di-2,6-diisopropylphenylcarbodiimide and poly (dicyclohexylmethanecarbodiimide) are preferable, and di-2,6-diisopropylphenylcarbodiimide is more preferable.
層P中の加水分解抑制剤の含有量は、耐久性を向上させる観点から、層Pのポリ乳酸樹脂100質量部に対して、0.05質量部以上が好ましく、0.1質量部以上がより好ましく、0.3質量部以上が更に好ましく、透明性向上の観点から3質量部以下が好ましく、2質量部以下がより好ましく、1質量部以下が更に好ましい。 From the viewpoint of improving durability, the content of the hydrolysis inhibitor in the layer P is preferably 0.05 parts by mass or more, and 0.1 parts by mass or more with respect to 100 parts by mass of the polylactic acid resin of the layer P. More preferably, 0.3 parts by mass or more is more preferable, 3 parts by mass or less is preferable from the viewpoint of improving transparency, 2 parts by mass or less is more preferable, and 1 part by mass or less is still more preferable.
層Pにおけるポリ乳酸樹脂組成物は、前記以外の他の成分として、滑剤、無機結晶核剤、充填剤(無機充填剤、有機充填剤)、難燃剤、酸化防止剤、紫外線吸収剤、帯電防止剤、防曇剤、光安定剤、顔料、防カビ剤、抗菌剤、発泡剤、衝撃改良剤等を、本発明の効果を損なわない範囲で含有することができる。また同様に、本発明の効果を阻害しない範囲内で他の高分子材料や他の樹脂組成物を含有することも可能である。これらの使用量は公知技術に従って適宜設定することができる。 The polylactic acid resin composition in the layer P includes lubricants, inorganic crystal nucleating agents, fillers (inorganic fillers, organic fillers), flame retardants, antioxidants, ultraviolet absorbers, antistatics as components other than those described above. An agent, an antifogging agent, a light stabilizer, a pigment, an antifungal agent, an antibacterial agent, a foaming agent, an impact modifier and the like can be contained within a range not impairing the effects of the present invention. Similarly, other polymer materials and other resin compositions can be contained within a range that does not impair the effects of the present invention. These amounts used can be appropriately set according to known techniques.
層Pにおけるポリ乳酸樹脂組成物は、前記成分(P−A)〜(P−C)を含有するものであれば特に限定なく調製することができ、例えば、ポリ乳酸樹脂、可塑剤、及び有機結晶核剤、さらに必要により、加水分解抑制剤を含む他の添加剤を含有する原料を、密閉式ニーダー、1軸もしくは2軸の押出機、オープンロール型混練機等の公知の混練機を用いて溶融混練して調製することができる。原料は、予めヘンシェルミキサー、スーパーミキサー等を用いて均一に混合した後に、溶融混練に供することも可能である。なお、ポリ乳酸樹脂組成物を調製する際にポリ乳酸樹脂の可塑性を促進させるため、超臨界ガスを存在させて溶融混合させてもよい。溶融混練後は、公知の方法に従って、溶融混練物を乾燥させてもよい。 The polylactic acid resin composition in the layer P can be prepared without particular limitation as long as it contains the components (PA) to (PC). For example, polylactic acid resin, plasticizer, and organic Using a known kneader such as a closed kneader, a single or twin screw extruder, an open roll kneader, and the like containing a crystal nucleating agent and, if necessary, other additives including a hydrolysis inhibitor. And can be prepared by melt-kneading. The raw materials can be subjected to melt kneading after being uniformly mixed in advance using a Henschel mixer, a super mixer, or the like. In preparing the polylactic acid resin composition, in order to promote the plasticity of the polylactic acid resin, it may be melt-mixed in the presence of a supercritical gas. After the melt-kneading, the melt-kneaded product may be dried according to a known method.
溶融混練温度は、分解抑制及び透明性の観点から、好ましくは170℃以上であり、好ましくは220℃以下、より好ましくは200℃以下である。溶融混練時間は、溶融混練温度、混練機の種類によって一概には決定できないが、15秒間以上900秒間以下が好ましい。 The melt kneading temperature is preferably 170 ° C. or higher, preferably 220 ° C. or lower, more preferably 200 ° C. or lower, from the viewpoints of suppression of decomposition and transparency. The melt-kneading time cannot be generally determined depending on the melt-kneading temperature and the type of the kneader, but is preferably 15 seconds or more and 900 seconds or less.
かくして得られた層Pにおけるポリ乳酸樹脂組成物は、公知の方法に従って、層状化(シート化)することができる。なお、本発明においては、層Pと層Qを別々にシート化した後それらを所望の順に積層してもよく、また、層Pと層Qの各ポリ乳酸樹脂組成物を所望の順に積層したものを同時にシート化してもよい。詳細は後述する。 The polylactic acid resin composition in the layer P thus obtained can be layered (sheeted) according to a known method. In the present invention, the layer P and the layer Q may be separately formed and then laminated in the desired order, and the polylactic acid resin compositions of the layer P and the layer Q are laminated in the desired order. Things may be made into sheets at the same time. Details will be described later.
〔層Q〕
本発明における層Qは、(Q−A)ポリ乳酸樹脂、(Q−B)可塑剤、及び(Q−C)有機結晶核剤を含有するポリ乳酸樹脂組成物の層であって、可塑剤の含有量と有機結晶核剤の含有量が以下の含有量であることを特徴とする。
[Layer Q]
The layer Q in the present invention is a layer of a polylactic acid resin composition containing (QA) a polylactic acid resin, (QB) a plasticizer, and (QC) an organic crystal nucleating agent. The content of and the content of the organic crystal nucleating agent are the following contents.
[(Q−A)ポリ乳酸樹脂]
層Qにおけるポリ乳酸樹脂は、層Pにおけるポリ乳酸樹脂と同様のものを用いることができる。具体的には、層Pにおけるポリ乳酸樹脂の項に例示されたものである。なかでも、層Qのポリ乳酸樹脂組成物の透明性を向上する観点から、光学純度が好ましくは50%以上、より好ましくは70%以上、更に好ましくは80%以上であり、好ましくは99%以下のポリ乳酸樹脂が好ましく、例えば、Nature Works社製ポリ乳酸樹脂(NW2003D、4032D、4060D等)を用いることができる。
[(Q-A) polylactic acid resin]
As the polylactic acid resin in the layer Q, the same polylactic acid resin as in the layer P can be used. Specifically, it is exemplified in the section of the polylactic acid resin in the layer P. Among them, from the viewpoint of improving the transparency of the polylactic acid resin composition of the layer Q, the optical purity is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, preferably 99% or less. A polylactic acid resin (NW2003D, 4032D, 4060D, etc.) manufactured by Nature Works, for example, can be used.
ポリ乳酸樹脂の含有量は、耐衝撃性と透明性の観点から、層Qのポリ乳酸樹脂組成物中、95質量%以上が好ましく、実質的に100質量%がより好ましく、100質量%が更に好ましい。ここで、実質的に100質量%とは不可避的に微量の不純物を含む場合を言う。 From the viewpoint of impact resistance and transparency, the content of the polylactic acid resin is preferably 95% by mass or more, more preferably 100% by mass, and even more preferably 100% by mass in the polylactic acid resin composition of the layer Q. preferable. Here, “substantially 100% by mass” refers to the case of inevitably containing a trace amount of impurities.
[(Q−B)可塑剤]
層Qにおける可塑剤は、層Pにおける可塑剤と同様のものを用いることができ、具体的には、層Pにおける可塑剤の項に例示されたものが挙げられる。
[(Q-B) Plasticizer]
As the plasticizer in the layer Q, the same plasticizer as that in the layer P can be used. Specific examples include those exemplified in the section of the plasticizer in the layer P.
層Q中の可塑剤の含有量は、層Qのポリ乳酸樹脂100質量部に対して、透明性の観点から、6質量部以下が好ましく、5質量部以下がより好ましく、4質量部以下が更に好ましく、3質量部以下が更に好ましく、2質量部以下がより更に好ましい。下限は特に設定されないが、0質量部以上であればよい。 The plasticizer content in the layer Q is preferably 6 parts by mass or less, more preferably 5 parts by mass or less, and more preferably 4 parts by mass or less from the viewpoint of transparency with respect to 100 parts by mass of the polylactic acid resin of the layer Q. More preferred is 3 parts by mass or less, still more preferred is 2 parts by mass or less. Although a minimum in particular is not set, it should just be 0 mass parts or more.
また、層Qのポリ乳酸樹脂組成物中の可塑剤の含有量は、0質量%以上6質量%以下であるが、透明性の観点から、5.4質量%以下が好ましく、5質量%以下がより好ましく、4質量%以下が更に好ましく、3質量%以下がより更に好ましい。なお、本明細書において、可塑剤の含有量が0質量部又は0質量%とは、層Qにおけるポリ乳酸樹脂組成物に可塑剤が含まれない態様のことであり、本発明においては、層Qに可塑剤が添加されても、添加されなくてもよい。また、本発明においては、層Pから可塑剤成分が移行して層Q中に認められてもよく、前記範囲内の含有量となり、かつ、層P中の可塑剤含有量が多くなるのであれば本発明に含まれるものとする。 The content of the plasticizer in the polylactic acid resin composition of the layer Q is 0% by mass or more and 6% by mass or less, but is preferably 5.4% by mass or less from the viewpoint of transparency, and is 5% by mass or less. Is more preferable, 4 mass% or less is further more preferable, and 3 mass% or less is still more preferable. In addition, in this specification, content of a plasticizer is 0 mass part or 0 mass% is an aspect in which a plasticizer is not contained in the polylactic acid resin composition in the layer Q. In the present invention, a layer A plasticizer may or may not be added to Q. In the present invention, the plasticizer component may be transferred from the layer P and may be recognized in the layer Q, so that the content is within the above range and the plasticizer content in the layer P is increased. Are included in the present invention.
本発明においては、層P中の可塑剤と層Q中の可塑剤では、層P中の可塑剤の含有量が多いことを一つの特徴とする。層Qにおけるポリ乳酸樹脂の含有量を基準とし、層Qにおけるポリ乳酸樹脂100質量部に対する含有量として比較した場合、層P中の可塑剤の含有量は、層Q中の可塑剤の含有量に比べて、好ましくは1質量部以上、より好ましくは2質量部以上多ければよい。また、上限は特に設定されない。 In the present invention, the plasticizer in the layer P and the plasticizer in the layer Q are characterized in that the plasticizer content in the layer P is large. When the content of the polylactic acid resin in the layer Q is used as a reference and compared with the content of 100 parts by mass of the polylactic acid resin in the layer Q, the content of the plasticizer in the layer P is the content of the plasticizer in the layer Q. Compared to the above, it is preferable that the amount is preferably 1 part by mass or more, more preferably 2 parts by mass or more. Also, no upper limit is set.
また、本発明の積層シートに用いられる可塑剤の合計含有量としては、積層シート中のポリ乳酸樹脂の合計含有量を100質量部とした場合、2質量部以上が好ましく、3質量部以上がより好ましく、4.5質量部以上が更に好ましく、6質量部以上がより更に好ましく、16質量部以下が好ましく、12質量部以下がより好ましく、10質量部以下が更に好ましい。本発明では、可塑剤の全体としての使用量が前記範囲内のような量であっても十分な耐衝撃性が得られる。 Moreover, as total content of the plasticizer used for the laminated sheet of the present invention, when the total content of the polylactic acid resin in the laminated sheet is 100 parts by mass, 2 parts by mass or more is preferable, and 3 parts by mass or more is preferable. More preferably, 4.5 parts by mass or more is more preferable, 6 parts by mass or more is more preferable, 16 parts by mass or less is preferable, 12 parts by mass or less is more preferable, and 10 parts by mass or less is still more preferable. In the present invention, sufficient impact resistance can be obtained even when the total amount of plasticizer used is within the above range.
[(Q−C)有機結晶核剤]
層Qで用いられる有機結晶核剤としては、層Pにおける有機結晶核剤と同様のものを用いることができ、具体的には、層Pにおける有機結晶核剤の項に例示されたものが挙げられる。
[(QC) Organic crystal nucleating agent]
As the organic crystal nucleating agent used in the layer Q, those similar to the organic crystal nucleating agent in the layer P can be used, and specifically, those exemplified in the section of the organic crystal nucleating agent in the layer P can be mentioned. It is done.
層Q中の有機結晶核剤の含有量は、層Qのポリ乳酸樹脂100質量部に対して、透明性の観点から、0.9質量部以下が好ましく、0.5質量部以下がより好ましく、0.2質量部以下が更に好ましい。下限は特に設定されないが、0質量部以上であればよい。 The content of the organic crystal nucleating agent in the layer Q is preferably 0.9 parts by mass or less, more preferably 0.5 parts by mass or less, from the viewpoint of transparency with respect to 100 parts by mass of the polylactic acid resin of the layer Q. 0.2 parts by mass or less is more preferable. Although a minimum in particular is not set, it should just be 0 mass parts or more.
また、層Qのポリ乳酸樹脂組成物中の有機結晶核剤の含有量は、0質量%以上0.3質量%以下であるが、透明性の観点から、0.2質量%以下が好ましく、0.1質量%以下がより好ましい。なお、本明細書において、有機結晶核剤の含有量が0質量部又は0質量%とは、層Qにおけるポリ乳酸樹脂組成物に有機結晶核剤が含まれない態様のことであり、本発明においては、層Qに有機結晶核剤が添加されても、添加されなくてもよい。また、本発明においては、層Pから有機結晶核剤成分が移行して層Q中に認められてもよく、前記範囲内の含有量であれば本発明に含まれるものとする。 Further, the content of the organic crystal nucleating agent in the polylactic acid resin composition of the layer Q is 0% by mass or more and 0.3% by mass or less, but from the viewpoint of transparency, 0.2% by mass or less is preferable, 0.1 mass% or less is more preferable. In the present specification, the content of the organic crystal nucleating agent is 0 part by mass or 0% by mass, which is an aspect in which the organic nucleating agent is not contained in the polylactic acid resin composition in the layer Q. In this case, an organic crystal nucleating agent may or may not be added to the layer Q. In the present invention, the organic crystal nucleating agent component may migrate from the layer P and be recognized in the layer Q, and any content within the above range is included in the present invention.
層Qにおけるポリ乳酸樹脂組成物は、前記以外の他の成分として、加水分解抑制剤、滑剤、無機結晶核剤、充填剤(無機充填剤、有機充填剤)、難燃剤、酸化防止剤、紫外線吸収剤、帯電防止剤、防曇剤、光安定剤、顔料、防カビ剤、抗菌剤、発泡剤、衝撃改良剤、結晶化阻害剤等を、本発明の効果を損なわない範囲で含有することができる。また同様に、本発明の効果を阻害しない範囲内で他の高分子材料や他の樹脂組成物を含有することも可能である。これらの使用量は公知技術に従って適宜設定することができる。 The polylactic acid resin composition in the layer Q includes, as components other than the above, hydrolysis inhibitors, lubricants, inorganic crystal nucleating agents, fillers (inorganic fillers, organic fillers), flame retardants, antioxidants, ultraviolet rays It contains an absorbent, an antistatic agent, an antifogging agent, a light stabilizer, a pigment, an antifungal agent, an antibacterial agent, a foaming agent, an impact modifier, a crystallization inhibitor, and the like as long as the effects of the present invention are not impaired. Can do. Similarly, other polymer materials and other resin compositions can be contained within a range that does not impair the effects of the present invention. These amounts used can be appropriately set according to known techniques.
また、本発明においては、層Qの透明性を向上する観点から、層Q中のポリ乳酸樹脂の結晶性が低いことが好ましい。よって、例えば、層Qにおけるポリ乳酸樹脂組成物に結晶化阻害剤を配合することができる。結晶化阻害剤としては、ポリ乳酸との相互作用の観点から酸性基を持つものが好ましく、ポリマーの高次構造を乱す観点から非晶・非定形である事が好ましく、結晶化阻害効果の安定性の観点から無機物及び/又は高分子が好ましい。具体的には、例えば、アルミノシリケート、シリカ、ならびに、(メタ)アクリル酸、(メタ)アクリル酸エステル、及び(メタ)アクリル酸アミドから選ばれる1種又は2種以上を重合して得られる樹脂が好ましく、シリカ、ポリメタクリル酸メチルがより好ましい。結晶化阻害剤の含有量としては、特に設定されないが、例えば、層Qのポリ乳酸樹脂100質量部に対して、0.5質量部以上25質量部以下が例示される。また、結晶化阻害効果の安定性の観点から、無機物の場合は、層Qのポリ乳酸樹脂100質量部に対して、好ましくは0.5質量部以上、より好ましくは0.7質量部以上であり、好ましくは3質量部以下、より好ましくは1.3質量部以下である。高分子の場合は、層Qのポリ乳酸樹脂100質量部に対して、好ましくは10質量部以上、より好ましくは15質量部以上であり、好ましくは25質量部以下、より好ましくは22質量部以下である。 Moreover, in this invention, it is preferable that the crystallinity of the polylactic acid resin in the layer Q is low from a viewpoint of improving the transparency of the layer Q. Therefore, for example, a crystallization inhibitor can be added to the polylactic acid resin composition in the layer Q. The crystallization inhibitor preferably has an acidic group from the viewpoint of interaction with polylactic acid, and is preferably amorphous or amorphous from the viewpoint of disturbing the higher-order structure of the polymer. From the viewpoint of properties, inorganic substances and / or polymers are preferable. Specifically, for example, a resin obtained by polymerizing one or more selected from aluminosilicate, silica, and (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide. Are preferred, and silica and polymethyl methacrylate are more preferred. Although it does not set in particular as content of a crystallization inhibitor, For example, 0.5 mass part or more and 25 mass parts or less are illustrated with respect to 100 mass parts of polylactic acid resin of the layer Q. Further, from the viewpoint of stability of the crystallization inhibition effect, in the case of an inorganic substance, it is preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more with respect to 100 parts by mass of the polylactic acid resin of the layer Q. Yes, preferably 3 parts by mass or less, more preferably 1.3 parts by mass or less. In the case of a polymer, it is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, preferably 25 parts by mass or less, more preferably 22 parts by mass or less, relative to 100 parts by mass of the polylactic acid resin of the layer Q. It is.
層Qにおけるポリ乳酸樹脂組成物は、前記成分(Q−A)〜(Q−C)を含有するものであれば特に限定なく調製することができ、層Pにおけるポリ乳酸樹脂組成物と同様にして調製することができる。具体的には、層Pにおけるポリ乳酸樹脂組成物の調製方法の項を参照することができる。 The polylactic acid resin composition in layer Q can be prepared without particular limitation as long as it contains the components (QA) to (QC), and is the same as the polylactic acid resin composition in layer P. Can be prepared. Specifically, the section of the method for preparing the polylactic acid resin composition in the layer P can be referred to.
かくして得られた層Qにおけるポリ乳酸樹脂組成物は、公知の方法に従って、層状化(シート化)することができる。層Pと層Qの積層方法については、公知の方法を選択することができるが、以下に、層Pと層Qの各ポリ乳酸樹脂組成物を所望の順に同時にシート化する方法について説明する。 The polylactic acid resin composition in the layer Q thus obtained can be layered (made into a sheet) according to a known method. A known method can be selected as a method for laminating the layer P and the layer Q. Hereinafter, a method for simultaneously forming sheets of the polylactic acid resin compositions of the layer P and the layer Q in a desired order will be described.
具体的には、例えば、層Pと層Qの各ポリ乳酸樹脂組成物を、例えば、フィードブロック法、マルチマニホールド法等のTダイを用いた溶融共押出成形に供することで積層シートを調製することができる。ここで、得られた積層シートを直ぐに冷却ロール、次いで加熱ロールに接触させることでシートの結晶性を調整し、その後、裁断してもよい。また、得られた積層シートを必要に応じて一軸又は二軸延伸してもよい。なお、押出機に充填する際に、各ポリ乳酸樹脂組成物を構成する原料を充填して溶融混練後、押出成形してもよい。 Specifically, for example, each of the polylactic acid resin compositions of the layer P and the layer Q is subjected to melt coextrusion molding using a T die such as a feed block method or a multi-manifold method to prepare a laminated sheet. be able to. Here, the crystallinity of the sheet may be adjusted by immediately contacting the obtained laminated sheet with a cooling roll and then a heating roll, and then cut. Moreover, you may uniaxially or biaxially stretch the obtained lamination sheet as needed. In addition, when filling an extruder, you may extrude after filling the raw material which comprises each polylactic acid resin composition, melt-kneading.
押出機の温度は、層Pと層Qのポリ乳酸樹脂組成物の構成成分によって同じであっても異なっていてもよい。具体的には、透明性向上の観点から、好ましくは170℃以上、より好ましくは175℃以上、更に好ましくは180℃以上であり、好ましくは240℃以下、より好ましくは220℃以下、更に好ましくは210℃以下の温度範囲内で適宜設定することができる。なお、本発明において、押出機の温度とは押出機の二軸混練部のシリンダー温度を意味する。また、押出機における滞留時間は、シートの厚さや幅、巻き取り速度に依存するため一概には規定できないが、熱による劣化を避ける観点から、30秒から数分程度が好ましい。 The temperature of the extruder may be the same or different depending on the components of the polylactic acid resin composition of the layer P and the layer Q. Specifically, from the viewpoint of improving transparency, it is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, further preferably 180 ° C. or higher, preferably 240 ° C. or lower, more preferably 220 ° C. or lower, still more preferably. It can set suitably within the temperature range of 210 degrees C or less. In addition, in this invention, the temperature of an extruder means the cylinder temperature of the biaxial kneading part of an extruder. Further, the residence time in the extruder cannot be defined unconditionally because it depends on the thickness, width, and winding speed of the sheet, but is preferably about 30 seconds to several minutes from the viewpoint of avoiding deterioration due to heat.
冷却ロールの温度は、透明性向上と冷却ロールからの剥離性向上の観点から、40℃未満が好ましく、30℃以下がより好ましい。 The temperature of the cooling roll is preferably less than 40 ° C., more preferably 30 ° C. or less, from the viewpoint of improving transparency and improving peelability from the cooling roll.
冷却ロールに接する時間としては、冷却ロールの設定温度や冷却ロールの個数、押出速度、シート巻取速度によって異なるため必ずしも規定されるものではないが、例えば透明性向上と冷却ロールからの剥離性向上の観点から、好ましくは1秒以上、より好ましくは3秒以上、更に好ましくは5秒以上であり、好ましくは60秒以下、より好ましくは50秒以下、更に好ましくは40秒以下である。 The time for contact with the cooling roll is not necessarily specified because it varies depending on the set temperature of the cooling roll, the number of cooling rolls, the extrusion speed, and the sheet winding speed. For example, it improves transparency and improves peelability from the cooling roll. From this point of view, it is preferably 1 second or longer, more preferably 3 seconds or longer, still more preferably 5 seconds or longer, preferably 60 seconds or shorter, more preferably 50 seconds or shorter, still more preferably 40 seconds or shorter.
加熱ロールの表面温度は、透明性向上と結晶化度向上の観点から、65℃以上が好ましく、70℃以上がより好ましく、75℃以上が更に好ましく、100℃以下が好ましい。また加熱ロールに接触している時間の合計は、5秒以上が好ましく、10秒以上がより好ましく、15秒以上が更に好ましい。なお、冷却ロール及び加熱ロールの表面温度とは、ロール表面の実測した温度を意味し、接触式温度計を用いて測定することができる。 The surface temperature of the heating roll is preferably 65 ° C. or higher, more preferably 70 ° C. or higher, further preferably 75 ° C. or higher, and preferably 100 ° C. or lower, from the viewpoint of improving transparency and improving the crystallinity. The total time of contact with the heating roll is preferably 5 seconds or more, more preferably 10 seconds or more, and even more preferably 15 seconds or more. In addition, the surface temperature of a cooling roll and a heating roll means the temperature actually measured on the roll surface, and can be measured using a contact-type thermometer.
かくして、本発明のポリ乳酸樹脂組成物積層シートが得られる。得られた積層シートの厚みは、好ましくは10μm以上、より好ましくは100μm以上であり、好ましくは1000μm以下、より好ましくは700μm以下である。 Thus, the polylactic acid resin composition laminate sheet of the present invention is obtained. The thickness of the obtained laminated sheet is preferably 10 μm or more, more preferably 100 μm or more, preferably 1000 μm or less, more preferably 700 μm or less.
また、積層シートにおける各層は、例えば、層Pを複数含み、そのうち最も厚い1層の厚みが、積層シート全体の厚みに対して、耐衝撃性の観点から、好ましくは5%以上、より好ましくは7%以上、更に好ましくは11%以上、更に好ましくは15%以上であり、透明性の観点から、好ましくは40%以下、より好ましくは35%以下、更に好ましくは28%以下、更に好ましくは24%以下であることが好ましい。 Each layer in the laminated sheet includes, for example, a plurality of layers P, and the thickness of the thickest layer is preferably 5% or more, more preferably from the viewpoint of impact resistance with respect to the thickness of the entire laminated sheet. 7% or more, more preferably 11% or more, more preferably 15% or more. From the viewpoint of transparency, it is preferably 40% or less, more preferably 35% or less, still more preferably 28% or less, and still more preferably 24%. % Or less is preferable.
また、層Pの合計厚みと層Qの厚みの比(層P/層Q)としては、80/20〜10/90が好ましく、55/45〜30/70がより好ましい。 Further, the ratio of the total thickness of the layer P to the thickness of the layer Q (layer P / layer Q) is preferably 80/20 to 10/90, and more preferably 55/45 to 30/70.
層Pを複数含み、そのうち最も厚い1層の厚みが、積層シート全体の厚みに対して、5%以上28%以下であるとき、層P中の可塑剤の含有量は、耐衝撃性の観点から6質量%以上が好ましく、8質量%以上がより好ましく、10質量%以上が更に好ましく、透明性の観点から、15質量%以下が好ましく、14質量%以下がより好ましい。 When the thickness of the thickest one layer is 5% or more and 28% or less with respect to the total thickness of the laminated sheet, the content of the plasticizer in the layer P is in terms of impact resistance. To 6% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and from the viewpoint of transparency, 15% by mass or less is preferable, and 14% by mass or less is more preferable.
かくして得られた本発明のポリ乳酸樹脂組成物積層シートは、透明性が良好で、耐衝撃性に優れることから、各種用途、例えば、日用品、化粧品、家電製品などの包装材として、ブリスターパックやトレイ、お弁当の蓋等の食品容器、工業部品の輸送や保護に用いる工業用トレイ等の材として好適に用いることができる。 The thus obtained polylactic acid resin composition laminate sheet of the present invention has good transparency and excellent impact resistance, so that it can be used as a packaging material for various uses, for example, daily necessities, cosmetics, and home appliances. It can be suitably used as a material for trays, food containers such as lunch box lids, and industrial trays used for transportation and protection of industrial parts.
本発明はまた、本発明のポリ乳酸樹脂組成物積層シートの製造方法を提供する。 This invention also provides the manufacturing method of the polylactic acid resin composition laminated sheet of this invention.
製造方法としては、層Pにおけるポリ乳酸樹脂組成物と層Qにおけるポリ乳酸樹脂組成物を溶融共押出成形する工程を含む方法であればよく、例えば、以下の方法が好適に用いられる。 As a manufacturing method, what is necessary is just a method including the process of melt-coextrusion molding the polylactic acid resin composition in the layer P and the polylactic acid resin composition in the layer Q. For example, the following methods are used suitably.
具体的には、下記工程(1)〜(3)を有する製造方法が挙げられる。
工程(1):(P−A)ポリ乳酸樹脂、(P−B)可塑剤、及び(P−C)有機結晶核剤を含有する原料を溶融混練して、層Pを構成するポリ乳酸樹脂組成物を調製する工程であって、層中の(P−B)可塑剤の含有量が4質量%以上18質量%以下であり、(P−C)有機結晶核剤の含有量が0.05質量%以上1.0質量%以下である工程
工程(2):(Q−A)ポリ乳酸樹脂、(Q−B)可塑剤、及び(Q−C)有機結晶核剤を含有する原料を溶融混練して、層Qを構成するポリ乳酸樹脂組成物を調製する工程であって、層中の(Q−B)可塑剤の含有量が0質量%以上6質量%以下であり、(Q−C)有機結晶核剤の含有量が0質量%以上0.3質量%以下であり、
ここで、層P中の(P−B)可塑剤の含有量の方が層Q中の(Q−B)可塑剤の含有量より多い工程
工程(3):工程(1)で得られた層Pのポリ乳酸樹脂組成物と、工程(2)で得られた層Qのポリ乳酸樹脂組成物とを層Pがシートの表面側と裏面側の少なくとも一方の最外層になるように溶融共押出成形する工程
Specifically, the manufacturing method which has the following process (1)-(3) is mentioned.
Step (1): Polylactic acid resin constituting layer P by melting and kneading raw materials containing (PA) polylactic acid resin, (PB) plasticizer, and (PC) organic crystal nucleating agent In the step of preparing the composition, the content of the (P-B) plasticizer in the layer is 4% by mass or more and 18% by mass or less, and the content of the (PC) organic crystal nucleating agent is 0.00. Process step (2) which is not less than 05% by mass and not more than 1.0% by mass: A raw material containing (QA) polylactic acid resin, (QB) plasticizer, and (QC) organic crystal nucleating agent A step of preparing a polylactic acid resin composition constituting the layer Q by melt-kneading, wherein the content of the (Q-B) plasticizer in the layer is 0% by mass to 6% by mass, (Q -C) The content of the organic crystal nucleating agent is 0% by mass or more and 0.3% by mass or less,
Here, the content of the (P-B) plasticizer in the layer P is larger than the content of the (Q-B) plasticizer in the layer Q. The process step (3): obtained in the step (1). The polylactic acid resin composition of layer P and the polylactic acid resin composition of layer Q obtained in step (2) are melt-coagulated so that layer P is at least one of the outermost layers on the front side and the back side of the sheet. Extrusion process
工程(1)は、(P−A)ポリ乳酸樹脂、(P−B)可塑剤、及び(P−C)有機結晶核剤、さらに必要に応じて(P−D)加水分解抑制剤を含む他の添加剤を含む原料を、密閉式ニーダー、1軸もしくは2軸の押出機、オープンロール型混練機等の公知の混練機を用いて、好ましくは170℃以上であり、好ましくは220℃以下、より好ましくは200℃以下の温度で溶融混練して、層Pにおけるポリ乳酸樹脂組成物を調製する。原料や溶融混練の条件は、前記本発明のポリ乳酸樹脂組成物積層シートの項に準ずる。 Step (1) includes (PA) polylactic acid resin, (PB) plasticizer, and (PC) organic crystal nucleating agent, and (PD) hydrolysis inhibitor as necessary. The raw materials containing other additives are preferably 170 ° C. or higher, preferably 220 ° C. or lower, using a known kneader such as a closed kneader, a single or twin screw extruder, and an open roll kneader. More preferably, the polylactic acid resin composition in the layer P is prepared by melt-kneading at a temperature of 200 ° C. or lower. The raw material and melt kneading conditions are in accordance with the term of the polylactic acid resin composition laminated sheet of the present invention.
工程(2)は、(Q−A)ポリ乳酸樹脂、(Q−B)可塑剤、及び(Q−C)有機結晶核剤を含む原料を、密閉式ニーダー、1軸もしくは2軸の押出機、オープンロール型混練機等の公知の混練機を用いて、好ましくは170℃以上であり、好ましくは220℃以下、より好ましくは200℃以下の温度で溶融混練して、層Qにおけるポリ乳酸樹脂組成物を調製する。原料や溶融混練の条件は、前記本発明のポリ乳酸樹脂組成物積層シートの項に準ずる。 In step (2), a raw material containing (Q-A) polylactic acid resin, (Q-B) plasticizer, and (Q-C) organic crystal nucleating agent is used as a closed kneader, a single-screw or a twin-screw extruder. The polylactic acid resin in layer Q is melt kneaded at a temperature of preferably 170 ° C. or higher, preferably 220 ° C. or lower, more preferably 200 ° C. or lower, using a known kneader such as an open roll kneader. A composition is prepared. The raw material and melt kneading conditions are in accordance with the term of the polylactic acid resin composition laminated sheet of the present invention.
工程(3)では、工程(1)及び工程(2)で得られたポリ乳酸樹脂組成物を溶融共押出成形する。溶融共押出成形としては、公知の溶融共押出成形機を用いて成形することができ、層Pが得られるシートの表面側と裏面側の少なくとも一方の最外層になるように、条件を適宜設定することができる。例えば、冷却ロールと加熱ロールを備えた溶融共押出シート成形機(創研社製、300mmT−ダイ)を用いる場合は、結晶性が調整された積層シートを得ることができる。押出機の条件や、その後の冷却ロール、加熱ロールに接触させる場合の条件は、前記本発明のポリ乳酸樹脂組成物積層シートの項に準ずる。 In step (3), the polylactic acid resin composition obtained in step (1) and step (2) is melt-coextruded. As the melt coextrusion molding, it can be molded using a known melt coextrusion molding machine, and the conditions are appropriately set so that the layer P is at least one of the outermost layer on the front side and the back side of the sheet from which the layer P is obtained. can do. For example, when a melt coextrusion sheet forming machine (manufactured by Soken Co., Ltd., 300 mm T-die) equipped with a cooling roll and a heating roll is used, a laminated sheet with adjusted crystallinity can be obtained. The conditions for the extruder and the conditions for bringing it into contact with the subsequent cooling roll and heating roll are in accordance with the terms for the polylactic acid resin composition laminated sheet of the present invention.
溶融共押出成形後のシートは、端部を裁断して成形してもよく、裁断された端部は、溶融後、層P及び/又は層Qを構成するポリ乳酸樹脂組成物の原料と混合して、各層のポリ乳酸樹脂組成物として使用することができる。なかでも、層Qを構成するポリ乳酸樹脂組成物の原料と混合して使用することが好ましく、本発明のポリ乳酸樹脂組成物積層シートの製造方法の他の態様として、更に、下記工程(4)を含む態様を挙げることができる。
工程(4):工程(3)で得られた溶融共押出成形品の一部を裁断後、回収して工程(2)におけるポリ乳酸樹脂組成物の原料と混合して使用する工程
The sheet after the melt coextrusion molding may be formed by cutting the end, and the cut end is mixed with the raw material of the polylactic acid resin composition constituting the layer P and / or the layer Q after melting. And it can be used as a polylactic acid resin composition of each layer. Especially, it is preferable to mix and use with the raw material of the polylactic acid resin composition which comprises the layer Q, and also as a further aspect of the manufacturing method of the polylactic acid resin composition laminated sheet of this invention, following process (4) ).
Step (4): A step of cutting a part of the melt-coextruded product obtained in Step (3) and then recovering and mixing it with the raw material of the polylactic acid resin composition in Step (2).
工程(4)において端部の裁断は公知技術に従って行うことができる。端部を裁断する比率としては、生産性の観点から、ポリ乳酸樹脂組成物積層シートの50質量%以下が好ましく、40質量%以下がより好ましく、30質量%以下が更に好ましい。 In the step (4), the edge portion can be cut according to a known technique. As a ratio which cuts an edge part, from a viewpoint of productivity, 50 mass% or less of a polylactic acid resin composition lamination sheet is preferred, 40 mass% or less is more preferred, and 30 mass% or less is still more preferred.
以下、実施例を示して本発明を具体的に説明する。なお、この実施例は、単なる本発明の例示であり、何ら限定を意味するものではない。例中の部は、特記しない限り質量部である。なお、「常圧」とは101.3kPaを、「常温」とは25℃を示す。 Hereinafter, the present invention will be specifically described with reference to examples. Note that this example is merely illustrative of the present invention and is not meant to be limiting. The parts in the examples are parts by mass unless otherwise specified. “Normal pressure” indicates 101.3 kPa, and “normal temperature” indicates 25 ° C.
可塑剤の製造例1((MeEO3)2SA、コハク酸とトリエチレングリコールモノメチルエーテルとのジエステル化合物)
攪拌機、温度計、脱水管を備えた3Lフラスコに、無水コハク酸500g、トリエチレングリコールモノメチルエーテル(和光純薬社製、試薬)2463g、パラトルエンスルホン酸一水酸化物(和光純薬社製、試薬)9.5gを仕込み、空間部に窒素(500mL/分)を吹き込みながら、減圧下(4〜10.7kPa)、110℃で15時間反応させた。反応液の酸価は1.6mgKOH/gであった。反応液に吸着剤キョーワード500SH(協和化学工業社製)27gを添加して80℃、2.7kPaで45分間攪拌してろ過した後、液温115〜200℃、圧力0.03kPaでトリエチレングリコールモノメチルエーテルを留去し、80℃に冷却後、残液を減圧ろ過して、ろ液として、コハク酸とトリエチレングリコールモノメチルエーテルとのジエステル〔(MeEO3)2SA〕を得た。得られたジエステルは、重量平均分子量410、粘度(23℃)27mPa・s、酸価0.2mgKOH/g、鹸化価274mgKOH/g、水酸基価1mgKOH/g以下、色相APHA200であった。なお、本可塑剤は、水酸基1個当たりエチレンオキサイドを3モル付加したアルコールとのエステル化合物である。
Production Example 1 of Plasticizer ((MeEO 3 ) 2 SA, Diester Compound of Succinic Acid and Triethylene Glycol Monomethyl Ether)
In a 3 L flask equipped with a stirrer, a thermometer, and a dehydrating tube, 500 g of succinic anhydride, 2463 g of triethylene glycol monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd., reagent), paratoluenesulfonic acid monohydroxide (manufactured by Wako Pure Chemical Industries, Ltd., Reagent) (9.5 g) was charged and reacted at 110 ° C. for 15 hours under reduced pressure (4 to 10.7 kPa) while blowing nitrogen (500 mL / min) into the space. The acid value of the reaction solution was 1.6 mgKOH / g. After adding 27 g of adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) to the reaction solution and stirring and filtering at 80 ° C. and 2.7 kPa for 45 minutes, triethylene at a liquid temperature of 115 to 200 ° C. and a pressure of 0.03 kPa. After distilling off the glycol monomethyl ether and cooling to 80 ° C., the residual liquid was filtered under reduced pressure to obtain a diester [(MeEO 3 ) 2 SA] of succinic acid and triethylene glycol monomethyl ether as a filtrate. The obtained diester had a weight average molecular weight of 410, a viscosity (23 ° C.) of 27 mPa · s, an acid value of 0.2 mgKOH / g, a saponification value of 274 mgKOH / g, a hydroxyl value of 1 mgKOH / g or less, and a hue APHA200. In addition, this plasticizer is an ester compound with the alcohol which added 3 mol of ethylene oxide per hydroxyl group.
可塑剤の製造例2((MeEO4)2SA、コハク酸とテトラエチレングリコールモノメチルエーテルとのジエステル化合物)
攪拌機、温度計、脱水管を備えた3Lフラスコに、無水コハク酸500g、テトラエチレングリコールモノメチルエーテル3124g、パラトルエンスルホン酸一水酸化物9.5gを仕込み、空間部に窒素(500mL/分)を吹き込みながら、減圧下(4〜10.7kPa)、130℃で20時間反応させた。反応液の酸価は1.6mgKOH/gであった。反応液に吸着剤キョーワード500SH 27gを添加して80℃、2.7kPaで45分間攪拌してろ過した後、液温150〜250℃、圧力0.003kPaでテトラエチレングリコールモノメチルエーテルを留去し、80℃に冷却後、残液を減圧ろ過して、ろ液として、コハク酸とテトラエチレングリコールモノメチルエーテルとのジエステル〔(MeEO4)2SA〕を得た。得られたジエステルは、重量平均分子量499、粘度(23℃)35mPa・s、酸価0.2mgKOH/g、鹸化価225mgKOH/g、水酸基価1mgKOH/g以下、色相APHA230であった。なお、本可塑剤は、水酸基1個当たりエチレンオキサイドを4モル付加したアルコールとのエステル化合物である。
Production Example 2 of Plasticizer ((MeEO 4 ) 2 SA, Diester Compound of Succinic Acid and Tetraethylene Glycol Monomethyl Ether)
A 3 L flask equipped with a stirrer, thermometer, and dehydration tube was charged with 500 g of succinic anhydride, 3124 g of tetraethylene glycol monomethyl ether, and 9.5 g of paratoluenesulfonic acid monohydroxide, and nitrogen (500 mL / min) was added to the space. While blowing, the reaction was carried out at 130 ° C. for 20 hours under reduced pressure (4 to 10.7 kPa). The acid value of the reaction solution was 1.6 mgKOH / g. After adding 27 g of adsorbent Kyoward 500SH to the reaction liquid and stirring and filtering at 80 ° C. and 2.7 kPa for 45 minutes, tetraethylene glycol monomethyl ether was distilled off at a liquid temperature of 150 to 250 ° C. and a pressure of 0.003 kPa. After cooling to 80 ° C., the residual liquid was filtered under reduced pressure to obtain a diester [(MeEO 4 ) 2 SA] of succinic acid and tetraethylene glycol monomethyl ether as a filtrate. The obtained diester had a weight average molecular weight of 499, a viscosity (23 ° C.) of 35 mPa · s, an acid value of 0.2 mgKOH / g, a saponification value of 225 mgKOH / g, a hydroxyl value of 1 mgKOH / g or less, and a hue of APHA230. In addition, this plasticizer is an ester compound with the alcohol which added 4 mol of ethylene oxide per hydroxyl group.
可塑剤の製造例3((MeEO6)2SA、コハク酸とヘキサエチレングリコールモノメチルエーテルとのジエステル化合物)
攪拌機、温度計、脱水管を備えた3Lフラスコに、無水コハク酸500g、ヘキサエチレングリコールモノメチルエーテル4235g、パラトルエンスルホン酸一水酸化物9.5gを仕込み、空間部に窒素(500mL/分)を吹き込みながら、減圧下(4〜10.7kPa)、150℃で40時間反応させた。反応液の酸価は1.6mgKOH/gであった。反応液に吸着剤キョーワード500SH 27gを添加して80℃、2.7kPaで45分間攪拌してろ過した後、液温200〜280℃、圧力0.003kPaでヘキサエチレングリコールモノメチルエーテルを留去し、80℃に冷却後、残液を減圧ろ過して、ろ液として、コハク酸とヘキサエチレングリコールモノメチルエーテルとのジエステル〔(MeEO6)2SA〕を得た。得られたジエステルは、重量平均分子量674、粘度(23℃)42mPa・s、酸価0.2mgKOH/g、鹸化価166mgKOH/g、水酸基価1mgKOH/g以下、色相APHA280であった。なお、本可塑剤は、水酸基1個当たりエチレンオキサイドを6モル付加したアルコールとのエステル化合物である。
Production Example 3 of Plasticizer ((MeEO 6 ) 2 SA, Diester Compound of Succinic Acid and Hexaethylene Glycol Monomethyl Ether)
A 3 L flask equipped with a stirrer, thermometer, and dehydration tube was charged with 500 g of succinic anhydride, 4235 g of hexaethylene glycol monomethyl ether, and 9.5 g of paratoluenesulfonic acid monohydroxide, and nitrogen (500 mL / min) was added to the space. While blowing, the reaction was carried out at 150 ° C. under reduced pressure (4 to 10.7 kPa) for 40 hours. The acid value of the reaction solution was 1.6 mgKOH / g. After adding 27 g of adsorbent Kyoward 500SH to the reaction liquid and stirring and filtering at 80 ° C. and 2.7 kPa for 45 minutes, hexaethylene glycol monomethyl ether was distilled off at a liquid temperature of 200 to 280 ° C. and a pressure of 0.003 kPa. After cooling to 80 ° C., the remaining liquid was filtered under reduced pressure to obtain a diester [(MeEO 6 ) 2 SA] of succinic acid and hexaethylene glycol monomethyl ether as a filtrate. The obtained diester had a weight average molecular weight of 674, a viscosity (23 ° C.) of 42 mPa · s, an acid value of 0.2 mgKOH / g, a saponification value of 166 mgKOH / g, a hydroxyl value of 1 mgKOH / g or less, and a hue of APHA280. In addition, this plasticizer is an ester compound with the alcohol which added 6 mol of ethylene oxide per hydroxyl group.
可塑剤の製造例4(MeSA−1,3PD、コハク酸ジメチルと1,3−プロパンジオ−ルとのオリゴエステル化合物)
4ツロフラスコ(攪拌機、温度計、滴下漏斗、蒸留管、窒素吹き込み管付き)に1,3−プロパンジオール86.8g(1.14モル)及び触媒として28重量%ナトリウムメトキシド含有メタノール溶液2.2g(ナトリウムメトキシド0.011モル)を入れ、常圧、120℃で0.5時間攪拌しながらメタノールを留去した。その後、コハク酸ジメチル(和光純薬工業社製)500g(3.42モル)を2時間かけて滴下し、常圧、120℃で、反応により生じるメタノールを留去した。次に、75℃に冷却し、圧力を2時間かけて常圧から6.7kPaまで徐々に下げてメタノールを留去した後、常圧にもどし、さらに、触媒として28重量%ナトリウムメトキシド含有メタノール溶液2.0g(ナトリウムメトキシド0.010モル)を添加し、100℃で、圧力を3時間かけて常圧から2.9kPaまで徐々に下げてメタノールを留出させた。その後、80℃に冷却してキョーワード600S(協和化学工業社製)6gを添加し、圧力4.0kPa、80℃で1時間攪拌した後、減圧ろ過を行った。ろ液を圧力4.5kPaで、温度を1時間かけて114℃から194℃に上げて残存コハク酸ジメチルを留去し、常温黄色の液体として〔MeSA−1,3PD〕を得た。なお、触媒の使用量は、ジカルボン酸エステル100モルに対して0.61モルであった。なお、本可塑剤は、式(I)で表されるエステル化合物(R1はメチル基、R2はエチレン基、R3はプロピレン基であり、mは1、nは1.5)である。
Plasticizer Production Example 4 (MeSA-1,3PD, oligoester compound of dimethyl succinate and 1,3-propanediol)
A 4-throttle flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube) was charged with 16.8 propanediol (1.84 mol) of 1,3-propanediol and 2.2 g of methanol solution containing 28 wt% sodium methoxide as a catalyst. (Sodium methoxide 0.011 mol) was added, and methanol was distilled off with stirring at normal pressure and 120 ° C. for 0.5 hour. Thereafter, 500 g (3.42 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 75 ° C., the pressure was gradually reduced from normal pressure to 6.7 kPa over 2 hours to distill off methanol, and the pressure was returned to normal pressure. Further, 28 wt% sodium methoxide-containing methanol was used as a catalyst. 2.0 g of solution (0.010 mol of sodium methoxide) was added, and methanol was distilled by gradually lowering the pressure from normal pressure to 2.9 kPa over 3 hours at 100 ° C. Then, after cooling to 80 ° C., 6 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by vacuum filtration. The filtrate was heated at a pressure of 4.5 kPa and the temperature was raised from 114 ° C. to 194 ° C. over 1 hour to distill off the remaining dimethyl succinate, thereby obtaining [MeSA-1, 3PD] as a yellow liquid at room temperature. In addition, the usage-amount of the catalyst was 0.61 mol with respect to 100 mol of dicarboxylic acid ester. The plasticizer is an ester compound represented by formula (I) (R 1 is a methyl group, R 2 is an ethylene group, R 3 is a propylene group, m is 1, and n is 1.5). .
実施例1〜17及び比較例1〜6
層Pにおけるポリ乳酸樹脂組成物の調製
ポリ乳酸樹脂組成物として、表1〜3に示す組成物原料を、二軸押出機(Perker社製、HK25D、シリンダー直径25.2mm、回転数100rpm、吐出量8kg/h)を使用して、溶融混練温度180〜190℃で溶融混練し、ストランドカットを行い、ポリ乳酸樹脂組成物のペレットを得た。得られたペレットは、110℃減圧下で2時間乾燥し、水分量を500ppm以下とした。
Examples 1-17 and Comparative Examples 1-6
Preparation of polylactic acid resin composition in layer P As a polylactic acid resin composition, the composition raw materials shown in Tables 1 to 3 were mixed with a twin-screw extruder (Perker, HK25D, cylinder diameter 25.2 mm, rotation speed 100 rpm, discharge) The amount of 8 kg / h) was used for melt kneading at a melt kneading temperature of 180 to 190 ° C., and strand cutting was performed to obtain polylactic acid resin composition pellets. The obtained pellets were dried at 110 ° C. under reduced pressure for 2 hours, and the water content was adjusted to 500 ppm or less.
シート状成形体の調製
前記で得られた層Pのペレット及び、層Qの原料となるペレットをフィードブロック式のT−ダイ押出機(創研社製、300mmT−ダイ)を用いて、下記の条件にて幅250mmの共押出シート成形を行い、ポリ乳酸樹脂組成物積層シートを得た。
<押出成形条件>
二軸混練部のシリンダー温度:180℃
Tダイ(出口)温度:200℃
押出し速度:0.4m/min (加熱ロール接触時間が30秒となる速度)
冷却ロール表面温度:25℃
加熱ロール表面温度:80℃
シート厚み:300μm
Preparation of a sheet-like molded body The pellets of the layer P obtained above and the pellets as the raw material of the layer Q were fed using a feed block type T-die extruder (manufactured by Soken Co., Ltd., 300 mm T-die) as follows. Under the conditions, 250 mm wide coextrusion sheet molding was performed to obtain a polylactic acid resin composition laminated sheet.
<Extrusion conditions>
Cylinder temperature of biaxial kneading part: 180 ° C
T-die (outlet) temperature: 200 ° C
Extrusion speed: 0.4 m / min (speed at which the heating roll contact time is 30 seconds)
Cooling roll surface temperature: 25 ° C
Heating roll surface temperature: 80 ° C
Sheet thickness: 300 μm
なお、表1〜3における原料は以下の通りである。
<ポリ乳酸樹脂>
4032D:NatureWorksLLC製Ingeo(登録商標)Biopolymer4032D(ポリ−L−乳酸、光学純度98.5%、融点166℃、重量平均分子量180000)
2003D:NatureWorksLLC製Ingeo(登録商標)Biopolymer2003D(ポリ−L−乳酸、光学純度95.7%、融点145℃、重量平均分子量200000)
4060D:NatureWorksLLC製Ingeo(登録商標)Biopolymer4060D(ポリ−L−乳酸、光学純度88.0%、結晶化せず融点測定不可、重量平均分子量190000)
<可塑剤>
DAIFATTY−101:アジピン酸と、ジエチレングリコールモノメチルエーテル/ベンジルアルコール=1/1との混合ジエステル、大八化学工業社製
(MeEO3)2SA:前記可塑剤の製造例1で製造したジエステル化合物
(MeEO4)2SA:前記可塑剤の製造例2で製造したジエステル化合物
(MeEO6)2SA:前記可塑剤の製造例3で製造したジエステル化合物
MeSA−1,3PD:前記可塑剤の製造例4で製造したオリゴエステル化合物
プルロニックF68:ポリエチレングリコール/ポリプロピレングリコール共重合体、ADEKA社製
<衝撃改良剤>
プラメート PD−350:PLA−脂肪族ポリエステル共重合体、DIC社製
<有機結晶核剤>
スリパックスH:エチレンビス12−ヒドロキシステアリン酸アミド、日本化成社製
<加水分解抑制剤>
BioAdmide 100:ジイソプロピルフェニルカルボジイミド、ラインケミー社製
<結晶化阻害剤>
サイリシア530:シリカ、平均粒子径2.7μm、シリカ含有量99.8質量%、富士シリシア化学社製
スミペックスMGSV:ポリメチルメタアクリレート樹脂、住友化学社製
In addition, the raw material in Tables 1-3 is as follows.
<Polylactic acid resin>
4032D: Ingeo (registered trademark) Biopolymer 4032D manufactured by NatureWorks LLC (poly-L-lactic acid, optical purity 98.5%, melting point 166 ° C., weight average molecular weight 180000)
2003D: Ingeo (registered trademark) Biopolymer 2003D manufactured by NatureWorks LLC (poly-L-lactic acid, optical purity 95.7%, melting point 145 ° C., weight average molecular weight 200000)
4060D: Ingeo (registered trademark) Biopolymer 4060D manufactured by NatureWorks LLC (poly-L-lactic acid, optical purity 88.0%, no crystallization, no melting point measurement, weight average molecular weight 190000)
<Plasticizer>
DAIFATTY-101: a mixed diester of adipic acid and diethylene glycol monomethyl ether / benzyl alcohol = 1/1, manufactured by Daihachi Chemical Industry Co., Ltd.
(MeEO 3 ) 2 SA: Diester compound produced in Production Example 1 of the plasticizer
(MeEO 4 ) 2 SA: Diester compound produced in Production Example 2 of the plasticizer
(MeEO 6 ) 2 SA: Diester compound MeSA-1, 3PD produced in Production Example 3 of the plasticizer Oligoester compound Pluronic F68 produced in Production Example 4 of the plasticizer: Polyethylene glycol / polypropylene glycol copolymer, Made by ADEKA <impact modifier>
Puramate PD-350: PLA-aliphatic polyester copolymer, manufactured by DIC <organic crystal nucleating agent>
SLIPAX H: Ethylene bis 12-hydroxystearic acid amide, manufactured by Nippon Kasei Co., Ltd. <Hydrolysis inhibitor>
BioAdide 100: diisopropylphenylcarbodiimide, manufactured by Rhein Chemie <crystallization inhibitor>
Silicia 530: silica, average particle size 2.7 μm, silica content 99.8% by mass, Sumipex MGSV manufactured by Fuji Silysia Chemical Ltd .: polymethyl methacrylate resin, manufactured by Sumitomo Chemical Co., Ltd.
得られた積層シートの特性を、下記の試験例1〜2の方法に従って評価した。なお、層比については下記のようにして測定した。結果を表1〜3に示す。
<層比>
内層に用いる樹脂を黒顔料(カーボンブラック)で着色し、得られた積層シートの破断面をミクロトームを使用して作成し、光学顕微鏡(キーエンス社製、VHX−1000)を用いて、200倍で観察し、シート厚み、内層の着色層の厚みを測定し、層比を求めた。
The characteristics of the obtained laminated sheet were evaluated according to the methods of Test Examples 1 and 2 below. The layer ratio was measured as follows. The results are shown in Tables 1-3.
<Layer ratio>
The resin used for the inner layer is colored with a black pigment (carbon black), and a fracture surface of the obtained laminated sheet is prepared using a microtome, and is used at 200 times using an optical microscope (VHX-1000, manufactured by Keyence Corporation). Observation was made, the sheet thickness and the thickness of the inner colored layer were measured, and the layer ratio was determined.
試験例1<透明性>
成形後のシートから5cm×5cm×0.3mmのサンプルを作成し、JIS−K7105規定の積分球式光線透過率測定装置(HM−150 村上色彩技術研究所)を用い、Haze値を測定した。Haze値の値が小さいほど透明性が良好であることを示す。
Test Example 1 <Transparency>
A sample of 5 cm × 5 cm × 0.3 mm was prepared from the molded sheet, and the haze value was measured using an integrating sphere type light transmittance measuring device (HM-150 Murakami Color Research Laboratory) defined in JIS-K7105. It shows that transparency is so favorable that the value of Haze value is small.
試験例2<耐衝撃性>
成形後のシートから5cm×5cm×0.3mmのサンプルを作成し、デュポン式落下衝撃試験機(安田精機製作所製、No.517−L、落下高さ最大1000mm、間隔50mm、直径19.05mmの撃ち型、直径19.05mmの受け台、落下ウエイト100〜1000gを使用)により、JIS−K7211−1(2006)に従い、温度23℃の雰囲気下において測定した50%衝撃破壊エネルギーを衝撃強度とした。衝撃強度の数値が大きいほど耐衝撃性に優れることを示す。
Test example 2 <impact resistance>
A sample of 5 cm × 5 cm × 0.3 mm was prepared from the molded sheet, and a DuPont type drop impact tester (manufactured by Yasuda Seiki Seisakusho, No.517-L, a maximum drop height of 1000 mm, an interval of 50 mm, a diameter of 19.05 mm) 50% impact fracture energy measured in an atmosphere at a temperature of 23 ° C. according to JIS-K7211-1 (2006) using a shooting mold, a cradle with a diameter of 19.05 mm, and a drop weight of 100 to 1000 g) was defined as impact strength. . It shows that it is excellent in impact resistance, so that the numerical value of impact strength is large.
表1〜3より、実施例のポリ乳酸樹脂組成物積層シートは、耐衝撃性及び透明性のいずれにも優れるものであることが分かる。また、シート全体における可塑剤含有量としては同じ含有量が配合されている実施例2〜4、6と比較例1〜4をそれぞれ対比すると、実施例の積層シートは、比較例のシートに比べて透明性が高く、また耐衝撃性にも優れるものである。一方、従来用いられている衝撃改良剤を用いた比較例6は、本発明のポリ乳酸樹脂組成物積層シートに比べて、透明性が低く、耐衝撃性も劣るものであった。 From Tables 1-3, it turns out that the polylactic acid resin composition laminated sheet of an Example is excellent in both impact resistance and transparency. Moreover, when Examples 2-4 and 6 and Comparative Examples 1-4 in which the same content is mix | blended as the plasticizer content in the whole sheet | seat are contrasted, the laminated sheet of an Example is compared with the sheet | seat of a comparative example. It is highly transparent and has excellent impact resistance. On the other hand, Comparative Example 6 using a conventionally used impact modifier was lower in transparency and inferior in impact resistance than the polylactic acid resin composition laminated sheet of the present invention.
また、実施例15〜17の対比により、層Qに結晶化阻害剤を配合することで、耐衝撃性は向上あるいは維持しながら、透明性が格段に向上することが分かる。 Moreover, it turns out that transparency improves markedly by mix | blending a crystallization inhibitor with the layer Q by contrast of Examples 15-17, improving or maintaining impact resistance.
本発明のポリ乳酸樹脂組成物積層シートは、透明性及び耐衝撃性に優れることから、食品容器、日用品や家電製品の包装材料、工業用部品のトレイ等、様々な用途に好適に使用することができる。 Since the polylactic acid resin composition laminate sheet of the present invention is excellent in transparency and impact resistance, it should be used suitably for various applications such as food containers, packaging materials for household goods and household appliances, trays for industrial parts, etc. Can do.
Claims (6)
層Pが、(P−A)ポリ乳酸樹脂、(P−B)可塑剤、及び(P−C)有機結晶核剤を含有するポリ乳酸樹脂組成物の層であり、層中の(P−B)可塑剤の含有量が4質量%以上18質量%以下であり、(P−C)有機結晶核剤の含有量が0.05質量%以上1.0質量%以下であり、
層Qが、(Q−A)ポリ乳酸樹脂、(Q−B)可塑剤、及び(Q−C)有機結晶核剤を含有するポリ乳酸樹脂組成物の層であり、層中の(Q−B)可塑剤の含有量が0質量%以上6質量%以下であり、(Q−C)有機結晶核剤の含有量が0質量%以上0.3質量%以下であり、
ここで、層P中の(P−B)可塑剤の含有量の方が層Q中の(Q−B)可塑剤の含有量より多く、シートの表面側と裏面側の少なくとも一方の最外層が層Pであるポリ乳酸樹脂組成物積層シート。 A polylactic acid resin composition laminate sheet comprising a plurality of polylactic acid resin composition layers, and a polylactic acid resin composition laminate sheet comprising at least the next layer P and layer Q,
Layer P is a layer of a polylactic acid resin composition containing (P-A) polylactic acid resin, (P-B) plasticizer, and (P-C) organic crystal nucleating agent, and (P- B) The content of the plasticizer is 4% by mass or more and 18% by mass or less, and the content of the (PC) organic crystal nucleating agent is 0.05% by mass or more and 1.0% by mass or less,
Layer Q is a layer of a polylactic acid resin composition containing (QA) polylactic acid resin, (QB) plasticizer, and (QC) organic crystal nucleating agent, and (Q- B) The content of the plasticizer is 0% by mass or more and 6% by mass or less, and the content of the (QC) organic crystal nucleating agent is 0% by mass or more and 0.3% by mass or less.
Here, the content of the (P-B) plasticizer in the layer P is greater than the content of the (Q-B) plasticizer in the layer Q, and at least one of the outermost layers on the front and back sides of the sheet Is a polylactic acid resin composition laminate sheet in which layer P is.
(i)分子中に2個以上のエステル基を有するエステル化合物であって、該エステル化合物を構成するアルコール成分の少なくとも1種が水酸基1個当たり炭素数2〜3のアルキレンオキサイドを平均0.5〜8モル付加したアルコールであるエステル化合物、及び
(ii)式(I):
R1O−CO−R2−CO−〔(OR3)mO−CO−R2−CO−〕nOR1 (I)
(式中、R1は炭素数が1〜4のアルキル基、R2は炭素数が2〜4のアルキレン基、R3は炭素数が2又は3のアルキレン基であり、mは1〜6の数、nは1〜12の数を示し、但し、全てのR2は同一でも異なっていてもよく、全てのR3は同一でも異なっていてもよい)
で表される化合物
からなる群から選ばれる1種又は2種以上を含んでなる、請求項1〜3いずれか記載のポリ乳酸樹脂組成物積層シート。 (PB) plasticizer and / or (QB) plasticizer,
(I) An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound has an average of 0.5 to 3 alkylene oxides per hydroxyl group. Ester compound which is an alcohol added to ˜8 mol, and (ii) Formula (I):
R 1 O—CO—R 2 —CO — [(OR 3 ) m O—CO—R 2 —CO—] n OR 1 (I)
(Wherein R 1 is an alkyl group having 1 to 4 carbon atoms, R 2 is an alkylene group having 2 to 4 carbon atoms, R 3 is an alkylene group having 2 or 3 carbon atoms, and m is 1 to 6) And n represents a number from 1 to 12, provided that all R 2 may be the same or different, and all R 3 may be the same or different.
The polylactic acid resin composition laminated sheet according to any one of claims 1 to 3, comprising one or more selected from the group consisting of compounds represented by:
工程(1):(P−A)ポリ乳酸樹脂、(P−B)可塑剤、及び(P−C)有機結晶核剤を含有する原料を溶融混練して、層Pを構成するポリ乳酸樹脂組成物を調製する工程であって、層中の(P−B)可塑剤の含有量が4質量%以上18質量%以下であり、(P−C)有機結晶核剤の含有量が0.05質量%以上1.0質量%以下である工程
工程(2):(Q−A)ポリ乳酸樹脂、(Q−B)可塑剤、及び(Q−C)有機結晶核剤を含有する原料を溶融混練して、層Qを構成するポリ乳酸樹脂組成物を調製する工程であって、層中の(Q−B)可塑剤の含有量が0質量%以上6質量%以下であり、(Q−C)有機結晶核剤の含有量が0質量%以上0.3質量%以下であり、
ここで、層P中の(P−B)可塑剤の含有量の方が層Q中の(Q−B)可塑剤の含有量より多い工程
工程(3):工程(1)で得られた層Pのポリ乳酸樹脂組成物と、工程(2)で得られた層Qのポリ乳酸樹脂組成物とを層Pがシートの表面側と裏面側の少なくとも一方の最外層になるように溶融共押出成形する工程 A method for producing a polylactic acid resin composition laminated sheet comprising a plurality of polylactic acid resin composition layers, comprising the following steps (1), (2) and (3).
Step (1): Polylactic acid resin constituting layer P by melting and kneading raw materials containing (PA) polylactic acid resin, (PB) plasticizer, and (PC) organic crystal nucleating agent In the step of preparing the composition, the content of the (P-B) plasticizer in the layer is 4% by mass or more and 18% by mass or less, and the content of the (PC) organic crystal nucleating agent is 0.00. Process step (2) which is not less than 05% by mass and not more than 1.0% by mass: A raw material containing (QA) polylactic acid resin, (QB) plasticizer, and (QC) organic crystal nucleating agent A step of preparing a polylactic acid resin composition constituting the layer Q by melt-kneading, wherein the content of the (Q-B) plasticizer in the layer is 0% by mass to 6% by mass, (Q -C) The content of the organic crystal nucleating agent is 0% by mass or more and 0.3% by mass or less,
Here, the content of the (P-B) plasticizer in the layer P is larger than the content of the (Q-B) plasticizer in the layer Q. The process step (3): obtained in the step (1). The polylactic acid resin composition of layer P and the polylactic acid resin composition of layer Q obtained in step (2) are melt-coagulated so that layer P is at least one of the outermost layers on the front side and the back side of the sheet. Extrusion process
工程(4):工程(3)で得られた溶融共押出成形品の一部を裁断後、回収して工程(2)におけるポリ乳酸樹脂組成物の原料と混合して使用する工程 Furthermore, the manufacturing method of Claim 5 including the following process (4).
Step (4): A step of cutting a part of the melt-coextruded product obtained in Step (3) and then recovering and mixing it with the raw material of the polylactic acid resin composition in Step (2).
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