JP6759700B2 - 積層シート及びこれを用いる成形体 - Google Patents
積層シート及びこれを用いる成形体 Download PDFInfo
- Publication number
- JP6759700B2 JP6759700B2 JP2016099596A JP2016099596A JP6759700B2 JP 6759700 B2 JP6759700 B2 JP 6759700B2 JP 2016099596 A JP2016099596 A JP 2016099596A JP 2016099596 A JP2016099596 A JP 2016099596A JP 6759700 B2 JP6759700 B2 JP 6759700B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- laminated sheet
- meth
- resin
- sheet
- 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.)
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 133
- -1 vinyl compound Chemical class 0.000 claims description 91
- 239000011347 resin Substances 0.000 claims description 60
- 229920005989 resin Polymers 0.000 claims description 60
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 52
- 239000000194 fatty acid Substances 0.000 claims description 52
- 229930195729 fatty acid Natural products 0.000 claims description 52
- 239000000178 monomer Substances 0.000 claims description 51
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 48
- 239000011248 coating agent Substances 0.000 claims description 43
- 229920000178 Acrylic resin Polymers 0.000 claims description 40
- 239000004925 Acrylic resin Substances 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 30
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 19
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
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- 239000011247 coating layer Substances 0.000 claims description 8
- 235000013305 food Nutrition 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- JQXYBDVZAUEPDL-UHFFFAOYSA-N 2-methylidene-5-phenylpent-4-enoic acid Chemical compound OC(=O)C(=C)CC=CC1=CC=CC=C1 JQXYBDVZAUEPDL-UHFFFAOYSA-N 0.000 claims description 3
- 229920003145 methacrylic acid copolymer Polymers 0.000 claims description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 39
- 238000000034 method Methods 0.000 description 39
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000003921 oil Substances 0.000 description 20
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- 238000006116 polymerization reaction Methods 0.000 description 19
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- 150000001875 compounds Chemical class 0.000 description 17
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- 229940105990 diglycerin Drugs 0.000 description 16
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 9
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- 229940070765 laurate Drugs 0.000 description 9
- 229940088594 vitamin Drugs 0.000 description 9
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- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- DUUKZBGYNMHUHO-UHFFFAOYSA-N 253MC0P0YV Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)COCC(O)CO DUUKZBGYNMHUHO-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000005639 Lauric acid Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical class OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
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- 239000003999 initiator Substances 0.000 description 2
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- 238000001308 synthesis method Methods 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
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Landscapes
- Wrappers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Description
<スチレン系樹脂シート(A)>
本発明で用いるスチレン系樹脂シート(A)は、スチレン系モノマー、及びこれと共重合可能な単量体とを重合させてなるスチレン系樹脂をシート状に成形したものであり、その厚みや成形方法等には特に限定されるものではない。
前述の、本発明で使用することができる複数の分岐を有し、且つ複数の重合性二重結合を有する多分岐状マクロモノマーとしては、ゲル物発生を抑制し、流動性を確保する観点から、多分岐状マクロモノマーの重量平均分子量(Mw)が、好ましくは1,000〜15,000、より好ましくは3,000〜8,000の範囲のものを用いる。
前記多分岐状マクロモノマーとスチレン系モノマー、必要に応じて併用されるその他の単量体類を共重合させると、多分岐状の樹脂と、重合条件により同時に生成する線状の樹脂及び低分岐樹脂との混合物である樹脂混合物が得られる。この時、前述の多分岐状マクロモノマーをこれ以外の単量体の総量に対して好ましくは50ppm〜1%、より好ましくは100ppm〜3000ppm(質量基準)の比率で用いることにより、多分岐状の樹脂の生成が容易であり、本発明に使用されるスチレン系樹脂の作製を安易にする。
スチレン系モノマー単独、又はこれと共重合可能な単量体との共重合体を得るための重合反応、更に前述の多分岐状マクロモノマーを併用してスチレン系樹脂シート(A)の原料とする樹脂(組成物)を製造する方法としては、種々の汎用されているスチレン系モノマーの重合方法を応用することができる。重合方式には特に限定はないが、塊状重合、懸濁重合、あるいは溶液重合が好ましい。中でも生産効率の点で特に連続塊状重合が好ましく、例えば一個以上の攪拌式反応器と可動部分の無い複数のミキシングエレメントが内部に固定されている管状反応器を組み込んだ連続塊状重合を行うことにより、優れた樹脂を得ることができる。重合開始剤を使用せずに熱重合させることもできるが、種々のラジカル重合開始剤を使用することが好ましい。また、重合に必要な懸濁剤や乳化剤などのような重合助剤は、通常のポリスチレンの製造に使用されるものを使用できる。
重合工程では、スチレン系モノマー、その他併用されるモノマーあるいは多分岐状マクロモノマーを単量体として用い、これらを共重合させることによって、スチレン系樹脂シート(A)の材料となるスチレン系樹脂(組成物)を得ることができる。重合装置の反応容器については特に限定されるものではない。重合工程の後に、未反応モノマーや溶剤分を揮発するための、好ましくは減圧下状態に調整した脱揮槽を通過させる。その後ペレット化され、本発明で用いるスチレン系樹脂シート(A)の材料となるスチレン系樹脂を得ることができる。
無延伸シートは、上記で得られたスチレン系樹脂(組成物)のペレットを押出機で溶融押出後、T−ダイによりシート状に溶融押出した後、冷却ロール等により冷却し作製できる。冷却温度としては、70〜90℃が好ましい。
二軸延伸シートは、押出機での溶融押出後、延伸機で縦横ニ軸に延伸することで得られる。例えば、まず、押出機にスチレン系樹脂(組成物)を供給し、T−ダイよりシート状に溶融押出する。その際、延伸前のシートが所定厚みになるようにキャスティングする。その後、二軸延伸可能な温度、例えば110〜145℃にシートを冷却して、縦方向(流れ方向)及び横方向(流れ方向に対するクロス方向)に延伸することで得られる。
本発明で用いるコート剤(B)は、アクリル系樹脂を樹脂成分とするものであり、水溶性であることを必須とする。なお、本発明において水溶性とは、25℃の蒸留水に対して任意の割合で溶解することを示す。
測定装置 ;東ソー株式会社製 HLC−8220GPC
カラム ;東ソー株式会社製 TSK−GUARDCOLUMN SuperHZ−L
+東ソー株式会社製 TSK−GEL SuperHZM−M×4
検出器 ;RI(示差屈折計)
データ処理;東ソー株式会社製 マルチステーションGPC−8020modelII
測定条件 ;カラム温度 40℃
溶媒 テトラヒドロフラン
流速 0.35ml/分
標準 ;単分散ポリスチレン
試料 ;樹脂固形分換算で0.2質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
100/Tg=W1/Tg1+W2/Tg2+W3/Tg3+W4/Tg4
式中、W1、W2は、各種成分の質量分率(質量%)を示す。
式中、Tg1、Tg2は、各種成分のホモポリマーのガラス転移温度(K)を示す。
本発明では、前述の水酸基含有水溶性アクリル樹脂(b1)に、少なくとも1種類以上の防曇剤(b2)を含有させることを特徴とする。
本発明の積層シートは、前述のスチレン系樹脂シート(A)の少なくとも片面に前記コート剤(B)を塗布し、乾燥させることで得ることができる。乾燥方法としては特に限定されるものではなく、例えば、樹脂シート(A)の温度がTgを超えない様に制御された乾燥装置を用い0.1〜30分程度の加熱乾燥にてコート剤(B)からなる被覆層を樹脂シート(A)上に形成させることができる。
前記で得られた積層シートは、これを直接加熱方式または間接加熱方式によって加熱され、成形されて、本発明の成形体とすることができる。加熱成形の方法は、特に限定されるものではなく、真空成形機、熱板圧空成形機、真空圧空成形機等を用いて行うことができるが、温度制御が良好で、短時間加熱が可能なことから、熱板圧空成形機を用いての加熱成形が好適である。
前記で得られた本発明の成形体は、特に食品包装容器として好適に用いることができ、その防曇性、耐油性、それらの持続性、及びスチレン系樹脂シートが本来有する透明性の観点から、蓋材として使用することが最も好ましい。この時、本発明の積層シートにおける被覆層が内容物側になるように成形されていることが好ましい使用方法である。
還流冷却器、撹拌機および窒素導入管を具備した反応容器に、n−ブタノール250部を仕込んで撹拌を開始し、100℃まで昇温した。ここに窒素気流下で、メタクリル酸メチル123部、アクリル酸エチル33部、メタクリル酸2ヒドロキシエチル21部、スチレン30部、メタクリル酸93部からなる単量体混合物と、t−ブチルパーオキシ−2−エチルヘキサノエート3部、n−ブタノール40部からなる反応開始剤混合物とを3時間かけて連続滴下した。同温度で3時間撹拌後、t−ブチルパーオキシ−2−エチルヘキサノエート0.3部、n−ブタノール10部からなる反応開始剤混合物を2時間かけて連続滴下した。同温度で5時間撹拌後、80℃に降温し、5%安水により中和を行い、続いてイオン交換水を用いて水溶化を行い、水酸基価30、酸価199、ガラス転移温度90℃の水溶性アクリル樹脂を得た。その後、蒸留水により希釈を行い不揮発分10%に調整した。更に、ショ糖脂肪酸エステル(理研ビタミン株式会社社製リケマールA、HLB=15、固形分40%)を水溶性アクリル樹脂とショ糖脂肪酸酸エステルのそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しコート剤B1を得た。
メタクリル酸メチル130.5部、アクリル酸エチル39部、メタクリル酸2ヒドロキシエチル7.5部、スチレン30部、メタクリル酸93部としたこと以外は合成例1と同様の方法で、不揮発分10%の水酸基価10、酸価200、ガラス転移温度90℃の水溶性アクリル樹脂を得た。更に、ショ糖脂肪酸エステルを水溶性アクリル樹脂とショ糖脂肪酸エステルのそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しコート剤B2を得た。
メタクリル酸メチル78部、アクリル酸エチル15部、メタクリル酸2ヒドロキシエチル84部、スチレン30部、メタクリル酸93部としたこと以外は合成例1と同様の方法で、不揮発分10%の水酸基価119、酸価199、ガラス転移温度90℃の水溶性アクリル樹脂を得た。更に、ショ糖脂肪酸エステルを水溶性アクリル樹脂とショ糖脂肪酸エステルのそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しコート剤B3を得た。
メタクリル酸メチル201部、アクリル酸エチル21部、メタクリル酸2ヒドロキシエチル21部、スチレン30部、メタクリル酸27部としたこと以外は合成例1と同様の方法で、不揮発分10%の水酸基価30、酸価58、ガラス転移温度90℃の水溶性アクリル樹脂を得た。更に、ショ糖脂肪酸エステルを水溶性アクリル樹脂とショ糖脂肪酸エステルのそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しコート剤B4を得た。
メタクリル酸メチル120部、アクリル酸エチル18部、メタクリル酸2ヒドロキシエチル21部、メタクリル酸141部としたこと以外は合成例1と同様の方法で、不揮発分10%の水酸基価30、酸価302、ガラス転移温度106℃の水溶性アクリル樹脂を得た。更に、ショ糖脂肪酸エステルを水溶性アクリル樹脂とショ糖脂肪酸エステルのそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しコート剤B5を得た。
メタクリル酸メチル114部、アクリル酸エチル120部、メタクリル酸2ヒドロキシエチル21部、メタクリル酸45部としたこと以外は合成例1と同様の方法で、不揮発分10%の水酸基価30、酸価97、ガラス転移温度41℃の水溶性アクリル樹脂を得た。更に、ショ糖脂肪酸エステルを水溶性アクリル樹脂とショ糖脂肪酸エステルのそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しコート剤B6を得た。
合成例1において、作製した不揮発分10%のアクリル樹脂水溶液に、ポリグリセリン脂肪酸エステル(理研ビタミン株式会社社製ポエムDO−100V、HLB=7.3)を水溶性アクリル樹脂とポリグリセリン脂肪酸エステルのそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しコート剤B7を得た。
合成例8:コート剤B8の合成
メタクリル酸メチル126部、アクリル酸エチル21部、スチレン60部、メタクリル酸93部としたこと以外は合成例1と同様の方法で、不揮発分10%の水酸基価0、酸価260、ガラス転移温度80℃のアクリル系樹脂を得た。更に、ショ糖脂肪酸エステルをアクリル樹脂とショ糖脂肪酸エステルのそれぞれの固形分が2.4%と0.6%になる様に蒸留水で希釈しコート剤B8を得た。
合成例1と同様の方法で、不揮発分10%の水酸基価30、酸価199、ガラス転移温度90℃のアクリル系樹脂を得た。更に、固形分が2.4%になる様に蒸留水で希釈しコート剤B9を得た。
ショ糖脂肪酸エステルを固形分が3.0%となる様に蒸留水で希釈しコート剤B11を得た。
ポリグリセリン脂肪酸エステルを固形分が3.0%となる様に蒸留水で希釈しコート剤B11を得た。
表1〜3に示すモノマー組成比(MAA:メタクリル酸)を用い、連続塊状重合により共重合体を合成し、押出機にて1000μmの無延伸シートとした後、単発延伸機により縦方向(MD)2倍、横方向(CD)2倍に延伸を施した二軸延伸スチレン系樹脂シートを得た。
耐油性評価:成形品内側に中鎖脂肪酸油(不二精機株式会社製ホワイトF−1)を塗布し、80℃の恒温槽中に5分放置した直後の外観を目視により確認し評価を行った。評価は白化の発生しなかったものを○、問題のないレベルのごく僅かな白化が見られたものを△、明らかな白化が発生したものを×とした。
DIC株式会社製多分岐ポリスチレンHP−780ANを押出機にて1000μmの無延伸シートとした後、単発延伸機により縦方向(MD)2倍、横方向(CD)2倍に延伸を施した二軸延伸スチレン系樹脂シートを得た。その他は実施例1と同様に積層シートを作製後、同様の評価を実施した。
Claims (9)
- スチレン系樹脂シート(A)の少なくとも片面に、水酸基含有水溶性アクリル樹脂(b1)と、防曇剤(b2)と、を含むコート剤(B)の被覆層を有する積層シートであって、
前記水酸基含有水溶性アクリル樹脂(b1)の酸価が、80〜260の範囲であり、
前記水酸基含有水溶性アクリル樹脂(b1)が、少なくとも水酸基含有アクリル系単量体とメタクリル酸と(メタ)アクリル酸アルキルエステルと芳香環を有するビニル化合物とを含む単量体混合物の共重合体であることを特徴とする積層シート。 - 前記被覆層が、乾燥後の質量として50mg/m2以上である請求項1記載の積層シート。
- 前記水酸基含有水溶性アクリル樹脂(b1)の水酸基価が5〜120の範囲である請求項1又は2記載の積層シート。
- 前記芳香環を有するビニル化合物が、スチレンである請求項1記載の積層シート。
- 前記防曇剤(b2)が、糖由来の脂肪酸エステル又はグリセリン由来の脂肪酸エステルである請求項1〜4の何れか1項記載の積層シート。
- 前記スチレン系樹脂シート(A)が二軸延伸スチレン系樹脂シートである請求項1〜5の何れか1項記載の積層シート。
- 前記スチレン系樹脂シート(A)が、ポリスチレン、スチレン−(メタ)アクリルエステル共重合体、スチレン−メタクリル酸共重合体、または多分岐状ポリスチレンのシートである請求項1〜6の何れか1項記載の積層シート。
- 請求項1〜7の何れか1項記載の積層シートを成形してなることを特徴とする成形体。
- 前記コート剤(B)の被覆層が内容物側になるように成形され、且つ内容物が食品である請求項8記載の成形体。
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