JP7410798B2 - Biaxially stretched sheets and molded products - Google Patents
Biaxially stretched sheets and molded products Download PDFInfo
- Publication number
- JP7410798B2 JP7410798B2 JP2020094681A JP2020094681A JP7410798B2 JP 7410798 B2 JP7410798 B2 JP 7410798B2 JP 2020094681 A JP2020094681 A JP 2020094681A JP 2020094681 A JP2020094681 A JP 2020094681A JP 7410798 B2 JP7410798 B2 JP 7410798B2
- Authority
- JP
- Japan
- Prior art keywords
- biaxially stretched
- stretched sheet
- resin
- polyester 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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- 229920001225 polyester resin Polymers 0.000 claims description 95
- 239000004645 polyester resin Substances 0.000 claims description 95
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 94
- 229920005989 resin Polymers 0.000 claims description 67
- 239000011347 resin Substances 0.000 claims description 67
- 150000002009 diols Chemical class 0.000 claims description 61
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 40
- 239000011342 resin composition Substances 0.000 claims description 31
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 23
- 125000006841 cyclic skeleton Chemical group 0.000 claims description 21
- 230000009477 glass transition Effects 0.000 claims description 21
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- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 17
- 229960002479 isosorbide Drugs 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 9
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
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- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 3
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- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 description 2
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-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
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- HXEWWQYSYQOUSD-UHFFFAOYSA-N 2-[5-ethyl-5-(hydroxymethyl)-1,3-dioxan-2-yl]-2-methylpropan-1-ol Chemical compound CCC1(CO)COC(C(C)(C)CO)OC1 HXEWWQYSYQOUSD-UHFFFAOYSA-N 0.000 description 1
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- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
本発明はスチレン系樹脂を含む樹脂組成物を二次延伸してなる二軸延伸シート及びそれを用いた成形品に関する。 The present invention relates to a biaxially stretched sheet obtained by secondarily stretching a resin composition containing a styrene resin, and a molded article using the same.
ポリスチレンから作られる二軸延伸シートは、無味、無毒、無臭であり、安価で、耐水性及び寸法安定性が高いため、食品包装容器、雑貨等の軽量容器として従来から使用されている。例えば、特許文献1に記載されているように、真空成形法、圧空成形法等の熱成形法によって二軸延伸シートを二次成形することにより、二軸延伸シートから軽量容器等の成形品を作製することができる。 Biaxially oriented sheets made from polystyrene are tasteless, nontoxic, odorless, inexpensive, and have high water resistance and dimensional stability, so they have traditionally been used as lightweight containers for food packaging containers, miscellaneous goods, etc. For example, as described in Patent Document 1, molded products such as lightweight containers are made from biaxially stretched sheets by secondary forming biaxially stretched sheets by thermoforming methods such as vacuum forming and pressure forming. It can be made.
二次成形により二軸延伸シートから良質な成形品を得るためには、二軸延伸シートの引張伸びが大きく、二軸延伸シートの厚みムラが小さいことが好ましい。また、二軸延伸シートを容器として用いる場合、容器を壊れにくくするために、二軸延伸シートの耐折性が優れていることが好ましい。さらに、二軸延伸シートを食品包装容器として用いる場合、食品包装容器は電子レンジにより加熱される可能性があるので、二軸延伸シートの加熱収縮率は小さいことが好ましい。そこで、本発明は、引張伸びが大きく、厚みムラが小さく、耐折性に優れ、加熱収縮率が小さい二軸延伸シート及びそれを用いた成形品を提供することを目的とする。 In order to obtain a high-quality molded product from a biaxially stretched sheet by secondary molding, it is preferable that the biaxially stretched sheet has a large tensile elongation and a small thickness unevenness. Further, when a biaxially stretched sheet is used as a container, it is preferable that the biaxially stretched sheet has excellent folding durability in order to make the container difficult to break. Furthermore, when a biaxially stretched sheet is used as a food packaging container, the food packaging container may be heated in a microwave oven, so it is preferable that the heat shrinkage rate of the biaxially stretched sheet is small. Accordingly, an object of the present invention is to provide a biaxially stretched sheet with large tensile elongation, small thickness unevenness, excellent folding durability, and small heat shrinkage rate, and a molded article using the same.
本発明者らは、上記の目的を達成すべく鋭意研究を進めたところ、スチレン系樹脂を含む樹脂組成物に対して所定の含有量の所定のポリエステル樹脂を含有させることにより、上記の目的を達成することができることを見出した。
本発明は、上記の知見に基づくものであり、以下を要旨とする。
[1]スチレン系樹脂(A)と、ジカルボン酸成分(b-1)が主成分としてテレフタル酸を含むポリエステル樹脂(B)とを含み、スチレン系樹脂(A)及びポリエステル樹脂(B)の合計100質量部に対して、スチレン系樹脂(A)の含有量が75~99質量部であり、ポリエステル樹脂(B)の含有量が1~25質量部である樹脂組成物からなる二軸延伸シート。
[2]二軸延伸シートを120℃の温度で1時間加熱した後の縦方向及び横方向の二軸延伸シートの加熱収縮率をそれぞれZM(%)及びZT(%)とし、二軸延伸シートの縦方向及び横方向の延伸倍率をそれぞれXM及びXTとし、縦方向及び横方向において、加熱収縮率(ZM,ZT)及び延伸倍率(XM,XT)が次の式(1)及び式(2)をそれぞれ満たす場合、YM及びYTがそれぞれ40~99%である上記[1]に記載の二軸延伸シート。
ZM(%)=(1-1/XM)×YM (1)
ZT(%)=(1-1/XT)×YT (2)
[3]ポリエステル樹脂(B)のジオール成分(b-2)が環状骨格を有するジオールを含む上記[1]又は[2]に記載の二軸延伸シート。
[4]環状骨格を有するジオールがイソソルビドである上記[3]に記載の二軸延伸シート。
[5]ポリエステル樹脂(B)のガラス転移温度が90~135℃である上記[1]~[4]のいずれか1つに記載の二軸延伸シート。
[6]ポリエステル樹脂(B)の平均分散粒径が10~500nmである上記[1]~[5]のいずれか1つに記載の二軸延伸シート。
[7]スチレン系樹脂(A)がポリスチレンである上記[1]~[6]のいずれか1つに記載の二軸延伸シート。
[8]厚みが0.01~0.7mmであり、縦方向及び横方向の延伸倍率がそれぞれ1.5~3.5倍である上記[1]~[7]のいずれか1つに記載の二軸延伸シート。
[9]縦方向と横方向の配向緩和応力がそれぞれ0.3~1.2MPaである上記[1]~[8]のいずれか1つに記載の二軸延伸シート。
[10]上記[1]~[9]のいずれか1つに記載の二軸延伸シートを二次成形して得られる成形品。
The present inventors conducted intensive research to achieve the above object, and found that the above object could be achieved by incorporating a predetermined amount of a predetermined polyester resin into a resin composition containing a styrene resin. I found out what can be achieved.
The present invention is based on the above knowledge and has the following gist.
[1] Contains styrene resin (A) and polyester resin (B) whose dicarboxylic acid component (b-1) contains terephthalic acid as a main component, the total of styrene resin (A) and polyester resin (B) A biaxially stretched sheet made of a resin composition in which the content of the styrene resin (A) is 75 to 99 parts by mass and the content of the polyester resin (B) is 1 to 25 parts by mass relative to 100 parts by mass. .
[2] After heating the biaxially stretched sheet at a temperature of 120°C for 1 hour, the heat shrinkage rates of the biaxially stretched sheet in the longitudinal direction and the transverse direction are respectively Z M (%) and Z T (%), and the biaxially stretched sheet is The stretching ratios in the longitudinal and lateral directions of the stretched sheet are X M and XT , respectively, and the heat shrinkage rate (Z M , Z T ) and the stretching ratio (X M , XT ) in the longitudinal and transverse directions are as follows. The biaxially stretched sheet according to the above [1], wherein when formulas (1) and (2) are satisfied, Y M and Y T are each 40 to 99%.
Z M (%) = (1-1/X M ) x Y M (1)
Z T (%) = (1-1/X T ) x Y T (2)
[3] The biaxially stretched sheet according to [1] or [2] above, wherein the diol component (b-2) of the polyester resin (B) contains a diol having a cyclic skeleton.
[4] The biaxially stretched sheet according to [3] above, wherein the diol having a cyclic skeleton is isosorbide.
[5] The biaxially stretched sheet according to any one of [1] to [4] above, wherein the polyester resin (B) has a glass transition temperature of 90 to 135°C.
[6] The biaxially stretched sheet according to any one of [1] to [5] above, wherein the polyester resin (B) has an average dispersed particle size of 10 to 500 nm.
[7] The biaxially stretched sheet according to any one of [1] to [6] above, wherein the styrenic resin (A) is polystyrene.
[8] The film according to any one of [1] to [7] above, wherein the thickness is 0.01 to 0.7 mm, and the stretching ratio in the longitudinal direction and the transverse direction is 1.5 to 3.5 times, respectively. biaxially oriented sheet.
[9] The biaxially stretched sheet according to any one of [1] to [8] above, wherein the orientation relaxation stress in the longitudinal direction and the transverse direction is 0.3 to 1.2 MPa, respectively.
[10] A molded article obtained by secondary molding the biaxially stretched sheet according to any one of [1] to [9] above.
本発明によれば、引張伸びが大きく、厚みムラが小さく、耐折性に優れ、加熱収縮率が小さい二軸延伸シート及びそれを用いた成形品を提供することができる。 According to the present invention, it is possible to provide a biaxially stretched sheet with large tensile elongation, small thickness unevenness, excellent folding durability, and small heat shrinkage rate, and a molded article using the same.
以下、本発明の二軸延伸シートを説明する。
[二軸延伸シート]
本発明の二軸延伸シートは、スチレン系樹脂(A)と、ジカルボン酸成分(b-1)が主成分としてテレフタル酸を含むポリエステル樹脂(B)とを含み、スチレン系樹脂(A)及びポリエステル樹脂(B)の合計100質量部に対して、スチレン系樹脂(A)の含有量が75~99質量部であり、ポリエステル樹脂(B)の含有量が1~25質量部である樹脂組成物からなるものである。これにより、引張伸びが大きく、厚みムラが小さく、耐折性に優れ、加熱収縮率が小さい二軸延伸シートを提供することができる。
Hereinafter, the biaxially stretched sheet of the present invention will be explained.
[Biaxially stretched sheet]
The biaxially oriented sheet of the present invention contains a styrene resin (A) and a polyester resin (B) in which the dicarboxylic acid component (b-1) contains terephthalic acid as a main component, and the dicarboxylic acid component (b-1) contains the styrene resin (A) and the polyester resin A resin composition in which the content of the styrene resin (A) is 75 to 99 parts by mass and the content of the polyester resin (B) is 1 to 25 parts by mass, based on a total of 100 parts by mass of the resin (B). It consists of Thereby, it is possible to provide a biaxially stretched sheet with large tensile elongation, small thickness unevenness, excellent folding durability, and low heat shrinkage rate.
(樹脂組成物)
樹脂組成物は、スチレン系樹脂(A)及びポリエステル樹脂(B)を含む。
(Resin composition)
The resin composition contains a styrene resin (A) and a polyester resin (B).
<スチレン系樹脂(A)>
スチレン系樹脂(A)は、スチレンモノマーまたはスチレン誘導体を単一で重合させたり、合成ゴムを配合したり、あるいは他のモノマーと共重合させたものである。スチレンモノマーは、例えば、ケイ皮酸の分解蒸留、アセトフェノンの還元脱水、塩化エチルベンゾールの脱塩酸、フェニルアルコールの脱水、またはエチルベンゾールの合成及び脱水素により製造することができる。スチレン誘導体には、例えば、オルト-メチルスチレン、メタ-メチルスチレン、パラ-メチルスチレン、α-メチルスチレン、ジクロロスチレン等が挙げられる。
<Styrenic resin (A)>
The styrenic resin (A) is one obtained by polymerizing a styrene monomer or a styrene derivative alone, blending a synthetic rubber, or copolymerizing it with other monomers. Styrene monomers can be produced, for example, by decomposition distillation of cinnamic acid, reductive dehydration of acetophenone, dehydrochlorination of ethylbenzole chloride, dehydration of phenyl alcohol, or synthesis and dehydrogenation of ethylbenzole. Examples of styrene derivatives include ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, α-methylstyrene, dichlorostyrene, and the like.
スチレンモノマーまたはスチレン誘導体の重合は、一般にビニル基を持つモノマーの連鎖反応と同様に進行する。スチレンモノマーまたはスチレン誘導体の工業規模における重合法には、例えば、塊状重合法、溶液重合法、イオン重合法、乳化重合法、懸濁重合法等が挙げられる。塊状重合法では、スチレンモノマーまたはスチレン誘導体に触媒を加え、加熱、重合を誘導し、重合反応が進むにつれて反応熱を除去しつつ終結点を調節する。溶液重合法では、重合物を溶解し得る溶媒を使用して、スチレンモノマーまたはスチレン誘導体の重合を行う。イオン重合法では、触媒として、BF3、SnCl4等を用い、スチレン分子は一度、複塩を形成し、スチレン分子が複塩から外れた後、他のスチレン分子と重合して、高分子物質が形成される。乳化重合法及び懸濁重合法においては、いずれも多量に水の共存する系内において、スチレンまたはスチレン誘導体を小球状に分散させて重合反応を行う。スチレンモノマーを単一で重合させたポリスチレンは、一般に、一般用ポリスチレン(GPポリスチレン)と呼ばれている。 Polymerization of styrene monomers or styrene derivatives generally proceeds in the same manner as the chain reaction of monomers having vinyl groups. Examples of industrial-scale polymerization methods for styrene monomers or styrene derivatives include bulk polymerization, solution polymerization, ionic polymerization, emulsion polymerization, and suspension polymerization. In the bulk polymerization method, a catalyst is added to a styrene monomer or a styrene derivative, heated to induce polymerization, and as the polymerization reaction progresses, the reaction heat is removed and the termination point is adjusted. In the solution polymerization method, a styrene monomer or a styrene derivative is polymerized using a solvent that can dissolve the polymer. In the ionic polymerization method, BF3 , SnCl4 , etc. are used as catalysts, and styrene molecules once form a double salt. After the styrene molecules are separated from the double salt, they are polymerized with other styrene molecules to form a polymeric substance. is formed. In both the emulsion polymerization method and the suspension polymerization method, the polymerization reaction is carried out by dispersing styrene or a styrene derivative into small spheres in a system in which a large amount of water coexists. Polystyrene obtained by polymerizing a single styrene monomer is generally called general purpose polystyrene (GP polystyrene).
合成ゴムを配合したポリスチレンは、一般に、ハイ・インパクト・ポリスチレン(HIポリスチレン)と呼ばれている。配合する合成ゴムには、例えば、ポリブタジエン、スチレン-ブタジエン共重合体、ポリイソプレン、ブタジエン-イソプレン共重合体等が挙げられ、特にポリブタジエン、スチレン-ブタジエン共重合体が好ましい。合成ゴムを配合したスチレン系樹脂(A)は、例えば、合成ゴムをスチレンモノマーに溶解した後、塊状重合、溶液重合、または懸濁重合により作製することができる。 Polystyrene blended with synthetic rubber is generally called high impact polystyrene (HI polystyrene). Examples of the synthetic rubber to be blended include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, etc., and polybutadiene and styrene-butadiene copolymer are particularly preferred. The styrenic resin (A) blended with synthetic rubber can be produced, for example, by dissolving the synthetic rubber in a styrene monomer and then performing bulk polymerization, solution polymerization, or suspension polymerization.
スチレンモノマーまたはスチレン誘導体を他のモノマーと共重合させたスチレン系樹脂(A)には、例えば、スチレン-メタクリル酸共重合体、スチレン-無水マレイン酸共重合体、スチレン-アルキル(メタ)アクリレート共重合体類、スチレンアクリロニトリル共重合体(SAN、AB樹脂)、スチレン-アクリロニトリル-ブタジエン共重合体(ABS樹脂)、スチレン-共役ジエンブロック共重合体(SBBC)等が挙げられる。 Styrene resins (A) made by copolymerizing styrene monomers or styrene derivatives with other monomers include, for example, styrene-methacrylic acid copolymers, styrene-maleic anhydride copolymers, and styrene-alkyl (meth)acrylate copolymers. Polymers such as styrene-acrylonitrile copolymer (SAN, AB resin), styrene-acrylonitrile-butadiene copolymer (ABS resin), styrene-conjugated diene block copolymer (SBBC), and the like.
これらのスチレン系樹脂は、1種を単独で、または2種以上を組み合わせて使用することができる。これらのスチレン系樹脂の中で、安価で透明で光沢がよく塗装も容易であるという観点から、GPポリスチレン、HIポリスチレン等のポリスチレンが好ましく、GPポリスチレンがより好ましい。 These styrene resins can be used alone or in combination of two or more. Among these styrene resins, polystyrenes such as GP polystyrene and HI polystyrene are preferred, and GP polystyrene is more preferred, from the viewpoint of being inexpensive, transparent, glossy, and easy to paint.
樹脂組成物におけるスチレン系樹脂(A)の含有量は、スチレン系樹脂(A)及びポリエステル樹脂(B)の合計100質量部に対して、75~99質量部である。スチレン系樹脂(A)の含有量が75質量部未満であると、結晶開始部位となるポリエステル樹脂(B)の含有量が大きくなり、その結果、スチレン系樹脂(A)の結晶化が進行しすぎてしまい、二軸延伸シートの引張伸びが小さくなったり、厚みムラが大きくなったりする場合がある。一方、スチレン系樹脂(A)の含有量が99質量部よりも大きいと、二軸延伸シートの引張伸びが小さくなったり、二軸延伸シートの厚みムラが大きくなったり、二軸延伸シートの耐折性が悪くなったりする場合がある。また、二軸延伸シートの結晶化が十分に進まず、二軸延伸シートの加熱収縮率が大きくなる場合がある。このような観点から、樹脂組成物におけるスチレン系樹脂(A)の含有量は、スチレン系樹脂(A)及びポリエステル樹脂(B)の合計100質量部に対して、好ましくは80~99質量部であり、より好ましくは85~97質量部である。 The content of the styrene resin (A) in the resin composition is 75 to 99 parts by mass based on the total of 100 parts by mass of the styrene resin (A) and the polyester resin (B). If the content of the styrenic resin (A) is less than 75 parts by mass, the content of the polyester resin (B), which becomes a crystallization initiation site, becomes large, and as a result, the crystallization of the styrene resin (A) progresses. If the film is stretched too much, the tensile elongation of the biaxially stretched sheet may become small or the thickness unevenness may become large. On the other hand, if the content of the styrene resin (A) is greater than 99 parts by mass, the tensile elongation of the biaxially oriented sheet may become small, the thickness unevenness of the biaxially oriented sheet may become large, or the biaxially oriented sheet may have a The bending properties may deteriorate. Further, the crystallization of the biaxially stretched sheet may not proceed sufficiently, and the heat shrinkage rate of the biaxially stretched sheet may increase. From this point of view, the content of the styrene resin (A) in the resin composition is preferably 80 to 99 parts by mass based on a total of 100 parts by mass of the styrene resin (A) and the polyester resin (B). The amount is more preferably 85 to 97 parts by mass.
<ポリエステル樹脂(B)>
ポリエステル樹脂(B)はジカルボン酸成分(b-1)とジオール成分(b-2)とのエステル化によって得られる樹脂である。ジカルボン酸成分(b-1)は主成分としてテレフタル酸を含む。ジオール成分(b-2)は、特に限定されないが、環状骨格を有するジオール及び直鎖脂肪族ジオールからなる群から選択される少なくとも1種のジオールを含むことが好ましく、環状骨格を有するジオールを含むことがより好ましい。
<Polyester resin (B)>
The polyester resin (B) is a resin obtained by esterifying a dicarboxylic acid component (b-1) and a diol component (b-2). The dicarboxylic acid component (b-1) contains terephthalic acid as a main component. The diol component (b-2) is not particularly limited, but preferably contains at least one diol selected from the group consisting of diols having a cyclic skeleton and straight-chain aliphatic diols, and includes a diol having a cyclic skeleton. It is more preferable.
(1)ジカルボン酸成分(b-1)
ジカルボン酸成分(b-1)は、主成分としてテレフタル酸を含む。なお、主成分とは、ジカルボン酸成分(b-1)に含まれるジカルボン酸の中で、テレフタル酸の割合(モル%)が最も大きいことを意味する。ジカルボン酸成分(b-1)は、テレフタル酸のみであってもよいが、テレフタル酸以外のジカルボン酸を含んでもよい。テレフタル酸以外のジカルボン酸には、例えば、マロン酸、コハク酸、グルタル酸、アジピン酸、スベリン酸、セバシン酸、メチルマロン酸、エチルマロン酸、イソフタル酸、フタル酸、1,4-ナフタレンジカルボン酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸等が挙げられる。ジカルボン酸成分(b-1)は、テレフタル酸以外に、これらのジカルボン酸の1種を、またはこれらのジカルボン酸の2種以上を含むことができる。ジカルボン酸成分(b-1)全体に対するテレフタル酸以外のジカルボン酸の割合は、好ましくは0~40モル%であり、より好ましくは0~25モル%である。ジカルボン酸成分(b-1)は、テレフタル酸のみであることが好ましい。
(1) Dicarboxylic acid component (b-1)
The dicarboxylic acid component (b-1) contains terephthalic acid as a main component. Note that the term "main component" means that the proportion (mol %) of terephthalic acid is the largest among the dicarboxylic acids contained in the dicarboxylic acid component (b-1). The dicarboxylic acid component (b-1) may be only terephthalic acid, but may also contain dicarboxylic acids other than terephthalic acid. Examples of dicarboxylic acids other than terephthalic acid include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, methylmalonic acid, ethylmalonic acid, isophthalic acid, phthalic acid, and 1,4-naphthalenedicarboxylic acid. , 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid and the like. The dicarboxylic acid component (b-1) can contain one or more of these dicarboxylic acids in addition to terephthalic acid. The proportion of dicarboxylic acids other than terephthalic acid to the entire dicarboxylic acid component (b-1) is preferably 0 to 40 mol%, more preferably 0 to 25 mol%. The dicarboxylic acid component (b-1) is preferably terephthalic acid only.
(2)ジオール成分(b-2)
上述したように、ジオール成分(b-2)は、特に限定されないが、環状骨格を有するジオール及び直鎖脂肪族ジオールからなる群から選択される少なくとも1種のジオールを含むことが好ましく、環状骨格を有するジオールを含むことがより好ましい。
(2) Diol component (b-2)
As mentioned above, the diol component (b-2) is not particularly limited, but preferably contains at least one diol selected from the group consisting of diols having a cyclic skeleton and straight-chain aliphatic diols; It is more preferable to include a diol having the following.
(i)環状骨格を有するジオール
ジオール成分(b-2)は、環状骨格を有するジオールを含むことが好ましい。環状骨格を有するジオールには、例えば、シクロブタンジオール、シクロペンタンジオール、シクロへキサンジオール、シクロヘプタンジオール、シクロオクタンジオール、シクロプロパンジメタノール、シクロブタンジメタノール、シクロペンタンジメタノール、シクロへキサンジメタノール、2,2,4,4-テトラメチル-1,3-シクロブタンジオール、イソソルビド、3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカン、5-メチロール-5-エチル-2-(1,1-ジメチル-2-ヒドロキシエチル)-1,3-ジオキサン等が挙げられる。ジオール成分(b-2)は、これらの環状骨格を有するジオールの1種を、またはこれらの環状骨格を有するジオールの2種以上を含むことができる。これらの環状骨格を有するジオールの中で、ポリエステル樹脂(B)のガラス転移温度を上昇させて、耐折性をさらに改善し、加熱収縮率をさらに小さくするという観点から、シクロへキサンジメタノール、2,2,4,4-テトラメチル-1,3-シクロブタンジオール、イソソルビド及び3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカンが好ましく、シクロへキサンジメタノール及びイソソルビドがより好ましく、イソソルビドがさらに好ましい。なお、イソソルビドは、再生可能資源、例えば糖類及びでんぷんから容易に得ることができ、例えば、D-グルコースを水添し、脱水反応をすればイソソルビドを得ることができる。したがって、環状骨格を有するジオールとして、イソソルビドを用いることにより、二酸化炭素の排出を削減できる。
(i) Diol having a cyclic skeleton The diol component (b-2) preferably contains a diol having a cyclic skeleton. Examples of diols having a cyclic skeleton include cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclopropanedimethanol, cyclobutane dimethanol, cyclopentanedimethanol, cyclohexane dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro [ 5.5] undecane, 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-dioxane, and the like. The diol component (b-2) can contain one type of diol having these cyclic skeletons, or two or more types of diols having these cyclic skeletons. Among these diols having a cyclic skeleton, cyclohexane dimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, isosorbide and 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[ 5.5] Undecane is preferred, cyclohexanedimethanol and isosorbide are more preferred, and isosorbide is even more preferred. Note that isosorbide can be easily obtained from renewable resources such as sugars and starch. For example, isosorbide can be obtained by hydrogenating D-glucose and performing a dehydration reaction. Therefore, by using isosorbide as the diol having a cyclic skeleton, carbon dioxide emissions can be reduced.
ジオール成分(b-2)全体に対する環状骨格を有するジオールの割合は、好ましくは25モル%以上である。ジオール成分(b-2)全体に対する環状骨格を有するジオールの割合が25モル%以上であると、ポリエステル樹脂(B)のガラス転移温度を高くして二軸延伸シートの加熱収縮率をさらに小さくすることができ、さらに、厚みムラが小さくし、耐折性を改善することができる。このような観点から、ジオール成分(b-2)全体に対する環状骨格を有するジオールの割合は、より好ましくは40モル%以上であり、さらに好ましくは50モル%以上であり、よりさらに好ましくは55モル%以上である。また、二軸延伸シートの引張伸びをさらに大きくするという観点から、ジオール成分(b-2)全体に対する環状骨格を有するジオールの割合は、好ましくは90モル%以下であり、より好ましくは85モル%以下であり、さらに好ましくは80モル%以下である。 The ratio of the diol having a cyclic skeleton to the entire diol component (b-2) is preferably 25 mol% or more. When the ratio of the diol having a cyclic skeleton to the entire diol component (b-2) is 25 mol% or more, the glass transition temperature of the polyester resin (B) is increased to further reduce the heat shrinkage rate of the biaxially stretched sheet. Furthermore, thickness unevenness can be reduced and folding durability can be improved. From this point of view, the ratio of the diol having a cyclic skeleton to the entire diol component (b-2) is more preferably 40 mol% or more, still more preferably 50 mol% or more, even more preferably 55 mol%. % or more. Furthermore, from the viewpoint of further increasing the tensile elongation of the biaxially oriented sheet, the proportion of the diol having a cyclic skeleton to the entire diol component (b-2) is preferably 90 mol% or less, more preferably 85 mol%. or less, more preferably 80 mol% or less.
ジオール成分(b-2)全体に対するイソソルビドの割合は、好ましくは5~45モル%である。ジオール成分(b-2)全体に対するイソソルビドの割合が5モル%以上であると、二酸化炭素の排出を削減できるとともに、ポリエステル樹脂(B)のガラス転移温度を高くして二軸延伸シートの加熱収縮率がさらに小さくすることができる。また、ジオール成分(b-2)全体に対するイソソルビドの割合が45モル%以下であると、二軸延伸シートの引張伸びがさらに大きくなったり、二軸延伸シートの厚みムラがさらに小さくなったりする場合がある。このような観点から、ジオール成分(b-2)全体に対するイソソルビドの割合は、より好ましくは7~40モル%であり、さらに好ましくは8~35モル%である。 The proportion of isosorbide to the total diol component (b-2) is preferably 5 to 45 mol%. When the ratio of isosorbide to the entire diol component (b-2) is 5 mol% or more, carbon dioxide emissions can be reduced, and the glass transition temperature of the polyester resin (B) can be increased to improve heat shrinkage of the biaxially stretched sheet. The rate can be made even smaller. In addition, if the proportion of isosorbide to the entire diol component (b-2) is 45 mol% or less, the tensile elongation of the biaxially oriented sheet may further increase or the thickness unevenness of the biaxially oriented sheet may further decrease. There is. From this point of view, the proportion of isosorbide to the entire diol component (b-2) is more preferably 7 to 40 mol%, and still more preferably 8 to 35 mol%.
ジオール成分(b-2)がイソソルビドを含む場合、ジオール成分(b-2)はシクロへキサンジメタノールをさらに含むことが好ましく、1,4-シクロへキサンジメタノールをさらに含むことがより好ましい。これにより、本発明の二軸延伸シートの耐衝撃性がさらに改善される。このような観点から、ジオール成分(b-2)全体に対するシクロへキサンジメタノールの割合は、好ましくは40~65モル%であり、より好ましくは45~55モル%である。 When the diol component (b-2) contains isosorbide, the diol component (b-2) preferably further contains cyclohexanedimethanol, and more preferably further contains 1,4-cyclohexanedimethanol. This further improves the impact resistance of the biaxially stretched sheet of the present invention. From this viewpoint, the proportion of cyclohexanedimethanol to the entire diol component (b-2) is preferably 40 to 65 mol%, more preferably 45 to 55 mol%.
(ii)直鎖脂肪族ジオール
直鎖脂肪族ジオールには、例えば、1,2-プロパンジオール、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、ポリアルキレングリコール、ヒドロキノン、ビスフェノール、1,2-ブタンジオール、1,3-ブタンジオール等が挙げられる。ジオール成分(b-2)は、これらの直鎖脂肪族ジオールの1種を、またはこれらの直鎖脂肪族ジオールの2種以上を含むことができる。これらの中で、エチレングリコール及びジエチレングリコールが好ましく、エチレングリコールがより好ましい。
(ii) Straight chain aliphatic diol Straight chain aliphatic diols include, for example, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Examples include hexanediol, neopentyl glycol, ethylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycol, hydroquinone, bisphenol, 1,2-butanediol, 1,3-butanediol, and the like. The diol component (b-2) can contain one kind of these straight chain aliphatic diols or two or more kinds of these straight chain aliphatic diols. Among these, ethylene glycol and diethylene glycol are preferred, and ethylene glycol is more preferred.
二軸延伸シートの引張伸びをさらに大きくする観点から、ジオール成分(b-2)全体に対する直鎖脂肪族ジオールの割合は、好ましくは10モル%以上であり、より好ましくは15モル%以上であり、さらに好ましくは20モル%以上である。また、ポリエステル樹脂(B)のガラス転移温度を高くして二軸延伸シートの加熱収縮率をさらに小さくするという観点から、ジオール成分(b-2)全体に対する直鎖脂肪族ジオールの割合は、好ましくは75モル%以下であり、より好ましくは60モル%以下であり、さらに好ましくは50モル%以下であり、よりさらに好ましくは40モル%以下である。 From the viewpoint of further increasing the tensile elongation of the biaxially oriented sheet, the proportion of the linear aliphatic diol to the entire diol component (b-2) is preferably 10 mol% or more, more preferably 15 mol% or more. , more preferably 20 mol% or more. In addition, from the viewpoint of increasing the glass transition temperature of the polyester resin (B) and further reducing the heat shrinkage rate of the biaxially oriented sheet, the proportion of the linear aliphatic diol to the entire diol component (b-2) is preferably is 75 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, even more preferably 40 mol% or less.
ジオール成分(b-2)がエチレングリコールを含む場合、二軸延伸シートの引張伸びをさらに大きくする観点から、ジオール成分(b-2)全体に対するエチレングリコールの割合は、好ましくは10モル%以上であり、より好ましくは15モル%以上であり、さらに好ましくは20モル%以上である。また、ポリエステル樹脂(B)のガラス転移温度を高くして二軸延伸シートの加熱収縮率をさらに小さくするという観点から、ジオール成分(b-2)全体に対するエチレングリコールの割合は、好ましくは75モル%以下であり、より好ましくは60モル%以下であり、さらに好ましくは50モル%以下であり、よりさらに好ましくは40モル%以下である。 When the diol component (b-2) contains ethylene glycol, from the viewpoint of further increasing the tensile elongation of the biaxially oriented sheet, the ratio of ethylene glycol to the entire diol component (b-2) is preferably 10 mol% or more. The content is more preferably 15 mol% or more, and still more preferably 20 mol% or more. In addition, from the viewpoint of increasing the glass transition temperature of the polyester resin (B) and further reducing the heat shrinkage rate of the biaxially oriented sheet, the ratio of ethylene glycol to the entire diol component (b-2) is preferably 75 mol. % or less, more preferably 60 mol% or less, still more preferably 50 mol% or less, even more preferably 40 mol% or less.
ジオール成分(b-2)がエチレングリコール以外の直鎖脂肪族ジオールを含む場合、ジオール成分(b-2)全体に対するエチレングリコール以外の直鎖脂肪族ジオールの割合は、好ましくは0.5~8.0モル%であり、より好ましくは1.0~5.0モル%であり、さらに好ましくは1.5~3.5モル%である。 When the diol component (b-2) contains a straight chain aliphatic diol other than ethylene glycol, the ratio of the straight chain aliphatic diol other than ethylene glycol to the entire diol component (b-2) is preferably 0.5 to 8. 0 mol%, more preferably 1.0 to 5.0 mol%, still more preferably 1.5 to 3.5 mol%.
ジオール成分(b-2)全体における環状骨格を有するジオールの割合及び直鎖脂肪族ジオールの割合の合計は、好ましくは80モル%以上であり、より好ましくは90モル%以上であり、さらに好ましくは95モル%以上であり、特に好ましくは100モル%である。 The total proportion of the diol having a cyclic skeleton and the proportion of the linear aliphatic diol in the entire diol component (b-2) is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably It is 95 mol% or more, particularly preferably 100 mol%.
(3)ポリエステル樹脂(B)の含有量
樹脂組成物におけるポリエステル樹脂(B)の含有量は、スチレン系樹脂(A)及びポリエステル樹脂(B)の合計100質量部に対して、1~25質量部である。ポリエステル樹脂(B)の含有量が1質量部未満であると、二軸延伸シートの伸び及び曲げに対する強度を向上させるというポリエステル樹脂(B)の効果が十分には発現せず、二軸延伸シートの引張伸びが小さくなったり、二軸延伸シートの厚みムラが大きくなったり、二軸延伸シートの耐折性が悪くなったりする場合がある。また、スチレン系樹脂(A)の結晶化が十分に進まず、二軸延伸シートの加熱収縮率が大きくなる場合がある。一方、ポリエステル樹脂(B)の含有量が25質量部より大きいと、スチレン系樹脂(A)の結晶化が進行しすぎてしまい、二軸延伸シートの引張伸びが小さくなったり、厚みムラが大きくなったりする場合がある。このような観点から、樹脂組成物におけるポリエステル樹脂(B)の含有量は、スチレン系樹脂(A)及びポリエステル樹脂(B)の合計100質量部に対して、好ましくは3~20質量部であり、より好ましくは5~15質量部である。
(3) Content of polyester resin (B) The content of polyester resin (B) in the resin composition is 1 to 25 parts by mass based on a total of 100 parts by mass of styrene resin (A) and polyester resin (B). Department. If the content of the polyester resin (B) is less than 1 part by mass, the effect of the polyester resin (B) to improve the strength against elongation and bending of the biaxially oriented sheet will not be fully expressed, and the biaxially oriented sheet The tensile elongation of the biaxially oriented sheet may become small, the thickness unevenness of the biaxially oriented sheet may become large, and the folding durability of the biaxially oriented sheet may deteriorate. Further, the crystallization of the styrenic resin (A) may not proceed sufficiently, and the heat shrinkage rate of the biaxially stretched sheet may increase. On the other hand, if the content of the polyester resin (B) is more than 25 parts by mass, the crystallization of the styrene resin (A) will progress too much, resulting in a decrease in the tensile elongation of the biaxially stretched sheet and a large thickness unevenness. It may happen. From this point of view, the content of the polyester resin (B) in the resin composition is preferably 3 to 20 parts by mass with respect to a total of 100 parts by mass of the styrene resin (A) and the polyester resin (B). , more preferably 5 to 15 parts by mass.
(4)ポリエステル樹脂(B)のガラス転移温度
ポリエステル樹脂(B)のガラス転移温度は、好ましくは90~135℃である。ポリエステル樹脂(B)のガラス転移温度が90℃以上であると、耐折性がさらに改善したり、加熱収縮率がさらに小さくなったりする場合がある。ポリエステル樹脂(B)のガラス転移温度が135℃以下であると、引張伸びがさらに大きくなったり、厚みムラがさらに小さくなったりする場合がある。このような観点から、ポリエステル樹脂(B)のガラス転移温度は、より好ましくは92~133℃であり、さらに好ましくは95~130℃である。なお、ガラス転移温度は、JIS K7198Aに従って、動的粘弾性の温度分散測定を用いて歪み0.1%、周波数10Hz、昇温速度3℃/分にて測定される損失正接(tanδ)の主分散のピークで評価される。また、ポリエステル樹脂樹脂(B)のガラス転移温度は、ジオール成分全体に対する環状骨格を有するジオールの割合を調節することにより調整することができる。例えば、ジオール成分全体に対する環状骨格を有するジオールの割合を高くすると、ポリエステル樹脂(B)のガラス転移温度を高くすることができる。
(4) Glass transition temperature of polyester resin (B) The glass transition temperature of polyester resin (B) is preferably 90 to 135°C. When the glass transition temperature of the polyester resin (B) is 90° C. or higher, the folding durability may be further improved or the heat shrinkage rate may be further reduced. If the glass transition temperature of the polyester resin (B) is 135° C. or lower, the tensile elongation may further increase or the thickness unevenness may further decrease. From this point of view, the glass transition temperature of the polyester resin (B) is more preferably 92 to 133°C, and even more preferably 95 to 130°C. In addition, the glass transition temperature is the main loss tangent (tan δ) measured according to JIS K7198A using temperature dispersion measurement of dynamic viscoelasticity at a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3°C/min. Evaluated at the peak of the dispersion. Further, the glass transition temperature of the polyester resin (B) can be adjusted by adjusting the ratio of the diol having a cyclic skeleton to the entire diol component. For example, by increasing the ratio of diol having a cyclic skeleton to the entire diol component, the glass transition temperature of the polyester resin (B) can be increased.
<その他の樹脂成分>
樹脂組成物は、本発明の効果を阻害しない範囲で、スチレン系樹脂(A)及びポリエステル樹脂(B)以外の樹脂成分を含んでもよい。樹脂組成物におけるスチレン系樹脂(A)及びポリエステル樹脂(B)以外の樹脂成分の含有量の合計は、全樹脂成分100質量部に対して、好ましくは10質量部以下であり、より好ましくは5質量部以下である。なお、スチレン系樹脂(A)及びポリエステル樹脂(B)以外の樹脂成分の含有量の合計の範囲の下限値は、特に限定されないが、例えば0質量部である。スチレン系樹脂(A)及びポリエステル樹脂(B)以外の樹脂成分には、例えば、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、塩素化ポリエチレン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリアセタール系樹脂、アクリル系樹脂、エチレン酢酸ビニル共重合体、ポリメチルペンテン系樹脂、ポリビニルアルコール系樹脂、環状オレフィン系樹脂、ポリ乳酸系樹脂、ポリブチレンサクシネート系樹脂、ポリアクリロニトリル系樹脂、ポリエチレンオキサイド系樹脂、セルロース系樹脂、ポリイミド系樹脂、ポリウレタン系樹脂、ポリフェニレンスルフィド系樹脂、ポリフェニレンエーテル系樹脂、ポリビニルアセタール系樹脂、ポリブタジエン系樹脂、ポリブテン系樹脂、ポリアミドイミド系樹脂、ポリアミドビスマレイミド系樹脂、ポリアリレート系樹脂、ポリエーテルイミド系樹脂、ポリエーテルエーテルケトン系樹脂、ポリエーテルケトン系樹脂、ポリエーテルスルホン系樹脂、ポリケトン系樹脂、ポリサルフォン系樹脂、アラミド系樹脂、フッ素系樹脂等が挙げられる。
<Other resin components>
The resin composition may contain resin components other than the styrene resin (A) and the polyester resin (B) as long as the effects of the present invention are not impaired. The total content of resin components other than styrene resin (A) and polyester resin (B) in the resin composition is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of all resin components. Parts by mass or less. Note that the lower limit of the total content of resin components other than the styrene resin (A) and the polyester resin (B) is not particularly limited, but is, for example, 0 parts by mass. Examples of resin components other than styrene resin (A) and polyester resin (B) include polyvinyl chloride resin, polyvinylidene chloride resin, chlorinated polyethylene resin, polycarbonate resin, polyamide resin, and polyacetal resin. , acrylic resin, ethylene vinyl acetate copolymer, polymethylpentene resin, polyvinyl alcohol resin, cyclic olefin resin, polylactic acid resin, polybutylene succinate resin, polyacrylonitrile resin, polyethylene oxide resin, Cellulose resin, polyimide resin, polyurethane resin, polyphenylene sulfide resin, polyphenylene ether resin, polyvinyl acetal resin, polybutadiene resin, polybutene resin, polyamideimide resin, polyamide bismaleimide resin, polyarylate resin , polyetherimide resin, polyetheretherketone resin, polyetherketone resin, polyethersulfone resin, polyketone resin, polysulfone resin, aramid resin, fluorine resin, and the like.
<添加剤>
樹脂組成物は、シリカ、タルク、カオリン、炭酸カルシウム等の無機粒子、酸化チタン、カーボンブラック等の顔料、難燃剤、耐候性安定剤、耐熱安定剤、帯電防止剤、溶融粘度改良剤、架橋剤、滑剤、核剤、可塑剤、老化防止剤、酸化防止剤、光安定剤、紫外線吸収剤、中和剤、防曇剤、アンチブロッキング剤、スリップ剤、及び、着色剤等の添加剤をさらに含んでもよい。
<Additives>
The resin composition includes inorganic particles such as silica, talc, kaolin, and calcium carbonate, pigments such as titanium oxide and carbon black, flame retardants, weather-resistant stabilizers, heat-resistant stabilizers, antistatic agents, melt viscosity improvers, and crosslinking agents. , lubricants, nucleating agents, plasticizers, anti-aging agents, antioxidants, light stabilizers, ultraviolet absorbers, neutralizing agents, antifogging agents, anti-blocking agents, slip agents, and coloring agents. May include.
引張伸びが大きく、厚みムラが小さく、耐折性に優れ、加熱収縮率が小さい二軸延伸シートを得るという観点から、本発明の二軸延伸シートにおける上記樹脂組成物の含有量は、好ましくは90質量%以上であり、より好ましくは95質量%以上であり、さらに好ましくは98質量%以上であり、特に好ましくは100質量%である。 From the viewpoint of obtaining a biaxially oriented sheet with large tensile elongation, small thickness unevenness, excellent folding durability, and low heat shrinkage rate, the content of the resin composition in the biaxially oriented sheet of the present invention is preferably The content is 90% by mass or more, more preferably 95% by mass or more, further preferably 98% by mass or more, and particularly preferably 100% by mass.
(二軸延伸)
本発明の二軸延伸シートは、好ましくは上記樹脂組成物を二軸延伸してなるものである。樹脂組成物の二軸延伸に伴って、樹脂組成物の分子配向が進行し、上記樹脂組成物から得られるシートの機械的強度を高くすることができる。樹脂組成物の二軸延伸法には、例えば、フラットダイ法、サーキュラダイ法等が挙げられる。また、フラットダイ法には、例えば逐次二軸延伸法、同時二軸延伸法等が挙げられる。サーキュラダイ法には、例えばインフレーション二軸成形法等が挙げられる。これらの二軸延伸法の中で、生産性の観点から、逐次二次延伸法が好ましい。逐次二次延伸法は、例えば、押出工程、原反成形工程、縦延伸工程、横延伸工程、及び巻取り工程を含む。
(biaxial stretching)
The biaxially stretched sheet of the present invention is preferably obtained by biaxially stretching the above resin composition. As the resin composition is biaxially stretched, the molecular orientation of the resin composition progresses, and the mechanical strength of the sheet obtained from the resin composition can be increased. Examples of the biaxial stretching method for the resin composition include flat die method, circular die method, and the like. Moreover, the flat die method includes, for example, a sequential biaxial stretching method, a simultaneous biaxial stretching method, and the like. Examples of the circular die method include an inflation biaxial molding method. Among these biaxial stretching methods, the sequential secondary stretching method is preferred from the viewpoint of productivity. The sequential secondary stretching method includes, for example, an extrusion process, a fabric forming process, a longitudinal stretching process, a horizontal stretching process, and a winding process.
押出工程では、スチレン系樹脂(A)及びポリエステル樹脂(B)を押出機で均一に溶融した後、溶融された樹脂組成物をダイからキャスティングロール上に押し出して、シート状の樹脂組成物を作製する。原反成形工程では、ダイより押し出されたシート状の樹脂組成物を、冷却ロールに密着させて、均一に冷却固化して原反シートを作製する。縦延伸工程では、原反シートを加熱して、周速の異なるロール間で縦方向に、原反シートを延伸する。縦延伸温度は、例えば120~130℃である。横延伸工程では、縦方向に延伸した原反シートの横方向両端をテンタークリップで把持して、シートの上面及び下面より熱風を吹き付けながら均一にシートを予熱し、所定のパターンに設定されたクリップ案内レールに沿って、所定の倍率にシートを横延伸し、横延伸したシートを熱処理した後に冷却する。横延伸温度は、例えば120~130℃である。巻取り工程では、冷却したシートを巻き取る。 In the extrusion process, the styrene resin (A) and polyester resin (B) are uniformly melted in an extruder, and then the molten resin composition is extruded from a die onto a casting roll to produce a sheet-shaped resin composition. do. In the original fabric forming process, the sheet-shaped resin composition extruded from a die is brought into close contact with a cooling roll, and uniformly cooled and solidified to produce an original fabric sheet. In the longitudinal stretching step, the raw sheet is heated and stretched in the longitudinal direction between rolls having different circumferential speeds. The longitudinal stretching temperature is, for example, 120 to 130°C. In the lateral stretching process, tenter clips are used to hold both lateral ends of the original sheet stretched in the longitudinal direction, and the sheet is uniformly preheated by blowing hot air from the top and bottom surfaces of the sheet, and the clips are set in a predetermined pattern. The sheet is laterally stretched along the guide rail to a predetermined magnification, and the laterally stretched sheet is heat treated and then cooled. The transverse stretching temperature is, for example, 120 to 130°C. In the winding process, the cooled sheet is rolled up.
シート状の樹脂組成物に縦方向の分子配向を付与して、縦方向の機械的物性を効果的に向上させるという観点から、二軸延伸シートの縦方向の延伸倍率は、好ましくは1.5~3.5倍であり、より好ましくは1.7~3.5倍であり、さらに好ましくは2.0~3.3倍である。また、縦方向に延伸した樹脂組成物のシートに横方向の分子配向をさらに付与して、横方向の機械的物性を効果的に向上させるという観点から、二軸延伸シートの横方向の延伸倍率は、好ましくは1.5~3.5倍であり、より好ましくは1.7~3.5倍であり、さらに好ましくは2.0~3.3倍である。 From the viewpoint of imparting longitudinal molecular orientation to the sheet-like resin composition and effectively improving the longitudinal mechanical properties, the longitudinal stretching ratio of the biaxially stretched sheet is preferably 1.5. ~3.5 times, more preferably 1.7 to 3.5 times, still more preferably 2.0 to 3.3 times. In addition, from the viewpoint of further imparting transverse molecular orientation to the longitudinally stretched sheet of the resin composition and effectively improving the transverse mechanical properties, the transverse stretching ratio of the biaxially stretched sheet is is preferably 1.5 to 3.5 times, more preferably 1.7 to 3.5 times, even more preferably 2.0 to 3.3 times.
なお、二軸延伸シートの縦方向及び横方向の延伸倍率は、例えば、二軸延伸シートから以下のようにして測定することができる。二軸延伸シートにおいて縦方向および横方向に100mm長の直線を引く。直線を引いた二軸延伸シートをビカット軟化温度より20℃高い温度のオーブンに、60分間静置し収縮させ、収縮後の上記縦方向の直線の長さLM(mm)及び上記横方向の直線の長さLT(mm)を測定する。そして、縦方向の延伸倍率(XM)および横方向の延伸倍率(XT)はそれぞれ、次式によって算出できる。
延伸倍率(XM) = 100/LM
延伸倍率(XT) = 100/LT
なお、ビカット軟化温度は、後述の実施例に記載の条件で測定した。
Note that the stretching ratios of the biaxially stretched sheet in the longitudinal and lateral directions can be measured from the biaxially stretched sheet as follows, for example. A straight line with a length of 100 mm is drawn in the longitudinal and transverse directions on the biaxially stretched sheet. The biaxially stretched sheet with a straight line drawn thereon is left standing in an oven at a temperature 20°C higher than the Vicat softening temperature for 60 minutes to shrink, and the length of the straight line in the vertical direction after shrinkage L M (mm) and the length in the horizontal direction are Measure the length of the straight line L T (mm). The stretching ratio in the longitudinal direction (X M ) and the stretching ratio in the lateral direction (X T ) can each be calculated using the following equations.
Stretching ratio ( XM ) = 100/ LM
Stretching ratio (X T ) = 100/L T
Note that the Vicat softening temperature was measured under the conditions described in Examples below.
(二軸延伸シートの加熱収縮率)
樹脂組成物がポリエステル樹脂(B)を含むことにより、本発明の二軸延伸シートの加熱収縮率を、例えば、ポリスチレンの二軸延伸シートの加熱収縮率よりも小さくすることができる。また、本発明の二軸延伸シートを120℃の温度で1時間加熱した後の縦方向及び横方向の前記二軸延伸シートの加熱収縮率をそれぞれZM(%)及びZT(%)とし、前記二軸延伸シートの縦方向及び横方向の延伸倍率をそれぞれXM及びXTとし、縦方向及び横方向において、前記加熱収縮率(ZM,ZT)及び前記延伸倍率(XM,XT)が次の式(1)及び式(2)をそれぞれ満たす場合、YM及びYTは、それぞれ、好ましくは40~99%である。YM及びYTが、それぞれ、40~99%であると、熱成形において本発明の二軸延伸シートを容易に伸張賦形することができる。このような観点から、上記YM及びYTは、それぞれ、より好ましくは60~99%であり、さらに好ましくは70~99%である。なお、二軸延伸シートの加熱収縮率は、後述の実施例に記載の測定方法により測定することができる。
ZM(%)=(1-1/XM)×YM (1)
ZT(%)=(1-1/XT)×YT (2)
(Heat shrinkage rate of biaxially stretched sheet)
By including the polyester resin (B) in the resin composition, the heat shrinkage rate of the biaxially stretched sheet of the present invention can be made smaller than that of the biaxially stretched sheet of polystyrene, for example. In addition, after heating the biaxially stretched sheet of the present invention at a temperature of 120° C. for 1 hour, the heat shrinkage rates of the biaxially stretched sheet in the longitudinal direction and the transverse direction are Z M (%) and Z T (%), respectively. , the stretching ratios of the biaxially stretched sheet in the longitudinal and lateral directions are X M and XT , respectively, and the heat shrinkage rate (Z M , Z T ) and the stretching ratio (X M , When X T ) satisfies the following formulas (1) and (2), respectively, Y M and Y T are preferably 40 to 99%. When Y M and Y T are each from 40 to 99%, the biaxially stretched sheet of the present invention can be easily stretched and shaped by thermoforming. From this point of view, the above Y M and Y T are each more preferably 60 to 99%, and even more preferably 70 to 99%. The heat shrinkage rate of the biaxially stretched sheet can be measured by the measuring method described in Examples below.
Z M (%) = (1-1/X M ) x Y M (1)
Z T (%) = (1-1/X T ) x Y T (2)
(二軸延伸シートの厚み)
食品包装容器、雑貨等の軽量容器に好適な厚みになるように、本発明の二軸延伸シートを二次成形できるという観点から、本発明に二軸延伸シートの厚みは、好ましくは0.01~0.7mmであり、より好ましくは0.05~0.5mmであり、さらに好ましくは0.1~0.4mmである。
(Thickness of biaxially stretched sheet)
The thickness of the biaxially stretched sheet of the present invention is preferably 0.01 mm from the viewpoint that the biaxially stretched sheet of the present invention can be secondary formed to have a thickness suitable for lightweight containers such as food packaging containers and miscellaneous goods. 0.7 mm, more preferably 0.05 to 0.5 mm, still more preferably 0.1 to 0.4 mm.
(二軸延伸シートの配向緩和応力)
本発明の二軸延伸シートにおける縦方向及び横方向の配向緩和応力は、それぞれ、好ましくは0.3~1.2MPaである。配向緩和応力が0.3MPa以上であると、二軸延伸によって、スチレン系樹脂の分子を十分に配向させることができ、二軸延伸シートの耐折性をさらに高くし、二軸延伸シートから作製した成形品を割れにくくすることができる。一方、配向緩和応力が1.2MPa以下であると、二軸延伸シートの加熱収縮をさらに小さくして二軸延伸シートの成形性を改善し、二軸延伸シートの厚みムラをさらに抑制できる。このような観点から、本発明の二軸延伸シートにおける縦方向及び横方向の配向緩和応力は、それぞれ、より好ましくは0.4~1.0MPaであり、さらに好ましくは0.5~0.8MPaである。なお、二軸延伸シートの配向緩和応力は、延伸倍率及び延伸温度を調節することにより調整することができる。また、二軸延伸シートの配向緩和応力は、後述の実施例に記載の測定方法により測定することができる。
(Orientation relaxation stress of biaxially stretched sheet)
The orientation relaxation stress in the machine direction and the transverse direction in the biaxially stretched sheet of the present invention is preferably 0.3 to 1.2 MPa, respectively. When the orientation relaxation stress is 0.3 MPa or more, the molecules of the styrene resin can be sufficiently oriented by biaxial stretching, further increasing the folding durability of the biaxially stretched sheet, and making it possible to fabricate from the biaxially stretched sheet. molded products can be made less likely to break. On the other hand, when the orientation relaxation stress is 1.2 MPa or less, the heat shrinkage of the biaxially oriented sheet is further reduced, the formability of the biaxially oriented sheet is improved, and the thickness unevenness of the biaxially oriented sheet can be further suppressed. From this point of view, the orientation relaxation stress in the longitudinal direction and the transverse direction in the biaxially stretched sheet of the present invention is more preferably 0.4 to 1.0 MPa, and even more preferably 0.5 to 0.8 MPa. It is. Note that the orientation relaxation stress of the biaxially stretched sheet can be adjusted by adjusting the stretching ratio and stretching temperature. Further, the orientation relaxation stress of the biaxially stretched sheet can be measured by the measuring method described in Examples below.
(二軸延伸シート中のポリエステル樹脂(B)の平均分散粒径)
工業的な実施が容易であるという観点から、本発明の二軸延伸シートに用いる樹脂組成物において、スチレン系樹脂(A)及びポリエステル樹脂(B)は、機械的な混合及び混練操作を加えることによってブレンドされることが好ましい。その結果、本発明の二軸延伸シートは、スチレン系樹脂(A)のマトリックス中にポリエステル樹脂(B)の粒子が分散した相分離構造を有する。この場合、ポリエステル樹脂(B)の平均分散粒径は、好ましくは10~500nmである。ポリエステル樹脂(B)の平均分散粒径が10nm以上であると、二軸延伸シートの伸び及び曲がりに対する強度を改善するというポリエステル樹脂(B)の効果をより大きく発現させることができる。その結果、二軸延伸シートの引張伸びをさらに大きくし、二軸延伸シートの厚みムラをさらに小さくし、耐折性をさらに改善することができる。ポリエステル樹脂(B)の平均分散粒径が500nm以下であると、スチレン系樹脂(A)及びポリエステル樹脂(B)の間の界面でボイドが発生することを抑制し、耐折性をさらに改善することができる。このような観点から、本発明の延伸二軸シートにおけるポリエステル樹脂(B)の平均分散粒径は、より好ましくは30~300nmであり、さらに好ましくは50~200nmである。なお、本発明の延伸二軸シートにおけるポリエステル樹脂(B)の平均分散粒径は、例えば樹脂組成物の混合及び混練に使用する押出機のスクリューの回転数(rpm)、吐出量(kg/時)等の押出条件を調節することにより調整することができる。また、ポリエステル樹脂(B)の平均分散粒径は、後述の実施例に記載の方法で測定することができる。
(Average dispersed particle size of polyester resin (B) in biaxially stretched sheet)
From the viewpoint of ease of industrial implementation, in the resin composition used for the biaxially oriented sheet of the present invention, the styrene resin (A) and the polyester resin (B) may be subjected to mechanical mixing and kneading operations. Preferably, the mixture is blended by As a result, the biaxially stretched sheet of the present invention has a phase-separated structure in which particles of the polyester resin (B) are dispersed in a matrix of the styrene resin (A). In this case, the average dispersed particle size of the polyester resin (B) is preferably 10 to 500 nm. When the average dispersed particle size of the polyester resin (B) is 10 nm or more, the effect of the polyester resin (B) in improving the strength against elongation and bending of the biaxially stretched sheet can be more greatly exhibited. As a result, the tensile elongation of the biaxially stretched sheet can be further increased, the thickness unevenness of the biaxially stretched sheet can be further reduced, and the folding durability can be further improved. When the average dispersed particle size of the polyester resin (B) is 500 nm or less, generation of voids at the interface between the styrene resin (A) and the polyester resin (B) is suppressed, and folding durability is further improved. be able to. From this viewpoint, the average dispersed particle size of the polyester resin (B) in the stretched biaxial sheet of the present invention is more preferably 30 to 300 nm, and even more preferably 50 to 200 nm. Note that the average dispersed particle size of the polyester resin (B) in the stretched biaxial sheet of the present invention is determined by, for example, the rotation speed (rpm) of the screw of the extruder used for mixing and kneading the resin composition, and the discharge rate (kg/hour). ) can be adjusted by adjusting the extrusion conditions. Further, the average dispersed particle size of the polyester resin (B) can be measured by the method described in Examples below.
次に、本発明の成形品を説明する。
[成形品]
本発明の成形品は本発明の二軸延伸シートを二次成形して得られる。上述したように、本発明の二軸延伸シートは、厚みムラが小さく、耐折性に優れ、加熱収縮率が小さい。このような二軸延伸シートから得られる本発明の成形品も厚みムラが小さく、耐折性に優れ、加熱収縮率が小さい。なお、本明細書において、シート成形が一次成形であり、シート成形により得られたシートの熱成形が二次成形である。
Next, the molded article of the present invention will be explained.
[Molding]
The molded article of the present invention is obtained by secondary molding the biaxially stretched sheet of the present invention. As described above, the biaxially stretched sheet of the present invention has small thickness unevenness, excellent folding durability, and low heat shrinkage rate. The molded product of the present invention obtained from such a biaxially stretched sheet also has small thickness unevenness, excellent folding durability, and low heat shrinkage. Note that in this specification, sheet molding is primary molding, and thermoforming of the sheet obtained by sheet molding is secondary molding.
本発明の成形品を得るための二次成形(熱成形)には、例えば、真空成形、圧空成形、絞り成形、ツインシートフォーミング、プレス成形等が挙げられる。これらの二次成形(熱成形)の中で、二軸延伸シートを成形型に密着させて二軸延伸シートの加熱収縮をさらに抑制できるという観点から、真空成形及び圧空成形が好ましく、圧空成形がより好ましい。 Examples of secondary forming (thermoforming) for obtaining the molded article of the present invention include vacuum forming, pressure forming, drawing forming, twin sheet forming, press forming, and the like. Among these secondary forming methods (thermoforming), vacuum forming and pressure forming are preferable from the viewpoint that the biaxially stretched sheet can be brought into close contact with the mold to further suppress heat shrinkage of the biaxially stretched sheet, and pressure forming is preferable. More preferred.
真空成形では、例えば、二軸延伸シートを輻射で加熱し、軟化した二軸延伸シートもしくは型を移動して、真空吸引のための小孔を多数開けた型の上部に、二軸延伸シートと型との間の空気が漏れないようにして、二軸延伸シートを固定する。そして、真空孔から内部の空気を急速に排除して大気圧により軟化した二軸延伸シートを型面に押し付けて二軸延伸シートを賦形する。賦形された二軸延伸シートは、冷却後、取り出され、賦形された二軸延伸シートから成形品が打ち抜かれる。その後、成形品に仕上げ加工が施されて、成形品は製品となる。なお、成形温度は、例えば120~130℃であり、型温度は、例えば70~100℃である。また、二軸延伸シートは、所定寸法に切断したカートシートの形態で断続的に成形機に供給されてもよいし、ロール巻きシートの形態で連続的に成形機に供給されてもよい。 In vacuum forming, for example, a biaxially stretched sheet is heated by radiation, the softened biaxially stretched sheet or mold is moved, and the biaxially stretched sheet and the mold are placed on top of a mold with many small holes for vacuum suction. Fix the biaxially stretched sheet so that no air leaks between it and the mold. Then, the internal air is rapidly removed from the vacuum holes, and the biaxially stretched sheet, which has been softened by atmospheric pressure, is pressed against the mold surface to shape the biaxially stretched sheet. The shaped biaxially stretched sheet is taken out after cooling, and a molded product is punched out from the shaped biaxially stretched sheet. After that, the molded product is subjected to finishing processing to become a product. Note that the molding temperature is, for example, 120 to 130°C, and the mold temperature is, for example, 70 to 100°C. Further, the biaxially stretched sheet may be intermittently supplied to the molding machine in the form of a cart sheet cut into predetermined dimensions, or may be continuously supplied to the molding machine in the form of a rolled sheet.
圧空成型では、例えば、多数の通気孔を有する金属製加熱盤を所定温度に加熱した後、二軸延伸シートを熱盤上に送り、通気孔より真空吸引して熱盤に二軸延伸シートを密着して二軸延伸シートを加熱して軟化させる。そして、熱盤通気孔から加圧空気(0.15~0.5MPa)を吹き出して軟化した二軸延伸シートを熱盤に接して設けた成形型面に押し付けて二軸延伸シートを賦形する。賦形された二軸延伸シートは、冷却後、取り出され、賦形された二軸延伸シートから成形品が打ち抜かれる。その後、成形品に仕上げ加工が施されて、成形品は製品となる。なお、成形温度は、例えば120~130℃であり、型温度は、例えば70~100℃である。また、二軸延伸シートは、所定寸法に切断したカートシートの形態で断続的に成形機に供給されてもよいし、ロール巻きシートの形態で連続的に成形機に供給されてもよい。 In pressure forming, for example, after heating a metal heating plate with many ventilation holes to a predetermined temperature, the biaxially stretched sheet is fed onto the heating platen, and the biaxially stretched sheet is placed on the heating platen by vacuum suction through the ventilation holes. The biaxially stretched sheet is heated and softened in close contact. Then, pressurized air (0.15 to 0.5 MPa) is blown out from the hot platen ventilation holes to press the softened biaxially stretched sheet against a mold surface provided in contact with the hot platen to shape the biaxially stretched sheet. . The shaped biaxially stretched sheet is taken out after cooling, and a molded product is punched out from the shaped biaxially stretched sheet. After that, the molded product is subjected to finishing processing to become a product. Note that the molding temperature is, for example, 120 to 130°C, and the mold temperature is, for example, 70 to 100°C. Further, the biaxially stretched sheet may be intermittently supplied to the molding machine in the form of a cart sheet cut into predetermined dimensions, or may be continuously supplied to the molding machine in the form of a rolled sheet.
(成形品の用途)
本発明の成形品は、例えば、食品包装容器、雑貨等の軽量容器として好適に使用することができる。食品包装容器には、例えば、トレー、パック、弁当、惣菜、麺、丼等を入れる容器等が挙げられる。雑貨には、例えば、玩具、文房具等が挙げられる。これらの中で、本発明の特徴を十分に発揮できるため、食品包装容器が好ましい。
(Applications of molded products)
The molded article of the present invention can be suitably used as, for example, a food packaging container, a lightweight container for miscellaneous goods, and the like. Examples of food packaging containers include trays, packs, containers for boxed lunches, side dishes, noodles, bowls, and the like. Examples of miscellaneous goods include toys, stationery, and the like. Among these, food packaging containers are preferred because they can fully exhibit the features of the present invention.
以下、本発明について、実施例及び比較例により、詳細に説明する。なお、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to the following examples.
実施例及び比較例の二軸延伸シートに対して以下の評価を行った。
(二軸延伸シートの厚み)
マイクロメータを用いて二軸延伸シートの厚さを無作為に5箇所測定し、その平均値を二軸延伸シートの厚みとした。
The following evaluations were performed on the biaxially stretched sheets of Examples and Comparative Examples.
(Thickness of biaxially stretched sheet)
The thickness of the biaxially stretched sheet was measured at five random locations using a micrometer, and the average value was taken as the thickness of the biaxially stretched sheet.
(二軸延伸シートの加熱収縮率)
縦方向に平行な長さ10cmの直線と、横方向に平行な長さ10cmの直線とからなる十字線を二軸延伸シートに引いた。そして、120℃のオーブンの中に十字線を引いた二軸延伸シートを配置して、二軸延伸シートを1時間加熱した。十字線を引いた二軸延伸シートをオーブンから取り出し、縦方向に平行な直線の長さ(LM)(cm)と横方向に平行な直線の長さ(LT)(cm)を測定した。そして、次の式(3)及び式(4)から縦方向及び横方向の加熱収縮率(ZM,ZT)(%)をそれぞれ算出した。
加熱収縮率(ZM)(%) = (1-LM/10)×100 (3)
加熱収縮率(ZT)(%) = (1-LT/10)×100 (4)
(Heat shrinkage rate of biaxially stretched sheet)
A cross line consisting of a 10 cm long straight line parallel to the longitudinal direction and a 10 cm long straight line parallel to the lateral direction was drawn on the biaxially stretched sheet. Then, the biaxially stretched sheet with crosshairs drawn thereon was placed in an oven at 120° C., and the biaxially stretched sheet was heated for 1 hour. The biaxially stretched sheet with the crosshairs drawn was taken out of the oven, and the length of a straight line parallel to the longitudinal direction ( LM ) (cm) and the length of a straight line parallel to the horizontal direction ( LT ) (cm) were measured. . Then, the heat shrinkage rates (Z M , Z T ) (%) in the vertical direction and the horizontal direction were calculated from the following equations (3) and (4), respectively.
Heat shrinkage rate (Z M ) (%) = (1-L M /10) x 100 (3)
Heat shrinkage rate (Z T ) (%) = (1-L T /10) x 100 (4)
(二軸延伸シートの加熱収縮率及び延伸倍率の関係式)
縦方向及び横方向において、加熱収縮率(ZM,ZT)及び延伸倍率(XM,XT)が上記式(1)及び式(2)をそれぞれ満たす場合のYMの値及びYTの値を、次の式(5)及び(6)からそれぞれ算出した。
YM(%)=ZM/(1-1/XM) (5)
YT(%)=ZT/(1-1/XT) (6)
(Relational formula between heating shrinkage rate and stretching ratio of biaxially stretched sheet)
The value of Y M and Y T when the heat shrinkage rate (Z M , Z T ) and the stretching ratio (X M , X T ) satisfy the above formulas (1) and (2), respectively, in the longitudinal direction and the transverse direction. The values were calculated from the following equations (5) and (6), respectively.
Y M (%) = Z M / (1-1/X M ) (5)
Y T (%) = Z T / (1-1/X T ) (6)
(二軸延伸シートの配向緩和応力)
縦方向及び横方向の二軸延伸シートの配向緩和応力は、ASTM D1504にしたがって、シートを構成する樹脂組成物のビカット軟化温度より30℃高い温度のシリコーンオイル中でのピーク応力値として、それぞれ測定した。
なお、ビカット軟化温度は、JISK7206に従って、昇温速度50℃/時、試験荷重50Nの条件で測定した。
(Orientation relaxation stress of biaxially stretched sheet)
The orientational relaxation stress of a biaxially stretched sheet in the longitudinal and transverse directions is measured as the peak stress value in silicone oil at a temperature 30° C. higher than the Vicat softening temperature of the resin composition constituting the sheet, according to ASTM D1504. did.
Note that the Vicat softening temperature was measured according to JIS K7206 under the conditions of a temperature increase rate of 50° C./hour and a test load of 50 N.
(ポリエステル樹脂の平均分散粒径)
二軸延伸シート中のポリエステル成分の平均分散粒径は、クライオミクロトームにて観察面がシート平面と平行方向となるよう切削し、導電処理(オスミウムコーティング)後電界放出形走査顕微鏡(日本電子株式会社製 JSM-7400F)を用い加速電圧3kVの条件でポリエステル成分の粒子100個の粒子径を測定し、以下の式により算出した値である。
平均分散粒径=Σni(Di)4/Σni(Di)3
ここで、niは測定個数、Diは粒子の面積から換算して得られる粒子径、すなわち測定した粒子の面積を0.5乗して得られる値を示す。
(Average dispersed particle size of polyester resin)
The average dispersed particle size of the polyester component in the biaxially stretched sheet was determined by cutting it with a cryomicrotome so that the observation surface was parallel to the sheet plane, and after conductive treatment (osmium coating), using a field emission scanning microscope (JEOL Ltd. The particle size of 100 particles of the polyester component was measured at an accelerating voltage of 3 kV using an accelerator (manufactured by JSM-7400F), and the value was calculated using the following formula.
Average dispersed particle size=Σni(Di) 4 /Σni(Di) 3
Here, ni is the number of particles measured, and Di is the particle diameter calculated from the area of the particles, that is, the value obtained by raising the area of the measured particles to the 0.5 power.
(二軸延伸シートの耐折性)
ASTM D2176に従って、二軸延伸シートの縦方向及び横方向の耐折曲げ強さをそれぞれ測定し、最小値を求めた。そして、折曲げ強さが最小値のときの折り曲げ回数を、縦方向及び横方向における二軸延伸シートのそれぞれの耐折性の評価値とした。折り曲げ回数が多いほど、二軸延伸シートの耐折性は優れている。
(Folding durability of biaxially stretched sheet)
In accordance with ASTM D2176, the bending strength in the machine direction and the transverse direction of the biaxially stretched sheet was measured, and the minimum value was determined. The number of times the sheet was bent when the bending strength was at its minimum value was used as an evaluation value for the folding durability of the biaxially stretched sheet in the longitudinal direction and the transverse direction. The greater the number of folds, the better the folding durability of the biaxially stretched sheet.
(二軸延伸シートの引張り伸び)
試験片の長手方向が二軸延伸シートの縦方向と平行になるようにJIS Z1702に従ってダンベル形の試験片を二軸延伸シートから切り出した。そして、株式会社島津製作所製引張試験機AGS-5kNXを使用して、引張試験機のチャック間隔を5mmとし、5±0.2mm/秒の速さで引っ張り、試験片の破断時点での引張り伸びを測定した。この試験を10回行って、引張り伸びの平均値を算出し、その平均値を上記チャック間隔で割り算することで、二軸延伸シートの縦方向の引張り伸びを求めた。同様にして、試験片の長手方向が二軸延伸シートの横方向と平行になるように、JIS Z1702に従ってダンベル形の試験片を用いて、二軸延伸シートの横方向の引張り伸びを求めた。
二軸延伸シートの引張伸びは好ましくは10%以上、より好ましくは15%以上である。引張伸びが10%未満であるとき、成形後の賦形性が低下するため好ましくない。
(Tensile elongation of biaxially stretched sheet)
Dumbbell-shaped test pieces were cut out from the biaxially stretched sheet in accordance with JIS Z1702 so that the longitudinal direction of the test piece was parallel to the longitudinal direction of the biaxially stretched sheet. Then, using a tensile testing machine AGS-5kNX manufactured by Shimadzu Corporation, the chuck interval of the tensile testing machine was set to 5 mm, and the test piece was pulled at a speed of 5 ± 0.2 mm/sec to determine the tensile elongation at the point of fracture. was measured. This test was performed 10 times, the average value of the tensile elongation was calculated, and the average value was divided by the chuck interval to determine the longitudinal tensile elongation of the biaxially stretched sheet. Similarly, the tensile elongation in the lateral direction of the biaxially stretched sheet was determined using a dumbbell-shaped test piece according to JIS Z1702 so that the longitudinal direction of the test piece was parallel to the lateral direction of the biaxially stretched sheet.
The tensile elongation of the biaxially stretched sheet is preferably 10% or more, more preferably 15% or more. When the tensile elongation is less than 10%, it is not preferable because the formability after molding deteriorates.
(二軸延伸シートの厚みムラ)
二軸延伸シートに縦方向および横方向に20mm間隔で直線を5本ずつ格子状に引いた時の交点25点についてマイクロゲージを用いて厚みを測定し、その最大値及び最小値の間の差で評価した。
二軸延伸シートの厚みムラは好ましくは45μm以下、より好ましくは30μm以下である。厚みムラが45μmを超えると、成形品の賦形性及び外観が悪化するため好ましくない。
(Thickness unevenness of biaxially stretched sheet)
When five straight lines are drawn in a grid pattern at 20 mm intervals in the vertical and horizontal directions on the biaxially stretched sheet, the thickness is measured using a microgauge at 25 points of intersection, and the difference between the maximum and minimum values is measured. It was evaluated by
The thickness unevenness of the biaxially stretched sheet is preferably 45 μm or less, more preferably 30 μm or less. If the thickness unevenness exceeds 45 μm, it is not preferable because the formability and appearance of the molded product will deteriorate.
実施例及び比較例の二軸延伸シートは以下のようにして作製した。
[実施例1]
ポリスチレン(東洋スチレン社製、型番:HRM63)90質量部、ポリエステル樹脂(PEs-1)(SK Chemicals社製、型番:ECOZEN BS100D、ジオール成分:エチレングリコール/1,4-シクロへキサンジメタノール/イソソルビド=37.2/50.3/12.5モル%、ジカルボン酸成分:テレフタル酸=100モル%、非晶質、ガラス転移温度(Tg)=108℃)の各ペレットをハンドブレンドした。ペレット押出機(真空ベント付き二軸同方向押出機TEM35B(東芝機械株式会社製))を用い、押出温度230℃、スクリュー回転数250rpm、ベント脱気圧力-760mmHg、吐出量25kg/時の押出条件にて、ダイプレートを通して、ペレットをストランドとした。その後、水槽にて冷却したのち、ペレタイザーを通してペレット化し、樹脂組成物のペレットを得た。なお、ベント脱気圧力は、常圧に対する差圧値として示した。上記樹脂組成物のペレットを棚式乾燥機にて90℃で5時間乾燥した後、シート押出機(Tダイ幅500mm、リップ開度1.5mm、φ40mmのエキストルーダー(田辺プラスチック機械株式会社製))を用い、押出温度230℃、吐出量20kg/時にて未延伸シートを得た。バッチ式二軸延伸機(株式会社東洋精機製作所製)を用いてこのシートを予熱し、延伸温度128℃、歪み速度0.1/秒で、縦方向2.0倍、横方向2.0倍に延伸し、厚み0.25mmの実施例1の二軸延伸シートを得た。
Biaxially stretched sheets of Examples and Comparative Examples were produced as follows.
[Example 1]
90 parts by mass of polystyrene (manufactured by Toyo Styrene Co., Ltd., model number: HRM63), polyester resin (PEs-1) (manufactured by SK Chemicals, model number: ECOZEN BS100D, diol component: ethylene glycol/1,4-cyclohexanedimethanol/isosorbide =37.2/50.3/12.5 mol%, dicarboxylic acid component: terephthalic acid = 100 mol%, amorphous, glass transition temperature (Tg) = 108°C) pellets were hand blended. Using a pellet extruder (vacuum vented twin-screw codirectional extruder TEM35B (manufactured by Toshiba Machine Co., Ltd.)), extrusion temperature 230°C, screw rotation speed 250 rpm, vent degassing pressure -760 mmHg, extrusion rate 25 kg/hour. The pellets were made into strands through a die plate. Thereafter, the mixture was cooled in a water tank and then pelletized through a pelletizer to obtain pellets of the resin composition. Note that the vent degassing pressure was shown as a differential pressure value with respect to normal pressure. After drying the pellets of the above resin composition at 90°C for 5 hours in a shelf dryer, the pellets were dried using a sheet extruder (T-die width 500mm, lip opening 1.5mm, φ40mm extruder (manufactured by Tanabe Plastic Machinery Co., Ltd.)). ), an unstretched sheet was obtained at an extrusion temperature of 230° C. and a discharge rate of 20 kg/hour. This sheet was preheated using a batch type biaxial stretching machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a stretching temperature of 128°C and a strain rate of 0.1/sec, stretching 2.0 times in the longitudinal direction and 2.0 times in the transverse direction. A biaxially stretched sheet of Example 1 having a thickness of 0.25 mm was obtained.
[実施例2]
ポリスチレンの配合量を90質量部から99質量部に変更した。また、ポリエステル樹脂(PEs-1)の配合量を10質量部から1質量部に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例2の二軸延伸シートを作製した。
[Example 2]
The amount of polystyrene blended was changed from 90 parts by mass to 99 parts by mass. Additionally, the amount of polyester resin (PEs-1) was changed from 10 parts by mass to 1 part by mass. Other than that, the biaxially stretched sheet of Example 2 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例3]
ポリスチレンの配合量を90質量部から75質量部に変更した。また、ポリエステル樹脂(PEs-1)の配合量を10質量部から25質量部に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例3の二軸延伸シートを作製した。
[Example 3]
The blending amount of polystyrene was changed from 90 parts by mass to 75 parts by mass. In addition, the amount of polyester resin (PEs-1) was changed from 10 parts by mass to 25 parts by mass. Other than that, the biaxially stretched sheet of Example 3 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例4]
ペレット押出機の押出条件において、吐出量を25kg/時から15kg/時に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例4の二軸延伸シートを作製した。
[Example 4]
Under the extrusion conditions of the pellet extruder, the discharge rate was changed from 25 kg/hour to 15 kg/hour. Other than that, the biaxially stretched sheet of Example 4 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例5]
ペレット押出機の押出条件において、スクリュー回転数を250rpmから100rpmに変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例5の二軸延伸シートを作製した。
[Example 5]
In the extrusion conditions of the pellet extruder, the screw rotation speed was changed from 250 rpm to 100 rpm. Other than that, the biaxially stretched sheet of Example 5 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例6]
ペレット押出機の押出条件において、吐出量を25kg/時から5kg/時に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例6の二軸延伸シートを作製した。
[Example 6]
Under the extrusion conditions of the pellet extruder, the discharge rate was changed from 25 kg/hour to 5 kg/hour. Other than that, the biaxially stretched sheet of Example 6 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例7]
ペレット押出機の押出条件において、スクリュー回転数を250rpmから80rpmに変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例7の二軸延伸シートを作製した。
[Example 7]
In the extrusion conditions of the pellet extruder, the screw rotation speed was changed from 250 rpm to 80 rpm. Other than that, the biaxially stretched sheet of Example 7 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例8]
縦方向の延伸倍率を2.0倍から1.5倍に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例8の二軸延伸シートを作製した。
[Example 8]
The stretching ratio in the longitudinal direction was changed from 2.0 times to 1.5 times. Other than that, the biaxially stretched sheet of Example 8 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例9]
縦方向の延伸倍率を2.0倍から3.5倍に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例9の二軸延伸シートを作製した。
[Example 9]
The stretching ratio in the longitudinal direction was changed from 2.0 times to 3.5 times. Other than that, the biaxially stretched sheet of Example 9 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例10]
横方向の延伸倍率を2.0倍から1.5倍に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例10の二軸延伸シートを作製した。
[Example 10]
The stretching ratio in the transverse direction was changed from 2.0 times to 1.5 times. Other than that, the biaxially stretched sheet of Example 10 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例11]
横方向の延伸倍率を2.0倍から3.5倍に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例11の二軸延伸シートを作製した。
[Example 11]
The stretching ratio in the transverse direction was changed from 2.0 times to 3.5 times. Other than that, the biaxially stretched sheet of Example 11 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例12]
ポリエステル樹脂(PEs-1)をポリエステル樹脂(PEs-2)(SK Chemicals社製、型番:ECOZEN BS400D、ジオール成分:エチレングリコール/1,4-シクロへキサンジメタノール/イソソルビド=21.5/46.0/32.5モル%、ジカルボン酸成分:テレフタル酸=100モル%、非晶質、ガラス転移温度(Tg)=130℃)に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例12の二軸延伸シートを作製した。
[Example 12]
Polyester resin (PEs-1) was mixed with polyester resin (PEs-2) (manufactured by SK Chemicals, model number: ECOZEN BS400D, diol component: ethylene glycol/1,4-cyclohexanedimethanol/isosorbide = 21.5/46. 0/32.5 mol%, dicarboxylic acid component: terephthalic acid = 100 mol%, amorphous, glass transition temperature (Tg) = 130°C). Other than that, the biaxially stretched sheet of Example 12 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例13]
ポリエステル樹脂(PEs-1)をポリエステル樹脂(PEs-3)(SK Chemicals社製、型番:SKYGREEN J2003、ジオール成分:エチレングリコール/1,4-シクロへキサンジメタノール/ジエチレングリコール=36.4/61.7/1.9モル%、ジカルボン酸成分:テレフタル酸=100モル%、非晶質、ガラス転移温度(Tg)=94℃)に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例13の二軸延伸シートを作製した。
[Example 13]
Polyester resin (PEs-1) was mixed with polyester resin (PEs-3) (manufactured by SK Chemicals, model number: SKYGREEN J2003, diol component: ethylene glycol/1,4-cyclohexanedimethanol/diethylene glycol = 36.4/61. 7/1.9 mol%, dicarboxylic acid component: terephthalic acid = 100 mol%, amorphous, glass transition temperature (Tg) = 94°C). Other than that, the biaxially stretched sheet of Example 13 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例14]
ポリエステル樹脂(PEs-1)をポリエステル樹脂(PEs-4)(三菱ガス化学株式会社製、型番:ALTESTER S3000、ジオール成分:エチレングリコール/3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカン=70/30モル%、ジカルボン酸成分:テレフタル酸=100モル%、非晶質、ガラス転移温度(Tg)=100℃)に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例14の二軸延伸シートを作製した。
[Example 14]
Polyester resin (PEs-1) was mixed with polyester resin (PEs-4) (manufactured by Mitsubishi Gas Chemical Co., Ltd., model number: ALTESTER S3000, diol component: ethylene glycol/3,9-bis(1,1-dimethyl-2-hydroxyethyl) )-2,4,8,10-tetraoxaspiro[5.5]undecane = 70/30 mol%, dicarboxylic acid component: terephthalic acid = 100 mol%, amorphous, glass transition temperature (Tg) = 100°C ) was changed. Other than that, the biaxially stretched sheet of Example 14 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例15]
ポリエステル樹脂(PEs-1)をポリエステル樹脂(PEs-5)(Eastman Chemical Company製、型番:Tritan FX-200、ジオール成分:1,4-シクロへキサンジメタノール/2,2,4,4-テトラメチル-1,3-シクロブタンジオール=65/35モル%、ジカルボン酸成分:テレフタル酸=100モル%、非晶質、ガラス転移温度(Tg)=118℃)に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例15の二軸延伸シートを作製した。
[Example 15]
Polyester resin (PEs-1) was mixed with polyester resin (PEs-5) (manufactured by Eastman Chemical Company, model number: Tritan FX-200, diol component: 1,4-cyclohexanedimethanol/2,2,4,4-tetra Methyl-1,3-cyclobutanediol = 65/35 mol%, dicarboxylic acid component: terephthalic acid = 100 mol%, amorphous, glass transition temperature (Tg) = 118°C). Other than that, the biaxially stretched sheet of Example 15 was produced in the same manner as the biaxially stretched sheet of Example 1.
[実施例16]
ポリエステル樹脂(PEs-1)をポリエステル樹脂(PEs-6)(ジオール成分:エチレングリコール=100モル%、ジカルボン酸成分:テレフタル酸=100モル%、ガラス転移温度(Tg)=85℃)に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例16の二軸延伸シートを作製した。
[Example 16]
Polyester resin (PEs-1) was changed to polyester resin (PEs-6) (diol component: ethylene glycol = 100 mol%, dicarboxylic acid component: terephthalic acid = 100 mol%, glass transition temperature (Tg) = 85 ° C.) . A biaxially stretched sheet of Example 16 was produced in the same manner as the biaxially stretched sheet of Example 1 except for the above.
[実施例17]
ポリエステル樹脂(PEs-1)をポリエステル樹脂(PEs-7)(ジオール成分:エチレングリコール/1,4-シクロヘキサンジメタノール/イソソルビド=20/36/44モル%、ジカルボン酸成分:テレフタル酸=100モル%、ガラス転移温度(Tg)=140℃)に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、実施例17の二軸延伸シートを作製した。
[Example 17]
Polyester resin (PEs-1) was mixed with polyester resin (PEs-7) (diol component: ethylene glycol/1,4-cyclohexanedimethanol/isosorbide = 20/36/44 mol%, dicarboxylic acid component: terephthalic acid = 100 mol%) , glass transition temperature (Tg) = 140°C). Other than that, the biaxially stretched sheet of Example 17 was produced in the same manner as the biaxially stretched sheet of Example 1.
[比較例1]
ポリスチレンの配合量を90質量部から100質量部に変更した。また、ポリエステル樹脂(PEs-1)は配合しなかった。それ以外は、実施例1の二軸延伸シートと同様な方法で、比較例1の二軸延伸シートを作製した。
[Comparative example 1]
The amount of polystyrene blended was changed from 90 parts by mass to 100 parts by mass. Further, polyester resin (PEs-1) was not blended. A biaxially stretched sheet of Comparative Example 1 was produced in the same manner as the biaxially stretched sheet of Example 1 except for the above.
[比較例2]
ポリスチレンの配合量を90質量部から70質量部に変更した。また、ポリエステル樹脂(PEs-1)の配合量を10質量部から30質量部に変更した。それ以外は、実施例1の二軸延伸シートと同様な方法で、比較例2の二軸延伸シートを作製した。
[Comparative example 2]
The amount of polystyrene blended was changed from 90 parts by mass to 70 parts by mass. Furthermore, the amount of polyester resin (PEs-1) was changed from 10 parts by mass to 30 parts by mass. A biaxially stretched sheet of Comparative Example 2 was produced in the same manner as the biaxially stretched sheet of Example 1 except for the above.
評価結果を次の表1~4に示す。
以上の評価結果から、スチレン系樹脂(A)と、ジカルボン酸成分(b-1)が主成分としてテレフタル酸を含むポリエステル樹脂(B)とを含み、スチレン系樹脂(A)及びポリエステル樹脂(B)の合計100質量部に対して、スチレン系樹脂(A)の含有量が75~99質量部であり、ポリエステル樹脂(B)の含有量が1~25質量部である樹脂組成物からなる二軸延伸シートは、引張伸びが大きく、厚みムラが小さく、耐折性に優れ、加熱収縮率が小さいことがわかった。 From the above evaluation results, it was found that the dicarboxylic acid component (b-1) contains styrene resin (A) and polyester resin (B) containing terephthalic acid as a main component. ), the content of the styrene resin (A) is 75 to 99 parts by mass, and the content of the polyester resin (B) is 1 to 25 parts by mass. It was found that the axially stretched sheet had large tensile elongation, small thickness unevenness, excellent folding durability, and low heat shrinkage.
Claims (8)
前記スチレン系樹脂(A)がポリスチレンであり、
前記ポリエステル樹脂(B)のガラス転移温度が90~135℃である二軸延伸シート。 The dicarboxylic acid component (b-1) contains a styrene resin (A) and a polyester resin (B) containing terephthalic acid as a main component, and the total of the styrene resin (A) and the polyester resin (B) is 100%. Consisting of a resin composition in which the content of the styrene resin (A) is 75 to 99 parts by mass and the content of the polyester resin (B) is 1 to 25 parts by mass , based on parts by mass,
The styrenic resin (A) is polystyrene,
A biaxially stretched sheet in which the polyester resin (B) has a glass transition temperature of 90 to 135°C .
ZM(%)=(1-1/XM)×YM (1)
ZT(%)=(1-1/XT)×YT (2) After heating the biaxially stretched sheet at a temperature of 120° C. for 1 hour, the heat shrinkage rates of the biaxially stretched sheet in the longitudinal direction and the transverse direction are respectively Z M (%) and Z T (%), and the biaxially stretched sheet is The stretching ratios in the longitudinal and lateral directions of the stretched sheet are X M and XT , respectively, and the heat shrinkage rate (Z M , Z T ) and the stretching ratio (X M , XT ) in the longitudinal and lateral directions are The biaxially stretched sheet according to claim 1, wherein Y M and Y T are each 40 to 99% when the following formulas (1) and (2) are satisfied.
Z M (%) = (1-1/X M ) x Y M (1)
Z T (%) = (1-1/X T ) x Y T (2)
縦方向及び横方向の延伸倍率がそれぞれ1.5~3.5倍である請求項1~5のいずれか1項に記載の二軸延伸シート。 The thickness is 0.01 to 0.7 mm,
The biaxially stretched sheet according to any one of claims 1 to 5 , wherein the stretching ratio in the longitudinal direction and the transverse direction is 1.5 to 3.5 times, respectively.
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JP2005060597A (en) | 2003-08-19 | 2005-03-10 | Ps Japan Corp | Styrenic resin composition |
JP2009096921A (en) | 2007-10-18 | 2009-05-07 | Teijin Ltd | Highly insulating film |
JP2017002323A (en) | 2016-09-26 | 2017-01-05 | リケンテクノス株式会社 | Polyester resin composition sheet |
JP2018203884A (en) | 2017-06-05 | 2018-12-27 | Psジャパン株式会社 | Polystyrene resin composition, production method, and foam molding |
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JP2005060597A (en) | 2003-08-19 | 2005-03-10 | Ps Japan Corp | Styrenic resin composition |
JP2009096921A (en) | 2007-10-18 | 2009-05-07 | Teijin Ltd | Highly insulating film |
JP2017002323A (en) | 2016-09-26 | 2017-01-05 | リケンテクノス株式会社 | Polyester resin composition sheet |
JP2018203884A (en) | 2017-06-05 | 2018-12-27 | Psジャパン株式会社 | Polystyrene resin composition, production method, and foam molding |
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