JPH01121346A - Styrene resin composition for foamed sheet - Google Patents
Styrene resin composition for foamed sheetInfo
- Publication number
- JPH01121346A JPH01121346A JP27906587A JP27906587A JPH01121346A JP H01121346 A JPH01121346 A JP H01121346A JP 27906587 A JP27906587 A JP 27906587A JP 27906587 A JP27906587 A JP 27906587A JP H01121346 A JPH01121346 A JP H01121346A
- Authority
- JP
- Japan
- Prior art keywords
- methyl methacrylate
- copolymer
- unit
- weight
- units
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 12
- -1 aromatic vinyl compound Chemical group 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 3
- 229920006249 styrenic copolymer Polymers 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001890 Novodur Polymers 0.000 claims description 5
- 229920001897 terpolymer Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 239000000470 constituent Substances 0.000 abstract 1
- 238000010411 cooking Methods 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 16
- 238000000465 moulding Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 14
- 238000005187 foaming Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 2
- 229940099364 dichlorofluoromethane Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- 241000272814 Anser sp. Species 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000004795 extruded polystyrene foam Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規な耐熱性と熱成形性の優れた発泡シート
原反の製造に有用なスチレン系樹脂組成物に関し、更に
詳しくは、発泡倍率が６〜２５倍で発泡層のシート厚み
が１．５〜１０．Ｏａｎの発泡シート原反を熱成形によ
り製造する際に、シート引取り又は巻き取りにおける耐
割れ性が優れ、更には、該発泡シート原反からトレー、
カップ等を作るための二次成形（熟成形）において、優
れた探しぼり成形性と耐熱性を示す、スチレン系樹脂組
成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a styrenic resin composition useful for producing a new foamed sheet material having excellent heat resistance and thermoformability. The magnification is 6 to 25 times and the sheet thickness of the foam layer is 1.5 to 10. When Oan's original foam sheet is produced by thermoforming, it has excellent cracking resistance during sheet take-up or winding, and furthermore, trays,
This invention relates to a styrenic resin composition that exhibits excellent moldability and heat resistance in secondary molding (ripened molding) for making cups and the like.
押出成形されたポリスチレン発泡体は、剛性があり、断
熱性に優れ、又、緩衝性をも有することから、トレー、
食品容器等種々の成形品の製造に用いられている。Extruded polystyrene foam is rigid, has excellent heat insulation properties, and also has cushioning properties, so it can be used for trays,
It is used to manufacture various molded products such as food containers.
しかしながら、これら従来のポリスチレン発泡体から得
られる成形品は、９０℃前後の熱を受けた場合に寸法変
化を生じ、耐熱性に乏しい欠点があった。However, molded articles obtained from these conventional polystyrene foams suffer from dimensional changes when subjected to heat of around 90° C., and have the disadvantage of poor heat resistance.
一方、近年電子レンジの普及とそれに伴う即席調理食品
の普及により、電子レンジでの加熱に耐え得る耐熱性と
電子レンジから火傷せずに直接取り出せるような断熱性
を有する食品容器用素材が求められている。On the other hand, in recent years, with the spread of microwave ovens and the accompanying spread of instant cooked foods, there is a need for materials for food containers that have heat resistance that can withstand heating in microwave ovens and insulation properties that allow them to be removed directly from the microwave oven without getting burned. ing.
これらの要求を満たす為のポリスチレンの耐熱性の改良
法が提案されている０例えば、アクリル酸、メタクリル
酸、又は無水マレイン酸を共重合成分とするスチレン系
共重合体とそれからの発泡シートが提案されている（例
えば、特開昭５７−７２８３０号公報）。To meet these demands, methods for improving the heat resistance of polystyrene have been proposed. For example, a styrenic copolymer containing acrylic acid, methacrylic acid, or maleic anhydride as a copolymerization component and a foam sheet made from the same have been proposed. (For example, Japanese Patent Laid-Open No. 57-72830).
しかしながら、これらの共重合体も、一般に使用されて
いる核剤、発泡剤と共に押出機に供給して熔融・混練し
、押出機のグイより押出して、発泡シート原反を得る場
合、冷却引取り、巻き取りの過程で、シートが割れ易く
、裂は易い等の欠点が見られ、更には、この発泡シート
原反を熟成形して、トレー、容器等の二次成形品を製造
する場合に、熟成形時の樹脂の伸びが劣り、そのために
二次成形品に亀裂が入る等の欠点が見られた。この為種
々のデザインの食品容器、特に探しぼりの容器を成形す
るための発泡シート原反としては、必ずしも充分に満足
し得るものでないことが判明した。However, when these copolymers are supplied to an extruder together with commonly used nucleating agents and blowing agents, melted and kneaded, and extruded through the extruder's goose to obtain a foamed sheet material, they must be cooled and collected. In the process of winding up, there are drawbacks such as the sheet being easily broken and tearing, and furthermore, when this foamed sheet material is matured to produce secondary molded products such as trays and containers. , the elongation of the resin during ripening was poor, which caused defects such as cracks in the secondary molded product. For this reason, it has been found that the foamed sheet material is not necessarily fully satisfactory for forming food containers of various designs, especially containers for finding items.
本発明は、従来品が内蔵する上記問題点を解消して、電
子レンジ用としての市場の要求に応えるために鋭意研究
を進めた結果、樹脂組成物の発泡シート原反への熱成形
時及び該発泡シート原反の二次成形時の成形性と耐熱性
が共に優れた発泡シート原反製造用スチレン系樹脂組成
物を見いだし、本発明をなすに至った。The present invention has been developed as a result of intensive research to solve the above-mentioned problems inherent in conventional products and to meet market demands for microwave ovens. A styrenic resin composition for producing a foamed sheet material that has excellent moldability and heat resistance during secondary molding of the foamed sheet material has been discovered, and the present invention has been completed.
即ち、本発明は、（Ａ）アクリル酸、メタクリル酸、及
び無水マレイン酸の群から選ばれる少なくとも１つから
なる成分単位の５〜２５重量％とスチレン単位の９５〜
７５重量％とからなる共重合体で、その加熱変形温度が
９６℃以上であるスチレン系共重合体と（Ｂ）メタクリ
ル酸メチル単位とアクリル酸アルキル単位からなる共重
合体、メタクリル酸メチル単位とメタクリル酸メチルを
除くメタクリル酸アルキル単位からなる共重合体、メタ
クリル酸メチル単位と芳香族ビニル化合物単位からなる
共重合体、メタクリル酸メチル単位とアクリル酸アルキ
ル単位とメタクリル酸メチルを除くメタクリル酸アルキ
ル単位との三元共重合体、又は、メタクリル酸メチル単
位とメタクリル酸メチルを除く （メタ）アクリル酸ア
ルキル単位と芳香族ビニル化合物単位とからなる三元共
重合体、又は、それらの共重合体の混合物からなるメタ
クリル酸メチル系共重合体と、からなる樹脂組成物であ
って、（Ａ）成分が９５〜７０重量％、（Ｂ）成分が５
〜３０重量％であることを特徴とする改良された熱成形
性と耐熱性を有する発泡シート製造用スチレン系樹脂組
成物に関するものである。That is, the present invention provides (A) 5 to 25% by weight of component units consisting of at least one selected from the group of acrylic acid, methacrylic acid, and maleic anhydride, and 95 to 95% by weight of styrene units.
(B) a copolymer consisting of methyl methacrylate units and alkyl acrylate units, a copolymer consisting of methyl methacrylate units and alkyl acrylate units; Copolymers consisting of alkyl methacrylate units excluding methyl methacrylate, copolymers consisting of methyl methacrylate units and aromatic vinyl compound units, methyl methacrylate units, alkyl acrylate units, and alkyl methacrylate units excluding methyl methacrylate or terpolymers consisting of methyl methacrylate units and alkyl (meth)acrylate units excluding methyl methacrylate and aromatic vinyl compound units, or copolymers thereof. A resin composition consisting of a methyl methacrylate copolymer consisting of a mixture, comprising 95 to 70% by weight of component (A) and 5% by weight of component (B).
The present invention relates to a styrenic resin composition for producing foamed sheets having improved thermoformability and heat resistance, characterized in that the content is 30% by weight.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の樹脂組成物の主成分（Ａ）であるスチレン系共
重合体のスチレン成分としては、スチレン、α−メチル
スチレン、ｐ−メチルスチレン、ジメチルスチレン、Ｐ
−ｔｅｒｔ−ブチルスチレン、クロロスチレン等が挙げ
られる。中でもスチレンが好ましい。The styrene component of the styrenic copolymer which is the main component (A) of the resin composition of the present invention includes styrene, α-methylstyrene, p-methylstyrene, dimethylstyrene, P
-tert-butylstyrene, chlorostyrene and the like. Among them, styrene is preferred.
スチレン系共重合体（Ａ）の共重合単量体は、アクリル
酸、メタクリル酸、無水マレイン酸から選ばれる。これ
ら共重合単量体からの成分単位がスチレン系共重合体（
Ａ）に占める割合は、５〜２５重量％である。５重量％
未満では、共重合体の耐熱性が充分でなく、２５重量％
を超えると、共重合体の熱安定性が低下し、溶融流動性
が著しく低下し、更には、得られる発泡シート原反の耐
応力クレージング性が低下する。The comonomer of the styrenic copolymer (A) is selected from acrylic acid, methacrylic acid, and maleic anhydride. The component units from these copolymerized monomers are styrenic copolymers (
The proportion in A) is 5 to 25% by weight. 5% by weight
If it is less than 25% by weight, the heat resistance of the copolymer will be insufficient.
If it exceeds the above, the thermal stability of the copolymer decreases, the melt fluidity significantly decreases, and furthermore, the stress craze resistance of the resulting foamed sheet material decreases.
本発明組成物の他の成分（Ｂ）であるメタクリル酸メチ
ル系共重合体は、メタクリル酸メチル単位５０〜９９．
５重量％とアクリル酸アルキル単位０．５〜２０重量％
からなる共重合体、メタクリル酸メチル単位５０〜９９
．５重量％とメタクリル酸メチルを除くメタクリル酸ア
ルキル単位０．５〜２０重量％からなる共重合体、メタ
クリル酸メチル単位５０〜９９．５重量％と芳香族ビニ
ル化合物単位０．５〜５０重量％からなる共重合体、又
はメタクリル酸メチル単位５０〜９９．５重量％とメタ
クリル酸メチルを除く （メタ）アクリル酸アルキル単
位０．５〜２０重量％と芳香族ビニル化合物単位Ｏ〜５
０重量％とからなる三元共重合体等、又は、それらの共
重合体の混合物からなる。The methyl methacrylate copolymer which is the other component (B) of the composition of the present invention has 50 to 99 methyl methacrylate units.
5% by weight and 0.5-20% by weight of alkyl acrylate units.
Copolymer consisting of 50 to 99 methyl methacrylate units
．． 5% by weight and 0.5 to 20% by weight of alkyl methacrylate units excluding methyl methacrylate, 50 to 99.5% by weight of methyl methacrylate units and 0.5 to 50% by weight of aromatic vinyl compound units. or a copolymer consisting of 50-99.5% by weight of methyl methacrylate units, 0.5-20% by weight of alkyl (meth)acrylate units excluding methyl methacrylate, and O-5 aromatic vinyl compound units.
0% by weight, or a mixture of these copolymers.
これらの共重合体（Ｂ）において、アクリル酸アルキル
単位、又はメタクリル酸アルキル単位（メタクリル酸メ
チルを除＜）〔以後単に（メタ）アクリル酸アルキル単
位と略称する〕の含有量が２０重量％を超えると、組成
物の耐熱性が低下し、芳香族ビニル化合物の単位が５０
重量％を超えると、共重合体の機械的強度が低下し、何
れも好ましくない。In these copolymers (B), the content of alkyl acrylate units or alkyl methacrylate units (excluding methyl methacrylate) [hereinafter simply referred to as alkyl (meth)acrylate units] is 20% by weight. If it exceeds 50%, the heat resistance of the composition decreases, and the unit of aromatic vinyl compound exceeds 50%.
If it exceeds % by weight, the mechanical strength of the copolymer decreases, which is not preferable.
好ましい共重合体（Ｂ）は、メタクリル酸メチル単位８
０〜９９．５重量％及びアクリル酸アルキル単位０．５
〜２０重量％からなるメタクリル酸メチル−アクリル酸
アルキル共重合体で、このものは通常ポリメタクリル酸
メチル（ＰＭＭＡ）として市販されている。他の好まし
い例としては、メタクリル酸単位５０〜９９．５重量％
と芳香族ビニル化合物０．５〜５０重量％からなる共重
合体、メタクリル酸アルキル単位単位７０〜９８．９ｉ
ｉ量％、アクリル酸アルキル単位０．１〜１０重量％、
及び芳香族ビニル化合物単位１〜２０重量％からなる三
元共重合体である。A preferred copolymer (B) has 8 methyl methacrylate units.
0-99.5% by weight and 0.5 alkyl acrylate units
A methyl methacrylate-alkyl acrylate copolymer consisting of ~20% by weight, which is usually commercially available as polymethyl methacrylate (PMMA). Another preferred example is 50 to 99.5% by weight of methacrylic acid units.
Copolymer consisting of 0.5 to 50% by weight of an aromatic vinyl compound, 70 to 98.9 i of alkyl methacrylate units
i amount%, alkyl acrylate unit 0.1 to 10% by weight,
and a terpolymer consisting of 1 to 20% by weight of aromatic vinyl compound units.
上記アクリル酸アルキルとしては、アクリル酸メチル、
アクリル酸エチルが好ましく、メタクリル酸アルキルと
しては、メタクリル酸エチルが最も好ましいが、炭素数
３以上のアルキル基を有するメタクリル酸アルキルでも
良い。The above alkyl acrylates include methyl acrylate,
Ethyl acrylate is preferred, and as the alkyl methacrylate, ethyl methacrylate is most preferred, but an alkyl methacrylate having an alkyl group having 3 or more carbon atoms may also be used.
本発明の樹脂組成物は、スチレン系共重合体。The resin composition of the present invention is a styrene copolymer.
（Ａ）９５〜７Ｏｆｆｉ量％とメタクリル酸メチル系共
重合体（Ｂ）５〜３０重量％からなる。共重合体（Ａ）
の含有量が７０重量％未満では、耐熱性の低下が起こり
、メタクリル酸メチル系共重合体（Ｂ）が５重量％未満
では、成形性の改良効果が実質的に少ないからである。(A) 95 to 7% by weight and methyl methacrylate copolymer (B) 5 to 30% by weight. Copolymer (A)
If the content of the methyl methacrylate copolymer (B) is less than 70% by weight, the heat resistance will decrease, and if the content of the methyl methacrylate copolymer (B) is less than 5% by weight, the effect of improving moldability will be substantially small.
本発明の樹脂組成物は、発泡倍率６〜２０倍で発泡層の
シート厚みが１．５〜１０ｍＩＩ＋の発泡シート原反を
熱成形により製造するのに好適に用いられる。The resin composition of the present invention is suitably used for producing a foamed sheet original fabric having a foaming ratio of 6 to 20 times and a foam layer sheet thickness of 1.5 to 10 mII+ by thermoforming.
その製造法の概要は、次の通りである０本発明の樹脂組
成物に展着剤、核剤、発泡剤等各種の添加剤を加えて溶
融・混練し、押出機先端より押出し発泡させる。The outline of the manufacturing method is as follows. Various additives such as a spreading agent, a nucleating agent, and a foaming agent are added to the resin composition of the present invention, the mixture is melted and kneaded, and the resin composition is extruded from the tip of an extruder and foamed.
抛泡剤としては、通常、炭化水素系、フレオン系、ハロ
ゲン化炭化水素系等の揮発性発泡剤やガスを用いるのが
適当であり、場合によっては、分解型や反応型の発泡剤
を用いることもできる。As the foaming agent, it is usually appropriate to use a volatile foaming agent or gas such as a hydrocarbon type, freon type, or halogenated hydrocarbon type, and in some cases, a decomposition type or reactive type foaming agent is used. You can also do that.
核剤としては、タルク、ホワイトカーボン、重曹、酸化
チタン等の通常のものが用いられ、展着剤としては、流
動パラフィン、ポリブテン、ポリエチレングリコール等
必要に応じて種々用いられる。このように、本発明の発
泡シートには、これらの各種の添加剤が含まれても良い
。As the nucleating agent, usual ones such as talc, white carbon, sodium bicarbonate, and titanium oxide are used, and as the spreading agent, various types such as liquid paraffin, polybutene, polyethylene glycol, etc. are used as required. Thus, the foamed sheet of the present invention may contain these various additives.
本発明の樹脂組成物から製造される発泡シート原反は、
発泡倍率６〜２０倍、シートの厚みが１．５〜１０１１
ＩＩ１１のものが好ましい０発泡倍率が６倍未満では、
発泡体としては発泡が不十分でシートは未発泡シートに
似た性質を示し好ましくない。又、このような低発泡倍
率では、シートへの成形時の耐割れ性、該シートの二次
成形時の探しぼり成形性は、共重合体（Ａ）単独でも問
題はなく、共重合体（Ｂ）配合の必要はない、つまり本
発明の（Ｂ）成分配合による効果の優位性が低い、又、
発泡倍率が２０倍以上になると、発泡体としての強度が
低下し、更には二次成形性が劣り、実用性に乏しくなる
。又、シート厚みが１．５１未満で、発泡倍率が６〜２
０倍であると、製品強度が低下し、厚みが１０闘を超え
ると、二次成形品は実用性の乏しいものとなるからであ
る。The foam sheet material produced from the resin composition of the present invention is
Foaming ratio 6-20 times, sheet thickness 1.5-1011
II11 is preferable 0 When the foaming ratio is less than 6 times,
As a foam, the foaming is insufficient and the sheet exhibits properties similar to unfoamed sheets, which is not preferable. In addition, at such a low expansion ratio, there is no problem with copolymer (A) alone in terms of cracking resistance during molding into a sheet and finding moldability during secondary molding of the sheet; B) There is no need for blending, that is, the effect of blending component (B) of the present invention is low, and
When the expansion ratio is 20 times or more, the strength as a foam decreases, furthermore, the secondary moldability becomes poor, and the foam becomes impractical. In addition, the sheet thickness is less than 1.51 and the foaming ratio is 6 to 2.
This is because if the thickness is 0 times, the product strength will decrease, and if the thickness exceeds 10 mm, the secondary molded product will have poor practicality.
本発明の樹脂組成物から熱成形により発泡シート原反を
得る場合の成形性及び該発泡シート原反を二次成形する
場合の探しぼり成形性が著しく改善される理由は、必ず
しも明らかではないが、従来のアクリル酸、メタクリル
酸、又は無水マレイン酸を含むスチレン系共重合体（Ａ
）単独からの発泡シートは耐応力クレージング性に劣り
、更には二次成形において、探しぼり成形がし難（、裂
け、亀裂等が入り易い等の欠点がある。これらの欠点を
有するスチレン系共重合体（Ａ）に、本発明のように、
メタクリル酸メチル系樹脂（Ｂ）を配合することにより
、メタクリル酸メチル系樹脂の特長でもある耐クレージ
ング性と更には高温時の伸びの良さが付加され、その結
果、発泡シートへの成形に特に必要な耐クレージング性
及び二次成形時の探しぼり成形性が発現されるものと思
われる。Although it is not necessarily clear why the moldability when obtaining a foamed sheet original fabric from the resin composition of the present invention by thermoforming and the finding moldability when secondary forming the foamed sheet original fabric are significantly improved, , conventional styrenic copolymers (A) containing acrylic acid, methacrylic acid, or maleic anhydride.
) Foamed sheets made alone have poor stress crazing resistance, and furthermore, they have drawbacks such as being difficult to find and form in secondary molding (and easily tearing, cracking, etc.). In the polymer (A), as in the present invention,
By blending methyl methacrylate resin (B), crazing resistance, which is a feature of methyl methacrylate resin, and good elongation at high temperatures are added, which is especially necessary for forming into foam sheets. It is thought that good crazing resistance and search formability during secondary molding will be exhibited.
何れにせよ、本発明の樹脂組成物の熟成形によって得ら
れる発泡シート原反は、従来のスチレン系共重合体（Ａ
）単独からの発泡シートに比べて、発泡シート成形時に
おけるシートの引取り、巻き取り時の耐割れ性、又、該
原反の二次成形時における探しぼり成形性が著しく改善
され、工業上極めて有用である。In any case, the foamed sheet material obtained by aging the resin composition of the present invention is made of a conventional styrenic copolymer (A
) Compared to a foamed sheet made from a single foamed sheet, the cracking resistance during take-up and winding of the foamed sheet during molding, as well as the finding formability during secondary molding of the original fabric, are significantly improved, making it an industrially viable material. Extremely useful.
以下、実施例によって本発明の詳細な説明するが、本発
明はこれらの例によって制限されるものではない。EXAMPLES Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples.
なお、各物性及び成形性の評価法は、次の通りである。The evaluation methods for each physical property and moldability are as follows.
又、部は重量部を表す。Moreover, parts represent parts by weight.
１、物性測定法 加熱変形温度： ＡＳＴＭ−Ｄ−６４８による。1. Physical property measurement method Heating deformation temperature: According to ASTM-D-648.
２、成形性
■発泡シート成形
第１図に示す発泡押出成形機（４０ｎ＋ｍφ）で、樹脂
を展着剤、核剤等各種添加剤と共に熔融混練し、押出機
の途中に設けられた注入口より、ジクロロフルオロメタ
ン５〜８％を注入混合し、押出機先端に設けられた口径
３０ＩＩＩＩＩＩφの環状ダイスから常温常圧下の大気
中に押出発泡させ、厚み２．５ｍｍ、幅３５０＠Ｉ１１
、発泡倍率１２倍の発泡シート原反を得る。2. Formability ■ Foam sheet molding In a foam extrusion molding machine (40n+mφ) shown in Figure 1, the resin is melted and kneaded together with various additives such as a spreading agent and a nucleating agent, and then the resin is melted and kneaded through an injection port provided in the middle of the extruder. , 5 to 8% dichlorofluoromethane was injected and mixed, and extruded into the atmosphere at normal temperature and pressure through an annular die with a diameter of 30IIIφ provided at the tip of the extruder to form a foam with a thickness of 2.5 mm and a width of 350 @ I11.
, obtain a foamed sheet material with a foaming ratio of 12 times.
■探しぼり成形性
上記により得られた発泡シート成形により得られる発泡
シート原反から縦２０抛−横２００＋＋＋ｍのシート板
を１０枚作り、第２図に示す真空（圧空）成形機にτ、
直径１００ｍｍ φ、深さ２０ｍｍ （第３図）の成形
品を１０個得る。１０個の成形品夫々の亀裂の有無を調
べ、１０個中亀裂の入った価数により、探しぼり成形性
の優劣を判定する。■Searching moldability Ten sheet plates with a length of 20 m and a width of 200+++ m are made from the foam sheet material obtained by the foam sheet molding process obtained above, and are placed in a vacuum (pressure) molding machine shown in Fig. 2.
Ten molded products with a diameter of 100 mm and a depth of 20 mm (Fig. 3) were obtained. The presence or absence of cracks in each of the 10 molded products is examined, and the superiority or inferiority of the moldability is determined based on the number of cracks found among the 10 molded products.
■シート成形時の耐割れ性
前記発泡シート成形においてシートの引取り及び巻き取
り時のシート割れ有無にて判定する。(2) Resistance to cracking during sheet molding Judgment is made based on the presence or absence of cracks in the sheet when the sheet is taken up and rolled up in the foamed sheet molding process.
■成形品の耐熱試験法
■探しぼり成形性の項で作られた成形品に、８０ｃｃの
水を入れ、蓋の代わりに市販のランプ（サランランプ［
Ｆ］、塩化ビニリデン製）でシールし、電子レンジ（松
下ＮＥ−Ａ７５５．６００Ｗ）で４分間加温した後、成
形品の変形の有無を調べる。■Heat resistance test method for molded products■Pour 80cc of water into the molded product made in the moldability section, and use a commercially available lamp (Saran lamp) instead of a lid.
F], made of vinylidene chloride) and heated in a microwave oven (Matsushita NE-A755.600W) for 4 minutes, and then inspected for deformation of the molded product.
■実施例、比較例に用いた樹脂 第１表に示す。■Resin used in Examples and Comparative Examples Shown in Table 1.
（以下余白）
実施例１
第１表に示す耐熱性スチレン系共重合体樹脂（Ａ−１）
、（Ａ−２）、（Ａ −３）、（Ａ−４）４種の７５部
とメタクリル酸メチル系樹脂（Ｂ−１）の２５部を流動
パラフィン０．１部、タルク０．２〜０．４部と共に予
めブレンダーにて均一に混合した。(Left below) Example 1 Heat-resistant styrenic copolymer resin (A-1) shown in Table 1
, (A-2), (A-3), and (A-4) and 25 parts of methyl methacrylate resin (B-1), 0.1 part of liquid paraffin, and 0.2 to 0.2 parts of talc. It was mixed uniformly with 0.4 part in a blender in advance.
これを第１図に示す発泡押出成形機で溶融混合し、押出
機の途中に設けられた注入口よりジクロロフルオロメタ
ン５〜８重量％を注入混練し、押出機先端に設けられた
口径３０ｍｍφの環状ダイスより常温常圧下の大気中に
押出し発泡させ、厚み２．５１１１ｆｆ＋、巾３５０
ｍｍ、発泡倍率１２倍の発泡シートを得た。This was melted and mixed in a foaming extrusion molding machine shown in Figure 1, and 5 to 8% by weight of dichlorofluoromethane was injected and kneaded through an injection port provided in the middle of the extruder. Extruded into the atmosphere at room temperature and pressure from an annular die and foamed, thickness 2.5111ff+, width 350mm.
A foamed sheet with a foaming ratio of 12 times and a foaming ratio of 12 times was obtained.
実施例２
第１表の耐熱性スチレン系共重合体（Ａ−１）、（Ａ−
２）、（Ａ−３）、（Ａ−４）４種の樹脂９０部とメタ
クリル酸メチル系樹脂（Ｂ−１）の１０部にブレンド比
を変更した以外は、実施例１と同じ方法、条件で、厚み
２．５ｍｍ、巾３５０１１ＩＩ１１１発泡倍率１２倍の
発泡シートを得た。Example 2 Heat-resistant styrenic copolymers (A-1) and (A-
2), (A-3), (A-4) Same method as Example 1 except that the blend ratio was changed to 90 parts of the four types of resin and 10 parts of the methyl methacrylate resin (B-1), Under these conditions, a foamed sheet having a thickness of 2.5 mm, a width of 35011II111, and a foaming ratio of 12 times was obtained.
実施例３
第１表の耐熱性スチレン系共重合体（Ａ−１）、（Ａ−
２）、（Ａ−３）、（Ａ−４）４種の樹脂８５部とメタ
クリル酸メチル系樹脂（Ｂ−１）の１５部にブレンド比
を変更した以外は、実施例１と同じ方法、条件で厚み２
．５ｍｍ、巾３５０ ｍｍ、発泡倍率１２倍の発泡シー
トを得た。Example 3 Heat-resistant styrenic copolymers (A-1) and (A-
2), (A-3), (A-4) Same method as Example 1 except that the blend ratio was changed to 85 parts of the four types of resin and 15 parts of the methyl methacrylate resin (B-1), Thickness 2 under conditions
．． A foamed sheet having a size of 5 mm, a width of 350 mm, and a foaming ratio of 12 times was obtained.
比較例１
第１表の耐熱スチレン系共重合体（Ａ−１）、（Ａ−２
）、（Ａ−３）、（Ａ−４）４種の樹脂１００部とした
ことの他は、実施例１と同じ方法、条件で、厚み２．５
＋ｎｍ、巾３５０ ｍｓ、発泡倍率１２倍の発泡シート
を得た。Comparative Example 1 Heat-resistant styrenic copolymers (A-1) and (A-2) shown in Table 1
), (A-3), (A-4) The thickness was 2.5 mm using the same method and conditions as in Example 1, except that 100 parts of the four types of resin were used.
A foamed sheet with a width of +nm, a width of 350 ms, and a foaming ratio of 12 times was obtained.
比較例２
第１表の比較樹脂のＢＬ−１、ＢＬ−２を使用し、その
他は実施例１と同じ方法で発泡シートを得た。Comparative Example 2 A foamed sheet was obtained using the comparative resins BL-1 and BL-2 shown in Table 1, but in the same manner as in Example 1, except that the same procedure was used as in Example 1.
以上実施例１．２．３、比較例１．２によって得られた
発泡シートを、成形性の評価の項で述べた２、−〇探し
ぼり成形性、２．−〇シート成形時の耐割れ性、及び２
．−■成形品の耐熱試験法に従って評価判定した結果を
第２表に示す。The foamed sheets obtained in Example 1.2.3 and Comparative Example 1.2 were evaluated as follows: 2.-〇 Search moldability, 2. -〇Crack resistance during sheet molding, and 2
．． -■ Table 2 shows the results of evaluation and judgment according to the heat resistance test method for molded products.
第２表から分かるように、本発明の発泡シートは、探し
ぼり成形性、耐割れ性等成形性の優れたものである。As can be seen from Table 2, the foamed sheet of the present invention has excellent moldability such as search moldability and cracking resistance.
第１図は、本発明で用いた発泡シート原反成形用押出発
泡成形機の概略側面図、第２図は本発明で用いた真空（
圧空）成形機の概略図、第３図は本発明実施例の成形品
の断面図である。
１・・・ホッパー
２・・・押出機
３・・・発泡剤注入口
４・・・温調器
５・・・ダイス
６・・・パリソン
７・・・デフレータ−
８・・・ピンチロール
９・・・発泡シート
１０・・・セラミックヒータ−
１１・・・クランプ
１２・・・プラグアシスト
１３・・・二次成形トレー
特許出願人 旭化成工業株式会社Figure 1 is a schematic side view of an extrusion foam molding machine for forming a foam sheet material used in the present invention, and Figure 2 is a vacuum (
FIG. 3 is a sectional view of a molded product according to an embodiment of the present invention. 1... Hopper 2... Extruder 3... Foaming agent inlet 4... Temperature controller 5... Dice 6... Parison 7... Deflator 8... Pinch roll 9. ...Foam sheet 10...Ceramic heater 11...Clamp 12...Plug assist 13...Secondary molding tray Patent applicant Asahi Kasei Corporation
Claims (1)
イン酸の群から選ばれる少なくとも１つからなる成分単
位の５〜２５重量％とスチレン単位の９５〜７５重量％
とからなる共重合体で、その加熱変形温度が９６℃以上
であるスチレン系共重合体と、 （Ｂ）メタクリル酸メチル単位とアクリル酸アルキル単
位からなる共重合体、メタクリル酸メチル単位とメタク
リル酸メチルを除くメタクリル酸アルキル単位からなる
共重合体、メタクリル酸メチル単位と芳香族ビニル化合
物単位からなる共重合体、メタクリル酸メチル単位とア
クリル酸アルキル単位とメタクリル酸メチルを除くメタ
クリル酸アルキル単位との三元共重合体、又は、メタク
リル酸メチル単位とメタクリル酸メチルを除く（メタ）
アクリル酸アルキル単位と芳香族ビニル化合物単位とか
らなる三元共重合体、又は、それらの共重合体の混合物
からなるメタクリル酸メチル系共重合体とからなる樹脂
組成物であって、（Ａ）成分が９５〜７０重量％、（Ｂ
）成分が５〜３０重量％であることを特徴とする改良さ
れた熱成形性と耐熱性を有する発泡シート製造用スチレ
ン系樹脂組成物。(1) (A) 5 to 25% by weight of component units consisting of at least one selected from the group of acrylic acid, methacrylic acid, and maleic anhydride and 95 to 75% by weight of styrene units
(B) a copolymer consisting of methyl methacrylate units and alkyl acrylate units, a styrenic copolymer consisting of methyl methacrylate units and methacrylic acid, whose heating deformation temperature is 96°C or higher; A copolymer consisting of an alkyl methacrylate unit excluding methyl, a copolymer consisting of a methyl methacrylate unit and an aromatic vinyl compound unit, a copolymer consisting of a methyl methacrylate unit, an alkyl acrylate unit, and an alkyl methacrylate unit excluding methyl methacrylate. Terpolymer or methyl methacrylate unit and excluding methyl methacrylate (meth)
A resin composition comprising a terpolymer comprising an alkyl acrylate unit and an aromatic vinyl compound unit, or a methyl methacrylate copolymer comprising a mixture of these copolymers, comprising (A) The component is 95-70% by weight, (B
1. A styrenic resin composition for producing a foamed sheet having improved thermoformability and heat resistance, characterized in that the component (a) is contained in an amount of 5 to 30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27906587A JPH01121346A (en) | 1987-11-06 | 1987-11-06 | Styrene resin composition for foamed sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27906587A JPH01121346A (en) | 1987-11-06 | 1987-11-06 | Styrene resin composition for foamed sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01121346A true JPH01121346A (en) | 1989-05-15 |
Family
ID=17605920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27906587A Pending JPH01121346A (en) | 1987-11-06 | 1987-11-06 | Styrene resin composition for foamed sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01121346A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997017394A1 (en) * | 1995-11-09 | 1997-05-15 | Imperial Chemical Industries Plc | Foamed articles |
| US7960443B2 (en) * | 2007-09-10 | 2011-06-14 | Jsp Corporation | Extruded styrenic resin foam and method for producing the same |
-
1987
- 1987-11-06 JP JP27906587A patent/JPH01121346A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997017394A1 (en) * | 1995-11-09 | 1997-05-15 | Imperial Chemical Industries Plc | Foamed articles |
| US7960443B2 (en) * | 2007-09-10 | 2011-06-14 | Jsp Corporation | Extruded styrenic resin foam and method for producing the same |
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