JPH06856B2 - Styrenic resin stretch sheet - Google Patents
Styrenic resin stretch sheetInfo
- Publication number
- JPH06856B2 JPH06856B2 JP61086075A JP8607586A JPH06856B2 JP H06856 B2 JPH06856 B2 JP H06856B2 JP 61086075 A JP61086075 A JP 61086075A JP 8607586 A JP8607586 A JP 8607586A JP H06856 B2 JPH06856 B2 JP H06856B2
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- styrene
- resin
- good
- silicon dioxide
- 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.)
- Expired - Fee Related
Links
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、２軸延伸シートとした際、透明性にすぐれ、
かつシリコンオイルの均一塗布性、シートの剥離性およ
び積み重ね成型品の剥離性が良好なスチレン系樹脂延伸
シートに関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention has excellent transparency when formed into a biaxially stretched sheet,
The present invention also relates to a stretched styrene-based resin sheet having a uniform coating property of silicone oil, a peeling property of a sheet, and a peeling property of a stacked molded product.
（従来の技術） ２軸延伸されたスチレン系樹脂シートは、その透明性お
よび腰の強さから食品包装分野に広く利用されている。
しかしこの２軸延伸されたシートはブロツキング性が強
く、また前記シートより得た容器は積み重ねておくと使
用時に剥離し難い欠点を有している。(Prior Art) A biaxially stretched styrene resin sheet is widely used in the field of food packaging because of its transparency and elasticity.
However, this biaxially stretched sheet has a strong blocking property, and the containers obtained from the sheet have a drawback that they are difficult to peel off when used when stacked.
この欠点を改良するための方法としては、スチレ系樹脂
にゴムを添加してシートを２軸延伸した際に、前記ゴム
をシート表面に突出させてシートの剥離を良好とするこ
と（特開昭50-74649号公報）および前記シート表面にシ
リコンオイルを塗布すること（特開昭５２−８０８０号
公報）が提案されている。As a method for improving this drawback, when a rubber is added to a styrenic resin and the sheet is biaxially stretched, the rubber is projected on the surface of the sheet so that the sheet can be peeled off favorably (Japanese Patent Laid-Open Publication No. Sho. 50-74649) and coating the surface of the sheet with silicone oil (JP-A-52-8080).
しかしながら、ゴム添加樹脂は、２軸延伸するとゴムが
偏平となるためシート表面への突出される割合が一定と
なり難く、シートの剥離を良くするためにはゴム量を多
く添加する必要から透明性の低下を招く恐れを生じた
り、またゴムを多く用いると長期運転中およびリサイク
ル品を添加することによるヤケからくる異物を生じ、シ
ート外観不良およびシート破断の原因となる欠点があ
る。However, since the rubber-added resin becomes flat when biaxially stretched, the ratio of protrusion to the surface of the sheet is less likely to be constant. If the rubber is used in a large amount, foreign matters may be generated due to burns due to addition of recycled products during long-term operation, resulting in defective sheet appearance and sheet breakage.
さらにゴム量を減少させゴムの粒子径を大きくする例え
ば６〜１０μm程度とすることもできるが、この方法で
は２軸延伸シートの表面の肌荒れや光沢低下が生じ、実
用上使用することができない。The amount of rubber can be further reduced and the particle size of rubber can be increased, for example, about 6 to 10 μm, but this method causes roughening of the surface of the biaxially stretched sheet and deterioration of gloss, and cannot be practically used.
（発明が解決しようとする問題点） 本発明は、かかる欠点を解決するためスチレン系樹脂と
合成二酸化ケイ素との樹脂組成物を２軸延伸することに
より、合成二酸化ケイ素は延伸時に偏平に引伸ばされな
いためスチレン系樹脂シート表面に微細な凹凸を均一に
生じさせてシリコンオイル塗布性能を向上させ、従来の
熱劣化によるゴムのヤケに起因する外観不良およびシー
ト破断を回避し、さらに延伸シート同志のブロツキング
性を弱め、前記シートを多数枚重ねて打抜いた成型品の
剥離性を向上させたスチレン系樹脂延伸シートを完成す
るに至つた。(Problems to be Solved by the Invention) In order to solve the above drawbacks, the present invention biaxially stretches a resin composition of a styrene-based resin and synthetic silicon dioxide, whereby the synthetic silicon dioxide is flattened during stretching. Since it does not occur, fine unevenness is uniformly generated on the surface of the styrene-based resin sheet to improve the silicone oil application performance, avoiding the poor appearance and sheet breakage due to the rubber burn due to the conventional heat deterioration. The styrenic resin stretched sheet was completed in which the blocking property was weakened and the peelability of the molded product obtained by punching by stacking a large number of the above sheets was improved.
（問題点を解決するための手段） すなわち本発明は、透明なスチレン系樹脂と該透明なス
チレン系樹脂中に５０〜５００ppm含有させた平均粒子
径１〜５μmの合成二酸化ケイ素からなる樹脂組成物を
２軸延伸してなることを特徴とする。(Means for Solving Problems) That is, the present invention provides a resin composition comprising a transparent styrene resin and a synthetic silicon dioxide having an average particle diameter of 1 to 5 μm which is contained in the transparent styrene resin in an amount of 50 to 500 ppm. Is biaxially stretched.
本発明に用いる透明なスチレン系樹脂のスチレン単量体
としては、例えば、スチレン、アラルキルスチレン（た
とえばｏ−、ｍ−およびｐ−メチルスチレン、−エチル
スチレン、−イソプロピルスチレン、−ブチルスチレ
ン、−第３級ブチルスチレン）、種々のアルフアアルキ
ルスチレン（たとえばメチルスチレン、エチルスチレ
ン）、種々のアルハロスチレン（例えばｏ−、ｍ−およ
びｐ−クロロスチレン、ブロモスチレン、フルオロスチ
レン）、種々のジ、トリ、テトラおよびペンタ置換クロ
ロスチレン、ブロモスチレンおよびフルオロスチレンお
よび種々のアルフアーおよびベーターハロ置換スチレン
（たとえばアルフアクロロスチレン、アルフアブロモス
チレン、ベータークロロスチレンおよびベータープロモ
スチレン）および前記単量体と共重合が可能な例えばア
クリロニトリル、メチルメタアクリレート等である。ま
た前記透明なスチレン系樹脂の製法は、通常の重合方法
であれば、何んら制限がない。Examples of the styrene monomer of the transparent styrene resin used in the present invention include styrene, aralkyl styrene (for example, o-, m- and p-methyl styrene, -ethyl styrene, -isopropyl styrene, -butyl styrene, -th styrene). Tertiary butyl styrene), various alpha alkyl styrenes (eg methyl styrene, ethyl styrene), various arhalo styrenes (eg o-, m- and p-chloro styrene, bromo styrene, fluoro styrene), various di, tri , Tetra- and penta-substituted chlorostyrenes, bromostyrenes and fluorostyrenes and various alpha- and beta-halo-substituted styrenes (eg alpha-chlorostyrene, alpha-bromostyrene, beta-chlorostyrene and beta-promostyrene) and said Mer copolymerizable capable such as acrylonitrile, methyl methacrylate and the like. Further, the method for producing the transparent styrene resin is not particularly limited as long as it is an ordinary polymerization method.
次に本発明の合成二酸素ケイ素は、ケイ酸ナトリウムと
酸とを反応させることにより生成したものが好ましい。
該ケイ素の平均粒子径は、一次粒子がシロキサン結合に
よつて三次元的に結合した二次凝集体の状態で１〜５μ
mが好ましい。１μm未満ではシートに再凝集による分散
不良が生じたり、フイツシユアイができてシート表面外
観不良を起し、また５μmを越えると、粗大粒子が多く
含まれるので、シート表面外観が損われたり、延伸時に
シート破断を生じるので好ましくない。Next, the synthetic silicon dioxide of the present invention is preferably produced by reacting sodium silicate with an acid.
The average particle diameter of the silicon is 1 to 5 μm in the state of a secondary aggregate in which primary particles are three-dimensionally bonded by siloxane bonds.
m is preferred. If it is less than 1 μm, the sheet may be poorly dispersed due to re-aggregation, or may cause the appearance of fibers, resulting in poor surface appearance of the sheet. It is not preferable because it causes sheet breakage.
さらに樹脂中に含有される割合は５０〜５００ppmが好
ましく、５０ppm未満では、シート表面への突出割合が
少なく、シートブロツキング性を弱くしたり、該シート
から得た成型品の積み重ねによる剥離性が劣り、また５
００ppmを越えると、二酸化ケイ素の再凝集を起す機会
が多くなり、シートの透明性および外観の低下、延伸時
のシート破断を生じる欠点がある。Further, the content in the resin is preferably 50 to 500 ppm, and if it is less than 50 ppm, the projection ratio to the sheet surface is small, the sheet blocking property is weakened, and the peelability due to stacking of molded products obtained from the sheet is high. Is inferior, again 5
If it exceeds 00 ppm, the chances of re-aggregation of silicon dioxide are increased, the transparency and appearance of the sheet are deteriorated, and the sheet is broken during stretching.
また本発明の樹脂組成物は必要に応じて、滑剤、可塑
剤、着色剤等の添加剤を用いることができる。Further, the resin composition of the present invention may contain additives such as a lubricant, a plasticizer and a colorant, if necessary.
本発明の延伸シート用としての樹脂組成物は、透明なス
チレン系樹脂と合成二酸化ケイ素とをヘンシエルミキサ
ー、Ｖブレンダー等でドライブレンドしてもよく、また
合成二酸化ケイ素を多量に含んだ樹脂組成物のマスター
ペレツトを作り、未充てん剤の透明なスチレン系樹脂と
混合する方法等いずれの方法でもよい。The resin composition for the stretched sheet of the present invention may be obtained by dry blending a transparent styrene resin and synthetic silicon dioxide with a Henschel mixer, a V blender, or the like, and a resin composition containing a large amount of synthetic silicon dioxide. Any method may be used, such as a method of preparing a master pellet of the product and mixing it with an unfilled transparent styrene resin.
また本発明のスチレン系樹脂延伸シートはその表面にオ
ストワルド粘度（２０℃）が１００〜２０0,０００セン
チストークスの構造式 を主成分とするシリコンオイル単独および乳化剤を含有
したエマルジヨンを単独または、防曇剤、帯電防止剤等
と併用して均一に塗布することができる。また、シリコ
ンオイルの塗布量は、手にべたつきが感じられない程
度、１０〜１５０mg／m2の範囲である。The styrene-based resin stretched sheet of the present invention has a structural formula having an Ostwald viscosity (20 ° C) of 100 to 200,000 centistokes on its surface. It is possible to uniformly apply the silicone oil containing as the main component and the emulsion containing the emulsifier alone or in combination with the antifogging agent and the antistatic agent. The amount of silicone oil applied is in the range of 10 to 150 mg / m 2 to the extent that no stickiness is felt on the hand.
（実施例） 以下実施例により本発明を詳細に説明する。なお平均粒
子径の測定方法は、コールターカウンター法により５０
％体積平均粒子径である。(Example) Hereinafter, the present invention will be described in detail with reference to Examples. The average particle size is measured by the Coulter counter method at 50
% Volume average particle diameter.
実施例１〜３ 透明なスチレン系樹脂中に表に示すとおりの量および平
均粒子径の合成二酸化ケイ素（富士デビソン（株）、商
品明「サイロイド」）を混入した樹脂組成物を押出機か
らシート状に押出し、タテおよびヨコに2.5倍延伸して
１５０μmの２軸延伸シートを得た。次に前記延伸シー
トの表面にシリコーンオイルを５０mg／m2となるように
塗布した。Examples 1 to 3 Sheets of resin compositions in which transparent styrene-based resin was mixed with synthetic silicon dioxide (Fuji Devison Co., Ltd., product name "Cyloid") in the amounts and average particle sizes shown in the table from an extruder. It was extruded into a shape and stretched 2.5 times in the vertical and horizontal directions to obtain a biaxially stretched sheet of 150 μm. Next, silicone oil was applied to the surface of the stretched sheet so as to have a concentration of 50 mg / m 2 .
特性を測定した結果は、表に示すとおり良好な結果であ
つた。The results of measuring the characteristics were good as shown in the table.
比較例１〜２ 合成二酸化ケイ素の量および平均粒子径を表に示した以
外は、実施例１と同様に操作した。特性の結果を表に示
す。特性評価欄に示すとおり、粒子径が大きい場合には
透明性が劣り、また粗大粒子の数が多くシート外観の悪
いシートであつた。Comparative Examples 1 to 2 The same operation as in Example 1 was carried out except that the amounts of synthetic silicon dioxide and the average particle size were shown in the table. The results of the properties are shown in the table. As shown in the property evaluation column, when the particle size was large, the transparency was poor, and the number of coarse particles was large, resulting in a poor sheet appearance.
また粒子の小さい場合には、分散不良の二次凝集に基づ
く粗大粒子が散在し、同様に外観の悪いシートであつ
た。When the particles were small, coarse particles due to poorly dispersed secondary aggregation were scattered, and the sheet was similarly inferior in appearance.
比較例３〜５ 透明なスチレン樹脂に表に示す平均粒子径とゴム分換算
のスチレングラフトゴムを混合した以外は実施例１と同
様に操作した。その結果表に示すとおり、特性値のすべ
てを満足するものは得られていない。Comparative Examples 3 to 5 The same operation as in Example 1 was carried out except that a transparent styrene resin was mixed with the styrene-grafted rubber having the average particle size and the rubber content shown in the table. As a result, as shown in the table, none satisfying all the characteristic values was obtained.
なお表に示す特性評価方法は次のとおりである。 The characteristic evaluation methods shown in the table are as follows.
1, シートの剥離性、ASTM-D-１８９４に準拠 ◎（良好） ： 0.35以下 ○（良） ： 0.35超〜0.40 △（やや良）： 0.40超〜0.45 ×（不良） ： 0.45超 2, 透明性、日本電色製ＮＯＨ−２Ｄ濁度計でシート厚
１５０μm規準で曇り度を測定した。1, Sheet peelability, conforming to ASTM-D-1894 ◎ (Good): 0.35 or less ○ (Good): Over 0.35 to 0.40 △ (Somewhat good): Over 0.40 to 0.45 × (Poor): Over 0.45 2, Transparent The haze was measured with a NOH-2D turbidimeter manufactured by Nippon Denshoku Co., Ltd. based on a sheet thickness of 150 μm.
◎（良好） ： 0.5％以下 ○（良） ： 0.5超〜1.0％ △（やや良）： 1.0超〜1.5％ ×（不良） ： 1.5％超 3, シート表面の突起数、東京精密製の二次元表面粗さ
計により２０cm長さ中の0.1〜１μmの突起数を測定し
た。◎ (Good): 0.5% or less ○ (Good): Greater than 0.5 to 1.0% △ (Somewhat good): Greater than 1.0 to 1.5% × (Poor): Greater than 1.5% 3, Number of protrusions on sheet surface, manufactured by Tokyo Seimitsu The number of protrusions of 0.1 to 1 μm in the length of 20 cm was measured by a dimensional surface roughness meter.
◎（良好） ： １５１個以上 ○（良） ： １０１〜１５０個 △（やや良）： ５１〜１００個 ×（不良） ： ５０個以下 4, 粗大粒子の数、２５cm角シート中に含まれるφ１mm
以上の大きさのフイツシユアイ数を目視で測定した。◎ (good): 151 or more ○ (good): 101 to 150 △ (somewhat good): 51 to 100 × (poor): 50 or less 4, number of coarse particles, φ included in 25 cm square sheet 1 mm
The number of fish eyes having the above size was visually measured.
◎（良好） ： ０〜１個 ○（良） ： ２〜４個 △（やや良）： ５〜７個 ×（不良） ： ８個以上 5, シリコンオイルマーク、シートを２枚重ね合せた時
に生ずる、地図模様の面積（１００区画）を目視により
測定した。◎ (good): 0 to 1 ○ (good): 2 to 4 △ (somewhat good): 5 to 7 × (bad): 8 or more 5, when silicone oil mark and 2 sheets are superposed The area of the resulting map pattern (100 sections) was visually measured.
◎（良好） ： ５％以下 ○（良） ： ５超〜２５％ △（やや良）： ２５超〜５０％ ×（不良） ： ５０％超 6, フイシユアイ中の樹脂ヤケの数φ ０．２mm以上のフイシユアイに占める樹脂ヤケ（着
色、コンタミも含む）を５０倍ルーペにて目視判断で判
定した。◎ (Good): 5% or less ○ (Good): More than 5 to 25% △ (Somewhat good): More than 25 to 50% × (Poor): More than 50% 6, Number of resin burnt in the eye φ 0.2 mm The resin burnt color (including coloring and contamination) occupying the above-mentioned fibers was visually determined with a 50 times magnifier.
◎（良好） ： ５％以下 ○（良） ： ５超〜２５％ △（やや良）： ２５超〜５０％ ×（不良） ： ５０％超 （発明の効果） 以上のとおり本発明のスチレン系樹脂延伸シートは、シ
ート表面に微細な凹凸が均一にできるのでシリコンオイ
ル塗布が均一化となり、しかも従来のゴムの熱劣化によ
る異物混入からくる外観およびシート破断が回避でき、
さらに延伸シート同志のブロツキング性を弱め、かつ成
型品の積み重ねによる剥離性が良好である特徴を有する
ものである。◎ (good): 5% or less ○ (good): 5 to 25% △ (somewhat good): 25 to 50% × (poor): 50% (effect of the invention) As described above, the styrene-based resin of the present invention The resin stretched sheet can have uniform unevenness on the sheet surface so that the silicone oil can be applied uniformly, and the appearance and sheet breakage due to the inclusion of foreign matter due to the thermal deterioration of the conventional rubber can be avoided.
Further, it has the characteristics that the blocking properties of the stretched sheets are weakened and the peeling property by stacking the molded products is good.
Claims (1)
系樹脂中に５０〜５００ppm含有させた平均粒子径１〜
５μｍの合成二酸化ケイ素からなる樹脂組成物を２軸延
伸してなることを特徴とするスチレン系樹脂延伸シー
ト。1. A transparent styrene resin and an average particle diameter of 1 to 50 contained in the transparent styrene resin in an amount of 50 to 500 ppm.
A stretched styrene-based resin sheet, which is obtained by biaxially stretching a resin composition of 5 μm of synthetic silicon dioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61086075A JPH06856B2 (en) | 1986-04-16 | 1986-04-16 | Styrenic resin stretch sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61086075A JPH06856B2 (en) | 1986-04-16 | 1986-04-16 | Styrenic resin stretch sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62243623A JPS62243623A (en) | 1987-10-24 |
| JPH06856B2 true JPH06856B2 (en) | 1994-01-05 |
Family
ID=13876582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61086075A Expired - Fee Related JPH06856B2 (en) | 1986-04-16 | 1986-04-16 | Styrenic resin stretch sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06856B2 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4921100A (en) * | 1972-06-16 | 1974-02-25 | ||
| JPS528080A (en) * | 1975-07-09 | 1977-01-21 | Asahi Dow Ltd | Method of manufacturing stylene system resin sheet |
| JPS52130852A (en) * | 1976-04-27 | 1977-11-02 | Denki Kagaku Kogyo Kk | Resin compositions |
| JPS5852820A (en) * | 1981-09-24 | 1983-03-29 | Nec Corp | Manufacture of semiconductor device |
| JPS5898222A (en) * | 1981-12-07 | 1983-06-11 | Denki Kagaku Kogyo Kk | Biaxially stretched sheet of styrene resin |
| JPS59164345A (en) * | 1983-03-09 | 1984-09-17 | Nissan Chem Ind Ltd | Resin composition containing ultrafine silicic acid powder |
| JPH06855A (en) * | 1992-06-18 | 1994-01-11 | Sumitomo Jukikai Plast Mach Kk | Molding condition setting device |
-
1986
- 1986-04-16 JP JP61086075A patent/JPH06856B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4921100A (en) * | 1972-06-16 | 1974-02-25 | ||
| JPS528080A (en) * | 1975-07-09 | 1977-01-21 | Asahi Dow Ltd | Method of manufacturing stylene system resin sheet |
| JPS52130852A (en) * | 1976-04-27 | 1977-11-02 | Denki Kagaku Kogyo Kk | Resin compositions |
| JPS5852820A (en) * | 1981-09-24 | 1983-03-29 | Nec Corp | Manufacture of semiconductor device |
| JPS5898222A (en) * | 1981-12-07 | 1983-06-11 | Denki Kagaku Kogyo Kk | Biaxially stretched sheet of styrene resin |
| JPS59164345A (en) * | 1983-03-09 | 1984-09-17 | Nissan Chem Ind Ltd | Resin composition containing ultrafine silicic acid powder |
| JPH06855A (en) * | 1992-06-18 | 1994-01-11 | Sumitomo Jukikai Plast Mach Kk | Molding condition setting device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62243623A (en) | 1987-10-24 |
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