JP3567706B2 - Biaxially oriented polystyrene resin sheet - Google Patents
Biaxially oriented polystyrene resin sheet Download PDFInfo
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- JP3567706B2 JP3567706B2 JP33278097A JP33278097A JP3567706B2 JP 3567706 B2 JP3567706 B2 JP 3567706B2 JP 33278097 A JP33278097 A JP 33278097A JP 33278097 A JP33278097 A JP 33278097A JP 3567706 B2 JP3567706 B2 JP 3567706B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、防曇性能に優れた二軸延伸ポリスチレン系樹脂シートに関する。さらに詳しくは、食品包装材として、従来より優れた防曇性能を有する二軸延伸ポリスチレン系樹脂シートに関する。
【０００２】
【従来の技術】
二軸延伸ポリスチレン系樹脂シートは、透明性、耐水性に優れ、成形性にも優れていることから各種食料品等の包装材として広く使用されている。しかし、反面その表面が極めて疎水性であるために、気温、湿度の変化に応じて凝結する水分（水蒸気）が樹脂表面を均一に濡らすことなく微小水滴の集合体を形成し、いわゆる曇りが発生することが多い。このような曇りの発生は、食品用包装材分野においては収納物を見分けることが困難になるので、各種容器の商品価値を著しく低下させる。これは、透明性を特徴とする容器の重大な欠点であるばかりでなく、不均一に凝集、付着した水分は、容器に収納された食品にも影響を与え、品質の不良化、腐敗の一因となる。
従来、このような曇り現象を防ぐため、ショ糖脂肪酸エステルが安全性の高い防曇剤として広く使用されていた（特開昭５６−１６６２３４、特開昭５７−８０４３１、特公昭６１−３６８６４号各公報）。また、特開平９−１２７５１号公報には、ポリグリセリン脂肪酸エステルを使用する防曇性スチレン系樹脂シート・フィルムが提案されている。
【０００３】
【発明が解決しようとする課題】
近年二軸延伸ポリスチレン系樹脂シートは、容器成形時の深絞り（絞り深さ／開口比＝０．５以上）に対応した優れた防曇性能や、長時間持続する防曇性能を有することが求められている。しかしながら、従来の防曇剤では、目的とする防曇性能を得るには多量に添加する必要があるため、二軸延伸ポリスチレン系樹脂シートの透明性を損ねたり、べたついたりする問題が生じていた。
【０００４】
【課題を解決するための手段】
本発明者らは、優れた防曇性能を有し、二軸延伸ポリスチレン系樹脂シートの透明性を損なわない防曇剤について鋭意検討を行った結果、特定の構成脂肪酸からなるショ糖脂肪酸エステルと特定の構成脂肪酸からなるポリグリセリン脂肪酸エステルを含有する防曇剤を特定量被覆された二軸延伸ポリスチレン系樹脂シートが、優れた透明性、防曇性能を有することを見いだし、本発明を完成させた。すなわち、本発明は、構成脂肪酸が主としてオレイン酸及びラウリン酸からなり、その構成脂肪酸におけるオレイン酸：ラウリン酸のモル比が１：９〜９：１であるショ糖脂肪酸エステルと、構成脂肪酸の７０重量％以上が炭素数１２〜１６の飽和脂肪酸であるポリグリセリン脂肪酸エステルを含有する防曇剤５〜１５０ｍｇ／ｍ２により被覆されたことを特徴とする二軸延伸ポリスチレン系樹脂シート、に存する。
【０００５】
【発明の実施の形態】
以下、本発明を詳細に説明する。
本発明の防曇剤の有効成分である構成脂肪酸がオレイン酸及びラウリン酸からなるショ糖脂肪酸エステルの構成脂肪酸中のオレイン酸とラウリン酸の比率は、オレイン酸：ラウリン酸のモル比にて１：９〜９：１の範囲である。オレイン酸の比率が９を越えると樹脂シート等被処理物の透明性の低下が著しいことがあり、またオレイン酸の比率が１に満たないと防曇性が低下することがあるのでいずれも好ましくない。本発明におけるショ糖脂肪酸エステルは、これら二種類の構成脂肪酸を所定のモル比で一分子中に有していても、あるいは各々の脂肪酸純度の高いショ糖脂肪酸エステル同士を所定の割合で混合したものを用いてもよい。更に、本発明の効果を損なわない程度であれば、オレイン酸及びラウリン酸以外の構成脂肪酸を少量、例えば、最大１０モル％程度まで含んでいてもよい。
【０００６】
また、本発明のもう一方の有効成分であるポリグリセリン脂肪酸エステルは、その構成脂肪酸の７０重量％以上、好ましくは８０重量％以上が炭素数１２〜１６の飽和脂肪酸である。具体的には、ラウリン酸、ミリスチン酸、パルミチン酸の単独または２種以上を構成脂肪酸の７０重量％以上含有する必要があるが、残りはオレイン酸、ステアリン酸等の他の脂肪酸を含んでいても良い。炭素数１２〜１６の飽和脂肪酸の量が、構成脂肪酸の７０重量％未満では初期防曇性と防曇持続性のバランスが悪くなる。本発明のポリグリセリン脂肪酸エステルは、構成脂肪酸の７０重量％以上が炭素数１２〜１６の飽和脂肪酸であれば、ポリグリセリンの重縮合度、エステル化の程度については制限されないが、前者については食品添加物としての安全性の面から４〜２０が好ましく、６〜１２がさらに好ましい。また、後者については、モノエステルを５０モル％以上含有するのが好ましい。
【０００７】
ショ糖脂肪酸エステルとポリグリセリン脂肪酸エステルの割合は、両者の合計１００重量％に対して、前者が５０〜９０重量％、後者が５０〜１０重量％であるのが好ましい。両者の割合が上記範囲外の場合は、初期防曇性と防曇持続性のバランスが悪くなる傾向にある。また、後者が５０重量％を超えると二軸延伸ポリスチレン系樹脂シートに塗布した場合、ベタツキが酷くなり好ましくない。
【０００８】
本発明の防曇剤には、ショ糖脂肪酸エステルとポリグリセリン脂肪酸エステルの他に各種陰イオン性界面活性剤を添加してもよい。陰イオン性界面活性剤としては、脂肪酸塩、脂肪酸スルホン酸塩、脂肪酸乳酸エステル塩等が挙げられる。これらの脂肪酸塩、脂肪酸スルホン酸塩、脂肪酸乳酸エステル塩を構成する脂肪酸としては、炭素数８〜２２の飽和、不飽和、直鎖、分岐鎖状のものが用いられ、具体的にはカプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラギジン酸、オレイン酸、エライジン酸、リシノレイン酸、２−ブチルオクタン酸、２−ヒドロキシデカン酸等が挙げられる。これらの脂肪酸は、任意の割合からなる２種以上の混合物であっても良い。塩を構成する塩基性物質としては、ナトリウムやカリウム等のアルカリ金属もしくはマグネシウム等のアルカリ土類金属、あるいはエタノールアミン等のアルカノールアミン、トリブチルアミン等の低級アルキルアミン等が挙げられる。これらの中で、構成脂肪酸としては、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸が好ましく、特にラウリン酸が好ましい。また、塩基性物質としてはアルカリ金属が好ましく、特にカリウムが好ましい。これらの陰イオン性界面活性剤の添加量は、ショ糖脂肪酸エステルとポリグリセリン脂肪酸エステルの合計１００重量部に対して、通常３０重量部以下である。
【０００９】
二軸延伸ポリスチレン系樹脂シートは、公知の方法でシートされ、シートの厚みは通常１００〜７００μｍである。通常、該シートは熱成形されて容器として使用することができる。
本発明においては、ポリスチレン系樹脂を成形して得た二軸延伸ポリスチレン系樹脂シートの表面に直ちに防曇剤を塗布してよいが、予め、コロナ放電処理、高周波処理等の表面処理を行い、シート表面の状態を調整しておいた方が、防曇剤が良好に被覆されやすいので望ましく、好ましくは、コロナ放電処理によりシートの表面張力を５０〜６０ｄｙｎｅ／ｃｍに調整するとよい。
【００１０】
防曇剤は主としてシート表面に塗布して用いられる。この場合、０．１〜５重量％の防曇剤溶液として、防曇剤を５〜１５０ｍｇ／ｍ２（固形分換算）に塗布後、乾燥して用いる。防曇剤の塗布量の好ましい範囲は１０〜１００ｍｇ／ｍ２である。防曇剤の塗布量が５ｍｇ／ｍ２未満の場合は、防曇効果が低下することがあり、１５０ｍｇ／ｍ２を越えるとベタツキによるシート同士のブロッキングや透明性の低下が生じ表面白化を起こすことがある。
防曇剤の塗布方法としては、刷毛塗り、噴霧、ロールコーター、グラビアコーター、ナイフコーター、浸漬法等の既知の方法が用いられ、噴霧、ロールコーター法が好ましい。また、防曇剤溶液に用いる溶媒としては、例えば、水、アルコール等の防曇剤を溶解し、かつ樹脂シートを溶解しない溶媒で、しかも適用分野によっては安全性を満たす溶媒を適宜選択して用いるのがよい。
【００１１】
さらに、本発明の防曇剤においては、各種可塑剤、安定剤、潤滑剤、顔料、ブロッキング防止剤、粘度調節剤、消泡剤、紫外線吸収剤、着色防止剤等を常法により適宜併用することができる。
【００１２】
【実施例】
以下、本発明を実施例、比較例により、更に詳細に説明するが、本発明は、その要旨を越えない限り、以下の実施例に限定されるものではない。また、ここで行った評価方法を以下に示す。
＜防曇性＞
試料シートを９０℃の温水３００ｃｃを入れた５００ｃｃ（口径９０ｍｍφ）のビーカーの口に張り、これを９０℃で加熱しながらシート内面の水滴の付着状況を肉眼観察し、曇り始め時間を測定した。
評価基準
◎ ：５０分以上
○ ：３０分以上５０分未満
△ ：１０分以上３０分未満
× ：１分以上１０分未満
××：１分未満
＜シート透明性＞
シート透明性をＮＤＨ−３００Ａ（日本電色工業株式会社製）により測定した曇価（ヘーズ）Ｈ（％）と、肉眼観察した外観の双方で評価し、評価の低い方の結果をシート透明性の評価結果とした。
評価基準
◎：Ｈ＜１．５または塗り斑が全く見られない。
○：１．５≦Ｈ＜２またはごく僅かな塗り斑が見られる。
△：２≦Ｈ＜３または塗り斑が少し目立つ。
×：３≦Ｈまたは塗り斑がかなり目立つ。
【００１３】
＜実施例１〜１０、比較例１〜８＞
表−１に示すようなラウリン酸／オレイン酸モル比を有するショ糖脂肪酸エステルと表−１に示すような組成を有するポリグリセリン脂肪酸エステルからショ糖脂肪酸エステルとポリグリセリン脂肪酸エステルの合計量が１重量％の防曇剤水溶液を調製した（防曇剤中のショ糖脂肪酸エステルの重量比は表−１に示す。）。
この防曇剤水溶液を５４ｄｙｎｅ／ｃｍ以上のコロナ処理を施した二軸延伸ポリスチレンシートの片面に防曇剤固形分として１０ｍｇ／ｍ２を塗布した。評価結果を表１に示す。なお、比較例８では防曇剤を塗布しないで評価した。
なお、本実施例および比較例で使用したショ糖脂肪酸エステルは、ショ糖と表１に示す構成脂肪酸が所定のモル比のラウリン酸およびオレイン酸をジメチルスルフホキシド中２０ｔｏｒｒの減圧下で９０℃、３時間反応させ、中和後に濃縮して乾固して得たものを使用した。
【００１４】
【表１】
【発明の効果】
本発明の二軸延伸ポリスチレン系樹脂シートは、従来より優れた防曇効果を有するので、食品包装分野等に広く用いることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a biaxially oriented polystyrene resin sheet having excellent antifogging performance. More specifically, the present invention relates to a biaxially stretched polystyrene-based resin sheet having better anti-fog performance as a food packaging material than before.
[0002]
[Prior art]
BACKGROUND ART Biaxially stretched polystyrene resin sheets are widely used as packaging materials for various foods and the like because of their excellent transparency, water resistance, and excellent moldability. However, because the surface is extremely hydrophobic, water (water vapor) that condenses in response to changes in temperature and humidity forms aggregates of minute water droplets without uniformly wetting the resin surface, causing so-called clouding Often do. The occurrence of such fogging makes it difficult to identify stored items in the field of food packaging materials, and thus significantly reduces the commercial value of various containers. This is not only a serious drawback of containers characterized by transparency, but also non-uniformly agglomerated and adhered moisture affects foods stored in the containers, resulting in poor quality and spoilage. Cause.
Conventionally, in order to prevent such a clouding phenomenon, sucrose fatty acid esters have been widely used as highly safe antifoggants (Japanese Patent Application Laid-Open Nos. 56-166234, 57-80431, and 61-36864). Publications). JP-A-9-12751 proposes an antifogging styrene resin sheet / film using a polyglycerin fatty acid ester.
[0003]
[Problems to be solved by the invention]
In recent years, biaxially stretched polystyrene-based resin sheets have excellent anti-fog performance corresponding to deep drawing (drawing depth / opening ratio = 0.5 or more) during container molding and anti-fog performance that lasts for a long time. It has been demanded. However, in the conventional anti-fog agent, since it is necessary to add a large amount to obtain the desired anti-fog performance, there has been a problem that the transparency of the biaxially stretched polystyrene resin sheet is impaired or sticky. .
[0004]
[Means for Solving the Problems]
The present inventors have excellent antifogging performance, and as a result of intensive studies on an antifogging agent that does not impair the transparency of the biaxially stretched polystyrene resin sheet, a sucrose fatty acid ester composed of a specific constituent fatty acid and A biaxially stretched polystyrene resin sheet coated with a specific amount of an antifogging agent containing a polyglycerin fatty acid ester composed of a specific constituent fatty acid is found to have excellent transparency and antifogging performance, and completed the present invention. Was. That is, the present invention provides a sucrose fatty acid ester in which the constituent fatty acids are mainly composed of oleic acid and lauric acid, and the mole ratio of oleic acid: lauric acid in the constituent fatty acids is 1: 9 to 9: 1; A biaxially stretched polystyrene resin sheet, characterized in that the coating is coated with 5 to 150 mg / m 2 of an antifogging agent containing a polyglycerin fatty acid ester, which is a saturated fatty acid having 12 to 16 carbon atoms, in which the weight% or more is contained.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The ratio of oleic acid to lauric acid in the constituent fatty acids of the sucrose fatty acid ester comprising oleic acid and lauric acid as the constituent fatty acid as the active ingredient of the anti-fogging agent of the present invention is 1 in a molar ratio of oleic acid: lauric acid. : 9 to 9: 1. When the ratio of oleic acid exceeds 9, the transparency of the object to be treated such as a resin sheet may be remarkably reduced, and when the ratio of oleic acid is less than 1, the antifogging property may be reduced, so that both are preferable. Absent. The sucrose fatty acid ester in the present invention, even if these two types of constituent fatty acids are present in one molecule at a predetermined molar ratio, or a mixture of sucrose fatty acid esters having a high purity of each fatty acid at a predetermined ratio. A thing may be used. Furthermore, as long as the effects of the present invention are not impaired, constituent fatty acids other than oleic acid and lauric acid may be contained in a small amount, for example, up to about 10 mol%.
[0006]
The polyglycerol fatty acid ester as the other active ingredient of the present invention is a saturated fatty acid having 12 to 16 carbon atoms in which 70% by weight or more, preferably 80% by weight or more of the constituent fatty acids. Specifically, lauric acid, myristic acid, or palmitic acid alone or more than 70% by weight of the constituent fatty acids must be contained, and the rest contains other fatty acids such as oleic acid and stearic acid. Is also good. If the amount of the saturated fatty acid having 12 to 16 carbon atoms is less than 70% by weight of the constituent fatty acids, the balance between the initial antifogging property and the antifogging durability will be poor. The polyglycerol fatty acid ester of the present invention is not limited in the degree of polycondensation of polyglycerin and the degree of esterification, provided that 70% by weight or more of the constituent fatty acids is a saturated fatty acid having 12 to 16 carbon atoms. From the viewpoint of safety as an additive, 4 to 20 is preferable, and 6 to 12 is more preferable. The latter preferably contains a monoester in an amount of 50 mol% or more.
[0007]
The ratio of the sucrose fatty acid ester and the polyglycerin fatty acid ester is preferably 50 to 90% by weight, and the latter is preferably 50 to 10% by weight, based on a total of 100% by weight of both. When the ratio of both is out of the above range, the balance between the initial antifogging property and the antifogging durability tends to be poor. On the other hand, if the content of the latter exceeds 50% by weight, stickiness becomes severe when applied to a biaxially oriented polystyrene resin sheet, which is not preferable.
[0008]
Various anionic surfactants may be added to the antifogging agent of the present invention in addition to the sucrose fatty acid ester and the polyglycerin fatty acid ester. Examples of the anionic surfactant include a fatty acid salt, a fatty acid sulfonic acid salt, and a fatty acid lactic acid ester salt. As the fatty acid constituting these fatty acid salts, fatty acid sulfonic acid salts and fatty acid lactic acid ester salts, saturated, unsaturated, straight-chain, or branched-chain ones having 8 to 22 carbon atoms are used, and specifically, caprylic acid , Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, argidic acid, oleic acid, elaidic acid, ricinoleic acid, 2-butyloctanoic acid, 2-hydroxydecanoic acid and the like. These fatty acids may be a mixture of two or more kinds in an arbitrary ratio. Examples of the basic substance constituting the salt include an alkali metal such as sodium or potassium or an alkaline earth metal such as magnesium, an alkanolamine such as ethanolamine, and a lower alkylamine such as tributylamine. Among these, as the constituent fatty acids, lauric acid, myristic acid, palmitic acid, and oleic acid are preferable, and lauric acid is particularly preferable. As the basic substance, an alkali metal is preferable, and potassium is particularly preferable. The addition amount of these anionic surfactants is usually 30 parts by weight or less based on 100 parts by weight of the total of sucrose fatty acid ester and polyglycerin fatty acid ester.
[0009]
The biaxially stretched polystyrene resin sheet is formed by a known method, and the thickness of the sheet is usually 100 to 700 μm. Usually, the sheet can be thermoformed and used as a container.
In the present invention, the antifog agent may be immediately applied to the surface of the biaxially stretched polystyrene resin sheet obtained by molding the polystyrene resin, but in advance, a corona discharge treatment, a surface treatment such as a high-frequency treatment, It is desirable to adjust the state of the sheet surface because the antifogging agent is easily coated well. Preferably, the surface tension of the sheet is adjusted to 50 to 60 dyne / cm by corona discharge treatment.
[0010]
The antifogging agent is mainly used by applying it to the sheet surface. In this case, as a 0.1 to 5% by weight antifogging agent solution, the antifogging agent is applied at 5 to 150 mg / m 2 (in terms of solid content) and then dried. The preferred range of the application amount of the anti-fogging agent is 10 to 100 mg / m 2 . When the coating amount of the anti-fogging agent is less than 5 mg / m 2 , the anti-fogging effect may be reduced, and when it exceeds 150 mg / m 2 , blocking between sheets due to stickiness and a decrease in transparency are caused to cause surface whitening. Sometimes.
Known methods such as brush coating, spraying, a roll coater, a gravure coater, a knife coater, and a dipping method are used as a method of applying the anti-fogging agent, and the spraying and the roll coater methods are preferable. In addition, as the solvent used in the antifogging agent solution, for example, water, a solvent that dissolves the antifogging agent such as alcohol, and a solvent that does not dissolve the resin sheet, and depending on the application field, appropriately select a solvent that satisfies safety. Good to use.
[0011]
Further, in the anti-fogging agent of the present invention, various plasticizers, stabilizers, lubricants, pigments, anti-blocking agents, viscosity regulators, defoamers, ultraviolet absorbers, anti-coloring agents and the like are appropriately used in a conventional manner. be able to.
[0012]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded. The evaluation method performed here is described below.
<Anti-fogging property>
The sample sheet was placed in the mouth of a 500 cc (90 mmφ) beaker containing 300 cc of hot water at 90 ° C., and heated at 90 ° C., while visually observing the adhesion state of water droplets on the inner surface of the sheet, and measuring the time at which fogging started.
Evaluation criteria ◎: 50 minutes or more ○: 30 minutes or more and less than 50 minutes △: 10 minutes or more and less than 30 minutes X: 1 minute or more and less than 10 minutes XX: less than 1 minute <sheet transparency>
The sheet transparency was evaluated based on both the haze (haze) H (%) measured by NDH-300A (manufactured by Nippon Denshoku Industries Co., Ltd.) and the appearance observed with the naked eye. Of the evaluation results.
Evaluation criteria A: H <1.5 or no coating spots were observed.
：: 1.5 ≦ H <2 or very slight spots are observed.
Δ: 2 ≦ H <3 or coating spots are slightly conspicuous.
×: 3 ≦ H or spots are considerably conspicuous.
[0013]
<Examples 1 to 10, Comparative Examples 1 to 8>
The total amount of sucrose fatty acid ester and polyglycerin fatty acid ester from sucrose fatty acid ester having a lauric acid / oleic acid molar ratio as shown in Table 1 and polyglycerin fatty acid ester having a composition as shown in Table 1 is 1 A weight% aqueous solution of an antifogging agent was prepared (the weight ratio of sucrose fatty acid ester in the antifogging agent is shown in Table-1).
This antifogging agent aqueous solution was applied to one surface of a biaxially stretched polystyrene sheet which had been subjected to a corona treatment of 54 dyne / cm or more, at 10 mg / m 2 as a solid content of the antifogging agent. Table 1 shows the evaluation results. In Comparative Example 8, the evaluation was performed without applying the antifogging agent.
The sucrose fatty acid ester used in the present Example and Comparative Example was prepared by mixing sucrose and the constituent fatty acids shown in Table 1 in a predetermined molar ratio of lauric acid and oleic acid at 90 ° C. under reduced pressure of 20 torr in dimethyl sulfoxide. The reaction was carried out for 3 hours, neutralized, concentrated and dried to obtain a product.
[0014]
[Table 1]
【The invention's effect】
INDUSTRIAL APPLICABILITY The biaxially oriented polystyrene-based resin sheet of the present invention has a more excellent antifogging effect than conventionally, and can be widely used in the field of food packaging and the like.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33278097A JP3567706B2 (en) | 1997-12-03 | 1997-12-03 | Biaxially oriented polystyrene resin sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33278097A JP3567706B2 (en) | 1997-12-03 | 1997-12-03 | Biaxially oriented polystyrene resin sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11166061A JPH11166061A (en) | 1999-06-22 |
| JP3567706B2 true JP3567706B2 (en) | 2004-09-22 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33278097A Expired - Fee Related JP3567706B2 (en) | 1997-12-03 | 1997-12-03 | Biaxially oriented polystyrene resin sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3567706B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100542800C (en) | 2002-02-20 | 2009-09-23 | 旭迪爱生株式会社 | Antifog plastic resin sheet material hot in nature and formed products |
| JP4753417B2 (en) * | 2005-07-26 | 2011-08-24 | 竹本油脂株式会社 | Antifogging resin sheet and antifogging molded article |
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1997
- 1997-12-03 JP JP33278097A patent/JP3567706B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11166061A (en) | 1999-06-22 |
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