JP6461531B2 - Vinyl chloride resin composition - Google Patents
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Description
本発明は、塩化ビニル系樹脂組成物に関する。更に詳しくは、成形性、及び耐ブリード性に優れ、かつ食品衛生法に基づく食品、添加物等の規格基準昭和５７年厚生省告示２０号に定める蒸発残留物試験法にて測定したｎ−ヘプタン抽出量（以下、「ヘプタン抽出量」と略すことがある。）が少なく、そのため食品関連製品、特に食品と直接接する製品の材料として、好適に用いることのできる塩化ビニル系樹脂組成物に関する。
The present invention relates to a vinyl chloride resin composition. More specifically, n-heptane extraction, which is excellent in moldability and bleed resistance, and measured by the evaporation residue test method stipulated in the Ministry of Health and Welfare Notification No. 20 of the standard for food and additives based on the Food Sanitation Act The present invention relates to a vinyl chloride resin composition that has a small amount (hereinafter sometimes abbreviated as “heptane extraction amount”) and can be suitably used as a material for food-related products, particularly products that come into direct contact with food.
従来から、食品関連製品、特に精肉、鮮魚、及び青果などの生鮮食品と直接接する製品の材料としては、透明性、柔軟性、及びヒートシール性に優れていることから、塩化ビニル系樹脂、アジピン酸エステル系可塑剤、及びエポキシ化植物油を含む塩化ビニル系樹脂組成物が広く用いられている。 Conventionally, as a material for food-related products, especially products that come in direct contact with fresh food such as meat, fresh fish, and fruits and vegetables, it has excellent transparency, flexibility, and heat sealability. A vinyl chloride resin composition containing an acid ester plasticizer and an epoxidized vegetable oil is widely used.
食品と直接接する製品は、衛生性、安全性、及び食品等への非移行性が、重要である。そのため食品と直接接する製品の材料には、その原材料として、米国のＦＤＡ規格（Ｆｏｏｄ ａｎｄ Ｄｒｕｇ Ａｄｍｉｎｉｓｔｒａｔｉｏｎ）や日本のＰＬ規格（塩化ビニル樹脂製包装容器包装等に関する自主規制基準）等に記載された物質を用いることが求められている。また昭和５７年厚生省告示２０号は、油脂、及び脂肪性食品の疑似抽出溶媒としてｎ−ヘプタンを用いた蒸発残留物試験を定め、これが少量であることを求めている。 For products that are in direct contact with food, hygiene, safety, and non-migration to food are important. For this reason, as materials for products that come into direct contact with food, substances listed in the US FDA standards (Food and Drug Administration), Japanese PL standards (voluntary regulations concerning packaging containers and packaging made of vinyl chloride resin, etc.), etc. Is required to be used. In addition, Ministry of Health and Welfare Notification No. 20 in 1982 established an evaporation residue test using n-heptane as a pseudo-extraction solvent for fats and oils and fatty foods, and requires that this be a small amount.
近年、プラスチック材料、及びその添加剤の安全性に対する関心の高まりから、食品と直接接する製品の材料には、ヘプタン抽出量が少ないこと（材料中の成分が食品等へ移行しないこと）、及び用いられる原材料そのものの安全性が極めて高いことが求められている。 In recent years, because of increasing interest in the safety of plastic materials and their additives, the amount of heptane extracted from the materials of products that come into direct contact with food is low (the ingredients in the material do not migrate to food, etc.) and use The raw materials themselves are required to be extremely safe.
そこで、「１，２−シクロヘキサンジカルボン酸若しくはその無水物と、炭素数９の分岐鎖のアルコールを必須成分とする炭素数４〜１３の脂肪族一価混合アルコールとをエステル化反応して得られる１，２−シクロヘキサンジカルボン酸ジエステルであって、前記脂肪族一価混合アルコール中の炭素数９の分岐鎖のアルコールの含有率が７０〜９７重量％であり、炭素数９の分岐鎖のアルコール以外のアルコールの含有率が３〜３０重量％であることを特徴とする１，２−シクロヘキサンジカルボン酸ジエステルを含む塩化ビニル系樹脂用可塑剤。」を用いることが提案されている（特許文献１）。しかし、成形性、及び耐ブリードに優れ、かつヘプタン抽出量の少ない塩化ビニル系樹脂組成物を得ることはできなかった。
Therefore, “obtained by esterification of 1,2-cyclohexanedicarboxylic acid or its anhydride and an aliphatic monohydric mixed alcohol having 4 to 13 carbon atoms containing a branched alcohol having 9 carbon atoms as an essential component. 1,2-cyclohexanedicarboxylic acid diester, the content of the branched alcohol having 9 carbon atoms in the aliphatic monohydric mixed alcohol is 70 to 97% by weight, other than the branched alcohol having 9 carbon atoms It has been proposed to use a plasticizer for vinyl chloride resin containing 1,2-cyclohexanedicarboxylic acid diester characterized in that the content of alcohol is 3 to 30% by weight (Patent Document 1). . However, a vinyl chloride resin composition having excellent moldability and bleed resistance and having a small amount of heptane extraction could not be obtained.
本発明の課題は、成形性、及び耐ブリードに優れ、かつヘプタン抽出量が少なく、そのため食品関連製品、特に食品と直接接する製品の材料として、好適に用いることのできる塩化ビニル系樹脂組成物を提供することにある。
An object of the present invention is to provide a vinyl chloride resin composition that is excellent in moldability and bleed resistance and has a small amount of heptane extraction, and therefore can be suitably used as a material for food-related products, particularly products that are in direct contact with food. It is to provide.
本発明者は、鋭意研究した結果、特定の可塑剤を含む塩化ビニル系樹脂組成物により、上記課題を達成できることを見出した。 As a result of intensive studies, the present inventor has found that the above problems can be achieved by a vinyl chloride resin composition containing a specific plasticizer.
すなわち、本発明は、
成分（ａ）塩化ビニル系樹脂 １００質量部；及び
成分（ｂ）ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステルを水素添加して得られるシス異性体９０〜１００モル％、トランス異性体１０〜０モル％のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル １５〜１５０質量部；
を含む食品関連製品用塩化ビニル系樹脂組成物である。
That is, the present invention
Component (a) vinyl chloride resin 100 parts by mass; and component (b) casNo. Cycloisomer-1,2-dicarboxylic acid di (isononyl) ester 15 to 90 mol% obtained by hydrogenation of 28553-12-0 phthalic acid diisononyl ester 90 to 100 mol%, trans isomer 10 to 0 mol% 150 parts by weight;
A vinyl chloride resin composition for food-related products containing
第２の発明は、上記食品関連製品が、食品と直接接する製品であることを特徴とする第１の発明に記載の樹脂組成物である。 A second invention is the resin composition according to the first invention, wherein the food-related product is a product that is in direct contact with food.
第３の発明は、第１の発明又は第２の発明に記載の樹脂組成物を含む食品関連製品である。
A third invention is a food-related product including the resin composition according to the first invention or the second invention.
本発明の塩化ビニル系樹脂組成物は、成形性、及び耐ブリードに優れ、かつヘプタン抽出量が少ない。そのため食品関連製品、特に食品と直接接する製品、中でも油脂や脂肪を多く含む食品、例えば、ソーセージ、ベーコン、ハム、バター、マーガリン、獣肉、魚肉、鶏肉、食用油、及び飲料水（水、ジュースなど）などの食品と直接接する製品、例えば、包装用フィルム、包装用チューブ、収納瓶、獣肉等の搬送／加工用装置の搬送ベルト等、錠剤やカプセルの包装用シート、各種食品や飲料水等のデリバリー用ホース、食品を取り扱う手袋、食品用液体収納タンク、及びハンディポンプなどの製品の材料として、好適に用いることができる。
The vinyl chloride resin composition of the present invention is excellent in moldability and bleed resistance and has a small amount of heptane extraction. Therefore, food-related products, especially products that are in direct contact with food, especially foods rich in fats and fats, such as sausage, bacon, ham, butter, margarine, animal meat, fish, chicken, edible oil, and drinking water (water, juice, etc.) ) And other products that are in direct contact with food, such as packaging films, packaging tubes, storage bottles, transport belts for equipment for transporting and processing meat, etc., tablets and capsule packaging sheets, various foods and drinking water, etc. It can be suitably used as a material for products such as a delivery hose, gloves for handling food, a liquid storage tank for food, and a handy pump.
成分（ａ）「塩化ビニル樹脂」（必須成分）：
本発明の成分（ａ）として用いる塩化ビニル系樹脂は、−ＣＨ２−ＣＨＣｌ−で表される基を有する全ての重合体を指し、塩化ビニルの単独重合体；塩化ビニル・酢酸ビニル共重合体、塩化ビニル・（メタ）アクリル酸共重合体、塩化ビニル・（メタ）アクリル酸メチル共重合体、塩化ビニル・（メタ）アクリル酸エチル共重合体、塩化ビニル・マレイン酸エステル共重合体、塩化ビニル・エチレン共重合体、塩化ビニル・プロピレン共重合体、塩化ビニル・スチレン共重合体、塩化ビニル・イソブチレン共重合体、塩化ビニル・塩化ビニリデン共重合体、塩化ビニル・スチレン・無水マレイン酸三元共重合体、塩化ビニル・スチレン・アクリロニトリル三元共重合体、塩化ビニル・ブタジエン共重合体、塩化ビニル・イソプレン共重合体、塩化ビニル・塩素化プロピレン共重合体、塩化ビニル・塩化ビニリデン・酢酸ビニル三元共重合体、塩化ビニル・アクリロニトリル共重合体、塩化ビニル・各種ビニルエーテル共重合体等の塩化ビニルと塩化ビニルと共重合可能な他のモノマーとの共重合体；後塩素化ビニル共重合体等の塩化ビニル単独重合体や塩化ビニル系共重合体を改質したもの；さらには塩素化ポリエチレン等の構造上塩化ビニル樹脂と類似の塩素化ポリオレフィンを包含する。
Component (a) “vinyl chloride resin” (essential component):
The vinyl chloride resin used as component (a) of the present invention refers to all polymers having a group represented by —CH 2 —CHCl—, a vinyl chloride homopolymer; a vinyl chloride / vinyl acetate copolymer. , Vinyl chloride / (meth) acrylic acid copolymer, vinyl chloride / (meth) methyl acrylate copolymer, vinyl chloride / (meth) ethyl acrylate copolymer, vinyl chloride / maleic acid ester copolymer, chloride Vinyl / ethylene copolymer, vinyl chloride / propylene copolymer, vinyl chloride / styrene copolymer, vinyl chloride / isobutylene copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / styrene / maleic anhydride ternary Copolymer, vinyl chloride / styrene / acrylonitrile terpolymer, vinyl chloride / butadiene copolymer, vinyl chloride / isoprene copolymer Copolymerized with vinyl chloride and vinyl chloride, such as vinyl chloride / chlorinated propylene copolymer, vinyl chloride / vinylidene chloride / vinyl acetate terpolymer, vinyl chloride / acrylonitrile copolymer, vinyl chloride / various vinyl ether copolymers, etc. Copolymers with other possible monomers; Post-chlorinated vinyl copolymers and other vinyl chloride homopolymers and modified vinyl chloride copolymers; and structurally vinyl chloride resins such as chlorinated polyethylene And similar chlorinated polyolefins.
上記成分（ａ）は、成形性、耐ブリード性、及びヘプタン抽出量の観点から、数平均重合度が、好ましくは３００〜７０００、より好ましくは１０００〜２５００である。 The number average polymerization degree of the component (a) is preferably 300 to 7000, more preferably 1000 to 2500 from the viewpoints of moldability, bleed resistance, and heptane extraction amount.
上記成分（ａ）としては、これらの塩化ビニル系樹脂の１種又は２種以上の混合物を用いることができる。 As the component (a), one or a mixture of two or more of these vinyl chloride resins can be used.
成分（ｂ）「ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステルを水素添加して得られるシス異性体９０〜１００モル％、トランス異性体１０〜０モル％のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル」（必須成分）：
本発明の塩化ビニル系樹脂組成物は、成分（ｂ）ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステル（以下、ＤＩＮＰと略すことがある。）を水素添加して得られるシス異性体９０〜１００モル％、トランス異性体１０〜０モル％のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステルを含む。上記成分（ｂ）が、ＤＩＮＰを水素添加して得られるものであるため、本発明の樹脂組成物は、成形性、及び耐ブリード性に優れ、かつヘプタン抽出量の少ない樹脂組成物になる。
Component (b) “cyclohexane-1,2-dicarboxylic acid having 90 to 100 mol% of cis isomer and 10 to 0 mol% of trans isomer obtained by hydrogenation of diisononyl phthalate of cas No. 28553-12-0 Di (isononyl) ester "(essential component):
The vinyl chloride resin composition of the present invention comprises component (b) casNo. 28553-12-0 phthalic acid diisononyl ester (hereinafter sometimes abbreviated as DINP) obtained by hydrogenation of 90 to 100 mol% of cis isomer, 10 to 0 mol% of cyclohexane-1, 2-dicarboxylic acid di (isononyl) ester. Since the component (b) is obtained by hydrogenating DINP, the resin composition of the present invention is excellent in moldability and bleed resistance and becomes a resin composition with a small amount of heptane extraction.
上記ＤＩＮＰとしては、特に制限されず、公知の方法で合成されたＤＩＮＰを用いることができる。 The DINP is not particularly limited, and DINP synthesized by a known method can be used.
上記成分（ｂ）は、シス異性体９０〜１００モル％と、トランス異性体１０〜０モル％との混和物である。そのため成形性、及び耐ブリード性に優れ、かつヘプタン抽出量の極めて少ない樹脂組成物を得ることができる。好ましくは、シス異性体９５〜１００モル％と、トランス異性体５〜０モル％との混和物である。ここでシス異性体とトランス異性体との和は１００モル％である。 The component (b) is a mixture of 90 to 100 mol% of cis isomer and 10 to 0 mol% of trans isomer. Therefore, it is possible to obtain a resin composition that is excellent in moldability and bleed resistance and has a very small amount of heptane extraction. A mixture of 95 to 100 mol% of cis isomer and 5 to 0 mol% of trans isomer is preferable. Here, the sum of the cis isomer and the trans isomer is 100 mol%.
上記シス異性体と、トランス異性体との混和物は、ＤＩＮＰを公知の方法（例えば、特表２０１３−５１３４７７号公報に記載された技術。）で水素添加することにより得ることができる。 The mixture of the cis isomer and the trans isomer can be obtained by hydrogenating DINP by a known method (for example, a technique described in JP 2013-513477 A).
上記成分（ｂ）のシス異性体とトランス異性体との比率は、プロトンの核磁気共鳴スペクトル（以下、１Ｈ−ＮＭＲと略すことがある。）により求めることができる。ジアルキルヘキサヒドロフタレートのメチンのプロトンは２．５〜３．０ｐｐｍにシグナルが現れ、該シグナルのうち２．７〜３．０ｐｐｍはシス異性体に、２．５〜２．７ｐｐｍはトランス異性体に帰属される。従って、シス異性体の比率は２．５〜３．０ｐｐｍの積分面積に対する２．７〜３．０ｐｐｍの積分面積として、トランス異性体の比率は２．５〜３．０ｐｐｍの積分面積に対する２．５〜２．７ｐｐｍの積分面積として、求めることができる。１Ｈ−ＮＭＲの測定は、例えば、特表２００５−５０４１１９号公報などを参照して行うことができる。また株式会社三井化学分析センターなどに測定を依頼して行うこともできる。 The ratio of the cis isomer to the trans isomer of the component (b) can be determined from a nuclear magnetic resonance spectrum of proton (hereinafter sometimes abbreviated as 1 H-NMR). The methine proton of dialkyl hexahydrophthalate shows a signal at 2.5-3.0 ppm, of which 2.7-3.0 ppm is in the cis isomer and 2.5-2.7 ppm is in the trans isomer. Be attributed. Thus, the cis isomer ratio is 2.7-3.0 ppm integrated area to 2.5-3.0 ppm integrated area, and the trans isomer ratio is 2.5-3.0 ppm integrated area 2. It can be determined as an integrated area of 5 to 2.7 ppm. The measurement of 1 H-NMR can be performed with reference to, for example, JP-T-2005-504119. It can also be done by requesting measurements from Mitsui Chemical Analysis Center.
上記成分（ｂ）の配合量は、成形性、耐ブリード性、及びヘプタン抽出量の観点から、成分（ａ）１００質量部に対して、成分（ｂ）１５〜１５０質量部、好ましくは２０〜１２０質量部である。 The blending amount of the component (b) is from 15 to 150 parts by mass, preferably from 20 to 100 parts by mass with respect to 100 parts by mass of the component (a) from the viewpoints of moldability, bleed resistance, and heptane extraction amount. 120 parts by mass.
本発明の樹脂組成物には、本発明の目的に反しない限度において、上記成分（ｂ）以外の可塑剤、例えば、シス異性体とトランス異性体との比が規定範囲外のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル、ｃａｓＮｏ．６８５１５−４８−０のフタル酸ジイソノニルエステルを水素添加して得られるシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル、フタル酸エステル、トリメリット酸エステル、脂肪酸２塩基性エステル、リン酸エステル、エポキシ系可塑剤、及びポリエステル系可塑剤を１種又は２種以上含ませてもよい。 In the resin composition of the present invention, the plasticizer other than the component (b), for example, cyclohexane-1, whose ratio of cis isomer to trans isomer is outside the specified range, is not limited to the object of the present invention. 2-dicarboxylic acid di (isononyl) ester, casNo. Cyclohexane-1,2-dicarboxylic acid di (isononyl) ester, phthalic acid ester, trimellitic acid ester, fatty acid dibasic ester, phosphoric acid ester obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester, One or more epoxy plasticizers and polyester plasticizers may be included.
本発明の樹脂組成物には、塩化ビニル系樹脂及びその樹脂組成物に通常用いられる安定剤を、更に含ませることができる。上記安定剤としては、例えば、有機スズ化合物系、バリウム−亜鉛系、カルシウム−亜鉛系、及び鉛系の安定剤などをあげることができる。これらの中で、環境問題の観点から、有機スズ化合物系、バリウム−亜鉛系、及びカルシウム−亜鉛系の安定剤が好ましい。安定剤としては、これらの１種、又は２種以上の混合物を用いることができる。安定剤の配合量は、上記成分（ａ）１００質量部に対して、０．１〜１０質量部が好ましい。 The resin composition of the present invention may further contain a vinyl chloride resin and a stabilizer usually used for the resin composition. Examples of the stabilizer include organotin compound-based, barium-zinc-based, calcium-zinc-based, and lead-based stabilizers. Among these, from the viewpoint of environmental problems, organotin compound-based, barium-zinc-based, and calcium-zinc-based stabilizers are preferable. As a stabilizer, these 1 type, or 2 or more types of mixtures can be used. As for the compounding quantity of a stabilizer, 0.1-10 mass parts is preferable with respect to 100 mass parts of said components (a).
本発明の樹脂組成物には、各種金属セッケン、脂肪酸、及びポリエチレンワックスなどの滑剤を、更に含ませることができる。滑剤の配合量は、上記成分（ａ）１００質量部に対して、０．１〜１０質量部が好ましい。 The resin composition of the present invention may further contain various metal soaps, fatty acids, and lubricants such as polyethylene wax. The blending amount of the lubricant is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (a).
本発明の樹脂組成物には、本発明の目的に反しない限度において、所望により、塩化ビニル系樹脂及びその樹脂組成物に通常用いられる各種添加剤（例えば、熱安定剤、充填剤、滑剤、発泡剤、顔料、紫外線吸収剤など。）や各種充填材（例えば、炭酸カルシウム、クレー、タルクなど。）を更に含ませることができる。 In the resin composition of the present invention, the vinyl chloride resin and various additives usually used in the resin composition (for example, heat stabilizer, filler, lubricant, Foaming agents, pigments, ultraviolet absorbers, etc.) and various fillers (for example, calcium carbonate, clay, talc, etc.) can be further included.
本発明の樹脂組成物は、上記成分（ａ）、上記成分（ｂ）、及び所望に応じて用いる任意成分を、任意の溶融混練機（例えば、単軸押出機、二軸押出機、ロール、ミキサー、及び各種のニーダーなど。）を使用して溶融混練することにより得ることができる。好ましくは加圧ニーダーを用い、樹脂温度１５０〜１８０℃で溶融混練することにより得ることができる。
In the resin composition of the present invention, the above component (a), the above component (b), and an optional component used as desired can be mixed with any melt kneader (for example, a single screw extruder, a twin screw extruder, a roll, It can be obtained by melt-kneading using a mixer and various kneaders. Preferably, it can be obtained by melt kneading at a resin temperature of 150 to 180 ° C. using a pressure kneader.
以下、本発明を実施例により説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.
使用した原材料
成分（ａ）：
（ａ−１）数平均重合度Ｐ＝１０５０の塩化ビニル単独重合体。
（ａ−２）数平均重合度Ｐ＝１４００の塩化ビニル単独重合体。
（ａ−３）数平均重合度Ｐ＝１７００の塩化ビニル単独重合体。
（ａ−４）数平均重合度Ｐ＝２０００の塩化ビニル単独重合体。
（ａ−５）数平均重合度Ｐ＝２５００の塩化ビニル単独重合体。
Raw materials used Component (a):
(A-1) A vinyl chloride homopolymer having a number average degree of polymerization P = 1050.
(A-2) Vinyl chloride homopolymer having a number average degree of polymerization P = 1400.
(A-3) Vinyl chloride homopolymer having a number average polymerization degree P = 1700.
(A-4) A vinyl chloride homopolymer having a number average polymerization degree P = 2000.
(A-5) A vinyl chloride homopolymer having a number average degree of polymerization P = 2500.
成分（ｂ）：
（ｂ−１）ＤＩＮＰを水素添加して得られるシス異性体９２モル％、トランス異性体８モル％のジイソノニルシクロヘキサン−１，２−ジカルボキシレート可塑剤。
（ｂ−２）ＤＩＮＰを水素添加して得られるシス異性体１００モル％、トランス異性体０モル％のジイソノニルシクロヘキサン−１，２−ジカルボキシレート可塑剤。
Component (b):
(B-1) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 92 mol% of cis isomer and 8 mol% of trans isomer obtained by hydrogenating DINP.
(B-2) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 100 mol% of cis isomer and 0 mol% of trans isomer obtained by hydrogenating DINP.
比較成分（ｂ’）：
（ｂ’−１）ＤＩＮＰを水素添加して得られるシス異性体８５モル％、トランス異性体１５モル％のジイソノニルシクロヘキサン−１，２−ジカルボキシレート可塑剤。
（ｂ’−２）ｃａｓＮｏ．６８５１５−４８−０のフタル酸ジイソノニルエステルを水素添加して得られるシス異性体９５モル％、トランス異性体５モル％のジイソノニルシクロヘキサン−１，２−ジカルボキシレート可塑剤。
Comparative component (b ′):
(B′-1) A diisononylcyclohexane-1,2-dicarboxylate plasticizer having 85 mol% of cis isomer and 15 mol% of trans isomer obtained by hydrogenating DINP.
(B′-2) casNo. A diisononylcyclohexane-1,2-dicarboxylate plasticizer containing 95 mol% of cis isomer and 5 mol% of trans isomer obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester.
任意成分（Ｃ）：
（Ｃ−１）株式会社ＡＤＥＫＡのジオクチル錫メルカプト系安定剤「アデカスタブ４６５（商品名）」。
（Ｃ−２）株式会社ＡＤＥＫＡのバリウム−亜鉛系複合安定性。
（Ｃ−３）三井化学株式会社のポリエチレンワックス系滑剤「ハイワックス４２０２Ｅ（商品名）」。
Optional component (C):
(C-1) Dioctyl tin mercapto stabilizer “ADEKA STAB 465 (trade name)” by ADEKA Corporation.
(C-2) Barium-zinc composite stability of ADEKA Corporation.
(C-3) Polyethylene wax lubricant “High Wax 4202E (trade name)” manufactured by Mitsui Chemicals, Inc.
試験方法
（１）押出フィルム製膜性：
４０ｍｍφの単軸押出機、ダイ幅５００ｍｍのＴダイ、及び引巻取装置を備える装置を使用し、ダイス出口樹脂温度２００℃の条件で、厚み１０μｍのフィルムを製膜した。該フィルムの外観を目視観察し、以下の基準で評価した。
〇：透明性良好。色調問題なし。ブツなし。
△：透明性やや劣る。色調やや赤みがかっている。ブツあり。
×：透明性劣る。色調赤く焼けている。ブツ多い
Test Method (1) Extruded Film Formability:
Using a 40 mmφ single-screw extruder, a T die having a die width of 500 mm, and an apparatus equipped with a winding device, a film having a thickness of 10 μm was formed under the conditions of a die outlet resin temperature of 200 ° C. The appearance of the film was visually observed and evaluated according to the following criteria.
○: Excellent transparency. No color problem. No stuff.
Δ: Transparency is slightly inferior. The color is slightly reddish. There are stuff.
X: Inferior in transparency. The color is burnt red. Many
（２）耐ブリード性：
上記で得られたフィルムを１０ｃｍ×１０ｃｍの大きさに裁断し、温度７０℃、相対湿度９５％の環境下に７日間曝した後、フィルムの表面を目視観察し、以下の基準で評価した。
〇：試験前と変化なし。
△：試験前と比較してフィルム表面に若干の曇り感がある。しかし可塑剤等のブリードアウトは認められない。
×：可塑剤等のブリードアウトが認められる。
(2) Bleed resistance:
The film obtained above was cut into a size of 10 cm × 10 cm and exposed to an environment of 70 ° C. and 95% relative humidity for 7 days, and then the surface of the film was visually observed and evaluated according to the following criteria.
○: No change from before test.
Δ: There is a slight cloudiness on the film surface as compared to before the test. However, bleed-out of plasticizers is not recognized.
X: Bleed out such as plasticizer is recognized.
（３）ヘプタン抽出量：
上記で得られたフィルムを４５ｍｍ×８５ｍｍの大きさに裁断したものを２枚用意して、昭和５７年厚生省告示２０号に定める蒸発残留物試験法に従い、ｎ−ヘプタン抽出量を測定した。得られたヘプタン抽出量から、以下の基準で評価した。
○：ヘプタン抽出量が１５０ｐｐｍ未満である。
×：ヘプタン抽出量が１５０ｐｐｍ以上である。
(3) Heptane extraction amount:
Two pieces of the film obtained above cut to 45 mm × 85 mm were prepared, and the amount of n-heptane extracted was measured according to the evaporation residue test method defined in Ministry of Health and Welfare Notification No. 20 in 1982. The obtained heptane extract amount was evaluated according to the following criteria.
○: The amount of heptane extracted is less than 150 ppm.
X: The heptane extraction amount is 150 ppm or more.
実施例１〜１２、比較例１〜２
表１又は２に示す量（質量部）の成分を、加圧ニーダーを使用して排出時樹脂温度１６０℃の条件で溶融混練し、塩化ビニル樹脂組成物を得た。上記（１）〜（３）の評価を行った。結果を表１又は２に示す。
Examples 1-12, Comparative Examples 1-2
The components (parts by mass) shown in Table 1 or 2 were melt-kneaded using a pressure kneader at a resin temperature at discharge of 160 ° C. to obtain a vinyl chloride resin composition. The above evaluations (1) to (3) were performed. The results are shown in Table 1 or 2.
本発明の塩化ビニル樹脂組成物は、成形性、及び耐ブリード性に優れ、かつ昭和５７年厚生省告示２０号に定める蒸発残留物試験法にて測定したｎ−ヘプタン抽出量が１５０ｐｐｍ未満である。 The vinyl chloride resin composition of the present invention is excellent in moldability and bleed resistance, and has an n-heptane extract of less than 150 ppm as measured by the evaporation residue test method defined in Ministry of Health and Welfare Notification No. 20 in 1982.
一方、成分（ｂ）の替わりに、シス／トランス比が規定範囲外の可塑剤を用いた比較例１は、成形性、及び耐ブリード性に劣る。成分（ｂ）（ＤＩＮＰ（ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステル）を水素添加して得た可塑剤）の替わりに、ｃａｓＮｏ．６８５１５−４８−０のフタル酸ジイソノニルエステルを水素添加して得た可塑剤を用いた比較例２は、成形性、及び耐ブリード性に劣る。 On the other hand, Comparative Example 1 using a plasticizer having a cis / trans ratio outside the specified range instead of the component (b) is inferior in moldability and bleed resistance. Instead of component (b) (a plasticizer obtained by hydrogenating DINP (casino diesteronyl phthalate of cas No. 28553-12-0)), casNo. Comparative Example 2 using a plasticizer obtained by hydrogenating 68515-48-0 phthalic acid diisononyl ester is inferior in moldability and bleed resistance.
Claims (6)
成分（ｂ）ｃａｓＮｏ．２８５５３−１２−０のフタル酸ジイソノニルエステルを水素添加して得られるシス異性体９０〜１００モル％、トランス異性体１０〜０モル％のシクロヘキサン−１，２−ジカルボン酸ジ（イソノニル）エステル １５〜１５０質量部；
を含む食品関連製品用塩化ビニル系樹脂組成物。
ここで上記食品関連製品は食品と直接接する製品である。
Component (a) vinyl chloride resin 100 parts by mass; and component (b) casNo. Cycloisomer-1,2-dicarboxylic acid di (isononyl) ester 15 to 90 mol% obtained by hydrogenation of 28553-12-0 phthalic acid diisononyl ester 90 to 100 mol%, trans isomer 10 to 0 mol% 150 parts by weight;
A vinyl chloride resin composition for food-related products comprising
Here, the food-related product is a product in direct contact with food.
Furthermore, the resin composition of Claim 1 which contains 0.1-10 mass parts with respect to 100 mass parts of said component (a) vinyl chloride-type resin for a stabilizer.
The resin composition according to claim 1 or 2 , wherein the food-related product is a product that is in direct contact with foods rich in fats or fats.
The food related product containing the resin composition of any one of Claims 1-3 .
The food-related product according to claim 4, wherein the food-related product is a product in direct contact with a food containing a large amount of fat or fat.
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| DE10146848A1 (en) * | 2001-09-24 | 2003-04-24 | Oxeno Olefinchemie Gmbh | Mixture of alicyclic polycarboxylic acid esters with a high cis content |
| DE102005028752A1 (en) * | 2005-06-22 | 2007-01-04 | Oxeno Olefinchemie Gmbh | Mixture of diisononyl esters of 1,2-cyclohexanedicarboxylic acid, process for their preparation and use of these mixtures |
| JP2007262267A (en) * | 2006-03-29 | 2007-10-11 | Mitsubishi Plastics Ind Ltd | Vinyl chloride-based resin composition and stretch film |
| JP5128508B2 (en) * | 2008-05-14 | 2013-01-23 | 株式会社日本化学研究所 | Vinyl chloride plastisol composition and bottle cap for food and drink |
| MY151975A (en) * | 2008-12-05 | 2014-07-31 | Basf Se | Cyclohexane polycarboxylic acid derivatives as plasticizers for adhesives and sealants |
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| JP2012025851A (en) * | 2010-07-23 | 2012-02-09 | Dic Corp | Plasticizer for vinyl chloride resin, vinyl chloride resin composition using the same, and stretch film for packaging food |
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