JPH0336056B2 - - Google Patents
Info
- Publication number
- JPH0336056B2 JPH0336056B2 JP59010553A JP1055384A JPH0336056B2 JP H0336056 B2 JPH0336056 B2 JP H0336056B2 JP 59010553 A JP59010553 A JP 59010553A JP 1055384 A JP1055384 A JP 1055384A JP H0336056 B2 JPH0336056 B2 JP H0336056B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- hot water
- film
- stabilizer
- 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
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 10
- 239000004800 polyvinyl chloride Substances 0.000 claims description 10
- 230000002087 whitening effect Effects 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 238000002372 labelling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004609 Impact Modifier Substances 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- MXJJJAKXVVAHKI-WRBBJXAJSA-N (9z,29z)-octatriaconta-9,29-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O MXJJJAKXVVAHKI-WRBBJXAJSA-N 0.000 description 1
- 229920006257 Heat-shrinkable film Polymers 0.000 description 1
- YSCDKUPSJMMGGT-UHFFFAOYSA-L [dibutyl-[2-(6-methylheptylsulfanyl)acetyl]oxystannyl] 2-(6-methylheptylsulfanyl)acetate Chemical compound CC(C)CCCCCSCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CSCCCCCC(C)C YSCDKUPSJMMGGT-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- -1 dialkyl tin malate Chemical compound 0.000 description 1
- FFGHLLOLFQHABK-UHFFFAOYSA-L dibutyltin(2+);dodecane-1-thiolate Chemical compound CCCCCCCCCCCCS[Sn](CCCC)(CCCC)SCCCCCCCCCCCC FFGHLLOLFQHABK-UHFFFAOYSA-L 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、熱水処理等により温水白化しにくい
ラベル用ポリ塩化ビニル延伸フイルムに関する。
従来、熱収縮性ラベルとして、横一軸延伸され
たポリ塩化ビニルフイルム（以下「PVCフイル
ム」という。）を筒状に製袋したものがガラス容
器や各種合成樹脂製の容器に使用されている。通
常、上記PVCフイルムを容器に被覆し、熱収縮
ラベリングを行つた後、容器に内容物を充填する
ことがなされる。内容物が果汁等の高温殺菌処理
を必要とする場合、充填後容器全体に熱水を掛け
て殺菌処理を施すが、熱水のために、被覆した
PVCフイルムが白化（温水白化）し、商品価値
が著しく低下することがある。
本発明は、特定の配合組成によつて、上記問題
点を解消できるPVCフイルムを見出したもので
あり、その要旨とするところは、ポリ塩化ビニル
樹脂100重量部にCl-含有率が100ppm以下のMBS
樹脂３〜20重量部、含硫黄錫系安定剤１〜５重量
部及びエチレンビス脂肪酸アマイド0.1〜１重量
部を含有してなるシートを一軸方向に延伸した温
水白化しにくい熱収縮性ラベル用フイルムにあ
る。
本発明に使用するポリ塩化ビニル樹脂として
は、塩化ニル単独重合体のほか、塩化ビニルと酢
酸ビニル等の塩化ビニルと共重合可能なモノマー
との共重合体が含まれる。
本発明においては、このポリ塩化ビニル樹脂に
特定組成の衝撃改良剤、錫系安定剤及び滑剤を配
合する必要がある。上記衝撃改良剤はCl-含有率
が100ppm以下のMBS樹脂を使用することが必要
である。このCl-は、MBS樹脂製造時に使用され
る乳化剤を塩析するための塩が残留したものであ
つて、この数値が、100ppmを越すものは温水白
化しやすい。また、上記MBS樹脂の添加部数は
３〜20重量部の範囲とする。３重量部未満ではフ
イルムの衝撃強度が弱いため破断等が発生しやす
く、逆に20重量部を越すものは、衝撃改良効果が
余りなく、コスト的に不都合である。
錫系安定剤としては含硫黄錫系安定剤を使用す
る。硫黄を含有しない錫系安定剤、例えば、ジア
ルキル錫マレート等を使用した場合、熱安定性は
問題ないが、温水白化しやすい欠点がある。
本発明の含硫黄錫系安定剤としては、例えば、
ギブチル錫ビス（イソオクチルメルカプトアセテ
ート）、ジブチル錫ビス（ラウリルメルカプタイ
ド）等が挙げられる。
上記安定剤の添加部数は１〜５重量部の範囲と
する。１重量部未満では、熱安定性が悪く、逆に
５重量部を越すものは、熱安定性改良効果が余り
なく、コスト的に不都合である。
滑剤としては、エチレンビス脂肪酸アマイドを
使用する。具体的には、エチレンビスオレイン酸
アマイド、エチレンビスステアリン酸アマイド等
が挙げられる。添加部数は、0.1〜１重量部の範
囲とする。0.1重量部未満では、滑性効果がない
ため、押出成形性が悪く、１重量部を越すものは
温水白化しやすくなる。
なお、上記以外の添加剤につき、必要に応じて
可塑剤、紫外線吸収剤、安定助剤等を温水白化を
生じない添加部数で使用してもよい。
本発明のフイルムは、上述した組成物を押出成
形法等によりフイルム状に成形し、これを主とし
て一軸方向に延伸を行つて得られる。延伸倍率は
主方向延伸倍率1.3倍以上で行う。主方向と直交
する方向にわずか（1.1〜1.2倍程度）に延伸して
もよい。
以下、実施例により本発明を説明する。
実施例
共通配合
PVC（＝820） 100重量部
MBS（Cl-含有率30ppm） 10 〃
可塑剤（DOP） 10 〃
上記共通配合に表−１に示した安定剤及び滑剤
を加えた各組成物を押出成形機により押出後、縦
方向に1.2倍延伸後、横方向に2.5倍延伸して厚さ
50μのフイルムを得た。得られた各フイルムを80
℃の温水中に緊張状態で１時間浸漬後、ヘーズメ
ーターでヘーズを測定した。測定結果を表−１に
示した。
The present invention relates to a stretched polyvinyl chloride film for labels that is resistant to hot water whitening due to hot water treatment or the like. BACKGROUND ART Traditionally, heat-shrinkable labels made from polyvinyl chloride film (hereinafter referred to as "PVC film") that has been uniaxially stretched horizontally and made into cylindrical bags have been used for glass containers and containers made of various synthetic resins. Usually, a container is covered with the above-mentioned PVC film and heat-shrinkable labeling is performed, and then the container is filled with the contents. If the contents require high-temperature sterilization, such as fruit juice, the entire container is sterilized by pouring hot water over it after filling.
PVC film may whiten (hot water whitening) and its commercial value may decrease significantly. The present invention has discovered a PVC film that can solve the above problems by using a specific blending composition. MBS
A heat-shrinkable film for labels that is resistant to hot water whitening and is obtained by uniaxially stretching a sheet containing 3 to 20 parts by weight of a resin, 1 to 5 parts by weight of a sulfur-containing tin stabilizer, and 0.1 to 1 part by weight of ethylene bis fatty acid amide. It is in. The polyvinyl chloride resin used in the present invention includes not only a vinyl chloride homopolymer but also a copolymer of vinyl chloride and a monomer copolymerizable with vinyl chloride, such as vinyl acetate. In the present invention, it is necessary to blend a specific composition of an impact modifier, a tin-based stabilizer, and a lubricant into the polyvinyl chloride resin. For the above-mentioned impact modifier, it is necessary to use MBS resin with a Cl - content of 100 ppm or less. This Cl - is residual salt for salting out the emulsifier used in the production of MBS resin, and if this value exceeds 100 ppm, hot water whitening is likely to occur. Further, the number of parts of the MBS resin added is in the range of 3 to 20 parts by weight. If the amount is less than 3 parts by weight, the impact strength of the film is low and the film is likely to break, while if it exceeds 20 parts by weight, the impact improvement effect is not so great and it is disadvantageous in terms of cost. As the tin stabilizer, a sulfur-containing tin stabilizer is used. When a tin-based stabilizer that does not contain sulfur, such as dialkyl tin malate, is used, there is no problem in thermal stability, but there is a drawback that it is susceptible to hot water whitening. Examples of the sulfur-containing tin stabilizer of the present invention include:
Examples include dibutyltin bis(isooctylmercaptoacetate) and dibutyltinbis(lauryl mercaptide). The number of parts of the stabilizer added is in the range of 1 to 5 parts by weight. If it is less than 1 part by weight, the thermal stability is poor, and if it exceeds 5 parts by weight, the effect of improving thermal stability is not so great and it is disadvantageous in terms of cost. Ethylene bis fatty acid amide is used as the lubricant. Specifically, ethylenebisoleic acid amide, ethylenebisstearic acid amide, etc. can be mentioned. The number of parts added is in the range of 0.1 to 1 part by weight. If it is less than 0.1 part by weight, there will be no lubricity effect, resulting in poor extrusion moldability, and if it exceeds 1 part by weight, hot water whitening will occur easily. In addition, regarding additives other than those mentioned above, plasticizers, ultraviolet absorbers, stabilizing agents, etc. may be used in amounts that do not cause hot water whitening, if necessary. The film of the present invention is obtained by forming the above-mentioned composition into a film by extrusion molding or the like, and then stretching the film primarily in a uniaxial direction. The stretching ratio is 1.3 times or more in the main direction. It may be stretched slightly (about 1.1 to 1.2 times) in a direction perpendicular to the main direction. The present invention will be explained below with reference to Examples. Example Common blend PVC (=820) 100 parts by weight MBS (Cl - content 30 ppm) 10 Plasticizer (DOP) 10 Each composition was prepared by adding the stabilizer and lubricant shown in Table 1 to the above common blend. After extrusion using an extrusion molding machine, it is stretched 1.2 times in the longitudinal direction and 2.5 times in the transverse direction to obtain the thickness.
A 50μ film was obtained. Each film obtained 80
After being immersed under tension in warm water at ℃ for 1 hour, the haze was measured using a haze meter. The measurement results are shown in Table-1.
【表】
表−１から本発明のフイルムである、No.１、２
はヘーズが低く、温水白化が少ないことが判る。
ちなみに上述したヘーズの測定法における透明性
の実用上の限界は25％である。これに対し、本発
明品と滑剤が異なるNo.３及び安定剤が異なるNo.４
については、ヘーズが高く、温水白化が大である
ことが判る。[Table] From Table 1, films of the present invention, Nos. 1 and 2
It can be seen that the haze is low and there is little hot water whitening.
Incidentally, the practical limit of transparency in the haze measurement method described above is 25%. On the other hand, No. 3, which has a different lubricant from the product of the present invention, and No. 4, which has a different stabilizer.
It can be seen that the haze is high and hot water whitening is large.
Claims (1)
100ppm以下のMBS樹脂３〜20重量部、含硫黄錫
系安定剤１〜５重量部及びエチレンビス脂肪酸ア
マイド0.1〜１重量部を含有してなるシートを一
軸方向に延伸した温水白化しにくい熱収縮性ラベ
ル用フイルム。1 Cl - content in 100 parts by weight of polyvinyl chloride resin
Heat-shrinkable sheet containing 3 to 20 parts by weight of MBS resin of 100 ppm or less, 1 to 5 parts by weight of a sulfur-containing tin stabilizer, and 0.1 to 1 part by weight of ethylene bis fatty acid amide, which is uniaxially stretched to prevent whitening in hot water. Gender labeling film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59010553A JPS60155237A (en) | 1984-01-24 | 1984-01-24 | Heat-shrinkable labeling film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59010553A JPS60155237A (en) | 1984-01-24 | 1984-01-24 | Heat-shrinkable labeling film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60155237A JPS60155237A (en) | 1985-08-15 |
| JPH0336056B2 true JPH0336056B2 (en) | 1991-05-30 |
Family
ID=11753441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59010553A Granted JPS60155237A (en) | 1984-01-24 | 1984-01-24 | Heat-shrinkable labeling film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60155237A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2609031B2 (en) * | 1992-07-09 | 1997-05-14 | リンナイ株式会社 | Hot water outlet pipe |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014076717A1 (en) * | 2012-11-13 | 2014-05-22 | RESILIA S.r.l. | Use of pvc for manufacturing sterilisable containers |
| MX2019008926A (en) | 2017-02-06 | 2019-09-26 | Zeon Corp | Vinyl chloride resin composition, vinyl chloride resin molded article, and laminate. |
| CN111171471B (en) * | 2019-12-31 | 2021-12-21 | 安徽天安新材料有限公司 | PVC decorative film and production process of PVC film |
| CN111138779A (en) * | 2020-01-03 | 2020-05-12 | 上海蓝泉塑料制品有限公司 | PVC film for lamp box cloth and preparation method thereof |
-
1984
- 1984-01-24 JP JP59010553A patent/JPS60155237A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2609031B2 (en) * | 1992-07-09 | 1997-05-14 | リンナイ株式会社 | Hot water outlet pipe |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60155237A (en) | 1985-08-15 |
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