JPH0554864B2 - - Google Patents
Info
- Publication number
- JPH0554864B2 JPH0554864B2 JP62080809A JP8080987A JPH0554864B2 JP H0554864 B2 JPH0554864 B2 JP H0554864B2 JP 62080809 A JP62080809 A JP 62080809A JP 8080987 A JP8080987 A JP 8080987A JP H0554864 B2 JPH0554864 B2 JP H0554864B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- weight
- vinyl chloride
- film
- parts
- 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 - Lifetime
Links
- 229920005670 poly(ethylene-vinyl chloride) Polymers 0.000 claims description 26
- 239000003607 modifier Substances 0.000 claims description 15
- 239000011342 resin composition Substances 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000001879 gelation Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 238000003490 calendering Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 description 6
- -1 alcohol phthalate esters Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LVAGMBHLXLZJKZ-UHFFFAOYSA-N 2-o-decyl 1-o-octyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC LVAGMBHLXLZJKZ-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- MGFRKBRDZIMZGO-UHFFFAOYSA-N barium cadmium Chemical compound [Cd].[Ba] MGFRKBRDZIMZGO-UHFFFAOYSA-N 0.000 description 1
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Description
産業上の利用分野
本発明は、エチレン−塩化ビニル共重合体から
なるバンクマークのない半硬質フイルムの製造方
法に関する。
従来の技術
ポリ塩化ビニルを含む樹脂組成物をカレンダー
加工にてフイルムやシート（以下、単にフイルム
という。）に成形加工すれば、殆どの場合、得ら
れるフイルムには所謂バンクマークが存在してい
る。このバンクマークは、フイルムにおける厚み
差或いはフイルムにおけるポリ塩化ビニルや顔料
その他の添加物の不均一な分布であつて、特に、
化粧材の用途においては、重大な品質上の欠点と
されている。即ち、バンクマークは、鋼板用化粧
材においてはプレツシヤー・マーク、合板用化粧
材では艶むら、ステツカー用化粧材では艶むらの
ほか、これを透視し場合に着色の濃淡乃至むらと
して認められる。しかし、従来、かかるバンクマ
ークのないフイルムを得るための有効な手段は見
い出されていない。
発明が解決しようとする問題点
エチレン−塩化ビニル共重合体は、一般に、共
重合体中にエチレ基を有し、その内部可塑化作用
のために、ゲル化温度が低く、速やかにゲル化す
ると共に、カレンダー加工時の溶融粘度が低く、
更には、エチレ基を有するために、顔料の分散性
にもすぐれる。しかしながら、前述したような化
粧材用フルムとしては、可塑剤をエチレン−塩化
ビニル共重合体100重量部につて５〜35重量部含
有させた半硬質フイルムが要求されており、この
ように可塑剤を含有するエチレン−塩化ビニル共
重合体樹脂組成物は、溶融粘度が低すぎるため
に、ロールからの引剥し性、即ち、ロール加工性
に劣り、フイルムへの成形が困難である。
本発明者らは、上記のように、可塑剤を含有す
る半硬質エチレン−塩化ビニル共重合体樹脂フイ
ルムのカレンダー加工による製造において、ロー
ル加工性を改善すると共に、バンクマークのない
樹脂フイルムを得るために、樹脂組成物の配合に
ついて広範囲にわたる研究を行なつた結果、エチ
レン−塩化ビニル共重合体に所定の改質材及び／
又は加工助剤を配合することによつて、上記目的
を達成して、バンクマークのない半硬質エチレン
−塩化ビニル共重合体樹脂フイルムを得ることが
できることを見出して本発明に至つたものであ
る。
即ち、本発明は、エチレン−塩化ビニル共重合
体のカレンダー成形によつて、バンクマークのな
い半硬質フイルムを製造する方法を提供すること
を目的とする。
問題点を解決するための手段
本発明によるエチレン−塩化ビニル共重合体か
らなるバンクマークのない半硬質フイルムの製造
方法は、エチレン含量0.5重量％以上、平均重合
度700以上のエチレン−塩化ビニル共重合体100重
量部に可塑剤５〜35重量部と共に、エチレン−塩
化ビニル共重合体に配合することによつて、その
ゲル化速度を遅らせることなく、溶融粘度を高め
る性質を有するメタクリル酸メチルースチレン−
ブタジエン共重合体からなる改質剤３〜20重量部
を配合してなる樹脂組成物をカレンダー成形する
ことを特徴とする。
本発明において用いるエチレン−塩化ビニル共
重合体は、エチレン含量0.5重量％以上、平均重
合度700以上である。エチレン含量が0.5重量％よ
りも少ないエチレン−塩化ビニル共重合体は、ポ
リ塩化ビニルに近い性質を有し、その内部可塑化
作用が不十分であるので、樹脂組成物は高い流動
性をもたず、本発明に従つて改質剤や加工助剤を
用いても、得られるフイルムにバンクマークが発
生することが多い。他方、平均重合度が700より
も小さいエチレン−塩化ビニル共重合体の場合
も、改質剤や加工助剤を用いても、ロール加工性
を十分に改善することが困難であり、延いては、
バンクマークのない均質なフイルムを製造するこ
とが困難である。
本発明において用いる改質剤は、メタクリル酸
メチル−ブタジエン−スチレン共重合体からな
り、エチレン−塩化ビニル共重合体に配合するこ
とよつて、そのゲル化速度を遅らせることなし
に、溶融粘度を高める性質を有する改質剤であ
る。本発明においては、かかる改質剤として、例
えば、「カネエースＢ−11A」や「カネエースＢ
−22」（共に、鐘淵化学工業(株)製）が好適に用い
られる。しかし、メタクリル酸メチル−ブタジエ
ン−スチレン共重合体からなる改質剤であつて
も、例えば、「カネエースＢ−56」（鐘淵化学工業
(株)製）のように、これを配合することによつて、
エチレン−塩化ビニル共重合体のゲル化速度を遅
延させる性質を有する改質剤は、エチレン−塩化
ビニル共重合体の加工性を改善し得ても、バンク
マークの発生を防止することができない。
本発明においては、上記改質剤と共に、従来、
アクリル系加工助剤として知られている助剤を併
用してもよい。このようなアクリル系加工助剤と
しては、例えば、「メタブレンＰ−530」や「メタ
ブレンＰ−551」（共に、三菱レーヨン(株)製）や、
「カネエースPA−20」（鐘淵化学工業(株)製）を挙
げることができる。
エチレン−塩化ビニル共重合体のロール加工性
を改善すると共に、バンクマークのないフイルム
を得るために、上記改質剤は、エチレン−塩化ビ
ニル共重合体100重量部に対して３〜20重量部、
好ましくは５〜15重量部の範囲で用いられる。
本発明において用いる樹脂組成物は、化粧材用
の半硬質エチレン−塩化ビニル共重合体樹脂フイ
ルムの製造に好適であり、かかる用途のための樹
脂組成物は、エチレン−塩化ビニル共重合体100
重量部に対して、可塑剤３〜35重量部を含有す
る。用いる可塑剤は、特に限定されるものではな
く、従来よりポリ塩化ビニル系樹脂のフイルムの
製造に用いられる任意の可塑剤を用いることがで
きる。従つて、かかる可塑剤としては、例えば、
フタル酸ジブチル、フタル酸ジヘキシル、フタル
酸ジオクチル、フタル酸ジ−２−エチルヘキシ
ル、フタル酸オクチルデシル、フタル酸ジイソデ
シル、フタル酸ブチルベンジルや、高級アルコー
ルフタル酸エステル等のフタル酸エステル系、ト
リメリト酸トリ−２−エチルヘキシル等のトリメ
リト酸エステル系、アジピン酸ジ−２−エチルヘ
キシル、アゼライン酸ジ−２−エチルヘキシル、
セバシン酸ジブチル、セバシン酸−２−エチルヘ
キシル等の脂肪酸エステル系、リン酸トリ−２−
エチルヘキシル、リン酸トリクレジル等のリン酸
エステル系、更には、ポリエステル系可塑剤やエ
ポキシ化大豆油を挙げることができる。
更に、本発明において用いる樹脂組成物は、通
常の添加剤、例えば、安定剤、着色剤、充填剤、
滑剤、離型剤、増量剤、酸化防止剤、帯電防止
剤、紫外線吸収剤、螢光剤、防黴剤、防曇剤等を
必要に応じて適宜量含有していてもよい。例え
ば、安定剤としては、バリウム−亜鉛系、カドミ
ウム−バリウム系、スズ系安定剤等を用いること
ができる。
発明の効果
以上のように、本発明の方法は、所定のエチレ
ン含量と平均重合度を有するエチレン−塩化ビニ
ル共重合体に所定量の可塑剤と共に、所定のメタ
クリル酸メチル−スチレン−ブタジエ共重合体か
らなる改質剤を配合してなる樹脂組成物をカレン
ダー成形するものであり、ここに、上記改質剤が
樹脂組成物のゲル化を遅らせることなしに、その
溶融粘度を高め、他方において、樹脂組成物自体
も、エチレン基の内部可塑化作用によつて、すぐ
れた流動性や顔料の分散性を保持しているため
に、本発明の方法によれば、樹脂組成物がカレン
ダー加工性にすぐれ、バンク回転が円滑であるの
で、従来、得ることが困難であつたバンクマーク
のない半硬質のフイルムを容易に得ることができ
る。
実施例
以下に実施例を挙げて本発明を説明する。
実施例 １
エチレン含量５重量％、平均重合度800のエチ
レン−塩化ビニル共重合体100重量部、フタル酸
ジオクチル12.0重量部、バリウム−亜鉛系液状安
定剤3.0重量部、バリウム−亜鉛系粉状安定剤1.0
重量部、エポキシ大豆油3.0重量部及び顔料適量
からなる混合物を12インチ２本ロールを用いて、
170℃で30rpmにて７分間混練し、厚さ0.1mm、幅
20cmのシートに成形し、これに光を透過させるこ
とによつて、バンクマークの有無を調べた。結果
を第１表に示す。尚、第１表において、バンクマ
ークの評価基準は次のとおりである。○はバンク
マークなし、△は僅かにバンクマークが認められ
る、×はバンクマークが著しいことを示し、−はシ
ートへの成形ができず、評価できなかつたことを
示す。
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing a semi-rigid film without bank marks made of ethylene-vinyl chloride copolymer. Prior Art When a resin composition containing polyvinyl chloride is formed into a film or sheet (hereinafter simply referred to as a film) by calendering, in most cases, the resulting film has so-called bank marks. . These bank marks are caused by thickness differences in the film or uneven distribution of polyvinyl chloride, pigments, and other additives in the film.
In the application of decorative materials, it is considered to be a serious quality defect. That is, bank marks are recognized as pressure marks in decorative materials for steel plates, uneven gloss in decorative materials for plywood, uneven gloss in decorative materials for stickers, and as shading or uneven coloring when viewed through. However, no effective means for obtaining such bank mark-free film has been found so far. Problems to be Solved by the Invention Ethylene-vinyl chloride copolymers generally have an ethylene group in the copolymer, and due to its internal plasticizing action, the gelling temperature is low and gels quickly. In addition, the melt viscosity during calendering is low,
Furthermore, since it has an ethylene group, it has excellent pigment dispersibility. However, as mentioned above, a semi-rigid film containing 5 to 35 parts by weight of plasticizer per 100 parts by weight of ethylene-vinyl chloride copolymer is required as a film for decorative materials. The ethylene-vinyl chloride copolymer resin composition containing the ethylene-vinyl chloride copolymer resin composition has too low melt viscosity, so it has poor peelability from a roll, that is, roll processability, and is difficult to form into a film. As described above, the present inventors improved roll processability and obtained a resin film without bank marks in the production of a semi-rigid ethylene-vinyl chloride copolymer resin film containing a plasticizer by calendar processing. As a result of extensive research into the formulation of resin compositions, we found that ethylene-vinyl chloride copolymer was mixed with certain modifiers and/or
The present invention was achieved by discovering that it is possible to achieve the above object and obtain a semi-rigid ethylene-vinyl chloride copolymer resin film free of bank marks by incorporating a processing aid into the film. . That is, an object of the present invention is to provide a method for producing a semi-rigid film without bank marks by calendering an ethylene-vinyl chloride copolymer. Means for Solving the Problems The method for producing a bank mark-free semi-rigid film made of an ethylene-vinyl chloride copolymer according to the present invention is a method for producing an ethylene-vinyl chloride copolymer having an ethylene content of 0.5% by weight or more and an average degree of polymerization of 700 or more. Methyl methacrylate, which has the property of increasing the melt viscosity without slowing down the gelation rate, by blending it with ethylene-vinyl chloride copolymer along with 100 parts by weight of the polymer and 5 to 35 parts by weight of a plasticizer. Styrene
It is characterized in that a resin composition containing 3 to 20 parts by weight of a modifier made of a butadiene copolymer is calender-molded. The ethylene-vinyl chloride copolymer used in the present invention has an ethylene content of 0.5% by weight or more and an average degree of polymerization of 700 or more. An ethylene-vinyl chloride copolymer with an ethylene content of less than 0.5% by weight has properties similar to polyvinyl chloride, and its internal plasticizing effect is insufficient, so the resin composition has high fluidity. First, even if modifiers and processing aids are used according to the present invention, bank marks often occur on the resulting film. On the other hand, even in the case of ethylene-vinyl chloride copolymers with an average degree of polymerization lower than 700, it is difficult to sufficiently improve roll processability even if modifiers and processing aids are used, and even ,
It is difficult to produce a homogeneous film without bank marks. The modifier used in the present invention is composed of methyl methacrylate-butadiene-styrene copolymer, and by blending it with the ethylene-vinyl chloride copolymer, it increases the melt viscosity without slowing down the gelation rate. It is a modifier with properties. In the present invention, such modifiers include, for example, "Kane Ace B-11A" and "Kane Ace B
-22'' (both manufactured by Kanebuchi Kagaku Kogyo Co., Ltd.) is preferably used. However, even if the modifier is made of methyl methacrylate-butadiene-styrene copolymer, for example, "Kane Ace B-56" (Kanebuchi Chemical Co., Ltd.
By blending this, as in the product manufactured by Co., Ltd.
A modifier that has the property of retarding the gelation rate of an ethylene-vinyl chloride copolymer cannot prevent the occurrence of bank marks, even if it can improve the processability of the ethylene-vinyl chloride copolymer. In the present invention, together with the above modifier, conventional
Auxiliary agents known as acrylic processing aids may be used in combination. Examples of such acrylic processing aids include "Metablen P-530" and "Metablen P-551" (both manufactured by Mitsubishi Rayon Co., Ltd.),
"Kane Ace PA-20" (manufactured by Kanebuchi Chemical Industry Co., Ltd.) can be mentioned. In order to improve the roll processability of the ethylene-vinyl chloride copolymer and to obtain a film without bank marks, the above modifier is added in an amount of 3 to 20 parts by weight per 100 parts by weight of the ethylene-vinyl chloride copolymer. ,
It is preferably used in an amount of 5 to 15 parts by weight. The resin composition used in the present invention is suitable for producing a semi-rigid ethylene-vinyl chloride copolymer resin film for decorative materials, and the resin composition for such use is a 100% ethylene-vinyl chloride copolymer resin film.
It contains 3 to 35 parts by weight of plasticizer. The plasticizer used is not particularly limited, and any plasticizer conventionally used in the production of polyvinyl chloride resin films can be used. Therefore, such plasticizers include, for example,
Phthalate esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, octyldecyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, higher alcohol phthalate esters, and trimellitate trimellitic acid esters such as -2-ethylhexyl, di-2-ethylhexyl adipate, di-2-ethylhexyl azelaate,
Fatty acid esters such as dibutyl sebacate and 2-ethylhexyl sebacate, tri-2-phosphate
Examples include phosphate ester plasticizers such as ethylhexyl and tricresyl phosphate, as well as polyester plasticizers and epoxidized soybean oil. Furthermore, the resin composition used in the present invention may contain conventional additives such as stabilizers, colorants, fillers,
A lubricant, a mold release agent, an extender, an antioxidant, an antistatic agent, an ultraviolet absorber, a fluorescent agent, an antifungal agent, an antifogging agent, and the like may be contained in appropriate amounts as required. For example, as the stabilizer, a barium-zinc type stabilizer, a cadmium-barium type stabilizer, a tin type stabilizer, etc. can be used. Effects of the Invention As described above, the method of the present invention involves adding a predetermined methyl methacrylate-styrene-butadiene copolymer to an ethylene-vinyl chloride copolymer having a predetermined ethylene content and average degree of polymerization, together with a predetermined amount of a plasticizer. A resin composition prepared by blending a modifier consisting of coalescence is calender-molded, and the modifier increases the melt viscosity of the resin composition without delaying the gelation of the resin composition, and on the other hand, Since the resin composition itself maintains excellent fluidity and pigment dispersibility due to the internal plasticizing action of the ethylene group, according to the method of the present invention, the resin composition has excellent calendering properties. Since the bank rotation is smooth and the bank rotation is smooth, it is possible to easily obtain a semi-hard film without bank marks, which has been difficult to obtain in the past. Examples The present invention will be explained below with reference to Examples. Example 1 100 parts by weight of ethylene-vinyl chloride copolymer with an ethylene content of 5% by weight and an average degree of polymerization of 800, 12.0 parts by weight of dioctyl phthalate, 3.0 parts by weight of barium-zinc liquid stabilizer, barium-zinc powder stabilizer agent 1.0
Using two 12-inch rolls, a mixture consisting of parts by weight, 3.0 parts by weight of epoxy soybean oil, and an appropriate amount of pigment was mixed.
Kneaded at 170℃ for 7 minutes at 30rpm to a thickness of 0.1mm and width.
The presence or absence of bank marks was examined by forming a 20 cm sheet and transmitting light through it. The results are shown in Table 1. In Table 1, the evaluation criteria for bank marks are as follows. ◯ indicates that there is no bank mark, △ indicates that bank mark is slightly observed, × indicates that bank mark is significant, and - indicates that it could not be formed into a sheet and could not be evaluated.
【表】【table】
【表】【table】
【表】
また、上記と同様のロール加工において、ロー
ル引剥し性を評価した。評価基準は、○は所定の
厚さにシート加工できた、△は所定の厚さを得る
ことができなかつた、×はシートへの成形ができ
なかつたことを示す。
また、径１mm、長さ10mmのノズルを備えた高化
式フローテスターを用い、温度180℃、荷重50Kg
の条件にて粘度を測定した。更に、プラストミル
（東洋精機(株)製）にて150℃、60ｇ、60rpmの条件
にて最大トルクに達するまでの時間（秒）にてゲ
ル化速度を測定した。結果を第１表に示す。
実施例 ２
種々のエチレ含量及び平均重合度を有するエチ
レン−塩化ビニル共重合体を用いて、実施例１と
同様にして、改質剤「カネエースＢ−11A」及
び／又はアクリル系加工助剤「メタブレンＰ−
530」を配合した配合物について、実施例１と同
様に、粘度、ゲル化速度、ロール引剥し性及び得
られたフイルムにおけるバンクマークの有無につ
いて調べた。結果を第２表に示す。[Table] In addition, the roll peelability was evaluated in the same roll processing as above. The evaluation criteria were: ◯ indicates that the sheet could be processed to a predetermined thickness, △ indicates that the predetermined thickness could not be obtained, and × indicates that the sheet could not be formed. In addition, we used a high-quality flow tester equipped with a nozzle with a diameter of 1 mm and a length of 10 mm, at a temperature of 180°C and a load of 50 kg.
The viscosity was measured under the following conditions. Furthermore, the gelation rate was measured using a plastomill (manufactured by Toyo Seiki Co., Ltd.) under the conditions of 150° C., 60 g, and 60 rpm, and the time (seconds) required to reach the maximum torque. The results are shown in Table 1. Example 2 Using ethylene-vinyl chloride copolymers having various ethylene contents and average degrees of polymerization, the modifier "Kane Ace B-11A" and/or the acrylic processing aid " Metablen P-
In the same manner as in Example 1, the viscosity, gelation rate, roll peelability, and presence or absence of bank marks in the obtained film were examined for the formulation containing "530". The results are shown in Table 2.
Claims (1)
以上のエチレン−塩化ビニル共重合体100重量部
に可塑剤５〜35重量部と共に、エチレン−塩化ビ
ニル共重合体に配合することによつて、そのゲル
化速度を遅らせることなく、溶融粘度を高める性
質を有するメタクリル酸メチル−スチレン−ブタ
ジエン共重合体からなる改質剤３〜20重量部を配
合してなる樹脂組成物をカレンダー成形すること
を特徴とするバンクマークのないフイルムの製造
方法。1 Ethylene content 0.5% by weight or more, average degree of polymerization 700
By blending 100 parts by weight of the above ethylene-vinyl chloride copolymer with 5 to 35 parts by weight of a plasticizer, the melt viscosity can be increased without slowing down the gelation rate. 1. A method for producing a film without bank marks, which comprises calendering a resin composition containing 3 to 20 parts by weight of a modifier made of a methyl methacrylate-styrene-butadiene copolymer having the following properties.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62080809A JPS63245456A (en) | 1987-03-31 | 1987-03-31 | Ethylene/vinyl chloride copolymer resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62080809A JPS63245456A (en) | 1987-03-31 | 1987-03-31 | Ethylene/vinyl chloride copolymer resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63245456A JPS63245456A (en) | 1988-10-12 |
| JPH0554864B2 true JPH0554864B2 (en) | 1993-08-13 |
Family
ID=13728795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62080809A Granted JPS63245456A (en) | 1987-03-31 | 1987-03-31 | Ethylene/vinyl chloride copolymer resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63245456A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7148231B2 (en) * | 2017-09-20 | 2022-10-05 | バンドー化学株式会社 | Polyvinyl chloride film, marking film, decorative molding, and method for producing polyvinyl chloride film |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5474851A (en) * | 1977-11-28 | 1979-06-15 | Kureha Chem Ind Co Ltd | Vinyl chloride resin composition |
| JPS55127479A (en) * | 1979-03-24 | 1980-10-02 | Nitto Electric Ind Co Ltd | Tackifier for surface protection |
| JPS5667353A (en) * | 1979-11-07 | 1981-06-06 | Nissan Chem Ind Ltd | Rigid vinyl chloride resin composition |
| JPS5998151A (en) * | 1982-11-08 | 1984-06-06 | Mitsubishi Rayon Co Ltd | Vinyl chloride resin composition |
| JPS59217747A (en) * | 1983-05-25 | 1984-12-07 | Mitsubishi Rayon Co Ltd | Vinyl chloride resin composition |
| JPS604543A (en) * | 1983-06-22 | 1985-01-11 | Nippon Carbide Ind Co Ltd | Semirigid vinyl chloride molding resin |
| JPS6017219A (en) * | 1983-07-07 | 1985-01-29 | Nissan Motor Co Ltd | Exhaust emission control device for engine |
| JPS60161450A (en) * | 1984-02-01 | 1985-08-23 | Mitsubishi Rayon Co Ltd | Vinyl chloride based resin composition |
-
1987
- 1987-03-31 JP JP62080809A patent/JPS63245456A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5474851A (en) * | 1977-11-28 | 1979-06-15 | Kureha Chem Ind Co Ltd | Vinyl chloride resin composition |
| JPS55127479A (en) * | 1979-03-24 | 1980-10-02 | Nitto Electric Ind Co Ltd | Tackifier for surface protection |
| JPS5667353A (en) * | 1979-11-07 | 1981-06-06 | Nissan Chem Ind Ltd | Rigid vinyl chloride resin composition |
| JPS5998151A (en) * | 1982-11-08 | 1984-06-06 | Mitsubishi Rayon Co Ltd | Vinyl chloride resin composition |
| JPS59217747A (en) * | 1983-05-25 | 1984-12-07 | Mitsubishi Rayon Co Ltd | Vinyl chloride resin composition |
| JPS604543A (en) * | 1983-06-22 | 1985-01-11 | Nippon Carbide Ind Co Ltd | Semirigid vinyl chloride molding resin |
| JPS6017219A (en) * | 1983-07-07 | 1985-01-29 | Nissan Motor Co Ltd | Exhaust emission control device for engine |
| JPS60161450A (en) * | 1984-02-01 | 1985-08-23 | Mitsubishi Rayon Co Ltd | Vinyl chloride based resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63245456A (en) | 1988-10-12 |
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