JPH06286082A - Polyvinyl alcohol laminated film - Google Patents
Polyvinyl alcohol laminated filmInfo
- Publication number
- JPH06286082A JPH06286082A JP10041593A JP10041593A JPH06286082A JP H06286082 A JPH06286082 A JP H06286082A JP 10041593 A JP10041593 A JP 10041593A JP 10041593 A JP10041593 A JP 10041593A JP H06286082 A JPH06286082 A JP H06286082A
- Authority
- JP
- Japan
- Prior art keywords
- oxyalkylene group
- polyvinyl alcohol
- film
- laminated film
- containing polyvinyl
- 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.)
- Granted
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 50
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 50
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 238000007127 saponification reaction Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 28
- 230000008961 swelling Effects 0.000 abstract description 12
- 238000004806 packaging method and process Methods 0.000 abstract description 9
- -1 polyoxyethylene Polymers 0.000 description 20
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 13
- 239000003513 alkali Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 12
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 125000006353 oxyethylene group Chemical group 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000003599 detergent Substances 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルカリ性物質のユニ
ット包装に好適な積層フィルムに関する。TECHNICAL FIELD The present invention relates to a laminated film suitable for unit packaging of alkaline substances.
【０００２】[0002]
【従来の技術】近時、洗剤、糊剤、染料、農薬またはそ
の他の各種薬品等を単位量ずつ水溶性フィルムで密封包
装して、使用時に包装のまま必要個数を水中に投入し、
内容物を包装フィルムごと水に溶解または分散させて用
いることが行われている。このユニット包装によれば、
使用時に一々計算する手間が省けるのみならず、手を汚
染したりすることもないという利点がある。このような
ユニット包装に使用される水溶性フィルムは、大量の水
には容易に溶解もしくは膨潤してその形態を失うもので
あること、洗剤及び硼砂や炭酸ソーダーなどのアルカリ
性化学薬品等の包装用として耐アルカリ性であること、
更に包装用フィルムとしてかなりの機械的強度を有する
ことなどが要求される。かかる包装用フィルムとしてい
くつかの特許出願が行われており、本出願人もオキシ
アルキレン基含有ポリビニルアルコール系樹脂を製膜し
てなるアルカリ性物質包装用のポリビニルアルコールフ
ィルム（特開平６１−３１５６０４号公報）を開発し
た。2. Description of the Related Art Recently, detergents, sizing agents, dyes, agricultural chemicals, and various other chemicals are sealed in a water-soluble film in a unit amount, and the required number is put into the water as it is when used.
It is practiced to dissolve or disperse the contents together with the packaging film in water. According to this unit packaging,
There is an advantage that not only the time and effort for calculating each one at the time of use are saved, but also the hands are not contaminated. The water-soluble film used for such unit packaging shall dissolve or swell easily in a large amount of water and lose its form, and for packaging detergents and alkaline chemicals such as borax and sodium carbonate. As alkali resistant,
Furthermore, it is required that the packaging film has a considerable mechanical strength. Several patent applications have been filed for such a packaging film, and the applicant of the present invention has also formed a polyvinyl alcohol film containing an oxyalkylene group-containing polyvinyl alcohol resin for packaging an alkaline substance (Japanese Patent Laid-Open No. 61-315604). ) Was developed.
【０００３】[0003]
【発明が解決しようとする課題】かかるユニット包装用
水溶性フィルムはその用途が多様化され、近年において
は溶解または膨潤温度を自由に設定できるフィルムが要
求されている。そこで本出願人も上記で示したオキシア
ルキレン基含有ポリビニルアルコールからなるフィルム
を用いてかかる要求を試みた。しかしながら、かかるフ
ィルムはオキシアルキレン基含有量及びケン化度の組み
合わせによりある程度自由に溶解または膨潤温度を設定
できるのだが、溶解もしくは膨潤温度を高く設定した場
合には、耐アルカリ性が低下してフィルムを長時間アル
カリ性物質と接触させると該フィルムの水溶性が抑制さ
れ、該設定温度での溶解が起こらなかったり、また溶解
もしくは膨潤温度を低く設定した場合には、実用面での
耐水性が非常に小さくなり、例えば濡れた手でフィルム
を扱うだけで容易に溶解し始めるという欠点を生じ易く
なり、改善の余地がある。The use of such water-soluble films for unit packaging has been diversified, and in recent years, films capable of freely setting the melting or swelling temperature have been demanded. Therefore, the present applicant has also tried to make such a request by using the film made of the oxyalkylene group-containing polyvinyl alcohol shown above. However, in such a film, the dissolution or swelling temperature can be freely set to some extent depending on the combination of the oxyalkylene group content and the saponification degree, but when the dissolution or swelling temperature is set high, the alkali resistance is lowered and the film is When the film is contacted with an alkaline substance for a long time, the water solubility of the film is suppressed, dissolution at the set temperature does not occur, and when the dissolution or swelling temperature is set low, the water resistance in practical use is very high. There is room for improvement, because the size becomes small and the film tends to be dissolved easily by handling the film with wet hands.
【０００４】[0004]
【課題を解決するための手段】しかるに本発明者はかか
る課題を解決すべく鋭意研究を重ねた結果、オキシアル
キレン基含有量が５〜２０重量％、ケン化度が９５〜１
００モル％であるオキシアルキレン基含有ポリビニルア
ルコール系樹脂（Ａ）を外層とし、オキシアルキレン基
含有量が１５〜４０重量％、ケン化度が８０〜１００モ
ル％であるオキシアルキレン基含有ポリビニルアルコー
ル系樹脂（Ｂ）を内層とする積層フィルムであって、か
つ（Ｂ）のオキシアルキレン基含有ポリビニルアルコー
ル系樹脂中のオキシアルキレン基含有量と（Ａ）のオキ
シアルキレン基含有ポリビニルアルコール系樹脂中のオ
キシアルキレン基含有量の差が５重量％以上であるポリ
ビニルアルコール系積層フィルムがかかる目的に合致す
ることを見いだし本発明を完成するに至った。However, as a result of intensive studies to solve the above problems, the present inventor has found that the oxyalkylene group content is 5 to 20% by weight and the saponification degree is 95 to 1.
An oxyalkylene group-containing polyvinyl alcohol resin having an oxyalkylene group content of 15 to 40% by weight and a saponification degree of 80 to 100% by mole as an outer layer of the oxyalkylene group-containing polyvinyl alcohol resin (A) of 00 mol%. A laminated film having a resin (B) as an inner layer, wherein the oxyalkylene group content in the oxyalkylene group-containing polyvinyl alcohol-based resin (B) and the oxyalkylene group-containing polyvinyl alcohol-based resin (A) It has been found that a polyvinyl alcohol-based laminated film having a difference in alkylene group content of 5% by weight or more meets such an object, and has completed the present invention.
【０００５】本発明においては、特定のオキシアルキレ
ン基含有量及びケン化度をもつ２種類のオキシアルキレ
ン基含有ポリビニルアルコール系フィルムを積層するこ
とにより、即ち、外層には短時間内の耐水性を有しなが
ら水に対する溶解もしくは膨潤温度が自由に設定できる
フィルムを設け、内層には耐アルカリ性を有しかつ水温
に関係なく大量の水に容易に溶解するフィルムを設ける
ことにより、常に耐アルカリ性及び耐水性を充分に有し
ながら、溶解もしくは膨潤温度をある程度自由に設定で
きるユニット包装用の水溶性フィルムを開発し、かかる
フィルムの使用範囲を拡大した。以下、本発明について
詳述する。In the present invention, two kinds of oxyalkylene group-containing polyvinyl alcohol films having a specific oxyalkylene group content and saponification degree are laminated, that is, the outer layer has a water resistance within a short time. By providing a film that can freely set the dissolution or swelling temperature in water while having it, and by providing a film that has alkali resistance in the inner layer and can be easily dissolved in a large amount of water regardless of the water temperature, it is always alkali resistant and water resistant. We have developed a water-soluble film for unit packaging that has a sufficient solubility and can set the melting or swelling temperature to some extent, and expanded the range of use of such a film. Hereinafter, the present invention will be described in detail.
【０００６】本発明で用いられるオキシアルキレン基含
有ポリビニルアルコール系樹脂は、典型的には、酢酸ビ
ニルと、ポリオキシエチレン（メタ）アリルエーテル、
ポリオキシプロピレン（メタ）アリルエーテルなどのポ
リオキシアルキレン（メタ）アリルエーテルとを共重合
し、ついでケン化することにより得られる。なお、共重
合成分としてポリオキシアルキレン（メタ）アリルエー
テル以外の成分、例えばα−オレフィン（エチレン、プ
ロピレン、長鎖α−オレフィン等）、エチレン性不飽和
カルボン酸系モノマー、（アクリレート、メタクリレー
ト、アクリロニトリル、メタクリロニトリル、塩化ビニ
ル、ビニルエーテル等）を３０モル％以下程度であれば
含有してもよい。The oxyalkylene group-containing polyvinyl alcohol resin used in the present invention is typically vinyl acetate, polyoxyethylene (meth) allyl ether,
It can be obtained by copolymerizing with polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether and then saponifying. In addition, as a copolymerization component, components other than polyoxyalkylene (meth) allyl ether, for example, α-olefin (ethylene, propylene, long-chain α-olefin, etc.), ethylenically unsaturated carboxylic acid monomer, (acrylate, methacrylate, acrylonitrile). , Methacrylonitrile, vinyl chloride, vinyl ether, etc.) in an amount of about 30 mol% or less.
【０００７】オキシアルキレン基含有ポリビニルアルコ
ールを得るときの重合方法としては通常、溶液重合法が
採用され、場合により懸濁重合法、エマルジョン重合法
などを採用することもできる。ケン化反応としては、ア
ルカリケン化法、酸ケン化法などが採用される。オキシ
アルキレン基含有ポリビニルアルコールは上記のほか、
酢酸ビニルと、ポリオキシエチレン（メタ）アクリレー
ト、ポリオキシプロピレン（メタ）アクリレート、ポリ
オキシエチレン（メタ）アクリルアミド、ポリオキシプ
ロピレン（メタ）アクリルアミド、ポリオキシエチレン
（１−（メタ）アクリルアミド−１，１−ジメチルプロ
ピル）エステル、ポリオキシエチレンビニルエーテル、
ポリオキシプロピレンビニルエーテルなどを共重合し、
ついでケン化することによっても得ることができる。オ
キシアルキレン基含有ポリビニルアルコールは、そのほ
か、ポリビニルアルコールに対するアルキレンオキシド
の反応、あるいはポリオキシアルキレングリコールに対
する酢酸ビニルの重合およびそれに引き続くケン化によ
っても得ることができる。As a polymerization method for obtaining the oxyalkylene group-containing polyvinyl alcohol, a solution polymerization method is usually adopted, and a suspension polymerization method, an emulsion polymerization method or the like can be adopted depending on circumstances. As the saponification reaction, an alkali saponification method, an acid saponification method or the like is adopted. Oxyalkylene group-containing polyvinyl alcohol other than the above,
Vinyl acetate and polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, polyoxyethylene (meth) acrylamide, polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1 -Dimethylpropyl) ester, polyoxyethylene vinyl ether,
Copolymerize polyoxypropylene vinyl ether,
It can also be obtained by subsequent saponification. The oxyalkylene group-containing polyvinyl alcohol can also be obtained by reacting alkylene oxide with polyvinyl alcohol, or by polymerizing vinyl acetate with polyoxyalkylene glycol and subsequent saponification.
【０００８】外層（Ａ）として用いられるオキシアルキ
レン基含有ポリビニルアルコール系樹脂のポリオキシア
ルキレン（メタ）アリルエーテルの共重合割合は０．１
〜２０モル％、特に０．１〜５モル％、ポリオキシアル
キレン（メタ）アリルエーテルにおけるポリオキシアル
キレンの縮合度は１〜３００、特に３〜５０が適当であ
り、オキシアルキレン基含有ポリビニルアルコール全体
に占めるオキシアルキレン単位の割合が５〜２０重量
％、特に８〜２０重量％であることが好ましい。かかる
割合が２０重量％を越える場合は短時間の耐水性能が充
分に得られない。５重量％未満の場合は水に対する充分
な溶解性能が得られない。かかるオキシアルキレン基含
有ポリビニルアルコール系樹脂からなるフィルムは、そ
の溶解もしくは膨潤温度をオキシアルキレン基含有量及
びケン化度の組み合わせにより自由に設定できる。かか
る温度を高く設定して常温の水には不溶とする場合に
は、得られたフィルムを更に熱処理または熱延伸すると
有利である。また、かかる温度を低く設定した場合にも
かかるフィルムは耐水性を有しているので例え濡れた手
で扱っても容易に溶解することはない。The polyoxyalkylene (meth) allyl ether copolymerization ratio of the oxyalkylene group-containing polyvinyl alcohol resin used as the outer layer (A) is 0.1.
To 20 mol%, particularly 0.1 to 5 mol%, and the polyoxyalkylene condensation degree in the polyoxyalkylene (meth) allyl ether is preferably 1 to 300, particularly 3 to 50, and the entire oxyalkylene group-containing polyvinyl alcohol is suitable. It is preferable that the proportion of oxyalkylene units is 5 to 20% by weight, particularly 8 to 20% by weight. If this proportion exceeds 20% by weight, water resistance cannot be sufficiently obtained in a short time. If it is less than 5% by weight, sufficient dissolution performance in water cannot be obtained. The dissolution or swelling temperature of the film made of such an oxyalkylene group-containing polyvinyl alcohol-based resin can be freely set by the combination of the oxyalkylene group content and the saponification degree. When such a temperature is set to be high to make it insoluble in water at room temperature, it is advantageous to further heat-treat or stretch the obtained film. Even when the temperature is set low, the film does not dissolve easily even if it is handled with wet hands because it has water resistance.
【０００９】内層（Ｂ）として用いられるオキシアルキ
レン基含有ポリビニルアルコール系樹脂のポリオキシア
ルキレン（メタ）アリルエーテルの共重合割合は０．１
〜２０モル％、特に０．１〜５モル％、ポリオキシアル
キレン（メタ）アリルエーテルにおけるポリオキシアル
キレンの縮合度は１〜３００、特に３〜５０が適当であ
り、オキシアルキレン基含有ポリビニルアルコール全体
に占めるオキシアルキレン単位の割合が１５〜４０重量
％、特に１８〜４０重量％であることが好ましい。かか
る割合が４０重量％を越える場合は溶解温度のコントロ
ールが困難となり、１５重量％未満の場合は充分な耐ア
ルカリ性が得られない。かかるオキシアルキレン基含有
ポリビニルアルコール系樹脂からなるフィルムは耐アル
カリ性を充分に有し、かつ水温に関係なく大量の水に容
易に溶解する水溶性フィルムである。The oxyalkylene group-containing polyvinyl alcohol resin used as the inner layer (B) has a polyoxyalkylene (meth) allyl ether copolymerization ratio of 0.1.
To 20 mol%, particularly 0.1 to 5 mol%, and the polyoxyalkylene condensation degree in the polyoxyalkylene (meth) allyl ether is preferably 1 to 300, particularly 3 to 50, and the entire oxyalkylene group-containing polyvinyl alcohol is suitable. It is preferable that the proportion of the oxyalkylene unit is 15 to 40% by weight, particularly 18 to 40% by weight. If the proportion exceeds 40% by weight, it becomes difficult to control the melting temperature, and if it is less than 15% by weight, sufficient alkali resistance cannot be obtained. The film made of such an oxyalkylene group-containing polyvinyl alcohol-based resin is a water-soluble film which has sufficient alkali resistance and is easily dissolved in a large amount of water regardless of the water temperature.
【００１０】本発明において（Ｂ）のオキシアルキレン
基含有ポリビニルアルコール中のオキシアルキレン基含
有量と（Ａ）のオキシアルキレン基含有ポリビニルアル
コール中のオキシアルキレン基含有量との差が５重量％
以上、好ましくは８重量％以上であることが必須であ
る。かかる差が５重量％未満であると溶解温度のコント
ロール、短時間における耐水性の付与、耐アルカリ性の
付与など全て実現することは困難である。本発明におけ
るフィルムの製造方法としては特に制限はなく既知の方
法がとられ、（Ａ）及び（Ｂ）を押出し成形法などによ
り別々に成形してから積層するか、あるいは共押出し成
形、多層インフレーション成形、多層ブロー成形による
方法などがとられる。In the present invention, the difference between the oxyalkylene group content in the oxyalkylene group-containing polyvinyl alcohol (B) and the oxyalkylene group content in the oxyalkylene group-containing polyvinyl alcohol (A) is 5% by weight.
It is essential that the content is at least 8% by weight, preferably at least 8% by weight. When the difference is less than 5% by weight, it is difficult to control the melting temperature, impart water resistance in a short time, impart alkali resistance, and so on. The method for producing the film in the present invention is not particularly limited, and known methods can be used. For example, (A) and (B) are separately molded by an extrusion molding method or the like and then laminated, or coextrusion molding or multilayer inflation is performed. A method such as molding or multi-layer blow molding may be used.
【００１１】かかる成形時には、必要に応じて着色料、
香料、増量剤、消泡剤、剥離剤、紫外線吸収剤等の通常
の添加剤を適宜配合してもよく、更に特性を失わない範
囲で通常のポリビニルアルコール、澱粉、カルボキシメ
チルセルロース、メチルセルロース、ヒドロキシメチル
セルロース等の水溶性樹脂を混合しても良い。かかるポ
リビニルアルコール系積層フィルムは２層系で耐水性、
耐アルカリ性、耐熱性、機械的強度などに充分に優れて
いるが、必要であれば更に中間層として、部分ケン化タ
イプのオキシアルキレン基含有ポリビニルアルコール系
樹脂などを積層することも可能である。かくして得られ
る積層フィルムを用い包装して有利な物質としては、ア
ルカル性を呈する固体状物で使用時に水に溶解して用い
るものであれば特に制限はなく、例えば、洗剤や農業用
化学物質、肥料、写真現像剤、染料などのユニット包装
に好適に用いられる。At the time of molding, if necessary, a coloring agent,
You may mix | blend usual additives, such as a fragrance | flavor, an extender, a defoaming agent, a peeling agent, and an ultraviolet absorber suitably, and also a normal polyvinyl alcohol, starch, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose within the range which does not lose a characteristic. You may mix water-soluble resin, such as. Such a polyvinyl alcohol-based laminated film is a two-layer system and has water resistance,
Although it is sufficiently excellent in alkali resistance, heat resistance, mechanical strength, etc., if necessary, it is also possible to laminate a partially saponified type oxyalkylene group-containing polyvinyl alcohol resin as an intermediate layer. The advantageous substance to be packaged using the thus obtained laminated film is not particularly limited as long as it is used by dissolving it in water at the time of use as a solid substance exhibiting alcal property, for example, a detergent or an agricultural chemical substance, It is suitable for unit packaging of fertilizers, photographic developers, dyes, etc.
【００１２】[0012]
【作 用】本発明においては、特定のオキシアルキレ
ン基含有量及びケン化度をもつ２種類のオキシアルキレ
ン基含有ポリビニルアルコール系フィルムを積層するこ
とにより、常に耐アルカリ性及び耐水性を充分有しなが
ら、溶解もしくは膨潤温度をある程度自由に設定するこ
とに成功し、かかるフィルムの使用範囲を拡大した。[Working] In the present invention, two kinds of oxyalkylene group-containing polyvinyl alcohol-based films having a specific oxyalkylene group content and a specific saponification degree are laminated to always have sufficient alkali resistance and water resistance. We succeeded in freely setting the melting or swelling temperature to some extent, and expanded the range of use of such films.
【００１３】[0013]
【実施例】以下、本発明において実例を挙げて更に詳述
する。 実施例１ 外層として平均重合度５５０、ポリオキシエチレンモノ
アリルエーテル（オキシエチレンの縮合度１０）単位の
共重合割合１．５モル％、ポリマー全体に占めるオキシ
アルキレン単位の割合１２．９重量％、酢酸ビニル成分
のケン化度は９９モル％からなるオキシアルキレン基含
有ポリビニルアルコール系樹脂を、内層として平均重合
度５６０、ポリオキシエチレンモノアリルエーテル（オ
キシエチレンの縮合度１０）単位の共重合割合２．５モ
ル％、ポリマー全体に占めるオキシアルキレン単位の割
合１９．２重量％、酢酸ビニル成分のケン化度は９５モ
ル％からなるオキシアルキレン基含有ポリビニルアルコ
ール系樹脂を２層用のリングダイを備えた押出機に供給
して温度２１０℃で溶融し、スリット径１００ｍｍ、ス
リットクリアランス１．５ｍｍのリングダイスリットよ
り２１０℃で吐出し、冷却空気を吹き込んで筒状フィル
ムを成形し、安定板で扁平にしてピンチローラーで巻き
取り厚さ１００μｍの積層フィルム（それぞれ５０μｍ
ずつ）を得た。かかる樹脂の吐出量はそれぞれ１０ｋｇ
／ｈｒ、フィルム引取速度は１０ｍ／ｍｉｎとした。か
かる積層フィルムは７０℃に溶解するように設定した。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to actual examples. Example 1 As the outer layer, the average degree of polymerization was 550, the copolymerization ratio of polyoxyethylene monoallyl ether (condensation degree of oxyethylene was 10) units was 1.5 mol%, and the ratio of oxyalkylene units in the entire polymer was 12.9 wt%. The saponification degree of the vinyl acetate component is 99 mol% of an oxyalkylene group-containing polyvinyl alcohol-based resin, the inner layer has an average degree of polymerization of 560, and a polyoxyethylene monoallyl ether (degree of condensation of oxyethylene is 10) copolymerization ratio of 2 An oxyalkylene group-containing polyvinyl alcohol resin comprising 0.5 mol%, a ratio of oxyalkylene units in the entire polymer of 19.2% by weight, and a saponification degree of a vinyl acetate component of 95 mol% is provided with a ring die for two layers. Supplied to the extruder and melted at a temperature of 210 ° C, slit diameter 100 mm, slit It is discharged from a ring die slit with a rear lance of 1.5 mm at 210 ° C, blown with cooling air to form a tubular film, flattened with a stabilizer and wound with a pinch roller to form a laminated film with a thickness of 100 μm (each 50 μm.
Each)). The discharge amount of such resin is 10 kg each
/ Hr, the film take-up speed was 10 m / min. The laminated film was set so as to melt at 70 ° C.
【００１４】かかる積層フィルムの物性を下記で示す方
法により測定した。 （１）耐水性 ２０ｃｍ×２０ｃｍの積層フィルムを調製した。この積
層フィルムを外層が上側になるように水平な平面上に置
き、駒込ピヘットで蒸留水の水滴１０滴を滴下して３０
分間放置したのち水滴をふき取り、フィルムを目視によ
り観察した。 膨潤が全くなし・・・○ 若干膨潤する・・・・△ フィルムが破れる・・× （２）温水水溶性 ２ｃｍ×２ｃｍの積層フィルムを溶解設定温度に調整し
た水中に浸漬して完溶時間を測定した。 ３分以内で完溶・・・・・・・◎ ３〜１０分で完溶・・・・・・○ １０〜３０分で完溶・・・・・△ ３０分以上でも完溶しない・・× （３）耐アルカリ性 アルカリ性洗剤１０ｇを５ｃｍ×５ｃｍの積層フィルム
からなる袋に入れヒートシールした後、２０℃、６５％
ＲＨの環境下に２カ月間放置した。放置後の洗剤入りフ
ィルムを溶解設定温度に調整した水中に投入して完溶時
間を測定した。 ３分以内で完溶・・・・・・・◎ ３〜１０分で完溶・・・・・・○ １０〜３０分で完溶・・・・・△ ３０分以内でも完溶しない・・×The physical properties of the laminated film were measured by the methods described below. (1) Water resistance A 20 cm × 20 cm laminated film was prepared. This laminated film is placed on a horizontal flat surface with the outer layer facing upward, and 10 drops of distilled water are dropped with a Komagome pipette.
After standing for a minute, water drops were wiped off and the film was visually observed. No swelling ∘ Slightly swelling ・ ・ ・ ・ △ Film broke ・ × (2) Hot water water solubility 2cm × 2cm Laminated film was immersed in water adjusted to the set temperature for complete dissolution time It was measured. Completely dissolved within 3 minutes ... ◎ Completely dissolved within 3 to 10 minutes ... ○ Completely dissolved within 10 to 30 minutes ... △ Not completely dissolved within 30 minutes ... × (3) Alkali resistance After 10 g of alkaline detergent was placed in a bag made of a laminated film of 5 cm × 5 cm and heat-sealed, 20 ° C, 65%
It was left for 2 months in the RH environment. The film containing the detergent after standing was placed in water adjusted to the set temperature for dissolution to measure the complete dissolution time. Completely dissolved within 3 minutes ... ◎ Completely dissolved within 3 to 10 minutes ... ○ Completely dissolved within 10 to 30 minutes ... △ Not completely dissolved within 30 minutes ... ×
【００１５】実施例２ 外層として平均重合度５５０、ポリオキシエチレンモノ
アリルエーテル（オキシエチレンの縮合度２０）単位の
共重合割合１．０モル％、ポリマー全体に占めるオキシ
アルキレン単位の割合１６．５重量％、酢酸ビニル成分
のケン化度は９９モル％からなるオキシアルキレン基含
有ポリビニルアルコール系樹脂を、内層として平均重合
度５６０、ポリオキシエチレンモノアリルエーテル（オ
キシエチレンの縮合度１０）単位の共重合割合３．０モ
ル％、ポリマー全体に占めるオキシアルキレン単位の割
合２２．２重量％、酢酸ビニル成分のケン化度は９５モ
ル％からなるオキシアルキレン基含有ポリビニルアルコ
ール系樹脂を用いた以外は実施例１に準じて積層フィル
ムを得た。かかる積層フィルムは６０℃に溶解するよう
に設定した。かかる積層フィルムの物性を同例に準じて
測定した。結果はまとめて表１に示す。Example 2 As the outer layer, the average degree of polymerization was 550, the copolymerization ratio of polyoxyethylene monoallyl ether (oxyethylene condensation degree: 20) units was 1.0 mol%, and the ratio of oxyalkylene units in the entire polymer was 16.5. % By weight, and the saponification degree of the vinyl acetate component is 99 mol%. An oxyalkylene group-containing polyvinyl alcohol-based resin is used as an inner layer having an average polymerization degree of 560 and polyoxyethylene monoallyl ether (condensation degree of oxyethylene of 10) units. Polymerization ratio 3.0 mol%, ratio of oxyalkylene units in the whole polymer 22.2% by weight, saponification degree of vinyl acetate component was 95 mol% except that an oxyalkylene group-containing polyvinyl alcohol resin was used. A laminated film was obtained according to Example 1. The laminated film was set so as to melt at 60 ° C. The physical properties of this laminated film were measured according to the same example. The results are summarized in Table 1.
【００１６】実施例３ 外層として平均重合度６１０、ポリオキシエチレンモノ
アリルエーテル（オキシエチレンの縮合度２０）単位の
共重合割合１．０モル％、ポリマー全体に占めるオキシ
アルキレン単位の割合１６．４重量％、酢酸ビニル成分
のケン化度は９８モル％からなるオキシアルキレン基含
有ポリビニルアルコール系樹脂を、内層として平均重合
度６２０、ポリオキシエチレンモノアリルエーテル（オ
キシエチレンの縮合度３０）単位の共重合割合１．０モ
ル％、ポリマー全体に占めるオキシアルキレン単位の割
合２１．８重量％、酢酸ビニル成分のケン化度は９２モ
ル％からなるオキシアルキレン基含有ポリビニルアルコ
ール系樹脂を用いて押出機に供給して２１０℃で共押出
して厚さ１００μｍの積層フィルムを得た。かかる積層
フィルムは５５℃で溶解するように設定した。かかる積
層フィルムの物性を実施例１に準じて測定した。結果は
まとめて表１に示す。Example 3 As the outer layer, the average degree of polymerization was 610, the copolymerization ratio of polyoxyethylene monoallyl ether (oxyethylene condensation degree 20) units was 1.0 mol%, and the ratio of oxyalkylene units in the entire polymer was 16.4. % By weight, and the saponification degree of the vinyl acetate component is 98 mol%. An oxyalkylene group-containing polyvinyl alcohol-based resin is used as an inner layer, and an average degree of polymerization is 620 and a polyoxyethylene monoallyl ether (condensation degree of oxyethylene is 30) units is used. A polymerization ratio of 1.0 mol%, a ratio of oxyalkylene units in the whole polymer of 21.8 wt%, and a saponification degree of vinyl acetate component of 92 mol% are used in an extruder using an oxyalkylene group-containing polyvinyl alcohol resin. It was supplied and coextruded at 210 ° C. to obtain a laminated film having a thickness of 100 μm. The laminated film was set to melt at 55 ° C. The physical properties of this laminated film were measured according to Example 1. The results are summarized in Table 1.
【００１７】実施例４ 外層として平均重合度３９０、ポリオキシエチレンアク
リルアミドモノマー（オキシエチレンの縮合度５）単位
の共重合割合２．０モル％、ポリマー全体に占めるオキ
シアルキレン単位の割合８．９重量％、酢酸ビニル成分
のケン化度は９９モル％からなるオキシアルキレン基含
有ポリビニルアルコール系樹脂を、内層として平均重合
度４５０、ポリオキシエチレンモノアリルエーテル（オ
キシエチレンの縮合度３０）単位の共重合割合２．０モ
ル％、ポリマー全体に占めるオキシアルキレン単位の割
合３７．５重量％、酢酸ビニル成分のケン化度は９３モ
ル％からなるオキシアルキレン基含有ポリビニルアルコ
ール系樹脂を用いて押出機に供給して２１０℃で共押出
して厚さ１００μｍの積層フィルムを得た。かかる積層
フィルムは７５℃で溶解するように設定した。かかる積
層フィルムの物性を実施例１に準じて測定した。結果は
まとめて表１に示す。Example 4 As an outer layer, the average degree of polymerization was 390, the copolymerization ratio of polyoxyethylene acrylamide monomer (condensation degree of oxyethylene was 5) units was 2.0 mol%, and the ratio of oxyalkylene units in the entire polymer was 8.9% by weight. %, The saponification degree of the vinyl acetate component is 99 mol%, and an oxyalkylene group-containing polyvinyl alcohol resin is used as the inner layer, and the average degree of polymerization is 450, and polyoxyethylene monoallyl ether (condensation degree of oxyethylene is 30) units is copolymerized. A ratio of 2.0 mol%, a ratio of oxyalkylene units in the whole polymer of 37.5% by weight, and a saponification degree of a vinyl acetate component of 93 mol% are supplied to an extruder using an oxyalkylene group-containing polyvinyl alcohol resin. Then, it was coextruded at 210 ° C. to obtain a laminated film having a thickness of 100 μm. The laminated film was set to melt at 75 ° C. The physical properties of this laminated film were measured according to Example 1. The results are summarized in Table 1.
【００１８】実施例５ 外層として平均重合度６１０、ポリオキシエチレンビニ
ルエーテルモノマー（オキシエチレンの縮合度１５）単
位の共重合割合１．６モル％、ポリマー全体に占めるオ
キシアルキレン単位の割合１９．１重量％、酢酸ビニル
成分のケン化度は９８モル％からなるオキシアルキレン
基含有ポリビニルアルコール系樹脂を、内層として平均
重合度６３０、ポリオキシエチレンモノアリルエーテル
（オキシエチレンの縮合度１５）単位の共重合割合２．
５モル％、ポリマー全体に占めるオキシアルキレン単位
の割合２５．４重量％、酢酸ビニル成分のケン化度は９
０モル％からなるオキシアルキレン基含有ポリビニルア
ルコール系樹脂を用いて実施例１に準じて厚さ１００μ
ｍの積層フィルムを得た。かかる積層フィルムは４５℃
で溶解するように設定した。かかる積層フィルムの物性
を同例に準じて測定した。結果はまとめて表１に示す。Example 5 As the outer layer, the average degree of polymerization was 610, the copolymerization ratio of polyoxyethylene vinyl ether monomer (oxyethylene condensation degree 15) units was 1.6 mol%, and the ratio of oxyalkylene units in the whole polymer was 19.1% by weight. %, The saponification degree of the vinyl acetate component is 98 mol%, and an oxyalkylene group-containing polyvinyl alcohol-based resin is used as an inner layer and has an average degree of polymerization of 630 and polyoxyethylene monoallyl ether (condensation degree of oxyethylene of 15) units. Ratio 2.
5 mol%, the proportion of oxyalkylene units in the whole polymer is 25.4% by weight, and the degree of saponification of the vinyl acetate component is 9
Using an oxyalkylene group-containing polyvinyl alcohol-based resin consisting of 0 mol%, the thickness was 100 μm in accordance with Example 1.
A laminated film of m was obtained. Such laminated film is 45 ° C
It was set to dissolve in. The physical properties of this laminated film were measured according to the same example. The results are summarized in Table 1.
【００１９】比較例１ 実施例１において内層のオキシアルキレン基含有ポリビ
ニルアルコール系樹脂中のオキシアルキレン基含有量を
１６重量％とした以外は同例に準じて実験を行った。結
果はまとめて表１に示す。 比較例２ 溶解設定温度が７０℃になるように、オキシアルキレン
基含有量１２．９重量％、ケン化度９９モル％であるオ
キシアルキレン基含有ポリビニルアルコール系樹脂を用
いてフィルムを得た。かかるフィルムの物性を実施例１
に準じて測定した。結果はまとめて表１に示す。 比較例３ 溶解設定温度が４５℃になるように、オキシアルキレン
基含有量２２．２重量％、ケン化度９５モル％であるオ
キシアルキレン基含有ポリビニルアルコール系樹脂を用
いてフィルムを得た。かかるフィルムに物性を実施例１
に準じて測定した。結果はまとめて表１に示す。Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that the oxyalkylene group content in the oxyalkylene group-containing polyvinyl alcohol resin of the inner layer was 16% by weight. The results are summarized in Table 1. Comparative Example 2 A film was obtained using an oxyalkylene group-containing polyvinyl alcohol-based resin having an oxyalkylene group content of 12.9% by weight and a saponification degree of 99 mol% so that the set dissolution temperature was 70 ° C. The physical properties of such a film are shown in Example 1.
It was measured according to. The results are summarized in Table 1. Comparative Example 3 A film was obtained using an oxyalkylene group-containing polyvinyl alcohol-based resin having an oxyalkylene group content of 22.2% by weight and a saponification degree of 95 mol% so that the dissolution set temperature was 45 ° C. The physical properties of this film are shown in Example 1.
It was measured according to. The results are summarized in Table 1.
【００２０】[0020]
【表１】 耐水性 温水水溶性 耐アルカリ性 実施例１ ○ ○ ○ 実施例２ ○ ◎ ◎ 実施例３ ○ ◎ ◎ 実施例４ ○ ○ ○実施例５ △ ◎ ◎ 比較例１ ○ ○ △ 比較例２ ○ ○ ×比較例３ × ◎ ○ [Table 1] Water resistance Hot water water solubility Alkali resistance Example 1 ○ ○ ○ Example 2 ○ ◎ ◎ ◎ Example 3 ○ ◎ ◎ ◎ Example 4 ○ ○ ○ Example 5 △ ◎ ◎ Comparative Example 1 ○ ○ △ Comparative Example 2 ○ ○ × Comparative Example 3 × ◎ ○
【００２１】[0021]
【発明の効果】本発明においては、特定のオキシアルキ
レン基含有量及びケン化度をもつ２種類のオキシアルキ
レン基含有ポリビニルアルコール系フィルムを積層する
ことにより、常に耐アルカリ性及び軽度の耐水性を充分
に有しながら、溶解もしくは膨潤温度をある程度自由に
設定することに成功し、かかるフィルムの使用範囲が拡
大できたので産業上非常に有利である。In the present invention, by laminating two kinds of oxyalkylene group-containing polyvinyl alcohol-based films having a specific oxyalkylene group content and saponification degree, sufficient alkali resistance and mild water resistance can be obtained. However, the melting or swelling temperature can be freely set to some extent, and the range of use of such a film can be expanded, which is industrially very advantageous.
Claims (1)
量％、ケン化度が９５〜１００モル％であるオキシアル
キレン基含有ポリビニルアルコール系樹脂（Ａ）を外層
とし、オキシアルキレン基含有量が１５〜４０重量％、
ケン化度が８０〜１００モル％であるオキシアルキレン
基含有ポリビニルアルコール系樹脂（Ｂ）を内層とする
積層フィルムであって、かつ（Ｂ）のオキシアルキレン
基含有ポリビニルアルコール系樹脂中のオキシアルキレ
ン基含有量と（Ａ）のオキシアルキレン基含有ポリビニ
ルアルコール系樹脂中のオキシアルキレン基含有量の差
が５．０重量％以上であることを特徴とするポリビニル
アルコール系積層フィルム1. An oxyalkylene group-containing polyvinyl alcohol resin (A) having an oxyalkylene group content of 5 to 20% by weight and a saponification degree of 95 to 100 mol% is used as an outer layer, and the oxyalkylene group content is 15. ~ 40% by weight,
A laminated film having, as an inner layer, an oxyalkylene group-containing polyvinyl alcohol resin (B) having a saponification degree of 80 to 100 mol%, and an oxyalkylene group in (B) the oxyalkylene group-containing polyvinyl alcohol resin. The difference between the content and the oxyalkylene group content in the oxyalkylene group-containing polyvinyl alcohol resin of (A) is 5.0% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10041593A JP3255486B2 (en) | 1993-04-02 | 1993-04-02 | Polyvinyl alcohol-based laminated film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10041593A JP3255486B2 (en) | 1993-04-02 | 1993-04-02 | Polyvinyl alcohol-based laminated film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06286082A true JPH06286082A (en) | 1994-10-11 |
| JP3255486B2 JP3255486B2 (en) | 2002-02-12 |
Family
ID=14273357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10041593A Expired - Fee Related JP3255486B2 (en) | 1993-04-02 | 1993-04-02 | Polyvinyl alcohol-based laminated film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3255486B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6040024A (en) * | 1997-03-26 | 2000-03-21 | Kyodo Shiko Co., Ltd. | Laminated film, method for production thereof, and bag and package using the laminated film |
| US6244746B1 (en) | 1995-10-09 | 2001-06-12 | Kyodo Shiko Co. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| JP2002003896A (en) * | 2000-06-20 | 2002-01-09 | Kao Corp | Laundry utensil |
| JP2002180098A (en) * | 2000-12-15 | 2002-06-26 | Kao Corp | Tablet type detergent and method for producing the same |
| US6440508B1 (en) | 1997-11-13 | 2002-08-27 | Kyodo Shiko Co. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| JP2013095868A (en) * | 2011-11-02 | 2013-05-20 | Kuraray Co Ltd | Modified vinyl alcohol polymer |
-
1993
- 1993-04-02 JP JP10041593A patent/JP3255486B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6244746B1 (en) | 1995-10-09 | 2001-06-12 | Kyodo Shiko Co. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| US6984067B2 (en) | 1995-10-09 | 2006-01-10 | Kyodo Shiko Co., Ltd. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| US7364359B2 (en) | 1995-10-09 | 2008-04-29 | Kyodo Shiko Co., Ltd. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| US6040024A (en) * | 1997-03-26 | 2000-03-21 | Kyodo Shiko Co., Ltd. | Laminated film, method for production thereof, and bag and package using the laminated film |
| US6440508B1 (en) | 1997-11-13 | 2002-08-27 | Kyodo Shiko Co. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| US6471401B1 (en) | 1997-11-13 | 2002-10-29 | Kyodo Shiko Co., Ltd. | Laminated film, method for production thereof, bag and package using the laminated film, and method for separation thereof |
| JP2002003896A (en) * | 2000-06-20 | 2002-01-09 | Kao Corp | Laundry utensil |
| JP2002180098A (en) * | 2000-12-15 | 2002-06-26 | Kao Corp | Tablet type detergent and method for producing the same |
| JP4619526B2 (en) * | 2000-12-15 | 2011-01-26 | 花王株式会社 | Tablet detergent |
| JP2013095868A (en) * | 2011-11-02 | 2013-05-20 | Kuraray Co Ltd | Modified vinyl alcohol polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3255486B2 (en) | 2002-02-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |