JPH0756013B2 - Coating material - Google Patents
Coating materialInfo
- Publication number
- JPH0756013B2 JPH0756013B2 JP28741686A JP28741686A JPH0756013B2 JP H0756013 B2 JPH0756013 B2 JP H0756013B2 JP 28741686 A JP28741686 A JP 28741686A JP 28741686 A JP28741686 A JP 28741686A JP H0756013 B2 JPH0756013 B2 JP H0756013B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- vinyl acetate
- coating material
- solution
- ethylene
- 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.)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 A.産業上の利用分野 本発明は溶液安定性、塗膜の外観に優れたコーティング
材料に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a coating material excellent in solution stability and appearance of a coating film.
B.従来の技術 従来エチレン−酢酸ビニル共重合体けん化物（以下EVOH
と記す）は耐気体透過性、耐油性、耐溶剤性に優れ、種
々の包装分野の包装材料、フイルム、シート、容器等に
好適に用いられてきた。又溶液コーティング方法にて被
膜を形成する方法も行われつつある。EVOHの溶剤として
は含水アルコールが一般的に使用される（特公昭47−48
489号）。しかし従来のEVOHでは溶液安定性が悪く、溶
液がゲル化し易く、50℃以上の高温で保存するか、又塗
工前に再加熱により再溶解しなければならなかつた。又
乾燥条件によっては塗膜に白化、くもり等の発生が起り
厳密な管理が必要である等の欠点を有していた。B. Conventional technology Saponified ethylene-vinyl acetate copolymer (hereinafter EVOH)
Has excellent gas permeation resistance, oil resistance and solvent resistance, and has been suitably used for packaging materials, films, sheets, containers and the like in various packaging fields. In addition, a method of forming a film by a solution coating method is being used. Hydrous alcohol is generally used as a solvent for EVOH (Japanese Patent Publication No. 47-48).
No. 489). However, conventional EVOH had poor solution stability and the solution was prone to gelation, and it had to be stored at a high temperature of 50 ° C or higher or redissolved by reheating before coating. Further, depending on the drying conditions, the coating film has a drawback that whitening, clouding, etc. occur and strict control is required.
C.発明が解決しようとする問題点 本発明は前記欠点、すなわち溶液安定性の悪さ、塗膜の
白化を改善したものである。C. Problems to be Solved by the Invention The present invention has improved the above-mentioned drawbacks, that is, poor solution stability and whitening of a coating film.
D.問題点を解決するための手段 本発明者らは鋭意研究を重ねた結果、ピロリドン環を含
む単位、エチレン単位及び酢酸ビニル単位の各々を特定
の量含む三元共重合体のけん化物が、溶液の安定性が良
好で、塗膜の透明性が良く極めて美麗であると共に、耐
気体透過性が高く、コーティング材料に優れていること
を見出だし、本発明を完成するに至った。D. Means for Solving the Problems As a result of intensive studies by the present inventors, a saponified product of a terpolymer containing a specific amount of a unit containing a pyrrolidone ring, an ethylene unit and a vinyl acetate unit was found. The inventors have found that the stability of the solution is good, the transparency of the coating film is good and the coating is very beautiful, and the gas permeation resistance is high, and the coating material is excellent, and thus the present invention has been completed.
E.発明のより詳細な説明 本発明はピロリドン環を含む単位の0.1〜５モル％、エ
チレン単位の含量20〜55モル％、及び酢酸ビニル単位か
らなる三元共重合体をけん化して得られた、酢酸ビニル
成分のけん化度98モル％以上で、かつ好ましくはフェノ
ール85重量％と水15重量％との混合溶媒中、30℃の温度
で測定した固有粘度が0.07〜0.17 l/gの範囲にある、
変性エチレン−ビニルアルコールからなるコーティング
材料である。E. More Detailed Description of the Invention The present invention is obtained by saponifying a terpolymer containing 0.1 to 5 mol% of units containing a pyrrolidone ring, 20 to 55 mol% of ethylene units, and vinyl acetate units. The vinyl acetate component has a saponification degree of 98 mol% or more, and preferably in a mixed solvent of 85% by weight of phenol and 15% by weight of water, the intrinsic viscosity measured at a temperature of 30 ° C. is in the range of 0.07 to 0.17 l / g. It is in,
It is a coating material composed of modified ethylene-vinyl alcohol.
ピロリドン環を含む単位の含量は0.1〜５モル％の範囲
にあることが重要で、いっそう好適な範囲は0.5〜３モ
ル％である。ピロリドン環を含む単位の含量が0.1モル
％より小さいと、溶液安定性、塗工時の透明性が改善さ
れない。他方５モル％より大きいと耐水性、耐湿性が低
下するとともに高温時の耐気体透過性が損なわれて好ま
しくない。エチレン単位の含量は20〜55モル％の範囲に
あることが重要で、いっそう好適な範囲は25〜50モル％
である。エチレン単位の含量が20モル％より小さいと、
耐水性、耐湿性が低下するとともに高温時の耐気体透過
性が損なわれ、他方55モル％より大きいと耐水性、耐湿
性は改善されるものの、低湿時の耐気体透過性が悪化し
不適当である。酢酸ビニルのけん化度は98モル％以上で
あることが必要で、いっそう好適には99モル％以上であ
る。けん化度が98モル％より小さいと耐気体透過性が不
良となって好ましくない。さらに、該共重合体の固有粘
度が0.07 l/gより小さいと塗膜の機械的性質が不良に
なり、他方0.17 l/gより大きいと溶液粘度が高くな
り、コーティング溶液としては好ましくない。ピロリド
ン環を含む単位、エチレン単位及び酢酸ビニル単位から
なる三元共重合体けん化物は従来の公知の方法で工業的
に製造出来る。すなわち、メタノール等のアルコール存
在下、あるいは無存在下に、ピロリドン環を含む単量
体、エチレン及び酢酸ビニルをαα′−アゾビスイソブ
チロニトリル等の公知のラジカル重合開始剤を用いて共
重合し、ついで得られた重合体を水酸化ナトリウム等の
アルカリ触媒を用いてアルコール溶液中でけん化して得
られる。ピロリドン環を含む単量体としては、Ｎ−ビニ
ル−２−ピロリドンあるいはその誘導体が適している
が、経済的に見てＮ−ビニル−２−ピロリドンが好まし
い。このようにして得られた変性EVOHは溶媒に溶解され
て、各種基材にコーティングされる。ここで溶媒として
は、ジメチルスルホキシド、ジメチルフォルムアミド、
メタノール、エタノール、プロピルアルコール類、ブチ
ルアルコール類など炭素数４以下の脂肪族アルコール
類、該アルコール類−水系溶媒等が用いられるが、溶解
性、溶解温度、揮発性（乾燥速度）、経済性等の見地か
ら該アルコール類−水系溶媒が好ましい。就中、該アル
コールがｎ−プロピルアルコール、iso−プロピルアル
コール、ｎ−ブチルアルコール、sec−ブチルアルコー
ル、ｔ−ブチルアルコールの中から選ばれた１種または
２種以上の混合物であるアルコール−水系溶媒が好適に
用いられる。このうちｎ−プロピルアルコールが最適で
ある。該アルコール−水系溶媒の最適組成は溶解性、溶
液の放置安定性等から決められるが、多くの場合、アル
コール濃度50重量％以上の範囲（好ましくは50〜80重量
％）であり、アルコールの種別、エチレン含有量等によ
り適宜決められる。It is important that the content of the unit containing the pyrrolidone ring is in the range of 0.1 to 5 mol%, and a more preferable range is 0.5 to 3 mol%. When the content of the unit containing a pyrrolidone ring is less than 0.1 mol%, the solution stability and the transparency during coating are not improved. On the other hand, if it is more than 5 mol%, water resistance and moisture resistance are deteriorated and gas permeation resistance at high temperature is impaired, which is not preferable. It is important that the content of ethylene units is in the range of 20-55 mol%, a more preferred range is 25-50 mol%
Is. If the content of ethylene units is less than 20 mol%,
Water resistance and moisture resistance are reduced and gas permeation resistance at high temperature is impaired. On the other hand, if it is more than 55 mol%, water resistance and moisture resistance are improved, but gas permeation resistance at low humidity is deteriorated and it is inappropriate. Is. The degree of saponification of vinyl acetate must be 98 mol% or more, and more preferably 99 mol% or more. If the saponification degree is less than 98 mol%, the gas permeation resistance becomes poor, which is not preferable. Further, if the intrinsic viscosity of the copolymer is less than 0.07 l / g, the mechanical properties of the coating film will be poor, and if it is greater than 0.17 l / g, the solution viscosity will be high, which is not preferable as a coating solution. A saponified terpolymer containing a unit containing a pyrrolidone ring, an ethylene unit and a vinyl acetate unit can be industrially produced by a conventionally known method. That is, a monomer containing a pyrrolidone ring, ethylene and vinyl acetate are copolymerized with a known radical polymerization initiator such as αα′-azobisisobutyronitrile in the presence or absence of alcohol such as methanol. Then, the obtained polymer is saponified in an alcohol solution using an alkali catalyst such as sodium hydroxide. As the monomer containing a pyrrolidone ring, N-vinyl-2-pyrrolidone or a derivative thereof is suitable, but N-vinyl-2-pyrrolidone is preferable from the economical viewpoint. The modified EVOH thus obtained is dissolved in a solvent and coated on various substrates. Here, as the solvent, dimethylsulfoxide, dimethylformamide,
Methanol, ethanol, propyl alcohols, butyl alcohols, and other aliphatic alcohols having 4 or less carbon atoms, alcohols / aqueous solvents, and the like are used, but solubility, dissolution temperature, volatility (drying rate), economical efficiency, etc. From the viewpoint of, the alcohol-water solvent is preferable. Above all, an alcohol-water solvent in which the alcohol is one kind or a mixture of two or more kinds selected from n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, sec-butyl alcohol and t-butyl alcohol. Is preferably used. Of these, n-propyl alcohol is most suitable. The optimum composition of the alcohol-water-based solvent is determined based on solubility, stability of leaving the solution, etc., but in many cases, the alcohol concentration is in the range of 50% by weight or more (preferably 50 to 80% by weight). , Ethylene content, etc.
この溶液中の変性EVOH濃度は２〜20重量％が好ましく、
最適には５〜15重量％である。２重量％より低くなると
溶媒の使用量が増加し経済的に不利があり、又20重量％
より高くなると溶液粘度が高くなり過ぎ塗工し難くなる
不利がある。The modified EVOH concentration in this solution is preferably 2 to 20% by weight,
Optimally, it is 5 to 15% by weight. If it is lower than 2% by weight, the amount of solvent used increases, which is economically disadvantageous.
If it is higher, the solution viscosity becomes too high, and there is a disadvantage that coating becomes difficult.
このようにして得られた溶液を各種基材にコーティング
する方法としては、キャスティングヘッドからの吐出、
ロールコート、ドクターナイフコート、スプレーコート
浸漬、刷毛塗り等任意の手段を採用出来る。コーティン
グ後、塗膜は乾燥され、さらには必要に応じ熱処理され
る。ここで乾燥条件としては塗膜厚等により異なるが、
温度50〜130℃，時間10秒〜10分が好ましく、又熱処理
条件としては、温度100〜150℃、時間10秒〜10分が好ま
しい。又塗膜の厚さ（ドライベース）は０、５〜20μ、
好適には１〜15μである。As a method of coating various substrates with the solution thus obtained, ejection from a casting head,
Any means such as roll coating, doctor knife coating, spray coating dipping, and brush coating can be adopted. After coating, the coating film is dried and further heat treated if necessary. Here, the drying conditions vary depending on the coating thickness, etc.,
The temperature is preferably 50 to 130 ° C. and the time is 10 seconds to 10 minutes, and the heat treatment condition is preferably the temperature 100 to 150 ° C. and the time is 10 seconds to 10 minutes. The thickness of the coating film (dry base) is 0, 5 to 20μ,
It is preferably 1 to 15 μ.
本発明の変性EVOHからなるコーティング材料はフイル
ム、シート、容器等の基材、特に耐気体透過性が要求さ
れる食品包装材（フィルム、シート、容器等）の表面コ
ーティング材料として有用である。又これらのフイル
ム、シート、容器等の基材としてはポリオレフィン（ポ
リエチレン、ポリプロピレン等）、エチレン−プロピレ
ン共重合体、エチレン−酢酸ビニル重合体、熱可塑性ポ
リエステル、ポリアミド、ポリスチレン、ポリ塩化ビニ
ル、ポリカーボネート、等が代表的なものとしてあげら
れる。また本発明のコーティング材料は食品包装材以外
の、たとえば塩ビ壁紙（可塑剤含有ポリ塩化ビニルフイ
ルム、またはシート）の表面コーティング材料としても
有用である。この場合、本発明のコーティング材料は塩
ビ壁紙中からの可塑剤のブリーディングを防止し、さら
に表面の汚れを防止する機能を有する。The coating material comprising the modified EVOH of the present invention is useful as a surface coating material for substrates such as films, sheets and containers, particularly food packaging materials (films, sheets, containers, etc.) that require gas permeation resistance. Further, as the base material of these films, sheets, containers, etc., polyolefin (polyethylene, polypropylene etc.), ethylene-propylene copolymer, ethylene-vinyl acetate polymer, thermoplastic polyester, polyamide, polystyrene, polyvinyl chloride, polycarbonate, Etc. are listed as typical ones. The coating material of the present invention is also useful as a surface coating material other than food packaging materials, for example, vinyl chloride wallpaper (plasticizer-containing polyvinyl chloride film or sheet). In this case, the coating material of the present invention has a function of preventing bleeding of the plasticizer from the vinyl chloride wallpaper and further preventing surface stains.
本発明のコーティング材料を前記基材にコーティングす
る場合、基材のコーティング面は、コロナ処理などの物
理的処理（たとえば、基材が、ポリエチレンなどのポリ
オレフィンである場合、該フィルム等の表面張力が37〜
45dyne/cmとなる程度に施す）を行い、ポリウレタン系
のアンカーコート剤、接着剤を施すことが基材面とコー
ティング層との接着をより確実にする為に好ましい。When the coating material of the present invention is coated on the substrate, the coated surface of the substrate is subjected to physical treatment such as corona treatment (for example, when the substrate is polyolefin such as polyethylene, the surface tension of the film or the like is reduced). 37 ~
45 dyne / cm) and then a polyurethane-based anchor coating agent or adhesive is preferable in order to more reliably bond the base material surface to the coating layer.
次に実施例をあげて本発明をさらに詳しく説明するが、
これらの実施例は本発明を何ら限定するものではない。Next, the present invention will be described in more detail with reference to Examples.
These examples do not limit the invention in any way.
F.実施例 実施例 １ Ｎ−ビニル−２−ピロリドン含量1.1モル％、エチレン
含量34.3モル％、酢酸ビニル含量64.4モル％のＮ−ビニ
ル−２−ピロリドン−エチレン−酢酸ビニル共重合体を
メタノール中で水酸化ナトリウムを触媒としてけん化
し、酢酸ビニル成分のけん化度99.4モル％のけん化物
（共重合体Ａ）を得た。該共重合体のフェノール85重量
％と水15重量％との混合溶媒中、30℃の温度で測定した
固有粘度（以下［η］phと記す）は0.108 l/gであり、
メルトインデックス（190℃荷重2160g）は2.3g/10分で
あった。該共重合体をｎ−プロパノール／水比65/35
（重量比）の溶媒に溶解し濃度15重量％の溶液とした。
この溶液の20℃での放置安定性は30日以上経過後もゲル
化せず安定であった。該溶液をポリエチレンテレフタレ
ート（PET）フィルム（厚さ25μ）上にポリウレタン系
アンカーコート剤をバーコーターで1g/m2塗工後、厚さ
５μ（ドライベース）をバーコーターでコーティングを
行い、60℃の熱風乾燥機で３分間乾燥した。該コートフ
ィルムは白化、くもりがなく非常に透明で美麗であっ
た。F. Examples Example 1 An N-vinyl-2-pyrrolidone-ethylene-vinyl acetate copolymer having an N-vinyl-2-pyrrolidone content of 1.1 mol%, an ethylene content of 34.3 mol% and a vinyl acetate content of 64.4 mol% was dissolved in methanol. Was saponified with sodium hydroxide as a catalyst to obtain a saponified product (copolymer A) having a saponification degree of the vinyl acetate component of 99.4 mol%. The intrinsic viscosity (hereinafter referred to as [η] ph) measured at a temperature of 30 ° C. in a mixed solvent of 85% by weight of phenol and 15% by weight of water of the copolymer is 0.108 l / g,
The melt index (190 ° C load 2160g) was 2.3g / 10 minutes. The copolymer was mixed with an n-propanol / water ratio of 65/35.
It was dissolved in a solvent (weight ratio) to give a solution having a concentration of 15% by weight.
The storage stability of this solution at 20 ° C was stable without gelation even after 30 days or more. The solution was applied onto a polyethylene terephthalate (PET) film (thickness 25 μm) with a polyurethane anchor coating agent with a bar coater at 1 g / m 2 and then with a thickness 5 μm (dry base) with a bar coater at 60 ° C. Was dried for 3 minutes with the hot air dryer. The coated film was very transparent and beautiful without whitening or clouding.
また対照例としてエチレン含量34.2モル％、酢酸ビニル
含量65.8モル％のエチレン−酢酸ビニル共重合体をけん
化して得た、酢酸ビニル成分のけん化度99.5モル％、
［η］ph0.11 l/g、メルトインデックス（190℃荷重の
2160g）2.2g/10分のEVOH（共重合体Ｂ）を用いた外は実
施例１と同様にしてEVOH溶液を得た。該溶液は20℃の条
件で５日で白化しゲル化を起こした。溶解１日後の溶液
を実施例１と同様にして得たコートフイルムはくもりを
発生して透明性が悪かった。実施例１で得たPETフィル
ム（25μ）に変性EVOH（５μ）をコートしたフィルムの
酸素透過率を20℃×65％RH条件下にて、酸素透過率測定
器（OX−10−10/50A,MODERN CONTROLS社）で測定し
た。該コートフィルムの酸素透過率は2.4cc/m2・24hr・
atmであった。同様にして測定した対照例で得たコート
フィルムの酸素透過率は20.5cc/m2・24hr・atmであっ
た。As a control example, ethylene content 34.2 mol%, vinyl acetate content 65.8 mol% obtained by saponifying ethylene-vinyl acetate copolymer, saponification degree of vinyl acetate component 99.5 mol%,
[Η] ph 0.11 l / g, melt index (190 ° C load
2160 g) An EVOH solution was obtained in the same manner as in Example 1 except that 2.2 g / 10 min of EVOH (Copolymer B) was used. The solution whitened and gelled in 5 days at 20 ° C. The coated film obtained after 1 day from the dissolution in the same manner as in Example 1 had fog and had poor transparency. The oxygen permeability of a film obtained by coating the PET film (25μ) obtained in Example 1 with modified EVOH (5μ) was measured under the conditions of 20 ° C x 65% RH (OX-10-10 / 50A). , MODERN CONTROLS). The oxygen permeability of the coated film is 2.4 cc / m 2 · 24 hr ·
It was atm. The oxygen permeability of the coated film obtained in the control example measured in the same manner was 20.5 cc / m 2 · 24 hr · atm.
実施例 ２ Ｎ−ビニル−２−ピロリドン含量4.5モル％、エチレン
含量40.4モル％、酢酸ビニル含量55.5モル％のＮ−ビニ
ル−２−ピロリドン−エチレン−酢酸ビニル共重合体を
けん化し、酢酸ビニル成分のけん化度99.6モル％、
［η］ph0.097 l/g、メルトインデックス（190℃荷重2
160g）は5.0g/10分の共重合体（共重合体Ｃ）を得た。
該共重体をｎ−プロパノール／水の比が65/35（重量
比）の溶媒に溶解し濃度10％の溶液を得た。該溶液の20
℃での放置安定性は20日以上経過後もゲル化せず安定で
あった。該溶液を軟質塩シート（厚さ100μ）上にポリ
ウレタン系アンカーコート剤をバーコーターで1g/m2塗
工後、厚さ３μ（ドライベース）をバーコーターでコー
ティングを行い、80℃の熱風乾燥機で５分間乾燥した。
該コートシートは白化、くもりがなく非常に透明で美麗
であった。また対照例としてエチレン含量42.2モル％、
酢酸ビニル含量57.8モル％のエチレン−酢酸ビニル共重
合体をけん化して得た。酢酸ビニル成分のけん化度99.5
モル％、［η］ph0.098 l/g、メルトインデックス（19
0℃荷重の2160g）4.8g/10分のEVOH（共重合体Ｄ）を用
いた外は実施例２と同様にしてEVOH溶液を得た。該溶液
は20℃の条件で２日で白化しゲル化を起こした。溶解直
後の溶液を実施例２と同様にして得たコートシートはく
もりを発生し良好な塗膜が得られなかった。Example 2 N-vinyl-2-pyrrolidone-ethylene-vinyl acetate copolymer having an N-vinyl-2-pyrrolidone content of 4.5 mol%, an ethylene content of 40.4 mol% and a vinyl acetate content of 55.5 mol% was saponified to obtain a vinyl acetate component. Saponification degree of 99.6 mol%,
[Η] ph 0.097 l / g, melt index (190 ℃ load 2
160 g) gave 5.0 g / 10 min of copolymer (Copolymer C).
The copolymer was dissolved in a solvent having an n-propanol / water ratio of 65/35 (weight ratio) to obtain a solution having a concentration of 10%. 20 of the solution
The storage stability at ℃ was stable without gelation even after 20 days. The solution was applied on a soft salt sheet (thickness 100μ) with a polyurethane anchor coating agent with a bar coater at 1g / m 2 and then with a thickness 3μ (dry base) with a bar coater, and dried with hot air at 80 ° C. Machine dried for 5 minutes.
The coated sheet had no whitening and no cloudiness and was very transparent and beautiful. As a control example, ethylene content 42.2 mol%,
Obtained by saponifying an ethylene-vinyl acetate copolymer having a vinyl acetate content of 57.8 mol%. Saponification degree of vinyl acetate component 99.5
Mol%, [η] ph0.098 l / g, melt index (19
An EVOH solution was obtained in the same manner as in Example 2 except that EVOH (Copolymer D) at 0 ° C load of 2160 g) and 4.8 g / 10 min was used. The solution whitened and gelled in 2 days at 20 ° C. The coated sheet obtained from the solution immediately after dissolution in the same manner as in Example 2 caused clouding and a good coating film could not be obtained.
実施例 ３ Ｎ−ビニル−２−ピロリドン含量0.5モル％、エチレン
含量28.2モル％、酢酸ビニル含量71.3モル％のＮ−ビニ
ル−２−ピロリドン−エチレン−酢酸ビニル共重合体を
けん化し、酢酸ビニル成分のけん化度99.7モル％、
［η］ph0.127 l/g、メルトインデックス（190℃荷重2
160g）は0.66g/10分の共重合体（共重合体Ｅ）を得た。
該共重合体を用いて実施例１と同様にして、変性EVOH溶
液を得た。この溶液の20℃放置安定性は20日経過後もゲ
ル化せず安定であった。該溶液を実施例と同様にして得
た塗膜は透明性が良く外観が良好であった。Example 3 N-vinyl-2-pyrrolidone-ethylene-vinyl acetate copolymer having an N-vinyl-2-pyrrolidone content of 0.5 mol%, an ethylene content of 28.2 mol% and a vinyl acetate content of 71.3 mol% was saponified to obtain a vinyl acetate component. Saponification degree of 99.7 mol%,
[Η] ph 0.127 l / g, melt index (190 ℃ load 2
160 g) gave 0.66 g / 10 min of copolymer (Copolymer E).
A modified EVOH solution was obtained in the same manner as in Example 1 using the copolymer. The stability of this solution when allowed to stand at 20 ° C. was stable even after 20 days without gelation. The coating film obtained by using the solution in the same manner as in Example had good transparency and good appearance.
また対照例としてエチレン含量28.4モル％、酢酸ビニル
含量71.6モル％のエチレン−酢酸ビニル共重合体をけん
化して得た、酢酸ビニル成分のけん化度99.4モル％、
［η］ph0.128 l/g、メルトインデックス（200℃荷重2
160g）1.0g/10分のEVOH（共重合体Ｆ）を用いた外は実
施例１と同様にしてEVOH溶液を得た。該溶液は20℃の条
件で５日で白化しゲル化を起こした。該溶液を実施例１
と同様にして得た塗膜は、くもりを生じ、むらがあっ
た。As a control example, ethylene content 28.4 mol%, obtained by saponifying ethylene-vinyl acetate copolymer having a vinyl acetate content of 71.6 mol%, the saponification degree of the vinyl acetate component is 99.4 mol%,
[Η] ph 0.128 l / g, melt index (200 ℃ load 2
An EVOH solution was obtained in the same manner as in Example 1 except that 160 g) 1.0 g / 10 min EVOH (copolymer F) was used. The solution whitened and gelled in 5 days at 20 ° C. The solution was used in Example 1.
The coating film obtained in the same manner as above had fog and was uneven.
実施例３で得たコートフィルムを実施例１と同様に測定
した酸素透過率は2.2cc/m2・24hr・atmであった。対照
例のコートフイルムの酸素透過率は、24.3cc/m2・24hr
・atmであった。The oxygen permeability of the coated film obtained in Example 3 measured in the same manner as in Example 1 was 2.2 cc / m 2 · 24 hr · atm. Oxygen permeability of the coated film of the control example, 24.3cc / m 2 · 24hr
・ It was atm.
G.発明の効果 本発明によればピロリドン環を含む単位、エチレン単位
及び酢酸ビニル単位の各々を特定の量含む三元共重合体
のけん化物は溶液の放置安定性が非常に優れており、ま
た塗膜を形成する場合、白化、くもりの発生が全くない
透明性の良い美麗な塗膜が得られるという特徴を有して
いる。又この塗膜は優れた耐気体透過性、耐油性塩ビ可
塑剤等のブリード防止性を有しており、各種フィルム、
シート、容器等のコーティング材料に好適に用いられ
る。G. Effect of the Invention According to the present invention, a saponified product of a terpolymer containing a pyrrolidone ring-containing unit, an ethylene unit and a vinyl acetate unit in a specific amount is very excellent in leaving stability of a solution, Further, when a coating film is formed, it has a characteristic that a beautiful coating film with good transparency can be obtained without any whitening or clouding. In addition, this coating film has excellent gas permeation resistance and bleed prevention properties such as oil-resistant PVC plasticizers.
It is preferably used as a coating material for sheets, containers and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 守谷 健 岡山県倉敷市酒津1621番地 株式会社クラ レ内 (72)発明者 米津 潔 岡山県倉敷市酒津1621番地 株式会社クラ レ内 (72)発明者 田中 信雄 岡山県倉敷市酒津1621番地 株式会社クラ レ内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Ken Moriya Ken 1621 Sakata, Kurashiki, Okayama Prefecture, Kuraray Co., Ltd. (72) Inventor Kiyoshi Yonezu 1621 Sakata, Kurashiki, Okayama, Inc. (72) Inventor, Kuraray Nobuo Tanaka 1621 Satsuki, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd.
Claims (5)
ル％，エチレン単位の含量20〜55モル％及び酢酸ビニル
成分のけん化度が98モル％以上である変性エチレン−酢
酸ビニル共重合体けん化物からなるコーテイング材料。1. A modified ethylene-vinyl acetate copolymer soap in which the content of units containing a pyrrolidone ring is 0.1 to 5 mol%, the content of ethylene units is 20 to 55 mol%, and the degree of saponification of vinyl acetate component is 98 mol% or more. A coating material made of a compound.
２−ピロリドンである特許請求の範囲第１項記載のコー
テイング材料。2. A unit containing a pyrrolidone ring is N-vinyl-
The coating material according to claim 1, which is 2-pyrrolidone.
物が固有粘度（フエノール85重量％と水15重量％との混
合溶媒中、30℃の温度で測定した値）0.07〜0.17 l/g
である特許請求の範囲第１項記載のコーテイング材料。3. The modified ethylene-vinyl acetate copolymer saponified product has an intrinsic viscosity (measured in a mixed solvent of 85% by weight of phenol and 15% by weight of water at a temperature of 30 ° C.) of 0.07 to 0.17 l / g.
The coating material according to claim 1, wherein
ニル共重合体けん化物の溶液である特許請求の範囲第１
項記載のコーテイング材料。4. The coating material is a solution of a modified ethylene-vinyl acetate copolymer saponified product.
The coating material according to the item.
物溶媒が、水−アルコール混合溶媒である特許請求の範
囲第４項記載のコーテイング材料。5. The coating material according to claim 4, wherein the saponified solvent of the modified ethylene-vinyl acetate copolymer is a water-alcohol mixed solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28741686A JPH0756013B2 (en) | 1986-12-01 | 1986-12-01 | Coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28741686A JPH0756013B2 (en) | 1986-12-01 | 1986-12-01 | Coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63139954A JPS63139954A (en) | 1988-06-11 |
| JPH0756013B2 true JPH0756013B2 (en) | 1995-06-14 |
Family
ID=17717046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28741686A Expired - Fee Related JPH0756013B2 (en) | 1986-12-01 | 1986-12-01 | Coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0756013B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2574197B2 (en) * | 1992-04-24 | 1997-01-22 | 日本ペイント株式会社 | Hydrophilizing surface treatment agent for aluminum heat exchanger and hydrophilizing surface treatment method |
-
1986
- 1986-12-01 JP JP28741686A patent/JPH0756013B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63139954A (en) | 1988-06-11 |
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