JP2000302821A - Vinylidene chloride copolymer and coating agent - Google Patents
Vinylidene chloride copolymer and coating agentInfo
- Publication number
- JP2000302821A JP2000302821A JP11110250A JP11025099A JP2000302821A JP 2000302821 A JP2000302821 A JP 2000302821A JP 11110250 A JP11110250 A JP 11110250A JP 11025099 A JP11025099 A JP 11025099A JP 2000302821 A JP2000302821 A JP 2000302821A
- Authority
- JP
- Japan
- Prior art keywords
- vinylidene chloride
- weight
- coating agent
- barrier properties
- copolymer
- 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.)
- Pending
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- Polyurethanes Or Polyureas (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、バリヤー性、耐変
色性に優れた塩化ビニリデン系共重合体およびこの共重
合体とイソシアネート化合物を有機溶剤に溶解させたコ
ーティング剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinylidene chloride copolymer having excellent barrier properties and discoloration resistance, and a coating agent obtained by dissolving the copolymer and an isocyanate compound in an organic solvent.
【０００２】[0002]
【従来の技術】塩化ビニリデン系共重合体の被膜は、バ
リヤー性に優れているという特徴をもっている。そのた
め、塩化ビニリデン系共重合体を塗工したフィルムは主
に食品包装材料用として、酸素や水蒸気を遮断し包装さ
れた食品を湿ったり酸化させずに長期間保存することを
可能にするために使用されている。フィルムの中には、
酸素あるいは水蒸気に対するバリヤー性に優れたものは
あるが、酸素と水蒸気の両方を高度な水準で遮断できる
ものは塩化ビニリデン系共重合体を除いては稀有であ
る。そのため、塩化ビニリデン系共重合体を塗工したフ
ィルムはおもに食品包装材料として広く使用されてい
る。2. Description of the Related Art A coating film of a vinylidene chloride-based copolymer is characterized by having excellent barrier properties. Therefore, a film coated with a vinylidene chloride copolymer is mainly used for food packaging materials, in order to block oxygen and water vapor and to preserve the packaged food for a long time without moistening or oxidizing it. It is used. In the film,
While some have excellent barrier properties against oxygen or water vapor, those that can block both oxygen and water vapor at a high level are rare except for vinylidene chloride copolymers. For this reason, films coated with a vinylidene chloride-based copolymer are widely used mainly as food packaging materials.
【０００３】塩化ビニリデン系コーティング剤の中で
も、塩化ビニリデン系共重合体の粉末を有機溶剤に溶解
した溶剤系のコーティング剤は、エマルジョン系のコー
ティング剤に比べ、界面活性剤等の水溶性物質を含んで
いないため、被膜のバリアー性が非常に優れている。ま
た、塩化ビニリデン系樹脂はプラスチックフィルムに対
する接着力が十分ではない。そのため、塩化ビニリデン
系エマルジョンをプラスチックフィルム上に塗布する場
合には、塩化ビニリデン系エマルジョンを塗布する前に
溶剤系の接着剤を塗布するが、溶剤系の塩化ビニリデン
系コーティング剤の場合には一般にコーティング剤の中
に接着増強剤を添加して塗布する。この場合、添加する
接着増強剤はイソシアネート化合物が最も好ましい。し
かし、イソシアネート化合物をコーティング剤に添加す
ると、被膜のバリヤー性が低下し、さらに被膜が著しく
着色するという問題がある。[0003] Among vinylidene chloride-based coating agents, a solvent-based coating agent obtained by dissolving a vinylidene chloride-based copolymer powder in an organic solvent contains a water-soluble substance such as a surfactant in comparison with an emulsion-based coating agent. Therefore, the barrier property of the coating is very excellent. Further, the vinylidene chloride-based resin does not have sufficient adhesive strength to a plastic film. For this reason, when applying a vinylidene chloride-based emulsion on a plastic film, a solvent-based adhesive is applied before applying the vinylidene chloride-based emulsion, but in the case of a solvent-based vinylidene chloride-based coating agent, the coating is generally performed. An adhesion enhancer is added to the composition and applied. In this case, the added adhesion enhancer is most preferably an isocyanate compound. However, when the isocyanate compound is added to the coating agent, there is a problem that the barrier property of the film is reduced and the film is significantly colored.
【０００４】溶剤系の塩化ビニリデン系コーティング剤
として、例えば、特公昭４７ー３８６２７号公報、米国
特許第３２９７６６６号、第３８１７７８０号およびイ
ギリス特許１３３３５６６号の各明細書に溶剤系コーテ
ィング剤に使用する各種の塩化ビニリデン系共重合体が
提案されている。しかし、近年の市場の要求レベルの高
度化に伴い、従来よりさらにバリヤー性及び耐変色性の
優れたコーティング剤が現在求められている。As solvent-based vinylidene chloride-based coating agents, for example, Japanese Patent Publication No. 47-38627, US Pat. Nos. 3,297,666 and 3,817,780 and British Patent 1,333,566 describe various types of solvent-based coating agents. Has been proposed. However, with the sophistication of the demand level in the market in recent years, a coating agent having more excellent barrier properties and discoloration resistance than ever has been demanded.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、従来の塩化
ビニリデン系コーティング剤に比し優れたバリヤー性と
耐変色性に優れた溶剤系の塩化ビニリデン系コーティン
グ剤を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a solvent-based vinylidene chloride-based coating agent having excellent barrier properties and discoloration resistance as compared with conventional vinylidene chloride-based coating agents. .
【０００６】[0006]
【課題を解決するための手段】本発明者らは前記課題を
解決するため鋭意検討した結果、特定のモノマー組成か
らなる塩化ビニリデン系共重合体が優れたバリヤー性と
耐変色性を有することを見い出し、本発明を完成するに
至った。すなわち本発明は、塩化ビニリデン８８〜９３
重量％とメタクリロニトリル１１．５〜７重量％、アク
リル酸０．３〜２．０重量％からなるモノマー混合物を
乳化重合することにより得られるバリヤー性、耐変色性
に優れた塩化ビニリデン系共重合体に関するものであ
る。Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a vinylidene chloride-based copolymer having a specific monomer composition has excellent barrier properties and discoloration resistance. They have found and completed the present invention. That is, the present invention relates to vinylidene chlorides 88 to 93.
% By weight of a monomer mixture consisting of 11.5 to 7% by weight of methacrylonitrile and 0.3 to 2.0% by weight of acrylic acid. It relates to a polymer.
【０００７】また本発明は、塩化ビニリデン８８〜９３
重量％とメタクリロニトリル１１．５〜７重量％、アク
リル酸０．３〜２．０重量％からなるモノマー混合物を
乳化重合することにより得られる塩化ビニリデン系共重
合体とイソシアネート化合物を有機溶剤に溶解したバリ
ヤー性、耐変色性に優れたコーティング剤に関するもの
である。更にまた本発明は、プラスチックフィルム層
と、前記の塩化ビニリデン系共重合体の層で構成された
バリヤー性、耐変色性に優れた積層フィルムに関するも
のである。[0007] The present invention also relates to a vinylidene chloride of 88-93.
A vinylidene chloride copolymer and an isocyanate compound obtained by emulsion polymerization of a monomer mixture consisting of 1% to 7% by weight of methacrylonitrile and 0.3% to 2.0% by weight of acrylic acid in an organic solvent. The present invention relates to a coating agent having excellent dissolved barrier properties and discoloration resistance. Furthermore, the present invention relates to a laminated film comprising a plastic film layer and the above-mentioned vinylidene chloride copolymer layer and having excellent barrier properties and discoloration resistance.
【０００８】ここでいうプラスチックフィルムは特に限
定されないが、例えば、ポリエステル、ポリアミド、ポ
リイミド、ポリプロピレン、ポリエチレン、ポリビニル
アルコール、セロファン、ポリスチレン、ポリ塩化ビニ
ル、エチレンービニルアルコール共重合体、ポリカーボ
ネート等が挙げられる。本発明の塩化ビニリデン系共重
合体は、塩化ビニリデンの比率が９３重量％を越える場
合には、溶媒に対する溶解性に乏しくなり通常の溶解条
件では完全溶解しなくなるため好ましくない。また、８
８重量％未満の場合にはバリヤー性に乏しく、かつ本発
明のバリヤー性などの効果が小さくなるため好ましくな
い。そのため共重合体の塩化ビニリデン含有量は８８〜
９３重量％の範囲内であることが必要であり、９０〜９
２重量％の範囲内であることがより好ましい。The plastic film referred to herein is not particularly limited, but examples thereof include polyester, polyamide, polyimide, polypropylene, polyethylene, polyvinyl alcohol, cellophane, polystyrene, polyvinyl chloride, ethylene-vinyl alcohol copolymer, and polycarbonate. . When the vinylidene chloride-based copolymer of the present invention has a vinylidene chloride ratio of more than 93% by weight, the solubility in a solvent becomes poor, and the vinylidene chloride is not completely dissolved under ordinary dissolution conditions. Also, 8
If the content is less than 8% by weight, the barrier properties are poor, and the effects of the present invention such as the barrier properties are reduced. Therefore, the vinylidene chloride content of the copolymer is 88 to
It must be in the range of 93% by weight,
More preferably, it is in the range of 2% by weight.
【０００９】また、アクリル酸は０．３重量％未満の場
合には密着性に乏しくなり好ましくない。また、２重量
％を越える場合にはバリヤー性が低下し好ましくない。
そのため共重合体中のアクリル酸含有量は０．３〜２重
量％の範囲内であることが必要であり、０．５〜１．５
重量％の範囲内であることがより好ましい。また、メタ
クリル酸、イタコン酸、マレイン酸等のアクリル酸以外
の不飽和カルボン酸を共重合させた場合には、イソシア
ネート化合物をコーティング剤中に添加した場合に着色
し易くなり好ましくない。よって、不飽和カルボン酸と
してアクリル酸は必須成分である。On the other hand, if the content of acrylic acid is less than 0.3% by weight, the adhesion becomes poor, which is not preferable. On the other hand, if it exceeds 2% by weight, the barrier properties are undesirably reduced.
Therefore, the acrylic acid content in the copolymer needs to be in the range of 0.3 to 2% by weight, and 0.5 to 1.5% by weight.
More preferably, it is within the range of weight%. Further, when unsaturated carboxylic acids other than acrylic acid such as methacrylic acid, itaconic acid and maleic acid are copolymerized, it is not preferable because an isocyanate compound is easily colored when added to the coating agent. Therefore, acrylic acid is an essential component as an unsaturated carboxylic acid.
【００１０】また、塩化ビニリデンと共重合させる単量
体として、アクリル酸以外にはメタクリロニトリルだけ
を共重合させた場合が最もバリヤー性に優れ好ましい。
しかし、樹脂組成物中に１重量％未満ならば他のモノマ
ーを共重合させる単量体として加えてもよい。共重合可
能な単量体としては、塩化ビニル、アクリル酸メチ
ル、、メタクリル酸メチル、アクリロニトリルのうち一
種又は二種以上を選択して用いることができる。本発明
に用いる有機溶剤は、良溶媒単独あるいは良溶媒と貧溶
媒の混合物である。良溶媒としては、テトラヒドロフラ
ン、メチルエチルケトン等が挙げられるが特にテトラヒ
ドロフランが好ましい。また貧溶媒としては、トルエ
ン、キシレン等の芳香族炭化水素、酢酸エチル、酢酸ブ
チル等のエステル類などが挙げられるが、特にトルエン
が好ましい。[0010] In addition, as a monomer to be copolymerized with vinylidene chloride, a case where only methacrylonitrile other than acrylic acid is copolymerized is most preferable because of excellent barrier properties.
However, if less than 1% by weight in the resin composition, another monomer may be added as a monomer to be copolymerized. As the copolymerizable monomer, one or more of vinyl chloride, methyl acrylate, methyl methacrylate, and acrylonitrile can be selected and used. The organic solvent used in the present invention is a good solvent alone or a mixture of a good solvent and a poor solvent. Examples of the good solvent include tetrahydrofuran and methyl ethyl ketone, and tetrahydrofuran is particularly preferable. Examples of the poor solvent include aromatic hydrocarbons such as toluene and xylene, and esters such as ethyl acetate and butyl acetate, and toluene is particularly preferable.
【００１１】また、本発明のコーティング剤に添加する
イソシアネート化合物とはイソシアネート基を有する化
合物であり、例えばトリレンジイソシアネート等の芳香
族ジイソシアネートやヘキサメチレンジイソシアネー
ト、イソホロンジイソシアネート等の脂肪族又は脂環族
ジイソシアネート或いはこれらイソシアネート化合物の
二量体や多量体、あるいは多価アルコールにジイソシア
ネートを付加させた化合物等が挙げられる。イソシアネ
ート化合物の添加量は少ないほどバリヤー性の低下が少
なくて好ましいが、基材フィルムとの密着性のため、あ
る程度の量は必ず必要である。そのため、イソシアネー
ト化合物の添加量は基材フィルムの種類により異なる
が、通常塩化ビニリデン系共重合体１００重量％に対し
１〜４重量％の範囲内が好ましい。The isocyanate compound to be added to the coating agent of the present invention is a compound having an isocyanate group. Alternatively, a dimer or multimer of these isocyanate compounds, a compound obtained by adding a diisocyanate to a polyhydric alcohol, or the like may be used. The smaller the amount of the isocyanate compound added, the smaller the decrease in the barrier property, which is preferable. However, a certain amount is necessarily required for the adhesion to the base film. Therefore, the amount of the isocyanate compound to be added varies depending on the type of the base film, but is usually preferably in the range of 1 to 4% by weight based on 100% by weight of the vinylidene chloride-based copolymer.
【００１２】本発明において塩化ビニリデン系共重合体
の粉体を作成する好ましい方法としては、乳化重合にて
得られた水分散体を凝固剤水溶液中に添加して凝集させ
たのち、洗浄、乾燥させて得る方法が挙げられる。この
場合、水分散体を凝固剤水溶液に添加したときにポリマ
ー粒子が凝集する温度に調整しておくことが必要であ
る。また、この方法において使用される凝固剤の具体例
としては、例えば、塩酸、硫酸、硝酸、酢酸、リン酸な
どの酸類あるいは塩化ナトリウムなどのアルカリ金属
塩、塩化カルシウム、硫酸マグネシウムなどのアルカリ
土類金属塩、硫酸アルミニウムなどのアルミニウム金属
塩が挙げられ、これらを単独あるいは混合して使用でき
る。添加量は特に限定されないが、通常は共重合体に対
し０．０５〜１０重量％程度であり、添加量が少ないほ
ど粉末に含有される量を減少させることができるため好
ましい。In the present invention, as a preferred method for preparing a powder of a vinylidene chloride copolymer, a water dispersion obtained by emulsion polymerization is added to an aqueous solution of a coagulant for coagulation, followed by washing and drying. And the method of obtaining it. In this case, it is necessary to adjust the temperature at which the polymer particles aggregate when the aqueous dispersion is added to the aqueous solution of the coagulant. Specific examples of the coagulant used in this method include, for example, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and phosphoric acid; alkali metal salts such as sodium chloride; and alkaline earth salts such as calcium chloride and magnesium sulfate. Examples thereof include metal salts and aluminum metal salts such as aluminum sulfate, and these can be used alone or as a mixture. The addition amount is not particularly limited, but is usually about 0.05 to 10% by weight based on the copolymer, and the smaller the addition amount is, the more preferable the amount contained in the powder can be reduced.
【００１３】また、塩化ビニリデン系共重合体の水分散
体を凝集させる方法例としては、他に以下の方法が挙げ
られる。 １）メタノール、トルエン等の貧溶媒中に塩化ビニリデ
ン系共重合体の水分散体を滴下もしくはノズルより液中
に噴出させることにより凝集させる方法。 ２）塩化ビニリデン系共重合体の水分散体を高速で攪拌
することにより凝集させる方法。Further, as an example of a method of aggregating an aqueous dispersion of a vinylidene chloride-based copolymer, the following method may be mentioned. 1) A method in which an aqueous dispersion of a vinylidene chloride-based copolymer is dropped into a poor solvent such as methanol or toluene, or is coagulated by being ejected from a nozzle into a liquid. 2) A method in which an aqueous dispersion of a vinylidene chloride-based copolymer is aggregated by stirring at a high speed.
【００１４】[0014]
【発明の実施の形態】以下、実施例などにより本発明を
さらに具体的に説明するが、本発明は実施例などにより
限定されるものではない。また、例中で単に部または％
としているのは、重量部または重量％のことである。な
お、物性評価は以下の方法により求めた。 （１）酸素透過率 ＪＩＳ−Ｋ−７１２６、Ｂ法（等圧法）に準じ、ＯＸＴ
ＲＡＮー１００（ｍｏｄｅｒｎ Ｃｏｎｔｒｏｌ社製）
を用いて、２０℃で相対湿度７０％ＲＨの条件下で酸素
透過率を測定し、測定値を乾燥塗布量２. ５ｇ／ｍ2 に
換算した。 （２）耐変色性 塩化ビニリデン系コーティング剤を塗布したフィルムを
ロール状に巻いた時の断面の着色度合いを目視にて判定
した。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples and the like, but the present invention is not limited to the examples and the like. Also, in the examples, simply parts or%
Means parts by weight or% by weight. In addition, physical property evaluation was calculated | required by the following method. (1) Oxygen permeability OXT according to JIS-K-7126, Method B (isobaric method)
RAN-100 (manufactured by modern Control)
Was used to measure the oxygen permeability under the conditions of 20 ° C. and 70% RH, and the measured value was converted to a dry coating amount of 2.5 g / m 2 . (2) Discoloration resistance The degree of coloring of the cross section when the film coated with the vinylidene chloride-based coating agent was wound into a roll was visually determined.
【００１５】[0015]
【実施例１】ガラスライニングを施した耐圧反応器内
に、イオン交換水１００部、アルキル硫酸ナトリウム
０．１部、過硫酸ナトリウム０．６部を仕込み脱気を行
った後、内容物の温度を５０℃に保った。別の容器に塩
化ビニリデン９１重量％、メタクリロニトリル８．４重
量％、アクリル酸０．６重量％を計量混合してモノマー
混合物を作成した。前記反応器内にモノマー混合物１０
部を添加した後、内圧が最高圧よりも0.02MPa 降下した
ら前述のモノマー混合物の残り９０部を１６時間かけて
全量連続添加した。モノマー混合物を全量添加した後内
圧が0.05MPa 降下するまで反応を進行させて塩化ビニリ
デン系共重合体の水分散体を得た。得られた塩化ビニリ
デン系共重合体の水分散体３０ｇを６０℃に加温した塩
化カルシウムの３％水溶液１００ｇの中に攪拌しながら
少しずつ滴下した後、生成した凝集物を水洗、乾燥して
白色の粉末を得た。Example 1 100 parts of ion-exchanged water, 0.1 part of sodium alkyl sulfate, and 0.6 part of sodium persulfate were charged into a pressure-resistant reactor lined with glass, deaerated, and then heated to a temperature of the contents. Was kept at 50 ° C. In a separate container, 91% by weight of vinylidene chloride, 8.4% by weight of methacrylonitrile, and 0.6% by weight of acrylic acid were weighed and mixed to prepare a monomer mixture. The monomer mixture 10 in the reactor
When the internal pressure dropped by 0.02 MPa from the maximum pressure after the addition of parts, the remaining 90 parts of the above monomer mixture was continuously added over 16 hours. After the entire amount of the monomer mixture was added, the reaction was allowed to proceed until the internal pressure dropped to 0.05 MPa to obtain an aqueous dispersion of a vinylidene chloride copolymer. 30 g of the obtained aqueous dispersion of vinylidene chloride copolymer was added dropwise with stirring to 100 g of a 3% aqueous solution of calcium chloride heated to 60 ° C., and the resulting aggregates were washed with water and dried. A white powder was obtained.
【００１６】こうして得られた塩化ビニリデン系共重合
体の粉末１０ｇをテトラヒドロフラン３０ｇ、メチルエ
チルケトン１８ｇ、トルエン１２ｇの混合溶剤中に添加
後、６５℃まで温度を上げてポリマーを完全溶解した。
この溶液中にイソシアネート化合物としてコロネートＬ
（日本ポリウレタン工業社製商品名、固形分７５％）３
部を添加したのち、４５℃まで冷却して１時間放置し
た。こうして得られたコーティング剤を、２軸延伸ポリ
プロピレンフィルム（厚み１８μm）上に乾燥塗布量が
２．５ｇ／ｍ2 になるように塗工し、１２０℃に保った
オーブン中で３０秒乾燥したのち、４０℃に保ったオー
ブン中で１日間加熱処理してコートフィルムを得た。得
られたコートフィルムについて酸素透過率、耐変色性の
評価を行った。評価結果を表１に示した。After adding 10 g of the vinylidene chloride copolymer powder thus obtained to a mixed solvent of 30 g of tetrahydrofuran, 18 g of methyl ethyl ketone and 12 g of toluene, the temperature was raised to 65 ° C. to completely dissolve the polymer.
Coronate L as an isocyanate compound in this solution
(Nippon Polyurethane Industry Co., Ltd., solid content 75%) 3
Then, the mixture was cooled to 45 ° C. and left for 1 hour. The thus obtained coating agent is applied on a biaxially stretched polypropylene film (thickness: 18 μm) so that the dry coating amount is 2.5 g / m 2, and dried in an oven maintained at 120 ° C. for 30 seconds. For 1 day in an oven maintained at 40 ° C. to obtain a coated film. The resulting coated film was evaluated for oxygen permeability and discoloration resistance. Table 1 shows the evaluation results.
【００１７】[0017]
【実施例２】実施例１のモノマー混合物を塩化ビニリデ
ン９１．５重量％、メタクリロニトリル７．５重量％、
アクリル酸１重量％に変えた以外は実施例１と同様の方
法にて行いコートフィルムを得、同様に評価を行い、結
果を表１に示した。EXAMPLE 2 91.5% by weight of vinylidene chloride, 7.5% by weight of methacrylonitrile,
A coating film was obtained in the same manner as in Example 1 except that the amount was changed to 1% by weight of acrylic acid, and evaluation was performed in the same manner. The results are shown in Table 1.
【実施例３】実施例１のモノマー混合物を塩化ビニリデ
ン９１．５重量％、メタクリロニトリル７．５重量％、
メタクリル酸メチル０．５重量％、アクリル酸０．５重
量％に変えた以外は実施例１と同様の方法にて行いコー
トフィルムを得、同様に評価を行い、結果を表１に示し
た。Example 3 91.5% by weight of vinylidene chloride, 7.5% by weight of methacrylonitrile,
A coating film was obtained in the same manner as in Example 1 except that the amount was changed to 0.5% by weight of methyl methacrylate and 0.5% by weight of acrylic acid, and a coated film was evaluated. The results are shown in Table 1.
【００１８】[0018]
【実施例４】実施例１のモノマー混合物を塩化ビニリデ
ン９０．５重量％、メタクリロニトリル９重量％、アク
リル酸０．５重量％に変えた以外は実施例１と同様の方
法にて行いコートフィルムを得、同様に評価を行い、結
果を表１に示した。Example 4 Coating was carried out in the same manner as in Example 1 except that the monomer mixture of Example 1 was changed to 90.5% by weight of vinylidene chloride, 9% by weight of methacrylonitrile and 0.5% by weight of acrylic acid. A film was obtained and evaluated in the same manner. The results are shown in Table 1.
【比較例１】実施例１のモノマー混合物を塩化ビニリデ
ン９１重量％、メタクリロニトリル５重量％、メタクリ
ル酸メチル３重量％、メタクリル酸１重量％にした以外
は実施例１と同様の方法にて行いコートフィルムを得、
同様に評価を行い、結果を表１に示した。Comparative Example 1 The procedure of Example 1 was repeated except that the monomer mixture of Example 1 was changed to 91% by weight of vinylidene chloride, 5% by weight of methacrylonitrile, 3% by weight of methyl methacrylate, and 1% by weight of methacrylic acid. To obtain a coated film,
Evaluation was performed in the same manner, and the results are shown in Table 1.
【００１９】[0019]
【比較例２】実施例１のモノマー混合物を塩化ビニリデ
ン９１重量％、メタクリル酸メチル８重量％、アクリル
酸１重量％にした以外は実施例１と同様の方法にて行い
コートフィルムを得、同様に評価を行い、結果を表１に
示した。Comparative Example 2 A coated film was obtained in the same manner as in Example 1 except that the monomer mixture of Example 1 was changed to 91% by weight of vinylidene chloride, 8% by weight of methyl methacrylate, and 1% by weight of acrylic acid. The results are shown in Table 1.
【比較例３】実施例１のモノマー混合物を塩化ビニリデ
ン９１重量％、アクリロニトリル８重量％、アクリル酸
１重量％にした以外は実施例１と同様の方法にて行いコ
ートフィルムを得、同様に評価を行い、結果を表１に示
した。Comparative Example 3 A coated film was obtained in the same manner as in Example 1 except that the monomer mixture of Example 1 was changed to 91% by weight of vinylidene chloride, 8% by weight of acrylonitrile, and 1% by weight of acrylic acid. And the results are shown in Table 1.
【００２０】[0020]
【比較例５】実施例１のモノマー混合物を塩化ビニリデ
ン９１重量％、メタクリロニトリル８重量％、メタクリ
ル酸１重量％にした以外は実施例１と同様の方法にて行
いコートフィルムを得、同様に評価を行い、結果を表１
に示した。Comparative Example 5 A coated film was obtained in the same manner as in Example 1 except that the monomer mixture of Example 1 was changed to 91% by weight of vinylidene chloride, 8% by weight of methacrylonitrile, and 1% by weight of methacrylic acid. Table 1 shows the results.
It was shown to.
【比較例６】実施例１のモノマー混合物を塩化ビニリデ
ン９１重量％、メタクリロニトリル８重量％、イタコン
酸１重量％にした以外は実施例１と同様の方法にて行い
コートフィルムを得、同様に評価を行い、結果を表１に
示した。Comparative Example 6 A coated film was obtained in the same manner as in Example 1 except that the monomer mixture of Example 1 was changed to 91% by weight of vinylidene chloride, 8% by weight of methacrylonitrile, and 1% by weight of itaconic acid. The results are shown in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】なお、表中における略号は下記の通りであ
る。 ＶＤＣ：塩化ビニリデン ＭＡＮ：メタクリロニトリル ＡＡ：アクリル酸 ＭＭＡ：メタクリル酸メチル ＡＮ：アクリロニトリル ＭＡＡ：メタクリル酸 ＩＡ：イタコン酸 表１から明らかなように、実施例１〜４で得られた塗膜
は比較例１〜５のものに比べて、バリヤー性、耐変色性
ともに優れている。The abbreviations in the table are as follows. VDC: vinylidene chloride MAN: methacrylonitrile AA: acrylic acid MMA: methyl methacrylate AN: acrylonitrile MAA: methacrylic acid IA: itaconic acid As apparent from Table 1, the coating films obtained in Examples 1 to 4 are compared. Both the barrier property and the discoloration resistance are superior to those of Examples 1 to 5.
【００２３】[0023]
【発明の効果】本発明の塩化ビニリデン系コーティング
剤は従来よりもバリヤー性に優れかつ着色の程度が少な
い。そのため従来よりも少ない塗工量で同じバリヤー性
が達成でき、かつ溶剤系コーティング剤の欠点であった
着色も軽減されたためコートコスト低減及び品質の向上
を達成することができる。The vinylidene chloride-based coating agent of the present invention has better barrier properties and a lower degree of coloring than conventional ones. Therefore, the same barrier property can be achieved with a smaller coating amount than in the past, and coloring, which is a drawback of the solvent-based coating agent, has been reduced, so that a reduction in coating cost and an improvement in quality can be achieved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） //(Ｃ０８Ｆ 214/08 220:44 220:06） Ｆターム(参考） 4F100 AK01B AK07 AK16A AK25A AK27A AL01A AL05A BA02 EH462 EJ422 EJ862 GB15 GB23 JD01A JN28A 4J034 BA03 DA05 DB07 DD08 DP03 DP16 DP18 HA07 HB11 HC03 HC12 HC18 HC22 SA01 4J038 CD081 CG031 CG161 PB03 PC08 4J100 AC04P AJ02R AM02Q CA05 DA22 EA01 FA20 JA01 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // (C08F 214/08 220: 44 220: 06) F term (Reference) 4F100 AK01B AK07 AK16A AK25A AK27A AL01A AL05A BA02 EH462 EJ422 EJ862 GB15 GB23 JD01A JN28A 4J034 BA03 DA05 DB07 DD08 DP03 DP16 DP18 HA07 HB11 HC03 HC12 HC18 HC22 SA01 4J038 CD081 CG031 CG161 PB03 PC08 4J100 AC04P AJ02R AM02Q CA05 DA22 EA01 FA
Claims (3)
クリロニトリル１１．５〜７重量％、アクリル酸０．３
〜２．０重量％からなるモノマー混合物を乳化重合する
ことにより得られるバリヤー性、耐変色性に優れた塩化
ビニリデン系共重合体。1. 88 to 93% by weight of vinylidene chloride, 11.5 to 7% by weight of methacrylonitrile, 0.3 of acrylic acid
A vinylidene chloride-based copolymer having excellent barrier properties and discoloration resistance, which is obtained by emulsion-polymerizing a monomer mixture of from 2.0 to 2.0% by weight.
クリロニトリル１１．５〜７重量％、アクリル酸０．３
〜２．０重量％からなるモノマー混合物を乳化重合する
ことにより得られる塩化ビニリデン系共重合体とイソシ
アネート化合物を有機溶剤に溶解したバリヤー性、耐変
色性に優れたコーティング剤。2. 88 to 93% by weight of vinylidene chloride, 11.5 to 7% by weight of methacrylonitrile, 0.3 of acrylic acid
A coating agent having excellent barrier properties and discoloration resistance in which a vinylidene chloride-based copolymer and an isocyanate compound obtained by emulsion-polymerizing a monomer mixture of from 2.0 to 2.0% by weight are dissolved in an organic solvent.
載の塩化ビニリデン系共重合体の層で構成されたバリヤ
ー性、耐変色性に優れた積層フィルム。3. A laminated film comprising a plastic film layer and a layer of the vinylidene chloride-based copolymer according to claim 1 and having excellent barrier properties and discoloration resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11110250A JP2000302821A (en) | 1999-04-19 | 1999-04-19 | Vinylidene chloride copolymer and coating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11110250A JP2000302821A (en) | 1999-04-19 | 1999-04-19 | Vinylidene chloride copolymer and coating agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000302821A true JP2000302821A (en) | 2000-10-31 |
Family
ID=14530928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11110250A Pending JP2000302821A (en) | 1999-04-19 | 1999-04-19 | Vinylidene chloride copolymer and coating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000302821A (en) |
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-
1999
- 1999-04-19 JP JP11110250A patent/JP2000302821A/en active Pending
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| JP2018127523A (en) * | 2017-02-07 | 2018-08-16 | 旭化成株式会社 | Vinylidene chloride-based copolymer latex |
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