JP3830237B2 - Vinylidene chloride copolymer latex - Google Patents
Vinylidene chloride copolymer latex Download PDFInfo
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- JP3830237B2 JP3830237B2 JP21021797A JP21021797A JP3830237B2 JP 3830237 B2 JP3830237 B2 JP 3830237B2 JP 21021797 A JP21021797 A JP 21021797A JP 21021797 A JP21021797 A JP 21021797A JP 3830237 B2 JP3830237 B2 JP 3830237B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、ガス（特に酸素）及び水蒸気の遮断性（バリヤー性）が高度に優れ、かつ、熱、光に対して優れた耐変色性を有する塗膜を形成し得る塩化ビニリデン系共重合体ラテックスに関するものである。
【０００２】
【従来の技術】
塩化ビニリデン系ラテックスは、ポリプロピレン、ポリエステル、ナイロン等のプラスチックフィルムに直接又はアンカーコート剤を塗布した上に塗布され、そのガス及び水蒸気の遮断性を向上せしめるために重用されているが、近年さらに高度なバリヤー性が市場で要求されている。
この市場要求に応ぜんと従来から多数の技術が提案されており、商品化されているものもある。これらは主に、塩化ビニリデン共重合体塗膜の単位厚みあたりのバリヤー性を改良すべく塩化ビニリデンと共重合体を構成するモノマーユニットの種類やその比率、すなわち共重合体組成を変更したもの、被覆物構成する塩化ビニリデン共重合体塗膜の総厚みを大としたもの、もしくは上記両者を組み合わせたものであった。
【０００３】
しかしながら、これら従来の技術により得られた高バリヤー性の被覆物は耐変色性に不満があることが判明した。
塩化ビニリデン系共重合体は熱、光による脱塩化水素により着色することが知られている。食品包装用材料においては、商品の美しい外観を保つことは重要なポイントであり、乾燥のために加熱される加工工程および食品殺菌のための熱水処理での熱変色、商品となった後のディスプレイ時の蛍光灯等での光変色は、その商品価値を損なうことから、耐変色性を抑える技術が求められる。
【０００４】
塗膜の変色を抑える技術としては例えば、特公昭４９−２１３０４公報には酸化防止能を有するフェノール化合物、および紫外線吸収能を有するベンゾトリアゾール誘導体をその重合系内に添加することにより塩化ビニリデン系ラテックスを製造する方法が、また、特公平２−１９１２８号公報にはノニオン性乳化剤の乳化重合における使用量、添加方法を規定し、メタノールによる共重合体からの乳化剤抽出率を規定した塩化ビニリデン共重合体の製造法が開示されている。
【０００５】
しかし、ここにあげられた例では高バリヤー性というには不十分であるか、また、高バリヤー性である場合でも、耐変色性は十分であるとはいえない。
ここで言う高バリヤー性というのは、塗布量が５ｇ／ｍ2 換算で、防湿性においては４０℃相対湿度９０％の条件下での水蒸気透過率（ＷＶＴＲ）が４ｇ／ｍ2 日以下であり、ガスバリヤー性においては２０℃相対湿度７０％条件下での酸素透過率（Ｏ2 ＴＲ）が２ｃｃ／ｍ2 ・ａｔｍ・日以下であることを示す。
【０００６】
【発明が解決しようとする課題】
本発明は、上記の欠点を除いて耐変色性の優れた高バリヤー性の塩化ビニリデン系ラテックスを提供することである。
【０００７】
【課題を解決するための手段】
塩化ビニリデン系共重合体ラテックスにおいては、熱、光などにより共重合体から塩素原子と水素原子が抜けて塩化水素が発生する。
本発明者らは、前記従来技術の課題を克服すべく鋭意検討の結果、驚くべきことに、共重合体組成を規定し、ラテックス共重合体の脱塩化水素速度を一定量以下にまで低下させることによって、該ラテックスを塗布して形成した塗膜の耐変色性が著しく優れて、かつ、高バリヤー性を有するものが得られることを見出し、本発明を完成するに至った。
【０００８】
すなわち、本発明は、８９〜９３重量％の塩化ビニリデン、２〜８重量％のメタクリロニトリル、０．５〜３重量％のアクリル酸−２−ヒドロキシエチルおよび０〜３重量％のこれらと共重合可能な１種以上のビニル系単量体を乳化重合してなる塩化ビニリデン系共重合体を含むラテックスであって、１２０℃における脱塩化水素速度が１ｍｇ／ｌ／１０分以下であることを特徴とする塩化ビニリデン系共重合体ラテックスである。
【０００９】
以下に本発明の詳細を説明する。
本発明において使用するモノマー混合物は、塩化ビニリデンが８９〜９３重量％、望ましくは９０〜９２重量％であり、メタクリロニトリルが２〜８重量％、望ましくは４〜６重量％であり、アクリル酸−２−ヒドロキシエチルが０．５〜３重量％、望ましくは１〜２重量％および０〜３重量％のこれらと共重合可能な１種以上のビニル単量体である。
塩化ビニリデンが８９重量％以下では、目標の高バリヤー性が得られない。一方、９３重量％以上では、ラテックス状の共重合体で短時間で結晶化してしまい、ラテックスを成膜して使用する用途には使用できなくなる。
【００１０】
メタクリロニトリルが２重量％以下では目標の高バリヤー性が得られず、８重量％以上では１２０℃における脱塩化水素速度が１ｍｇ／ｌ／１０分を越えてしまい、良好な耐変色性が得られない。
アクリル酸−２−ヒドロキシエチルが０．５重量％以下では１２０℃における脱塩化水素速度が１ｍｇ／ｌ／１０分を越えてしまい、良好な耐変色性が得られず、３重量％以上では目標とする高バリヤー性、特に水蒸気バリヤー性が得られない。
【００１１】
本発明の塩化ビニリデン系共重合体ラテックスの重合に用いる乳化剤、重合開始剤、界面活性剤等々の種類は特に限定しないが、これらの物質はラテックスから生成させた塗膜中に残存してガス及び水蒸気遮断性を劣化させる要因となりうるので、その使用量は可能な限り少量であることが好ましく、乳化重合に引き続き透析処理を施すことで可能な限り除去するのが、さらに望ましい。
また、低分子量の塩化ビニリデン系共重合体は熱、光に対する安定性が劣ることが知られており、耐変色性はこれら安定性と平行する関係が認められているので分子量はゲルパーミエーションクロマトグラフィーによって測定された重量平均分子量にて１０万以上あることが望ましい。
【００１２】
【発明の実施の形態】
以下で、本発明を実施例等を用いてさらに具体的に説明するが、本発明はこれら実施例等により何ら限定させるものではない。なお、部および％は、特に断らない限り重量基準による。
本発明の実施例等で用いる分析手段などは以下の通りである。
（イ）脱塩化水素速度の測定方法
５０ｍｌの三角フラスコにラテックスの凍結乾燥ポリマー約０．１ｇを入れ、２０ｍｌ／分に流量調整された窒素キャリヤーで５分間置換する。そして、キャリヤーを１００ｍｌの純水を入れた電極槽に５分間導入しイオンメータの指示を読みブランク値とする。そして直ちに、所定温度のオイルバスに所定時間浸積し、その後すばやく取り出し、イオンメータの指示が安定するのを待って（約３０分）指示を読みとる。また、導入ホースを４ｍｌの純水で洗浄し再度指示を読み塩化物イオン量を求める。
また、ポリマー中の塩化水素量を測定するために、熱処理したポリマーの入った三角フラスコにＴＨＦを５ｇ添加しポリマーを溶解または膨潤させ純水を５５ｇ添加しイオンメータで塩化物イオン量を測定する。
【００１３】
【数１】
【数２】
【数３】
（ロ）塗工フィルムの作成
コロナ放電処理を施した延伸ポリプロピレンフィルムまたはポリエステルフィルムに、アンカーコート剤（武田薬品工業（株）製、タケラックＡ−３１０（商品名）／タケネートＡ−３（商品名）／酢酸エチル＝１２／２／９８重量比）を、塗工量０．２ｇ／ｍ2 となるよう塗布乾燥し、次いで塩化ビニリデン系ラテックスをメイヤーロッドを用いて乾燥後塗膜重量が５ｇ／ｍ2 となるように塗布し、熱風循環乾燥機中１２０℃、１０秒にて乾燥した後、４０℃で２日エージング処理を行った。
【００１７】
（ハ）酸素透過率
延伸ポリプロピレンフィルム（２２μ）を用い上述（ロ）項によって作成した塗工フィルムを、室温で相対湿度１００％にて充分調湿した後、ＯＸ−ＴＲＡＮ１００（Ｍｏｄｅｒｎ Ｃｏｎｔｒｏｌ社製）を用い、２０℃、相対湿度１００％にて測定した。塗布量５ｇ／ｍ2 での値である。
（ニ）水蒸気透過率
延伸ポリエステルフィルム（１２μ）を用い、上述（ロ）項によって作成した塗工フィルムを、室温で相対湿度１００％にて充分調湿した後、ＰＥＲＭＡＴＲＡＮ Ｗ３／３１（Ｍｏｄｅｒｎ Ｃｏｎｔｒｏｌ社製）を用い、４０℃、相対湿度９０％にて測定した。塗布量５ｇ／ｍ2 での値である。
【００１８】
（ホ）耐変色性
上述（イ）項によって熱処理したポリマーをテトラヒドロフランに濃度が０．２重量％となるように溶解し、得られた溶液の着色度を色差計（日本電色工業（株）製、Ｚ−３００Ａ型）で測定し、ＹＩ値で表した。
また、２軸延伸ナイロンフィルム（１５μ）を用い上述（ロ）項によって作成した塗工フィルムを８０℃、４日間熱処理、フェードメータに３時間照射した後、コートフィルムをロール状に巻いたもの、およびロール状に巻いたコートフィルムを蛍光灯下１４日間放置したものの端面を目視判定した。
【００１９】
【実施例１】
塩化ビニリデン系共重合体ラテックスを下記の方法により製造した。
ガラスライニングを施した耐圧反応器中に水８５部、アルキルスルホン酸ソーダ（バイエルワロラートＵ、以下同じ）０．１５部および過硫酸ソーダ０．１部を仕込み、脱気した後、内容物の温度を５５℃に保った。これとは別の容器に塩化ビニリデン９１．３部、メタクリロニトリル５．５部、メタクリル酸メチル２部、アクリル酸−２−ヒドロキシエチル１．２部を計量混合してモノマー混合物を作成した。前記耐圧反応器中にモノマー混合物のうち１０部を一括添加し、撹拌下反応器の内圧が降下するまで重合した。続いて、単量体混合物残り９０部を１２時間にわたって連続的に定量添加した。並行して、アルキルスルホン酸ソーダ１部も１０時間にわたって連続的に定量添加した。この間内容物を５５℃に保ち、内圧が十分に降下するまで反応を進行させた。重合収率は９９．９％であった。重合収率はほぼ１００％なので、共重合体の組成は仕込比にほぼ等しい。
【００２０】
かくして得られたラテックスにアルキルスルホン酸ソーダの１５％水溶液を加えて、２０℃における気液表面張力が４２ｍＮ／ｍとなるよう調整した。この後、水蒸気ストリッピングによって未反応モノマーを除去し、セルロ−ス系半透膜を用い透析処理を施した。
得られた塩化ビニリデン系共重合体ラテックスについて、コーティング塗膜の性能、脱塩化水素速度を、後の他の実施例、比較例と共に表１に示す。
【００２１】
【実施例２】
モノマー混合物を塩化ビニリデン９０．５部、メタクリロニトリル６．０部、アクリロニトリル２．５部、アクリル酸−２−ヒドロキシエチル１．０部とした以外は実施例１と全く同様とした。
【実施例３】
モノマー混合物を塩化ビニリデン９２．０部、メタクリロニトリル４．０部、メタクリル酸メチル２．０部、アクリル酸メチル０．５部、アクリル酸−２−ヒドロキシエチル１．５部とした以外は実施例１と全く同様とした。
【００２２】
【比較例１】
モノマー混合物を塩化ビニリデン９１．５部、メタクリロニトリル５．５部、メタクリル酸メチル２．５部、アクリル酸メチル０．５部とした以外は実施例１と全く同様とした。
【比較例２】
モノマー混合物を塩化ビニリデン９１．８部、アクリロニトリル１．０部、メタクリル酸メチル６．３部、アクリル酸メチル０．９部とした以外は実施例１と全く同様とした。
【００２３】
【比較例３】
モノマー混合物を塩化ビニリデン９０．３部、アクリロニトリル１．１部、メタクリル酸メチル６．８部、アクリル酸−２−ヒドロキシエチル１．８部とした以外は実施例１と全く同様とした。
以上の実施例１、２、３および比較例１、２、３のモノマー混合物組成において、第１表のバリヤー性と脱塩化水素速度に示されるごとく、モノマー組成の組み合わせと脱塩化水素速度が本発明の条件を満たすときに、高バリヤー性と耐変色性が兼備できることが明示されている。
【００２４】
【表１】
BACKGROUND OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention is a vinylidene chloride copolymer capable of forming a coating film having a high gas (particularly oxygen) and water vapor barrier property (barrier property) and excellent discoloration resistance to heat and light. It is about latex.
[0002]
[Prior art]
Vinylidene chloride latex is applied directly to plastic films such as polypropylene, polyester, nylon, etc. or after applying an anchor coating agent, and has been heavily used to improve the gas and water vapor barrier properties. Barrier properties are required in the market.
In response to this market demand, many techniques have been proposed and some have been commercialized. These are mainly the types and ratios of the monomer units constituting the vinylidene chloride and the copolymer in order to improve the barrier property per unit thickness of the vinylidene chloride copolymer coating film, that is, the copolymer composition is changed, The total thickness of the vinylidene chloride copolymer coating constituting the coating was increased, or a combination of the two.
[0003]
However, it has been found that the high barrier coatings obtained by these conventional techniques are unsatisfactory in resistance to discoloration.
It is known that vinylidene chloride copolymers are colored by dehydrochlorination by heat and light. In food packaging materials, it is important to maintain a beautiful appearance of the product. After the product has become a product, heat discoloration in the processing process heated for drying and hot water treatment for food sterilization. Since the optical discoloration with a fluorescent lamp or the like at the time of display impairs its commercial value, a technique for suppressing discoloration resistance is required.
[0004]
As a technique for suppressing discoloration of the coating film, for example, Japanese Patent Publication No. 49-21304 discloses a vinylidene chloride latex by adding a phenol compound having an antioxidant ability and a benzotriazole derivative having an ultraviolet absorbing ability into the polymerization system. In addition, in Japanese Patent Publication No. 2-19128, the amount of nonionic emulsifier used in emulsion polymerization and the method of addition are defined, and the extraction rate of the emulsifier from the copolymer with methanol is regulated. A method for producing coalescence is disclosed.
[0005]
However, the examples given here are not sufficient for high barrier properties, and even if they have high barrier properties, they cannot be said to have sufficient discoloration resistance.
The high barrier property referred to here means that the coating amount is 5 g / m 2 conversion, and the moisture permeability is 4 g / m 2 day or less under the condition of 40 ° C. and 90% relative humidity. The gas barrier property indicates that the oxygen transmission rate (O 2 TR) at 20 ° C. and 70% relative humidity is 2 cc / m 2 · atm · day or less.
[0006]
[Problems to be solved by the invention]
The present invention is to provide a high barrier vinylidene chloride latex having excellent discoloration resistance, excluding the above-mentioned drawbacks.
[0007]
[Means for Solving the Problems]
In vinylidene chloride copolymer latex, chlorine and hydrogen atoms are removed from the copolymer by heat, light, etc., and hydrogen chloride is generated.
As a result of intensive studies to overcome the problems of the prior art, the present inventors have surprisingly specified the copolymer composition and reduced the dehydrochlorination rate of the latex copolymer to a certain level or less. As a result, it has been found that a coating film formed by applying the latex has extremely excellent discoloration resistance and has a high barrier property, and has completed the present invention.
[0008]
That is, the present invention relates to 89-93% by weight of vinylidene chloride, 2-8% by weight of methacrylonitrile, 0.5-3% by weight of 2-hydroxyethyl acrylate and 0-3% by weight of these. A latex containing a vinylidene chloride copolymer obtained by emulsion polymerization of at least one polymerizable vinyl monomer, wherein the dehydrochlorination rate at 120 ° C. is 1 mg / l / 10 min or less. This is a characteristic vinylidene chloride copolymer latex.
[0009]
Details of the present invention will be described below.
The monomer mixture used in the present invention is 89 to 93% by weight of vinylidene chloride, preferably 90 to 92% by weight, 2 to 8% by weight of methacrylonitrile, preferably 4 to 6% by weight, and acrylic acid. 2-Hydroxyethyl is 0.5 to 3% by weight, desirably 1 to 2% by weight and 0 to 3% by weight of one or more vinyl monomers copolymerizable therewith.
When vinylidene chloride is 89% by weight or less, the target high barrier property cannot be obtained. On the other hand, if it is 93% by weight or more, it will crystallize in a short time with a latex-like copolymer, and it cannot be used for applications in which latex is formed into a film.
[0010]
If methacrylonitrile is 2% by weight or less, the target high barrier property cannot be obtained, and if it is 8% by weight or more, the dehydrochlorination rate at 120 ° C. exceeds 1 mg / l / 10 minutes, and good discoloration resistance is obtained. I can't.
When the content of -2-hydroxyethyl acrylate is 0.5% by weight or less, the dehydrochlorination rate at 120 ° C. exceeds 1 mg / l / 10 minutes, and good discoloration resistance cannot be obtained. High barrier properties, particularly water vapor barrier properties, cannot be obtained.
[0011]
The type of the emulsifier, polymerization initiator, surfactant and the like used for the polymerization of the vinylidene chloride copolymer latex of the present invention is not particularly limited, but these substances remain in the coating film formed from the latex, and the gas and The amount used is preferably as small as possible since it can cause deterioration in water vapor barrier properties, and it is more desirable to remove as much as possible by performing dialysis after emulsion polymerization.
In addition, low molecular weight vinylidene chloride copolymers are known to be inferior in stability to heat and light, and discoloration resistance has been found to be parallel to these stability, so the molecular weight is determined by gel permeation chromatography. It is desirable that the weight average molecular weight measured by lithography is 100,000 or more.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described more specifically using examples and the like, but the present invention is not limited to these examples and the like. Parts and% are based on weight unless otherwise specified.
The analysis means used in the examples of the present invention are as follows.
(I) Method for measuring dehydrochlorination rate In a 50 ml Erlenmeyer flask, about 0.1 g of a freeze-dried polymer of latex is placed and replaced with a nitrogen carrier whose flow rate is adjusted to 20 ml / min for 5 minutes. Then, the carrier is introduced into an electrode tank containing 100 ml of pure water for 5 minutes, and the instruction of the ion meter is read to obtain a blank value. Immediately after that, it is immersed in an oil bath at a predetermined temperature for a predetermined time, then quickly taken out, and after waiting for the ion meter to stabilize (about 30 minutes), the instruction is read. In addition, the introduction hose is washed with 4 ml of pure water, and the instruction is read again to determine the amount of chloride ions.
In order to measure the amount of hydrogen chloride in the polymer, 5 g of THF is added to the Erlenmeyer flask containing the heat-treated polymer to dissolve or swell the polymer, 55 g of pure water is added, and the amount of chloride ions is measured with an ion meter. .
[0013]
[Expression 1]
[Expression 2]
[Equation 3]
(B) Creation of coating film An anchor coating agent (Takelac A-310 (trade name) / Takenate A-3 (trade name) manufactured by Takeda Pharmaceutical Co., Ltd.) is applied to a stretched polypropylene film or polyester film subjected to corona discharge treatment. ) / Ethyl acetate = 12/2/98 weight ratio) was applied and dried to a coating amount of 0.2 g / m 2, and then the vinylidene chloride latex was dried using a Mayer rod, and the coating weight was 5 g / After applying to m 2 and drying at 120 ° C. for 10 seconds in a hot air circulating dryer, aging treatment was performed at 40 ° C. for 2 days.
[0017]
(C) The coated film prepared according to the above item (b) using a stretched polypropylene film with oxygen permeability (22μ) was sufficiently conditioned at 100% relative humidity at room temperature, and then OX-TRAN100 (manufactured by Modern Control). Was measured at 20 ° C. and 100% relative humidity. It is a value at a coating amount of 5 g / m 2 .
(D) Using a stretched polyester film with water vapor transmission rate (12 μm), the coated film prepared according to the above item (b) was fully conditioned at a relative humidity of 100% at room temperature, and then PERMATRAN W3 / 31 (manufactured by Modern Control). The measurement was performed at 40 ° C. and 90% relative humidity. It is a value at a coating amount of 5 g / m 2 .
[0018]
(E) Discoloration resistance The polymer heat-treated according to the above item (a) is dissolved in tetrahydrofuran so that the concentration becomes 0.2% by weight, and the color degree of the resulting solution is measured with a color difference meter (Nippon Denshoku Industries Co., Ltd.). Manufactured by Z-300A type) and represented by YI value.
In addition, a biaxially stretched nylon film (15μ) prepared by the above item (b) was heat treated at 80 ° C. for 4 days, and the fade meter was irradiated for 3 hours, and then the coated film was wound into a roll, And the end surface of the coated film wound in a roll shape was left for 14 days under a fluorescent lamp, and the end face was visually judged.
[0019]
[Example 1]
A vinylidene chloride copolymer latex was produced by the following method.
Into a pressure-resistant reactor with glass lining, 85 parts of water, 0.15 part of alkyl sulfonic acid soda (Bayer Valorate U, the same applies hereinafter) and 0.1 part of sodium persulfate were charged and degassed. The temperature was kept at 55 ° C. In a separate container, 91.3 parts of vinylidene chloride, 5.5 parts of methacrylonitrile, 2 parts of methyl methacrylate, and 1.2 parts of 2-hydroxyethyl acrylate were weighed and mixed to prepare a monomer mixture. Ten parts of the monomer mixture were added all at once to the pressure-resistant reactor, and polymerization was performed with stirring until the internal pressure of the reactor dropped. Subsequently, the remaining 90 parts of the monomer mixture was continuously added quantitatively over 12 hours. In parallel, 1 part of alkyl sulfonic acid soda was continuously added quantitatively over 10 hours. During this time, the contents were kept at 55 ° C., and the reaction was allowed to proceed until the internal pressure dropped sufficiently. The polymerization yield was 99.9%. Since the polymerization yield is almost 100%, the composition of the copolymer is almost equal to the charge ratio.
[0020]
A 15% aqueous solution of alkyl sulfonic acid soda was added to the latex thus obtained to adjust the gas-liquid surface tension at 20 ° C. to 42 mN / m. Thereafter, unreacted monomers were removed by steam stripping, and dialysis was performed using a cellulose semipermeable membrane.
About the obtained vinylidene chloride copolymer latex, the performance of the coating film and the dehydrochlorination rate are shown in Table 1 together with other examples and comparative examples later.
[0021]
[Example 2]
Except that the monomer mixture was 90.5 parts of vinylidene chloride, 6.0 parts of methacrylonitrile, 2.5 parts of acrylonitrile and 1.0 part of 2-hydroxyethyl acrylate, it was exactly the same as Example 1.
[Example 3]
Implemented except that the monomer mixture was 92.0 parts vinylidene chloride, 4.0 parts methacrylonitrile, 2.0 parts methyl methacrylate, 0.5 parts methyl acrylate and 1.5 parts 2-hydroxyethyl acrylate Exactly the same as Example 1.
[0022]
[Comparative Example 1]
Except that the monomer mixture was 91.5 parts of vinylidene chloride, 5.5 parts of methacrylonitrile, 2.5 parts of methyl methacrylate and 0.5 parts of methyl acrylate, it was exactly the same as Example 1.
[Comparative Example 2]
Except that the monomer mixture was 91.8 parts of vinylidene chloride, 1.0 part of acrylonitrile, 6.3 parts of methyl methacrylate, and 0.9 part of methyl acrylate, it was exactly the same as Example 1.
[0023]
[Comparative Example 3]
Except for using 90.3 parts of vinylidene chloride, 1.1 parts of acrylonitrile, 6.8 parts of methyl methacrylate, and 1.8 parts of 2-hydroxyethyl acrylate, the monomer mixture was exactly the same as Example 1.
In the monomer mixture compositions of Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3, the combination of the monomer compositions and the dehydrochlorination rate are the same as indicated by the barrier properties and the dehydrochlorination rate in Table 1. It is clearly stated that both high barrier properties and discoloration resistance can be achieved when the conditions of the invention are satisfied.
[0024]
[Table 1]
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21021797A JP3830237B2 (en) | 1997-07-22 | 1997-07-22 | Vinylidene chloride copolymer latex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21021797A JP3830237B2 (en) | 1997-07-22 | 1997-07-22 | Vinylidene chloride copolymer latex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1135763A JPH1135763A (en) | 1999-02-09 |
| JP3830237B2 true JP3830237B2 (en) | 2006-10-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21021797A Expired - Lifetime JP3830237B2 (en) | 1997-07-22 | 1997-07-22 | Vinylidene chloride copolymer latex |
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| Country | Link |
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| JP (1) | JP3830237B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997039061A1 (en) * | 1996-04-18 | 1997-10-23 | Asahi Kasei Kogyo Kabushiki Kaisha | Coating material and films excellent in barrier properties and process for the production thereof |
| JP5804738B2 (en) * | 2011-03-23 | 2015-11-04 | 旭化成ケミカルズ株式会社 | Paints for ceramic siding materials and ceramic siding materials |
| JP7293496B2 (en) * | 2020-03-27 | 2023-06-19 | 旭化成株式会社 | Aqueous dispersion and film of vinyl halide copolymer |
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1997
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| JPH1135763A (en) | 1999-02-09 |
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