JPH0672172B2 - Vinyl chloride copolymer for surface protection film - Google Patents
Vinyl chloride copolymer for surface protection filmInfo
- Publication number
- JPH0672172B2 JPH0672172B2 JP29148585A JP29148585A JPH0672172B2 JP H0672172 B2 JPH0672172 B2 JP H0672172B2 JP 29148585 A JP29148585 A JP 29148585A JP 29148585 A JP29148585 A JP 29148585A JP H0672172 B2 JPH0672172 B2 JP H0672172B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- weight
- film
- vinyl chloride
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、帯電防止性を有する表面保護膜を得ることが
できる表面保護膜用塩化ビニル系共重合体に関する。TECHNICAL FIELD The present invention relates to a vinyl chloride-based copolymer for a surface protective film, which is capable of obtaining a surface protective film having an antistatic property.
（従来の技術） 表面保護膜用組成物には、塩化ビニル−酢酸ビニル共重
合体を主体とし，必要に応じて可塑剤などを添加した組
成物がある。この組成物を有機溶媒に溶解させ，溶液を
被保護物の表面に塗布または噴霧するか，あるいは被保
護物を溶液中に浸漬することにより，皮膜が形成され
る。組成物は溶解性が高くしかも得られた皮膜は機械的
強度に優れているものの，塩化ビニル−酢酸ビニル共重
合体が帯電しやすいため，皮膜にゴミや汚れが付着す
る。また皮膜形成時において、帯電による静電気を着火
源とし，これが有機溶媒に引火して爆発する危険があ
る。(Prior Art) As a composition for a surface protective film, there is a composition containing a vinyl chloride-vinyl acetate copolymer as a main component and a plasticizer or the like added as necessary. A film is formed by dissolving this composition in an organic solvent and applying or spraying the solution onto the surface of the object to be protected, or by immersing the object to be protected in the solution. Although the composition has a high solubility and the resulting film has excellent mechanical strength, dust and dirt adhere to the film because the vinyl chloride-vinyl acetate copolymer is easily charged. Further, during film formation, static electricity due to electrification serves as an ignition source, which may ignite organic solvents and explode.
このような欠点を解決するために，組成物の導電性を高
めることにより，帯電を防止する方法が提案されてい
る。例えば，組成物に界面活性剤やカーボンブラック，
金属粉，導電性繊維などを添加して導電性を高めてい
る。特開昭60−181175号公報は，ポリビニルアルコール
に界面活性剤を添加した剥離性皮膜形成組成物を開示し
ている。しかし，このような組成物は，界面活性剤が容
易にブリードするため，皮膜を剥離した後，界面活性剤
が被保護物の表面に汚れとして残る。また，特開昭60−
6733号公報は，塩素化ポリプロピレン−アクリル系樹脂
に金属粉などの導電性フィラーを添加した組成物を開示
しているものの，この組成物は，樹脂に異質の添加剤を
加えてなるため，機械的強度の低下やブリードなどが生
じやすい。カーボンブラックや導電性繊維を添加した組
成物も同様の欠点を有する。In order to solve such a defect, a method of preventing electrification by increasing the conductivity of the composition has been proposed. For example, if the composition contains a surfactant or carbon black,
Metal powder, conductive fibers, etc. are added to improve conductivity. JP-A-60-181175 discloses a peelable film-forming composition in which a surfactant is added to polyvinyl alcohol. However, in such a composition, since the surfactant easily bleeds, the surfactant remains as a stain on the surface of the protected object after the film is peeled off. In addition, JP-A-60-
Japanese Patent No. 6733 discloses a composition in which a conductive filler such as metal powder is added to a chlorinated polypropylene-acrylic resin, but since this composition includes a resin and a different additive, Strength and bleeding tend to occur. A composition to which carbon black or conductive fiber is added has the same drawback.
（発明が解決しようとする問題点） 本発明は上記従来の問題点を解決するものであり，その
目的とするところは，帯電防止性を有しかつ機械的強度
に優れた表面保護膜用塩化ビニル系共重合体を提供する
ことにある。(Problems to be Solved by the Invention) The present invention is to solve the above-mentioned conventional problems, and an object thereof is to provide a chloride for a surface protective film having antistatic properties and excellent mechanical strength. It is to provide a vinyl-based copolymer.
（問題点を解決するための手段） 本発明は，表面保護膜用塩化ビニル系共重合体の骨格中
に，導電性を有するモノマー単位を含有させることによ
り，この塩化ビニル系共重合体により形成された表面保
護膜の帯電防止性が得られるうえに機械的強度が維持さ
れうる，との発明者の知見にもとづいて完成された。(Means for Solving the Problems) The present invention forms a vinyl chloride-based copolymer for a surface protective film by incorporating a monomer unit having conductivity into the skeleton of the vinyl chloride-based copolymer. It was completed based on the inventor's knowledge that the antistatic property of the formed surface protective film can be obtained and the mechanical strength can be maintained.
本発明の表面保護膜用塩化ビニル系共重合体は，（１）
塩化ビニル単位50〜96重量％，（２）（Ｉ）式で示され
る置換アンモニウム基含有（メタ）アクリル酸エステル
誘導体単位１〜10重量％，および（３）（II）式で示さ
れる（メタ）アクリル酸ポリアルキレンオキシドエステ
ル単位３〜40％，を有する平均重合度200〜1000の塩化
ビニル系共重合体であり、そのことにより上記目的が達
成される。The vinyl chloride-based copolymer for a surface protective film of the present invention comprises (1)
50 to 96% by weight of vinyl chloride unit, 1 to 10% by weight of (2) substituted ammonium group-containing (meth) acrylic acid ester derivative unit represented by formula (I), and (3) represented by formula (II) ) A vinyl chloride-based copolymer having an average degree of polymerization of 200 to 1000 and having a polyalkylene oxide ester unit of 3 to 40%, thereby achieving the above object.
ここで， R1およびR6は，同一または相異なり，水素原子またはメ
チル基， R2およびR7は，同一または相異なり，炭素原子数２〜６
の低級アルキレン基， R3,R4およびR5は，同一または相異なり，炭素原子数１
〜４のアルキル基またはアルケニル基， Ｘはハロゲン，そして ｎは１〜23の整数である。 Here, R 1 and R 6 are the same or different, a hydrogen atom or a methyl group, and R 2 and R 7 are the same or different and have 2 to 6 carbon atoms.
Lower alkylene groups, R 3 , R 4 and R 5 are the same or different and have 1 carbon atom
~ 4 alkyl or alkenyl groups, X is halogen, and n is an integer from 1 to 23.
本発明の共重合体は，適当な有機溶媒に溶解させ，この
溶液を被保護物の表面に塗布または噴霧するか，あるい
は被保護物をこの溶液中に浸漬することにより，皮膜と
される。The copolymer of the present invention is formed into a film by dissolving it in a suitable organic solvent and coating or spraying this solution on the surface of the object to be protected, or by immersing the object to be protected in this solution.
塩化ビニル系共重合体中には，塩化ビニル単位が50〜96
重量％，好ましくは75〜94重量％の範囲で含有される。
50重量％を下まわると，皮膜の機械的強度が低下し，そ
のために，剥離時に破れなどが発生する。96重量％を上
まわると，所望の帯電防止性が得られない。共重合体中
には，（Ｉ）式で示される置換アンモニウム基含有（メ
タ）アクリル酸エステル誘導体単位が,1〜10重量％，好
ましくは２〜６重量％の範囲で含有される。１重量％を
下まわると，所望の帯電防止性が得られない。10重量％
を上まわると，帯電防止性は良好となるものの溶媒に対
する溶解性が低下し，そのために，皮膜の形成が困難と
なる。（II）式で示される（メタ）アクリル酸ポリアル
キレンオキシドエステル単位は，共重合体中において,3
〜40重量％，好ましくは５〜20重量％の範囲で含有され
る。３重量％を下まわると，溶媒に対する溶解性が低下
するため，皮膜の形成が困難となる。40重量％を上まわ
ると，皮膜の機械的強度が低下し，そのために，剥離時
に破れなどが発生する。共重合体の平均重合度は200〜1
000,好ましくは350〜700とされる。200を下まわると，
組成物がもろくなり，そのために，皮膜の機械的強度が
低下する。1000を上まわると，溶媒に対する溶解性が低
下するため，皮膜の形成が困難となる。The vinyl chloride copolymer contains 50 to 96 vinyl chloride units.
It is contained in an amount of, preferably 75 to 94% by weight.
If it is less than 50% by weight, the mechanical strength of the coating decreases, and as a result, breakage occurs during peeling. If it exceeds 96% by weight, the desired antistatic property cannot be obtained. The substituted ammonium group-containing (meth) acrylic acid ester derivative unit represented by the formula (I) is contained in the copolymer in an amount of 1 to 10% by weight, preferably 2 to 6% by weight. If it is less than 1% by weight, the desired antistatic property cannot be obtained. 10% by weight
If it exceeds, the antistatic property becomes good, but the solubility in the solvent decreases, which makes it difficult to form a film. In the copolymer, the (meth) acrylic acid polyalkylene oxide ester unit represented by the formula (II) is
It is contained in the range of up to 40% by weight, preferably 5 to 20% by weight. When the amount is less than 3% by weight, the solubility in the solvent is lowered, so that it becomes difficult to form a film. If it exceeds 40% by weight, the mechanical strength of the film will be reduced, and as a result, breakage will occur during peeling. The average degree of polymerization of the copolymer is 200-1
000, preferably 350-700. Below 200,
The composition becomes brittle, which reduces the mechanical strength of the coating. If it exceeds 1000, the solubility in the solvent decreases and it becomes difficult to form a film.
（Ｉ）式で示される置換アンモニウム基含有（メタ）ア
クリル酸誘導体単位を与える単量体としては，例えば,2
−ヒドロキシ−３−アクリロイルオキシプロピルトリメ
チルアンモニウムクロライド,2−ヒドロキシ−３−メタ
クリロイルオキシプロピルトリメチルアンモニウムクロ
ライド，アクリロイルオキシエチルトリメチルアンモニ
ウムクロライド，メタクリロイルオキシエチルトリメチ
ルアンモニウムクロライドが挙げられる。また，（II）
式で示される（メタ）アクリル酸ポリアルキレンオキシ
ドエステル単位を与える単量体としては，例えば，ポリ
プロピレングリコールメタクリレート，ポリエチレング
リコールメタクリレート，ポリエチレングリコールポリ
プロピレングリコールメタクリレート，ポリエチレング
リコールポリブチレングリコールメタクリレートが挙げ
られる。Examples of the monomer providing the substituted ammonium group-containing (meth) acrylic acid derivative unit represented by the formula (I) include, for example, 2
-Hydroxy-3-acryloyloxypropyltrimethylammonium chloride, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride. Also, (II)
Examples of the monomer providing the (meth) acrylic acid polyalkylene oxide ester unit represented by the formula include polypropylene glycol methacrylate, polyethylene glycol methacrylate, polyethylene glycol polypropylene glycol methacrylate, and polyethylene glycol polybutylene glycol methacrylate.
本発明の塩化ビニル系共重合体中には，帯電防止性を損
なわない範囲内で，塩化ビニルと共重合可能な他のモノ
マー単位を含有させてもよい。モノマーとしては，例え
ば，エチレン，プロピレン，酢酸ビニル，塩化ビニリデ
ン，ヒドロキシエチルアクリレート，ヒドロキシプロピ
ルアクリレートがある。このようなモノマー単位は，通
常,10重量％以下の範囲で含有される。The vinyl chloride-based copolymer of the present invention may contain other monomer units copolymerizable with vinyl chloride within a range that does not impair the antistatic property. Examples of the monomer include ethylene, propylene, vinyl acetate, vinylidene chloride, hydroxyethyl acrylate and hydroxypropyl acrylate. Such a monomer unit is usually contained in the range of 10% by weight or less.
共重合体の合成方法としては，公知のあらゆる重合方法
が使用でき，例えば，乳化重合法，懸濁重合法，溶液重
合法，沈澱重合法がある。As a method for synthesizing the copolymer, any known polymerization method can be used, and examples thereof include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a precipitation polymerization method.
溶媒としては，塩化ビニル系共重合体を溶解しうる公知
のあらゆる溶媒が使用でき，例えば，アセトン，メチル
エチルケトン，メチルイソブチルケトン，酢酸メチル，
酢酸エチル，トルエンがある。これらは，単独もしくは
２種以上混合して用いられる。溶媒は，揮発性の高い方
が好ましい。揮発性が高いと，共重合体の溶液を塗布し
た後，常温ですみやかに蒸散して皮膜を形成しやすい。As the solvent, any known solvent capable of dissolving a vinyl chloride copolymer can be used, and examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate,
There are ethyl acetate and toluene. These may be used alone or in combination of two or more. The solvent is preferably highly volatile. When the volatility is high, it is easy to evaporate at room temperature to form a film after applying the solution of the copolymer.
（実施例） 以下に本発明を実施例について述べる。(Examples) The present invention will be described below with reference to Examples.
実施例１ 塩化ビニル，置換アンモニウム基含有（メタ）アクリル
酸エステル誘導体としてメタクリロイルオキシエチレン
トリメチルアンモニウムクロライドおよび（メタ）アク
リル酸ポリアルキレンオキシドエステルとしてテトラエ
チレングリコールモノメタクリレートをメタノールに加
え，触媒としてラウロイルパーオキサイドを添加して,6
0℃で10時間重合させた。遠心分離によりメタノールを
除去した後,50℃で24時間真空乾燥して共重合体を得
た。共重合体中には，塩化ビニル単位が86重量％，
（Ｉ）式で示される置換アンモニウム基含有（メタ）ア
クリル酸エステル誘導体単位が４重量％，そして，（I
I）式で示される（メタ）アクリル酸ポリアルキレンオ
キシド単位が10重量％含有されていた。共重合体の組成
は，酢酸銀法によるクロル分析およびナトリウムメトキ
シドを用いた水酸基の定量により行なった。また，共重
合体の平均重合度をJISK-6721により測定したところ,68
0であった。この共重合体100重量部をメチルエチルケト
ン／トルエン混合溶媒（重量比1/1）900重量部に溶解さ
せた。共重合体の溶解性は，溶液の粘度をＢ型粘度計を
用いて測定することにより行なった。この溶液をガラス
板上に塗布し，常温にて風乾して皮膜を形成した。皮膜
の表面固有抵抗値，機械的強度および剥離性は，次のよ
うにして測定した。Example 1 Vinyl chloride, methacryloyloxyethylene trimethyl ammonium chloride as a (meth) acrylic acid ester derivative containing a substituted ammonium group, and tetraethylene glycol monomethacrylate as a (meth) acrylic acid polyalkylene oxide ester were added to methanol, and lauroyl peroxide was used as a catalyst. Add 6
Polymerization was carried out at 0 ° C for 10 hours. After removing methanol by centrifugation, a copolymer was obtained by vacuum drying at 50 ° C for 24 hours. The copolymer contains 86% by weight of vinyl chloride units,
4% by weight of the substituted ammonium group-containing (meth) acrylic acid ester derivative unit represented by the formula (I), and (I
It contained 10% by weight of a polyalkylene oxide unit of (meth) acrylic acid represented by the formula (I). The composition of the copolymer was determined by chlorination analysis by the silver acetate method and quantification of hydroxyl groups using sodium methoxide. The average degree of polymerization of the copolymer was measured according to JIS K-6721.
It was 0. 100 parts by weight of this copolymer was dissolved in 900 parts by weight of a mixed solvent of methyl ethyl ketone / toluene (weight ratio 1/1). The solubility of the copolymer was determined by measuring the viscosity of the solution using a B type viscometer. This solution was applied on a glass plate and air dried at room temperature to form a film. The surface resistivity, mechanical strength and peelability of the coating were measured as follows.
表面固有抵抗値；皮膜をコートしたガラス板について,2
0℃,65％RHでHIGH MEGOHM METER TR-8601（タケダ理研
社製）を用いて,JISK-6911により，その抵抗値を測定し
た。Surface resistivity; for coated glass plates, 2
The resistance value was measured by JIS K-6911 using a HIGH MEGOHM METER TR-8601 (manufactured by Takeda Riken) at 0 ° C and 65% RH.
機械的強度；共重合体の溶液をガラス板上に塗布し，常
温にて風乾した後,50℃にて24時間真空乾燥を行い，皮
膜を形成した。この皮膜をガラス板から剥離して試供フ
ィルムとし，その機械的強度をJISK-6732により測定し
た。Mechanical strength: The copolymer solution was applied on a glass plate, air-dried at room temperature, and then vacuum-dried at 50 ° C for 24 hours to form a film. This film was peeled from the glass plate to give a sample film, and its mechanical strength was measured according to JIS K-6732.
剥離性；共重合体の溶液を150×150mmのガラス板上に膜
厚20μｍに塗布し，常温にて風乾して皮膜を形成した。
これを20℃の恒温室に24時間放置した後，端部にセロテ
ープを貼着してピーリングした。ピーリングによる皮膜
の破壊状況を目視観察し，剥離性の評価とした。Peelability: A solution of the copolymer was applied on a glass plate of 150 × 150 mm to a film thickness of 20 μm and air-dried at room temperature to form a film.
After leaving this in a thermostatic chamber at 20 ° C for 24 hours, a cellophane tape was attached to the end and peeled. The state of breakage of the film due to peeling was visually observed and the peelability was evaluated.
これらの測定結果を下表に示す。The results of these measurements are shown in the table below.
実施例２ 共重合体中における塩化ビニル単位を88重量％，（Ｉ）
式で示される置換アンモニウム基含有（メタ）アクリル
酸エステル誘導体単位を２重量％としたこと以外は，実
施例１と同様にして共重合体を合成した。共重合体の組
成，平均重合度および溶解性は，実施例１と同様の方法
により測定した。共重合体の平均重合度は680であっ
た。この共重合体を用いて，実施例１と同様の方法によ
り皮膜を形成し，その表面固有抵抗値，機械的強度およ
び剥離性を測定した。これらの測定結果を下表に示す。Example 2 88% by weight of vinyl chloride unit in the copolymer, (I)
A copolymer was synthesized in the same manner as in Example 1 except that the substituted ammonium group-containing (meth) acrylic acid ester derivative unit represented by the formula was 2% by weight. The composition, average degree of polymerization and solubility of the copolymer were measured by the same method as in Example 1. The average degree of polymerization of the copolymer was 680. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
実施例３ 共重合体中における塩化ビニル単位を82重量％，（Ｉ）
式で示される置換アンモニウム基含有（メタ）アクリル
酸エステル誘導体単位を８重量％としたこと以外は，実
施例１と同様にして共重合体を合成した。共重合体の組
成，平均重合度および溶解性は，実施例１と同様の方法
により測定した。共重合体の平均重合度は420であっ
た。この共重合体を用いて，実施例１と同様の方法によ
り皮膜を形成し，その表面固有抵抗値，機械的強度およ
び剥離性を測定した。これらの測定結果を下表に示す。Example 3 82% by weight of vinyl chloride units in the copolymer, (I)
A copolymer was synthesized in the same manner as in Example 1 except that the substituted ammonium group-containing (meth) acrylic acid ester derivative unit represented by the formula was 8% by weight. The composition, average degree of polymerization and solubility of the copolymer were measured by the same method as in Example 1. The average degree of polymerization of the copolymer was 420. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
実施例４ 共重合体中における塩化ビニル単位を90重量％，（II）
式で示される（メタ）アクリル酸ポリアルキレンオキシ
ドエステル単位を６重量％としたこと以外は，実施例１
と同様にして共重合体を合成した。共重合体の組成，平
均重合度および溶解性は，実施例１と同様の方法により
測定した。共重合体の平均重合度は680であった。この
共重合体を用いて，実施例１と同様の方法により皮膜を
形成し，その表面固有抵抗値，機械的強度および剥離性
を測定した。これらの測定結果を下表に示す。Example 4 90% by weight of vinyl chloride unit in the copolymer, (II)
Example 1 except that the (meth) acrylic acid polyalkylene oxide ester unit represented by the formula was 6% by weight.
A copolymer was synthesized in the same manner as in. The composition, average degree of polymerization and solubility of the copolymer were measured by the same method as in Example 1. The average degree of polymerization of the copolymer was 680. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
実施例５ 共重合体中における塩化ビニル単位を64重量％，（II）
式で示される（メタ）アクリル酸ポリアルキレンオキシ
ドエステル単位を32重量％としたこと以外，実施例１と
同様にして共重合体を合成した。共重合体の組成，平均
重合度および溶解性は，実施例１と同様の方法により測
定した。共重合体の平均重合度は420であった。この共
重合体を用いて，実施例１と同様の方法により皮膜を形
成し，その表面固有抵抗値，機械的強度および剥離性を
測定した。これらの測定結果を下表に示す。Example 5 64% by weight of vinyl chloride units in the copolymer, (II)
A copolymer was synthesized in the same manner as in Example 1 except that the (meth) acrylic acid polyalkylene oxide ester unit represented by the formula was 32% by weight. The composition, average degree of polymerization and solubility of the copolymer were measured by the same method as in Example 1. The average degree of polymerization of the copolymer was 420. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
実施例６ 共重合体の平均重合度を280としたこと以外は，実施例
１と同様にして共重合体を合成した。共重合体の組成，
平均重合度および溶解性は，実施例１と同様の方法によ
り測定した。この共重合体を用いて，実施例１と同様の
方法により皮膜を形成し，その表面固有抵抗値，機械的
強度および剥離性を測定した。これらの測定結果を下表
に示す。Example 6 A copolymer was synthesized in the same manner as in Example 1 except that the average degree of polymerization of the copolymer was 280. Copolymer composition,
The average degree of polymerization and the solubility were measured by the same method as in Example 1. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
比較例１ 共重合体中における塩化ビニル単位を89.5重量％，
（Ｉ）式で示される置換アンモニウム基含有（メタ）ア
クリル酸エステル誘導体単位を0.5重量％としたこと以
外は，実施例１と同様にして共重合体を合成した。共重
合体の組成，平均重合度および溶解性は，実施例１と同
様の方法により測定した。共重合体の平均重合度は680
であった。この共重合体を用いて，実施例１と同様の方
法により皮膜を形成し，その表面固有抵抗値，機械的強
度および剥離性を測定した。これらの測定結果を下表に
示す。Comparative Example 1 89.5% by weight of vinyl chloride unit in the copolymer,
A copolymer was synthesized in the same manner as in Example 1 except that the substituted ammonium group-containing (meth) acrylic acid ester derivative unit represented by the formula (I) was 0.5% by weight. The composition, average degree of polymerization and solubility of the copolymer were measured by the same method as in Example 1. The average degree of polymerization of the copolymer is 680
Met. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
比較例２ 共重合体中における塩化ビニル単位を78重量％，（Ｉ）
式で示される置換アンモニウム基含有（メタ）アクリル
酸エステル誘導体単位を12重量％としたこと以外は，実
施例１と同様にして共重合体を合成した。共重合体の組
成，平均重合度および溶解性は，実施例１と同様の方法
により測定した。共重合体の平均重合度は420であっ
た。この共重合体を用いて，実施例１と同様の方法によ
り皮膜を形成し，その表面固有抵抗値，機械的強度およ
び剥離性を測定した。これらの測定結果を下表に示す。
ただし，共重合体はメチルエチルケトン／トルエン混合
溶媒（重量比1/1）に不溶なため,N,N−ジメチルホルム
アミドに溶解させて皮膜を形成した。Comparative Example 2 78% by weight of vinyl chloride unit in the copolymer, (I)
A copolymer was synthesized in the same manner as in Example 1 except that the substituted ammonium group-containing (meth) acrylic acid ester derivative unit represented by the formula was 12% by weight. The composition, average degree of polymerization and solubility of the copolymer were measured by the same method as in Example 1. The average degree of polymerization of the copolymer was 420. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
However, the copolymer was insoluble in a mixed solvent of methyl ethyl ketone / toluene (weight ratio 1/1), so it was dissolved in N, N-dimethylformamide to form a film.
比較例３ 共重合体中における塩化ビニル単位を93重量％，（II）
式で示される（メタ）アクリル酸ポリアルキレンオキシ
ドエステル単位を２重量％としたこと以外は，実施例１
と同様にして共重合体を合成した。共重合体の組成，平
均重合度および溶解性は，実施例１と同様にして共重合
体を合成した。共重合体の組成，平均重合度および溶解
性は，実施例１と同様の方法により測定した。共重合体
の平均重合度は420であった。この共重合体を用いて，
実施例１と同様の方法により皮膜を形成し，その表面固
有抵抗値，機械的強度および剥離性を測定した。これら
の測定結果を下表に示す。ただし，共重合体はメチルエ
チルケトン／トルエン混合溶媒（重量比1/1）に不溶な
ため,N,N−ジメチルホルムアミドに溶解させて皮膜を形
成した。Comparative Example 3 93% by weight of vinyl chloride unit in the copolymer, (II)
Example 1 except that the (meth) acrylic acid polyalkylene oxide ester unit represented by the formula was 2% by weight.
A copolymer was synthesized in the same manner as in. The copolymer was synthesized in the same manner as in Example 1 with respect to the composition, average degree of polymerization and solubility. The composition, average degree of polymerization and solubility of the copolymer were measured by the same method as in Example 1. The average degree of polymerization of the copolymer was 420. Using this copolymer,
A film was formed by the same method as in Example 1 and the surface resistivity, mechanical strength and peelability were measured. The results of these measurements are shown in the table below. However, the copolymer was insoluble in a mixed solvent of methyl ethyl ketone / toluene (weight ratio 1/1), so it was dissolved in N, N-dimethylformamide to form a film.
比較例４ 共重合体中における塩化ビニル単位を61重量％，（II）
式で示される（メタ）アクリル酸ポリアルキレンオキシ
ドエステル単位を45重量％としたこと以外は，実施例１
と同様にして共重合体を合成した。共重合体の組成，平
均重合度および溶解性は，実施例１と同様の方法により
測定した。共重合体の平均重合度は680であった。この
共重合体を用いて，実施例１と同様の方法により皮膜を
形成し，その表面固有抵抗値，機械的強度および剥離性
を測定した。これらの測定結果を下表に示す。Comparative Example 4 61% by weight of vinyl chloride unit in the copolymer, (II)
Example 1 except that the (meth) acrylic acid polyalkylene oxide ester unit represented by the formula was 45% by weight.
A copolymer was synthesized in the same manner as in. The composition, average degree of polymerization and solubility of the copolymer were measured by the same method as in Example 1. The average degree of polymerization of the copolymer was 680. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
比較例５ 共重合体の平均重合度を150としたこと以外は，実施例
１と同様にして共重合体を合成した。共重合体の組成，
平均重合度および溶解性は，実施例１と同様の方法によ
り測定した。この共重合体を用いて，実施例１と同様の
方法により皮膜を形成し，その表面固有抵抗値，機械的
強度および剥離性を測定した。これらの測定結果を下表
に示す。Comparative Example 5 A copolymer was synthesized in the same manner as in Example 1 except that the average degree of polymerization of the copolymer was 150. Copolymer composition,
The average degree of polymerization and the solubility were measured by the same method as in Example 1. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below.
比較例６ 共重合体の平均重合度を1200としたこと以外は，実施例
１と同様にして共重合体を合成した。共重合体の組成，
平均重合度および溶解性は，実施例１と同様の方法によ
り測定した。この共重合体を用いて，実施例１と同様の
方法により皮膜を形成し，その表面固有抵抗値，機械的
強度および剥離性を測定した。これらの測定結果を下表
に示す。ただし，共重合体はメチルエチルケトン／トル
エン混合溶媒（重量比1/1）に不溶なため,N,N−ジメチ
ルホルムアミドに溶解させて皮膜を形成した。Comparative Example 6 A copolymer was synthesized in the same manner as in Example 1 except that the average degree of polymerization of the copolymer was 1200. Copolymer composition,
The average degree of polymerization and the solubility were measured by the same method as in Example 1. Using this copolymer, a film was formed in the same manner as in Example 1, and the surface specific resistance value, mechanical strength and peelability were measured. The results of these measurements are shown in the table below. However, the copolymer was insoluble in methyl ethyl ketone / toluene mixed solvent (weight ratio 1/1), so it was dissolved in N, N-dimethylformamide to form a film.
実施例および比較例から明らかなように，本発明の表面
保護膜用塩化ビニル系共重合体は，表面固有抵抗値が低
いため，誘導性に優れており，従って，帯電防止性が高
い。有機溶媒に対する溶解性も良好である。しかも，こ
の共重合体により形成された皮膜は，機械的強度および
剥離性に優れている。（Ｉ）式で示される置換アンモニ
ウム基含有（メタ）アクリル酸エステル誘導体単位を0.
5重量％しか有しない共重合体は，表面固有抵抗値が高
く，所望の帯電防止性が得られない。上記単位を12重量
％有する共重合体は，メチルエチルケトン／トルエン混
合溶媒（重量比1/1）に不溶であり,N,N−ジメチルホル
ムアミドのような揮発性が低く，従って皮膜の形成が困
難な溶媒を用いる必要がある。（II）式で示される（メ
タ）アクリル酸ポリアルキレンオキシドエステル単位を
２重量％しか有しない共重合体も，上記混合溶媒に不溶
であり,45重量％有する共重合体は，これにより形成さ
れた皮膜の機械的強度や剥離性に欠ける。平均重合度が
150の共重合体は，もろくてフィルムが形成できず,1200
の共重合体は上記混合溶媒に不溶である。As is clear from the examples and comparative examples, the vinyl chloride-based copolymer for a surface protective film of the present invention has a low surface specific resistance value and thus is excellent in inducibility, and therefore has a high antistatic property. It also has good solubility in organic solvents. Moreover, the film formed by this copolymer has excellent mechanical strength and peeling property. The substituted ammonium group-containing (meth) acrylic acid ester derivative unit represented by the formula (I) is added to
A copolymer containing only 5% by weight has a high surface resistivity and cannot obtain a desired antistatic property. The copolymer containing 12% by weight of the above units is insoluble in methylethylketone / toluene mixed solvent (weight ratio 1/1), has low volatility like N, N-dimethylformamide, and therefore difficult to form a film. It is necessary to use a solvent. A copolymer having only 2% by weight of a (meth) acrylic acid polyalkylene oxide ester unit represented by the formula (II) is also insoluble in the above mixed solvent, and a copolymer having 45% by weight is formed by this. The film lacks mechanical strength and peelability. Average degree of polymerization
The copolymer of 150 was brittle and could not form a film.
Is insoluble in the above mixed solvent.
（発明の効果） 本発明の表面保護膜用塩化ビニル系共重合体は，このよ
うに，帯電防止性を有しかつ機械的強度に優れている。
有機溶媒に対する溶解性も高いため，皮膜を形成しやす
い。この皮膜は、表面保護膜として被覆された被保護物
から容易に剥離することができる。従って，本発明の共
重合体は，ガラスの表面保護用のフィルムなどに有効に
利用されうる。 (Effect of the Invention) As described above, the vinyl chloride-based copolymer for a surface protective film of the present invention has antistatic properties and excellent mechanical strength.
Since it has high solubility in organic solvents, it is easy to form a film. This film can be easily peeled off from the protected object coated as the surface protective film. Therefore, the copolymer of the present invention can be effectively used as a film for protecting the surface of glass.
Claims (1)
タ）アクリル酸エステル誘導体単位１〜10重量％、およ
び （３）（II）式で示される（メタ）アクリル酸ポリアル
キレンオキシドエステル単位３〜40重量％、を有する平
均重合度200〜1000の表面保護膜用塩化ビニル系共重合
体。 ここで、 R1およびR6は、同一または相異なり、水素原子またはメ
チル基、 R2およびR7は、同一または相異なり、炭素原子数１〜４
のアルキル基またはアルケニル基、 Ｘはハロゲン、そして ｎは１〜23の整数である。1. A vinyl chloride unit of 50 to 96% by weight, (2) a substituted ammonium group-containing (meth) acrylic acid ester derivative unit of the formula (I) of 1 to 10% by weight, and (3) ( A vinyl chloride-based copolymer for a surface protective film, having an average degree of polymerization of 200 to 1000 and having (meth) acrylic acid polyalkylene oxide ester unit of 3 to 40% by weight represented by the formula II) Here, R 1 and R 6 are the same or different, a hydrogen atom or a methyl group, R 2 and R 7 are the same or different, and have 1 to 4 carbon atoms.
Is an alkyl group or an alkenyl group, X is halogen, and n is an integer of 1 to 23.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29148585A JPH0672172B2 (en) | 1985-12-24 | 1985-12-24 | Vinyl chloride copolymer for surface protection film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29148585A JPH0672172B2 (en) | 1985-12-24 | 1985-12-24 | Vinyl chloride copolymer for surface protection film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62149762A JPS62149762A (en) | 1987-07-03 |
| JPH0672172B2 true JPH0672172B2 (en) | 1994-09-14 |
Family
ID=17769483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29148585A Expired - Lifetime JPH0672172B2 (en) | 1985-12-24 | 1985-12-24 | Vinyl chloride copolymer for surface protection film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0672172B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2011221917B2 (en) * | 2010-03-04 | 2015-12-24 | Sekisui Chemical Co., Ltd. | Macromolecular water-treatment membrane and manufacturing method therefor |
-
1985
- 1985-12-24 JP JP29148585A patent/JPH0672172B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62149762A (en) | 1987-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0210068B1 (en) | Protective overcoat for photographic elements | |
| WO1982000033A1 (en) | Film-forming composition and the method of making cellulose ester film | |
| JP2944210B2 (en) | Crosslinked conductive polymer and antistatic layer using the same | |
| JPH0672172B2 (en) | Vinyl chloride copolymer for surface protection film | |
| EP0435330A1 (en) | Coating composition | |
| JPH06123806A (en) | Protective film for polarizing plate | |
| JP2968019B2 (en) | Resin adhesion inhibitor | |
| JP2988268B2 (en) | Radiation-sensitive resin composition | |
| JPH0613584B2 (en) | Electron- and X-ray-sensitive polymers | |
| EP0530317A1 (en) | Cross-linked conductive polymers and antistat coatings employing the same. | |
| JPH0629374B2 (en) | Antistatic method for vinyl chloride resin moldings | |
| JP3461366B2 (en) | Anti-adhesion agent | |
| JPS6329713B2 (en) | ||
| JP3147385B2 (en) | Antistatic acrylic resin composition | |
| US5147924A (en) | Selectively soluble, protective coating compositions derived from vinyl acetate/monoalkyl maleate copolymers | |
| US3502608A (en) | Vinyl chloride copolymeric paint solutions in aromatic hydrocarbons | |
| JP2780028B2 (en) | Antistatic agent | |
| JP2747913B2 (en) | Transfer paper overcoat and baking coloring method | |
| JPS6218478A (en) | Removable transparent paint with antistatic and antifogging properties | |
| JPS624078B2 (en) | ||
| JPH04274233A (en) | Charge preventing film base and photograph material comprising charge preventing film base | |
| JP2541637B2 (en) | Antistatic film | |
| JPS6216187B2 (en) | ||
| GB2109705A (en) | Photographic paper | |
| JP3044585B2 (en) | Protective coating agent |