JP2006291049A - Water-dispersion composition for protective coating agent for glass bottle - Google Patents
Water-dispersion composition for protective coating agent for glass bottle Download PDFInfo
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本発明は、厚塗り可能で耐衝撃保護性と耐汚染性が優れた、水分散型ガラス瓶保護コート剤用組成物に関する。 The present invention relates to a composition for a water-dispersed glass bottle protective coating agent that can be thickly coated and has excellent impact resistance and stain resistance.
ガラス瓶は耐衝撃性が低いため割れ難くし、また、例え割れても破片が飛び散るのを防ぐ目的で樹脂フィルムで覆うなどの安全対策を講じている。一般に、ガラス瓶はシュリンクフィルムを用いたりや樹脂溶液などにディッピングする方法により保護コートされる。しかし、地球環境保全に対する関心の高まりを背景にしたＶＯＣ排出規制の強化等からコ―ティング分野でも従来の溶剤型から水分散型への転換が進んでいる。現在、水分散型ポリウレタンがガラス瓶の保護コート剤として使用されているが、このコート剤を用いると、垂れたソースやケチャップがガラス瓶に付着すると容易に除去できなくなるという問題がある。また、食品を充填するガラス瓶のコート剤としては、ポリウレタンは安全性に問題がある。
一方、既にエチレン−アクルル酸またはエチレン−メタクリル酸共重合体を金属イオンで中和した各種のアイオノマーエマルションが上市され、食品包装用等のアルミ箔や紙のヒートシール剤として使用されている（特許文献１）。これらのアイオノマーエマルションはポリオレフィンに属して表面張力が低いため耐汚染性が優れ、フィルム強度とガラス密着性、安全性も高い。しかし、アイオノマーエマルションは塗膜が数十μｍになるよう塗布して焼き付けるとクラックが入り、ガラス瓶の保護コート剤としては不適であることがわかった。一方、アンモニア等のアミンで中和したアイオノマーは焼き付けてもクラックは入らないものの、フィルム強度が低く、アミンを使用している関係上、安全性や臭気の問題があるので、食品用ガラス瓶のコート剤としては好ましくない。そこで、厚塗りしても塗膜にクラックが入らず、かつ、フィルム強度とガラス密着性、安全性が高い水分散型ガラス瓶用保護コート剤を開発するため種々検討した。
On the other hand, various ionomer emulsions obtained by neutralizing ethylene-acrylic acid or ethylene-methacrylic acid copolymer with metal ions have been put on the market and used as heat sealants for aluminum foil and paper for food packaging (patents) Reference 1). These ionomer emulsions belong to polyolefins and have low surface tension, so they are excellent in stain resistance, film strength, glass adhesion, and safety. However, it was found that the ionomer emulsion cracks when applied and baked so that the coating film has a thickness of several tens of μm, making it unsuitable as a protective coating agent for glass bottles. On the other hand, ionomers neutralized with amines such as ammonia do not crack even when baked, but the film strength is low, and because of the use of amines, there are safety and odor problems. It is not preferable as an agent. Therefore, various studies were made to develop a water-dispersible glass bottle protective coating agent that does not crack even when thickly applied, and has high film strength, glass adhesion, and safety.
本発明の目的は、従来の問題点であるクラックの発生を抑えた、すなわち、厚塗りしても塗膜にクラックが入らず、かつ、フィルム強度とガラスに対する密着性、安全性が高い水分散型ガラス瓶用保護コート剤耐水性を提供することにある。 The purpose of the present invention is to suppress the occurrence of cracks, which is a conventional problem, that is, the coating film does not crack even when thickly applied, and the water dispersion has high film strength, adhesion to glass, and high safety. It is in providing the water resistance of the protective coating agent for a type glass bottle.
本発明者らは鋭意研究の結果、特定のエチレン−不飽和カルボン酸共重合体を一価または二価のアルカリ金属で部分中和した特定のアイオノマー樹脂が耐水性と低温ヒートシール性に優れることを見出し、本発明を完成した。 As a result of intensive research, the present inventors have found that a specific ionomer resin obtained by partially neutralizing a specific ethylene-unsaturated carboxylic acid copolymer with a monovalent or divalent alkali metal is excellent in water resistance and low-temperature heat sealability. The present invention has been completed.
すなわち、本発明は以下の（１）〜（５）で特定される。
（１）不飽和カルボン酸のカルボキシル基の５０〜９５％が一価または二価の金属イオンで中和されたエチレン−不飽和カルボン酸共重合体の水分散体を必須成分として含有する水分散型ガラス瓶保護コート剤用組成物。
（２）エチレン−不飽和カルボン酸共重合体におけるエチレンと不飽和カルボン酸の含有割合は、エチレン８６〜９５モル％に対して不飽和カルボン酸５〜１４モル％の割合であり、かつ、ＧＰＣで測定した重量平均分子量（Ｍｗ）２０，０００〜１００，０００である水分散型ガラス瓶保護コート剤用組成物。
（３）不飽和カルボン酸がアクリル酸またはメタクリル酸である水分散型ガラス瓶保護コート剤用組成物。
（４）金属イオンがＮａイオンまたはＫイオンである水分散型ガラス瓶保護コート剤用組成物。
（５）水分散体の平均粒径が０．０１〜０．５μｍ以下である水分散型ガラス瓶保護コート剤用組成物。
That is, the present invention is specified by the following (1) to (5).
(1) Water dispersion containing, as an essential component, an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer in which 50 to 95% of the carboxyl groups of the unsaturated carboxylic acid are neutralized with monovalent or divalent metal ions. Type glass bottle protective coating composition.
(2) The content ratio of ethylene and unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer is a ratio of 5 to 14 mol% of unsaturated carboxylic acid with respect to 86 to 95 mol% of ethylene, and GPC A composition for a water-dispersed glass bottle protective coating agent having a weight average molecular weight (Mw) of 20,000 to 100,000 measured in 1.
(3) A composition for a water-dispersed glass bottle protective coating agent, wherein the unsaturated carboxylic acid is acrylic acid or methacrylic acid.
(4) A composition for a water-dispersed glass bottle protective coating agent, wherein the metal ions are Na ions or K ions.
(5) A composition for water-dispersed glass bottle protective coating agent, wherein the average particle size of the water dispersion is 0.01 to 0.5 μm or less.
本発明の水分散型コート剤用組成物によれば、厚塗りしても塗膜にクラックが入らず、ガラス、紙、アルミ箔に対する密着性が高くて耐衝撃保護性と耐汚染性が優れるため、特に、ガラス瓶保護コート剤として好適に用いることができる。 According to the composition for water-dispersed coating agent of the present invention, the coating film does not crack even when thickly applied, and has high adhesion to glass, paper, and aluminum foil, and is excellent in impact resistance protection and stain resistance. Therefore, it can be suitably used as a glass bottle protective coating agent.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の水分散型ヒートシール剤用組成物（以下、組成物と略す）の主成分であるエチレン−不飽和カルボン酸共重合体は、特定の不飽和カルボン酸共重合体を含み、また、特定の分子量を有している。そして、該重合体は、水中では側鎖のカルボキシル基が部分的に金属イオンで中和されてアイオノマー樹脂となり、小粒径粒子となった状態で分散している。このアイオノマ−樹脂の主鎖を構成するエチレン−不飽和カルボン酸共重合体は、ランダム共重合体でもよいし、ブロック共重合体でもよいが、透明性が優れる点で、エチレン−不飽和カルボン酸ランダム共重合体が好ましい。 The ethylene-unsaturated carboxylic acid copolymer which is the main component of the composition for water-dispersed heat sealant of the present invention (hereinafter abbreviated as composition) includes a specific unsaturated carboxylic acid copolymer, Has a specific molecular weight. In water, the carboxyl group in the side chain is partially neutralized with metal ions to form an ionomer resin in water, and the polymer is dispersed in the form of small particle size particles. The ethylene-unsaturated carboxylic acid copolymer constituting the main chain of the ionomer resin may be a random copolymer or a block copolymer. However, the ethylene-unsaturated carboxylic acid is excellent in transparency. Random copolymers are preferred.
エチレン−不飽和カルボン酸共重合体は、ＧＰＣで測定した重量平均分子量（ＭＷ）が２０，０００〜１００，０００の範囲が好ましく、特に、２５，０００〜８０，０００が好ましい。分子量が２０，０００未満の場合は、厚さ数十μｍに塗布して焼き付けるとクラックが入り易い。また、分子量が１００，０００を越えると、ガラス密着性が低くなり易い。エチレン−不飽和カルボン酸共重合体の成分である不飽和カルボン酸としては、炭素数３〜８の不飽和カルボン酸などを挙げることができる。炭素数３〜８の不飽和カルボン酸の具体的例としては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、シトラコン酸、アリルコハク酸、メサコン酸、グルタコン酸などを挙げることができる。これらの中では、特に、アクリル酸が好ましい。 The ethylene-unsaturated carboxylic acid copolymer preferably has a weight average molecular weight (MW) in the range of 20,000 to 100,000, particularly 25,000 to 80,000 as measured by GPC. When the molecular weight is less than 20,000, cracks are likely to occur when applied to a thickness of several tens of μm and baked. On the other hand, when the molecular weight exceeds 100,000, the glass adhesion tends to be low. Examples of the unsaturated carboxylic acid that is a component of the ethylene-unsaturated carboxylic acid copolymer include unsaturated carboxylic acids having 3 to 8 carbon atoms. Specific examples of the unsaturated carboxylic acid having 3 to 8 carbon atoms include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, citraconic acid, allyl succinic acid, mesaconic acid, and glutaconic acid. Among these, acrylic acid is particularly preferable.
また、このアイオノマー樹脂の主鎖を構成するエチレン−不飽和カルボン酸共重合体は、エチレンと不飽和カルボン酸に加えて第３成分を含んでいてもよい。この第３成分としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソブチルなどの不飽和カルボン酸エステル、酢酸ビニルエステルを挙げることができる。このエチレン−不飽和カルボン酸共重合体におけるエチレンと不飽和カルボン酸の含有割合は、エチレン８６〜９５モル％に対して、不飽和カルボン酸５〜１４モル％の割合であり、好ましくは、エチレン８７〜９４重量部に対して、不飽和カルボン酸６〜１３重量部の割合であり、特に、エチレン８８〜９３重量部に対して、不飽和カルボン酸７〜１２重量部の割合であることが好ましい。また、エチレン−不飽和カルボン酸共重合体が第３成分を含む場合は、第３成分は２０モル％以下の量で存在することが好ましい。 Further, the ethylene-unsaturated carboxylic acid copolymer constituting the main chain of the ionomer resin may contain a third component in addition to ethylene and the unsaturated carboxylic acid. Examples of the third component include unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and isobutyl (meth) acrylate, and vinyl acetate. The content ratio of ethylene and unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid copolymer is a ratio of 5 to 14 mol% of unsaturated carboxylic acid with respect to 86 to 95 mol% of ethylene, preferably ethylene. It is a ratio of 6 to 13 parts by weight of unsaturated carboxylic acid with respect to 87 to 94 parts by weight, and particularly a ratio of 7 to 12 parts by weight of unsaturated carboxylic acid with respect to 88 to 93 parts by weight of ethylene. preferable. Further, when the ethylene-unsaturated carboxylic acid copolymer contains a third component, the third component is preferably present in an amount of 20 mol% or less.
エチレン含有割合が上記の範囲外にあって高すぎる場合は、分散体の粒径が大きくなり安定した分散体が得られず、また、強度をだすため厚さ数十μｍに塗布して焼き付けるとクラックが入り易い。一方、逆に低すぎる場合には、耐汚染性が悪化し易い。
このアイオノマー樹脂において、エチレン−不飽和カルボン酸共重合体の側鎖であるカルボキシル基は部分的に一価または二価の金属イオンで中和されている。三価の金属イオンで中和されたアイオノマー樹脂では、平均粒径が大きくなり安定した水分散体が得られない。
If the ethylene content ratio is outside the above range and too high, the particle size of the dispersion becomes large and a stable dispersion cannot be obtained, and when it is applied and baked to a thickness of several tens of μm to increase the strength. Easy to crack. On the other hand, if it is too low, the contamination resistance tends to deteriorate.
In this ionomer resin, the carboxyl group which is the side chain of the ethylene-unsaturated carboxylic acid copolymer is partially neutralized with a monovalent or divalent metal ion. In the ionomer resin neutralized with trivalent metal ions, the average particle size becomes large and a stable aqueous dispersion cannot be obtained.
本発明において、アイオノマー樹脂を中和する一価の金属イオンとしては、ＮａイオンとＫイオン、Ｌｉイオン、Ｒｂイオンを挙げることができる。また、二価の金属イオンとしては、ＭｇイオンとＣａイオン、Ｚｎイオンなどを挙げることができる。勿論、これらの金属イオンを2種類以上併用することもできる。これらの金属イオンの中でも、ＮａイオンとＫイオンは水分散体の粒径が小さくなり、水分散体の安定性も優れる点で好ましい。アイオノマー樹脂において、エチレン−不飽和カルボン酸共重合体の側鎖であるカルボキシル基の全量に対して、一価または二価の金属イオンで中和されたカルボキシル基の割合、すなわち、中和率は、５０〜９５％が好ましく、特に、５０〜８５％が好ましい。 In the present invention, examples of the monovalent metal ions that neutralize the ionomer resin include Na ions, K ions, Li ions, and Rb ions. Examples of divalent metal ions include Mg ions, Ca ions, and Zn ions. Of course, two or more of these metal ions can be used in combination. Among these metal ions, Na ions and K ions are preferable in that the particle size of the aqueous dispersion is reduced and the stability of the aqueous dispersion is excellent. In the ionomer resin, the ratio of the carboxyl groups neutralized with monovalent or divalent metal ions with respect to the total amount of carboxyl groups that are side chains of the ethylene-unsaturated carboxylic acid copolymer, that is, the neutralization rate is 50 to 95% is preferable, and 50 to 85% is particularly preferable.
一価または二価の金属で中和されたカルボキシル基の割合が９５％を越えると、ガラス密着性が低下し易く、一価のまたは二価の金属で中和されたカルボキシル基の割合が５０％未満になると、焼き付け後の塗膜にクラックが入り易い。
水分散体の平均粒径は０．０１〜０．５μｍの範囲が好ましい。粒径が０．５μｍを越えると、焼き付け条件によっては造膜性が低下して良好な塗膜が得られず、クラックが入る原因の一つになる。
When the proportion of carboxyl groups neutralized with monovalent or divalent metals exceeds 95%, the glass adhesion tends to be lowered, and the proportion of carboxyl groups neutralized with monovalent or divalent metals is 50. If it is less than%, cracks are likely to occur in the coating film after baking.
The average particle size of the aqueous dispersion is preferably in the range of 0.01 to 0.5 μm. If the particle size exceeds 0.5 μm, the film-forming property is lowered depending on the baking condition, and a good coating film cannot be obtained, which is one of the causes of cracks.
本組成物において、必要に応じて少量の溶剤を添加して水分散化すると、水分散体の平均粒径が小さくなり、水分散体の安定性が増すので好ましい。このような溶剤として、ベンジルアルコールとチルアルコール、エチレングリコールとグリセリン、トルエン、、キシレンなどの芳香族炭化水素などを挙げることができる。このうち、ベンジルアルコールとエチルアルコール、グリセリンが好ましく、特に、ベンジルアルコールとエチルアルコールが好ましい。添加する溶剤量は特に限定されないが、普通、エチレン−不飽和カルボン酸共重合体に対して５０重量％以下が好ましい。添加量が５０重量％を越えても粒径はほとんど小さくならず、溶剤をほとんど使用しないという特徴を失うので、好ましくない。 In the present composition, it is preferable to add a small amount of a solvent as necessary to disperse in water, since the average particle size of the aqueous dispersion becomes small and the stability of the aqueous dispersion increases. Examples of such a solvent include aromatic hydrocarbons such as benzyl alcohol and til alcohol, ethylene glycol and glycerin, toluene, and xylene. Of these, benzyl alcohol, ethyl alcohol, and glycerin are preferable, and benzyl alcohol and ethyl alcohol are particularly preferable. The amount of the solvent to be added is not particularly limited, but it is usually preferably 50% by weight or less based on the ethylene-unsaturated carboxylic acid copolymer. Even if the addition amount exceeds 50% by weight, the particle diameter is not almost reduced, and the characteristics of hardly using a solvent are lost, which is not preferable.
なお、本発明の組成物においては、エチレン−不飽和カルボン酸共重合体の濃度は、特に制限されず、塗装方法、塗装に使用される装置に応じて適宜調整される。通常はエチレン−不飽和カルボン酸共重合体の１００重量部に対して水１００〜２０００重量部の割合が好ましい。
本発明の組成物は、必要に応じて、各種の樹脂、配合剤等の他の成分を、本発明の目的を損なわない範囲で含有してもよい。他の成分としては、水分散樹脂、有機増粘剤、無機増粘剤、酸化防止剤、シランカップリング剤、濡れ性改良剤、シリカ等の充填剤等が挙げられる。本発明の組成物は、ソースやケチャップなどの食品を充填したガラス瓶などに塗布し、乾燥、硬化して塗膜を形成する。組成物の塗布は、浸漬、スプレー、刷毛塗りなどのいずれの方法によっても行うことができる。
In the composition of the present invention, the concentration of the ethylene-unsaturated carboxylic acid copolymer is not particularly limited, and is appropriately adjusted according to the coating method and the apparatus used for coating. Usually, a ratio of 100 to 2000 parts by weight of water is preferable with respect to 100 parts by weight of the ethylene-unsaturated carboxylic acid copolymer.
The composition of this invention may contain other components, such as various resin and a compounding agent, in the range which does not impair the objective of this invention as needed. Examples of other components include water-dispersed resins, organic thickeners, inorganic thickeners, antioxidants, silane coupling agents, wettability improvers, and fillers such as silica. The composition of the present invention is applied to a glass bottle filled with food such as sauce or ketchup, dried and cured to form a coating film. The composition can be applied by any method such as dipping, spraying or brushing.
以下、実施例及び比較例により本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to these Examples.
[物性の測定]
分子量の測定
水分散化する前のエチレン−不飽和カルボン酸共重合体をメチルエステル化した後、下記の条件でＧＰＣ分析して分子量を測定した。
カラム：ＴＳＫgelＧＭＨ６−ＨＴ×２+ＴＳＫgelＧＭＨ６−ＨＴＬ×２
検出器：示差屈折率計、 展開液：ｏ−ジクロロベンゼン、評準物質：ＰＳ。
平均粒径の測定
Microtrac UPAを用いて分散体の平均粒径を測定した。
[Measurement of physical properties]
Measurement of molecular weight After the ethylene-unsaturated carboxylic acid copolymer before water dispersion was methyl esterified, the molecular weight was measured by GPC analysis under the following conditions.
Column: TSKgelGMH6-HT × 2 + TSKgelGMH6-HTL × 2
Detector: differential refractometer, developing solution: o-dichlorobenzene, reference substance: PS.
Average particle size measurement
The average particle size of the dispersion was measured using Microtrac UPA.
[評価方法]
Ｎｏ．７０バーコーターを使用して水分散体の乾燥後の膜厚が３０μｍになるようにガラス板に塗布し、１５０℃のエアーオーブンに１分間入れて焼き付けて水分散体を塗布したサンプル片を調製した。サンプル片について目視で塗膜のクラックの有無と密着性を評価した。
外観検査（クラックの有無評価）
エマルションを焼き付けたガラス板の塗装面にクラックが有るか否かを目視で評価した。評点結果は３段階で次のように示した。○：クラックなし、△：小さなクラックあり、×：大きなクラックあり
ガラス密着性
エマルションを塗布したガラス板を常態で３日間放置後、粘着テープを貼り付けて一気に剥がして、剥離状態を評価した。評点結果は３段階で次のように示した。○：剥離せず、△：部分剥離、×：全面剥離。
[Evaluation methods]
No. Using a 70 bar coater, prepare a sample piece that was applied to a glass plate so that the film thickness after drying of the aqueous dispersion was 30 μm, and was baked in an air oven at 150 ° C. for 1 minute. did. About the sample piece, the presence or absence of the crack of a coating film and adhesiveness were evaluated visually.
Appearance inspection (evaluation of cracks)
It was visually evaluated whether or not there was a crack on the coated surface of the glass plate on which the emulsion was baked. The score results are shown as follows in three stages. ○: No crack, △: Small crack, ×: Large crack
After leaving the glass plate coated with the glass adhesive emulsion in a normal state for 3 days, an adhesive tape was applied and peeled off at a stretch to evaluate the peeled state. The score results are shown as follows in three stages. ○: No peeling, Δ: Partial peeling, ×: Whole peeling.
[実施例１]
内容積１．５Lのオートクレーブにエチレン−アクリル酸共重合体（Ｍｗ：３４，０００、アクリル酸含量：８．９モル％）２００ｇ、水５７０ｇ、ＮａＯＨ（純度：９６％）１１．６ｇ（中和率：５０％）を入れて１６０℃に昇温した後、２時間攪拌して水分散体を得た。得られた水分散体は、固形分濃度２６．６％、粘度２５０ｍＰａ・ｓ、ｐＨ８．９、平均粒径０．0５μｍであった。
Ｎｏ．７０バーコーターを使用してこの水分散体の乾燥後の膜厚が３０μｍになるようにガラス板に塗布し、１５０℃のエア−オーブンに入れて１分間焼き付けてサンプルを作製した。このガラス板について外観検査と剥離試験を行い、その結果を表１に示した。
[Example 1]
200 g of ethylene-acrylic acid copolymer (Mw: 34,000, acrylic acid content: 8.9 mol%), water 570 g, NaOH (purity: 96%) 11.6 g (neutralized) (Rate: 50%) and the temperature was raised to 160 ° C., followed by stirring for 2 hours to obtain an aqueous dispersion. The obtained aqueous dispersion had a solid content concentration of 26.6%, a viscosity of 250 mPa · s, a pH of 8.9, and an average particle size of 0.05 μm.
No. Using a 70 bar coater, this aqueous dispersion was coated on a glass plate so that the film thickness after drying was 30 μm, and was placed in an air oven at 150 ° C. and baked for 1 minute to prepare a sample. The glass plate was subjected to an appearance inspection and a peel test, and the results are shown in Table 1.
[実施例２]
内容積１．５Lのオートクレーブにエチレン−メタクリル酸共重合体（Ｍｗ：４２，０００、メタクリル酸含量：７．５モル％）２００ｇ、水５７０ｇ、ＮａＯＨ（純度：９６％）９．２ｇ（中和率：６０％）を入れて１６０℃に昇温した後、２時間攪拌して水分散体を得た。得られた水分散体は、固形分濃度２６．６％、粘度２５０ｍＰａ・ｓ、ｐＨ１０．５、平均粒径０．０２μｍであった。
Ｎｏ．７０バーコーターを使用してこの水分散体の乾燥後の膜厚が３０μｍになるようにガラス板に塗布し、１５０℃のエア−オーブンに入れて１分間焼き付けてサンプルを作製した。このガラス板について外観検査と剥離試験を行い、その結果を表１に示した。
[Example 2]
200 g of ethylene-methacrylic acid copolymer (Mw: 42,000, methacrylic acid content: 7.5 mol%), water 570 g, NaOH (purity: 96%) 9.2 g (neutralized) (Rate: 60%) and the temperature was raised to 160 ° C., followed by stirring for 2 hours to obtain an aqueous dispersion. The obtained aqueous dispersion had a solid content concentration of 26.6%, a viscosity of 250 mPa · s, a pH of 10.5, and an average particle size of 0.02 μm.
No. Using a 70 bar coater, this aqueous dispersion was coated on a glass plate so that the film thickness after drying was 30 μm, and was placed in an air oven at 150 ° C. and baked for 1 minute to prepare a sample. The glass plate was subjected to an appearance inspection and a peel test, and the results are shown in Table 1.
[実施例３]
内容積１．５Lのオートクレーブにエチレン−アクリル酸共重合体（Ｍｗ：８４，０００、アクリル酸含量：５．０モル％）２００ｇ、水５７０ｇ、ＫＯＨ（純度：８６％）１６．３ｇ（中和率：７５％）を入れて１６０℃に昇温した後、２時間攪拌して水分散体を得た。得られた水分散体は、固形分濃度２６．６％、粘度３００ｍＰａ・ｓ、ｐＨ１０．０、平均粒径０．０２μｍであった。
Ｎｏ．７０バーコーターを使用してこの水分散体の乾燥後の膜厚が３０μｍになるようにガラス板に塗布し、１５０℃のエア−オーブンに入れて１分間焼き付けてサンプルを作製した。このガラス板について外観検査と剥離試験を行い、その結果を表１に示した。
[Example 3]
In an autoclave with an internal volume of 1.5 L, ethylene-acrylic acid copolymer (Mw: 84,000, acrylic acid content: 5.0 mol%) 200 g, water 570 g, KOH (purity: 86%) 16.3 g (neutralization) (Rate: 75%) and the temperature was raised to 160 ° C., followed by stirring for 2 hours to obtain an aqueous dispersion. The obtained aqueous dispersion had a solid content concentration of 26.6%, a viscosity of 300 mPa · s, a pH of 10.0, and an average particle size of 0.02 μm.
No. Using a 70 bar coater, this aqueous dispersion was coated on a glass plate so that the film thickness after drying was 30 μm, and was placed in an air oven at 150 ° C. and baked for 1 minute to prepare a sample. The glass plate was subjected to an appearance inspection and a peel test, and the results are shown in Table 1.
[比較例１]
中和剤にＮａＯＨ（純度：９６％）６．９ｇ（中和率：３０％）を用いた以外は実施例１と同様にしてサンプルを作製し、このガラス板について外観検査と剥離試験を行い、その結果を表１に示した。なお、平均粒径は０．４８μｍであった。
[Comparative Example 1]
A sample was prepared in the same manner as in Example 1 except that 6.9 g (neutralization rate: 30%) of NaOH (purity: 96%) was used as the neutralizing agent, and an appearance inspection and a peel test were performed on this glass plate. The results are shown in Table 1. The average particle size was 0.48 μm.
[比較例２]
中和剤にＮａＯＨ（純度：９６％）９．３ｇ（中和率：４０％）を用いた以外は実施例１と同様にしてサンプルを作製し、このガラス板を用いて外観検査と剥離試験を行い、その結果を表１に示した。なお、平均粒径は０．０7μｍであった。
[Comparative Example 2]
A sample was prepared in the same manner as in Example 1 except that 9.3 g (neutralization rate: 40%) of NaOH (purity: 96%) was used as a neutralizing agent, and an appearance inspection and a peel test were performed using this glass plate. The results are shown in Table 1. The average particle size was 0.07 μm.
[比較例３]
中和剤にＫＯＨ（純度：８６％）２１．７ｇ（中和率：１００％）を用いた以外は実施例３と同様にしてサンプルを作製し、このガラス板について外観検査と剥離試験を行い、その結果を表１に示した。なお、平均粒径は０．０１μｍであった。
[Comparative Example 3]
A sample was prepared in the same manner as in Example 3 except that 21.7 g of KOH (purity: 86%) (neutralization rate: 100%) was used as the neutralizing agent, and an appearance inspection and a peel test were performed on this glass plate. The results are shown in Table 1. The average particle size was 0.01 μm.
Claims (5)
The composition for water-dispersed glass bottle protective coating agents according to claim 1, wherein the average particle size of the water dispersion is from 0.01 to 0.5 µm or less.
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| JP2014125393A (en) * | 2012-12-27 | 2014-07-07 | Kikusui Chemical Industries Co Ltd | Protection film for glass processing |
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| JPS573869A (en) * | 1980-06-11 | 1982-01-09 | Ishizuka Glass Ltd | Coating agent |
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