JPS6060947A - Manufacture of glass bottle having increased scratch resistance after washing - Google Patents

Abstract

PURPOSE:To provide scratch resistance after washing to a glass bottle by coating the surface of the bottle with photosetting paint and irradiating active light to form a paint film of a specified thickness by setting. CONSTITUTION:The surface of a glass bottle is coated with photosetting paint prepd. by adding 0.01-50wt% photopolymn. initiator such as benzoin methyl ether, p-dimethylaminobenzophenone or diphenyl monosulfide to polyamide resin, acrylic resin, polyester resin, polyether resin or the like. Active light having 2,000-7,000Angstrom wavelengths is irradiated on the coated surface from an ultraviolet fluorescent lamp, a carbon arc lamp, a tungsten lamp or the like to cause a cross-linking reaction. A paint film of <=10mum thickness is formed by the reaction.

Description

【発明の詳細な説明】 本発明はガラス壜の耐加傷性増大方法に関する。[Detailed description of the invention] The present invention relates to a method for increasing the scratch resistance of glass bottles.

従来、ガラス壜に種々のコーティングを施し、潤滑性及
び耐加傷性分付与する方法が提案されている。例えばガ
ラス壜の表面に種々の界面活性剤、アイオノマ樹脂（商
品名サーリン）、ンラン系−樹脂をコーティングする方
法がある。Conventionally, methods have been proposed in which various coatings are applied to glass bottles to impart lubricity and scratch resistance. For example, there is a method in which the surface of a glass bottle is coated with various surfactants, ionomer resin (trade name: Surlyn), and Nuran-based resin.

しかしこれらの方法はガラス壜に光分に付着しておれば
潤滑性や耐加傷性を有しているものの、一度洗壜工程を
受けると容易に洗い落でれてその効果がほとんど失われ
てしまうと共にアルカリ洗浄てれた時に白化現象を生じ
て、外観的に商品価値を著しく損うという欠点を有して
いた。However, although these methods have lubricity and scratch resistance when the light adheres to the glass bottle, once the bottle is washed, it is easily washed off and most of its effectiveness is lost. In addition, when washed with alkali, a whitening phenomenon occurs, which significantly impairs the commercial value in terms of appearance.

本発明はこのような欠点を解消し洗場工程にも洗い落と
されず依然として耐加傷性を有し、又白化現象を生じな
いガラス壜の製造方法を提供する。The present invention eliminates these drawbacks and provides a method for manufacturing a glass bottle that is not washed away even in the washing process, remains scratch resistant, and does not cause any whitening phenomenon.

本発明で使用する光硬化型塗料は活性光線の照射によっ
て光化学的に架橋反応が生起され硬化するものであれば
いかなるものでもよい。The photocurable paint used in the present invention may be any paint that can be cured by photochemically causing a crosslinking reaction upon irradiation with actinic rays.

例えばアクリル系樹脂、ポリアミド樹脂、ポリエステル
樹脂、ポリエーテル樹脂、アミノ樹脂、ポリウレタン樹
脂、エポキシ樹脂等に光重合開始剤として例えば、ベン
ゾインメグ・ルエーテル、Ｐ−ジメチルアミノベンゾフ
ェノン、ジフェニルモノサルファイド、ナフタレンスル
ホニルクロライド等を混合して得られるものである。こ
の重合開始剤は一種又は二種以上混合してもよい。混合
割合は上記樹脂に対して００１〜５０重ｉチである。更
に必要に応じて、可塑剤、充填剤、顔料並びにその他の
助剤類を併用することもできる。For example, as a photopolymerization initiator for acrylic resin, polyamide resin, polyester resin, polyether resin, amino resin, polyurethane resin, epoxy resin etc. It is obtained by mixing etc. These polymerization initiators may be used alone or in combination. The mixing ratio is 0.001 to 50% based on the above resin. Furthermore, if necessary, plasticizers, fillers, pigments, and other auxiliary agents may be used in combination.

光硬化型塗料はスプレィ塗装、ローラー塗装、カーテン
塗装、浸漬塗装、ノ・ケ塗り等種々の塗装方法によって
ガラス壜の表面に塗布される。The photocurable paint is applied to the surface of the glass bottle by various coating methods such as spray coating, roller coating, curtain coating, dipping coating, and coating.

塗装後に、活性光線（２０００〜７０００＾）を照射し
、光化学的に架橋反応を生起させ、塗膜を硬化式せる。After painting, actinic light (2000 to 7000^) is irradiated to cause a photochemical crosslinking reaction, thereby curing the coating film.

この活性光線を照射する光源として、紫外螢光灯、炭素
アーク灯、タングステン灯、キセノンランプ、水銀灯等
がある。Light sources for irradiating this actinic ray include ultraviolet fluorescent lamps, carbon arc lamps, tungsten lamps, xenon lamps, mercury lamps, and the like.

硬化後の塗膜の厚みは約１０μ以内とするのがよく、好
ましくけ５μ以内とするのがよい０１０μ以内としたの
け、１０μを超えても洗場後の耐加傷性に大差ｌ′ｌｔ
なく、塗布跡がついて外観的に見苦しくなると共に、経
済的に不利となるからである。The thickness of the coating film after curing is preferably within about 10 μm, preferably within 5 μm, and preferably within 10 μm; however, even if it exceeds 10 μm, there is a large difference in scratch resistance after washing. lt
This is because it leaves coating marks, which makes the appearance unsightly, and is economically disadvantageous.

以下、実施例によって本発明を具体的に説明する。但し
以下の部は全て重量基準による。Hereinafter, the present invention will be specifically explained with reference to Examples. However, all the following parts are based on weight.

〈実施例・１〉 液状エポキシ樹脂恥部にトリメチロールグルパントリア
クリレート４０部、ペンタエリスリトールトリアクリレ
ート５部、２−ヒドロキシエチルアクリレート５部、Ｐ
−ジメチルアミノベンゾフェノン６部を加え、約（資）
℃に加熱し、均一に溶解して光硬化型塗料（４）を調製
した。<Example 1> 40 parts of trimethylolglupane triacrylate, 5 parts of pentaerythritol triacrylate, 5 parts of 2-hydroxyethyl acrylate, P in liquid epoxy resin pubic area
- Add 6 parts of dimethylaminobenzophenone, approx.
The mixture was heated to 0.degree. C. and uniformly dissolved to prepare a photocurable coating material (4).

この塗料（４）をガラス増容ｚ　ｔｏｏｏ−の表面に浸
漬塗装法により塗装した後、壜を回転させながら、ｕＶ
　ランプの下を通過させ、約１分間活性光線を照射し硬
化後の塗膜の厚みが約１μであるガラス壜を得た。After coating this paint (4) on the surface of the glass volume increaser z tooo- by dip coating method, while rotating the bottle,
The glass bottle was passed under a lamp and irradiated with actinic rays for about 1 minute to obtain a glass bottle with a coating film having a thickness of about 1 μm after curing.

〈実施例２〉 ウレタンｆｍ　１ｍ　９０部、２−ヒドロキシプロピル
アクリレート溶液１０部、アクリル酸ブチル溶液α５部
、ベンゾインメチルエーテル２部を均一に混合して光硬
化型塗料（Ｂ）を調製した。<Example 2> A photocurable coating material (B) was prepared by uniformly mixing 90 parts of urethane fm 1 m, 10 parts of 2-hydroxypropyl acrylate solution, 5 parts of butyl acrylate solution α, and 2 parts of benzoin methyl ether.

この塗料（Ｂ）を用いて実施例１と同様の手順で塗装及
び硬化し、硬化後の塗膜の厚みが約１μであるガラス壜
を得た。This coating material (B) was coated and cured in the same manner as in Example 1 to obtain a glass bottle with a coating film thickness of approximately 1 μm after curing.

〈参考例１〉 実施例と比較のため、同一のガラス壜を用い下記のポリ
エチレン乳化液をその表面に均一にスプレィし、約１μ
の被膜を形成した。<Reference Example 1> For comparison with the example, the following polyethylene emulsion was uniformly sprayed onto the surface of the same glass bottle, and a coating of approximately 1 μm was applied.
A film was formed.

ＡＣポリエチレン４６２９　４０重量部オレイン酸　１
１１ 水酸化カリウム　２重量部 蒸留水　２０７１ −記の乳化液を水２００容量部で希釈し、ポリエチレン
乳化液とした。AC polyethylene 4629 40 parts by weight Oleic acid 1
11 Potassium hydroxide 2 parts by weight Distilled water 2071 The emulsion described in - was diluted with 200 parts by volume of water to obtain a polyethylene emulsion.

〈参考例２〉 実施例と比較のため、同一のガラス壜を用い、アイオノ
マー重合体をその表面に均一にスプレィし、乾燥後約１
μの被膜を形成した。<Reference Example 2> For comparison with the example, the same glass bottle was used, and the ionomer polymer was sprayed uniformly on the surface of the bottle, and after drying, about 1
A film of μ was formed.

このアイオノマー重合体はエチレンとメタアクリル酸と
の共重合体でありその酸基の一部がアルカリ金属と反応
、又は中和されており、商品名Ｅｔｖａｘ　Ｄ　−１２
２０の名称でＥ、　Ｉ、　Ｄｕｐｏｎｔ社より市販され
ている。このアイオノマー重合体は、それが００６重量
％存在する水性分散液として適用した。This ionomer polymer is a copolymer of ethylene and methacrylic acid, and some of its acid groups are reacted with or neutralized with an alkali metal, and is available under the trade name Etvax D-12.
It is commercially available under the names E, I and DuPont. This ionomeric polymer was applied as an aqueous dispersion in which it was present at 0.06% by weight.

上記４種類の壜（ｎ　＝　１０本）を４チカセインーダ
及びα４％ンルコン酸ソーダーの８０℃溶液に（９）分
間浸漬後、ホ出し水洗した。The above four types of bottles (n = 10 bottles) were immersed in a solution of 4% sodium chloride and α4% sodium luconic acid at 80° C. for 9 minutes, then drained and washed with water.

水洗後、ＡＧＲ社製のラインシミュレーターにて１分間
の加傷を行い、これを１トリ、ブとした。After rinsing with water, scratching was performed for 1 minute using a line simulator manufactured by AGR, and this was treated as one test.

力ｎ礁移の壜について、強廖試験を行うだ。その測定結
果を表１に示す。（アルカリ洗浄後の白化現象について
も併せて示す。） 表　１ 上表の如く、耐内圧強度に於ける１トリ、プ後処理壜で
ｔｉｔ　７０　％　、参考例では約４０−強度が低下し
ているのに対し本発明では約ｌθ％しか強度が低下して
いない。本発明のアルカリ洗浄後の耐加傷性が優れてい
る事は明白である。一方白化現象については参考例（２
）において白化が発生したけれども、本発明でセ発生し
なかった。We will conduct a strength test on the bottle of force n reef transfer. The measurement results are shown in Table 1. (The whitening phenomenon after alkaline washing is also shown.) Table 1 As shown in the above table, the tit of the bottle after the post-treatment treatment was 70%, and the strength of the reference example was about 40% lower. In contrast, in the present invention, the strength decreases by only about lθ%. It is clear that the present invention has excellent scratch resistance after alkaline cleaning. On the other hand, regarding the bleaching phenomenon, reference example (2
), but whitening did not occur in the present invention.

以上の如く本発明の壜は耐アルカリ洗浄性、耐加傷性が
あり、白化現象も生じないのでリタナブル壜に好適に採
用されうる。又強度が高く維持されるため、その分だけ
軽量化も出来るという利点を有する。As described above, the bottle of the present invention has alkali cleaning resistance and scratch resistance, and does not cause any whitening phenomenon, so it can be suitably employed as a returnable bottle. Moreover, since the strength is maintained high, it has the advantage that the weight can be reduced accordingly.

特許出願人　山村硝子株式会社Patent applicant: Yamamura Glass Co., Ltd.

Claims (1)

【特許請求の範囲】[Claims] ガラス壜の表面に光硬化型塗料を塗布した後、活性光線
を照射して硬化させ、１０μ以内の塗膜を形成して成る
洗場後の耐加傷性を増大させたガラス壜を製造する方法
。After applying a photocurable paint to the surface of the glass bottle, it is cured by irradiation with actinic rays to form a coating film of less than 10μ, thereby producing a glass bottle with increased scratch resistance after washing. Method.