JPWO2007141921A1 - Coating liquid and coating method - Google Patents
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- JPWO2007141921A1 JPWO2007141921A1 JP2008520137A JP2008520137A JPWO2007141921A1 JP WO2007141921 A1 JPWO2007141921 A1 JP WO2007141921A1 JP 2008520137 A JP2008520137 A JP 2008520137A JP 2008520137 A JP2008520137 A JP 2008520137A JP WO2007141921 A1 JPWO2007141921 A1 JP WO2007141921A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/16—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
Abstract
本発明は、ポリアルキルシラザンとペルヒドロポリシラザンとを、これら２者の合計として１〜４０質量％の濃度で不活性有機溶剤中に溶解してなることを特徴とするコーティング液およびコーティング方法である。上記本発明によれば、プラスチック成形品、金属成形品、ガラス成形品、ゴム成形品、革成形品、木工品または紙製品などの物品表面に優れた特性を与えるコーティング液およびコーティング方法を提供することができる。The present invention is a coating liquid and a coating method, wherein polyalkylsilazane and perhydropolysilazane are dissolved in an inert organic solvent at a concentration of 1 to 40% by mass as the total of these two. . According to the present invention, it is possible to provide a coating liquid and a coating method that give excellent properties to the surface of an article such as a plastic molded product, a metal molded product, a glass molded product, a rubber molded product, a leather molded product, a woodwork product, or a paper product. be able to.
Description
本発明は、各種物品の表面改質に有用であるコーティング液およびコーティング方法に関する。 The present invention relates to a coating solution and a coating method useful for surface modification of various articles.
従来、各種プラスチック（なお、本発明における「プラスチック」とは「熱可塑性樹脂」および「熱硬化性樹脂」の双方を意味する）成形品が多種多量に使用されている。これらのプラスチック成形品としてはフィルム、シート、各種立体形状の物品がある。また、金属成形品、ガラス成形品、ゴム成形品、革成形品、木工品または紙製品も同様に各種の形状の物品が多量に使用されている。 Conventionally, various types of plastic products (in the present invention, “plastic” means both “thermoplastic resin” and “thermosetting resin”) are used in large quantities. These plastic molded products include films, sheets, and various three-dimensional shaped articles. Similarly, a large amount of articles having various shapes are used for metal molded products, glass molded products, rubber molded products, leather molded products, woodwork products, and paper products.
プラスチック成形品は、成形容易性、着色容易性、電気絶縁性、耐候性などの各種耐久性などの各種物性に優れているという利点があるが、他方では、ガラスや金属などに比較して表面が本質的に柔らかい材料であることから、表面耐擦傷性やガスバリヤー性が劣るなどの欠点も多い。特に耐擦傷性やガスバリヤー性の向上に関してはプラスチック成形品の表面に硬質樹脂塗料（ハードコート塗料）からなる硬質膜やアルミニウムや金属酸化物からなるガスバリヤー性蒸着膜を形成する技術が知られている。 Plastic molded products have the advantage of being excellent in various physical properties such as ease of molding, ease of coloring, electrical insulation, weather resistance, etc., but on the other hand, the surface is superior to glass or metal. Are inherently soft materials, and thus have many drawbacks such as poor surface scratch resistance and gas barrier properties. In particular, with respect to the improvement of scratch resistance and gas barrier properties, a technique for forming a hard film made of a hard resin paint (hard coat paint) or a gas barrier vapor-deposited film made of aluminum or metal oxide on the surface of a plastic molded product is known. ing.
上記表面耐擦傷性やガスバリヤー性の改良などに関する大部分の方法は、プラスチック成形品の表面に当該プラスチック成形品とは異なる材質からなるハードコート層や蒸着層などの機能性層を形成することを内容としている。それ故にプラスチック成形品とその表面に形成する機能性層との密着性に問題が残っている。例えば、紫外線・電子線硬化性ハードコート塗料やポリシラザンを含む塗料によりプラスチック成形品表面に高硬度のハードコート層やガスバリヤー層を形成することによって、プラスチック成形品の表面耐擦傷性やガスバリヤー層を向上させることができるが、プラスチック成形品表面とハードコート層やガスバリヤー層との密着性に問題があり、成形品の折り曲げなどによってハードコート層やガスバリヤー層の白化や剥離が生じる。また、ポリシラザン塗料を用いる方法では、被膜形成に高温を要し、耐熱性の低いプラスチック成形品には適用が困難である。また、ガラスや金属成形品の表面改質においても様々な課題が残っている（特許文献１、２）。
従って本発明の目的は、プラスチック成形品、金属成形品、ガラス成形品、ゴム成形品、革成形品、木工品または紙製品などの物品表面に優れた特性を与えるコーティング液およびコーティング方法を提供することである。 Accordingly, an object of the present invention is to provide a coating liquid and a coating method which give excellent properties to the surface of an article such as a plastic molded product, a metal molded product, a glass molded product, a rubber molded product, a leather molded product, a woodwork product or a paper product. That is.
上記目的は以下の本発明によって達成される。
１．ポリアルキルシラザン（以下単に「Ａ成分」と云う場合がある）とペルヒドロポリシラザン（以下単に「Ｂ成分」と云う場合がある）とを、これら２者の合計として１〜４０質量％の濃度で不活性有機溶剤中に溶解してなることを特徴とするコーティング液（以下「第１のコーティング液」という）。The above object is achieved by the present invention described below.
1. Polyalkylsilazane (hereinafter sometimes simply referred to as “component A”) and perhydropolysilazane (hereinafter sometimes simply referred to as “component B”) at a concentration of 1 to 40% by mass as the total of these two components. A coating liquid which is dissolved in an inert organic solvent (hereinafter referred to as “first coating liquid”).
２．さらに水酸基含有油脂または水酸基含有脂肪酸あるいはそのエステル（以下単に「Ｃ成分」と云う場合がある）を含有する第１のコーティング液（以下「第２のコーティング液」という）。 2. Furthermore, a first coating liquid (hereinafter referred to as “second coating liquid”) containing a hydroxyl group-containing oil or fat, a hydroxyl group-containing fatty acid or an ester thereof (hereinafter sometimes simply referred to as “C component”).
３．Ａ成分とＣ成分とを、これら２者の合計として１〜４０質量％の濃度で不活性有機溶剤中に溶解してなることを特徴とするコーティング液（以下「第３のコーティング液」という）。 3. A coating liquid (hereinafter referred to as “third coating liquid”) characterized in that the A component and the C component are dissolved in an inert organic solvent at a concentration of 1 to 40% by mass as the total of these two components. .
４．Ｂ成分とＣ成分とを、これら２者の合計として１〜４０質量％の濃度で不活性有機溶剤中に溶解してなることを特徴とするコーティング液（以下「第４のコーティング液」という）。 4). A coating liquid (hereinafter referred to as “fourth coating liquid”), wherein B component and C component are dissolved in an inert organic solvent at a concentration of 1 to 40% by mass as the total of these two components. .
５．前記本発明のコーティング液を物品の表面に塗布し、Ａ成分および／またはＢ成分と水との反応生成物であるシリカまたは該シリカとＣ成分との反応生成物を含む複合化層を上記物品の表層部に形成することを特徴とする物品のコーティング方法。 5). The composite liquid containing silica or a reaction product of the silica and the C component, which is a reaction product of the component A and / or the component B and water, is applied to the surface of the article by applying the coating liquid of the present invention to the article. A method for coating an article, characterized in that the article is formed on the surface layer of the article.
本発明のコーティング液は、各種成形品表面に短時間で幾重にも重ね塗りすることができ、１〜１０μｍ以上の厚膜に形成して屈曲させても、被塗布物の表面から剥離することがない。また、好ましい実施形態では膜の硬さは鉛筆硬度で６〜９Ｈ或いはそれ以上にすることができ、しかも優れた成膜性、可撓性、耐衝撃性、密着性を有する。 The coating liquid of the present invention can be repeatedly applied to various molded article surfaces in a short time, and even if it is formed into a thick film of 1 to 10 μm or more and bent, it can be peeled off from the surface of the object to be coated. There is no. In a preferred embodiment, the hardness of the film can be 6-9H or more in terms of pencil hardness, and has excellent film formability, flexibility, impact resistance, and adhesion.
成膜にあたっては、特に高温で処理することなく、放置または加水処理することによって、各種成形品の表層部中にシリカおよび／またはシリカとＣ成分との反応生成物を含む複合化層が生成し、該表層部は成形品の構成材料とシリカおよび／またはシリカとＣ成分との反応生成物との混合複合化層となる。プラスチック、ゴム、革、紙などの成形品の表層部はこの混合複合化層と一体化しており、成形品を屈曲させても上記複合化層が表面剥離することがない。また、金属成形品の場合は、各成分がその表面の酸化膜との反応を起こすことにより表層部にも高い密着性が認められた。 In film formation, a composite layer containing silica and / or a reaction product of silica and C component is formed in the surface layer portion of various molded articles by leaving or adding water without treatment at a particularly high temperature. The surface layer portion is a mixed composite layer of the constituent material of the molded product and silica and / or a reaction product of silica and C component. The surface layer portion of a molded product such as plastic, rubber, leather, paper or the like is integrated with the mixed composite layer, and the composite layer does not peel off even if the molded product is bent. Moreover, in the case of a metal molded product, high adhesion was recognized also in the surface layer part by causing each component to react with the oxide film on the surface.
次に発明を実施するための最良の形態を挙げて本発明をさらに具体的に説明する。
［第１のコーティング液］
本発明の第１のコーティング液の主たる成分は、Ａ成分とＢ成分と不活性有機溶剤である。Ａ成分としては、ヘキサメチルジシラザン、オクタメチルシラザン、シクロテトラシラザンおよびテトラメチルジシラザンから選ばれる少なくとも１種が挙げられる。これらのＡ成分は市場から入手して使用することができる。特に好ましいのは信越化学工業（株）からＨＭＤＳ３の商品名で入手できるヘキサメチルジシラザンである。Next, the present invention will be described in more detail with reference to the best mode for carrying out the invention.
[First coating solution]
The main components of the first coating liquid of the present invention are an A component, a B component and an inert organic solvent. Examples of the component A include at least one selected from hexamethyldisilazane, octamethylsilazane, cyclotetrasilazane, and tetramethyldisilazane. These A components can be obtained from the market and used. Particularly preferred is hexamethyldisilazane available from Shin-Etsu Chemical Co., Ltd. under the trade name HMDS3.
本発明で使用するＢ成分とは、珪素、窒素および水素のみから構成される化合物であり、炭素などの有機成分を含まない無機のポリマーであり、−（ＳｉＨ2ＮＨ）−ユニットから構成されている。これらのＢ成分は登録商標「アクアミカ」として、商品番号ＮＮ１１０、ＮＮ３１０、ＮＬ１１０Ａ、ＮＬ１２０Ａ、ＮＬ１５０Ａ、ＮＬ１６０Ａ、ＮＰ１１０、ＮＰ１４０、ＳＰ１４０、ＵＰ１４０で市販されており、これらの商品は各種の固形分濃度の有機溶剤溶液として入手して使用することができる。特に好ましいものはジブチルエーテルの溶液となっている商品番号ＮＬ１２０Ａである。The B component used in the present invention is a compound composed only of silicon, nitrogen and hydrogen, is an inorganic polymer not containing an organic component such as carbon, and is composed of-(SiH 2 NH) -units. Yes. These B components are marketed under the registered trademark “AQUAMICA” under the product numbers NN110, NN310, NL110A, NL120A, NL150A, NL160A, NP110, NP140, SP140, and UP140. It can be obtained and used as a solvent solution. Particularly preferred is product number NL120A in a dibutyl ether solution.
本発明の第１のコーティング液は、前記Ａ成分と前記Ｂ成分とを有機溶剤に溶解してなる。使用する有機溶剤としては、上記化合物に対して不活性な有機溶剤であれば特に限定されないが、プラスチック成形品などの表面に対する適度の膨潤性、揮発性、環境衛生上からは、エーテル系有機溶剤、例えば、ジメチルエーテル、ジエチルエーテル、ジプロピルエーテル、ジブチルエーテルおよびリモネンから選ばれる少なくとも１種であることが好ましい。 The first coating liquid of the present invention is obtained by dissolving the A component and the B component in an organic solvent. The organic solvent to be used is not particularly limited as long as it is inactive with respect to the above-mentioned compounds, but from the viewpoint of moderate swelling, volatility and environmental hygiene on the surface of plastic molded articles, etc. For example, it is preferably at least one selected from dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether and limonene.
これらの有機溶剤に溶解する前記Ａ成分と前記Ｂ成分は、両者の合計量を１００質量部とした場合、Ａ：Ｂ＝３０〜９０：７０〜１０の質量比であることが好ましい。Ａ成分の使用量が少なすぎると２μｍ以上の厚膜形成の際に膜にクラックが入り、一方、Ａ成分の使用量が多すぎると厚膜の複合化層の形成が困難である。また、形成される膜に６Ｈ以上の鉛筆硬度が要求される場合には、Ａ：Ｂ＝３０〜７０：７０〜３０の質量比とすることが好ましい。 The A component and the B component dissolved in these organic solvents are preferably in a mass ratio of A: B = 30 to 90: 70-10 when the total amount of both is 100 parts by mass. If the amount of component A used is too small, the film will crack when a thick film of 2 μm or more is formed. On the other hand, if the amount of component A used is too large, it is difficult to form a thick composite layer. Moreover, when the pencil hardness of 6H or more is requested | required by the film | membrane formed, it is preferable to set it as the mass ratio of A: B = 30-70: 70-30.
本発明の第１のコーティング液中における前記Ａ成分と前記Ｂ成分との合計の濃度は１〜４０質量％である。上記濃度が低すぎると所望の膜厚の複合化層の形成に多量のコーティング液を使用しなければならず、一方、上記濃度が高すぎると上記成分が空気中の水分と反応し、コーティング液が容易にゲル化するので好ましくない。なお、本発明のコーティング液は加水分解触媒などの各種添加剤を含んでもよい。また、ナノレベルの金属粒子を添加し成膜することもできる。 The total concentration of the A component and the B component in the first coating liquid of the present invention is 1 to 40% by mass. If the concentration is too low, a large amount of coating solution must be used to form a composite layer having a desired film thickness. On the other hand, if the concentration is too high, the components react with moisture in the air, and the coating solution Is not preferred because it gels easily. In addition, the coating liquid of this invention may contain various additives, such as a hydrolysis catalyst. Further, it is possible to form a film by adding nano-level metal particles.
［第２のコーティング液］
本発明の第２のコーティング液は、前記第１のコーティング液がさらにＣ成分を含む。本発明で使用するＣ成分としては、ヒマシ油などの構成化学物質である水酸基を構造中に持つヒドロキシ脂肪酸、およびそのグリセリンエステル類、ヒマシ油の加水分解主成分であるヒマシ油脂肪酸、ヒマシ油脂肪酸の主成分であるリシノール酸およびそのエステル類などの誘導体、あるいはラノリン油脂などの水酸基を持つコレステロール類含有油脂とその加水分解物であるラノリン脂肪酸とそのエステル類などが挙げられる。上記エステルのアルコール成分は炭素数１〜５の低級アルコールであることが好ましい。特に好ましいＣ成分はヒマシ油およびラノリン油脂である。上記第２のコーティング液は、Ａ成分とＢ成分とＣ成分との合計量として１〜４０質量％の濃度で前記ジブチルエーテルなどの不活性有機溶剤中に溶解して調製する。なお、上記Ｃ成分は更にウルシオールなどを含んでもよい。[Second coating liquid]
In the second coating liquid of the present invention, the first coating liquid further contains a C component. The component C used in the present invention includes hydroxy fatty acid having a hydroxyl group in its structure, which is a constituent chemical substance such as castor oil, and glycerin esters thereof, castor oil fatty acid and castor oil fatty acid which are the main hydrolysis components of castor oil. Derivatives such as ricinoleic acid and its esters, which are the main components, or cholesterol-containing fats and oils having hydroxyl groups such as lanolin fats and oils, and lanolin fatty acids and esters thereof that are hydrolysed thereof. The alcohol component of the ester is preferably a lower alcohol having 1 to 5 carbon atoms. Particularly preferred component C is castor oil and lanolin oil. The second coating solution is prepared by dissolving in an inert organic solvent such as dibutyl ether at a concentration of 1 to 40% by mass as the total amount of the A component, B component and C component. The C component may further contain urushiol.
上記Ｃ成分を使用することで形成される被膜の可撓性が高くなり、被膜を屈曲させてもひび割れやクラックが生じる可能性が激減する。また、コーティング剤のレベリング性が向上し、塗布適性も向上し厚膜形成が可能となる。また、形成された被膜の撥水性、平滑性も向上する。このような改善効果の理由は不明であるが、被膜を溶剤抽出してもＣ成分が溶出しないことから、Ｃ成分がその水酸基により、Ａ成分またはＢ成分と化学的に反応していることによると思われる。また、Ｃ成分がケン化して脂肪酸のモノクリセリド、ジグリセリド、あるいはグリセリンが生成し、これらの生成物がＡ成分またはＢ成分と化学的に反応していることによるとも思われる。 By using the C component, the flexibility of the coating formed is increased, and the possibility of cracking or cracking is greatly reduced even if the coating is bent. In addition, the leveling property of the coating agent is improved, the coating suitability is improved, and a thick film can be formed. In addition, the water repellency and smoothness of the formed film are also improved. The reason for such an improvement effect is unknown, but the C component does not elute even if the film is solvent-extracted. Therefore, the C component is chemically reacted with the A component or the B component by its hydroxyl group. I think that the. It is also considered that C component is saponified to produce fatty acid monochrylide, diglyceride, or glycerin, and these products are chemically reacted with A component or B component.
上記においてＡ成分とＢ成分との使用割合は、前記の通りであり、Ｃ成分の使用割合は、Ａ成分とＢ成分との合計量１００質量部あたり、１０〜５０質量部の範囲が好ましい。Ａ成分およびＢ成分の使用割合の理由は前記の通りであるが、Ｃ成分については、Ｃ成分の使用割合が前記範囲未満であると、前記の改善効果が低く、一方、Ｃ成分の使用割合が前記範囲を超えると、形成される被膜の硬度が低下する。 In the above, the usage ratio of A component and B component is as above-mentioned, and the usage ratio of C component has the preferable range of 10-50 mass parts per 100 mass parts of total amounts of A component and B component. The reason for the use ratio of the A component and the B component is as described above, but for the C component, when the use ratio of the C component is less than the above range, the above improvement effect is low, while the use ratio of the C component. If the value exceeds the above range, the hardness of the coating film to be formed decreases.
［第３のコーティング液］
また、本発明の第３のコーティング液は、前記Ａ成分とＣ成分とを、これら２者の合計として１〜４０質量％の濃度で前記ジブチルエーテルなどの不活性有機溶剤中に溶解してなる。前記Ａ成分に加えて前記Ｃ成分を用いることにより、Ａ成分単独で形成される被膜より可撓性の高い被膜が形成され、該被膜を屈曲させてもひび割れやクラックが生じる可能性が激減する。また、コーティング剤のレベリング性が向上し、塗布適性も向上し厚膜形成が可能となる。また、形成された被膜の撥水性、平滑性も向上する。このような改善効果の理由は不明であるが、前記第２のコーティング液と同様の理由によると思われる。[Third coating solution]
The third coating liquid of the present invention is obtained by dissolving the A component and the C component in an inert organic solvent such as dibutyl ether at a concentration of 1 to 40% by mass as the total of these two components. . By using the C component in addition to the A component, a coating having higher flexibility than the coating formed by the A component alone is formed, and the possibility of cracking or cracking is greatly reduced even if the coating is bent. . In addition, the leveling property of the coating agent is improved, the coating suitability is improved, and a thick film can be formed. In addition, the water repellency and smoothness of the formed film are also improved. Although the reason for such an improvement effect is unknown, it is considered to be due to the same reason as the second coating solution.
この第３のコーティング液におけるＡ成分とＣ成分との使用割合は、Ａ成分とＣ成分との合計量を１００質量部とした場合、Ａ：Ｃ＝５０〜９０：５０〜１０の質量比であることが好ましい。Ｃ成分の使用割合が前記範囲未満であると、前記の改善効果が低く、一方、Ｃ成分の使用割合が前記範囲を超えると、形成される被膜の硬度が低下する。 The use ratio of the A component and the C component in the third coating liquid is a mass ratio of A: C = 50 to 90: 50-10 when the total amount of the A component and the C component is 100 parts by mass. Preferably there is. When the use ratio of the C component is less than the above range, the improvement effect is low. On the other hand, when the use ratio of the C component exceeds the above range, the hardness of the formed film is reduced.
［第４のコーティング液］
また、本発明の第４のコーティング液は、前記Ｂ成分とＣ成分とを、これら２者の合計として１〜４０質量％の濃度で前記ジブチルエーテルなどの不活性有機溶剤中に溶解してなる。前記Ｂ成分に加えて前記Ｃ成分を用いることにより、Ｂ成分単独で形成される被膜より可撓性の高い被膜が形成され、該被膜を屈曲させてもひび割れやクラックが生じる可能性が激減する。また、コーティング剤のレベリング性が向上し、塗布適性も向上し厚膜形成が可能となる。また、形成された被膜の撥水性、平滑性も向上する。このような改善効果の理由は不明であるが、前記第２のコーティング液と同様の理由によると思われる。[Fourth coating solution]
Further, the fourth coating liquid of the present invention is obtained by dissolving the B component and the C component in an inert organic solvent such as dibutyl ether at a concentration of 1 to 40% by mass as the total of these two components. . By using the C component in addition to the B component, a coating with higher flexibility than the coating formed by the B component alone is formed, and the possibility of cracking or cracking is greatly reduced even if the coating is bent. . In addition, the leveling property of the coating agent is improved, the coating suitability is improved, and a thick film can be formed. In addition, the water repellency and smoothness of the formed film are also improved. Although the reason for such an improvement effect is unknown, it is considered to be due to the same reason as the second coating solution.
第４のコーティング液におけるＢ成分とＣ成分との使用割合は、Ｂ成分とＣ成分との合計量を１００質量部とした場合、Ｂ：Ｃ＝５０〜９０：５０〜１０の質量比であることが好ましい。Ｃ成分の使用割合が前記範囲未満であると、前記の改善効果が低く、一方、Ｃ成分の使用割合が前記範囲を超えると、形成される被膜の硬度が低下する。 The use ratio of the B component and the C component in the fourth coating liquid is a mass ratio of B: C = 50 to 90: 50-10 when the total amount of the B component and the C component is 100 parts by mass. It is preferable. When the use ratio of the C component is less than the above range, the improvement effect is low. On the other hand, when the use ratio of the C component exceeds the above range, the hardness of the formed film is reduced.
本発明のコーティング方法は、上記本発明のコーティング液を物品の表面に塗布し、Ａ成分および／またはＢ成分をシリカに加水分解し、またはこれらのシリカとＣ成分と反応させて、上記物品の表層部に透明なシリカおよび／またはシリカとＣ成分との反応生成物を含む複合化層を形成することを特徴としている。本発明のコーティング方法でコーティングされる物品としては、特に限定されない。特に有効である物品はプラスチック成形品および金属成形品であるが、その他ガラス成形品、ゴム成形品、革成形品、木工品または紙製品などが挙げられる。 In the coating method of the present invention, the coating liquid of the present invention is applied to the surface of an article, the component A and / or the component B is hydrolyzed to silica, or these silica and component C are reacted with each other. A composite layer containing transparent silica and / or a reaction product of silica and C component is formed on the surface layer. The article to be coated by the coating method of the present invention is not particularly limited. Articles that are particularly effective are plastic molded products and metal molded products, and other examples include glass molded products, rubber molded products, leather molded products, woodwork products, and paper products.
プラスチック成形品の材料としては、例えば、ポリエチレン、ポリプロピレン、ポリスチレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ポリアミド（ナイロン）、塩化ビニル樹脂、アクリル樹脂、シリコーン樹脂、フッ素樹脂、ポリイミド樹脂、ポリスルホン樹脂などの公知の熱可塑性樹脂、エポキシ樹脂、メラミン樹脂、フェノール樹脂、不飽和ポリエステル樹脂などの熱硬化性樹脂などが挙げられ、特に限定されるものではない。これらの材料からなるプラスチック成形品の形状は、フィルム、シート、板状体、その他の各種の立体的成形品が挙げられる。 Examples of the plastic molding material include polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyamide (nylon), vinyl chloride resin, acrylic resin, silicone resin, fluorine resin, polyimide resin, polysulfone resin, and the like. Known thermosetting resins such as thermoplastic resins, epoxy resins, melamine resins, phenol resins, unsaturated polyester resins, and the like can be mentioned, and are not particularly limited. Examples of the shape of the plastic molded product made of these materials include films, sheets, plates, and other various three-dimensional molded products.
金属成形品の材料としては、例えば、鉄、アルミニウム、ジュラルミン、ステンレススチール、銅、金、銀、チタン、ニッケルなどが挙げられるが、これらに特に限定されない。これらの材料からなる金属成形品の形状は、板、棒、その他の立体的成形品が挙げられる。 Examples of the material of the metal molded product include, but are not limited to, iron, aluminum, duralumin, stainless steel, copper, gold, silver, titanium, nickel, and the like. Examples of the shape of the metal molded product made of these materials include a plate, a rod, and other three-dimensional molded products.
上記各種物品の表面に対する前記本発明のコーティング液の塗布方法は特に限定されず、被塗布物品の形状に適した塗布方法、例えば、スプレー法、ディッピング法、刷毛塗り法、ロールコート法、グラビアコート法、フレキソ法、インクジェット法などが挙げられる。塗布量についても特に限定されないが、被塗布物品に要求される表面性能に対応して塗布量を決定すればよい。一般的には、固形分換算にて０．１〜１００ｇ／ｍ2であり、好ましくは１〜２０ｇ／ｍ2である。塗布量が０．１ｇ／ｍ2未満であると充分な特性を有する表面複合化層が形成されず、一方、塗布量が１００ｇ／ｍ2を超えると複合化層が過剰品質になる他に複合化層の透明性が失われる場合がある。The application method of the coating liquid of the present invention on the surface of the above various articles is not particularly limited, and an application method suitable for the shape of the article to be coated, for example, spray method, dipping method, brush coating method, roll coating method, gravure coating Method, flexo method, ink jet method and the like. The coating amount is not particularly limited, but the coating amount may be determined in accordance with the surface performance required for the article to be coated. Generally, it is 0.1-100 g / m < 2 > in conversion of solid content, Preferably it is 1-20 g / m < 2 >. If the coating amount is less than 0.1 g / m 2 , a surface composite layer having sufficient characteristics will not be formed. On the other hand, if the coating amount exceeds 100 g / m 2 , the composite layer will be over-quality. The transparency of the chemical layer may be lost.
本発明のコーティング方法の顕著な特徴は、上記で塗布した塗布層の硬化に特別の加熱を必須としないことである。塗布層を加熱することによって複合化層の形成が促進されるが、上記塗布層の硬化は塗布後に空気中に放置しておいても進行する。放置による硬化は、コーティング液の溶剤の蒸発とともに、空気中の水分の吸収による水との反応であり、放置後の硬化速度は、例えば、２時間で指触乾燥し２日程度で鉛筆硬度６〜９Ｈ或いはそれ以上の硬度を有する膜となる。上記の水との反応は加熱によって促進されるが、加熱する場合には１２０℃以下の温度で十分である。なお、１２０℃を超える温度、例えば、３００℃での加熱を行うことも何らの支障もなく、１，０００℃までの耐熱性を持っている。 A prominent feature of the coating method of the present invention is that no special heating is essential for curing the coating layer applied as described above. Although the formation of the composite layer is promoted by heating the coating layer, the curing of the coating layer proceeds even when left in the air after coating. Curing by standing is a reaction with water due to the absorption of moisture in the air as the solvent of the coating solution evaporates. The curing rate after standing is, for example, a finger hardness of 2 hours and a pencil hardness of 6 in about 2 days. It becomes a film having a hardness of ˜9H or more. Although the reaction with water is promoted by heating, a temperature of 120 ° C. or lower is sufficient for heating. It should be noted that heating at a temperature exceeding 120 ° C., for example, 300 ° C. has no problem and has heat resistance up to 1,000 ° C.
以上の如くして本発明のコーティング方法が完了して各種成形品の表層部に、シリカまたはシリカとＣ成分との反応生成物を含む複合化層が形成される。当該複合化層の密着性は特に強く塗布面の変形に対して追従性があることが衝撃変形試験により確認された。 As described above, the coating method of the present invention is completed, and a composite layer containing silica or a reaction product of silica and component C is formed on the surface layer of various molded articles. It was confirmed by an impact deformation test that the adhesiveness of the composite layer was particularly strong and had followability to deformation of the coated surface.
以上の如くして得られた各種成形品の表面は、シリカに類似した無機性を有しており、成形品の構成材料の種類にかかわらず、その鉛筆硬度は６Ｈ〜９Ｈ或いはそれ以上に向上しており、耐擦傷性やガスバリヤー性が顕著に向上している。しかも表面処理した成形品を多数回繰り返し屈曲テストを行なっても表面複合化層に変化がなく、剥離や白化（クラックによる）が認められない。これらの事実は、本発明のコーティング液によって形成される層がシリカあるいはシリカとＣ成分の反応生成物が成形品基材との化学結合をした複合化層となっていることを示唆している。 The surface of various molded products obtained as described above has an inorganic property similar to that of silica, and the pencil hardness is improved to 6H to 9H or higher regardless of the type of constituent material of the molded product. As a result, the scratch resistance and gas barrier properties are remarkably improved. Moreover, even if the surface-treated molded product is repeatedly subjected to a bending test, the surface composite layer does not change, and no peeling or whitening (due to cracks) is observed. These facts suggest that the layer formed by the coating liquid of the present invention is a composite layer in which the reaction product of silica or silica and component C is chemically bonded to the molded article substrate. .
また、上記複合化層の表面はシリカリッチであることから、当該表面は高硬度、絶縁性であり、耐熱性、防食性、ガスバリヤー性、耐汚染性に優れている。特にＣ成分を含む被膜は厚膜形成が可能であり、無機物であるシリカと有機物である前記Ｃ成分との複合化膜であることから、さらに撥水性に優れる。 Further, since the surface of the composite layer is silica-rich, the surface has high hardness and insulation, and is excellent in heat resistance, corrosion resistance, gas barrier properties, and contamination resistance. In particular, a coating film containing a C component can form a thick film, and is a composite film of silica, which is an inorganic substance, and the C component, which is an organic substance, and therefore has excellent water repellency.
以下に実施例および比較例を挙げて本発明をより具体的に説明する。なお、以下の文中の「部」および「％」は全て質量基準である。
［第１のコーティング液］
実施例１
ペルヒドロポリシラザンのジブチルエーテル１０％溶液（商品名アクアミカＮＬ１２０Ａ、クラリアントジャパン（株）製の希釈品）（ａ液）とヘキサメチルジシラザン（信越化学工業（株）製、商品名ＨＭＤＳ３）のジブチルエーテル１０％溶液（ｂ液）とを下記表１に記載の割合で混合して本発明の第１のコーティング液（Ｎｏ．１〜９）を得た。Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following text, “part” and “%” are all based on mass.
[First coating solution]
Example 1
Dibutyl ether of perhydropolysilazane 10% dibutyl ether (trade name Aquamica NL120A, diluted product manufactured by Clariant Japan KK) (liquid a) and hexamethyldisilazane (trade name HMDS3 manufactured by Shin-Etsu Chemical Co., Ltd.) The first coating liquid (Nos. 1 to 9) of the present invention was obtained by mixing the 10% solution (liquid b) with the ratio shown in Table 1 below.
比較例１〜２
実施例１におけるａ液単独を比較例１（コーティング液Ｎｏ．１０）とし、ｂ液単独を比較例２（コーティング液Ｎｏ．１１）とした。Comparative Examples 1-2
Liquid a alone in Example 1 was designated as Comparative Example 1 (coating liquid No. 10), and liquid b alone was designated as Comparative Example 2 (coating liquid No. 11).
実施例２
前記実施例および比較例のコーティング液（Ｎｏ．１〜１１）をそれぞれスプレー缶に装入した。一方、２０ｃｍ×１０ｃｍサイズで厚み２ｍｍの鉄板を用意し、鉄板の表面に前記スプレー缶よりコーティング液（Ｎｏ．１〜１１）を約３０ｇ／ｍ2の割合でスプレー塗布した。温度７０℃に加熱して溶剤の大部分を除去した後、温度２５℃、相対湿度６０％の雰囲気に４８時間放置した。得られた１１種の鉄板（Ｎｏ．１〜１１）の水との接触角、表面硬度（鉛筆硬度）、重ね塗り性、曲げ剥離性、衝撃変形性および成膜性を調べたところ下記表２の結果が得られた。Example 2
The coating liquids (Nos. 1 to 11) of the examples and comparative examples were charged into spray cans. On the other hand, an iron plate having a size of 20 cm × 10 cm and a thickness of 2 mm was prepared, and the coating liquid (No. 1 to 11) was spray-applied to the surface of the iron plate at a rate of about 30 g / m 2 from the spray can. After heating to a temperature of 70 ° C. to remove most of the solvent, it was left for 48 hours in an atmosphere at a temperature of 25 ° C. and a relative humidity of 60%. When the contact angle with water, surface hardness (pencil hardness), overcoatability, bending peelability, impact deformability, and film formability of the obtained 11 types of iron plates (No. 1 to 11) were examined, the following Table 2 was obtained. Results were obtained.
上記において、水の接触角は接触角計により測定し、表面硬度はＪＩＳ規定による鉛筆硬度であり、重ね塗り性は、指触乾燥後同量のコーティング剤を塗布した時の表面状態を肉眼で観察し、透明性および反応性があるかどうかを調べた。曲げ剥離性も肉眼観察により調べた。衝撃変形性はデュポン衝撃変形試験を採用した。成膜性は肉眼観察で行った。 In the above, the contact angle of water is measured with a contact angle meter, the surface hardness is the pencil hardness according to JIS regulations, and the overcoatability is the surface condition when the same amount of coating agent is applied after drying with the touch. Observed and examined for transparency and reactivity. Bending peelability was also examined by visual observation. For impact deformation, a DuPont impact deformation test was adopted. Film formation was performed by visual observation.
実施例３
前記コーティング液（Ｎｏ．１〜１１）をそれぞれスプレー缶に装入した。一方、２０ｃｍ×２０ｃｍサイズで厚み１ｍｍの透明アクリル板を用意し、該アクリル板の表面に前記スプレー缶よりコーティング液（Ｎｏ．１〜１１）を約２０ｇ／ｍ2の割合でスプレー塗布した。温度４５℃に加熱して溶剤の大部分を除去した後、温度８０℃、相対湿度８０％の雰囲気に４８時間放置した。得られた１１種のアクリル板の透明性、表面硬度、重ね塗り性、曲げ剥離性、衝撃変形性および成膜性を調べたところ下記表３の結果が得られた。Example 3
Each of the coating liquids (No. 1 to 11) was charged into a spray can. On the other hand, a transparent acrylic plate having a size of 20 cm × 20 cm and a thickness of 1 mm was prepared, and the coating liquid (No. 1 to 11) was spray-applied to the surface of the acrylic plate from the spray can at a rate of about 20 g / m 2 . After heating to a temperature of 45 ° C. to remove most of the solvent, it was left in an atmosphere at a temperature of 80 ° C. and a relative humidity of 80% for 48 hours. When the transparency, surface hardness, overcoatability, bending peelability, impact deformation property and film formability of the 11 kinds of acrylic plates obtained were examined, the results shown in Table 3 below were obtained.
上記において、透明性は肉眼で観察し、未処理アクリル板と同等の透明性を有するか否かについて調べた。その他の性能は実施例２の場合と同様である。 In the above, the transparency was observed with the naked eye, and it was examined whether or not the transparency was equivalent to that of the untreated acrylic board. Other performances are the same as those in the second embodiment.
［第２のコーティング剤］
実施例４
前記第１のコーティング液Ｎｏ．１〜Ｎｏ．９に市販のヒマシ油のジブチルエーテル１０％溶液を下記表４に記載の割合で混合して第２のコーティング液（Ｎｏ．２−１〜２−５）を得た。[Second coating agent]
Example 4
The first coating liquid No. 1-No. 9 was mixed with a commercially available castor oil dibutyl ether 10% solution in the proportions shown in Table 4 below to obtain second coating solutions (No. 2-1 to 2-5).
実施例５
前記実施例４の第２のコーティング液を使用した以外は実施例３と同様にして作製した５種のアクリル板（２−１〜２−５）の透明性、表面硬度、重ね塗り性、曲げ剥離性、衝撃変形性および成膜性を調べたところ下記表５の結果が得られた。
Example 5
Transparency, surface hardness, overcoatability, bending of five types of acrylic plates (2-1 to 2-5) produced in the same manner as in Example 3 except that the second coating liquid of Example 4 was used. When the peelability, impact deformability and film formability were examined, the results shown in Table 5 below were obtained.
［第３のコーティング液］
実施例６
前記ｂ液と前記のヒマシ油のジブチルエーテル１０％溶液を下記表６に記載の割合で混合して第３のコーティング液（Ｎｏ．３−１〜３−５）を得た。[Third coating solution]
Example 6
The said b liquid and the dibutyl ether 10% solution of the said castor oil were mixed in the ratio of the following Table 6, and the 3rd coating liquid (No.3-1 to 3-5) was obtained.
実施例７
前記実施例６の第３のコーティング液を使用した以外は実施例３と同様にして作製した５種のアクリル板（３−１〜３−５）の透明性、表面硬度、重ね塗り性、曲げ剥離性、衝撃変形性および成膜性を調べたところ下記表７の結果が得られた。Example 7
Transparency, surface hardness, overcoatability, bending of five types of acrylic plates (3-1 to 3-5) produced in the same manner as in Example 3 except that the third coating liquid of Example 6 was used. When the peelability, impact deformability and film formability were examined, the results shown in Table 7 below were obtained.
［第４のコーティング液］
実施例８
前記ａ液と前記のヒマシ油のジブチルエーテル１０％溶液を下記表８に記載の割合で混合して第４のコーティング液（Ｎｏ．４−１〜４−５）を得た。[Fourth coating solution]
Example 8
The said a liquid and said dibutyl ether 10% solution of castor oil were mixed in the ratio of the following Table 8, and the 4th coating liquid (No. 4-1 to 4-5) was obtained.
実施例９
前記実施例８の第４のコーティング液を使用した以外は実施例３と同様にして作製した５種のアクリル板（４−１〜４−５）の透明性、表面硬度、重ね塗り性、曲げ剥離性、衝撃変形性および成膜性を調べたところ下記表９の結果が得られた。Example 9
Transparency, surface hardness, overcoatability, bending of five types of acrylic plates (4-1 to 4-5) produced in the same manner as in Example 3 except that the fourth coating liquid of Example 8 was used. When the peelability, impact deformability and film formability were examined, the results shown in Table 9 below were obtained.
実施例１０
上記実施例４〜９において、ヒマシ油に代えて、ヒマシ油脂肪酸、ヒマシ油脂肪酸メチルエステル、リシノール酸、リシノール酸メチルエステル、ラノリン、ラノリン脂肪酸、ラノリン脂肪酸メチルエステルを同様にして使用したところ、実施例４〜９におけると同様な結果が得られた。Example 10
In the above Examples 4 to 9, instead of castor oil, castor oil fatty acid, castor oil fatty acid methyl ester, ricinoleic acid, ricinoleic acid methyl ester, lanolin, lanolin fatty acid, lanolin fatty acid methyl ester were used in the same manner. Similar results were obtained as in Examples 4-9.
以上の本発明によれば、各種物品の表面改質に有用であるコーティング液および厚膜コーティング方法を提供することができる。 According to the present invention described above, it is possible to provide a coating solution and a thick film coating method useful for surface modification of various articles.
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| JP5428310B2 (en) * | 2008-12-01 | 2014-02-26 | 株式会社リコー | Pretreatment liquid, cartridge using the same, liquid ejection apparatus, and recording method |
| JP7161190B2 (en) * | 2017-12-13 | 2022-10-26 | ハドラスホールディングス株式会社 | Coating method of coating material, and metal material coated with coating material |
| JP7211620B2 (en) * | 2018-12-30 | 2023-01-24 | 京葉ケミカル株式会社 | Manufacturing method of material with glass film |
| JP6567788B1 (en) * | 2019-02-27 | 2019-08-28 | アーテック株式会社 | Glass coating layer forming method and glass coating layer obtained thereby |
| WO2020245972A1 (en) * | 2019-06-06 | 2020-12-10 | ヤマモトホールディングス株式会社 | Method for covering with coating material, and metal material covered with coating material |
| JP2021014514A (en) * | 2019-07-11 | 2021-02-12 | ヤマモトホールディングス株式会社 | Coating liquid and coating method |
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| JP3042537B2 (en) * | 1990-06-30 | 2000-05-15 | 東燃株式会社 | Modified polysilazane and method for producing the same |
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