JP2014070128A - Water-based surface treating agent and article using the same - Google Patents
Water-based surface treating agent and article using the same Download PDFInfo
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Abstract
Description
本発明は、各種物品の表面に様々な意匠性を付与することのできる水性表面処理剤及びそれを用いた成形品に関する。 The present invention relates to an aqueous surface treating agent capable of imparting various design properties to the surface of various articles and a molded article using the same.
各種物品は、意匠性の向上、高級感の付与を目的として、その表面に塗料が塗装されることが多い。例えば、家電製品の筐体、パソコン、携帯電話、スマートフォン等の電子機器の筐体、自動車内外装材などのプラスチック成形品の表面を艶消し処理して、高級感のある意匠性を付与するために、表面処理剤が用いられている。この表面処理剤として、従来は溶剤系のものが多かったが、揮発性有機化合物(以下、「VOC」と略記する。)を発生して環境負荷が大きいことから、VOCの排出量の削減が求められ、表面処理剤の水性化が進められている(例えば、特許文献1及び2を参照。)。 Various articles are often coated with a paint on the surface for the purpose of improving design properties and imparting a high-class feeling. For example, the surface of plastic molded products such as housings for home appliances, housings for electronic devices such as personal computers, mobile phones, and smartphones, and interior and exterior materials for automobiles should be given a high-class design. In addition, a surface treatment agent is used. Conventionally, many of these surface treatment agents are solvent-based. However, since a volatile organic compound (hereinafter abbreviated as “VOC”) is generated and the environmental load is large, the amount of VOC emissions can be reduced. Therefore, the surface treatment agent is being made water-based (see, for example, Patent Documents 1 and 2).
しかしながら、水性表面処理剤は、溶剤系表面処理剤と比較して、耐薬品性、特に耐溶剤性に劣り、水性表面処理剤の塗膜表面を、アルコール等の溶剤を含む洗浄剤で拭き取る等を行うとその拭き取った痕が目立つという問題があった。 However, the aqueous surface treatment agent is inferior in chemical resistance, particularly solvent resistance, compared to the solvent-based surface treatment agent, and the surface of the aqueous surface treatment agent is wiped with a cleaning agent containing a solvent such as alcohol. There was a problem that the wiped-out traces were noticeable.
そこで、塗膜表面が溶剤と接触してもその痕が目立たない水性表面処理剤が求められていた。 Therefore, there has been a demand for an aqueous surface treatment agent that does not show noticeable marks even when the surface of the coating film comes into contact with a solvent.
本発明が解決しようとする課題は、各種物品の表面に様々な意匠性を付与するとともに、塗膜表面が溶剤と接触してもその痕(以下、「溶剤痕」と略記する。)が目立たない水性表面処理剤及びそれを用いた物品を提供することである。 The problem to be solved by the present invention is to impart various design properties to the surfaces of various articles, and even when the surface of the coating film comes into contact with a solvent, the marks (hereinafter abbreviated as “solvent marks”) are conspicuous. It is to provide a non-aqueous surface treatment agent and an article using the same.
本発明者等は、上記課題を解決すべく鋭意研究を重ねた結果、カルボキシル基及び/又は水酸基を有する水性ポリウレタン、特定の溶融範囲を有するポリオレフィンワックス及び架橋剤を含有する水性表面処理剤は、物品の表面に様々な意匠性を付与できるとともに、塗膜表面が溶剤と接触しても溶剤痕が目立たないことを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that an aqueous polyurethane having a carboxyl group and / or a hydroxyl group, a polyolefin wax having a specific melting range, and an aqueous surface treating agent containing a crosslinking agent are: The present invention was completed by finding that various design properties can be imparted to the surface of an article, and that solvent marks are not noticeable even when the coating film surface is in contact with a solvent.
すなわち、本発明は、カルボキシル基及び/又は水酸基を有する水性ポリウレタン(A)、溶融範囲が140〜180℃であるポリオレフィンワックス(B)及び架橋剤(C)を含有することを特徴とする水性表面処理剤及びそれを用いた物品に関する。 That is, the present invention includes an aqueous surface comprising an aqueous polyurethane (A) having a carboxyl group and / or a hydroxyl group, a polyolefin wax (B) having a melting range of 140 to 180 ° C., and a crosslinking agent (C). The present invention relates to a treatment agent and an article using the same.
本発明の水性表面処理剤は、物品の表面に様々な意匠性を付与できるとともに、塗膜表面が溶剤と接触しても溶剤痕が目立たないため、各種物品の表面処理剤として用いることができる。特に、プラスチック成形品に好適に用いることができ、プラスチック成形品の中でも熱可塑性オレフィン(Thermo Plastic Olefin;以下、「TPO」と略記する。)の成形品であるTPOレザーやTPOシートにより好適に用いることができる。 The aqueous surface treating agent of the present invention can be used as a surface treating agent for various articles because it can impart various design properties to the surface of the article, and even if the surface of the coating film is in contact with a solvent, solvent traces are not noticeable. . In particular, it can be suitably used for plastic molded products, and among plastic molded products, it is suitably used for TPO leather and TPO sheets which are molded products of thermoplastic olefin (hereinafter abbreviated as “TPO”). be able to.
本発明の水性表面処理剤は、カルボキシル基及び/又は水酸基を有する水性ポリウレタン(A)、ポリプロピレンワックス(B)及び架橋剤(C)を含有するものである。 The aqueous surface treating agent of the present invention contains an aqueous polyurethane (A) having a carboxyl group and / or a hydroxyl group, a polypropylene wax (B) and a crosslinking agent (C).
前記水性ポリウレタン(A)は、カルボキシル基及び/又は水酸基を有するポリウレタンで、水性媒体中に分散可能なものである。この水性ポリウレタン(A)のうち、水酸基を有するポリウレタンの製造方法としては、例えば、過剰量のポリオール及び/又はグリコールとポリイソシアネートとを反応させて末端に水酸基を有するポリウレタンを得る方法、イソシアネート基末端のウレタンプレポリマーに2−アミノエタノール、2−アミノエチルエタノールアミン、ジエタノールアミン等のアミノアルコール、アミノフェノール等を反応させて水酸基を有するポリウレタンを得る方法等が挙げられる。一方、カルボキシル基を有するポリウレタンの製造方法としては、例えば、カルボキシル基を有する化合物を原料としてウレタン化反応の際に使用する方法が挙げられる。 The aqueous polyurethane (A) is a polyurethane having a carboxyl group and / or a hydroxyl group, and can be dispersed in an aqueous medium. Among these aqueous polyurethanes (A), examples of the method for producing a polyurethane having a hydroxyl group include a method of reacting an excess amount of polyol and / or glycol with polyisocyanate to obtain a polyurethane having a hydroxyl group at the terminal, an isocyanate group terminal And a method of obtaining a polyurethane having a hydroxyl group by reacting 2-urethane prepolymer with amino alcohol such as 2-aminoethanol, 2-aminoethylethanolamine and diethanolamine, aminophenol and the like. On the other hand, examples of the method for producing a polyurethane having a carboxyl group include a method of using a compound having a carboxyl group as a raw material in the urethanization reaction.
前記水性ポリウレタン(A)の原料として用いるポリオールとしては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリアセタールポリオール、ポリアクリレートポリオール、ポリエステルアミドポリオール、ポリチオエーテルポリオール、ポリブタジエン系等のポリオレフィンポリオールなどが挙げられる。これらの中でも、耐久性が優れていることから、ポリカーボネートポリオールが好ましい。また、カルボキシル基を有するポリウレタンの原料として用いるカルボキシル基を有する化合物としては、例えば、2,2’−ジメチロールプロピオン酸、2,2’−ジメチロールブタン酸、2,2’−ジメチロール酪酸、2,2’−ジメチロール吉草酸等が挙げられる。これらの中でも、2,2’−ジメチロールプロピオン酸が好ましい。 Examples of the polyol used as a raw material for the aqueous polyurethane (A) include polyester polyols, polyether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyester amide polyols, polythioether polyols, and polybutadiene polyols such as polybutadiene. It is done. Among these, polycarbonate polyol is preferable because of its excellent durability. Moreover, as a compound which has a carboxyl group used as a raw material of the polyurethane which has a carboxyl group, 2,2'- dimethylol propionic acid, 2,2'- dimethylol butanoic acid, 2,2'- dimethylol butyric acid, 2 2,2'-dimethylol valeric acid and the like. Among these, 2,2'-dimethylolpropionic acid is preferable.
上記の製造方法により得られる前記水性ポリウレタン(A)の中でも、ポリカーボネートポリオールを原料として用いたポリカーボネート系水性ポリウレタンは、塗膜強度が高いことから好ましい。また、前記水性ポリウレタン(A)は、単独で用いることも2種以上併用することもできる。 Among the water-based polyurethanes (A) obtained by the above production method, a polycarbonate-based water-based polyurethane using a polycarbonate polyol as a raw material is preferable because of high coating film strength. Moreover, the said water-based polyurethane (A) can be used individually or can be used together 2 or more types.
前記ポリオレフィンワックス(B)は、その溶融範囲が140〜180℃であるものであるが、145〜175℃であるものがより好ましく、150〜170℃であるものがさらに好ましい。このようなポリオレフィンワックス(B)としては、ポリエチレンワックス、ポリプロピレンワックス等が挙げられる。これらのポリオレフィンワックス(B)は、単独で用いることも2種以上併用することもできる。なお、本発明において、ポリオレフィンワックス(B)として、2種以上のものを併用した場合、その溶融範囲は、混合物での溶融範囲とする。また、溶融範囲は、JIS試験方法K0064−1992に準拠して測定したものである。 The polyolefin wax (B) has a melting range of 140 to 180 ° C, more preferably 145 to 175 ° C, and still more preferably 150 to 170 ° C. Examples of such polyolefin wax (B) include polyethylene wax and polypropylene wax. These polyolefin waxes (B) can be used alone or in combination of two or more. In the present invention, when two or more kinds of polyolefin waxes (B) are used in combination, the melting range is the melting range in the mixture. The melting range is measured in accordance with JIS test method K0064-1992.
上記のポリオレフィンワックス(B)の中でも、ポリプロピレンワックスを主成分としたものが、溶剤痕を低減できることから好ましい。また、前記ポリオレフィンワックス(B)の使用量としては、溶剤痕の低減効果と塗膜強度を高めることができるから、前記水性ポリウレタン(A)の樹脂分100質量部に対して、0.1〜20質量部の範囲が好ましく、3〜15質量部の範囲がより好ましい。 Among the above-mentioned polyolefin waxes (B), those mainly composed of polypropylene wax are preferable because solvent traces can be reduced. Moreover, as the usage-amount of the said polyolefin wax (B), since the reduction effect of a solvent trace and the coating-film intensity | strength can be improved, it is 0.1-0.1 with respect to 100 mass parts of resin parts of the said water-based polyurethane (A). The range of 20 parts by mass is preferable, and the range of 3 to 15 parts by mass is more preferable.
前記架橋剤(C)としては、オキサゾリン、カルボジイミド、ポリイソシアネート、ブロックイソシアネート、エポキシ、ポリシロキサン、アジリジン、アルキル化メラミン等の尿素樹脂系架橋剤、ヒドラジド系架橋剤などが挙げられる。これらの中でも、架橋性能と安全性の面から、カルボジイミドが好ましい。また、これらの架橋剤(C)は、単独で用いることも2種以上併用することもできる。前記架橋剤(C)の使用量としては、塗膜強度の観点から、前記水性ポリウレタン(A)の樹脂分100質量部に対して、0.5〜30質量部の範囲が好ましく、2〜25質量部の範囲がより好ましい。 Examples of the crosslinking agent (C) include urea resin-based crosslinking agents such as oxazoline, carbodiimide, polyisocyanate, blocked isocyanate, epoxy, polysiloxane, aziridine, and alkylated melamine, and hydrazide-based crosslinking agents. Among these, carbodiimide is preferable from the viewpoint of crosslinking performance and safety. Moreover, these crosslinking agents (C) can be used alone or in combination of two or more. As a usage-amount of the said crosslinking agent (C), the range of 0.5-30 mass parts is preferable with respect to 100 mass parts of resin parts of the said water-based polyurethane (A) from a viewpoint of coating-film strength, 2-25 The range of parts by mass is more preferable.
本発明の水性表面処理剤のうち、上記の成分(A)〜(C)を含有するものを物品に塗工すると、いわゆるクリア塗料となり、物品の表面に光沢性を付与することができる。また、物品の表面に高級感を付与するためマット調の意匠を付与したい場合には、上記の成分(A)〜(C)に加えて、マット剤(D)を本発明の水性表面処理剤に配合することが好ましい。 When the article containing the above components (A) to (C) among the aqueous surface treating agent of the present invention is applied to an article, a so-called clear paint is formed, and glossiness can be imparted to the surface of the article. In addition to the above components (A) to (C), the matting agent (D) is added to the aqueous surface treating agent of the present invention when it is desired to impart a matte design to the surface of the article. It is preferable to blend in.
前記マット剤(D)としては、例えば、シリカ粒子、有機ビーズ、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、タルク、水酸化アルミニウム、硫酸カルシウム、カオリン、雲母、アスベスト、マイカ、ケイ酸カルシウム、アルミナシリケイト等が挙げられる。 Examples of the matting agent (D) include silica particles, organic beads, calcium carbonate, magnesium carbonate, barium carbonate, talc, aluminum hydroxide, calcium sulfate, kaolin, mica, asbestos, mica, calcium silicate, alumina silicate, and the like. Is mentioned.
前記シリカ粒子としては、乾式シリカ、湿式シリカ等が挙げられる。これらの中でも、散乱効果が高く光沢値の調整範囲が広くなること、溶剤痕の低減効果が高くなることから、乾式シリカが好ましい。また、組成物中に分散しやすくなることから、有機化合物で表面修飾した乾式シリカがより好ましい。これらシリカ粒子の平均粒子径としては、2〜14μmの範囲が好ましく、3〜12μmの範囲がより好ましい。 Examples of the silica particles include dry silica and wet silica. Among these, dry silica is preferable because it has a high scattering effect and a wide adjustment range of gloss value, and a high effect of reducing solvent marks. Moreover, since it becomes easy to disperse | distribute in a composition, the dry-type silica surface-modified with the organic compound is more preferable. The average particle diameter of these silica particles is preferably in the range of 2 to 14 μm, more preferably in the range of 3 to 12 μm.
前記シリカ粒子の使用量としては、所望のマット調の意匠が得られる光沢値が達成できることから、前記水性ポリウレタン(A)の樹脂分100質量部に対して、0.1〜40質量部の範囲が好ましく、10〜30質量部の範囲がより好ましい。 As the usage-amount of the said silica particle, since the gloss value from which the desired mat-like design is obtained can be achieved, it is the range of 0.1-40 mass parts with respect to 100 mass parts of resin parts of the said water-based polyurethane (A). Is preferable, and the range of 10 to 30 parts by mass is more preferable.
前記有機ビーズとしては、例えば、アクリルビーズ、ウレタンビーズ、シリコンビーズ、オレフィンビーズ等が挙げられる。 Examples of the organic beads include acrylic beads, urethane beads, silicon beads, and olefin beads.
前記マット剤(D)は、単独で用いることも2種以上併用することもできる。 The matting agent (D) can be used alone or in combination of two or more.
本発明の水性表面処理剤には、上記の成分(A)〜(D)以外に、各種界面活性剤、消泡剤、レベリング剤、粘弾性調整剤、消泡剤、湿潤剤、分散剤、防腐剤、膜形成剤、可塑剤、浸透剤、香料、殺菌剤、殺ダニ剤、防かび剤、紫外線吸収剤、酸化防止剤、帯電防止剤、難燃剤、染料、顔料(例えば、チタン白、ベンガラ、フタロシアニン、カーボンブラック、パーマネントイエロー等)等の添加剤を配合しても構わない。 In addition to the above components (A) to (D), the aqueous surface treatment agent of the present invention includes various surfactants, antifoaming agents, leveling agents, viscoelasticity adjusting agents, antifoaming agents, wetting agents, dispersing agents, Preservatives, film formers, plasticizers, penetrants, fragrances, bactericides, acaricides, fungicides, UV absorbers, antioxidants, antistatic agents, flame retardants, dyes, pigments (eg, titanium white, Bengala, phthalocyanine, carbon black, permanent yellow, etc.) may be added.
本発明の物品は、本発明の水性表面処理剤の塗膜を有するものである。また、物品としては、例えば、家電製品(冷蔵庫、洗濯機、エアコン、テレビ等)の筐体、電子機器(パソコン、携帯電話、スマートフォン等)の筐体、楽器(ピアノ、エレクトーン、電子楽器等)の材料;自動車又は鉄道車両の内装材(インスツルメントパネル、ドアトリム、ヘッドライニング、トノーカバー等)、建材又は家具材(壁紙、合板用化粧シート、鋼板用化粧シート、椅子貼り用レザー等)、包装材料(ラッピングフィルム等)などのプラスチック成形品;木質材料(合板、集成材、単層積層材等);セラミック材料(内装タイル、煉瓦等);が挙げられる。スポーツ(スキー、アーチェリー、ゴルフ、テニス等)用具材料;履物材料(靴の甲材、底、芯材、ヒール、トップリフト、中敷等);金属材料(鉄、銅、亜鉛、アルミニウム等)などが挙げられる。これらの物品の中でも、本発明の水性表面処理剤は、プラスチック成形品に好適に用いることができ、そのプラスチック成形品の中でも、TPOレザー、TPOシートに用いることが好ましい。 The article of the present invention has a coating film of the aqueous surface treating agent of the present invention. In addition, examples of articles include housings for home appliances (refrigerators, washing machines, air conditioners, televisions, etc.), housings for electronic devices (computers, mobile phones, smartphones, etc.), musical instruments (pianos, electric tones, electronic musical instruments, etc.) Materials: Interior materials for automobiles or railway vehicles (instrument panels, door trims, headlinings, tonneau covers, etc.), building materials or furniture materials (wallpaper, decorative sheets for plywood, decorative sheets for steel plates, leather for chairs, etc.), Examples include plastic molded products such as packaging materials (such as wrapping films); wood materials (plywood, laminated materials, single-layer laminated materials, etc.); and ceramic materials (interior tiles, bricks, etc.). Sport (ski, archery, golf, tennis, etc.) equipment materials; footwear materials (shoe upper, bottom, core material, heel, top lift, insole, etc.); metal materials (iron, copper, zinc, aluminum, etc.), etc. Is mentioned. Among these articles, the aqueous surface treating agent of the present invention can be suitably used for plastic molded products, and among these plastic molded products, it is preferable to use them for TPO leather and TPO sheets.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically by way of examples.
(実施例1)
水性ポリウレタン(DIC株式会社製「ハイドラン WLS−210」、ポリカーボネート系水性ポリウレタン、不揮発分35質量%)47.1質量部(水性ポリウレタンとして16.5質量部)、ポリプロピレンワックス(Micro Powders社製「MICROMATTE 1213UVW」;溶融範囲150〜156℃)1.1質量部、架橋剤(日清紡ケミカル株式会社製「カルボジライト E−04」、カルボジイミド系架橋剤)3.5質量部、ノニオン系界面活性剤(第一工業製薬株式会社製「ノイゲン EA−157」)0.1質量部、フッ素系界面活性剤(DIC株式会社製「メガファック F−444」)0.1質量部、粘弾性調整剤(サンノプコ株式会社製「SNシックナー 612NC」)0.9質量部及びイオン交換水44.2質量部を均一に混合して、水性表面処理剤(1)を得た。
Example 1
Aqueous polyurethane (“Hydran WLS-210” manufactured by DIC Corporation, polycarbonate-based aqueous polyurethane, non-volatile content 35% by mass) 47.1 parts by mass (16.5 parts by mass as aqueous polyurethane), polypropylene wax (“MICROMATETE” manufactured by Micro Powders) 1213 UVW "; melting range 150 to 156 ° C.) 1.1 parts by mass, crosslinking agent (Nisshinbo Chemical Co., Ltd.“ Carbodilite E-04 ”, carbodiimide type crosslinking agent) 3.5 parts by mass, nonionic surfactant (first "Neugen EA-157" manufactured by Kogyo Seiyaku Co., Ltd.) 0.1 parts by mass, 0.1 parts by mass of a fluorosurfactant ("Megafac F-444" manufactured by DIC Corporation), viscoelasticity modifier (San Nopco Co., Ltd.) "SN thickener 612NC") 0.9 parts by mass and ion-exchanged water 4 4.2 parts by mass were uniformly mixed to obtain an aqueous surface treating agent (1).
[評価用塗膜の作製]
上記で得られた水性表面処理剤(1)をバーコーターNo.14を用いてTPOシート(厚さ0.4mm)上に塗工し、120℃で1分間乾燥して評価用の塗膜を得た。
[Preparation of coating film for evaluation]
The aqueous surface treating agent (1) obtained above was converted into a bar coater No. 14 was coated on a TPO sheet (thickness 0.4 mm) and dried at 120 ° C. for 1 minute to obtain a coating film for evaluation.
[耐溶剤性の評価]
上記で得られた評価用塗膜の表面にエタノールを0.05ml滴下し、そのまま3時間放置した後、エタノールの滴下痕の直径を測定した。得られた測定値から、下記の基準にしたがって耐溶剤性を評価した。
○:滴下痕の直径が25mm未満である。
×:滴下痕の直径が25mm以上である。
[Evaluation of solvent resistance]
After 0.05 ml of ethanol was dropped on the surface of the coating film for evaluation obtained above and left as it was for 3 hours, the diameter of the ethanol drop mark was measured. From the measured values obtained, the solvent resistance was evaluated according to the following criteria.
A: The diameter of the dropping mark is less than 25 mm.
X: The diameter of a drop mark is 25 mm or more.
(実施例2〜11)
下記表1の配合組成にしたがって、実施例1と同様に操作して水性表面処理剤(2)〜(11)を得た。また、実施例1と同様に、得られた水性表面処理剤について、耐溶剤性の評価を行った。
(Examples 2 to 11)
Aqueous surface treatment agents (2) to (11) were obtained in the same manner as in Example 1 according to the formulation composition shown in Table 1 below. In addition, as in Example 1, the obtained aqueous surface treating agent was evaluated for solvent resistance.
(比較例1〜9)
下記表2の配合組成にしたがって、実施例1と同様に操作して水性表面処理剤(R1)〜(R9)を得た。また、実施例1と同様に、得られた水性表面処理剤について、耐溶剤性の評価を行った。
(Comparative Examples 1-9)
According to the composition of Table 2 below, aqueous surface treating agents (R1) to (R9) were obtained in the same manner as in Example 1. In addition, as in Example 1, the obtained aqueous surface treating agent was evaluated for solvent resistance.
上記の実施例1〜11の水性表面処理剤(1)〜(11)の配合組成及び耐溶剤性の評価結果を表1に、比較例1〜9の水性表面処理剤(R1)〜(R9)の配合組成及び耐溶剤性の評価結果を表2に示す。 Table 1 shows the composition of the aqueous surface treatment agents (1) to (11) of the above Examples 1 to 11 and the evaluation results of the solvent resistance, and the aqueous surface treatment agents (R1) to (R9) of Comparative Examples 1 to 9. Table 2 shows the evaluation results of the composition and solvent resistance.
上記表1及び2に記載した各配合成分の詳細は下記の通りである。
「ハイドラン WLS−210」:DIC株式会社製のポリカーボネート系水性ポリウレタン(不揮発分35質量%)
「ACEMATT TS−100」:エボニックデグサ社製の乾式法で製造されたシリカ粒子
「ACEMATT 3300」:エボニックデグサ社製の乾式法で製造し、表面を有機処理されたシリカ粒子
「NIPGEL AZ−200」:東ソー・シリカ株式会社製の湿式法で製造されたシリカ粒子
「ACEMATT EXP−3600」:エボニックデグサ社製の湿式法で製造し、表面を有機処理されたシリカ粒子
「アートパール G−800」:根上工業株式会社製の架橋ポリマー微粒子
「タフチック ASF−7」:東洋紡績株式会社製のポリアクリロニトリルを主成分とする艶消し剤
「MICROMATTE 1213UVW」:Micro Powders社製のポリプロピレンワックス(溶融範囲150〜156℃)
「MICROPRO 440W」:Micro Powders社製のポリプロピレンワックス(溶融範囲150〜156℃)
「MPP−620XF」:Micro Powders社製のポリエチレンワックス(溶融範囲114〜116℃)
「CERAFLOUR 998」:ビックケミー・ジャパン株式会社製のPTPF(ポリテトラフルオロエチレン)変性ポリエチレンワックス(溶融範囲113〜116℃)
「カルボジライト E−04」:日清紡ケミカル株式会社製のカルボジイミド系架橋剤
「ノイゲン EA−157」:第一工業製薬株式会社製のノニオン系界面活性剤
「メガファック F−444」:DIC株式会社製のフッ素系界面活性剤
「SNシックナー 612NC」:サンノプコ株式会社製の粘弾性調整剤
The detail of each compounding component described in the said Table 1 and 2 is as follows.
"Hydran WLS-210": Polycarbonate water-based polyurethane manufactured by DIC Corporation (non-volatile content 35% by mass)
“ACEMATT TS-100”: silica particles “ACEMATT 3300” manufactured by a dry method manufactured by Evonik Degussa: silica particles “NIPGEL AZ-200” manufactured by a dry method manufactured by Evonik Degussa and subjected to organic treatment on the surface. : Silica particles “ACEMATT EXP-3600” manufactured by a wet method manufactured by Tosoh Silica Co., Ltd .: Silica particles “Art Pearl G-800” manufactured by a wet method manufactured by Evonik Degussa and treated with an organic surface. Cross-linked polymer fine particles “Toughtic ASF-7” manufactured by Negami Kogyo Co., Ltd .: Matting agent “MICROMATETE 1213UVW” based on polyacrylonitrile manufactured by Toyobo Co., Ltd .: Polypropylene wax manufactured by Micro Powders (melting range: 150 to 156) ℃)
“MICROPRO 440W”: Polypropylene wax manufactured by Micro Powders (melting range: 150 to 156 ° C.)
“MPP-620XF”: polyethylene powder manufactured by Micro Powders (melting range: 114 to 116 ° C.)
“CERAFLOUR 998”: PTPF (polytetrafluoroethylene) -modified polyethylene wax (melting range: 113 to 116 ° C.) manufactured by BYK Japan
“Carbodilite E-04”: Carbodiimide type crosslinking agent “Neugen EA-157” manufactured by Nisshinbo Chemical Co., Ltd .: Nonionic surfactant “Megafac F-444” manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: manufactured by DIC Corporation Fluorosurfactant “SN Thickener 612NC”: Viscoelasticity modifier manufactured by San Nopco
表1に示した結果から、本発明の水性表面処理剤である実施例1〜11の水性表面処理剤(1)〜(11)は、エタノールの滴下痕の直径が9〜16mmとあまり大きくなく、小さい滴下痕しか残らないことから、高い耐溶剤性を有することが分かった。 From the results shown in Table 1, the aqueous surface treatment agents (1) to (11) of Examples 1 to 11 which are the aqueous surface treatment agents of the present invention have a diameter of ethanol dropping marks of 9 to 16 mm, which is not so large. Since only a small drop mark remains, it was found that the film has high solvent resistance.
一方、比較例1は、本発明で用いる溶融範囲が140〜180℃であるポリオレフィンワックス(B)を用いず、マット剤も用いなかった例である。この比較例1〜4のものは、エタノールの滴下痕の直径が34mmと比較的大きく、耐溶剤性が十分でないことが分かった。 On the other hand, Comparative Example 1 is an example in which the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention was not used and no matting agent was used. In Comparative Examples 1 to 4, it was found that the diameter of ethanol drop marks was relatively large at 34 mm, and the solvent resistance was not sufficient.
一方、比較例2〜5は、本発明で用いる溶融範囲が140〜180℃であるポリオレフィンワックス(B)を用いず、マット剤としてシリカ粒子を用いた例である。この比較例2〜5のものは、エタノールの滴下痕の直径が40〜48mmと大きく、耐溶剤性が十分でないことが分かった。 On the other hand, Comparative Examples 2 to 5 are examples using silica particles as a matting agent without using the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention. In Comparative Examples 2 to 5, it was found that the diameter of ethanol dropping marks was as large as 40 to 48 mm, and the solvent resistance was not sufficient.
比較例6及び7は、本発明で用いる溶融範囲が140〜180℃であるポリオレフィンワックス(B)を用いず、マット剤として有機ビーズを用いた例である。この比較例6及び7のものは、エタノールの滴下痕の直径が46〜57mmと大きく、耐溶剤性が十分でないことが分かった。 Comparative Examples 6 and 7 are examples in which organic beads were used as the matting agent without using the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention. In Comparative Examples 6 and 7, it was found that the diameter of ethanol drop marks was as large as 46 to 57 mm, and the solvent resistance was not sufficient.
比較例8は、本発明で用いる溶融範囲が140〜180℃であるポリオレフィンワックス(B)の代わりに、溶融範囲が114〜116℃であるポリエチレンワックスを用いた例である。この比較例8のものは、エタノールの滴下痕の直径が46mmと大きく、耐溶剤性が十分でないことが分かった。 Comparative Example 8 is an example in which polyethylene wax having a melting range of 114 to 116 ° C. was used instead of the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention. In Comparative Example 8, it was found that the diameter of the ethanol drop mark was as large as 46 mm, and the solvent resistance was not sufficient.
比較例9は、本発明で用いる溶融範囲が140〜180℃であるポリオレフィンワックス(B)の代わりに、溶融範囲が113〜116℃であるPTFE変性ポリエチレンワックスを用いた例である。この比較例9のものは、エタノールの滴下痕の直径が45mmと大きく、耐溶剤性が十分でないことが分かった。 Comparative Example 9 is an example in which PTFE-modified polyethylene wax having a melting range of 113 to 116 ° C. was used instead of the polyolefin wax (B) having a melting range of 140 to 180 ° C. used in the present invention. The thing of this comparative example 9 turned out that the diameter of the drop mark of ethanol was as large as 45 mm, and solvent resistance was not enough.
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