JP2010222559A - Water and oil repellent resin composition and coated product - Google Patents
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本発明は、撥水・撥油性の塗膜を形成するために用いられる低温硬化型の撥水・撥油性樹脂組成物及び、この撥水・撥油性樹脂組成物で塗膜を形成した塗装品に関するものである。 The present invention relates to a low-temperature curable water- and oil-repellent resin composition used for forming a water- and oil-repellent coating film, and a coated product in which a coating film is formed from this water- and oil-repellent resin composition It is about.
近年、住宅の内装設備部材（キッチン、バス、トイレなど）や家電商品を中心に、水垢や湯垢、手垢、汗など汚れが付着し難く、除去し易いといった撥水・撥油機能を表面に保持した製品への要求が高くなってきている。通常、水の接触角が９０°以上で、油（特にオレイン酸）の接触角が４０°以上である被膜が撥水・撥油性被膜と呼ばれており、このような撥水・撥油性被膜を形成するためのコーティング材の開発が盛んに行なわれている。 In recent years, water and oil repellency functions such as water stains, scales, dirt and sweat are less likely to adhere to and are easy to remove, mainly on interior components (kitchens, baths, toilets, etc.) and home appliances. The demand for such products is increasing. Usually, a film having a water contact angle of 90 ° or more and an oil (especially oleic acid) contact angle of 40 ° or more is called a water / oil repellent coating, and such a water / oil repellent coating is used. Development of a coating material for forming the film has been actively conducted.
このような撥水・撥油性に優れたコーティング材用の樹脂組成物としては、フッ素樹脂やシリコーン化合物を主成分とするものが一般的であり、通常よく使用されるフッ素樹脂は、−ＣＦ２−ＣＦＸ−や−ＣＦ２−ＣＦ２−などの骨格を導入したものである。 As such a resin composition for a coating material having excellent water and oil repellency, those having a fluororesin or a silicone compound as a main component are generally used, and a commonly used fluororesin is -CF 2 A skeleton such as —CFX— or —CF 2 —CF 2 — is introduced.
例えば、特許文献１には、アクリル樹脂とフッ素樹脂を用いた撥水・撥油性の塗料用組成物が提案されている。また特許文献２には、基材への密着性に優れた撥水・撥油性のフッ素樹脂材料が提案されている。さらに特許文献３には、撥水・撥油性のフッ素樹脂硬化性組成物からなる塗料組成物が提案されている。 For example, Patent Document 1 proposes a water / oil repellent coating composition using an acrylic resin and a fluororesin. Patent Document 2 proposes a water- and oil-repellent fluororesin material having excellent adhesion to a substrate. Further, Patent Document 3 proposes a coating composition comprising a water- and oil-repellent fluororesin curable composition.
しかしながら、上記のようなフッ素樹脂を主成分とする樹脂組成物は、形成される塗膜が柔らかいという問題があり、また拭き取り時に要求される耐磨耗性においても問題があって、十分な耐久性を保持した硬度や汚れの拭き取り性を塗膜に確保することは非常に困難であるという問題があった。 However, the resin composition mainly composed of the fluororesin as described above has a problem that the formed coating film is soft, and there is also a problem in the abrasion resistance required at the time of wiping, and it is sufficiently durable. There is a problem that it is very difficult to secure the coating film with sufficient hardness and dirt wiping property.
一方、フッ素樹脂と並んで広く検討されている撥水・撥油性樹脂として、Ｓｉ−ＣＨ３基を含有するシリコーン樹脂が挙げられる。例えば、特許文献４には、撥水性の加水分解性シラン化合物を使用した表面処理剤組成物が提案されている。また特許文献５には、シリコン系の化合物を使用した撥水・撥油性の表面処理剤が提案されている。 On the other hand, a water- and oil-repellent resin widely studied along with the fluororesin includes a silicone resin containing a Si—CH 3 group. For example, Patent Document 4 proposes a surface treatment composition using a water-repellent hydrolyzable silane compound. Patent Document 5 proposes a water- and oil-repellent surface treatment agent using a silicon-based compound.
しかし、シリコン系化合物の樹脂は、フッ素系の樹脂と比較して汚れの拭き取り性（耐磨耗性）には優れているが、プラスチックなどの基材に塗装した塗膜は基材の軟らかさの影響を受けて硬度が劣るという問題があった。また、耐磨耗性についてはフッ素系に比べ優れているものの、十分な耐久性を保持するまでには至らないものであった。 However, silicon-based compound resins are superior to fluorine-based resins in terms of wiping off dirt (abrasion resistance), but the coating film applied to a substrate such as plastic is softer than the substrate. There was a problem that the hardness was inferior under the influence of. In addition, the abrasion resistance is superior to that of fluorine, but it does not reach a sufficient durability.
上記のように、汚れが付着し難く除去し易いといった撥水・撥油性の塗膜を表面に形成した塗装品において、表面に付着した汚れを拭き取る（乾拭きや、水拭き、溶剤等）際の耐摩耗性や付着力を確保するために、塗膜には高い硬度、耐磨耗性が要求される。 As mentioned above, in a coated product that has a water / oil-repellent coating on its surface that is difficult to remove and easy to remove, the surface has to be cleaned (dry wipe, water wipe, solvent, etc.) In order to ensure wear resistance and adhesion, the coating film is required to have high hardness and wear resistance.
しかしながら、長期間汚れの拭き取りを実施すると、次第に塗膜が磨耗し、拭き取り時に使用される溶剤等の塗膜への浸漬により、塗膜が磨耗により剥がされ、撥水・撥油性の信頼性を保つことができなくなるのが現状である。また、コーティングされた基材の表面形状、例えばしぼ等の凹凸が基材の表面にあると、塗膜の膜厚が不均一になって、塗膜の薄い部分が剥がれ易くなり、同様に撥水・撥油性の信頼性を保つことができなくなるものであった。 However, when wiping off dirt for a long period of time, the coating film gradually wears out, and the coating film is peeled off by abrasion by immersion in the coating film of the solvent used at the time of wiping, and the reliability of water and oil repellency is improved. The current situation is that it cannot be maintained. In addition, if the surface shape of the coated substrate, for example, irregularities such as wrinkles, is present on the surface of the substrate, the film thickness of the coating film becomes non-uniform, and the thin part of the coating film is easily peeled off. The reliability of water and oil repellency could not be maintained.
従って、撥水・撥油性の樹脂組成物を住宅の内装設備などの部材や家電商品等に幅広く適用するために、十分な硬度があり且つ十分な耐磨耗性を保持し、高い撥水・撥油性の持続性に優れた塗膜を得ることができる樹脂組成物が求められているのが現状であり、さらにプラスチック基材に適用することができるように、低温で硬化する樹脂組成物であることも求められている。 Therefore, in order to widely apply the water / oil repellency resin composition to members such as interior equipment of homes and home appliances, it has sufficient hardness and sufficient wear resistance, and has high water repellency / There is currently a need for a resin composition that can provide a coating film with excellent oil repellency, and a resin composition that cures at a low temperature so that it can be applied to a plastic substrate. There is also a need to be.
本発明は上記の点に鑑みてなされたものであり、高い撥水・撥油の持続性を有し、且つ高い塗膜硬度を保持し、また高い耐磨耗性を備え、ポリカーボネートなどのプラスチック基材に対しても高い付着力を備えた塗膜を形成することができる低温硬化型の撥水・撥油性樹脂組成物及び塗装品を提供することを目的とするものである。 The present invention has been made in view of the above points, and has high water / oil repellency, high coating film hardness, high wear resistance, and a plastic such as polycarbonate. An object of the present invention is to provide a low-temperature curable water- and oil-repellent resin composition and a coated product that can form a coating film having high adhesion even on a substrate.
本発明に係る撥水・撥油性樹脂組成物は、式（１），式（２）のうち少なくとも一方で表されるポリシロキサン骨格を含む側鎖を持ち、且つフルオロアルキル基を有するアクリルポリオールと、架橋剤としてのイソシアネート樹脂と、含有比率が組成物中の固形分に対して１．０〜２０質量％の高分子微粒子とを含有して成ることを特徴とするものである。 The water / oil repellent resin composition according to the present invention includes an acrylic polyol having a side chain containing a polysiloxane skeleton represented by at least one of formula (1) and formula (2) and having a fluoroalkyl group, It is characterized by comprising an isocyanate resin as a cross-linking agent and polymer fine particles having a content ratio of 1.0 to 20% by mass with respect to the solid content in the composition.
式（２）中、Ｒ６，Ｒ７，Ｒ８，Ｒ９及びＲ１０は水素原子又は炭素原子数１〜１０の炭化水素基であり、それぞれ同一であっても異なっていてもよい。ｐは０〜１０の整数、ｑは２以上の整数である。）
この発明によれば、水酸基と反応するイソシアネート樹脂でアクリルポリオールを架橋して低温硬化させることができると共に、この架橋アクリル樹脂内に所定量の高分子微粒子を含有させることによって、高い硬度を保持し、且つ優れた耐磨耗性や、すべり感を持つ塗膜を形成することができるものであり、またアクリルポリオールに側鎖として付加するポリシロキサン骨格や、フルオロアルキル基を有することによって、持続性に優れた高い撥水・撥油性を有し、且つ耐磨耗性をさらに向上した塗膜を形成することができるものである。特にポリシロキサン骨格が式（１）や式（２）のものであることによって、より持続性に優れた高い撥水・撥油性を有し、且つ耐磨耗性をさらに向上した塗膜を形成することができるものである。
In the formula (2), R 6 , R 7 , R 8 , R 9 and R 10 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. p is an integer of 0 to 10, and q is an integer of 2 or more. )
According to this invention, an acrylic polyol can be crosslinked with an isocyanate resin that reacts with a hydroxyl group and cured at a low temperature, and a high amount of fine polymer particles is contained in the crosslinked acrylic resin to maintain high hardness. In addition, it is possible to form a coating film with excellent wear resistance and slipperiness, and it has durability by having a polysiloxane skeleton added as a side chain to an acrylic polyol and a fluoroalkyl group. It is possible to form a coating film having excellent water and oil repellency and excellent wear resistance. In particular, the polysiloxane skeleton is of formula (1) or formula (2) to form a coating film that has higher water and oil repellency with superior durability and further improved wear resistance. Is something that can be done.
また本発明において、上記の高分子微粒子は、アクリル系微粒子であることを特徴とするものである。 In the present invention, the polymer fine particles are acrylic fine particles.
この発明によれば、塗膜にアクリル系微粒子を導入することによって、硬度を向上させ、耐磨耗性を向上した塗膜を形成することができるものである。 According to this invention, by introducing acrylic fine particles into the coating film, it is possible to form a coating film having improved hardness and improved wear resistance.
本発明に係る塗装品は、基材の表面に、上記の撥水・撥油性樹脂組成物の塗膜を設けて形成され、塗膜の膜厚ｔと高分子微粒子の平均粒径Ｄとの関係が
０．３≦Ｄ／ｔ≦３
であり、且つ塗膜の膜厚ｔが５μｍ以上であることを特徴とするものである。
The coated product according to the present invention is formed by providing a coating film of the above water- and oil-repellent resin composition on the surface of a substrate, and has a film thickness t of the coating film and an average particle diameter D of the polymer fine particles. The relationship is 0.3 ≦ D / t ≦ 3
The film thickness t of the coating film is 5 μm or more.
このように膜厚と高分子微粒子の粒径の関係を規定して塗膜を形成することによって、高い硬度を保持し、耐磨耗性、持続性に優れた低温硬化撥水・撥油性の表面を有する塗装品を得ることができるものである。 By defining the relationship between the film thickness and the particle size of the polymer particles in this way, the coating film is formed to maintain high hardness, low temperature curing water and oil repellency with excellent wear resistance and durability. A coated product having a surface can be obtained.
また本発明において、上記基材は、プラスチック材料で形成されたものであることを特徴とするものである。 In the present invention, the base material is formed of a plastic material.
この発明によれば、プラスチック材料で形成された柔らかい基材を用いて、高い硬度を保持し、耐磨耗性、付着力、すべり感、持続力に優れた高い撥水・撥油性の表面を有する塗装体を得ることができるものである。そして本発明の撥水・撥油性樹脂組成物は上記のように低温硬化することができるので、プラスチック材料の基材に塗膜を形成することが可能になるものである。 According to the present invention, a soft substrate made of a plastic material is used to maintain a high hardness and a highly water- and oil-repellent surface with excellent wear resistance, adhesion, slipperiness, and durability. The coating body which has can be obtained. Since the water / oil repellent resin composition of the present invention can be cured at a low temperature as described above, a coating film can be formed on the base material of the plastic material.
本発明によれば、水酸基と反応するイソシアネート樹脂でアクリルポリオールを架橋して低温硬化させることができると共に、この架橋アクリル樹脂内に所定量の高分子微粒子を含有させることによって、高い硬度を保持し、且つ優れた耐磨耗性や、すべり感を持つ塗膜を形成することができるものである。またアクリルポリオールに側鎖として付加する式（１）、式（２）のポリシロキサン骨格や、フルオロアルキル基を有することによって、持続性に優れた高い撥水・撥油性を有し、且つ耐磨耗性をさらに向上した塗膜を形成することができるものである。 According to the present invention, an acrylic polyol can be cross-linked with an isocyanate resin that reacts with a hydroxyl group and cured at low temperature, and a high amount of fine polymer particles is contained in the cross-linked acrylic resin to maintain high hardness. In addition, it is possible to form a coating film having excellent wear resistance and slipperiness. In addition, by having a polysiloxane skeleton of formula (1) and formula (2) added to the acrylic polyol as a side chain and a fluoroalkyl group, it has excellent water and oil repellency with excellent durability and abrasion resistance. It is possible to form a coating film with further improved wear characteristics.
以下、本発明の実施の形態を説明する。 Embodiments of the present invention will be described below.
本発明において用いるアクリルポリオールは、ポリシロキサン骨格を含む側鎖を有し、また水酸基が側鎖として結合した分子構造を有するものである。本発明においてポリシロキサン骨格を含む側鎖のポリシロキサン構造は、上記の式（１），式（２）のうち少なくとも一方で表されるものである。 The acrylic polyol used in the present invention has a side chain containing a polysiloxane skeleton and a molecular structure in which hydroxyl groups are bonded as side chains. In the present invention, the side chain polysiloxane structure containing a polysiloxane skeleton is represented by at least one of the above formulas (1) and (2).
上記の式（１），式（２）において、Ｒ１〜Ｒ１０は、互いに同一であっても異なっていてもよい水素原子又は炭素原子数１〜１０の炭化水素基であり、例えばメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、フェニル基、シクロへキシル基を挙げることができ、好ましくはメチル基またはエチル基である。これらの炭化水素基は直鎖状であってもよいし、分岐鎖状でもよい。また式（１），式（２）のｎ及びｑは２以上の整数であり、上限は特に設定されないが、３０以下であることが好ましい。 In the above formulas (1) and (2), R 1 to R 10 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may be the same as or different from each other, for example, a methyl group , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, phenyl group, cyclohexyl group, preferably methyl group or ethyl group . These hydrocarbon groups may be linear or branched. Moreover, n and q of Formula (1) and Formula (2) are integers of 2 or more, and the upper limit is not particularly set, but is preferably 30 or less.
このアクリルポリオールにおいて、式（１）や式（２）で表されるジメチルシリコン基等が撥水・撥油基となって、撥水・撥油性が発現されるものである。また水酸基がイソシアネート樹脂のイソシアネート基と反応して架橋する架橋部位となるものである。 In this acrylic polyol, the dimethylsilicon group represented by the formula (1) or the formula (2) becomes a water / oil repellency group to exhibit water / oil repellency. Further, the hydroxyl group becomes a cross-linked site that reacts with the isocyanate group of the isocyanate resin to cross-link.
ここで、式（１）や式（２）で表されるポリシロキサン骨格は、アクリルポリオール（側鎖も含む）中に１０〜７０質量％の範囲で含有されているのが好ましい。アクリルポリオール中のこのポリシロキサン骨格の含有量が多すぎると、基材に対する塗膜の密着性が低下する傾向があり、含有量が少なすぎると、撥水・撥油性が低下する傾向がある。このポリシロキサン骨格はアクリルポリオールの分子骨格と直接結合しているため、容易に脱落せず、長期的にも安定な撥水・撥油性能を示す塗膜を得ることができるものであり、またすべり性を向上させることで耐磨耗性能も向上した塗膜を得ることができるものである。 Here, it is preferable that the polysiloxane skeleton represented by the formula (1) or the formula (2) is contained in the acrylic polyol (including the side chain) in the range of 10 to 70% by mass. When the content of the polysiloxane skeleton in the acrylic polyol is too large, the adhesion of the coating film to the substrate tends to be lowered, and when the content is too small, the water / oil repellency tends to be lowered. Since this polysiloxane skeleton is directly bonded to the molecular skeleton of the acrylic polyol, it does not easily fall off, and a coating film that exhibits stable water and oil repellency can be obtained over a long period of time. By improving the slip property, a coating film with improved wear resistance can be obtained.
またアクリルポリオールの水酸基価は７０〜２３０ｍｇＫＯＨ／ｇの範囲が好ましく、更に好ましくは１００〜２００ｍｇＫＯＨ／ｇの範囲である。水酸基価が低すぎると、イソシアネートと反応して架橋する水酸基の数が少なくなるので、得られる塗膜の架橋密度が低下して、硬度が低い塗膜になる傾向がある。逆に水酸基価が高すぎると、イソシアネートと反応して架橋する水酸基の数が多くなって、硬い塗膜が得られるが、アクリルポリオールと溶剤との相溶性が低下し、樹脂安定性が劣ることになる傾向がある。 The hydroxyl value of the acrylic polyol is preferably in the range of 70 to 230 mgKOH / g, more preferably in the range of 100 to 200 mgKOH / g. If the hydroxyl value is too low, the number of hydroxyl groups that crosslink by reacting with isocyanate decreases, so the crosslinking density of the resulting coating film tends to decrease, and the coating film tends to have low hardness. On the other hand, if the hydroxyl value is too high, the number of hydroxyl groups that react with the isocyanate to crosslink increases and a hard coating film is obtained, but the compatibility between the acrylic polyol and the solvent decreases, and the resin stability is poor. Tend to be.
アクリルポリオールには、撥水性の耐久性を高めるために、その樹脂骨格中にフッ素基を含有させている。フッ素基としては、次の式（３）〜（６）に例示するフルオロアルキル基が用いられるものであり、アクリルポリオールの合成時にアクリルポリオール骨格に結合させることができる。フルオロアルキル基の量が多くなればなるほど、得られる塗膜の撥水性能の持続性は向上していくが、アクリルポリオールの溶剤や他の樹脂との相溶性は低下していく傾向になる。このため、フルオロアルキル基の含有量は、アクリルポリオール（側鎖を含む）中、１〜７０質量％の範囲に調整するのが好ましい。 The acrylic polyol contains a fluorine group in the resin skeleton in order to enhance the durability of water repellency. As the fluorine group, fluoroalkyl groups exemplified in the following formulas (3) to (6) are used, and can be bonded to the acrylic polyol skeleton at the time of synthesis of the acrylic polyol. As the amount of the fluoroalkyl group increases, the durability of the water-repellent performance of the resulting coating film is improved, but the compatibility of the acrylic polyol with the solvent and other resins tends to decrease. For this reason, it is preferable to adjust content of a fluoroalkyl group in the range of 1-70 mass% in acrylic polyol (a side chain is included).
―（ＣＦ２―ＣＦ２）― （３）
―（ＣＦ２―ＣＦＨ）― （４）
―（ＣＦ２―ＣＨ２）― （５）
―（ＣＦＨ―ＣＨ２）― （６）
上記のように得られるアクリルポリオールは、重量平均分子量（Ｍｗ）が２００００〜１５００００のものが好適に用いられる。より好ましくは２５０００〜１０００００であり、更に好ましくは３００００〜５００００である。アクリルポリオールの分子量が高すぎると、溶剤や他の架橋剤との相溶性が悪くなる傾向があり、アクリルポリオールの分子量が低すぎると、得られる塗膜の物性が低下する傾向がある。
― (CF 2 ―CF 2 ) ― (3)
― (CF 2 ―CFH) ― (4)
— (CF 2 —CH 2 ) — (5)
― (CFH-CH 2 ) ― (6)
The acrylic polyol obtained as described above preferably has a weight average molecular weight (Mw) of 20,000 to 150,000. More preferably, it is 25000-100,000, More preferably, it is 30000-50000. If the molecular weight of the acrylic polyol is too high, the compatibility with the solvent and other crosslinking agents tends to be poor, and if the molecular weight of the acrylic polyol is too low, the physical properties of the resulting coating film tend to be reduced.
次に、架橋剤の役割について説明する。イソシアネート樹脂は、アクリルポリオールに含有される水酸基と反応してアクリル樹脂を架橋し、緻密な塗膜を形成する。得られた塗膜は、シリコン系の膜と比較して柔軟性に優れ、耐磨耗性に優れた膜を形成するものである。特に住宅の内装設備部材や家電商品は汚れを拭き取ることがあることから、必要とされる耐磨耗性、硬度は非常に厳しい品質が要求されており、イソシアネート樹脂の添加量が少ない場合は、これらの性能が低下する傾向がある。 Next, the role of the crosslinking agent will be described. The isocyanate resin reacts with the hydroxyl group contained in the acrylic polyol to crosslink the acrylic resin to form a dense coating film. The obtained coating film forms a film having excellent flexibility and abrasion resistance as compared with a silicon-based film. In particular, interior equipment and household appliances for homes may wipe off dirt, so the required wear resistance and hardness are required to be very strict, and if the amount of isocyanate resin added is small, Their performance tends to decrease.
イソシアネート樹脂としては、ヘキサメチレンジイソシアネート、トリレンジイソシアネート、キシレンジイソシアネート、イソホロンジイソシアネートや上記混合物を挙げることができる。イソシアネート樹脂の添加量が多すぎると、硬く緻密な塗膜を形成できるが、逆に脆く密着性が悪い塗膜となる傾向がある。従って、イソシアネート樹脂の添加量は、アクリルポリオール（側鎖を含む）の固形分に対して、１０〜２８０質量％の範囲に設定するのが好ましい。 Examples of the isocyanate resin include hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate and the above mixtures. If the amount of the isocyanate resin added is too large, a hard and dense coating film can be formed, but conversely, it tends to be a coating film that is brittle and has poor adhesion. Therefore, it is preferable to set the addition amount of the isocyanate resin in the range of 10 to 280% by mass with respect to the solid content of the acrylic polyol (including the side chain).
そして本発明の撥水・撥油性樹脂組成物は、上記のアクリルポリオール及び架橋剤に、さらに高分子微粒子を配合して調製されるものである。この高分子微粒子としては、特に限定されるものではないが、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ＡＢＳ樹脂、及びメラミン樹脂などを挙げることができる。高分子微粒子を配合して塗膜中に含有させることによって、塗膜の耐摩耗性を向上し、高い硬度の塗膜を得ることができるようにしたものであり、これらの中でも、耐磨耗性の向上、高い硬度の保持、塗膜との密着性の点から、アクリル樹脂微粒子などアクリル系微粒子を使用するのが好ましい。 The water / oil repellent resin composition of the present invention is prepared by further blending polymer fine particles with the acrylic polyol and the crosslinking agent. The polymer fine particles are not particularly limited, and examples thereof include acrylic resins, epoxy resins, polyester resins, polyurethane resins, ABS resins, and melamine resins. By incorporating polymer fine particles into the coating film, the wear resistance of the coating film is improved and a coating film with high hardness can be obtained. It is preferable to use acrylic fine particles such as acrylic resin fine particles from the viewpoint of improving the property, maintaining high hardness, and adhesion to the coating film.
ここで、高分子微粒子の添加量が少ないと、塗膜の硬度や耐磨耗性を向上する効果を十分に得ることができないものであり、逆に高分子微粒子の添加量が多すぎると、塗膜の表面の凹凸が多くなって、撥水・撥油性が低下する傾向がある。従って高分子微粒子の含有量は、撥水・撥油性樹脂組成物の全樹脂の固形分に対して、１．０〜２０質量％の範囲に設定されるものである。 Here, if the addition amount of the polymer fine particles is small, the effect of improving the hardness and abrasion resistance of the coating film cannot be sufficiently obtained. Conversely, if the addition amount of the polymer fine particles is too large, There is a tendency that the unevenness of the surface of the coating film increases and the water and oil repellency decreases. Therefore, the content of the polymer fine particles is set in the range of 1.0 to 20% by mass with respect to the solid content of the total resin of the water / oil repellent resin composition.
上記のようにアクリルポリオールに架橋剤及び高分子微粒子を配合して調製される本発明の撥水・撥油性樹脂組成物を基材の表面に塗装することによって、塗装品を得ることができる。 A coated product can be obtained by coating the surface of the substrate with the water / oil repellent resin composition of the present invention prepared by blending the acrylic polyol with the crosslinking agent and the polymer fine particles as described above.
また撥水・撥油性樹脂組成物を塗装する基材としては、特に制限されることなく任意のものを用いることができるが、本発明において特に適用して好ましい基材はプラスチック材料を成形して形成した成形品であり、プラスチック材料のなかでも好ましいものとして、ポリカーボネート、ポリプロピレン、ＡＢＳ樹脂、アクリル樹脂などを挙げることができる。ここで、本発明の撥水・撥油性樹脂組成物は、イソシアネート樹脂でアクリルポリオールの水酸基にイソシアネート樹脂を反応させて架橋することによって、高温に加熱する必要なく、低温で硬化させることができるものである。従って、基材としてこのようなプラスチック材料のものを用いて、撥水・撥油性樹脂組成物を塗装することが可能になるものである。本発明において、撥水・撥油性樹脂組成物の硬化温度は、特に限定されるものではないが、基材を形成するプラスチック材料の耐熱温度以下で、且つ常温（２５℃）〜１２０℃程度の範囲であることが望ましい。 In addition, as the base material on which the water / oil repellent resin composition is coated, any substrate can be used without any particular limitation. However, a preferable base material particularly applicable in the present invention is formed by molding a plastic material. Among the plastic materials that are formed, polycarbonate, polypropylene, ABS resin, acrylic resin, and the like can be cited as preferable examples of plastic materials. Here, the water / oil repellent resin composition of the present invention can be cured at a low temperature without the need for heating to a high temperature by reacting the isocyanate resin with a hydroxyl group of an acrylic polyol and crosslinking with an isocyanate resin. It is. Therefore, it is possible to apply a water / oil repellent resin composition using such a plastic material as a substrate. In the present invention, the curing temperature of the water- and oil-repellent resin composition is not particularly limited, but is not higher than the heat resistance temperature of the plastic material forming the substrate and is from room temperature (25 ° C.) to about 120 ° C. A range is desirable.
そして、本発明の撥水・撥油性樹脂組成物を基材の表面に塗装して塗膜を形成するにあたって、撥水・撥油性樹脂組成物に含有される高分子微粒子の平均粒径Ｄに対する塗膜の膜厚ｔの割合Ｄ／ｔが０．３〜３の範囲になるように設定するのが好ましい。Ｄ／ｔが０．３未満と、塗膜の膜厚に対して高分子微粒子の粒径が小さすぎると、高分子微粒子を含有させて塗膜の硬度や耐磨耗性を向上する効果が不十分になる。逆にＤ／ｔが３を超えて、塗膜の膜厚に対して高分子微粒子の粒径が大きくなりすぎると、塗膜の表面の凹凸が多くなって、撥水・撥油性が低下する傾向がある。また、膜厚ｔは５μｍ以上であることが好ましい。膜厚が５μｍ未満であると、塗膜の耐摩耗性が低下する傾向がある。塗膜の膜厚の上限は特に設定されるものではないが、一般に１００μｍ程度が膜厚の上限である。高分子微粒子の平均粒径Ｄは、塗膜の膜厚ｔとの関係で選定されるものであり、特に限定されるものではないが、２〜３０μｍの範囲に設定するのが好ましい。ここで、平均粒径はレーザー回折・散乱法によって測定した値である。尚、塗膜を形成する基材の表面にシボのような凹凸部がある場合には、高分子微粒子の平均粒径を、凹凸部の高さ寸法の１／６以上に設定するのが好ましい。また、アクリルポリオールのポリシロキサン骨格と高分子微粒子の相乗効果により、耐磨耗性が一層向上するものである。 Then, when forming a coating film by coating the surface of the substrate with the water / oil repellent resin composition of the present invention, the average particle diameter D of the polymer fine particles contained in the water / oil repellent resin composition It is preferable to set the ratio D / t of the film thickness t of the coating film to be in the range of 0.3-3. When D / t is less than 0.3 and the particle size of the polymer fine particle is too small relative to the film thickness of the coating film, the effect of improving the hardness and abrasion resistance of the coating film by incorporating the polymer fine particle is effective. It becomes insufficient. Conversely, if D / t exceeds 3 and the particle size of the polymer fine particle is too large relative to the film thickness of the coating film, the surface roughness of the coating film increases and the water and oil repellency decreases. Tend. The film thickness t is preferably 5 μm or more. There exists a tendency for the abrasion resistance of a coating film to fall that a film thickness is less than 5 micrometers. The upper limit of the film thickness of the coating film is not particularly set, but generally about 100 μm is the upper limit of the film thickness. The average particle diameter D of the polymer fine particles is selected in relation to the film thickness t of the coating film and is not particularly limited, but is preferably set in the range of 2 to 30 μm. Here, the average particle diameter is a value measured by a laser diffraction / scattering method. In addition, when there are uneven portions such as wrinkles on the surface of the substrate on which the coating film is formed, it is preferable to set the average particle size of the polymer fine particles to 1/6 or more of the height dimension of the uneven portions. . In addition, the wear resistance is further improved by the synergistic effect of the polysiloxane skeleton of the acrylic polyol and the polymer fine particles.
次に、本発明を実施例によって具体的に説明する。 Next, the present invention will be specifically described with reference to examples.
（実施例１）
式（１）及び式（２）で表されるジメチルシリコン骨格を有する側鎖と、フルオロアルキル基を有するアクリルポリオール（富士化成工業株式会社製「ＺＸ−０２２Ｈ」：ジメチルシリコン基・水酸基含有フッ素シリコン樹脂、固形分４６質量％、水酸基価１２０）を用いた。
Example 1
An acrylic polyol having a side chain having a dimethylsilicon skeleton represented by the formulas (1) and (2) and a fluoroalkyl group (“ZX-022H” manufactured by Fuji Chemical Industry Co., Ltd .: dimethylsilicon group / hydroxyl group-containing fluorine silicon Resin, solid content 46 mass%, hydroxyl value 120) was used.
またイソシアネート樹脂として、ヘキサメチレンジイソシアネート樹脂（三井化学株式会社製「タケネートＤ−１７０Ｎ」：固形分１００質量％）を用いた。 Further, as the isocyanate resin, hexamethylene diisocyanate resin (“Takenate D-170N” manufactured by Mitsui Chemicals, Inc .: solid content: 100% by mass) was used.
さらに高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−１２」、平均粒子径１２μｍ）を用いた。 Furthermore, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) were used as the polymer fine particles.
そして、アクリルポリオールに表１に示す量の高分子微粒子をディスパーにより分散し、さらに表１に示す量のイソシアネート樹脂と、溶剤として表１に示す量のメチルエチルケトンを添加して混合し、撥水・撥油性樹脂組成物を調製した。尚、全固形分中における高分子微粒子の含有比率は１０質量％である。 Then, the polymer fine particles in the amount shown in Table 1 are dispersed in the acrylic polyol with a disper, and the isocyanate resin in the amount shown in Table 1 and methyl ethyl ketone in the amount shown in Table 1 as a solvent are added and mixed. An oil repellent resin composition was prepared. The content ratio of the polymer fine particles in the total solid content is 10% by mass.
次に、基材としてポリカーボネート製のものを用い、このポリカーボネート基材に上記のように調製した撥水・撥油性樹脂組成物をエアースプレーによって、乾燥膜厚が１０μｍになるように塗装し、８０℃の温度で３０分間乾燥することによって、塗装板を作製した。 Next, a polycarbonate substrate is used, and the water- and oil-repellent resin composition prepared as described above is applied to the polycarbonate substrate by air spray so that the dry film thickness becomes 10 μm. A coated plate was prepared by drying at a temperature of 30 ° C. for 30 minutes.
（実施例２）
イソシアネート樹脂として、トリレンジイソシアネート樹脂（三井化学株式会社製「タケネートＤ−１０３Ｈ」：固形分５０質量％）を使用するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。そしてこの撥水・撥油性樹脂組成物を用いて実施例１と同様にして塗装板を作製した。
(Example 2)
As the isocyanate resin, a tolylene diisocyanate resin (“Takenate D-103H” manufactured by Mitsui Chemicals, Inc .: solid content 50% by mass) was used in the same manner as in Example 1, but with the formulation shown in Table 1. A water / oil repellent resin composition was prepared. A coated plate was prepared in the same manner as in Example 1 using this water / oil repellent resin composition.
（実施例３）
イソシアネート樹脂として、キシリレンジイソシアネート樹脂（三井化学株式会社製「タケネートＤ−１２０Ｎ」：固形分７５質量％）を使用するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。そしてこの撥水・撥油性樹脂組成物を用いて実施例１と同様にして塗装板を作製した。
Example 3
As the isocyanate resin, a xylylene diisocyanate resin (“Takenate D-120N” manufactured by Mitsui Chemicals, Inc .: solid content: 75% by mass) was used in the same manner as in Example 1, but with the formulation shown in Table 1. A water / oil repellent resin composition was prepared. A coated plate was prepared in the same manner as in Example 1 using this water / oil repellent resin composition.
（実施例４）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−１２」、平均粒子径１２μｍ）を用い、全固形分中における含有比率３質量％で配合するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
Example 4
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) are used and blended at a content ratio of 3% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.
そして、実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が１４μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 Then, this water- and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 14 μm, and dried in the same manner as in Example 1 to produce a coated plate. .
（実施例５）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−１２」、平均粒子径１２μｍ）を用い、全固形分中における含有比率２０質量％で配合するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
(Example 5)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) are used and blended at a content ratio of 20% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.
そして、実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が１７μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 Then, the same water-repellent / oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 17 μm, and dried in the same manner as in Example 1 to produce a coated plate. .
（実施例６）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−１２」、平均粒子径１２μｍ）を用い、全固形分中における含有比率１質量％で配合するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
(Example 6)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) are used and blended at a content ratio of 1% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.
そして、実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が８μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 And this water-repellent / oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 8 μm, and dried in the same manner as in Example 1 to produce a coated plate. .
（実施例７）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−５」、平均粒子径５μｍ）を用いるようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
(Example 7)
In the same manner as in Example 1 except that cross-linked polymethyl methacrylate fine particles (“MBX-5” manufactured by Sekisui Plastics Co., Ltd., average particle size of 5 μm) are used as the polymer fine particles, the composition shown in Table 1 A water / oil repellent resin composition was prepared.
そして、実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が５μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 And this water-repellent and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 5 μm, and dried in the same manner as in Example 1 to produce a coated plate. .
（実施例８）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−３０」、平均粒子径３０μｍ）を用いるようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
(Example 8)
In the same manner as in Example 1 except that cross-linked polymethyl methacrylate fine particles (“MBX-30” manufactured by Sekisui Plastics Co., Ltd., average particle size of 30 μm) are used as the polymer fine particles, the composition shown in Table 1 A water / oil repellent resin composition was prepared.
そして、実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が１５μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 Then, this water- and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 15 μm, and dried in the same manner as in Example 1 to produce a coated plate. .
（実施例９）
乾燥膜厚が１７μｍになるように塗装すること以外は、実施例１と同様にして、塗装板を作製した。
Example 9
A coated plate was produced in the same manner as in Example 1 except that coating was performed so that the dry film thickness was 17 μm.
（実施例１０）
乾燥膜厚が５μｍになるように塗装すること以外は、実施例１と同様にして、塗装板を作製した。
(Example 10)
A coated plate was produced in the same manner as in Example 1 except that coating was performed so that the dry film thickness was 5 μm.
（実施例１１）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−２Ｈ」、平均粒子径２μｍ）を用いるようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
(Example 11)
In the same manner as in Example 1 except that cross-linked polymethyl methacrylate fine particles (“MBX-2H” manufactured by Sekisui Plastics Co., Ltd., average particle size 2 μm) are used as the polymer fine particles, the composition shown in Table 1 A water / oil repellent resin composition was prepared.
そして実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が６μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 Then, the same polycarbonate substrate as in Example 1 was coated with this water / oil repellent resin composition so that the dry film thickness was 6 μm, and dried in the same manner as in Example 1 to prepare a coated plate.
（実施例１２）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−３０」、平均粒子径３０μｍ）を用い、全固形分中における含有比率１０質量％で配合するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
Example 12
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-30” manufactured by Sekisui Plastics Co., Ltd., average particle size: 30 μm) are used and blended at a content ratio of 10% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.
そして、実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が８μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 And this water-repellent / oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 8 μm, and dried in the same manner as in Example 1 to produce a coated plate. .
（実施例１３）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−２Ｈ」、平均粒子径２μｍ）を用い、全固形分中における含有比率１０質量％で配合するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
(Example 13)
Other polymer fine particles (cross-linked polymethyl methacrylate fine particles (“MBX-2H” manufactured by Sekisui Plastics Co., Ltd., average particle diameter: 2 μm)) were used and blended at a content ratio of 10% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.
そして、実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が１０μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 Then, this water- and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 10 μm, and dried in the same manner as in Example 1 to produce a coated plate. .
（実施例１４）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−５」、平均粒子径５μｍ）を用い、全固形分中における含有比率１質量％で配合するようにした他は、実施例１と同様にして撥水・撥油性樹脂組成物を調製した。
(Example 14)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-5” manufactured by Sekisui Plastics Co., Ltd., average particle size: 5 μm) are used and blended at a content ratio of 1% by mass in the total solid content. Was prepared in the same manner as in Example 1 to prepare a water / oil repellent resin composition.
そして実施例１と同じポリカーボネート基材に、この撥水・撥油性樹脂組成物を乾燥膜厚が１５μｍになるように塗装し、実施例１と同様に乾燥することによって、塗装板を作製した。 Then, this water- and oil-repellent resin composition was applied to the same polycarbonate substrate as in Example 1 so that the dry film thickness was 15 μm, and dried in the same manner as in Example 1 to produce a coated plate.
（実施例１５）
基材としてアクリル樹脂基材を用いるようにした他は、実施例１と同様にして、塗装板を作製した。
(Example 15)
A coated plate was produced in the same manner as in Example 1 except that an acrylic resin substrate was used as the substrate.
（実施例１６）
基材としてＡＢＳ樹脂基材を用いるようにした他は、実施例１と同様にして、塗装板を作製した。
(Example 16)
A coated plate was produced in the same manner as in Example 1 except that an ABS resin substrate was used as the substrate.
（比較例１）
高分子微粒子を用いない表１の配合で、実施例１と同様にして撥水・撥油性樹脂組成物を調製した。そしてこの撥水・撥油性樹脂組成物を用いて実施例１と同様にして塗装板を作製した。
(Comparative Example 1)
A water / oil repellent resin composition was prepared in the same manner as in Example 1 except that the polymer fine particles were not used. A coated plate was prepared in the same manner as in Example 1 using this water / oil repellent resin composition.
（比較例２）
ポリシロキサン骨格を含む側鎖を持たず、フルオロアルキル基を有するアクリルポリオール（ＤＩＣ株式会社製「フルオネートＫ-７０３」：水酸基含有フッ素樹脂、固形分６０質量％、水酸基価６６〜７８）を用いる表１の配合で、実施例１と同様にして撥水・撥油性樹脂組成物を調製した。そしてこの撥水・撥油性樹脂組成物を用いて実施例１と同様にして塗装板を作製した。
(Comparative Example 2)
Table using acrylic polyol having a side chain containing a polysiloxane skeleton and having a fluoroalkyl group ("Fluoronate K-703" manufactured by DIC Corporation: hydroxyl group-containing fluororesin, solid content 60 mass%, hydroxyl value 66-78) In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation of 1. A coated plate was prepared in the same manner as in Example 1 using this water / oil repellent resin composition.
（比較例３）
式（１）及び式（２）で表されるジメチルシリコン骨格を有する側鎖と、フルオロアルキル基を有するアクリルポリオール（富士化成工業株式会社製「ＺＸ−０２２Ｈ」：ジメチルシリコン基・水酸基含有フッ素シリコン樹脂、固形分４６質量％、水酸基価１２０）を用いた。
(Comparative Example 3)
An acrylic polyol having a side chain having a dimethylsilicon skeleton represented by the formulas (1) and (2) and a fluoroalkyl group (“ZX-022H” manufactured by Fuji Chemical Industry Co., Ltd .: dimethylsilicon group / hydroxyl group-containing fluorine silicon Resin, solid content 46 mass%, hydroxyl value 120) was used.
また硬化剤として、メラミン樹脂（三井化学株式会社製「ユーバン２２５」：固形分６０質量％）を用いた。 As a curing agent, a melamine resin (“Uban 225” manufactured by Mitsui Chemicals, Inc .: solid content 60% by mass) was used.
さらに高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−１２」、平均粒子径１２μｍ）を用いた。 Furthermore, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) were used as the polymer fine particles.
そしてこれらの材料を用いた表１の配合で、実施例１同様にして撥水・撥油性樹脂組成物を調製した。 Then, a water / oil repellent resin composition was prepared in the same manner as in Example 1 with the formulation shown in Table 1 using these materials.
次に、基材としてポリカーボネート製を用い、このポリカーボネート基材に上記のように調製した樹脂組成物をエアースプレーによって、乾燥膜厚が６μｍになるように塗装し、８０℃の温度で３０分間乾燥することによって、塗装板を作製した。 Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 6 μm, and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.
（比較例４）
アクリルポリオール（ＤＩＣ株式会社製「ＡＣＲＹＤＩＣ５２−６６６Ｂ」：水酸基含有樹脂、固形分５０質量％、水酸基価１４８）を用いる表１の配合で、実施例１と同様にして撥水・撥油性樹脂組成物を調製した。
(Comparative Example 4)
A water- and oil-repellent resin composition in the same manner as in Example 1, using an acrylic polyol (“ACRYDIC 52-666B” manufactured by DIC Corporation: hydroxyl group-containing resin, solid content 50 mass%, hydroxyl value 148). Was prepared.
次に、基材としてポリカーボネート製を用い、このポリカーボネート基材に上記のように調製した樹脂組成物をエアースプレーによって、乾燥膜厚が９μｍになるように塗装し、８０℃の温度で３０分間乾燥することによって、塗装板を作製した。 Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 9 μm and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.
（比較例５）
ポリシロキサン骨格を含む側鎖を持ち、フルオロアルキル基を有しないアクリルポリオール（東亜合成式会社製「ＧＳ−１０１５」：水酸基含有樹脂、固形分４５質量％、水酸基価７２）を用い用いる表１の配合で、実施例１と同様にして撥水・撥油性樹脂組成物を調製した。
(Comparative Example 5)
Using an acrylic polyol having a side chain containing a polysiloxane skeleton and having no fluoroalkyl group (“GS-1015” manufactured by Toagosei Co., Ltd .: hydroxyl group-containing resin, solid content 45 mass%, hydroxyl value 72) A water / oil repellent resin composition was prepared in the same manner as in Example 1 by blending.
次に、基材としてポリカーボネート製を用い、このポリカーボネート基材に上記のように調製した樹脂組成物をエアースプレーによって、乾燥膜厚が７μｍになるように塗装し、８０℃の温度で３０分間乾燥することによって、塗装板を作製した。 Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 7 μm and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.
（比較例６）
高分子微粒子の代わりにシリカ微粒子（富士シリシア化学株式会社社製「サイロスフェアＣ−１５１０」、平均粒子径１０μｍ）を用いる表１の配合で、実施例１と同様にして撥水・撥油性樹脂組成物を調製した。
(Comparative Example 6)
A water- and oil-repellent resin in the same manner as in Example 1 with the composition shown in Table 1 using silica fine particles (“Pyrospher C-1510” manufactured by Fuji Silysia Chemical Ltd., average particle size 10 μm) instead of the polymer fine particles. A composition was prepared.
次に、基材としてポリカーボネート製を用い、このポリカーボネート基材に上記のように調製した樹脂組成物をエアースプレーによって、乾燥膜厚が１３μｍになるように塗装し、８０℃の温度で３０分間乾燥することによって、塗装板を作製した。 Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 13 μm, and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.
（比較例７）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−１２」、平均粒子径１２μｍ）を用い、全固形分中における含有比率２２質量％で配合するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
(Comparative Example 7)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-12” manufactured by Sekisui Plastics Co., Ltd., average particle size: 12 μm) are used and blended at a content ratio of 22% by mass in the total solid content. In the same manner as in Example 1, a water / oil repellent resin composition was prepared with the formulation shown in Table 1.
次に、基材としてポリカーボネート製を用い、このポリカーボネート基材に上記のように調製した樹脂組成物をエアースプレーによって、乾燥膜厚が１８μｍになるように塗装し、８０℃の温度で３０分間乾燥することによって、塗装板を作製した。 Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 18 μm, and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.
（比較例８）
高分子微粒子として、架橋ポリメタクリル酸メチル微粒子（積水化成品工業株式会社製「ＭＢＸ−２Ｈ」、平均粒子径２μｍ）を用い、全固形分中における含有比率０．５質量％で配合するようにした他は、実施例１と同様にして、表１の配合で撥水・撥油性樹脂組成物を調製した。
(Comparative Example 8)
As polymer fine particles, cross-linked polymethyl methacrylate fine particles (“MBX-2H” manufactured by Sekisui Plastics Co., Ltd., average particle size: 2 μm) are used and blended at a content ratio of 0.5 mass% in the total solid content. The water / oil repellent resin composition was prepared in the same manner as in Example 1 with the formulation shown in Table 1.
次に、基材としてポリカーボネート製を用い、このポリカーボネート基材に上記のように調製した樹脂組成物をエアースプレーによって、乾燥膜厚が１０μｍになるように塗装し、８０℃の温度で３０分間乾燥することによって、塗装板を作製した。 Next, polycarbonate is used as the base material, and the resin composition prepared as described above is applied to the polycarbonate base material by air spray so that the dry film thickness becomes 10 μm, and dried at a temperature of 80 ° C. for 30 minutes. By doing so, a coated plate was produced.
（比較例９）
比較のために、未塗装のポリカーボネート基材を試験に供した。
(Comparative Example 9)
For comparison, an unpainted polycarbonate substrate was subjected to the test.
（比較例１０）
比較のために、未塗装のアクリル樹脂基材を試験に供した。
(Comparative Example 10)
For comparison, an unpainted acrylic resin substrate was subjected to the test.
（比較例１１）
比較のために、未塗装のＡＢＳ樹脂基材を試験に供した。
(Comparative Example 11)
For comparison, an unpainted ABS resin substrate was subjected to the test.
上記のようにして実施例１〜１６及び比較例１〜８で得た塗装板（比較例９〜１１は基材の表面）について、塗膜硬度、塗膜の摩耗性、塗膜の耐汚染性、接触角を試験して評価した。試験方法は以下の通りであり、結果を表１に示した。 About the coating board (Comparative Examples 9-11 is the surface of a base material) obtained by Examples 1-16 and Comparative Examples 1-8 as mentioned above, coating-film hardness, the abrasion property of a coating film, and stain resistance of a coating film And contact angle were tested and evaluated. The test method is as follows, and the results are shown in Table 1.
（１）塗膜硬度
ＪＩＳＫ５６００−５−４に従う鉛筆法により、塗膜の硬度を測定した。
(1) Coating film hardness The hardness of the coating film was measured by the pencil method according to JISK5600-5-4.
（２）磨耗性
大同理科製作所株式会社製「磨耗性試験装置」に取り付けられた染色堅ろう度試験用添付白布を、往復回数１０００回、１０００ｇ加重の条件で擦る摩耗試験を行ない、試験前後の外観変化を次の判定基準で評価した。
◎：５０００回の試験においても塗膜剥離などの外観変化がない。
○：塗膜剥離などの外観変化がない。
△：磨耗痕が部分的に生じている。
×：完全に磨耗し、基材が見えている。
(2) Abrasion Abrasion test is performed by rubbing the attached white cloth for dyeing fastness test attached to the "Abrasion tester" manufactured by Daido Science Co., Ltd. under the condition of 1000 reciprocations and 1000g load. Changes were evaluated according to the following criteria.
(Double-circle): There is no external appearance change, such as coating film peeling, in the test of 5000 times.
○: No change in appearance such as peeling of coating film.
(Triangle | delta): The abrasion trace has arisen partially.
X: It was completely worn and the substrate was visible.
（３）耐汚染性（マジック汚染性）
油性マジックインクで塗膜の表面に書いた跡の拭き取り除去性を、次の判定基準で評価した。
○：よくはじき、軽く取れ、染みなどがない。
△：はじきが弱く取れるが除去後にマジックインクの染みが残る。
×：はじかず、まったく取れない。
(3) Pollution resistance (magic contamination)
The removability of traces written on the surface of the coating film with oil-based magic ink was evaluated according to the following criteria.
○: Well repelled, lightly removed, no stains.
Δ: The repellency is weak and can be removed, but the magic ink stain remains after the removal.
X: Not repelled and cannot be removed at all.
（４）接触角
実施例１〜１６及び比較例１〜８で得た塗装板の塗膜表面（比較例９〜１１は基材の表面）のイオン交換水の接触角を接触角測定装置（協和界面化学株式会社製、型式ＣＡ−Ａ）により測定した。
(4) Contact angle Contact angle measuring device (contact angle measuring device) is used to determine the contact angle of ion-exchanged water on the coating film surface (comparative examples 9 to 11 are the surface of the substrate) of the coated plates obtained in Examples 1 to 16 and Comparative Examples 1 to 8. It was measured by Kyowa Interface Chemical Co., Ltd. model CA-A).
尚、実施例１〜３はイソシアネート樹脂を変更したものであり、イソシアネート樹脂の種類にかかわらず、いずれも耐摩耗性、防汚性に優れていた。実施例１及び実施例４〜６は、高分子微粒子の含有比率を変動させたものである。なかでも、高分子微粒子含有比率が３質量％、２０質量％である実施例４，５の塗装品は耐磨耗性に特に優れていた。実施例７〜１３は高分子微粒子の平均粒子径Ｄと塗膜の膜厚ｔの比Ｄ／ｔを変動させたものである。なかでもＤ／ｔが０．７〜２．６である実施例７〜１０の塗装品は耐摩耗性に特に優れていた。実施例１４は高分子微粒子の含有量及びＤ／ｔを変動させたものであるが、耐磨耗性、防汚性に優れていた。 In addition, Examples 1-3 changed the isocyanate resin, and were excellent in abrasion resistance and antifouling property irrespective of the kind of isocyanate resin. In Example 1 and Examples 4 to 6, the content ratio of the polymer fine particles was varied. Among these, the coated products of Examples 4 and 5 having polymer fine particle content ratios of 3% by mass and 20% by mass were particularly excellent in wear resistance. In Examples 7 to 13, the ratio D / t between the average particle diameter D of the polymer fine particles and the film thickness t of the coating film was varied. Among these, the coated articles of Examples 7 to 10 having D / t of 0.7 to 2.6 were particularly excellent in wear resistance. In Example 14, the content of the polymer fine particles and D / t were varied, but the wear resistance and antifouling property were excellent.
一方、比較例１にみられるように、高分子微粒子を含まない塗膜は硬度、耐摩耗性が低下するものであった。また比較例２に見られるように、ポリシロキサン骨格を持たないアクリルポリオールによって形成した塗膜は耐汚染性が低下するものであった。硬化剤としてメラミンを使用した比較例３では、塗膜硬度の向上は見られず、耐摩耗性においても劣るものであり、耐汚染性も低いものであった。またポリシロキサン骨格とフルオロアルキル基を有しないアクリルポリオールから形成された比較例４は、塗膜硬度の向上は見られるが、耐摩耗性や耐汚染性において劣るものであった。フルオロアルキル基を有しないアクリルポリオールから形成された比較例５は、耐摩耗性においても劣るものであり、耐汚染性も低いものであった。また、微粒子にシリカを使用した比較例６は、硬度の向上は見られるが、耐摩耗性が劣るものであった。また、高分子微粒子含有比率が２０質量％を超える比較例７は、硬度や耐摩耗性は向上するが、耐汚染性が低下するものであった。さらに、基材のみの比較例９〜１１は防汚性や耐摩耗性が大きく劣るものであった。 On the other hand, as seen in Comparative Example 1, the coating film not containing the polymer fine particles had reduced hardness and wear resistance. Further, as seen in Comparative Example 2, the coating film formed from the acrylic polyol having no polysiloxane skeleton had a reduced stain resistance. In Comparative Example 3 in which melamine was used as the curing agent, the coating film hardness was not improved, the wear resistance was inferior, and the contamination resistance was low. In Comparative Example 4 formed from an acrylic polyol having no polysiloxane skeleton and no fluoroalkyl group, although the coating film hardness was improved, the abrasion resistance and stain resistance were inferior. The comparative example 5 formed from the acrylic polyol which does not have a fluoroalkyl group was inferior also in abrasion resistance, and was also a thing with low stain resistance. In Comparative Example 6 in which silica was used for the fine particles, although the hardness was improved, the wear resistance was inferior. In Comparative Example 7 in which the polymer fine particle content ratio exceeds 20% by mass, the hardness and wear resistance are improved, but the stain resistance is lowered. Furthermore, Comparative Examples 9 to 11 having only the base material were greatly inferior in antifouling property and wear resistance.
Claims (4)
式（２）中、Ｒ６，Ｒ７，Ｒ８，Ｒ９及びＲ１０は水素原子又は炭素原子数１〜１０の炭化水素基であり、それぞれ同一であっても異なっていてもよい。ｐは０〜１０の整数、ｑは２以上の整数である。） An acrylic polyol having a side chain containing a polysiloxane skeleton represented by at least one of formula (1) and formula (2) and having a fluoroalkyl group, an isocyanate resin as a crosslinking agent, and a content ratio of the composition A water / oil repellent resin composition comprising 1.0 to 20% by mass of polymer fine particles based on the solid content therein.
In the formula (2), R 6 , R 7 , R 8 , R 9 and R 10 are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. p is an integer of 0 to 10, and q is an integer of 2 or more. )
０．３≦Ｄ／ｔ≦３
であり、且つ塗膜の膜厚ｔが５μｍ以上であることを特徴とする塗装品。 A coating film of the water / oil repellent resin composition according to claim 1 or 2 is provided on the surface of the substrate, and the relationship between the film thickness t of the coating film and the average particle diameter D of the polymer fine particles is 0.3 ≦ D / t ≦ 3
And a coated product having a coating film thickness t of 5 μm or more.
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