JP2017132157A - Artificial marble having antifouling performance, and production method therefor - Google Patents
Artificial marble having antifouling performance, and production method therefor Download PDFInfo
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- JP2017132157A JP2017132157A JP2016014707A JP2016014707A JP2017132157A JP 2017132157 A JP2017132157 A JP 2017132157A JP 2016014707 A JP2016014707 A JP 2016014707A JP 2016014707 A JP2016014707 A JP 2016014707A JP 2017132157 A JP2017132157 A JP 2017132157A
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- 239000002928 artificial marble Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 230000003373 anti-fouling effect Effects 0.000 title abstract description 7
- 239000005871 repellent Substances 0.000 claims abstract description 50
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 239000003973 paint Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 230000002940 repellent Effects 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920001187 thermosetting polymer Polymers 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 238000009835 boiling Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 239000004579 marble Substances 0.000 claims description 5
- 239000003921 oil Substances 0.000 description 33
- 235000019198 oils Nutrition 0.000 description 33
- 239000000463 material Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000758 substrate Substances 0.000 description 7
- 239000004033 plastic Substances 0.000 description 5
- 230000008439 repair process Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000004412 Bulk moulding compound Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000003677 Sheet moulding compound Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Abstract
Description
本発明は、水や油を弾き、汚れを落としやすい人工大理石及びその製造方法に関する。 The present invention relates to an artificial marble that can easily remove dirt by splashing water and oil, and a method for producing the same.
不飽和ポリエステル樹脂、アクリル樹脂、エポキシ樹脂などのプラスチック材料からなる人工大理石は、プレス成形や注型成形などの成形方法で製造されているが、前記人工大理石をキッチンや浴室などの水周りで使用する場合、汚れや水垢などが付着し易く、外観や清潔さに問題点があった。
上記問題点を解決する為、前記プラスチック材料にシリコーン等の撥水・撥油性を有する材料を添加する方法が考えられている。しかし、人工大理石の基材に撥水・撥油材料を添加すると撥水・撥油性能が必要な基材表面だけでなく、基材中にも撥水・撥油材料を添加させなければならずコスト増となり経済上好ましくない。また、基材表面に低表面自由エネルギー層を有する塗膜をスプレー塗装により付与することで水垢や汚れの付着力を小さくする方法が考えられる。しかし、前記方法では人工大理石の模様、色調、光沢を損ない、また塗膜への異物混入やその補修により多くの時間を費やし加工コストが増え、また異物混入対策として生産設備の投資も増え、生産上、経済上好ましくない。
Artificial marble made of plastic materials such as unsaturated polyester resin, acrylic resin, and epoxy resin is manufactured by molding methods such as press molding and cast molding, but the artificial marble is used around water in kitchens and bathrooms. In this case, dirt and scales are likely to adhere, and there are problems in appearance and cleanliness.
In order to solve the above problems, a method of adding a material having water / oil repellency such as silicone to the plastic material is considered. However, when water / oil repellent materials are added to the artificial marble base material, water / oil repellent materials must be added not only to the surface of the base material that requires water / oil repellent performance, but also to the base material. Therefore, the cost increases, which is not preferable from an economic viewpoint. Moreover, the method of making the adhesion force of scale or dirt small by providing the coating film which has a low surface free energy layer on the base-material surface by spray coating can be considered. However, the above-mentioned method impairs the pattern, color tone and gloss of artificial marble, spends a lot of time due to contamination and repair of the coating film, and increases the processing cost. In addition, it is not economically preferable.
そこで、人工大理石の基材表面に厚さ０．０１〜０．２μｍ程度の塗膜を設けることで人工大理石の外観を損なうことがなく、基材表面に低表面エネルギー層を形成した技術が開示されている（特許文献１参照）。 Therefore, a technique has been disclosed in which a low surface energy layer is formed on the surface of the base material without damaging the appearance of the artificial marble by providing a coating film having a thickness of about 0.01 to 0.2 μm on the base material surface of the artificial marble. (See Patent Document 1).
特許文献１に記載の人工大理石では、基材表面に塗布する塗料が常温乾燥タイプでありアルコールなどの溶剤に弱く、また塗膜の膜厚が薄すぎるため清掃時の磨耗など実使用上の耐久性に課題があった。 In the artificial marble described in Patent Document 1, the coating material applied to the surface of the base material is a room-temperature drying type, is weak against solvents such as alcohol, and the coating film thickness is too thin. There was a problem with sex.
本発明は、前記の課題に鑑みなされたものであって、本発明の目的は、人工大理石表面の外観を損なわず、安価で実使用上の耐久性がある防汚膜を付加させた人工大理石とその製造方法を提供することにある。 The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide an artificial marble to which an antifouling film that is inexpensive and has practical durability is added without impairing the appearance of the surface of the artificial marble. And providing a manufacturing method thereof.
本発明は、上記課題を解決する手段として、以下の構成を有する。
（１）本発明の人工大理石は、撥水・撥油コートが表面に形成された人工大理石であって、前記撥水・撥油コートが熱硬化系塗料の硬化物からなり、硬化後の膜厚が０．３〜１μｍであることを特徴とする。
膜厚０．３〜１μｍの熱硬化系塗料の硬化物からなる撥水・撥油コートが表面に形成されているならば、表面に汚れが付着し難く、防汚性能に優れる人工大理石を提供できる。また、膜厚０．３〜１μｍの撥水・撥油コートであるならば、必要な厚さを有し、繰り返しの清掃作業に耐えて撥水・撥油性が低下することがなく、また、膜が厚すぎることもないので大理石としての表面模様や色調などの外観を損なうこともなく、膜形成中に異物の巻き込みを起こすおそれもない。膜形成中に異物の巻き込みを無くすることで補修の必要が無くなり、製造時の加工コストの上昇も起こり難い人工大理石を提供できる。
The present invention has the following configuration as means for solving the above problems.
(1) The artificial marble of the present invention is an artificial marble having a water-repellent / oil-repellent coat formed on the surface thereof, the water-repellent / oil-repellent coat comprising a cured product of a thermosetting paint, and a film after curing The thickness is 0.3 to 1 μm.
If a water- and oil-repellent coat consisting of a cured product of a thermosetting paint with a film thickness of 0.3 to 1 μm is formed on the surface, it provides an artificial marble with excellent antifouling performance that prevents dirt from adhering to the surface. it can. Moreover, if it is a water-repellent / oil-repellent coat having a film thickness of 0.3 to 1 μm, it has a necessary thickness, can withstand repeated cleaning work, and does not deteriorate its water / oil repellency, Since the film is not too thick, it does not impair the appearance such as the surface pattern and color tone of the marble, and there is no possibility that foreign matter is involved during film formation. Eliminating foreign matter during film formation eliminates the need for repair, and can provide an artificial marble that does not easily increase the processing cost during manufacturing.
（２）本発明の人工大理石において、エタノールに２４時間浸漬後の水の接触角が９０度以上でかつオレイン酸の接触角が４０度以上であることが好ましい。
水の接触角とオレイン酸の接触角の両方が高いことで水の弾きが強く、植物油の弾きも良好な撥水・撥油コートを備えた人工大理石であるならば、実使用上拭き取り性が高く、防汚性能の優れた人工大理石を提供できる。
(2) In the artificial marble of the present invention, it is preferable that the contact angle of water after being immersed in ethanol for 24 hours is 90 degrees or more and the contact angle of oleic acid is 40 degrees or more.
If it is an artificial marble with a water- and oil-repellent coat that has a high water contact angle and a high contact angle of oleic acid, it has strong water repellent and good vegetable oil repellent, it can be wiped off in practical use. It can provide artificial marble with high antifouling performance.
（３）本発明において、前記熱硬化系塗料がシリコーン変性アクリルウレタン塗料であることが好ましい。
シリコーン変性アクリルウレタン塗料を硬化させた撥水・撥油コートであるならば人工大理石の基材に対する密着性に優れ、安価な特徴を有する。
(3) In the present invention, the thermosetting paint is preferably a silicone-modified acrylic urethane paint.
A water- and oil-repellent coat obtained by curing a silicone-modified acrylic urethane paint has excellent adhesion to an artificial marble substrate and is inexpensive.
（４）本発明において、前記熱硬化系塗料に沸点１２０℃以上の高沸点の溶剤が添加されていることが好ましい。
高沸点の溶剤を添加した熱硬化系塗料が熱硬化された撥水・撥油コートであるならば人工大理石の基材表面に塗装し易く、熱硬化後に人工大理石の基材に密着し易い特徴を有する。
(4) In the present invention, it is preferable that a solvent having a high boiling point of 120 ° C. or higher is added to the thermosetting paint.
If the thermosetting paint to which a high boiling point solvent is added is a water- and oil-repellent coat that has been heat-cured, it is easy to paint on the surface of the artificial marble substrate, and it is easy to adhere to the artificial marble substrate after thermosetting. Have
（５）本発明の撥水・撥油コートを表面に塗布した人工大理石の製造方法は、未コートの人工大理石の塗布面を洗浄する第１工程と、前記塗布面に前記熱硬化系塗料を塗布する第２工程と、前記塗布した塗料の９０〜９８質量％を拭き取り、前記未コートの人工大理石の外観と略等しくなるまで塗料を拭き上げる第３工程と、前記拭き上げた塗料を熱で硬化させる第４工程と、を含むことを特徴とする。
第３工程を行うことにより、余分な塗料を除去して必要な厚さの塗料を残し、硬化後に目的の膜厚を有する熱硬化系塗料の硬化物を得ることができる。
（６）本発明において、前記第２工程により塗料の塗布量を５〜２５ｃｃ／ｍ２の範囲とすることができる。
(5) The method for producing an artificial marble having the water-repellent / oil-repellent coat of the present invention applied to the surface includes a first step of washing the coated surface of the uncoated artificial marble, and the thermosetting paint on the coated surface. A second step of applying, a third step of wiping 90 to 98% by mass of the applied paint, and wiping the paint until it is substantially equal to the appearance of the uncoated artificial marble, and the wiped paint with heat And a fourth step of curing.
By performing the third step, it is possible to remove a surplus paint and leave a paint having a required thickness, and obtain a cured product of a thermosetting paint having a desired film thickness after curing.
(6) In the present invention, the coating amount of the paint can be in the range of 5 to 25 cc / m 2 by the second step.
本発明によれば、膜厚０．３〜１μｍの熱硬化系塗料の硬化物からなる撥水・撥油コートが表面に形成されているので、表面に汚れが付着し難く、防汚性能に優れる人工大理石を提供できる。また、膜厚０．３〜１μｍの撥水・撥油コートであるならば、繰り返しの清掃作業に耐えて撥水・撥油性が低下することがなく、表面模様や色調などの外観も綺麗な人工大理石を提供できる。
また、適切な膜厚の撥水・撥油コートを備えることで膜形成中に異物の巻き込みを引き起こすおそれもなく、製造時の補修の必要が無くなり、製造時の加工コストの上昇を生じることのない人工大理石を提供できる。
According to the present invention, since a water / oil repellent coat made of a cured product of a thermosetting paint having a film thickness of 0.3 to 1 μm is formed on the surface, dirt hardly adheres to the surface, and antifouling performance Can provide excellent artificial marble. In addition, a water- and oil-repellent coat with a film thickness of 0.3 to 1 μm can withstand repeated cleaning operations, and the water and oil repellency will not deteriorate, and the appearance such as the surface pattern and color tone is also beautiful. Artificial marble can be provided.
In addition, by providing a water / oil repellent coat with an appropriate film thickness, there is no risk of entrainment of foreign substances during film formation, and there is no need for repairs during production, resulting in increased processing costs during production. Can provide no artificial marble.
以下、本発明の実施形態を挙げて本発明の詳細を説明する。
本実施形態の人工大理石は、後述するプラスチック材料からなる基材の表面に所定厚さの撥水・撥油コートが被覆された構成を有する。
人工大理石の基材としては、ＳＭＣ（シートモールディングコンパウンド）、ＢＭＣ（バルクモールディングコンパウンド）、ＴＭＣ（シックモールディングコンパウンド）等の熱硬化系繊維強化材料を加熱加圧成形法にて成形したものや、主原料としてメタクリル酸メチル等、充填材としてシリカ等が含有された材料を注入成形にて成形したものなどを使用することができる。
人工大理石の基材を構成するプラスチック材料は、不飽和ポリエステル樹脂、アクリル樹脂、エポキシ樹脂など、人工大理石の基材用として知られているプラスチック材料を適宜用いることができ、これらの材料に強化繊維が混入されたもの、シリカ等の充填材が含有されたものが好適に用いられる。
撥水・撥油コートの材料としては、特に制限はないが、人工大理石の基材との密着性が良好であり、安価であるシリコーン変性アクリルウレタン塗料を用いることが好ましい。
撥水・撥油コートの材料としてその他、アクリルシリコーン樹脂系塗料、シリコーン樹脂系塗料、フッ素樹脂系塗料等の熱硬化性塗料を用いることができる。
Hereinafter, the details of the present invention will be described with reference to embodiments of the present invention.
The artificial marble of the present embodiment has a configuration in which a water repellent / oil repellent coat having a predetermined thickness is coated on the surface of a base material made of a plastic material described later.
Artificial marble base materials include thermo-compressed fiber reinforced materials such as SMC (Sheet Molding Compound), BMC (Bulk Molding Compound), TMC (Sick Molding Compound), etc. A material obtained by injection molding of a material containing methyl methacrylate or the like as a raw material and silica or the like as a filler can be used.
As the plastic material constituting the base material of the artificial marble, plastic materials known for the base material of the artificial marble such as unsaturated polyester resin, acrylic resin, and epoxy resin can be appropriately used. Those in which fillers such as silica are contained are preferably used.
The material for the water / oil repellent coating is not particularly limited, but it is preferable to use a silicone-modified acrylic urethane paint that has good adhesion to the artificial marble base material and is inexpensive.
In addition, thermosetting paints such as acrylic silicone resin paints, silicone resin paints, and fluororesin paints can be used as materials for the water / oil repellent coat.
前記塗料に使用する溶剤としては、塗料の塗布のし易さ、拭き上げる際の塗膜の斑を低減させることを考慮し、塗料が乾燥し難い、沸点が１２０℃以上の溶剤が好ましく、さらに好ましくは沸点が１５０℃以上の溶剤を選択できる。
撥水・撥油コートの接触角としては、水の接触角が９０度以上、オレイン酸の接触角が４０度以上であることが好ましい。水の接触角が９０度以下では水の弾きが弱く、またオレイン酸の接触角が４０度以下では植物油などの弾きが弱く、実使用上、拭取り性などの効果が実感し難い。
撥水・撥油コートの膜厚としては、硬化後の膜厚で０．３〜１μｍであることが好ましい。膜厚が０．３μｍ以下であると繰り返しの洗浄作業による撥水・撥油の機能の低下が著しく、実使用では使用できない。１．０μｍ以上の膜厚では人工大理石の模様や色調などの外観を損ない、また塗膜形成中に異物を巻き込み易く、その補修により多くの時間を費やし加工コストが増え生産上、経済上好ましくない。
The solvent used for the paint is preferably a solvent having a boiling point of 120 ° C. or more, in consideration of ease of application of the paint, reducing coating film spots when wiping up, Preferably, a solvent having a boiling point of 150 ° C. or higher can be selected.
The contact angle of the water / oil repellent coat is preferably 90 ° or more for water and 40 ° or more for oleic acid. When the contact angle of water is 90 degrees or less, the repelling of water is weak, and when the contact angle of oleic acid is 40 degrees or less, the repelling of vegetable oil or the like is weak, and it is difficult to realize effects such as wiping property in actual use.
The film thickness of the water / oil repellent coat is preferably 0.3 to 1 μm as the film thickness after curing. When the film thickness is 0.3 μm or less, the water and oil repellency functions are remarkably lowered by repeated cleaning operations, and cannot be used in actual use. When the film thickness is 1.0 μm or more, the appearance of artificial marble, such as the pattern and color tone, is impaired. In addition, foreign matter is easily involved in the formation of the coating film, and it takes a lot of time to repair it. .
塗料の硬化条件としては、特に制限はないが、シリコーン変性アクリルウレタン塗料にイソシアネートを硬化剤として使用した場合、塗膜の表面性能を確保する上で９０℃以上の硬化温度が必要である。これにより塗膜の耐溶剤性が向上し、除菌アルコール等のアルコール系洗剤を使用可能となる。一方、加熱温度を１２０℃以上に上げると基材である人工大理石の色調が黄変して人工大理石の外観を損ねてしまう。 The curing conditions for the coating are not particularly limited, but when an isocyanate is used as a curing agent in the silicone-modified acrylic urethane coating, a curing temperature of 90 ° C. or higher is necessary to ensure the surface performance of the coating film. Thereby, the solvent resistance of the coating film is improved, and alcohol-based detergents such as sterilizing alcohol can be used. On the other hand, when the heating temperature is raised to 120 ° C. or higher, the color tone of the artificial marble as a base material is yellowed and the appearance of the artificial marble is impaired.
塗料の塗布方法は、未コートの人工大理石の塗布面を洗浄する第１工程と、前記塗布面に前記熱硬化系塗料を塗布する第２工程と、前記塗布した塗料の９０〜９８質量％を拭き取り、前記未コートの人工大理石の外観と略等しくなるまで塗料を拭き上げる第３工程と、前記拭き上げた塗料を熱で硬化させる第４工程とからなる。 The coating method includes a first step of cleaning the coated surface of uncoated artificial marble, a second step of coating the thermosetting coating on the coated surface, and 90 to 98% by mass of the coated coating. It consists of a third step of wiping and wiping the paint until it becomes substantially equal to the appearance of the uncoated artificial marble, and a fourth step of curing the wiped paint with heat.
第１工程で使用する洗浄液は、特に制限は無いが人工大理石を変質させないアルコール系溶剤が好ましい。第２工程で熱硬化塗料を塗布する方法としては、特に制限はないがスポンジ、ローラー等に塗料を染み込ませ、塗り広げることができる。
第３工程で塗料を拭取る方法としては、特に制限は無いが、紙タオル、綿など塗料を吸収できるもので人工大理石上の塗料を軽い力で拭取ることができる。
この第３工程では余分な塗料を除去して薄く均一な塗膜を得ることを目的に拭き取り作業を行う。第３工程においては塗布された塗料の９０〜９８質量％を拭き取ることが好ましい。
また、拭き取り作業の終盤に紙タオル、綿などの新しい面で拭き上げることで目視した場合に未コートの人工大理石と同等の外観を得ることができる。
この第３工程は人工大理石基材表面の光沢や外観を損なわない程度に薄く均一な塗膜を得るために行う。拭き取り前の塗膜の塗布量として５〜２５ｃｃ／ｍ２の範囲とすることが好ましい。
第４工程で塗料を硬化させる方法としては、乾燥炉など熱を発生する装置で、熱硬化系塗料の硬化が完了するまで前述した如く９０〜１２０℃程度に必要時間加熱することで硬化した塗膜を得ることができる。
Although there is no restriction | limiting in particular in the washing | cleaning liquid used at a 1st process, The alcohol solvent which does not denature artificial marble is preferable. The method for applying the thermosetting paint in the second step is not particularly limited, but it can be spread by spreading the paint into a sponge, a roller or the like.
The method of wiping the paint in the third step is not particularly limited, but it can absorb paint such as paper towel and cotton, and the paint on the artificial marble can be wiped with a light force.
In this third step, the wiping operation is performed for the purpose of removing the extra paint and obtaining a thin and uniform coating film. In the third step, it is preferable to wipe off 90 to 98% by mass of the applied paint.
In addition, when wiping with a new surface such as a paper towel or cotton at the end of the wiping operation, an appearance equivalent to that of an uncoated artificial marble can be obtained.
This third step is performed in order to obtain a thin and uniform coating film so as not to impair the gloss and appearance of the artificial marble base material surface. The coating amount of the coating film before wiping is preferably in the range of 5 to 25 cc / m 2 .
As a method of curing the paint in the fourth step, the coating is cured by heating at a temperature of about 90 to 120 ° C. for a necessary time until the curing of the thermosetting paint is completed with an apparatus that generates heat such as a drying furnace. A membrane can be obtained.
以下、実施例により本発明を更に詳細に説明するが、本発明は以下の実施例の記載に制限されるものではない。各実施例において使用した人工大理石基材には、ＢＭＣを成形材料とするキッチンカウンターを使用した。
（実施例１）
熱硬化系塗料としてシリコーン変性アクリルウレタン塗料ＫＴＴ−０１（公進ケミカル株式会社製、商品名）１００質量部、高沸点溶剤としてソルフィットＡＣ（株式会社クラレ製、商品名、沸点１７４℃）３００質量部、イソシアネート硬化剤としてＫＴＴ−０１用硬化剤（公進ケミカル株式会社製、商品名）３３．３部を配合、混合し撥水・撥油塗料を作製した。
次に、人工大理石基材の表面をエタノールで洗浄し（第１工程）、洗浄後の表面に前記撥水・撥油塗料を１０ｃｃ／ｍ２になるように滴下し、メラミンスポンジで塗り広げた（第２工程）。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to description of a following example. The artificial marble base material used in each example was a kitchen counter using BMC as a molding material.
Example 1
100 mass parts of silicone-modified acrylic urethane paint KTT-01 (trade name, manufactured by Koshin Chemical Co., Ltd.) as a thermosetting paint, and 300 mass of Solfit AC (trade name, boiling point 174 ° C., manufactured by Kuraray Co., Ltd.) as a high boiling point solvent. Part and 33.3 parts of a curing agent for KTT-01 (trade name, manufactured by Koshin Chemical Co., Ltd.) as an isocyanate curing agent were mixed and mixed to prepare a water / oil repellent coating.
Next, the surface of the artificial marble substrate was washed with ethanol (first step), and the water- and oil-repellent paint was dropped onto the washed surface so as to be 10 cc / m 2 and spread with a melamine sponge. (Second step).
塗り広げた後、室温で約５分間放置し、プロワイプソフトタオル（大王製紙株式会社製、商品名）を使用し、約３ｇ／ｃｍ２の軽い力で前記塗り広げた塗料を拭取り、完全に拭取る前にプロワイプソフトタオルの新しい面で人工大理石と同等の外観になるまで拭きあげた（第３工程）。
その後、前記人工大理石を９０℃の乾燥炉に１時間入れ、前記撥水・撥油塗料を硬化させ（第４工程）、撥水・撥油コートを表面に塗布した人工大理石を得た。
（実施例２）
高沸点溶剤ソルフィットＡＣの添加量を２００質量部にした以外は実施例１と同様にして撥水・撥油コートを塗布した人工大理石を得た。
（実施例３）
高沸点溶剤ソルフィットＡＣの添加量を１００質量部にした以外は実施例１と同様にして高沸・撥油コートを塗布した人工大理石を得た。
After spreading, leave at room temperature for about 5 minutes, use a professional wipe soft towel (trade name, manufactured by Daio Paper Co., Ltd.), wipe off the spread paint with a light force of about 3 g / cm 2 and completely Before wiping, the new surface of the professional wipe soft towel was wiped until it had the same appearance as artificial marble (third step).
Thereafter, the artificial marble was placed in a drying oven at 90 ° C. for 1 hour to cure the water / oil repellent paint (fourth step) to obtain an artificial marble having a water / oil repellent coat applied on the surface.
(Example 2)
An artificial marble coated with a water / oil repellent coat was obtained in the same manner as in Example 1 except that the amount of the high-boiling solvent Solfit AC added was 200 parts by mass.
(Example 3)
An artificial marble coated with a high-boiling / oil-repellent coat was obtained in the same manner as in Example 1 except that the amount of the high-boiling solvent Solfit AC was 100 parts by mass.
（比較例１）
人工大理石基材表面に何も塗布していない人工大理石基材を使用した。
（比較例２）
溶剤に酢酸ブチル（沸点１２４℃）を使用した以外は実施例１と同様にして撥水・撥油コートを塗布した人工大理石を得た。
（比較例３）
高沸点溶剤ソルフィットＡＣの添加量を５００質量部にした以外は実施例１と同様にして撥水・撥油コートを塗布した人工大理石を得た。
（比較例４）
実施例２と同様の撥水・撥油塗料を作製し、人工大理石基材の表面をエタノールで洗浄した後、前記撥水・撥油塗料を小形スプレーガンＷ１０１（アネスト岩田株式会社、商品名）で塗布した。塗布後、室温で約５分間放置し、９０℃の乾燥炉に入れ前記撥水・撥油塗料を硬化させ、撥水・撥油コートを表面に塗布した人工大理石を得た。
（比較例５）
人工大理石用として市販されているシリコーン系撥水・撥油剤マーブルワックス（トクラス株式会社製、商品名）を人工大理石基材表面中央に少量滴下し、メラミンスポンジ、または軟らかい乾いた布で薄く延ばすように塗り広げた。塗り広げてから約５分間そのまま放置し、マーブルワックスを基材表面に浸透させる。その後、軟らかい乾いた布でから拭きした後、室温に８時間放置して完全に乾燥させ撥水・撥油コートを表面に塗布した人工大理石を得た。溶剤はＩＰＡ（イソプロピルアルコール：沸点８２．４℃）を用い、その他は実施例１と同等組成の塗料を用いた。
(Comparative Example 1)
An artificial marble substrate having nothing applied to the surface of the artificial marble substrate was used.
(Comparative Example 2)
An artificial marble coated with a water / oil repellent coat was obtained in the same manner as in Example 1 except that butyl acetate (boiling point: 124 ° C.) was used as a solvent.
(Comparative Example 3)
An artificial marble coated with a water- and oil-repellent coat was obtained in the same manner as in Example 1 except that the amount of the high-boiling solvent Solfit AC added was 500 parts by mass.
(Comparative Example 4)
A water / oil repellent paint similar to that of Example 2 was prepared, and the surface of the artificial marble base was washed with ethanol, and then the water / oil repellent paint was applied to the small spray gun W101 (Anest Iwata Corporation, trade name). It was applied with. After coating, the mixture was allowed to stand at room temperature for about 5 minutes, placed in a drying oven at 90 ° C. to cure the water / oil repellent coating, and an artificial marble coated with a water / oil repellent coat was obtained.
(Comparative Example 5)
Apply a small amount of silicone water / oil repellent marble wax (trade name, manufactured by Tocras Co., Ltd.), which is commercially available for artificial marble, to the surface of the artificial marble base and spread it thinly with a melamine sponge or soft dry cloth. Spread on. After spreading the coating, it is left as it is for about 5 minutes to allow the marble wax to penetrate into the substrate surface. Then, after wiping with a soft dry cloth, it was allowed to stand at room temperature for 8 hours to be completely dried to obtain an artificial marble having a water / oil repellent coat applied on the surface. As the solvent, IPA (isopropyl alcohol: boiling point 82.4 ° C.) was used, and for the others, a paint having the same composition as in Example 1 was used.
（評価方法）
得られた撥水・撥油コートを表面に塗布した人工大理石を用いて、膜厚、接触角、色調の測定、外観、耐エタノール性の評価を以下に記載する方法で行った。
以上の結果を以下の表１に記載する。
(Evaluation method)
Using the artificial marble with the water / oil repellent coat obtained applied to the surface, the film thickness, contact angle, color tone, appearance, and ethanol resistance were evaluated by the methods described below.
The above results are listed in Table 1 below.
「１」膜厚
撥水・撥油コートした人工大理石を切断し断面部をデジタルマイクロスコープＶＨＸ−５０００（株式会社キーエンス製、装置名）にて拡大し観察するか、撥水・撥油コートしたシリコンウエハーを破断し断面部を走査型電子顕微鏡Ｓ−４５００（株式会社日立ハイテクノロジーズ製、装置名）にて拡大観察し膜厚を測定した。
「２」外観
人工大理石表面の光沢を光沢度計で評価した。また、目視にて、異物の有無、塗料の斑を確認した。
「３」接触角
人工大理石上に１μＬの水、１μＬのオレイン酸を滴下し、θ／２法でそれぞれの接触角を測定した。
「４」耐エタノール性
切断した人工大理石をエタノール(９９．５)（和光純薬工業株式会社製）に２４時間全漬し、人工大理石をエタノールより取り出した後２４時間風乾させ接触角にて評価した。
「５」耐繰り返し洗浄性
試験片に水を含ませた綿１００％の布巾を当て、５ｇ／ｃｍ２の荷重をかけたまま７０００回往復摩擦操作を行い、試験後２４時間風乾させて摩擦部分の接触角にて評価した。
"1" film thickness Water-repellent / oil-repellent coated artificial marble is cut and the cross section is enlarged and observed with a digital microscope VHX-5000 (manufactured by Keyence Corporation, apparatus name), or water / oil-repellent coated. The silicon wafer was broken, and the cross section was enlarged and observed with a scanning electron microscope S-4500 (manufactured by Hitachi High-Technologies Corporation, apparatus name) to measure the film thickness.
“2” Appearance The gloss of the artificial marble surface was evaluated with a gloss meter. Moreover, the presence or absence of a foreign material and the spot of a paint were confirmed visually.
“3” Contact Angle 1 μL of water and 1 μL of oleic acid were dropped on the artificial marble, and each contact angle was measured by the θ / 2 method.
"4" Ethanol resistance Cut artificial marble is fully immersed in ethanol (99.5) (manufactured by Wako Pure Chemical Industries, Ltd.) for 24 hours, and the artificial marble is taken out of ethanol and then air-dried for 24 hours for evaluation at a contact angle. did.
“5” Repeated cleaning resistance A 100% cotton cloth with water is applied to the test piece, 7000 reciprocating rubbing operations are performed with a load of 5 g / cm 2 , and air-dried for 24 hours after the test. The contact angle was evaluated.
「６」
表１に示した結果から、実施例１〜３の人工大理石は、硬化後の膜厚を０．３〜１．０μｍにすることで、初期の接触角と同様にエタノール浸漬後及び繰り返し洗浄試験後の接触角が撥水・撥油性を有する人工大理石となる。
加えて、得られた実施例１〜３の人工大理石は未コートの人工大理石（比較例１）と外観は変わらず、異物の混入も無く補修の必要が無い人工大理石であった。
“6”
From the results shown in Table 1, the artificial marbles of Examples 1 to 3 have a film thickness after curing of 0.3 to 1.0 μm, so that after the ethanol immersion and the repeated cleaning test as in the initial contact angle. The later contact angle becomes an artificial marble having water and oil repellency.
In addition, the obtained artificial marbles of Examples 1 to 3 were artificial marbles having the same appearance as the uncoated artificial marble (Comparative Example 1), no foreign matter mixed therein, and no need for repair.
一方、比較例２の人工大理石では高沸点の溶剤を添加していない為、拭き上げる際の塗膜の斑を低減させることができず外観を損ねる結果となった。比較例３の人工大理石では、塗膜が薄すぎる為、繰り返し洗浄試験で撥水・撥油性が低下する。
比較例４では膜厚が厚く光沢が出たことにより人工大理石の外観を損ない、生産上、基材の光沢に合わせ都度塗料を調整する必要性があること、また異物の混入が確認されたことから補修が必要であり人工大理石を生産する上で経済的に好ましくない。
比較例５では塗膜が硬化物で無いためエタノール浸漬後や繰り返し洗浄試験後に撥水・撥油性が低下し、経年使用や除菌アルコールなどのアルコール系洗浄剤の使用により、次第に撥水・撥油性能が低下していき、実使用上耐久性のある人工大理石とは言えない。
On the other hand, in the artificial marble of Comparative Example 2, since no high boiling point solvent was added, the spots on the coating film when wiping up could not be reduced, and the appearance was impaired. In the artificial marble of Comparative Example 3, since the coating film is too thin, the water repellency and oil repellency are deteriorated by repeated cleaning tests.
In Comparative Example 4, the appearance of artificial marble was impaired due to the thick film and gloss, and it was necessary to adjust the paint each time according to the gloss of the base material in production, and it was confirmed that foreign matter was mixed in. Therefore, it is not economically preferable to produce artificial marble.
In Comparative Example 5, since the coating film is not a cured product, the water repellency and oil repellency decline after immersion in ethanol and after repeated cleaning tests. The oil performance declines, and it cannot be said that it is an artificial marble that is durable in actual use.
これら実施例相当の人工大理石であるならば、人工大理石をキッチンカウンターとして適用した場合、調理で使用した油や食品の油汚れによる汚れが付きにくく、防汚性に優れるとともに、汚れを落とし易い人工大理石のキッチンカウンターを提供できる。また、実施例相当の人工大理石であるならば、模様や色調などの外観に優れた人工大理石を提供できる。 If it is an artificial marble equivalent to these examples, when the artificial marble is applied as a kitchen counter, it is difficult to get oil stains due to oil or food used in cooking, and it has excellent antifouling properties and is easy to remove dirt. Marble kitchen counter can be provided. Further, if it is an artificial marble equivalent to the embodiment, it is possible to provide an artificial marble excellent in appearance such as a pattern and a color tone.
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