JP2002003282A - Water-repellent ceramics - Google Patents
Water-repellent ceramicsInfo
- Publication number
- JP2002003282A JP2002003282A JP2000179678A JP2000179678A JP2002003282A JP 2002003282 A JP2002003282 A JP 2002003282A JP 2000179678 A JP2000179678 A JP 2000179678A JP 2000179678 A JP2000179678 A JP 2000179678A JP 2002003282 A JP2002003282 A JP 2002003282A
- Authority
- JP
- Japan
- Prior art keywords
- water
- repellent
- glaze
- zirconium oxide
- ceramic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005871 repellent Substances 0.000 title claims abstract description 42
- 239000000919 ceramic Substances 0.000 title claims abstract description 38
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 238000010304 firing Methods 0.000 claims abstract description 6
- -1 alkylsilane compound Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000010409 thin film Substances 0.000 description 8
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 8
- 229910052845 zircon Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 101100340530 Homo sapiens MTIF3 gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 102100039649 Translation initiation factor IF-3, mitochondrial Human genes 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical compound CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YZERDTREOUSUHF-UHFFFAOYSA-N pentafluorobenzoic acid Chemical compound OC(=O)C1=C(F)C(F)=C(F)C(F)=C1F YZERDTREOUSUHF-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
- C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、衛生陶器、磁器、
タイル、ガラス、食器、琺瑯等のセラミックス表面を撥
水化させた撥水性セラミックスに関するものである。TECHNICAL FIELD The present invention relates to sanitary ware, porcelain,
The present invention relates to a water-repellent ceramic having a ceramic surface such as tile, glass, tableware, and enamel made water-repellent.
【０００２】[0002]
【従来の技術】衛生陶器のようなセラミックス表面を汚
れにくくしたり、洗浄性を向上させるために、セラミッ
クス表面を撥水化することが行われている。その方法と
して、シリコン樹脂やフッ素樹脂等の撥水剤で被覆する
ものがある。しかしこの方法では、撥水剤とセラミック
スとの密着性が悪いため、洗浄等の使用回数が増加する
と撥水剤が剥離してしまい、撥水効果が長期間持続しな
いという問題がある。また、撥水効果を長時間持続させ
るために、セラミックス表面にジルコニウムブトキシド
等の金属アルコキシドやケイ酸エチル等の有機金属化合
物等を塗布、焼成して薄膜を形成した後、薄膜上に撥水
剤を塗布する方法（特開平７−３１５８８２号公報、特
開平６−５６４７６号公報、特開平５−１７０４８８号
公報）や、オキシジルコニウム塩水溶液等を塗布、焼成
して薄膜を形成した後、薄膜上に撥水剤を塗布する方法
（特開平１０−２０３８８２号公報）がある。2. Description of the Related Art In order to make a ceramic surface such as sanitary ware difficult to be stained and to improve the cleaning property, it has been practiced to make the ceramic surface water-repellent. As a method therefor, there is a method of coating with a water repellent such as a silicone resin or a fluorine resin. However, in this method, since the adhesion between the water repellent and the ceramic is poor, the water repellent is peeled off when the number of uses such as cleaning is increased, and the water repellency is not maintained for a long time. In order to maintain the water-repellent effect for a long time, a metal alkoxide such as zirconium butoxide or an organic metal compound such as ethyl silicate is applied to the ceramic surface and baked to form a thin film. (JP-A-7-315882, JP-A-6-56476, JP-A-5-170488), or by coating and baking an aqueous solution of an oxyzirconium salt to form a thin film. (Japanese Patent Application Laid-Open No. 10-203882).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら従来のセ
ラミックス表面に薄膜を形成し、薄膜上に撥水性被膜を
形成する方法では、撥水効果の持続性は向上するもの
の、薄膜形成のための塗布工程および乾燥、焼成工程が
必要となってしまい、生産性が著しく低下する。さら
に、例えば便器のような大きな陶器製品のような場合、
再度焼成するためには多大なエネルギーが必要となる。
また、薄膜を形成する過程において、便器や洗面ボー
ル、食器、タイル等の複雑な形状を有するセラミックス
製品では、液だまりが発生しやすく、膜厚が厚くなりす
ぎた部分では焼成時に薄膜が剥離してしまうという問題
もある。したがって、薄膜を薄く均一に塗布するために
は、複雑な工程管理が必要となる。However, in the conventional method of forming a thin film on a ceramic surface and forming a water-repellent film on the thin film, the durability of the water-repellent effect is improved, but the coating process for forming the thin film is performed. In addition, drying and firing steps are required, and productivity is significantly reduced. Furthermore, in the case of large pottery products such as toilets,
A large amount of energy is required for firing again.
In the process of forming a thin film, ceramic products with complicated shapes, such as toilet bowls, wash bowls, tableware, and tiles, are liable to generate liquid pools, and the thin film peels off during firing in areas where the film thickness is too large. There is also a problem that. Therefore, complicated process control is required to apply a thin film uniformly.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
に本発明は、酸化ジルコニウムを混合して焼成したセラ
ミックスの表面に撥水性被膜を形成させたことを特徴と
するものである。In order to solve the above-mentioned problems, the present invention is characterized in that a water-repellent coating is formed on the surface of ceramics mixed with zirconium oxide and fired.
【０００５】本発明によれば、特別な作業工程を設ける
必要がなく、基材のセラミックスに酸化ジルコニウムを
含有させるのみで、撥水性被膜との密着力を向上させる
ことができる。したがって、セラミックス表面の撥水性
能を長期間持続することができる。According to the present invention, it is not necessary to provide a special operation step, and the adhesion to the water-repellent coating can be improved only by adding zirconium oxide to the ceramic of the base material. Therefore, the water repellency of the ceramic surface can be maintained for a long time.
【０００６】[0006]
【発明の実施の形態】本発明は、酸化ジルコニウムを混
合して焼成したセラミックスの表面に撥水性被膜を形成
させたものである。また前記セラミックスには、陶磁器
の素地表面に施される釉薬も含まれる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a water-repellent coating is formed on the surface of ceramics mixed with zirconium oxide and fired. The ceramics also include a glaze applied to the surface of a ceramic body.
【０００７】撥水性被膜は、撥水剤の官能基と釉薬等の
セラミックス表面に現れたシラノール基とシロキサン結
合等の化学結合によって密着されている。この結合は共
有結合性であって一般に強固な結合であるが、釉薬中に
含まれるナトリウムイオンやリチウムイオン等のアルカ
リ成分が結合部位に溶出することによって弱まる傾向が
ある。これは本発明の実施に先立って行ったソーダガラ
スと石英ガラスのそれぞれに撥水処理した撥水性被膜の
密着力の比較によって推測したものである。そして鋭意
検討の結果、釉薬中に酸化ジルコニウムを配合すること
によって密着力が増加することを見出した。酸化ジルコ
ニウムが釉薬中に分散してアルカリ成分の溶出をかなり
の程度抑えることができたためであると推定する。ま
た、塩基性触媒でもある酸化ジルコニウムの高い反応性
にも起因していると考えられる。この作用は、釉薬中に
一般に添加されている結晶性のジルコン（珪酸ジルコニ
ウム）と比較しても著しく高いものであった。釉薬中に
添加する酸化ジルコニウムの結晶性粉体の平均粒度は１
〜５μm程度が好ましが、この限りではない。また酸化
ジルコニウムの混入は、釉薬の成分調整時に同時に行え
ば良く、塗布、乾燥、焼成の工程は従来と同一工程であ
る。以上より、釉薬などのセラミックスに酸化ジルコニ
ウムを配合させることによって、特別な作業工程を設け
ることなく、撥水性被膜の密着性を向上させることがで
きる。したがって、セラミックス表面の撥水性能を長期
間持続することができる。The water-repellent film is adhered to the functional group of the water-repellent agent and a silanol group appearing on the ceramic surface such as a glaze by a chemical bond such as a siloxane bond. This bond is a covalent bond and is generally a strong bond, but tends to be weakened by elution of alkali components such as sodium ions and lithium ions contained in the glaze into the bond site. This is presumed from the comparison of the adhesion between the water-repellent coatings obtained by performing the water-repellent treatment on each of the soda glass and the quartz glass prior to the implementation of the present invention. As a result of intensive studies, they have found that blending zirconium oxide in the glaze increases the adhesion. It is presumed that zirconium oxide was dispersed in the glaze and elution of the alkali component could be suppressed to a considerable extent. It is also considered that this is due to the high reactivity of zirconium oxide, which is also a basic catalyst. This effect was significantly higher than that of crystalline zircon (zirconium silicate), which is generally added to glazes. The average particle size of the crystalline powder of zirconium oxide added to the glaze is 1
The thickness is preferably about 5 μm, but is not limited to this. The zirconium oxide may be mixed at the same time as adjusting the components of the glaze, and the steps of coating, drying and firing are the same as the conventional steps. As described above, by blending zirconium oxide with ceramics such as glaze, the adhesion of the water-repellent coating can be improved without providing a special operation step. Therefore, the water repellency of the ceramic surface can be maintained for a long time.
【０００８】また本発明は、酸化ジルコニウムの含有量
が、５重量％〜１５重量％であることを特徴とするもの
である。Further, the present invention is characterized in that the content of zirconium oxide is 5% by weight to 15% by weight.
【０００９】釉薬中に酸化ジルコニウムを添加すると、
撥水性被膜との密着力が増加するのは前述のとおりであ
るが、過剰な添加は釉薬の色調に変化を生じさせる。こ
れは酸化ジルコニウムの乳濁作用によるものである。乳
濁剤としてはジルコンを用いるのが一般的であり、その
含有量は１０重量％程度である。そこで、一般の乳濁剤
であるジルコン含有釉調と同等の釉調となるような酸化
ジルコニウムの含有量を決定した。目視による観察の結
果、酸化ジルコニウム含有量が５重量％未満の場合、色
調が薄くなる。また酸化ジルコニウム含有量が１５重量
％を越えると、乳濁度が強くなる。したがって、従来の
釉薬と同等の色調にするためには、酸化ジルコニウムの
含有量は５重量％〜１５重量％が適量である。しかし、
色調にこだわらない場合や意図的に色調を変化させる場
合は、前記の含有量に限定されず、適量の酸化ジルコニ
ウムを配合することができる。When zirconium oxide is added to the glaze,
As described above, the adhesion to the water-repellent coating is increased, but excessive addition causes a change in the color tone of the glaze. This is due to the emulsion effect of zirconium oxide. Zircon is generally used as an emulsifier, and its content is about 10% by weight. Thus, the content of zirconium oxide was determined so that the glaze tone was equivalent to that of a general emulsifier containing zircon. As a result of visual observation, when the zirconium oxide content is less than 5% by weight, the color tone becomes light. On the other hand, when the zirconium oxide content exceeds 15% by weight, the turbidity increases. Therefore, in order to obtain a color tone equivalent to that of the conventional glaze, the content of zirconium oxide is appropriately from 5% by weight to 15% by weight. But,
When the color tone is not particular or the color tone is intentionally changed, the content is not limited to the above-mentioned content, and an appropriate amount of zirconium oxide can be blended.
【００１０】前記発明に使用する撥水性被膜はアルキル
シラン化合物であったり、パーフルオロアルキルシラン
化合物であることを特徴とするものである。アルキルシ
ラン化合物として、例えばトリメチルメトキシシランま
たはトリメチルエトキシシラン（以下メトキシがエトキ
シやクロロであってもよい）、ジメチルジメトキシシラ
ン、メチルトリメトキシシラン、メチルジメトキシシラ
ン、ジメチルメトキシシラン、ジフェニルジメトキシシ
ラン、フェニルトリメトキシシラン等がある。パーフル
オロアルキルシラン化合物としては、前記アルキルシラ
ン化合物のアルキル基のいくつかがフッ化炭素基に置換
されたものであり、例えば、ＣＦ３（ＣＨ２）２Ｓｉ
（ＯＣＨ３）３、ＣＦ３（ＣＦ２）５（ＣＨ２）２Ｓｉ
（ＯＣＨ３）３、ＣＦ３（ＣＦ２）７（ＣＨ２）２Ｓｉ
（ＯＣＨ３）３、ＣＦ３（ＣＦ２）７（ＣＨ２）２Ｓｉ
ＣＨ３（ＯＣＨ３）２、ＣＦ３（ＣＦ２）３（ＣＨ２）
２Ｓｉ（ＯＣＨ３）３、ＣＦ３（ＣＦ２）７（ＣＨ２）
２ＳｉＣｌ３等の炭素数が１〜２０のシラン化合部があ
る。その他、ノニオン系フッ素系界面活性剤、パーフル
オロ安息香酸、ポリジメチルシロキサン等が挙げられ
る。パーフルオロアルキルシラン化合物による撥水性被
膜は、表面エネルギーの小さいフッ化炭素基によって置
換されているため、撥水性に優れている。[0010] The water-repellent coating used in the invention is an alkylsilane compound or a perfluoroalkylsilane compound. Examples of the alkylsilane compound include trimethylmethoxysilane or trimethylethoxysilane (hereinafter, methoxy may be ethoxy or chloro), dimethyldimethoxysilane, methyltrimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane. Methoxysilane and the like. The perfluoroalkylsilane compound is a compound in which some of the alkyl groups of the alkylsilane compound are substituted with a fluorocarbon group. For example, CF3 (CH2) 2Si
(OCH3) 3, CF3 (CF2) 5 (CH2) 2Si
(OCH3) 3, CF3 (CF2) 7 (CH2) 2Si
(OCH3) 3, CF3 (CF2) 7 (CH2) 2Si
CH3 (OCH3) 2, CF3 (CF2) 3 (CH2)
2Si (OCH3) 3, CF3 (CF2) 7 (CH2)
There is a silane compound having 1 to 20 carbon atoms such as 2SiCl3. Other examples include a nonionic fluorine-based surfactant, perfluorobenzoic acid, and polydimethylsiloxane. The water-repellent coating made of a perfluoroalkylsilane compound is excellent in water repellency because it is substituted by a fluorocarbon group having a small surface energy.
【００１１】[0011]
【実施例】以下本発明の実施例について陶器性タイルを
使用して説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below using ceramic tiles.
【００１２】（実施例１）釉薬の基本成分はゼーゲル式
で（０．２ＫＮａＯ、０．３ＺｎＯ、０．４ＣａＯ）・
０．５Ａｌ２Ｏ３・２．９ＳｉＯ２とした。これに酸化
ジルコニウムを添加し、ボールミルによって２４時間混
合した。混合した釉薬をおよそ１００mm×１００mm×１
０mmの粘土質の素地の片面に施し、８０℃で１時間乾燥
した。乾燥後の釉薬の厚さは１mm程度である。その後、
６時間かけて１２００℃まで昇温し、１２００℃で１時
間温度を維持し、その後６時間かけて室温まで冷却して
タイル状の陶器平板を作製した。次に、前記陶器平板の
釉薬側をエタノールによって洗浄した後、脱脂綿によっ
て撥水剤を施し、２５℃の室内で２４時間乾燥させた。
これを試験サンプルとする。添加した酸化ジルコニウム
の配合量は、釉薬原料全体の０重量％、３重量％、５重
量％、１０重量％、１５重量％、２０重量％、３０重量
％の７種類であり、それぞれを試験サンプル１〜７とし
た。(Example 1) The basic component of the glaze is a Zegel type (0.2KNaO, 0.3ZnO, 0.4CaO).
0.5Al2O3 · 2.9SiO2. Zirconium oxide was added thereto and mixed for 24 hours by a ball mill. Approximately 100mm x 100mm x 1 mixed glaze
It was applied to one side of a 0 mm clay body and dried at 80 ° C. for 1 hour. The thickness of the glaze after drying is about 1 mm. afterwards,
The temperature was raised to 1200 ° C. over 6 hours, maintained at 1200 ° C. for 1 hour, and then cooled to room temperature over 6 hours to produce a tile-shaped ceramic flat plate. Next, after washing the glaze side of the ceramic plate with ethanol, a water repellent was applied with absorbent cotton, and the plate was dried in a room at 25 ° C. for 24 hours.
This is used as a test sample. The amount of the added zirconium oxide is seven kinds of 0% by weight, 3% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, and 30% by weight of the whole glaze raw material. 1 to 7.
【００１３】（比較例１）実施例１と同様な釉薬の基本
成分に、ジルコンを１０重量％添加して調整した釉薬を
用いて、実施例１と同様な条件で、陶器平板を作製し
た。比較例１の陶器平板には酸化ジルコニウムを含んで
いない。それ以降の撥水被膜形成過程も実施例１と同様
である。これを試験サンプル８とした。Comparative Example 1 A ceramic flat plate was produced under the same conditions as in Example 1 except that the glaze was prepared by adding 10% by weight of zircon to the basic components of the glaze as in Example 1. The ceramic flat plate of Comparative Example 1 did not contain zirconium oxide. The subsequent process of forming the water-repellent film is the same as in the first embodiment. This was designated as Test Sample 8.
【００１４】これらの試験サンプル１〜８を使用して、
以下に記す釉調観察および耐水耐久試験を行った。Using these test samples 1 to 8,
The glaze observation and the water resistance durability test described below were performed.
【００１５】［釉調観察］試験サンプル１〜７の釉薬表
面の色調を目視によって評価した。評価指標を下記に記
す。[Observation of Glaze] The color of the glaze surface of each of Test Samples 1 to 7 was visually evaluated. The evaluation indices are described below.
【００１６】○：試験サンプル８の釉調とほぼ同等の色
調である。：: The color tone is almost the same as the glaze tone of the test sample 8.
【００１７】×：試験サンプル８の釉調と比べ、乳白度
合いが薄いあるいは濃い。×: Compared to the glaze tone of test sample 8, the degree of milk whiteness is thin or dark.
【００１８】［耐水耐久試験］試験サンプル１〜８を６
０℃の温水に水没させた。試験開始５０時間後、１００
時間後、１５０時間後の接触角を測定し、接触角の変化
によって撥水性被膜の耐久性を評価した。[Water resistance / durability test]
Submerged in warm water of 0 ° C. 50 hours after the start of the test, 100
After 150 hours, the contact angle was measured, and the durability of the water-repellent coating was evaluated based on the change in the contact angle.
【００１９】釉調観察結果は（表１）に、耐水耐久試験
結果は（表２）に示す。The results of the glaze observation are shown in Table 1 and the results of the water resistance and durability test are shown in Table 2.
【００２０】[0020]
【表１】 [Table 1]
【００２１】[0021]
【表２】 [Table 2]
【００２２】（表１）、（表２）より次の事項が明らか
となる。The following items become clear from (Table 1) and (Table 2).
【００２３】（１）酸化ジルコニウムを３重量％〜１５
重量％添加した釉薬の色調は、ジルコン含有釉薬の色調
とほぼ同等である。(1) 3% by weight to 15% by weight of zirconium oxide
The color tone of the glaze added by weight% is almost the same as that of the zircon-containing glaze.
【００２４】（２）酸化ジルコニウムを添加することに
よって、陶器性セラミックスと撥水性被膜の密着力が増
す。(2) The addition of zirconium oxide increases the adhesion between the ceramic ceramic and the water-repellent coating.
【００２５】（３）酸化ジルコニウムの添加量が増加す
るに従い、陶器性セラミックスと撥水性被膜の密着力が
増加する。(3) As the amount of zirconium oxide increases, the adhesion between the ceramic ceramic and the water-repellent coating increases.
【００２６】[0026]
【発明の効果】上記実施例から明らかなように、請求項
１、２、３、４記載の発明によれば、生産性を損なうこ
となく撥水性被膜との密着力の増加した撥水性セラミッ
クスを得ることができる。また請求項５記載の発明によ
れば、従来のジルコン含有釉薬と同等な釉調を示し、か
つ従来のジルコン含有釉薬より撥水性被膜との密着力が
向上した撥水性セラミックスを得ることができる。As is clear from the above embodiments, according to the first, second, third and fourth aspects of the present invention, a water-repellent ceramic having an increased adhesion to a water-repellent coating without impairing productivity can be obtained. Obtainable. According to the fifth aspect of the present invention, it is possible to obtain a water-repellent ceramic exhibiting a glaze tone equivalent to that of a conventional zircon-containing glaze and having improved adhesion with a water-repellent coating as compared with the conventional zircon-containing glaze.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 3/18 １０４ Ｃ０９Ｋ 3/18 １０４ (72)発明者 山冨 光代 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 生川 直子 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 4D075 CA36 DA23 DB14 DC38 EB42 4H020 BA31 BA36 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09K 3/18 104 C09K 3/18 104 (72) Inventor Mitsuyo Yamatomi 1006 Kazuma Kadoma, Kadoma City, Osaka Matsushita Inside Electric Industrial Co., Ltd. (72) Inventor Naoko Ikukawa 1006, Ojimon Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. F-term (reference) 4D075 CA36 DA23 DB14 DC38 EB42 4H020 BA31 BA36
Claims (5)
ラミックスの表面に撥水性被膜を形成させたことを特徴
とする撥水性セラミックス。1. A water-repellent ceramic, wherein a water-repellent coating is formed on the surface of a ceramic baked by mixing zirconium oxide.
塗布し、焼成して成る陶磁器表面に、撥水性被膜を形成
させたことを特徴とする請求項１記載の撥水性セラミッ
クス。2. The water-repellent ceramic according to claim 1, wherein a glaze mixed with zirconium oxide is applied, and a water-repellent coating is formed on a ceramic surface formed by firing.
ることを特徴とする請求項１または２記載の撥水性セラ
ミックス。3. The water-repellent ceramic according to claim 1, wherein the water-repellent coating is an alkylsilane compound.
ン化合物であることを特徴とする請求項１または２記載
の撥水性セラミックス。4. The water-repellent ceramic according to claim 1, wherein the water-repellent coating is a perfluoroalkylsilane compound.
〜１５重量％であることを特徴とする請求項１ないし４
のいずれか１項記載の撥水性セラミックス。5. The content of zirconium oxide is 5% by weight.
5 to 15% by weight.
The water-repellent ceramic according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000179678A JP2002003282A (en) | 2000-06-15 | 2000-06-15 | Water-repellent ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000179678A JP2002003282A (en) | 2000-06-15 | 2000-06-15 | Water-repellent ceramics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002003282A true JP2002003282A (en) | 2002-01-09 |
Family
ID=18680906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000179678A Pending JP2002003282A (en) | 2000-06-15 | 2000-06-15 | Water-repellent ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002003282A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7375972B1 (en) * | 2023-03-31 | 2023-11-08 | Toto株式会社 | Ceramic with excellent appearance and stain resistance |
| JP7375973B1 (en) * | 2023-03-31 | 2023-11-08 | Toto株式会社 | Ceramic with excellent appearance and stain resistance |
| JP7375971B1 (en) * | 2023-03-31 | 2023-11-08 | Toto株式会社 | Ceramic with excellent appearance and stain resistance |
| JP7375974B1 (en) * | 2023-03-31 | 2023-11-08 | Toto株式会社 | Ceramic with excellent appearance and stain resistance |
-
2000
- 2000-06-15 JP JP2000179678A patent/JP2002003282A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7375972B1 (en) * | 2023-03-31 | 2023-11-08 | Toto株式会社 | Ceramic with excellent appearance and stain resistance |
| JP7375973B1 (en) * | 2023-03-31 | 2023-11-08 | Toto株式会社 | Ceramic with excellent appearance and stain resistance |
| JP7375971B1 (en) * | 2023-03-31 | 2023-11-08 | Toto株式会社 | Ceramic with excellent appearance and stain resistance |
| JP7375974B1 (en) * | 2023-03-31 | 2023-11-08 | Toto株式会社 | Ceramic with excellent appearance and stain resistance |
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