JP2015110313A - Hydrophilic coating-formed article, hydrophilic coating-forming coat liquid and method for producing hydrophilic coating-formed article - Google Patents
Hydrophilic coating-formed article, hydrophilic coating-forming coat liquid and method for producing hydrophilic coating-formed article Download PDFInfo
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- JP2015110313A JP2015110313A JP2014013766A JP2014013766A JP2015110313A JP 2015110313 A JP2015110313 A JP 2015110313A JP 2014013766 A JP2014013766 A JP 2014013766A JP 2014013766 A JP2014013766 A JP 2014013766A JP 2015110313 A JP2015110313 A JP 2015110313A
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- Prior art keywords
- hydrophilic film
- coating
- forming
- film
- oxide
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- 239000007788 liquid Substances 0.000 title claims description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 25
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 63
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000005595 acetylacetonate group Chemical group 0.000 claims abstract description 17
- 125000000962 organic group Chemical group 0.000 claims abstract description 14
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical group CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 125000003545 alkoxy group Chemical group 0.000 claims description 12
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- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
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- 239000003054 catalyst Substances 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
本発明は、親水性被膜形成物品、親水性被膜形成用塗布液及び親水性被膜形成物品の製造方法に関する。 The present invention relates to a hydrophilic film-forming article, a coating liquid for forming a hydrophilic film, and a method for producing a hydrophilic film-forming article.
最近、ガラス板等の基板に防曇性等の特性を付与するために、基材の表面に親水性の被膜を形成する試みが種々行われている。その方法の一つとして、基材表面への界面活性剤の塗布（特許文献１参照）や、親水性・吸水性を有する樹脂を主体とするコーティング等が行われている（特許文献２参照）が、これらは耐久性等に問題があり、長期に渡って使用される物品には適していない。 In recent years, various attempts have been made to form a hydrophilic film on the surface of a base material in order to impart characteristics such as antifogging properties to a substrate such as a glass plate. As one of the methods, application of a surfactant to the surface of a substrate (see Patent Document 1), coating mainly composed of a hydrophilic / water-absorbing resin, etc. are performed (see Patent Document 2). However, these have problems in durability and the like, and are not suitable for articles used for a long time.
そこで、耐久性に優れた親水性被膜の形成方法として、金属アルコキシドと非反応性酸化物超微粒子を含むコロイド溶液を強酸性触媒の存在下で混合することにより調製した塗布液を基板に塗布して親水性塗膜を形成する方法が開示されている。
上記方法等により得られた非反応性酸化物超微粒子を含む親水性被膜は、水分を補給することにより長期間に渡って水膜を保持することができる。
Therefore, as a method for forming a hydrophilic coating having excellent durability, a coating solution prepared by mixing a colloid solution containing metal alkoxide and non-reactive oxide ultrafine particles in the presence of a strong acidic catalyst is applied to a substrate. A method for forming a hydrophilic coating film is disclosed.
The hydrophilic film containing the non-reactive oxide ultrafine particles obtained by the above method can retain the water film for a long period of time by supplying water.
しかし、上記親水性被膜にリンスやコンディショナーが接触すると、撥水化してしまうという問題があった。これは、非反応性酸化物超微粒子を含む親水性被膜は、大部分がシリカから構成されているため、水や水溶液との界面では、上記親水性被膜は負に帯電しており、そのため、リンスやコンディショナーに含まれる陽イオン界面活性剤が強力に吸着し、撥水化してしまうためと考えられる。このようにして、一旦撥水化した被膜は、通常の洗剤を使用して洗浄しても、陽イオン界面活性剤を除去することが難しく、防汚性という観点から改良が望まれていた。 However, when a rinse or a conditioner comes into contact with the hydrophilic coating, there is a problem that it becomes water repellent. This is because the hydrophilic coating containing non-reactive oxide ultrafine particles is mostly composed of silica, so the hydrophilic coating is negatively charged at the interface with water or an aqueous solution. This is probably because the cationic surfactant contained in the rinse or conditioner is strongly adsorbed and water-repellent. Thus, once the water-repellent coating is washed using a normal detergent, it is difficult to remove the cationic surfactant, and improvement has been desired from the viewpoint of antifouling properties.
上記親水性被膜に対して陽イオン界面活性剤を吸着しにくくするためには、上記親水性被膜を水や水溶液との界面において負に帯電しにくくする必要があり、そのためには、親水性被膜の等電位を中性に近づけることが有効であると考えられる。親水性被膜の等電位を中性に近づける方法としては、被膜中に等電位が８〜９のアルミナを含有させる方法が考えられる。 In order to make it difficult to adsorb the cationic surfactant to the hydrophilic coating, it is necessary to make the hydrophilic coating difficult to be negatively charged at the interface with water or an aqueous solution. It is considered that it is effective to make the equipotential of N2 close to neutral. As a method of bringing the equipotential of the hydrophilic coating close to neutral, a method of containing alumina having an equipotential of 8 to 9 in the coating is conceivable.
特許文献３には、金属アルコキシドと非反応性酸化物超微粒子を強酸性触媒の存在下で合成してなるゾル溶液を基材表面に塗布した後、１５０℃〜６００℃の温度で加熱処理することにより基材表面に親水性・防曇性を有する複合酸化物被膜を形成することを特徴とする防曇性被膜形成基材の製造方法が開示されており、明細書中には、アルミニウム源として、アルミニウムブトキシド等のアルミニウムアルコキシドを使用してもよいことが記載されている。 In Patent Document 3, a sol solution obtained by synthesizing a metal alkoxide and non-reactive oxide ultrafine particles in the presence of a strong acidic catalyst is applied to the surface of a substrate, and then heat-treated at a temperature of 150 ° C. to 600 ° C. A method for producing an antifogging film-forming substrate is disclosed, characterized in that a composite oxide film having hydrophilicity and antifogging property is formed on the surface of the substrate. As mentioned, aluminum alkoxide such as aluminum butoxide may be used.
また、特許文献４には、非晶質性の金属酸化物を形成する金属酸化物ゾル溶液または／および金属酸化物微粒子分散ゾルを添加した溶液からなるシリカ−アルミナ系複合ゾル溶液を、基板に塗布し、焼成することでシリカ−アルミナ系複合酸化物膜を成膜し、該膜付き基板を加温した後、純水の熱水に浸漬処理をすることを特徴とする防曇性被膜の製造方法が開示されている。 Further, in Patent Document 4, a silica-alumina composite sol solution composed of a metal oxide sol solution for forming an amorphous metal oxide or / and a solution to which a metal oxide fine particle dispersed sol is added is applied to a substrate. A silica-alumina composite oxide film is formed by coating and baking, and after heating the substrate with the film, it is immersed in hot water of pure water. A manufacturing method is disclosed.
特許文献５には、有機金属化合物と金属酸化物微粒子を含有する表面処理材が記載されており、金属アルコキシドとして、アルミニウムのアルコキシドが記載されており、具体的には、トリブトキシアルミニウム等のアルミニウムに３個のアルコキシドが結合した構成のアルミニウムアルコキシドが記載されている。 Patent Document 5 describes a surface treatment material containing an organometallic compound and metal oxide fine particles, and describes an alkoxide of aluminum as the metal alkoxide, specifically, aluminum such as tributoxyaluminum. Describes an aluminum alkoxide having a structure in which three alkoxides are bonded to each other.
特許文献３、５に記載の発明では、アルミニウム源として、トリイソプロポキシアルミニウム、トリブトキシアルミニウム等が記載されているが、アルミニウムに３個のアルコキシドが結合した構成のアルミニウムアルコキシドは、加水分解の速度等の関係で、実際には、親水性被膜を形成するのに適した塗布液を調製するのが非常に難しいという問題があった。
また、特許文献３、５に記載の発明では、シリカとアルミナの含有比率について記載されておらず、シリカとアルミナの含有比率を特定範囲にすることにより、汚れ除去性が改善されるとの記載は全くなかった。
In the inventions described in Patent Documents 3 and 5, triisopropoxyaluminum, tributoxyaluminum, and the like are described as the aluminum source, but the aluminum alkoxide having a structure in which three alkoxides are bonded to aluminum has a hydrolysis rate. Therefore, in practice, there is a problem that it is very difficult to prepare a coating solution suitable for forming a hydrophilic film.
In addition, in the inventions described in Patent Documents 3 and 5, the content ratio of silica and alumina is not described, and it is described that the soil removability is improved by making the content ratio of silica and alumina in a specific range. There was no.
特許文献４では、シリカ−アルミナ系複合酸化物膜を成膜すると記載されているが、実施例では、アルミナは酸化物の層中に分散する微粒子として添加されている。微粒子が分散した被膜では、微粒子はかなりの部分が酸化物の層中に埋まった状態であり、酸化物の層の表面積の方が大きいため、微粒子としてアルミナを使用しても防汚性を改善することは難しかった。 In Patent Document 4, it is described that a silica-alumina-based composite oxide film is formed, but in the examples, alumina is added as fine particles dispersed in the oxide layer. In the coating film in which the fine particles are dispersed, the fine particles are embedded in the oxide layer, and the surface area of the oxide layer is larger, so even if alumina is used as the fine particles, the antifouling property is improved. It was difficult to do.
本発明者らは、上記課題に鑑み、種々検討した結果、親水性被膜を構成する金属酸化物の層を形成する際、シリカとアルミナの含有比率を特定範囲に設定し、特定構造のアルミニウム酸化物前駆体を塗布液に含有させることにより、安定な塗布液を調製することができ、陽イオン界面活性剤等が吸着しにくい防汚性能（汚れ除去性）に優れる親水性被膜を形成することができ、これにより、該親水性被膜を有する親水性被膜形成物品、該親水性被膜形成物品の製造に用いられる親水性被膜形成用塗布液、及び、該親水性被膜形成用塗布液を用いた親水性被膜形成物品の製造方法を提供することができることを見出し、本発明に到達した。 As a result of various investigations in view of the above problems, the present inventors set the content ratio of silica and alumina in a specific range when forming a metal oxide layer constituting a hydrophilic film, and formed aluminum oxide with a specific structure. A stable coating solution can be prepared by adding a precursor to the coating solution, and a hydrophilic coating excellent in antifouling performance (stain removal property) that is difficult to adsorb cationic surfactants and the like is formed. Thus, a hydrophilic film-forming article having the hydrophilic film, a hydrophilic film-forming coating liquid used for the production of the hydrophilic film-forming article, and the hydrophilic film-forming coating liquid were used. The inventors have found that a method for producing a hydrophilic film-formed article can be provided, and have reached the present invention.
すなわち、本発明の親水性被膜形成物品は、
基材と、該基材の表面に酸化物微粒子を分散して金属酸化物の層で保持した被膜と、を有する親水性被膜形成物品であり、上記金属酸化物の層は、下記一般式［１］で表されるケイ素酸化物の少なくとも１種、及び、下記一般式［２］で表されるアルミニウム酸化物の少なくとも１種を含み、上記ケイ素酸化物と上記アルミニウム酸化物のモル比は、ケイ素酸化物：アルミニウム酸化物＝２０：８０〜８０：２０であることを特徴とする。
（Ｒ１）ａＳｉＯｂ ［１］
（式［１］中、Ｒ１は１価の有機基であり、ａは０〜３．５、ｂは０．５〜２である。）
（Ｒ２）ｃＡｌＯｄ ［２］
（式［２］中、Ｒ２はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、ｃは０〜２、ｄは０．５〜１．５である。）
That is, the hydrophilic film-forming article of the present invention is
A hydrophilic film-forming article having a base material and a film in which oxide fine particles are dispersed and held on the surface of the base material, and the metal oxide layer has the following general formula [ 1] and at least one kind of aluminum oxide represented by the following general formula [2], and the molar ratio of the silicon oxide to the aluminum oxide is as follows: Silicon oxide: aluminum oxide = 20: 80 to 80:20.
(R 1 ) a SiO b [1]
(In the formula [1], R 1 is a monovalent organic group, a is 0 to 3.5, and b is 0.5 to 2.)
(R 2 ) c AlO d [2]
(In the formula [2], R 2 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, c is 0 to 2, and d is 0.5 to 1.5.)
本発明の親水性被膜形成物品においては、上記ケイ素酸化物がＳｉＯ２であり、上記アルミニウム酸化物がＡｌＯ１．５であることが好ましい。 In the hydrophilic film-forming article of the present invention, the silicon oxide is preferably SiO 2 and the aluminum oxide is preferably AlO 1.5 .
本発明の親水性被膜形成物品においては、上記金属酸化物の層は、さらに、下記一般式［３］で表されるジルコニウム酸化物を含むことが好ましい。
（Ｒ３）ｅＺｒＯｆ ［３］
（式［３］中、Ｒ３は１価の有機基であり、ｅは０〜３．５、ｆは０．５〜２である。）
In the hydrophilic film-forming article of the present invention, the metal oxide layer preferably further contains a zirconium oxide represented by the following general formula [3].
(R 3 ) e ZrO f [3]
(In Formula [3], R 3 is a monovalent organic group, e is 0 to 3.5, and f is 0.5 to 2.)
本発明の親水性被膜形成物品においては、上記ジルコニウム酸化物がＺｒＯ２であることが好ましい。 In the hydrophilic film-forming article of the present invention, the zirconium oxide is preferably ZrO 2 .
本発明の親水性被膜形成物品においては、上記酸化物微粒子が、ＳｉＯ２、Ａｌ２Ｏ３及びＺｒＯ２からなる群から選ばれる少なくとも１種であることが好ましい。 In the hydrophilic film-forming article of the present invention, the oxide fine particles are preferably at least one selected from the group consisting of SiO 2 , Al 2 O 3 and ZrO 2 .
本発明の親水性被膜形成物品において、上記親水性の被膜を保護するための保護紙が、上記親水性の被膜を覆うように親水性被膜形成物品の表面に貼付されていることが好ましい。 In the hydrophilic film-forming article of the present invention, it is preferable that a protective paper for protecting the hydrophilic film is attached to the surface of the hydrophilic film-forming article so as to cover the hydrophilic film.
本発明の親水性被膜形成物品において、上記保護紙は、粘着成分として澱粉化合物を含むことが好ましく、さらに粘着成分中に親水剤及び界面活性剤から選ばれる少なくとも１種を含むことが好ましい。 In the hydrophilic film-forming article of the present invention, the protective paper preferably contains a starch compound as an adhesive component, and preferably contains at least one selected from a hydrophilic agent and a surfactant in the adhesive component.
本発明の親水性被膜形成用塗布液は、少なくとも、酸化物微粒子を含むコロイド溶液、下記一般式［４］で表されるケイ素酸化物前駆体、下記一般式［５］で表されるアルミニウム酸化物前駆体、酸、水及び溶媒を混合することにより調製された親水性被膜形成用塗布液であり、
上記酸化物微粒子、上記ケイ素酸化物前駆体の固形分、及び、上記アルミニウム酸化物前駆体の固形分の総量１００質量％に対して、上記酸化物微粒子の含有量が２０〜６０質量％であり、該酸化物微粒子４０質量部に対して、上記ケイ素酸化物前駆体が酸化物換算で６〜４０質量部、上記アルミニウム酸化物前駆体が酸化物換算で５〜３０質量部であることを特徴とする。
（Ｒ４）ｇＳｉ（Ｘ１）４−ｇ ［４］
（式［４］中、Ｒ４は１価の有機基であり、Ｘ１はアルコキシル基又はハロゲン元素であり、ｇは０〜３の整数である。）
（Ｒ５）ｈＡｌ（Ｘ２）３−ｈ ［５］
（式［５］中、Ｒ５はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、Ｘ２はアルコキシル基又はハロゲン元素であり、ｈは１〜３の整数である。）
The coating liquid for forming a hydrophilic film of the present invention comprises at least a colloidal solution containing fine oxide particles, a silicon oxide precursor represented by the following general formula [4], and an aluminum oxide represented by the following general formula [5]. A coating solution for forming a hydrophilic film, prepared by mixing a precursor of a product, an acid, water and a solvent,
The content of the oxide fine particles is 20 to 60% by mass with respect to 100% by mass of the solid content of the oxide fine particles, the solid content of the silicon oxide precursor, and the solid content of the aluminum oxide precursor. The silicon oxide precursor is 6 to 40 parts by mass in terms of oxide and the aluminum oxide precursor is 5 to 30 parts by mass in terms of oxide with respect to 40 parts by mass of the oxide fine particles. And
(R 4 ) g Si (X 1 ) 4-g [4]
(In the formula [4], R 4 is a monovalent organic group, X 1 is an alkoxyl group or a halogen element, and g is an integer of 0 to 3.)
(R 5 ) h Al (X 2 ) 3-h [5]
(In the formula [5], R 5 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, X 2 is an alkoxyl group or a halogen element, and h is an integer of 1 to 3. )
本発明の親水性被膜形成用塗布液においては、上記一般式［４］で表されるケイ素酸化物前駆体が、Ｓｉ（Ｘ１）４であり、上記一般式［５］で表されるアルミニウム酸化物前駆体が、Ｒ５Ａｌ（Ｘ２）２であることが好ましい。 In the coating liquid for forming a hydrophilic film of the present invention, the silicon oxide precursor represented by the general formula [4] is Si (X 1 ) 4 and the aluminum represented by the general formula [5]. It is preferable that the oxide precursor is R 5 Al (X 2 ) 2 .
本発明の親水性被膜形成用塗布液においては、上記親水性被膜形成用塗布液は、さらに、
下記一般式［６］及び［７］で表される化合物からなる群から選ばれる少なくとも１種のジルコニウム酸化物前駆体が添加されていることが好ましい。
ＺｒＯＹ２ ［６］
（式［６］中、ＹはＣｌ−、ＮＯ３ −又はＣＨ３ＣＯＯ−）
（Ｒ６）ｉＺｒ（Ｚ）４−ｉ ［７］
（式［７］中、Ｒ６はアセチルアセトナート基、Ｚは炭素数２〜４のアルコキシル基又はハロゲン、ｉは０〜４の整数）
In the hydrophilic film-forming coating solution of the present invention, the hydrophilic film-forming coating solution further comprises:
It is preferable that at least one zirconium oxide precursor selected from the group consisting of compounds represented by the following general formulas [6] and [7] is added.
ZrOY 2 [6]
(In the formula [6], Y is Cl − , NO 3 — or CH 3 COO − )
(R 6 ) i Zr (Z) 4-i [7]
(In formula [7], R 6 is an acetylacetonate group, Z is an alkoxyl group having 2 to 4 carbon atoms or halogen, and i is an integer of 0 to 4)
本発明の親水性被膜形成用塗布液においては、上記ジルコニウム酸化物前駆体が、上記一般式［６］で表される化合物、及び、上記一般式［７］のｉが０であるＺｒ（Ｚ）４で表される化合物からなる群から選ばれる少なくとも１種であることが好ましい。 In the coating liquid for forming a hydrophilic film of the present invention, the zirconium oxide precursor is a compound represented by the general formula [6], and Zr (Z in which i in the general formula [7] is 0. It is preferably at least one selected from the group consisting of compounds represented by 4 .
本発明の親水性被膜形成用塗布液においては、上記酸化物微粒子が、ＳｉＯ２、Ａｌ２Ｏ３及びＺｒＯ２からなる群から選ばれる少なくとも１種であることが好ましい。 In the coating liquid for forming a hydrophilic film of the present invention, the oxide fine particles are preferably at least one selected from the group consisting of SiO 2 , Al 2 O 3 and ZrO 2 .
本発明の親水性被膜形成用塗布液においては、親水性被膜形成用塗布液を調製する際に添加する水の量が、該塗布液の固形分の総量１００質量％に対して、１０〜３００質量％であることが好ましい。 In the coating liquid for forming a hydrophilic film of the present invention, the amount of water added when preparing the coating liquid for forming a hydrophilic film is 10 to 300 with respect to 100% by mass of the total solid content of the coating liquid. It is preferable that it is mass%.
本発明の親水性被膜形成用塗布液においては、さらに、三ハロゲン化アルミニウムが、固形分の総量１００質量％に対して、０．００１〜１質量％添加されていてもよい。 In the coating liquid for forming a hydrophilic film of the present invention, 0.001 to 1% by mass of aluminum trihalide may be further added to 100% by mass of the total solid content.
本発明の親水性被膜形成物品の製造方法は、上述した本発明の親水性被膜形成物品の製造方法であって、基材を準備する基材準備工程、上述した組成の親水性被膜形成用塗布液を準備する塗布液準備工程、上記基材の表面に上記塗布液を塗布して塗膜を形成する塗布工程、及び、塗布工程後の基材を１００〜４００℃で加熱して塗膜を硬化させて、該基材表面に親水性の被膜を形成する硬化工程を有することを特徴とする。 The method for producing a hydrophilic film-forming article of the present invention is the above-described method for producing the hydrophilic film-forming article of the present invention, wherein a base material preparing step for preparing a base material, and a coating for forming a hydrophilic film with the above-described composition are provided. A coating solution preparation step for preparing a liquid, a coating step for coating the surface of the substrate with the coating solution to form a coating film, and a substrate after the coating step is heated at 100 to 400 ° C. It has the hardening process which hardens | cures and forms a hydrophilic film on this base-material surface, It is characterized by the above-mentioned.
本発明の親水性被膜形成物品の製造方法においては、塗布工程後の塗膜表面、及び／又は、硬化工程後の被膜表面に対して、オゾン処理を施すことが好ましい。 In the manufacturing method of the hydrophilic film formation article of this invention, it is preferable to perform ozone treatment with respect to the coating-film surface after an application | coating process, and / or the coating-film surface after a hardening process.
本発明の親水性被膜形成物品の製造方法では、さらに、上記親水性の被膜を保護するための保護紙を、上記親水性の被膜を覆うように親水性被膜形成物品の表面に貼付する保護紙貼付工程を含むことが好ましい。 In the method for producing a hydrophilic film-formed article of the present invention, the protective paper for further protecting the hydrophilic film is applied to the surface of the hydrophilic film-formed article so as to cover the hydrophilic film. It is preferable to include an attaching step.
本発明の親水性被膜形成物品では、陽イオン界面活性剤等が吸着しにくい防汚性能（汚れ除去性）に優れたものとすることができる。 The hydrophilic film-forming article of the present invention can be excellent in antifouling performance (dirt removal property) in which a cationic surfactant or the like hardly adsorbs.
本発明の親水性被膜形成用塗布液では、上記したアルミニウム酸化物前駆体を上記割合で用いることにより、長期間に渡って安定な塗布液を調製することができ、該塗布液を基材に塗布し塗膜を硬化させることにより、上述した本発明の防汚性能（汚れ除去性）等に優れる親水性被膜形成物品を製造することができる。 In the coating liquid for forming a hydrophilic film of the present invention, a coating liquid that is stable over a long period of time can be prepared by using the above-described aluminum oxide precursor in the above proportion. By applying and curing the coating film, it is possible to produce a hydrophilic film-formed article having excellent antifouling performance (stain removal property) according to the present invention.
以下、本発明の実施形態について具体的に説明する。しかしながら、本発明は、以下の実施形態に限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。 Hereinafter, embodiments of the present invention will be specifically described. However, the present invention is not limited to the following embodiments, and can be applied with appropriate modifications without departing from the scope of the present invention.
［親水性被膜形成物品］
以下、本発明の親水性被膜形成物品について説明する。
本発明の親水性被膜形成物品は、基材と、該基材の表面に酸化物微粒子を分散して金属酸化物の層で保持した被膜と、を有する親水性被膜形成物品であり、
上記金属酸化物の層は、
下記一般式［１］で表されるケイ素酸化物の少なくとも１種、及び、
下記一般式［２］で表されるアルミニウム酸化物の少なくとも１種を含み、
上記ケイ素酸化物と上記アルミニウム酸化物のモル比は、ケイ素酸化物：アルミニウム酸化物＝２０：８０〜８０：２０であることを特徴とする。
（Ｒ１）ａＳｉＯｂ ［１］
（式［１］中、Ｒ１は１価の有機基であり、ａは０〜３．５、ｂは０．５〜２である。）
（Ｒ２）ｃＡｌＯｄ ［２］
（式［２］中、Ｒ２はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、ｃは０〜２、ｄは０．５〜１．５である。）
[Hydrophilic film-formed article]
Hereinafter, the hydrophilic film-formed article of the present invention will be described.
The hydrophilic film-forming article of the present invention is a hydrophilic film-forming article having a base material and a film in which oxide fine particles are dispersed on the surface of the base material and held by a metal oxide layer,
The metal oxide layer is
At least one silicon oxide represented by the following general formula [1], and
Including at least one aluminum oxide represented by the following general formula [2],
A molar ratio of the silicon oxide to the aluminum oxide is silicon oxide: aluminum oxide = 20: 80 to 80:20.
(R 1 ) a SiO b [1]
(In the formula [1], R 1 is a monovalent organic group, a is 0 to 3.5, and b is 0.5 to 2.)
(R 2 ) c AlO d [2]
(In the formula [2], R 2 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, c is 0 to 2, and d is 0.5 to 1.5.)
本発明の親水性被膜形成物品は、基材と、該基材の表面に酸化物微粒子を分散して金属酸化物の層で保持した被膜とを有する親水性被膜形成物品である。
本発明で用いる基材は、親水性、防曇性、汚れ除去性を期待されるものであれば、特に限定されるものではないが、例えば、ガラス板、鏡、反射板、保護板、タイル、食器、金属、金属メッキされた物品、セラミックス等が挙げられる。基材としては、防曇性を期待されるガラス板、鏡等が好ましい。
The hydrophilic film-forming article of the present invention is a hydrophilic film-forming article having a base material and a film in which fine oxide particles are dispersed and held by a metal oxide layer on the surface of the base material.
The substrate used in the present invention is not particularly limited as long as hydrophilicity, antifogging property, and dirt removal property are expected. For example, a glass plate, a mirror, a reflecting plate, a protective plate, a tile Tableware, metal, metal-plated articles, ceramics and the like. As the base material, a glass plate, a mirror or the like that is expected to have antifogging properties is preferable.
上記基材の表面に設けられた親水性の被膜は、分散された酸化物微粒子が金属酸化物の層で保持されたものである。
上記金属酸化物の層は、下記一般式［１］で表されるケイ素酸化物の少なくとも１種、及び、下記一般式［２］で表されるアルミニウム酸化物の少なくとも１種を含み、
上記ケイ素酸化物と上記アルミニウム酸化物のモル比は、ケイ素酸化物：アルミニウム酸化物＝２０：８０〜８０：２０であることを特徴とする。
（Ｒ１）ａＳｉＯｂ ［１］
（式［１］中、Ｒ１は１価の有機基であり、ａは０〜３．５、ｂは０．５〜２である。）
（Ｒ２）ｃＡｌＯｄ ［２］
（式［２］中、Ｒ２はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、ｃは０〜２、ｄは０．５〜１．５である。）
The hydrophilic coating provided on the surface of the substrate is one in which dispersed oxide fine particles are held by a metal oxide layer.
The metal oxide layer includes at least one silicon oxide represented by the following general formula [1] and at least one aluminum oxide represented by the following general formula [2].
A molar ratio of the silicon oxide to the aluminum oxide is silicon oxide: aluminum oxide = 20: 80 to 80:20.
(R 1 ) a SiO b [1]
(In the formula [1], R 1 is a monovalent organic group, a is 0 to 3.5, and b is 0.5 to 2.)
(R 2 ) c AlO d [2]
(In the formula [2], R 2 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, c is 0 to 2, and d is 0.5 to 1.5.)
上記金属酸化物の層は、上記一般式［１］で表されるケイ素酸化物を含む。上記一般式［１］で表されるケイ素酸化物において、Ｒ１で表される１価の有機基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｔｅｒｔ−ブチル基、３−メルカプトプロピル基、３−アミノプロピル基等が挙げられる。
一般式［１］で表されるケイ素酸化物の具体例としては、例えば、ＳｉＯ２、（ＣＨ３）ＳｉＯ１．５、（ＣＨ３）２ＳｉＯ、ＳＨ（ＣＨ２）３ＳｉＯ１．５、ＮＨ２（ＣＨ２）３ＳｉＯ１．５等が挙げられる。
The metal oxide layer includes a silicon oxide represented by the general formula [1]. In the silicon oxide represented by the general formula [1], examples of the monovalent organic group represented by R 1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, 3- A mercaptopropyl group, a 3-aminopropyl group, etc. are mentioned.
Specific examples of the silicon oxide represented by the general formula [1] include, for example, SiO 2 , (CH 3 ) SiO 1.5 , (CH 3 ) 2 SiO, SH (CH 2 ) 3 SiO 1.5 , NH 2 (CH 2) 3 SiO 1.5 , and the like.
（ＣＨ３）ＳｉＯ１．５は、上記金属酸化物の層中で、Ｓｉ原子に１個のメチル基が結合するとともに、他の３つの結合手は、Ｓｉ−Ｏ結合となっていることを意味している。
ＳｉＯ１．５と表示されているのは、Ｓｉに結合した３個の酸素（Ｏ）は、他の原子（Ｓｉ等）と共有しているので、１つの結合について、０．５で計算しており、３個の酸素の合計を１．５としているのである。以下、Ａｌ、Ｚｒについても同様の方法で計算した結果を、一般式［２］、一般式［３］として記載している。
従って、一般式［１］において、ｂとしては、０．５、１．０、１．５、２が挙げられ、ａとしては、０、１、２、３等が挙げられるが、その他の数値であってもよい。
(CH 3 ) SiO 1.5 indicates that in the metal oxide layer, one methyl group is bonded to the Si atom, and the other three bonds are Si—O bonds. I mean.
The reason why SiO 1.5 is displayed is that three oxygens (O) bonded to Si are shared with other atoms (Si, etc.), so one bond is calculated by 0.5. The total of the three oxygens is 1.5. Hereinafter, the results calculated by the same method for Al and Zr are described as general formula [2] and general formula [3].
Therefore, in the general formula [1], examples of b include 0.5, 1.0, 1.5, and 2. Examples of a include 0, 1, 2, 3, and the like. It may be.
上記金属酸化物の層は、一般式［２］で表されるアルミニウム酸化物を含む。Ｒ２は、アセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、アセチルアセトナート基が１個Ａｌ原子に結合していてもよく、エチルアセトアセテート基が１個Ａｌ原子に結合していてもよく、アセチルアセトナート基とエチルアセトアセテート基が１個ずつＡｌ原子に結合していてもよく、アセチルアセトナート基が２個Ａｌ原子に結合していてもよく、エチルアセトアセテート基が２個Ａｌ原子に結合していてもよい。ｃとしては、０、１、２が挙げられ、ｄとしては、０．５、１．０、１．５が挙げられるが、他の数値であってもよい。
一般式［２］で表されるアルミニウム酸化物の具体例としては、例えば、ＡｌＯ１．５、（Ｃ２Ｈ５Ｏ（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）ＡｌＯ、（ＣＨ３（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）ＡｌＯ、（ＣＨ３（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）２ＡｌＯ０．５、（ＣＨ３（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）（Ｃ２Ｈ５Ｏ（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）ＡｌＯ０．５等が挙げられる。
上記ケイ素酸化物のなかでは、ＳｉＯ２、（ＣＨ３）ＳｉＯ１．５が好ましく、ＳｉＯ２が特に好ましい。上記アルミニウム酸化物のなかでは、ＡｌＯ１．５（Ａｌ２Ｏ３）、（Ｃ２Ｈ５Ｏ（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）ＡｌＯ、（ＣＨ３（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）ＡｌＯ、（ＣＨ３（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）２ＡｌＯ０．５が好ましく、ＡｌＯ１．５（Ａｌ２Ｏ３）が特に好ましい。
The metal oxide layer includes an aluminum oxide represented by the general formula [2]. R 2 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, and the acetylacetonate group may be bonded to one Al atom, and the ethylacetoacetate group is one Al atom. May be bonded, one acetylacetonate group and one ethylacetoacetate group may be bonded to an Al atom, two acetylacetonate groups may be bonded to an Al atom, Two groups may be bonded to an Al atom. Examples of c include 0, 1, and 2. Examples of d include 0.5, 1.0, and 1.5, but other numerical values may be used.
Specific examples of the aluminum oxide represented by the general formula [2] include, for example, AlO 1.5 , (C 2 H 5 O (C═O) CH═C (CH 3 ) —O—) AlO, ( CH 3 (C═O) CH═C (CH 3 ) —O—) AlO, (CH 3 (C═O) CH═C (CH 3 ) —O—) 2 AlO 0.5 , (CH 3 (C ═O) CH═C (CH 3 ) —O—) (C 2 H 5 O (C═O) CH═C (CH 3 ) —O—) AlO 0.5 and the like.
Among the silicon oxides, SiO 2 and (CH 3 ) SiO 1.5 are preferable, and SiO 2 is particularly preferable. Among the aluminum oxides, AlO 1.5 (Al 2 O 3 ), (C 2 H 5 O (C═O) CH═C (CH 3 ) —O—) AlO, (CH 3 (C═O ) CH═C (CH 3 ) —O—) AlO, (CH 3 (C═O) CH═C (CH 3 ) —O—) 2 AlO 0.5 are preferred, AlO 1.5 (Al 2 O 3 Is particularly preferred.
上記金属酸化物の層に含まれるケイ素酸化物とアルミニウム酸化物のモル比は、ケイ素酸化物：アルミニウム酸化物＝２０：８０〜８０：２０である。すなわち、ケイ素酸化物とアルミニウム酸化物との合計量に対し、アルミニウム酸化物の割合は、２０〜８０モル％である。
上記金属酸化物の層に含まれるケイ素酸化物とアルミニウム酸化物のモル比が上記割合であると、被膜表面の帯電を防ぐことができ、リンス等に含まれる陽イオン性界面活性剤が被膜表面に付着しにくくし、また被膜に付着しても除去しやすくなり、汚れ除去性に優れる。
The molar ratio of silicon oxide to aluminum oxide contained in the metal oxide layer is silicon oxide: aluminum oxide = 20: 80 to 80:20. That is, the ratio of aluminum oxide is 20 to 80 mol% with respect to the total amount of silicon oxide and aluminum oxide.
When the molar ratio of the silicon oxide and the aluminum oxide contained in the metal oxide layer is the above ratio, the surface of the coating can be prevented from being charged, and the cationic surfactant contained in the rinse or the like is applied to the coating surface. It is easy to remove even if it adheres to the film, and it has excellent dirt removal properties.
アルミニウム酸化物の割合が２０モル％未満であると、アルミニウム酸化物の割合が少ないため、被膜表面の帯電を防ぐことが難しくなり、陽イオン界面活性剤等を充分に吸着しにくくすることが難しくなり、汚れ除去性に劣るようになる。一方、アルミニウム酸化物の割合が８０モル％を超えると、汚れ除去性は有するものの、形成される被膜の強度が不充分となる。 If the proportion of aluminum oxide is less than 20 mol%, the proportion of aluminum oxide is small, so it is difficult to prevent the coating surface from being charged, and it is difficult to sufficiently adsorb cationic surfactants and the like. It becomes inferior to dirt removal property. On the other hand, when the proportion of aluminum oxide exceeds 80 mol%, although the stain removal property is obtained, the strength of the formed film becomes insufficient.
金属酸化物の層は、さらに、下記一般式［３］で表されるジルコニウム酸化物を含んでいることが好ましい。
（Ｒ３）ｅＺｒＯｆ ［３］
（式［３］中、Ｒ３は１価の有機基であり、ｅは０〜３．５、ｆは０．５〜２である。）
The metal oxide layer preferably further contains a zirconium oxide represented by the following general formula [3].
(R 3 ) e ZrO f [3]
(In Formula [3], R 3 is a monovalent organic group, e is 0 to 3.5, and f is 0.5 to 2.)
上記一般式［３］において、Ｒ３で表される１価の有機基としては、アセチルアセトナート基、ＣＨ３（Ｃ＝Ｏ）−Ｏ−で表される基等が挙げられる。一般式［３］で表されるジルコニウム酸化物の具体例としては、例えば、ＺｒＯ２、（ＣＨ３（Ｃ＝Ｏ）ＣＨ＝Ｃ（ＣＨ３）−Ｏ−）ＺｒＯ１．５、（ＣＨ３（Ｃ＝Ｏ）−Ｏ−）ＺｒＯ１．５等が挙げられる。上記したジルコニウム酸化物のなかでは、ＺｒＯ２が好ましい。 In the general formula [3], examples of the monovalent organic group represented by R 3 include an acetylacetonate group and a group represented by CH 3 (C═O) —O—. Specific examples of the zirconium oxide represented by the general formula [3] include, for example, ZrO 2 , (CH 3 (C═O) CH═C (CH 3 ) —O—) ZrO 1.5 , (CH 3 (C═O) —O—) ZrO 1.5 and the like. Of the above zirconium oxides, ZrO 2 is preferred.
この基材の表面に形成された金属酸化物の層中には、酸化物微粒子が分散されている。酸化物微粒子の材料は、特に限定されるものではないが、ＳｉＯ２、Ａｌ２Ｏ３及びＺｒＯ２からなる群から選ばれる少なくとも１種からなることが好ましく、これらのなかでは、ＳｉＯ２が特に好ましい。 In the metal oxide layer formed on the surface of the base material, oxide fine particles are dispersed. The material of the oxide fine particles is not particularly limited, but is preferably made of at least one selected from the group consisting of SiO 2 , Al 2 O 3 and ZrO 2. Among these, SiO 2 is particularly preferable. preferable.
この酸化物微粒子は、原料として、シリカゾル、アルミナゾル、ジルコニアゾル等を用い、上記した金属アルコキシド等の酸化物前駆体と混合して親水性被膜形成用塗布液を調製し、該塗布液を基材に塗布して乾燥することにより、金属酸化物の層中に分散した状態で保持される。 The fine oxide particles are prepared by using silica sol, alumina sol, zirconia sol, or the like as a raw material, and mixing with an oxide precursor such as the above metal alkoxide to prepare a coating solution for forming a hydrophilic film. By being applied to and dried, it is held in a dispersed state in the metal oxide layer.
上記金属酸化物の層の中には、走査型電子顕微鏡観察から求めた一次粒子の平均粒子径が３０〜２５０ｎｍの酸化物微粒子が分散していることが好ましい。金属酸化物の層の厚さは、５〜１５０ｎｍの範囲が好ましく、９〜１００ｎｍがより好ましい。 In the metal oxide layer, it is preferable that oxide fine particles having an average primary particle diameter of 30 to 250 nm determined by observation with a scanning electron microscope are dispersed. The thickness of the metal oxide layer is preferably in the range of 5 to 150 nm, and more preferably 9 to 100 nm.
酸化物微粒子の平均粒子径及び金属酸化物層の厚さは、走査型電子顕微鏡（電界放出型電子顕微鏡（ＦＥ−ＳＥＭ）Ｓ−４５００、日立ハイテク（株）製）等を用いることにより、画像を撮影し、得られた画像を観察して決定する。 The average particle diameter of the oxide fine particles and the thickness of the metal oxide layer can be obtained by using a scanning electron microscope (field emission electron microscope (FE-SEM) S-4500, manufactured by Hitachi High-Tech Co., Ltd.). And determine by observing the obtained image.
酸化物微粒子の平均粒子径については、このようなＦＥ−ＳＥＭの断面画像より、例えば、縦１μｍ、横１μｍの正方形（１μｍ２当たり）に存在する粒子のそれぞれの幅を測定し、その平均値を平均粒子径とする。 About the average particle diameter of oxide fine particles, from the cross-sectional image of such FE-SEM, for example, the width of each particle present in a square of 1 μm in length and 1 μm in width (per 1 μm 2 ) is measured, and the average value thereof Is the average particle size.
本発明の親水性被膜形成物品において、基材表面に形成された金属酸化物の層から酸化物微粒子の一次粒子が突出しており、突出した粒子の表面は金属酸化物により覆われていても、覆われていなくても良い。このような表面形状により、被膜の表面積が増大しており、被膜の表面積の増大に起因して被膜の親水性が向上している。 In the hydrophilic film-forming article of the present invention, primary particles of oxide fine particles protrude from the metal oxide layer formed on the substrate surface, and the surface of the protruded particles is covered with metal oxide, It does not have to be covered. With such a surface shape, the surface area of the coating is increased, and the hydrophilicity of the coating is improved due to the increase in the surface area of the coating.
本発明の親水性被膜形成物品において、金属酸化物と酸化物微粒子の合計量に対する酸化物微粒子の含有量は、２０〜６０質量％が好ましい。金属酸化物と酸化物微粒子の合計量に対する酸化物微粒子の含有量が、２０質量％未満では、被膜表面の親水性が充分とはならず、一方、６０質量％を超えると、金属酸化物の層の含有割合が少なくなり、防汚性能が低下するといった問題や、被膜の硬度が低下するといった問題が生じる。金属酸化物と酸化物微粒子の合計量に対する酸化物微粒子の含有量は、より好ましくは２５〜５０質量％である。 In the hydrophilic film-forming article of the present invention, the content of oxide fine particles with respect to the total amount of metal oxide and oxide fine particles is preferably 20 to 60% by mass. When the content of the oxide fine particles with respect to the total amount of the metal oxide and the oxide fine particles is less than 20% by mass, the hydrophilicity of the coating surface is not sufficient. There arises a problem that the content ratio of the layer is reduced and the antifouling performance is lowered and the hardness of the coating is lowered. The content of the oxide fine particles with respect to the total amount of the metal oxide and the oxide fine particles is more preferably 25 to 50% by mass.
本発明の親水性被膜形成物品では、上記金属酸化物の層は、ケイ素酸化物とアルミニウム酸化物を含み、ケイ素酸化物とアルミニウム酸化物のモル比は、ケイ素酸化物：アルミニウム酸化物＝２０：８０〜８０：２０と所定割合のアルミニウム酸化物を含んでいるので、被膜が帯電しにくくなり、リンスやコンディショナー等の陽イオン界面活性剤等を吸着しにくくなり、防汚性能に優れる。 In the hydrophilic film-forming article of the present invention, the metal oxide layer contains silicon oxide and aluminum oxide, and the molar ratio of silicon oxide to aluminum oxide is silicon oxide: aluminum oxide = 20: Since 80-80: 20 and a predetermined ratio of aluminum oxide are included, the coating is less likely to be charged, and it is difficult to adsorb cationic surfactants such as rinses and conditioners, resulting in excellent antifouling performance.
本発明の親水性被膜形成物品には、親水性被膜形成物品の製造を完了した後、澱粉化合物を有するコーティング剤を塗布して、親水性部材を形成してもよい。該コーティング剤の溶媒は水であることが好ましい。該コーティング剤の調製方法乃至塗布方法としては、特に限定されるものではないが、予め一部をα化させ糊状にした澱粉化合物を水で希釈し、この希釈液を刷毛もしくは霧吹き等の機材を使用して容易に塗布することができる。コーティングの後、水を含んだ発泡性弾性体で部材表面をこすることによって効率良く、コーティング剤を固定することができ、親水性部材を形成することができる。上記のコーティング剤の塗布の後、該部材を５０℃〜１００℃で熱処理し、澱粉化合物のα化を促進することが好ましい。熱処理手段としては、汎用的に流通している熱風送風型のドライヤー等を使用することができる。また、親水性を増加させるため、上記澱粉化合物を本発明の親水性の被膜に含ませてもよい。 In the hydrophilic film-forming article of the present invention, a hydrophilic member may be formed by applying a coating agent having a starch compound after the production of the hydrophilic film-forming article is completed. The solvent for the coating agent is preferably water. The preparation method or coating method of the coating agent is not particularly limited, but a starch compound that has been partially gelatinized and gelatinized in advance is diluted with water, and the diluted solution is used for equipment such as a brush or a spray. Can be easily applied using. After coating, the coating agent can be fixed efficiently and a hydrophilic member can be formed by rubbing the surface of the member with a foamable elastic body containing water. After application of the coating agent, the member is preferably heat-treated at 50 to 100 ° C. to promote the gelatinization of the starch compound. As the heat treatment means, a hot air blowing dryer or the like that is widely used can be used. Moreover, in order to increase hydrophilicity, you may include the said starch compound in the hydrophilic film of this invention.
上記親水性部材は、親水性、防汚性に優れるので、汚染負荷の大きな環境での使用に適する。又、耐久性にも優れるので長期に渡って使用に奏功する。さらには、廉価に提供することができ、使用に際し、容易に親水性を回復させることができる。 Since the hydrophilic member is excellent in hydrophilicity and antifouling property, it is suitable for use in an environment with a large contamination load. Moreover, since it is excellent in durability, it can be used successfully for a long time. Furthermore, it can be provided at a low price, and the hydrophilicity can be easily recovered in use.
上記コーティングにより形成された親水性部材は、経時的に澱粉化合物が溶出し、澱粉化合物による親水性が低下していくので、澱粉化合物を有するコーティング剤を定期的に塗布し、水を含んだ発泡性弾性体で部材表面をこすることで親水性を回復させることができる。その際、澱粉化合物を有するコーティング剤を塗布した後に部材を、澱粉化合物のα化を促進し、微細な表面凹凸構造を有する部材により澱粉化合物を浸透させることができる、５０℃〜１００℃で熱処理することが好ましい。 The hydrophilic member formed by the above coating elutes the starch compound over time, and the hydrophilicity due to the starch compound decreases, so apply a coating agent containing the starch compound periodically and foam with water The hydrophilicity can be recovered by rubbing the surface of the member with the elastic elastic body. In that case, after applying the coating agent having a starch compound, the member is accelerated at 50 ° C. to 100 ° C., which accelerates the gelatinization of the starch compound and allows the starch compound to penetrate by the member having a fine surface uneven structure. It is preferable to do.
また、上記親水性部材中には、本発明の目的を損なわない限りにおいて、公知の親水剤、界面活性剤、酸化防止剤、紫外線吸収剤、光安定剤、赤外線吸収剤、難燃剤、加水分解防止剤、防黴剤等の成分が含有されていてもよい。
親水剤としては、例えば、親水基含有アルコキシオリゴマー（「Ｘ−４１−１０５３」、「Ｘ−４１−１０５９Ａ」、「Ｘ−４１−１０５６」、「Ｘ−４１−１８０５」、「Ｘ−４１−１８１８」、「Ｘ−４１−１８１０」、「Ｘ−４０−２６５１」、「Ｘ−４０−２６５５Ａ」、信越化学工業製）、水溶性のポリマーブラシ状化合物（商品名「ＬＡＭＢＩＣ」シリーズ、大阪有機化学工業製）、親水基含有水系シランカップリング剤（商品名「Ｘ−１２−６４１」、「Ｘ−１２−１０９８」、「Ｘ−１２−１１２１」、「Ｘ−１２−１１３５」、「Ｘ−１２−１１２６」、「Ｘ−１２−１１３１」、「Ｘ−１２−１１４１」、信越化学工業製）等が挙げられる。
界面活性剤としては、例えば、エチレンオキサイド含有非イオン性界面活性剤（商品名「ペポールＡＳ−０５３Ｘ」、「ペポールＡＳ−０５４Ｃ」、「ペポールＡ−０６３８」、「ペポールＡ−０８５８」、「ペポールＢ−１８１」、「ペポールＢ−１８２」、「ペポールＢ−１８４」、「ペポールＢ−１８８」、「ペポールＤ−３０１Ａ」、「ペポールＤ−３０４」、「ペポールＢＳ−１８４」、「ペポールＢＳ−２０１」、東邦化学工業製）、アセチレングリコール系界面活性剤（商品名「サーフィノール１０４Ｅ」、「サーフィノール１０４Ｈ」、「サーフィノール１０４Ａ」、「サーフィノール１０４ＰＡ」、「サーフィノール１０４ＰＧ−５０」、「サーフィノール１０４Ｓ」、「サーフィノール４２０」、「サーフィノール４４０」、「サーフィノール４６５」、「サーフィノール４８５」、「オルフィンＤ−１０ＰＧ」、以上日信化学工業製、「アセチレノールＥＯＯ」、「アセチレノールＥ１３Ｔ」、「アセチレノールＥ４０」、「アセチレノールＥ６０」、「アセチレノールＥ８１」、「アセチレノールＥ１００」、「アセチレノールＥ２００」、「アセチレノールＥ００Ｆ２４」、「アセチレノールＥ００Ｐ」、以上川研ファインケミカル製）等が挙げられる。
Further, in the above hydrophilic member, a known hydrophilic agent, surfactant, antioxidant, ultraviolet absorber, light stabilizer, infrared absorber, flame retardant, hydrolysis, etc., as long as the object of the present invention is not impaired. Components such as an inhibitor and an antifungal agent may be contained.
Examples of the hydrophilic agent include a hydrophilic group-containing alkoxy oligomer (“X-41-1053”, “X-41-1059A”, “X-41-1056”, “X-41-1805”, “X-41-”. 1818 "," X-41-1810 "," X-40-2651 "," X-40-2655A ", manufactured by Shin-Etsu Chemical Co., Ltd.), water-soluble polymer brush compounds (trade name" LAMBIC "series, Osaka Organics) Chemical Industry), hydrophilic group-containing aqueous silane coupling agent (trade names “X-12-641”, “X-12-1098”, “X-12-1121”, “X-12-1135”, “X -12-1126 "," X-12-1131 "," X-121-1141 ", manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
Surfactants include, for example, ethylene oxide-containing nonionic surfactants (trade names “Pepol AS-053X”, “Pepol AS-054C”, “Pepol A-0638”, “Pepol A-0858”, “Pepol”. "B-181", "Pepol B-182", "Pepol B-184", "Pepol B-188", "Pepol D-301A", "Pepol D-304", "Pepol BS-184", "Pepol BS -201 ", manufactured by Toho Chemical Industry Co., Ltd., acetylene glycol surfactants (trade names" Surfinol 104E "," Surfinol 104H "," Surfinol 104A "," Surfinol 104PA "," Surfinol 104PG-50 ""Surfinol104S","Surfinol420","Surfinol 44 "Surfinol 465", "Surfinol 485", "Orphine D-10PG", manufactured by Nissin Chemical Industry Co., Ltd., "acetylenol EOO", "acetylenol E13T", "acetylenol E40", "acetylenol E60", "acetylenol E81 "," acetylenol E100 "," acetylenol E200 "," acetylenol E00F24 "," acetylenol E00P ", manufactured by Kawaken Fine Chemical Co., Ltd.) and the like.
また、本発明の目的を損なわない限りにおいて、上記の親水剤、界面活性剤、酸化防止剤、紫外線吸収剤、光安定剤、赤外線吸収剤、難燃剤、加水分解防止剤、防黴剤等の成分を本発明の親水性の被膜に含ませてもよい。その場合、上記の成分は、上述した本発明の親水性被膜形成用塗布液に含有させて、該塗布液を基材に塗布して乾燥することにより被膜中に含有される。 In addition, as long as the object of the present invention is not impaired, the above hydrophilic agent, surfactant, antioxidant, ultraviolet absorber, light stabilizer, infrared absorber, flame retardant, hydrolysis inhibitor, antifungal agent, etc. Components may be included in the hydrophilic coating of the present invention. In that case, said component is contained in the film by making it contain in the coating liquid for hydrophilic film formation of this invention mentioned above, apply | coating this coating liquid to a base material, and drying.
また、本発明の親水性被膜形成物品には、上記親水性の被膜を保護するための保護紙が、上記親水性の被膜を覆うように親水性被膜形成物品の表面に貼付されていることが好ましい。
上記保護紙は、本発明の親水性被膜形成物品の梱包、運搬、施工の際に、親水性被膜形成物品に形成された親水性の被膜の損傷や汚染を防止する役割を果たす。
上記保護紙は、粘着成分として澱粉化合物を含むことが好ましく、さらに粘着成分中に親水剤及び界面活性剤から選ばれる少なくとも１種を含むことが好ましい。保護紙を剥離した際、これらの澱粉化合物や親水剤や界面活性剤が親水性の被膜の表面に残留し、これらの澱粉化合物や親水剤や界面活性剤をコーティングしたのと同様の効果をもたらす。すなわち、上記コーティング剤の塗布でも説明したように、澱粉化合物や親水剤や界面活性剤が親水性被膜中に存在すると、親水性被膜の親水性が増加し、親水剤や界面活性剤が存在すると、さらに防汚性が向上する。
親水剤や界面活性剤としては、上記コーティング剤の塗布において例示した化合物や商品を使用することができる。
なお、上記保護紙を親水性被膜形成物品の表面に貼付する工程（保護紙貼付工程）は、表面に予め粘着成分を有した保護紙を親水性被膜形成物品の被膜表面に貼付してもよいし、親水性被膜形成物品の被膜表面に粘着成分を塗布しその上に保護紙を密着させて貼付してもよい。
In the hydrophilic film-forming article of the present invention, a protective paper for protecting the hydrophilic film may be attached to the surface of the hydrophilic film-forming article so as to cover the hydrophilic film. preferable.
The protective paper plays a role of preventing damage and contamination of the hydrophilic coating formed on the hydrophilic coating-formed article during packaging, transportation, and construction of the hydrophilic coating-formed article of the present invention.
The protective paper preferably contains a starch compound as an adhesive component, and further preferably contains at least one selected from a hydrophilic agent and a surfactant in the adhesive component. When the protective paper is peeled off, these starch compounds, hydrophilic agents and surfactants remain on the surface of the hydrophilic film, and the same effect as when these starch compounds, hydrophilic agents and surfactants are coated is brought about. . That is, as described in the application of the coating agent, when a starch compound, a hydrophilic agent or a surfactant is present in the hydrophilic coating, the hydrophilicity of the hydrophilic coating is increased, and the hydrophilic agent or the surfactant is present. Further, the antifouling property is improved.
As the hydrophilic agent or surfactant, the compounds and products exemplified in the application of the coating agent can be used.
In the step of applying the protective paper to the surface of the hydrophilic film-forming article (protective paper application process), a protective paper having an adhesive component on the surface in advance may be applied to the surface of the hydrophilic film-forming article. Then, an adhesive component may be applied to the surface of the film of the hydrophilic film-formed article, and a protective paper may be stuck on the surface to be adhered.
［親水性被膜形成用塗布液］
次に、本発明の親水性被膜形成用塗布液について説明する。
本発明の親水性被膜形成用塗布液は、少なくとも、酸化物微粒子を含むコロイド溶液、下記一般式［４］で表されるケイ素酸化物前駆体、下記一般式［５］で表されるアルミニウム酸化物前駆体、酸、水及び溶媒を混合することにより調製された親水性被膜形成用塗布液であり、
上記酸化物微粒子、上記ケイ素酸化物前駆体の固形分、及び上記アルミニウム酸化物前駆体の固形分の総量１００質量％に対して、上記酸化物微粒子の含有量が２０〜６０質量％であり、該酸化物微粒子４０質量部に対して、上記ケイ素酸化物前駆体が酸化物換算で６〜４０質量部、上記アルミニウム酸化物前駆体が酸化物換算で５〜３０質量部であることを特徴とする。
（Ｒ４）ｇＳｉ（Ｘ１）４−ｇ ［４］
（式［４］中、Ｒ４は１価の有機基であり、Ｘ１はアルコキシル基又はハロゲン元素であり、ｇは０〜３の整数である。）
（Ｒ５）ｈＡｌ（Ｘ２）３−ｈ ［５］
（式［５］中、Ｒ５はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、Ｘ２はアルコキシル基又はハロゲン元素であり、ｈは１〜３の整数である。）
[Coating liquid for hydrophilic film formation]
Next, the coating liquid for forming a hydrophilic film of the present invention will be described.
The coating liquid for forming a hydrophilic film of the present invention comprises at least a colloidal solution containing fine oxide particles, a silicon oxide precursor represented by the following general formula [4], and an aluminum oxide represented by the following general formula [5]. A coating solution for forming a hydrophilic film, prepared by mixing a precursor of a product, an acid, water and a solvent,
The content of the oxide fine particles is 20 to 60% by mass with respect to 100% by mass of the solid content of the oxide fine particles, the solid content of the silicon oxide precursor, and the solid content of the aluminum oxide precursor, The silicon oxide precursor is 6 to 40 parts by mass in terms of oxide and the aluminum oxide precursor is 5 to 30 parts by mass in terms of oxide with respect to 40 parts by mass of the oxide fine particles. To do.
(R 4 ) g Si (X 1 ) 4-g [4]
(In the formula [4], R 4 is a monovalent organic group, X 1 is an alkoxyl group or a halogen element, and g is an integer of 0 to 3.)
(R 5 ) h Al (X 2 ) 3-h [5]
(In the formula [5], R 5 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, X 2 is an alkoxyl group or a halogen element, and h is an integer of 1 to 3. )
本発明の親水性被膜形成用塗布液の原料となる酸化物微粒子を含むコロイド溶液（ゾル）としては、シリカゾル（コロイダルシリカ）、アルミナゾル（コロイダルアルミナ）等が挙げられる。シリカゾルとしては、ナトリウムやアンモニウム等の１価の陽イオンで安定化したものが好ましく、例えば、市販品としては、スノーテックス（日産化学工業製）、ルドックス（デュポン社製）、カタロイド（触媒化成製）等を用いることができる。また、アルミナゾルの場合もシリカゾルの場合と同様に、ナトリウムやアンモニウム等の１価の陽イオンで安定化したものが好ましく、例えば、市販品としては、アルミナクリアゾル（川研ファインケミカル製）等を用いることができる。 Examples of the colloidal solution (sol) containing fine oxide particles that are the raw material of the coating liquid for forming a hydrophilic film of the present invention include silica sol (colloidal silica) and alumina sol (colloidal alumina). The silica sol is preferably stabilized with a monovalent cation such as sodium or ammonium. Examples of commercially available products include Snowtex (manufactured by Nissan Chemical Industries), Ludox (manufactured by DuPont), and cataloid (manufactured by Catalytic Chemicals). ) Etc. can be used. Also, in the case of alumina sol, as in the case of silica sol, those stabilized with monovalent cations such as sodium and ammonium are preferable. For example, alumina clear sol (manufactured by Kawaken Fine Chemical) is used as a commercial product. be able to.
本発明の親水性被膜形成用塗布液には、ＺｒＯ２のコロイド溶液（ゾル）を添加してもよい。
ジルコニアゾル（コロイダルジルコニア）としては、日産化学工業製のナノユース、第一稀元素化学工業製のＺＳＬ−１０Ａ、ＺＳＬ−２０Ｎ、堺化学工業製のＳＺＲ−Ｋ、ＳＺＲ−Ｍ等が挙げられる。
A hydrophilic film-forming coating liquid of the present invention, the ZrO 2 colloidal solution (sol) may be added.
Examples of the zirconia sol (colloidal zirconia) include nano-use manufactured by Nissan Chemical Industries, ZSL-10A and ZSL-20N manufactured by Daiichi Rare Element Chemical Industry, and SZR-K and SZR-M manufactured by Sakai Chemical Industry.
金属酸化物の層においてシリカ成分となる酸化物前駆体としては、下記の一般式［４］で表されるケイ素酸化物前駆体が挙げられる。
（Ｒ４）ｇＳｉ（Ｘ１）４−ｇ ［４］
（式［４］中、Ｒ４は１価の有機基であり、Ｘ１はアルコキシル基又はハロゲン元素であり、ｇは０〜３の整数である。）
Examples of the oxide precursor that becomes a silica component in the metal oxide layer include a silicon oxide precursor represented by the following general formula [4].
(R 4 ) g Si (X 1 ) 4-g [4]
(In the formula [4], R 4 is a monovalent organic group, X 1 is an alkoxyl group or a halogen element, and g is an integer of 0 to 3.)
上記ケイ素酸化物前駆体において、ｇが０の場合の化合物としては、テトラエトキシシラン、テトラメトキシシラン、テトラクロロシラン等が挙げられ、ｇが１の場合の化合物としては、モノメチルトリエトキシシラン、モノメチルトリメトキシシラン、モノメチルトリクロロシラン、（３−メルカプトプロピル）トリメトキシシラン、（３−アミノプロピル）トリメトキシシラン等が挙げられ、ｇが２の場合の化合物としては、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジクロロシラン等が挙げられる。
これらのなかでは、特に、一般式：Ｓｉ（Ｘ１）４で表わされるアルコキシシランを用いると、被膜の硬度が良好となるので好ましい。
In the above silicon oxide precursor, examples of the compound when g is 0 include tetraethoxysilane, tetramethoxysilane, tetrachlorosilane, and the like. Examples of the compound when g is 1 include monomethyltriethoxysilane and monomethyltrisilane. Examples include methoxysilane, monomethyltrichlorosilane, (3-mercaptopropyl) trimethoxysilane, (3-aminopropyl) trimethoxysilane, and the like. When g is 2, the compounds are dimethyldimethoxysilane, dimethyldiethoxysilane, Examples thereof include dimethyldichlorosilane.
Among these, it is particularly preferable to use an alkoxysilane represented by the general formula: Si (X 1 ) 4 since the hardness of the coating becomes good.
金属酸化物の層においてアルミナ成分となる酸化物前駆体としては、一般式［５］で表されるアルミニウム酸化物前駆体が挙げられる。
（Ｒ５）ｈＡｌ（Ｘ２）３−ｈ ［５］
（式［５］中、Ｒ５はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、Ｘ２はアルコキシル基又はハロゲン元素であり、ｈは１〜３の整数である。）
As an oxide precursor used as an alumina component in the metal oxide layer, an aluminum oxide precursor represented by the general formula [5] can be given.
(R 5 ) h Al (X 2 ) 3-h [5]
(In the formula [5], R 5 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, X 2 is an alkoxyl group or a halogen element, and h is an integer of 1 to 3. )
上記アルミニウム酸化物前駆体において、ｈが１の場合の化合物としては、例えば、アルミニウムエチルアセトアセテート・ジイソプロピレート、アルミニウムジノルマルブトキシモノエチルアセトアセテート等が挙げられる。ｈが３の場合の化合物としては、例えば、アルミニウムトリスアセチルアセトナート、アルミニウムトリスエチルアセトアセテート、アルミニウムビスエチルアセトアセテート・モノアセチルアセトネート等が挙げられる。これらのなかでは、Ｒ５Ａｌ（Ｘ２）２で表されるアルミニウムエチルアセトアセテート・ジイソプロピレート等が好ましい。また、ｈの値が大きいほど、すなわち、加水分解性の官能基Ｘ２の数が少ないほど、親水性被膜形成用塗布液のポットライフが良好となる傾向がある。 Examples of the compound in the case where h is 1 in the aluminum oxide precursor include aluminum ethyl acetoacetate / diisopropylate, aluminum dinormal butoxy monoethyl acetoacetate, and the like. Examples of the compound when h is 3 include aluminum trisacetylacetonate, aluminum trisethylacetoacetate, aluminum bisethylacetoacetate / monoacetylacetonate, and the like. Among these, aluminum ethyl acetoacetate / diisopropylate represented by R 5 Al (X 2 ) 2 is preferable. Further, the larger the value of h, that is, the smaller the number of hydrolyzable functional groups X 2 , the better the pot life of the hydrophilic film-forming coating solution.
また、金属酸化物の層においてジルコニア成分となる酸化物前駆体としては、一般式［６］及び［７］で表される化合物からなる群から選ばれる少なくとも１種のジルコニウム酸化物前駆体が挙げられる。
ＺｒＯＹ２ ［６］
（式［６］中、ＹはＣｌ−、ＮＯ３ −又はＣＨ３ＣＯＯ−）
（Ｒ６）ｉＺｒ（Ｚ）４−ｉ ［７］
（式［７］中、Ｒ６はアセチルアセトナート基、Ｚは炭素数２〜４のアルコキシル基又はハロゲン、ｉは０〜４の整数）
Examples of the oxide precursor that becomes a zirconia component in the metal oxide layer include at least one zirconium oxide precursor selected from the group consisting of compounds represented by the general formulas [6] and [7]. It is done.
ZrOY 2 [6]
(In the formula [6], Y is Cl − , NO 3 — or CH 3 COO − )
(R 6 ) i Zr (Z) 4-i [7]
(In formula [7], R 6 is an acetylacetonate group, Z is an alkoxyl group having 2 to 4 carbon atoms or halogen, and i is an integer of 0 to 4)
一般式［６］で表されるジルコニウム酸化物前駆体としては、例えば、オキシ塩化ジルコニウム、オキシ硝酸ジルコニウム、オキシ酢酸ジルコニウム等が挙げられる。一般式［７］で表されるジルコニウム酸化物前駆体において、ｉが０の場合の化合物としては、例えば、テトライソプロポキシジルコニウム、テトラノルマルブトキシジルコニウム、テトラエトキシジルコニウム等が挙げられ、ｉが４の場合の化合物としては、例えば、ジルコニウムテトラアセチルアセトナート等が挙げられる。 Examples of the zirconium oxide precursor represented by the general formula [6] include zirconium oxychloride, zirconium oxynitrate, and zirconium oxyacetate. In the zirconium oxide precursor represented by the general formula [7], examples of the compound when i is 0 include tetraisopropoxyzirconium, tetranormalbutoxyzirconium, tetraethoxyzirconium, and the like, and i is 4. Examples of the compound include zirconium tetraacetylacetonate and the like.
本発明の親水性被膜形成用塗布液において、上記酸化物微粒子、上記ケイ素酸化物前駆体の固形分、及び上記アルミニウム酸化物前駆体の固形分の総量１００質量％に対して、上記酸化物微粒子の含有量は、２０〜６０質量％である。上記酸化物微粒子の含有量が２０質量％未満では、得られる被膜の親水性が不充分となり、一方、上記酸化物微粒子の含有量が６０質量％を超えると、得られる被膜の防汚性能や硬度が不充分となる。 In the coating liquid for forming a hydrophilic film of the present invention, the oxide fine particles are used in a total amount of 100% by mass of the oxide fine particles, the solid content of the silicon oxide precursor, and the solid content of the aluminum oxide precursor. The content of is 20 to 60% by mass. When the content of the oxide fine particles is less than 20% by mass, the resulting coating has insufficient hydrophilicity. On the other hand, when the content of the oxide fine particles exceeds 60% by mass, Insufficient hardness.
また、本発明の親水性被膜形成用塗布液においては、酸化物微粒子４０質量部に対して、上記ケイ素酸化物前駆体が酸化物換算で６〜４０質量部、上記アルミニウム酸化物前駆体が酸化物換算で５〜３０質量部である。
酸化物換算したケイ素酸化物前駆体の質量に対する酸化物換算したアルミニウム酸化物前駆体の質量の割合は、５／４０〜３０／６＝０．１２５〜５となる。
In the coating liquid for forming a hydrophilic film of the present invention, the silicon oxide precursor is 6 to 40 parts by mass in terms of oxide and the aluminum oxide precursor is oxidized with respect to 40 parts by mass of the oxide fine particles. It is 5-30 mass parts in conversion of a thing.
The ratio of the mass of the aluminum oxide precursor converted to oxide with respect to the mass of the silicon oxide precursor converted to oxide is 5/40 to 30/6 = 0.125 to 5.
酸化物換算したケイ素酸化物前駆体の質量に対する酸化物換算したアルミニウム酸化物前駆体の質量の割合が０．１２５未満であると、アルミニウム酸化物の割合が少ないため、被膜の帯電の防止が難しくなり、陽イオン界面活性剤等を充分に吸着しにくくすることが難しく、得られる親水性被膜形成物品の防汚性能が不充分となる。一方、酸化物換算したケイ素酸化物前駆体の質量に対する酸化物換算したアルミニウム酸化物前駆体の質量の割合が５を超えると、汚れ除去性は有するものの、形成される被膜の硬度が不充分となる。 When the ratio of the mass of the oxide-converted aluminum oxide precursor to the mass of the oxide-converted silicon oxide precursor is less than 0.125, it is difficult to prevent the coating from being charged because the ratio of the aluminum oxide is small. Therefore, it is difficult to sufficiently adsorb the cationic surfactant or the like, and the antifouling performance of the resulting hydrophilic film-formed article becomes insufficient. On the other hand, if the ratio of the mass of the oxide-converted aluminum oxide precursor to the mass of the oxide-converted silicon oxide precursor is more than 5, the film formed is insufficient in hardness, although it has dirt removal properties. Become.
溶媒としては、アルコール系溶媒、エステル類、セロソルブ類、ジメチルホルムアミド等が挙げられる。アルコール系溶媒の具体例としては、例えば、メタノール、エタノール、プロパノール、ブタノール、エチレングリコール、プロピレングリコール、ブチレングリコール、ペンチレングリコール、ヘキシレングリコール、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール等が挙げられる。エステル類としては、例えば、酢酸エチル、酢酸ブチル、酢酸アミル等が挙げられ、セロソルブ類としては、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ等が挙げられる。これらの溶媒は、１種のみを使用してもよく、２種以上を混合して用いてもよい。 Examples of the solvent include alcohol solvents, esters, cellosolves, dimethylformamide and the like. Specific examples of the alcohol solvent include, for example, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2- Examples include propanol. Examples of esters include ethyl acetate, butyl acetate, and amyl acetate. Examples of cellosolves include methyl cellosolve, ethyl cellosolve, and butyl cellosolve. These solvents may be used alone or in combination of two or more.
親水性被膜形成用塗布液を調製する際には、無機酸もしくは有機酸等の酸を触媒として含むことが好ましい。上記無機酸としては、例えば、塩酸、硝酸、硫酸等が挙げられ、有機酸としては、酢酸、トリフルオロ酢酸、クエン酸、スルホン酸、メタンスルホン酸、エタンスルホン酸、マレイン酸、グリコール酸、ビニルスルホン酸等が挙げられる。一般式［６］で表されるジルコニウム酸化物前駆体のうち、水存在下で酸性を示すものを用いる場合は、その酸を触媒として用いることができる。 When preparing the coating liquid for forming a hydrophilic film, it is preferable to include an acid such as an inorganic acid or an organic acid as a catalyst. Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, and the like, and examples of the organic acid include acetic acid, trifluoroacetic acid, citric acid, sulfonic acid, methanesulfonic acid, ethanesulfonic acid, maleic acid, glycolic acid, and vinyl. A sulfonic acid etc. are mentioned. Among the zirconium oxide precursors represented by the general formula [6], when an acid that is acidic in the presence of water is used, the acid can be used as a catalyst.
本発明の親水性被膜形成用塗布液において、親水性被膜形成用塗布液を調製する際に添加する水の量は、該塗布液の固形分の総量１００質量％に対して、１０〜３００質量％であることが好ましい。上記固形分の総量とは、本発明の親水性被膜形成物品において、基材の表面に形成した酸化物微粒子を分散して金属酸化物の層で保持した被膜の全重量をいう。
添加する水の量が上記塗布液の固形分の総量１００質量％に対して、１０質量％未満であると、添加する水の量が少なすぎて、酸化物前駆体の加水分解が進まず、被膜の硬度が低くなる傾向がある。一方、添加する水の量が上記塗布液の固形分の総量１００質量％に対して、３００質量％を超えると、添加する水の量が多すぎて、沈殿等が発生し易くなり、ポットライフが短くなる傾向がある。
In the coating liquid for forming a hydrophilic film of the present invention, the amount of water added when preparing the coating liquid for forming a hydrophilic film is 10 to 300 mass with respect to 100 mass% of the total solid content of the coating liquid. % Is preferred. The total amount of the solid content means the total weight of the film in which the oxide fine particles formed on the surface of the base material are dispersed and held in the metal oxide layer in the hydrophilic film-formed article of the present invention.
If the amount of water to be added is less than 10% by mass relative to 100% by mass of the total solid content of the coating solution, the amount of water to be added is too small and hydrolysis of the oxide precursor does not proceed. There is a tendency for the hardness of the coating to decrease. On the other hand, if the amount of water added exceeds 300% by mass relative to the total amount of 100% by mass of the solid content of the coating solution, the amount of water to be added is too large and precipitation or the like is likely to occur. Tends to be shorter.
本発明の親水性被膜形成用塗布液には、レベリング剤としてジメチルシリコーンなどのメチルシリコーン類やフッ素系レベリング剤を適量加えても良い。また、例えばビックケミージャパン製の「ＢＹＫ−３００」、「ＢＹＫ−３０１」、「ＢＹＫ−３０２」、「ＢＹＫ−３０６」、「ＢＹＫ−３０７」、「ＢＹＫ−３１０」、「ＢＹＫ−３１３」、「ＢＹＫ−３１５」、「ＢＹＫ−３２０」、「ＢＹＫ−３２２」、「ＢＹＫ−３２３」、「ＢＹＫ−３２５」、「ＢＹＫ−３３０」、「ＢＹＫ−３３１」、「ＢＹＫ−３３３」、「ＢＹＫ−３３７」、「ＢＹＫ−３４１」、「ＢＹＫ−３４４」、「ＢＹＫ−３４５」、「ＢＹＫ−３４６」、「ＢＹＫ−３４７」、「ＢＹＫ−３４８」、「ＢＹＫ−３４９」、「ＢＹＫ−３７０」、「ＢＹＫ−３７５」、「ＢＹＫ−３７７」、「ＢＹＫ−３７８」、「ＢＹＫ−ＵＶ３５００」、「ＢＹＫ−ＵＶ３５１０」、「ＢＹＫ−ＵＶ３５７０」、「ＢＹＫ−３４０」、「ＢＹＫ−３５５０」、「ＢＹＫ−ＳＩＬＣＬＥＡＮ３７００」、「ＢＹＫ−ＳＩＬＣＬＥＡＮ３７２０」、「ＢＹＫ−ＤＹＮＷＥＴ８００」、共栄社化学製の「ポリフローＮｏ．３」、「ポリフローＮｏ．５０ＨＦ」、「ポリフローＮｏ．５４」、「ポリフローＮｏ．６４ＨＦ」、「ポリフローＮｏ．７５」、「ポリフローＮｏ．７７」、「ポリフローＮｏ．８５ＨＦ」、「ポリフローＮｏ．９０」、「ポリフローＮｏ．９５」、「ポリフローＮｏ．ＡＴＦ−２」、「グラノール１００」、「グラノール１１５」、「グラノール４００」、「グラノール４１０」、「グラノール４２０」、「グラノール４４０」、「グラノール４５０」、「グラノールＢ−１４８４」等を添加しても良い。 An appropriate amount of methyl silicones such as dimethyl silicone and a fluorine leveling agent may be added to the coating liquid for forming a hydrophilic film of the present invention as a leveling agent. Further, for example, “BYK-300”, “BYK-301”, “BYK-302”, “BYK-306”, “BYK-307”, “BYK-310”, “BYK-313”, manufactured by Big Chemie Japan, “BYK-315”, “BYK-320”, “BYK-322”, “BYK-323”, “BYK-325”, “BYK-330”, “BYK-331”, “BYK-333”, “BYK” -337 "," BYK-341 "," BYK-344 "," BYK-345 "," BYK-346 "," BYK-347 "," BYK-348 "," BYK-349 "," BYK-370 " ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK-378 ”,“ BYK-UV3500 ”,“ BYK-UV3510 ”,“ BYK-UV3570 ”,“ BYK-3 ” 0, “BYK-3550”, “BYK-SILCLEAN3700”, “BYK-SILCLEAN3720”, “BYK-DYNWET800”, “Polyflow No. 3”, “Polyflow No. 50HF”, “Polyflow No. 54” manufactured by Kyoeisha Chemical Co., Ltd. "," Polyflow No. 64HF "," Polyflow No. 75 "," Polyflow No. 77 "," Polyflow No. 85HF "," Polyflow No. 90 "," Polyflow No. 95 "," Polyflow No. ATF- " 2 ”,“ Granol 100 ”,“ Granol 115 ”,“ Granol 400 ”,“ Granol 410 ”,“ Granol 420 ”,“ Granol 440 ”,“ Granol 450 ”,“ Granol B-1484 ”, etc. good.
本発明の親水性被膜形成用塗布液中の固形分濃度は、０．１〜１０質量％が好ましく、
固形分濃度が上記の範囲にあると、金属酸化物前駆体の加水分解反応が良好に進行し、得られた被膜が良好な汚れ除去性や耐久性を発揮しやすい。
The solid content concentration in the coating liquid for forming a hydrophilic film of the present invention is preferably 0.1 to 10% by mass,
When the solid content concentration is in the above range, the hydrolysis reaction of the metal oxide precursor proceeds favorably, and the obtained coating film tends to exhibit good stain removability and durability.
本発明の親水性被膜形成用塗布液は、成膜性やポットライフの点で優れているという利点がある。
すなわち、従来、アルミニウム酸化物を含む金属酸化物を形成する際には、アルミニウムのトリアルコキシド等の３官能のアルミニウム化合物が用いられていたが、これらの３官能の化合物のみをアルミニウム酸化物源として用いようとすると、反応性が高すぎるため、親水性被膜形成用塗布液の調製時に過剰に重縮合反応が進行した縮合物が生成しやすく、その結果、上記塗布液が濁ったり、沈澱が生じたり、ゲル化してしまい、上記塗布液のポットライフが短い場合があった。またそのような塗布液を用いることで、最終的に得られる被膜にブツ欠陥が発生する場合があった。
The coating liquid for forming a hydrophilic film of the present invention has an advantage that it is excellent in terms of film forming properties and pot life.
That is, conventionally, when forming a metal oxide containing an aluminum oxide, a trifunctional aluminum compound such as a trialkoxide of aluminum has been used, but only these trifunctional compounds are used as an aluminum oxide source. If used, the reactivity is too high, so that a condensate that has undergone an excessive polycondensation reaction during the preparation of a coating solution for forming a hydrophilic film is likely to be formed. As a result, the coating solution becomes cloudy or precipitates are formed. In some cases, the pot life of the coating solution is short. Further, when such a coating solution is used, a defect may occur in the finally obtained film.
しかしながら、本発明では、一般式［５］で表されるアルミニウム酸化物前駆体を用いることで上記のような問題を生じることなく、良好な成膜性とポットライフを有する親水性被膜形成用塗布液が得られる。一般式［５］で表されるアルミニウム酸化物前駆体では、ｈは１以上であり、２官能以下の化合物である。
原料として、上記のようなアルミニウム酸化物前駆体を用い、親水性被膜形成用塗布液の調製時に用いる水の量が、親水性被膜形成用塗布液の固形分の総量１００質量％に対して、１５〜１２０質量％であると、ポットライフがより良好となる傾向がある。
また、本発明の親水性被膜形成用塗布液は、含有する水の量を上記した適切な範囲内とすることで、得られる被膜の鉛筆硬度を高く保ち易い。すなわち、含有する水の量を上記した適切な範囲内とすることで、被膜の鉛筆硬度を高く保ちながら、防汚性能（耐リンス性）を向上させ易い。
However, in the present invention, by using the aluminum oxide precursor represented by the general formula [5], the coating for forming a hydrophilic film having good film formability and pot life without causing the above-mentioned problems A liquid is obtained. In the aluminum oxide precursor represented by the general formula [5], h is 1 or more and a bifunctional or less functional compound.
Using the aluminum oxide precursor as described above as a raw material, the amount of water used when preparing the coating liquid for forming a hydrophilic film is 100% by mass of the total solid content of the coating liquid for forming a hydrophilic film, There exists a tendency for a pot life to become more favorable that it is 15-120 mass%.
Moreover, the coating liquid for hydrophilic film formation of this invention makes it easy to keep the pencil hardness of the film obtained high by making the quantity of the water to contain in the above-mentioned appropriate range. That is, by setting the amount of water contained within the above-described appropriate range, it is easy to improve the antifouling performance (rinse resistance) while keeping the pencil hardness of the coating film high.
本発明の親水性被膜形成用塗布液においては、さらに、三ハロゲン化アルミニウムが、固形分の総量１００質量％に対して、０．００１〜１質量％添加されていてもよい。該三ハロゲン化アルミニウムは金属酸化物の層においてアルミナ成分の一部となるものであるが、その添加量はわずかであり、ほとんどのアルミナ成分は上記一般式［５］で表されるアルミニウム酸化物前駆体に由来するものである。また、該三ハロゲン化アルミニウムは３官能のアルミニウム化合物であるが、添加量がわずかであるため、上述したような成膜性やポットライフの点で不具合を生じ難い。塗布液中に三ハロゲン化アルミニウムが上記の添加量で添加されると、得られる被膜の親水性が長期間維持されやすくなる。三ハロゲン化アルミニウムとしては、三フッ化アルミニウム、三塩化アルミニウム、三臭化アルミニウム等が挙げられ、それらは無水物であってもよいし、水和物であってもよい。なお、三ハロゲン化アルミニウムを添加した塗布液においては、上記酸化物微粒子４０質量部に対して、上記アルミニウム酸化物前駆体と該三ハロゲン化アルミニウムの総量が酸化物換算で５〜３０質量部であることが好ましい。 In the coating liquid for forming a hydrophilic film of the present invention, 0.001 to 1% by mass of aluminum trihalide may be further added to 100% by mass of the total solid content. The aluminum trihalide is a part of the alumina component in the metal oxide layer, but the amount added is small, and most of the alumina component is an aluminum oxide represented by the above general formula [5]. It is derived from the precursor. Further, the aluminum trihalide is a trifunctional aluminum compound, but since the addition amount is small, it is difficult to cause problems in terms of film forming properties and pot life as described above. When aluminum trihalide is added to the coating solution in the above amount, the hydrophilicity of the resulting coating is easily maintained for a long period of time. Examples of the aluminum trihalide include aluminum trifluoride, aluminum trichloride, aluminum tribromide and the like, and they may be anhydrides or hydrates. In addition, in the coating liquid to which aluminum trihalide is added, the total amount of the aluminum oxide precursor and the aluminum trihalide is 5 to 30 parts by mass in terms of oxide with respect to 40 parts by mass of the oxide fine particles. Preferably there is.
また、本発明の親水性被膜形成用塗布液やその原料に対して、過酸化水素処理、過マンガン酸塩処理のうち少なくとも１つの酸化処理を施し、塗布液の酸化を進行させてもよい。上記過酸化水素処理とは、過酸化水素水を塗布液やその原料に添加し、酸化を進行させる処理を意味する。上記過マンガン酸塩処理とは、過マンガン酸カリウムや過マンガン酸ナトリウムを塗布液やその原料に添加し、酸化を進行させる処理を意味する。 In addition, the coating liquid for forming a hydrophilic film of the present invention and its raw material may be subjected to at least one oxidation treatment among hydrogen peroxide treatment and permanganate treatment to advance the oxidation of the coating solution. The hydrogen peroxide treatment means a treatment in which a hydrogen peroxide solution is added to a coating solution or its raw material to promote oxidation. The permanganate treatment means a treatment in which potassium permanganate or sodium permanganate is added to a coating solution or its raw material to promote oxidation.
［親水性被膜形成用塗布液を用いた親水性被膜形成物品の製造方法］
本発明の親水性被膜形成物品の製造方法は、上記した親水性被膜形成物品の製造方法であって、基材を準備する基材準備工程、上述した組成の親水性被膜形成用塗布液を準備する塗布液準備工程、上記基材の表面に上記塗布液を塗布して塗膜を形成する塗布工程、及び、塗布工程後の基材を１００〜４００℃で加熱して塗膜を硬化させて、該基材表面に親水性の被膜を形成する硬化工程を有することを特徴とする。
[Method for producing hydrophilic film-forming article using coating liquid for forming hydrophilic film]
The method for producing a hydrophilic film-forming article of the present invention is the above-described method for producing a hydrophilic film-forming article, comprising preparing a base material and preparing a hydrophilic film-forming coating liquid having the composition described above. A coating solution preparation step, a coating step in which the coating solution is applied to the surface of the substrate to form a coating film, and the substrate after the coating step is heated at 100 to 400 ° C. to cure the coating film. And a curing step of forming a hydrophilic film on the surface of the substrate.
本発明の親水性被膜形成物品の製造方法では、最初に基材を準備する基材準備工程を行う。該基材準備工程として、ガラス板、鏡等の基材を準備する。この際、密着性を確保するために、酸化セリウム等で充分に研磨することにより、表面の汚れ等を丁寧に除去しておくことが好ましい。 In the manufacturing method of the hydrophilic film formation article of this invention, the base material preparation process which prepares a base material first is performed. As the substrate preparation step, a substrate such as a glass plate or a mirror is prepared. At this time, in order to ensure adhesion, it is preferable to carefully remove dirt and the like on the surface by sufficiently polishing with cerium oxide or the like.
次に、親水性被膜形成用塗布液を準備する塗布液準備工程を行う。上記塗布液準備工程では、上述した組成の親水性被膜形成用塗布液を準備する。
該塗布液準備工程では、少なくとも、酸化物微粒子を含むコロイド溶液、上記一般式［４］で表されるケイ素酸化物前駆体、上記一般式［５］で表されるアルミニウム酸化物前駆体、酸、水及び溶媒を混合することにより親水性被膜形成用塗布液を調製する。塗布液中で、原料の金属酸化物前駆体は加水分解・重縮合反応を進行させておくことが好ましいので、上記した割合の水が添加されることが好ましい。原料として液体の水や水溶液を用いても良いし、大気中から取り込まれる水分を利用しても良い。また、上記の加水分解や重縮合を促進するために上述したような酸が添加されても良い。さらには、上述したような、澱粉化合物、親水剤、界面活性剤、酸化防止剤、紫外線吸収剤、光安定剤、赤外線吸収剤、難燃剤、加水分解防止剤、防黴剤等の成分が添加されても良い。
Next, a coating solution preparing step for preparing a coating solution for forming a hydrophilic film is performed. In the coating liquid preparation step, a coating liquid for forming a hydrophilic film having the above-described composition is prepared.
In the coating solution preparation step, at least a colloidal solution containing fine oxide particles, a silicon oxide precursor represented by the general formula [4], an aluminum oxide precursor represented by the general formula [5], an acid Then, a coating liquid for forming a hydrophilic film is prepared by mixing water and a solvent. In the coating solution, since the raw material metal oxide precursor is preferably allowed to proceed with hydrolysis and polycondensation reaction, it is preferable to add water in the above ratio. Liquid water or an aqueous solution may be used as a raw material, or moisture taken in from the atmosphere may be used. Moreover, in order to accelerate | stimulate said hydrolysis and polycondensation, the above acids may be added. Furthermore, as described above, components such as starch compounds, hydrophilic agents, surfactants, antioxidants, ultraviolet absorbers, light stabilizers, infrared absorbers, flame retardants, hydrolysis inhibitors, and antifungal agents are added. May be.
上記の親水性被膜形成用塗布液を調製する際に、水、希釈溶媒、グリコール類を加えて成膜方法により固形分濃度を調整し、必要であればレベリング剤等の各種添加剤を添加することもできる。なお、親水性被膜形成用塗布液中の全固形分濃度は０．１〜１０質量％とするのが均一な塗布膜を形成する上で好ましい。 When preparing the above coating solution for forming a hydrophilic film, water, a diluting solvent, and glycols are added to adjust the solid content concentration by a film forming method, and if necessary, various additives such as a leveling agent are added. You can also. In addition, it is preferable when forming the uniform coating film that the total solid content concentration in the coating liquid for forming a hydrophilic film is 0.1 to 10% by mass.
次に、上記親水性被膜形成用塗布液を基材表面に塗布して塗膜を形成する塗布工程を行う。
塗布法としては、特に限定されるものではないが、生産性などの面からは、例えば、スピンコート法、バーコート法、リバースロールコート法、その他のロールコート法、カーテンコート法、スプレーコート法などの公知手段が採用でき、適宜マスキングすることにより、部分的な成膜はもちろん、任意の形状、図柄に被膜を形成することができる。なお、これらの塗布法で塗布成膜する際の親水性被膜形成用塗布液中の全固形分濃度としては約０．１〜１０質量％程度が好ましい。
Next, a coating process is performed in which the hydrophilic coating-forming coating solution is applied to the substrate surface to form a coating film.
The coating method is not particularly limited, but from the viewpoint of productivity, for example, spin coating method, bar coating method, reverse roll coating method, other roll coating methods, curtain coating method, spray coating method. Known means such as can be employed, and by appropriately masking, a film can be formed in an arbitrary shape and pattern as well as partial film formation. In addition, about 0.1-10 mass% is preferable as a total solid content concentration in the coating liquid for hydrophilic film formation at the time of carrying out the coating film formation by these coating methods.
次に、塗布工程後の基材を１００〜４００℃で加熱して塗膜を硬化させて、該基材表面に親水性の被膜を形成する硬化工程を行う。
塗布工程後の乾燥としては、１００〜２００℃の比較的低温で、５〜３０分間乾燥することが好ましく、より好ましくは、上記乾燥温度が１３０〜１８０℃程度、乾燥時間が１０分間程度である。
Next, the base material after an application | coating process is heated at 100-400 degreeC, a coating film is hardened, and the hardening process which forms a hydrophilic film on this base-material surface is performed.
As the drying after the coating step, it is preferable to dry at a relatively low temperature of 100 to 200 ° C. for 5 to 30 minutes, and more preferably, the drying temperature is about 130 to 180 ° C. and the drying time is about 10 minutes. .
本発明の親水性被膜形成物品の製造方法においては、塗布工程後の塗膜表面、及び／又は、硬化工程後の被膜表面に対して、オゾン処理を施し、被膜の酸化を進行させてもよい。 In the method for producing a hydrophilic film-formed article of the present invention, the coating film surface after the coating process and / or the coating film surface after the curing process may be subjected to ozone treatment to advance the coating oxidation. .
上記オゾン処理とは、塗布工程後の塗膜表面、及び／又は、硬化工程後の被膜表面に、ＵＶオゾン処理装置等を用い、特定波長の紫外線を照射し、オゾン（Ｏ３）を生成させ、その生成したオゾンを利用し、上記塗膜表面、及び／又は、上記被膜表面の酸化をより進行させる処理をいう。 The ozone treatment means that the surface of the coating film after the coating process and / or the surface of the coating film after the curing process is irradiated with ultraviolet rays having a specific wavelength using a UV ozone treatment device or the like to generate ozone (O 3 ). , Refers to a treatment that uses the generated ozone to further oxidize the coating film surface and / or the coating film surface.
本発明の親水性被膜形成物品で説明したように、本発明の親水性被膜形成物品の製造方法では、さらに、保護紙貼付工程として、上記親水性の被膜を保護するための保護紙を、上記親水性の被膜を覆うように親水性被膜形成物品の表面に貼付することが好ましい。 As described in the hydrophilic film-formed article of the present invention, in the method for producing a hydrophilic film-formed article of the present invention, a protective paper for protecting the hydrophilic film is further added as a protective paper pasting step. It is preferable to affix on the surface of a hydrophilic film formation article so that a hydrophilic film may be covered.
以下、実施例により本発明を具体的に説明する。但し、本発明はかかる実施例に限定されるものでない。
本実施例及び比較例では、親水性被膜形成物品の被膜を形成するための親水性被膜形成用塗布液を調製し、基材上に塗布し乾燥させて、親水性被膜形成物品を作製した。上記塗布液の調製方法及び親水性被膜形成物品の作製方法（製造方法）は後述の通りである。また、得られた親水性被膜形成物品について、以下に示す方法により品質評価を行った。
Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to such examples.
In this example and comparative example, a hydrophilic film-forming coating solution for forming a film of a hydrophilic film-forming article was prepared, applied onto a substrate and dried to prepare a hydrophilic film-forming article. A method for preparing the coating liquid and a method for producing a hydrophilic film-formed article (manufacturing method) are as described later. Moreover, quality evaluation was performed by the method shown below about the obtained hydrophilic film formation article.
［親水性被膜形成物品（被膜）の外観の観察］
得られた親水性被膜形成物品を肉眼で観察し、被膜に白濁やブツ欠陥が存在するかどうか確認した。なお、ブツ欠陥とは、被膜表面にある、肉眼で認識出来る程度の大きさの粒状の突起状の欠陥を意味する。
[Observation of appearance of hydrophilic film forming article (film)]
The obtained hydrophilic film-formed article was observed with the naked eye, and it was confirmed whether the film was cloudy or had defects. Note that the defect is a granular projection-like defect having a size that can be recognized with the naked eye on the surface of the coating.
［初期水接触角の測定］
得られた親水性被膜形成物品の初期接触角の評価として、被膜表面にイオン交換水２μｌを置き、液滴を置いた１０秒後の液滴と被膜表面とのなす角を、接触角計（ＣＡ−Ｘ２００、協和界面科学社製）を用いて室温（約２５℃）で測定した。測定は、親水性被膜形成物品を得た後、室温環境下で１日間放置後に行った。
[Measurement of initial water contact angle]
As an evaluation of the initial contact angle of the obtained hydrophilic film-formed article, 2 μl of ion-exchanged water was placed on the surface of the film, and the angle formed by the liquid droplet and the surface of the film 10 seconds after the liquid droplet was placed was measured using a contact angle meter ( It measured at room temperature (about 25 degreeC) using CA-X200, Kyowa Interface Science company make. The measurement was carried out after obtaining a hydrophilic film-formed article and leaving it for one day in a room temperature environment.
［汚れ除去性（耐リンス性）の評価］
親水性被膜形成物品の汚れ除去性の評価は、以下の処理を行った後、水接触角を測定することにより行った。
初期水接触角を評価した後の親水性被膜形成物品の被膜表面の全面にアジエンスコンディショナー（花王製）の５質量％水溶液を噴霧し、１時間室温で乾燥させた。該親水性被膜形成物品の被膜表面を約２０℃の流水にさらすとともに、ゴム手袋をした指にて該被膜表面を払拭して洗浄した。該親水性被膜形成物品を乾燥させた後、被膜表面の水接触角を測定した。初期接触角に対して、上記した処理後の水接触角の増大量が小さいほど汚れ除去性に優れる。
［鉛筆硬度の測定］
ＪＩＳ Ｋ ５６００−５−４（１９９９年）に準拠して、親水性被膜形成物品の被膜の鉛筆硬度を測定した。
[Evaluation of stain removability (rinse resistance)]
Evaluation of soil removability of the hydrophilic film-formed article was performed by measuring the water contact angle after the following treatment.
After evaluating the initial water contact angle, a 5% by mass aqueous solution of an Aziens conditioner (manufactured by Kao) was sprayed on the entire surface of the coating film of the hydrophilic film-formed article, and dried at room temperature for 1 hour. The surface of the hydrophilic film-formed article was exposed to running water at about 20 ° C., and the surface of the film was wiped with a finger wearing a rubber glove and washed. After the hydrophilic film-formed article was dried, the water contact angle on the film surface was measured. The smaller the amount of increase in the water contact angle after the above-described treatment with respect to the initial contact angle, the better the dirt removal property.
[Measurement of pencil hardness]
Based on JIS K 5600-5-4 (1999), the pencil hardness of the film of the hydrophilic film-formed article was measured.
［親水性被膜形成用塗布液の外観（ポットライフ）の観察による評価］
調製３時間後、１日後の親水性被膜形成用塗布液を肉眼で観察し、濁りや沈澱やゲル化等の不具合が生じているかどうかを確認した。
[Evaluation by observation of appearance (pot life) of coating liquid for forming hydrophilic film]
Three hours after the preparation, one day later, the coating liquid for forming a hydrophilic film was observed with the naked eye, and it was confirmed whether defects such as turbidity, precipitation, and gelation occurred.
［実施例１］
（１）親水性被膜形成用塗布液の調製
０．２０ｇ（０．９６ｍｍｏｌ）のテトラエトキシシラン（以降、「ＴＥＯＳ」とも記載する、多摩化学工業製）、０．１４ｇ（０．５１ｍｍｏｌ）のアルミニウムエチルアセトアセテート・ジイソプロピレート（以降、「ＡＬＣＨ」とも記載する、川研ファインケミカル製）、及び、０．７３ｍｍｏｌのオキシ塩化ジルコニウム８水和物（キシダ化学製）をエキネンＦ−１（日本アルコール販売製、エタノール、イソプロパノール、メチルエチルケトンの混合溶媒）で２６．２質量％に希釈した溶液０．９０ｇと、固形分濃度が４０．７質量％のコロイダルシリカ（ＭＡ−ＳＴ−Ｌ、日産化学工業製）０．３０ｇ（シリカ分は０．１２ｇ）と、０．６８ｇのイオン交換水（塗布液の固形分の総量１００質量％に対して、２３４質量％）と、５．４３ｇのエキネンＦ−１と、２．３８ｇの１−メトキシ−２−プロパノールとを、２５℃で３時間撹拌して固形分濃度が全酸化物換算で２．９質量％の溶液を得た。さらに、該溶液１．００ｇにエキネンＦ−１を１．３８ｇ、１−メトキシ−２−プロパノールを０．５２ｇ添加して、固形分濃度が全酸化物換算で１．０質量％である親水性被膜形成用塗布液を調製した。なお、本実施例では、オキシ塩化ジルコニウム８水和物と水が反応した際に生成した塩酸を酸として用いた。
なお、コロイダルシリカ（酸化物微粒子）、ＴＥＯＳ（ケイ素酸化物前駆体）の固形分、及びＡＬＣＨ（アルミニウム酸化物前駆体）の固形分の総量１００質量％に対して、コロイダルシリカの含有量は４１．４質量％であり、該コロイダルシリカ４０質量部に対して、ＴＥＯＳは酸化物換算で１９．２質量部、ＡＬＣＨは酸化物換算で８．７質量部である。
[Example 1]
(1) Preparation of coating solution for forming hydrophilic film 0.20 g (0.96 mmol) of tetraethoxysilane (hereinafter also referred to as “TEOS”, manufactured by Tama Chemical Industries), 0.14 g (0.51 mmol) of aluminum Ethynacetoacetate diisopropylate (hereinafter referred to as “ALCH”, manufactured by Kawaken Fine Chemical Co., Ltd.) and 0.73 mmol of zirconium oxychloride octahydrate (manufactured by Kishida Chemical Co., Ltd.) Echinen F-1 (Nihon Alcohol Sales) 0.90 g of a solution diluted to 26.2% by mass with a mixed solvent of ethanol, isopropanol and methyl ethyl ketone) and colloidal silica having a solid content concentration of 40.7% by mass (MA-ST-L, manufactured by Nissan Chemical Industries) 0.30 g (silica content is 0.12 g) and 0.68 g of ion exchange water (total amount of solid content of coating solution is 100 234% by mass with respect to the amount%), 5.43 g of Echinen F-1 and 2.38 g of 1-methoxy-2-propanol were stirred at 25 ° C. for 3 hours, and the solid content concentration was totally oxidized. A 2.9% by mass solution in terms of product was obtained. Furthermore, 1.38 g of Echinen F-1 and 0.52 g of 1-methoxy-2-propanol were added to 1.00 g of the solution, and the solid content concentration was 1.0% by mass in terms of total oxide. A coating solution for film formation was prepared. In this example, hydrochloric acid produced when zirconium oxychloride octahydrate and water reacted was used as the acid.
In addition, with respect to the total amount of solid content of colloidal silica (oxide fine particles), solid content of TEOS (silicon oxide precursor), and solid content of ALCH (aluminum oxide precursor), the content of colloidal silica is 41. TEOS is 19.2 parts by mass in terms of oxide and ALCH is 8.7 parts by mass in terms of oxide with respect to 40 parts by mass of the colloidal silica.
（２）親水性被膜形成物品の製造
ソーダライムガラス製のガラス基材（１００ｍｍ×１００ｍｍ×２ｍｍ）を使用し、コーティング面を酸化セリウムで十分に研磨した後、水洗後、乾燥させてコーティング用基材とした。
上記基材表面に上記の親水性被膜形成用塗布液をスピンコート法で塗布し、１７０℃で１０分間加熱処理して塗膜を硬化させて、該基材表面に被膜を形成し、親水性被膜形成物品を作製した。そして、最後に親水性の被膜を保護するための保護紙を、親水性の被膜を覆うように親水性被膜形成物品の表面に貼付し、保護膜を有する親水性被膜形成物品とした。なお、上記保護紙の貼付（保護紙貼付工程）は、水（７０質量％）と、粘着成分である澱粉化合物（２０質量％）と、親水剤である大阪有機化学工業製、製品名「ＬＡＭＢＩＣ７７０Ｗ」（１０質量％）との混合液を親水性被膜形成物品の被膜表面に塗布した後に、その上に保護紙として片艶クラフト紙（日本製紙製、製品名「キャピタルラップ」）を密着させて行った。
保護紙貼付前の親水性被膜形成物品について、上記した評価方法により評価し、保護紙貼付後の親水性被膜形成物品について、保護紙を剥離し、初期水接触角、及び、汚れ除去性（耐リンス性）を評価した。
(2) Manufacture of hydrophilic film-formed article Using a glass substrate (100 mm x 100 mm x 2 mm) made of soda lime glass, the coated surface is sufficiently polished with cerium oxide, washed with water, dried and then coated. A material was used.
The above coating liquid for forming a hydrophilic film is applied to the surface of the base material by a spin coating method, and the coating film is cured by heat treatment at 170 ° C. for 10 minutes to form a film on the surface of the base material. A film-formed article was prepared. And finally, the protective paper for protecting a hydrophilic film was stuck on the surface of the hydrophilic film formation article so that a hydrophilic film might be covered, and it was set as the hydrophilic film formation article which has a protective film. In addition, the sticking of the protective paper (protective paper sticking step) includes water (70% by mass), a starch compound (20% by mass) as an adhesive component, and a product name “LAMBIC 770W” manufactured by Osaka Organic Chemical Industry as a hydrophilic agent. ”(10% by mass) is applied to the coating surface of the hydrophilic film-forming article, and then glossy kraft paper (product name“ Capital Wrap ”, manufactured by Nippon Paper Industries Co., Ltd.) is used as a protective paper. went.
The hydrophilic film-formed article before application of protective paper is evaluated by the above-described evaluation method, and the hydrophilic film-formed article after application of protective paper is peeled off, and the initial water contact angle and dirt removal property (resistance to resistance) Rinse properties were evaluated.
［実施例２］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳを０．１６ｇ（０．７７ｍｍｏｌ）、ＡＬＣＨを０．２１ｇ（０．７７ｍｍｏｌ）用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 2]
The hydrophilic coating film was prepared in the same manner as in Example 1 except that 0.16 g (0.77 mmol) of TEOS and 0.21 g (0.77 mmol) of ALCH were used in the preparation of the coating solution for forming a hydrophilic coating film of Example 1. A coating solution for formation was prepared, and a coating film was formed on the surface of the substrate in the same procedure as in Example 1. Evaluation was performed in the same manner as in Example 1.
［実施例３］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳを０．０８ｇ（０．３８ｍｍｏｌ）、ＡＬＣＨを０．３１ｇ（１．１３ｍｍｏｌ）用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 3]
The hydrophilic coating film was prepared in the same manner as in Example 1 except that 0.08 g (0.38 mmol) of TEOS and 0.31 g (1.13 mmol) of ALCH were used in the preparation of the coating solution for forming a hydrophilic coating film of Example 1. A coating solution for formation was prepared, and a coating film was formed on the surface of the substrate in the same procedure as in Example 1. Evaluation was performed in the same manner as in Example 1.
［実施例４］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳを０．１８ｇ（０．８６ｍｍｏｌ）、ＡＬＣＨを０．２４ｇ（０．８７ｍｍｏｌ）、コロイダルシリカ（ＭＡ−ＳＴ−Ｌ）を０．２３ｇ用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 4]
In the preparation of the coating liquid for forming a hydrophilic film of Example 1, TEOS was 0.18 g (0.86 mmol), ALCH was 0.24 g (0.87 mmol), and colloidal silica (MA-ST-L) was 0.23 g. A coating solution for forming a hydrophilic film was prepared in the same manner as in Example 1 except that it was used, and a film was formed on the surface of the substrate in the same procedure as in Example 1. Evaluation was performed in the same manner as in Example 1.
［実施例５］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳを０．１３ｇ（０．６２ｍｍｏｌ）、ＡＬＣＨを０．１７ｇ（０．６２ｍｍｏｌ）、コロイダルシリカ（ＭＡ−ＳＴ−Ｌ）を０．３８ｇ用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 5]
In the preparation of the coating liquid for forming a hydrophilic coating film of Example 1, TEOS was 0.13 g (0.62 mmol), ALCH was 0.17 g (0.62 mmol), and colloidal silica (MA-ST-L) was 0.38 g. A coating solution for forming a hydrophilic film was prepared in the same manner as in Example 1 except that it was used, and a film was formed on the surface of the substrate in the same procedure as in Example 1. Evaluation was performed in the same manner as in Example 1.
［実施例６］
実施例２の親水性被膜形成用塗布液の調製において、ＴＥＯＳの代わりにメチルトリエトキシシラン（以降、「ＭＴＥＳ」とも記載する、キシダ化学製）を０．１３ｇ（０．７３ｍｍｏｌ）用いた以外は、実施例２と同様に親水性被膜形成用塗布液を調製し、実施例２と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 6]
Except for using 0.13 g (0.73 mmol) of methyltriethoxysilane (hereinafter also referred to as “MTES”, manufactured by Kishida Chemical Co.) in place of TEOS in the preparation of the coating liquid for forming a hydrophilic film of Example 2. A coating solution for forming a hydrophilic film was prepared in the same manner as in Example 2, a film was formed on the substrate surface in the same procedure as in Example 2, and evaluation was performed in the same manner as in Example 1.
［実施例７］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳを０．１８ｇ（０．８６ｍｍｏｌ）、ＡＬＣＨを０．１６ｇ（０．５８ｍｍｏｌ）、コロイダルシリカ（ＭＡ−ＳＴ−Ｌ）を０．２９ｇ、イオン交換水を０．１６ｇ（塗布液の固形分の総量１００質量％に対して、５５質量％）、エキネンＦ−１を６．５３ｇ、１−メトキシ−２−プロパノールを２．３５ｇ用い、オキシ塩化ジルコニウム８水和物をエキネンＦ−１で２６．２質量％に希釈した溶液の代わりにジルコニウムテトラ−ｎ−ブトキシドを１−プロパノールで８５質量％に希釈した溶液を０．３２ｇ（ジルコニウムテトラ−ｎ−ブトキシド自体は０．７１ｍｍｏｌ）用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 7]
In the preparation of the coating liquid for forming a hydrophilic film of Example 1, TEOS was 0.18 g (0.86 mmol), ALCH was 0.16 g (0.58 mmol), and colloidal silica (MA-ST-L) was 0.29 g. , 0.16 g of ion-exchanged water (55% by mass with respect to 100% by mass of the total solid content of the coating solution), 6.53 g of Echinen F-1, and 2.35 g of 1-methoxy-2-propanol, Instead of a solution obtained by diluting zirconium oxychloride octahydrate to 26.2% by mass with Echinen F-1, 0.32 g (zirconium tetra) of a solution obtained by diluting zirconium tetra-n-butoxide to 85% by mass with 1-propanol was used. A coating solution for forming a hydrophilic film was prepared in the same manner as in Example 1 except that -n-butoxide itself was 0.71 mmol). To form a film, it was evaluated in the same manner as in Example 1.
［実施例８］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳを０．１６ｇ（０．７７ｍｍｏｌ）、ＡＬＣＨの代わりにアルミニウムトリスアセチルアセトナート（川研ファインケミカル製）を０．２４ｇ（０．７４ｍｍｏｌ）用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 8]
In the preparation of the coating liquid for forming a hydrophilic film of Example 1, TEOS was 0.16 g (0.77 mmol), and aluminum trisacetylacetonate (manufactured by Kawaken Fine Chemical Co., Ltd.) instead of ALCH was 0.24 g (0.74 mmol). A coating solution for forming a hydrophilic film was prepared in the same manner as in Example 1 except that it was used, and a film was formed on the surface of the substrate in the same procedure as in Example 1. Evaluation was performed in the same manner as in Example 1.
［実施例９］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳを０．３１ｇ（１．４９ｍｍｏｌ）、ＡＬＣＨを０．４１ｇ（１．４９ｍｍｏｌ）用い、オキシ塩化ジルコニウム８水和物をエキネンＦ−１で２６．２質量％に希釈した溶液を用いなかった以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 9]
In the preparation of the coating solution for forming a hydrophilic coating film of Example 1, TE1 was used in 0.31 g (1.49 mmol), ALCH was used in 0.41 g (1.49 mmol), and zirconium oxychloride octahydrate was used as Echinen F-1. A coating solution for forming a hydrophilic coating was prepared in the same manner as in Example 1 except that the solution diluted to 26.2% by mass was not used, and a coating was formed on the substrate surface in the same procedure as in Example 1. Evaluation was performed in the same manner as in Example 1.
［実施例１０］
実施例１の親水性被膜形成用塗布液の調製において、イオン交換水を０．３３ｇ（塗布液の固形分の総量１００質量％に対して、１１４質量％）用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 10]
In the preparation of the coating liquid for forming a hydrophilic coating film of Example 1, ion exchange water was used in Example 1 except that 0.33 g (114 mass% with respect to 100 mass% of the total solid content of the coating liquid) was used. Similarly, a coating solution for forming a hydrophilic film was prepared, a film was formed on the substrate surface in the same procedure as in Example 1, and evaluation was performed in the same manner as in Example 1.
［実施例１１］
実施例１の親水性被膜形成用塗布液の調製において、イオン交換水を０．１６ｇ（塗布液の固形分の総量１００質量％に対して、５５質量％）用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 11]
In the preparation of the coating solution for forming a hydrophilic coating film of Example 1, ion exchange water was used in the same manner as in Example 1 except that 0.16 g (55% by mass with respect to 100% by mass of the total solid content of the coating solution) was used. Similarly, a coating solution for forming a hydrophilic film was prepared, a film was formed on the substrate surface in the same procedure as in Example 1, and evaluation was performed in the same manner as in Example 1.
［実施例１２］
実施例１の親水性被膜形成用塗布液の調製において、イオン交換水を０．１０ｇ（塗布液の固形分の総量１００質量％に対して、３４質量％）用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 12]
In the preparation of the coating liquid for forming a hydrophilic coating film of Example 1, 0.10 g of ion-exchanged water (34% by mass with respect to 100% by mass of the total solid content of the coating liquid) was used. Similarly, a coating solution for forming a hydrophilic film was prepared, a film was formed on the substrate surface in the same procedure as in Example 1, and evaluation was performed in the same manner as in Example 1.
［実施例１３］
実施例１の親水性被膜形成用塗布液の調製において、イオン交換水を０．０５ｇ（塗布液の固形分の総量１００質量％に対して、１７質量％）用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 13]
In the preparation of the coating liquid for forming a hydrophilic film of Example 1, Example 1 was used except that 0.05 g of ion-exchanged water (17% by mass with respect to 100% by mass of the total solid content of the coating liquid) was used. Similarly, a coating solution for forming a hydrophilic film was prepared, a film was formed on the substrate surface in the same procedure as in Example 1, and evaluation was performed in the same manner as in Example 1.
［実施例１４］
実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成した。その後、ＵＶオゾン処理装置を用いて該親水性被膜表面に６０秒間酸化処理を施した。この後、得られた親水性被膜形成物品について、実施例１と同様に評価を行った。
[Example 14]
A coating solution for forming a hydrophilic film was prepared in the same manner as in Example 1, and a film was formed on the substrate surface in the same procedure as in Example 1. Thereafter, the surface of the hydrophilic coating was oxidized for 60 seconds using a UV ozone treatment apparatus. Thereafter, the obtained hydrophilic film-formed article was evaluated in the same manner as in Example 1.
［実施例１５］
実施例１の親水性被膜形成物品の製造において、保護紙貼付工程で、水（５５質量％）と、粘着成分である澱粉化合物（２０質量％）と、界面活性剤として東邦化学工業製、製品名「ペポールＡＳ−０５３Ｘ」（２５質量％）との混合液を親水性被膜形成物品の被膜表面に塗布した以外は、実施例１と同様に行った。また、実施例１と同様に評価を行った。
[Example 15]
In the production of the hydrophilic film-formed article of Example 1, in the protective paper pasting step, water (55% by mass), starch compound (20% by mass) as an adhesive component, and a product made by Toho Chemical Industries as a surfactant, The same procedure as in Example 1 was conducted, except that a liquid mixture with the name “Pepol AS-053X” (25% by mass) was applied to the coating surface of the hydrophilic coating-formed article. The evaluation was performed in the same manner as in Example 1.
［実施例１６］
実施例１で得られた親水性被膜形成用塗布液に、さらに三塩化アルミニウム・六水和物を、固形分の総量１００質量％に対して、０．０１質量％となるように添加した以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。なお、コロイダルシリカ４０質量部に対して、ＡＬＣＨと三塩化アルミニウム・六水和物の総量は酸化物換算で８．７質量部である。
本実施例の親水性被膜形成物品の初期接触角（室温環境下で１日間放置後）は２９°であり、実施例１の親水性被膜形成物品の初期接触角（３０°）と同等であるが、それぞれの親水性被膜形成物品を室温環境下で８日間放置した後の接触角は、実施例１が３３°であったのに対し、本実施例は３０°であり、被膜の親水性が長期間にわたってより維持されやすいことがわかった。
[Example 16]
Except for adding aluminum trichloride / hexahydrate to the coating solution for forming a hydrophilic film obtained in Example 1 so as to be 0.01% by mass with respect to 100% by mass of the total solid content. Prepared a coating solution for forming a hydrophilic film in the same manner as in Example 1, formed a film on the surface of the substrate in the same procedure as in Example 1, and evaluated in the same manner as in Example 1. In addition, with respect to 40 mass parts of colloidal silica, the total amount of ALCH and aluminum trichloride hexahydrate is 8.7 mass parts in terms of oxide.
The initial contact angle of the hydrophilic film-formed article of this example (after standing for 1 day in a room temperature environment) is 29 °, which is equivalent to the initial contact angle (30 °) of the hydrophilic film-formed article of Example 1. However, the contact angle after leaving each hydrophilic film-formed article in a room temperature environment for 8 days was 33 ° in Example 1, whereas it was 30 ° in this example. Has been found to be more easily maintained over long periods of time.
［実施例１７］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳ、ＡＬＣＨ、オキシ塩化ジルコニウム８水和物、コロイダルシリカ（ＭＡ−ＳＴ−Ｌ）、イオン交換水を、表１に記載の量となるように用いた以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成し、実施例１と同様に評価を行った。
[Example 17]
In the preparation of the coating liquid for forming a hydrophilic film of Example 1, TEOS, ALCH, zirconium oxychloride octahydrate, colloidal silica (MA-ST-L), and ion-exchanged water are in the amounts shown in Table 1. In the same manner as in Example 1, a coating solution for forming a hydrophilic film was prepared, and a film was formed on the substrate surface in the same procedure as in Example 1. Evaluation was performed in the same manner as in Example 1. It was.
［比較例１］
実施例２の親水性被膜形成用塗布液の調製において、ＡＬＣＨの代わりにアルミニウムｓｅｃ−ブトキシド（キシダ化学製）を０．１９ｇ（０．７７ｍｍｏｌ）用いた以外は実施例２と同様に親水性被膜形成用塗布液を調製し、実施例２と同様の手順で基材表面に被膜を形成した。
[Comparative Example 1]
In the preparation of the coating solution for forming a hydrophilic coating film of Example 2, the hydrophilic coating film was prepared in the same manner as in Example 2 except that 0.19 g (0.77 mmol) of aluminum sec-butoxide (manufactured by Kishida Chemical) was used instead of ALCH. A coating solution for formation was prepared, and a coating film was formed on the surface of the substrate in the same procedure as in Example 2.
［比較例２］
実施例４の親水性被膜形成用塗布液の調製において、コロイダルシリカ４０質量部に対して、ＴＥＯＳが酸化物換算で５．１質量部、ＡＬＣＨが酸化物換算で３５．６質量部となるように親水性被膜形成用塗布液を調製し、実施例４と同様の手順で基材表面に被膜を形成した。
[Comparative Example 2]
In the preparation of the coating liquid for forming a hydrophilic coating film of Example 4, TEOS is 5.1 parts by mass in terms of oxide and ALCH is 35.6 parts by mass in terms of oxide with respect to 40 parts by mass of colloidal silica. A coating solution for forming a hydrophilic film was prepared, and a film was formed on the substrate surface in the same procedure as in Example 4.
［比較例３］
実施例４の親水性被膜形成用塗布液の調製において、コロイダルシリカ４０質量部に対して、ＴＥＯＳが酸化物換算で４２．４質量部、ＡＬＣＨが酸化物換算で４．１質量部となるように親水性被膜形成用塗布液を調製し、実施例４と同様の手順で基材表面に被膜を形成した。
[Comparative Example 3]
In the preparation of the coating liquid for forming a hydrophilic film of Example 4, TEOS is 42.4 parts by mass in terms of oxide and ALCH is 4.1 parts by mass in terms of oxide with respect to 40 parts by mass of colloidal silica. A coating solution for forming a hydrophilic film was prepared, and a film was formed on the substrate surface in the same procedure as in Example 4.
［比較例４］
実施例１の親水性被膜形成用塗布液の調製において、ＴＥＯＳを０．３１ｇ（１．４９ｍｍｏｌ）用い、ＡＬＣＨを用いず、各成分の比率を表１の通りにした以外は実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成した。
[Comparative Example 4]
In the preparation of the coating solution for forming a hydrophilic coating film of Example 1, TE1 was used in an amount of 0.31 g (1.49 mmol), ALCH was not used, and the ratio of each component was as shown in Table 1, and the same as in Example 1. A coating solution for forming a hydrophilic film was prepared, and a film was formed on the substrate surface in the same procedure as in Example 1.
［比較例５］
実施例１の親水性被膜形成用塗布液の調製において、ＡＬＣＨを０．４１ｇ（１．４９ｍｍｏｌ）用い、ＴＥＯＳを用いず、各成分の比率を表１の通りにした以外は、実施例１と同様に親水性被膜形成用塗布液を調製し、実施例１と同様の手順で基材表面に被膜を形成した。
[Comparative Example 5]
In the preparation of the coating solution for forming a hydrophilic film of Example 1, 0.41 g (1.49 mmol) of ALCH was used, TEOS was not used, and the ratio of each component was as shown in Table 1. Similarly, a coating liquid for forming a hydrophilic film was prepared, and a film was formed on the surface of the substrate in the same procedure as in Example 1.
各実施例及び各比較例について、親水性被膜形成用塗布液の各成分とその割合、酸化処理の有無、得られた親水性被膜の各成分、金属酸化物の層中のケイ素酸化物とアルミニウム酸化物とのモル比を表１に示す。また、各実施例及び各比較例で得られた親水性被膜形成物品（被膜）に関し、保護紙貼付前の外観の観察結果、初期水接触角の測定結果、汚れ除去性（耐リンス性）の水接触角による評価結果、鉛筆硬度の測定結果、親水性被膜形成用塗布液の外観（ポットライフ）の観察による評価結果を下記の表２に示す。また、保護紙貼付後に該保護紙を剥離した親水性被膜形成物品の評価結果を表３に示す。 About each Example and each comparative example, each component of the coating liquid for hydrophilic film formation, its ratio, the presence or absence of oxidation treatment, each component of the obtained hydrophilic film, silicon oxide and aluminum in the metal oxide layer The molar ratio with the oxide is shown in Table 1. In addition, regarding the hydrophilic film-formed articles (coating films) obtained in the respective Examples and Comparative Examples, the observation results of the appearance before applying the protective paper, the measurement results of the initial water contact angle, the soil removability (rinsing resistance) Table 2 below shows the evaluation results based on the water contact angle, the pencil hardness measurement results, and the observation results of the appearance (pot life) of the hydrophilic coating-forming coating solution. In addition, Table 3 shows the evaluation results of the hydrophilic film-formed article from which the protective paper was peeled after application of the protective paper.
表１及び表２より明らかなように、実施例１〜１７では、親水性被膜形成用塗布液は、少なくとも、酸化物微粒子を含むコロイド溶液、一般式［４］で表されるケイ素酸化物前駆体、一般式［５］で表されるアルミニウム酸化物前駆体、酸、水及び溶媒を混合することにより調製された親水性被膜形成用塗布液であり、上記酸化物微粒子、上記ケイ素酸化物前駆体の固形分、及び上記アルミニウム酸化物前駆体の固形分の総量１００質量％に対して、上記酸化物微粒子の含有量が２０〜６０質量％であり、該酸化物微粒子４０質量部に対して、上記ケイ素酸化物前駆体が酸化物換算で６〜４０質量部、上記アルミニウム酸化物前駆体が酸化物換算で５〜３０質量部であり、上記親水性被膜形成用塗布液のポットライフは、塗布液として用いるには問題のない期間を有するものであり、上記親水性被膜形成用塗布液を用いて製造した親水性被膜形成物品は、外観に問題はなく、汚れ除去性に優れ、被膜の硬度も充分であった。
また、水の添加量が、親水性被膜形成用塗布液の固形分の総量１００質量％に対して、１５〜１２０質量％の範囲内である実施例７、１０〜１３に係る親水性被膜形成用塗布液は、ポットライフがより良好となり、被膜の硬度も充分であった。
また、アルミニウム酸化物前駆体として、アルミニウムトリスアセチルアセトナート（一般式［５］のｈ＝３の構造）を用いた実施例８に係る親水性被膜形成用塗布液は、ポットライフがより良好であった。この前駆体は加水分解性の官能基を有していないため、水の添加量が比較的多いにもかかわらず、該前駆体の安定性によって、優れたポットライフが実現されたと考えられる。また、保護紙を貼付することにより、親水性、汚れ除去性がさらに改善された。
As is clear from Tables 1 and 2, in Examples 1 to 17, the coating liquid for forming a hydrophilic film is at least a colloidal solution containing fine oxide particles, and a silicon oxide precursor represented by the general formula [4]. Body, a coating solution for forming a hydrophilic coating prepared by mixing an aluminum oxide precursor represented by the general formula [5], an acid, water and a solvent, and the oxide fine particles and the silicon oxide precursor The content of the oxide fine particles is 20 to 60% by mass with respect to 100% by mass of the solid content of the body and the solid content of the aluminum oxide precursor, and with respect to 40 parts by mass of the oxide fine particles. The silicon oxide precursor is 6 to 40 parts by mass in terms of oxide, the aluminum oxide precursor is 5 to 30 parts by mass in terms of oxide, and the pot life of the coating liquid for forming a hydrophilic film is as follows: Use as coating solution Has a problem-free period, and the hydrophilic film-formed article produced by using the above-mentioned hydrophilic film-forming coating solution has no problem in appearance, has excellent stain removability, and has a sufficient film hardness. It was.
Moreover, hydrophilic film formation which concerns on Examples 7 and 10-13 whose addition amount of water exists in the range of 15-120 mass% with respect to 100 mass% of total amount of solid content of the coating liquid for hydrophilic film formation. The coating solution for pots had a better pot life and sufficient film hardness.
Further, the coating liquid for forming a hydrophilic film according to Example 8 using aluminum trisacetylacetonate (structure of h = 3 in the general formula [5]) as the aluminum oxide precursor has a better pot life. there were. Since this precursor does not have a hydrolyzable functional group, it is considered that an excellent pot life was realized by the stability of the precursor despite the relatively large amount of water added. Moreover, the hydrophilicity and dirt removal property were further improved by applying protective paper.
一方、比較例１では、表１に示すように、ＡＬＣＨの代わりにアルミニウムｓｅｃ−ブトキシドを用いたので、表２に示すように、調製した親水性被膜形成用塗布液には白色沈殿が生じており、該白色沈殿は１日後にも残っていた。また、得られた、被膜の表面には多数のブツ欠陥が存在しており、外観上問題があった。 On the other hand, in Comparative Example 1, since aluminum sec-butoxide was used instead of ALCH as shown in Table 1, as shown in Table 2, white precipitate was generated in the prepared coating liquid for forming a hydrophilic film. The white precipitate remained after 1 day. In addition, the surface of the obtained coating had a number of defects, and there was a problem in appearance.
比較例２では、表１に示すように、得られた被膜を構成する金属酸化物の層中のケイ素酸化物とアルミニウム酸化物の比率は、モル比で、ケイ素酸化物：アルミニウム酸化物＝１０．８：８９．２とアルミニウム酸化物の割合が多すぎる。
その結果、表２に示すように、得られた被膜は優れた汚れ除去性を示すものの、汚れ除去性（耐リンス性）の評価の際にゴム手袋をした指にて被膜表面を払拭して洗浄すると、該被膜表面に多数の傷が発生してしまい、膜強度が不充分であった。
In Comparative Example 2, as shown in Table 1, the ratio of silicon oxide to aluminum oxide in the metal oxide layer constituting the obtained film was a molar ratio of silicon oxide: aluminum oxide = 10. .8: 89.2 and the proportion of aluminum oxide is too large.
As a result, as shown in Table 2, although the obtained film showed excellent dirt removal property, the surface of the film was wiped with fingers wearing rubber gloves when evaluating the dirt removal property (rinse resistance). When washed, a large number of scratches were generated on the surface of the coating, and the film strength was insufficient.
比較例３では、表１に示すように、得られた被膜を構成する金属酸化物の層中のケイ素酸化物とアルミニウム酸化物の比率は、モル比で、ケイ素酸化物：アルミニウム酸化物＝８９．８：１０．２とアルミニウム酸化物の割合が少なすぎる。
その結果、表２に示すように、得られた被膜の耐リンス性試験後の水接触角は６０°（初期水接触角２２°）であり、耐リンス性が劣るものであった。
In Comparative Example 3, as shown in Table 1, the ratio of silicon oxide to aluminum oxide in the metal oxide layer constituting the obtained film was a molar ratio of silicon oxide: aluminum oxide = 89. .8: 10.2 and the proportion of aluminum oxide is too small.
As a result, as shown in Table 2, the water contact angle after the rinse resistance test of the obtained coating was 60 ° (initial water contact angle 22 °), and the rinse resistance was inferior.
比較例４では、表１に示すように、酸化物微粒子（コロイダルシリカ）、ケイ素酸化物前駆体（ＴＥＯＳ）の固形分、及びアルミニウム酸化物前駆体（無し）の固形分の総量１００質量％に対して、コロイダルシリカの含有量が４０質量％であり、該コロイダルシリカ４０質量部に対して、ＴＥＯＳが酸化物換算で２９．８質量部、アルミニウム酸化物前駆体が酸化物換算で０質量部である。得られた被膜を構成する金属酸化物の層中のケイ素酸化物とアルミニウム酸化物の比率は、モル比で、ケイ素酸化物：アルミニウム酸化物＝１００：０であり、アルミニウム酸化物が含まれていない。
その結果、表２に示すように、得られた親水性被膜の耐リンス性試験後の水接触角は５３°（初期水接触角３０°）であり、耐リンス性が劣るものであった。
In Comparative Example 4, as shown in Table 1, the total amount of oxide fine particles (colloidal silica), the solid content of the silicon oxide precursor (TEOS), and the solid content of the aluminum oxide precursor (none) was 100% by mass. On the other hand, the content of colloidal silica is 40% by mass, and 29.8 parts by mass of TEOS in terms of oxide and 0 parts by mass of aluminum oxide precursor in terms of oxide with respect to 40 parts by mass of colloidal silica. It is. The ratio of silicon oxide to aluminum oxide in the metal oxide layer constituting the obtained coating is a molar ratio of silicon oxide: aluminum oxide = 100: 0, and aluminum oxide is contained. Absent.
As a result, as shown in Table 2, the water contact angle after the rinse resistance test of the obtained hydrophilic coating was 53 ° (initial water contact angle 30 °), and the rinse resistance was inferior.
比較例５では、表１に示すように、酸化物微粒子（コロイダルシリカ）、ケイ素酸化物前駆体（無し）の固形分、及びアルミニウム酸化物前駆体（ＡＬＣＨ）の固形分の総量１００質量％に対して、コロイダルシリカの含有量が４１．４質量％であり、該コロイダルシリカ４０質量部に対して、ケイ素酸化物前駆体が酸化物換算で０質量部、ＡＬＣＨが酸化物換算で２５．３質量部である。得られた被膜を構成する金属酸化物の層中のケイ素酸化物とアルミニウム酸化物の比率は、モル比で、ケイ素酸化物：アルミニウム酸化物＝０：１００であり、ケイ素酸化物が含まれていない。
その結果、表２に示すように、得られた親水性被膜は優れた汚れ除去性を示すものの、汚れ除去性（耐リンス性）の評価の際にゴム手袋をした指にて被膜表面を払拭して洗浄すると、該被膜表面に多数の傷が発生してしまい、膜強度が不充分であった。
なお、上記のように、比較例１〜５については、得られた親水性被膜形成物品に不具合があるので、保護紙貼付による評価を行っていない。
In Comparative Example 5, as shown in Table 1, the total amount of oxide fine particles (colloidal silica), the solid content of the silicon oxide precursor (none), and the solid content of the aluminum oxide precursor (ALCH) was 100% by mass. On the other hand, the colloidal silica content is 41.4% by mass, and the silicon oxide precursor is 0 part by mass in terms of oxide and ALCH is 25.3 in terms of oxide with respect to 40 parts by mass of the colloidal silica. Part by mass. The ratio of silicon oxide to aluminum oxide in the metal oxide layer constituting the obtained coating is a molar ratio of silicon oxide: aluminum oxide = 0: 100, and silicon oxide is contained. Absent.
As a result, as shown in Table 2, although the obtained hydrophilic coating film exhibits excellent dirt removal properties, the surface of the coating film was wiped off with a finger wearing a rubber glove when evaluating the stain removal properties (rinse resistance). When washed, many scratches were generated on the surface of the coating, and the film strength was insufficient.
In addition, as above-mentioned, since Comparative Example 1-5 has a malfunction in the obtained hydrophilic film formation article, evaluation by sticking a protective paper is not performed.
Claims (18)
前記金属酸化物の層は、
下記一般式［１］で表されるケイ素酸化物の少なくとも１種、及び、
下記一般式［２］で表されるアルミニウム酸化物の少なくとも１種を含み、
前記ケイ素酸化物と前記アルミニウム酸化物のモル比は、ケイ素酸化物：アルミニウム酸化物＝２０：８０〜８０：２０であることを特徴とする親水性被膜形成物品。
（Ｒ１）ａＳｉＯｂ ［１］
（式［１］中、Ｒ１は１価の有機基であり、ａは０〜３．５、ｂは０．５〜２である。）
（Ｒ２）ｃＡｌＯｄ ［２］
（式［２］中、Ｒ２はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、ｃは０〜２、ｄは０．５〜１．５である。） A hydrophilic film-forming article having a base material and a film in which oxide fine particles are dispersed on the surface of the base material and held by a metal oxide layer,
The metal oxide layer comprises:
At least one silicon oxide represented by the following general formula [1], and
Including at least one aluminum oxide represented by the following general formula [2],
The molar ratio of the silicon oxide to the aluminum oxide is silicon oxide: aluminum oxide = 20: 80 to 80:20.
(R 1 ) a SiO b [1]
(In the formula [1], R 1 is a monovalent organic group, a is 0 to 3.5, and b is 0.5 to 2.)
(R 2 ) c AlO d [2]
(In the formula [2], R 2 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, c is 0 to 2, and d is 0.5 to 1.5.)
下記一般式［３］で表されるジルコニウム酸化物を含む請求項１又は２に記載の親水性被膜形成物品。
（Ｒ３）ｅＺｒＯｆ ［３］
（式［３］中、Ｒ３は１価の有機基であり、ｅは０〜３．５、ｆは０．５〜２である。） The metal oxide layer further comprises:
The hydrophilic film formation article of Claim 1 or 2 containing the zirconium oxide represented by following General formula [3].
(R 3 ) e ZrO f [3]
(In Formula [3], R 3 is a monovalent organic group, e is 0 to 3.5, and f is 0.5 to 2.)
下記一般式［４］で表されるケイ素酸化物前駆体、
下記一般式［５］で表されるアルミニウム酸化物前駆体、
酸、水及び溶媒を混合することにより調製された親水性被膜形成用塗布液であり、
前記酸化物微粒子、前記ケイ素酸化物前駆体の固形分、及び、前記アルミニウム酸化物前駆体の固形分の総量１００質量％に対して、前記酸化物微粒子の含有量が２０〜６０質量％であり、該酸化物微粒子４０質量部に対して、前記ケイ素酸化物前駆体が酸化物換算で６〜４０質量部、前記アルミニウム酸化物前駆体が酸化物換算で５〜３０質量部であることを特徴とする親水性被膜形成用塗布液。
（Ｒ４）ｇＳｉ（Ｘ１）４−ｇ ［４］
（式［４］中、Ｒ４は１価の有機基であり、Ｘ１はアルコキシル基又はハロゲン元素であり、ｇは０〜３の整数である。）
（Ｒ５）ｈＡｌ（Ｘ２）３−ｈ ［５］
（式［５］中、Ｒ５はアセチルアセトナート基及びエチルアセトアセテート基から選ばれる少なくとも１つの基であり、Ｘ２はアルコキシル基又はハロゲン元素であり、ｈは１〜３の整数である。） At least a colloidal solution containing fine oxide particles,
A silicon oxide precursor represented by the following general formula [4],
An aluminum oxide precursor represented by the following general formula [5],
A coating solution for forming a hydrophilic film prepared by mixing an acid, water and a solvent,
The content of the oxide fine particles is 20 to 60% by mass with respect to 100% by mass of the solid content of the oxide fine particles, the solid content of the silicon oxide precursor, and the solid content of the aluminum oxide precursor. The silicon oxide precursor is 6 to 40 parts by mass in terms of oxide and the aluminum oxide precursor is 5 to 30 parts by mass in terms of oxide with respect to 40 parts by mass of the oxide fine particles. A coating solution for forming a hydrophilic film.
(R 4 ) g Si (X 1 ) 4-g [4]
(In the formula [4], R 4 is a monovalent organic group, X 1 is an alkoxyl group or a halogen element, and g is an integer of 0 to 3.)
(R 5 ) h Al (X 2 ) 3-h [5]
(In the formula [5], R 5 is at least one group selected from an acetylacetonate group and an ethylacetoacetate group, X 2 is an alkoxyl group or a halogen element, and h is an integer of 1 to 3. )
前記一般式［５］で表されるアルミニウム酸化物前駆体が、Ｒ５Ａｌ（Ｘ２）２である請求項９に記載の親水性被膜形成用塗布液。 The silicon oxide precursor represented by the general formula [4] is Si (X 1 ) 4 ,
The coating solution for forming a hydrophilic film according to claim 9, wherein the aluminum oxide precursor represented by the general formula [5] is R 5 Al (X 2 ) 2 .
下記一般式［６］及び［７］で表される化合物からなる群から選ばれる少なくとも１種のジルコニウム酸化物前駆体が添加されている請求項９又は請求項１０に記載の親水性被膜形成用塗布液。
ＺｒＯＹ２ ［６］
（式［６］中、ＹはＣｌ−、ＮＯ３ −又はＣＨ３ＣＯＯ−）
（Ｒ６）ｉＺｒ（Ｚ）４−ｉ ［７］
（式［７］中、Ｒ６はアセチルアセトナート基、Ｚは炭素数２〜４のアルコキシル基又はハロゲン、ｉは０〜４の整数） The coating liquid for forming a hydrophilic film further comprises:
The hydrophilic film-forming film according to claim 9 or 10, wherein at least one zirconium oxide precursor selected from the group consisting of compounds represented by the following general formulas [6] and [7] is added. Coating liquid.
ZrOY 2 [6]
(In the formula [6], Y is Cl − , NO 3 — or CH 3 COO − )
(R 6 ) i Zr (Z) 4-i [7]
(In formula [7], R 6 is an acetylacetonate group, Z is an alkoxyl group having 2 to 4 carbon atoms or halogen, and i is an integer of 0 to 4)
基材を準備する基材準備工程、
請求項９〜１５のいずれかに記載の親水性被膜形成用塗布液を準備する塗布液準備工程、前記基材の表面に前記塗布液を塗布して塗膜を形成する塗布工程、及び、
塗布工程後の基材を１００〜４００℃で加熱して塗膜を硬化させて、該基材表面に親水性の被膜を形成する硬化工程
を有することを特徴とする親水性被膜形成物品の製造方法。 A method for producing a hydrophilic film-formed article according to any one of claims 1 to 8,
A base material preparation step for preparing a base material;
A coating solution preparing step of preparing the coating solution for forming a hydrophilic coating film according to any one of claims 9 to 15, a coating step of coating the coating solution on the surface of the substrate to form a coating film, and
Production of a hydrophilic film-forming article characterized by having a curing process in which the substrate after the coating step is heated at 100 to 400 ° C. to cure the coating film to form a hydrophilic film on the surface of the substrate. Method.
Furthermore, the protective paper sticking process of sticking the protective paper for protecting the said hydrophilic film on the surface of a hydrophilic film formation article so that the said hydrophilic film may be covered is included. A method for producing a hydrophilic film-formed article.
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| WO2018198937A1 (en) * | 2017-04-27 | 2018-11-01 | 日本板硝子株式会社 | Coating-film-coated transparent substrate, coating liquid for forming coating film for coating-film-coated transparent substrate, and production method for coating-film-coated transparent substrate |
| US20210172068A1 (en) * | 2017-10-31 | 2021-06-10 | Nihon Parkerizing Co., Ltd. | Pretreatment Agent and Chemical Conversion Treatment Agent |
| JP7393961B2 (en) | 2020-01-28 | 2023-12-07 | 川研ファインケミカル株式会社 | Heat resistant member and its manufacturing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018198937A1 (en) * | 2017-04-27 | 2018-11-01 | 日本板硝子株式会社 | Coating-film-coated transparent substrate, coating liquid for forming coating film for coating-film-coated transparent substrate, and production method for coating-film-coated transparent substrate |
| JPWO2018198937A1 (en) * | 2017-04-27 | 2020-03-12 | 日本板硝子株式会社 | Transparent substrate with film, coating liquid for forming film of transparent substrate with film, and method of manufacturing transparent substrate with film |
| JP7213177B2 (en) | 2017-04-27 | 2023-01-26 | 日本板硝子株式会社 | Film-coated transparent substrate, coating solution for forming film on film-coated transparent substrate, and method for producing film-coated transparent substrate |
| US20210172068A1 (en) * | 2017-10-31 | 2021-06-10 | Nihon Parkerizing Co., Ltd. | Pretreatment Agent and Chemical Conversion Treatment Agent |
| US11965247B2 (en) * | 2017-10-31 | 2024-04-23 | Nihon Parkerizing Co., Ltd. | Pretreatment agent and chemical conversion treatment agent |
| JP7393961B2 (en) | 2020-01-28 | 2023-12-07 | 川研ファインケミカル株式会社 | Heat resistant member and its manufacturing method |
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