JP2000351651A - Deep colored shading glass and its production - Google Patents
Deep colored shading glass and its productionInfo
- Publication number
- JP2000351651A JP2000351651A JP11163505A JP16350599A JP2000351651A JP 2000351651 A JP2000351651 A JP 2000351651A JP 11163505 A JP11163505 A JP 11163505A JP 16350599 A JP16350599 A JP 16350599A JP 2000351651 A JP2000351651 A JP 2000351651A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- dark
- glass
- solid content
- hydrolyzate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
- C03C2217/485—Pigments
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Glass Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラス板に濃色の
膜を成膜してなり、適度に遮光し、防眩する窓ガラスと
して各種分野で採用できるプライバシーガラスとも言わ
れる濃色着色遮光ガラス（以下「プライバシーガラス」
という）及びその製法に関するもので、該プライバシー
ガラスは、特に建築用、自動車等の車両用、船舶航空機
等の輸送機用窓ガラスとして、単板あるいは他のガラス
板との合わせ、複層ガラスとして最適に採用できるもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dark colored light-shielding, which is also called a privacy glass which can be employed in various fields as a window glass for forming a dark-colored film on a glass plate, appropriately shielding light and preventing glare. Glass (hereinafter "privacy glass")
And the manufacturing method thereof, and the privacy glass is used as a window glass for a building, a vehicle such as an automobile, a transport machine such as a marine aircraft, a single plate or another glass plate, and a double glazing. It can be optimally adopted.
【０００２】[0002]
【従来の技術】例えば、特公昭５４−４０５６８号公報
には高反射率高耐久性を有する熱線反射ガラスに関し、
鉄酸化物、クロム酸化物、およびコバルト酸化物を含む
金属酸化物皮膜をガラス表面に形成した熱線反射ガラス
であって、可視光線透過率が３５％以上ものが開示さ
れ、また、特開平６−８０４４１号公報には、熱処理可
能なスパッタ被膜されたガラス製品およびその成型方法
に関し、ａ）Ｎｉ（Ｎｉ合金）の酸化物または窒化物か
らなる第１層と、ｂ）Ｎｉ（Ｎｉ合金）金属からなる第
２層と、ｃ）前記ａ）に記載の金属酸化物または窒化物
からなる第３層と、更にｄ）Ｓｎ，Ｚｎ，Ｔｉ（それら
の合金）の酸化物からなる第４層とを含むコーティング
を有するガラス基板からなる熱処理可能なガラス製品で
あって、例えば膜面の可視光線反射率が３１〜３３％で
あることが開示されている。2. Description of the Related Art For example, Japanese Patent Publication No. 54-40568 discloses a heat reflecting glass having high reflectance and high durability.
A heat ray reflective glass having a metal oxide film containing an iron oxide, a chromium oxide, and a cobalt oxide formed on a glass surface and having a visible light transmittance of 35% or more is disclosed. No. 80441 discloses a heat-treatable sputter-coated glass product and a method for molding the same, comprising: a) a first layer made of an oxide or nitride of Ni (Ni alloy); and b) a metal (Ni alloy) metal. A) a third layer composed of the metal oxide or nitride described in a) above, and d) a fourth layer composed of an oxide of Sn, Zn, Ti (their alloy). It discloses a heat-treatable glass product comprising a glass substrate having a coating containing, for example, a film surface having a visible light reflectance of 31 to 33%.
【０００３】また、特開平４−２１９３４７号公報に
は、薄膜付窓ガラスの製造方法とその薄膜付窓ガラスに
関し、ガラス基板上に、光によりゲル化する塗布液をフ
レキソ印刷により塗布した後、光照射し、さらに熱処理
して薄膜を形成することが、また塗布液としてキレート
化剤と、その存在下で光によりゲル化する金属アルコキ
シドと、更に着色剤を含むことが開示され、あるいは更
に予め着色セラミックカラーインクにより印刷したうえ
で、前記塗布液を塗布し、上記した如くの処理により薄
膜を形成することが開示されている。Japanese Patent Application Laid-Open No. Hei 4-219347 discloses a method for manufacturing a window glass with a thin film and a window glass with the thin film, after applying a coating solution which gels by light onto a glass substrate by flexographic printing. It is disclosed that a thin film is formed by irradiating light and further heat-treating, and that a chelating agent, a metal alkoxide that gels by light in the presence of the coating solution, and a colorant are further contained as a coating solution, It is disclosed that after printing with a colored ceramic color ink, the coating liquid is applied and a thin film is formed by the above-described processing.
【０００４】或いは更に特開平８−２０８２７４号公報
には、着色膜形成用塗布液、着色膜及び着色膜を形成し
たガラス物品に関し、Ｔｉ，Ｖ，Ｃｒ，Ｍｎ，Ｆｅ，Ｃ
ｏ，Ｎｉ，Ｃｕ及びＺｎのうち１種以上の元素を含む複
合酸化物顔料を分散させた液を含む着色膜形成用塗布液
が、また該塗布液中に、Ｓｎ，Ｉｎ，Ｚｎ，Ａｌ，Ｔ
ｉ，Ｓｉ及びＧａの群から選ばれる１種以上の金属化合
物を含むことが、更に着色膜上に該着色膜より低屈折率
の被膜が順次形成されていることが開示されている。Further, Japanese Patent Application Laid-Open No. 8-208274 discloses a coating liquid for forming a colored film, a colored film, and a glass article on which the colored film is formed, Ti, V, Cr, Mn, Fe, C
A coating liquid for forming a colored film including a liquid in which a complex oxide pigment containing at least one of o, Ni, Cu and Zn is dispersed, and Sn, In, Zn, Al, T
It is disclosed that at least one metal compound selected from the group consisting of i, Si, and Ga is included, and that a film having a lower refractive index than the colored film is sequentially formed on the colored film.
【０００５】さらに、特開平１０−２９７９３８号公報
には、透明ガラス基板の表面に、２種以上の着色性の酸
化物成分からなる黒色原料を分散したシリカ系のゾルを
前躯体とする濃色グレー系の着色膜を形成してなるプラ
イバシーガラスであって、その可視光線透過率があ２０
〜４０％、可視光線反射率が１０％未満であるプライバ
シーガラスが開示されている。Further, Japanese Patent Application Laid-Open No. 10-297938 discloses a dark color having a silica-based sol in which a black raw material comprising two or more coloring oxide components is dispersed on the surface of a transparent glass substrate. A privacy glass formed with a gray colored film having a visible light transmittance of 20%.
A privacy glass having a visible light reflectance of less than 10% is disclosed.
【０００６】本発明は、それら公知例とは異なり、耐擦
傷性、耐摩耗性、および耐薬品性に優れ、無彩色のグレ
ー色調を有し、プライバシー性に優れ、また光反射性を
抑えてグレアー感がなく、目に対する刺激も小さく、周
辺環境との調和しやすいプライバシーガラスを提供する
ものである。The present invention is different from the known examples in that it has excellent scratch resistance, abrasion resistance, and chemical resistance, has an achromatic gray color tone, has excellent privacy, and has low light reflectivity. The object is to provide a privacy glass that has no glare, causes little irritation to the eyes, and easily harmonizes with the surrounding environment.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、特公昭
５４−４０５６８号公報あるいは特開平６−８０４４１
号公報記載のものは、金属化合物の熱分解法、あるいは
スパッタリング法により膜形成するもので、可視光線透
過率が比較的高いとともに、ガラス製品は反射が強く、
ギラツキ感、すなわちグレアーな感を呈し、目に対する
刺激が強く、周辺環境、特に自然環境に順応し得るもの
ではない。However, Japanese Patent Publication No. 54-40568 or Japanese Patent Application Laid-Open No. 6-80441.
The publication describes that a film is formed by a thermal decomposition method of a metal compound or a sputtering method, and has a relatively high visible light transmittance and a strong reflection of a glass product,
It has a glare feeling, that is, a glare feeling, has strong irritation to the eyes, and cannot adapt to the surrounding environment, particularly the natural environment.
【０００８】また、特開平４−２１９３４７号公報記載
のものは、ガラス基板上に成膜した後に高温熱処理する
ものであり、設備等が高価となる欠点がある。[0008] Japanese Unexamined Patent Publication No. Hei 4-219347 discloses a method in which a film is formed on a glass substrate and then subjected to a high-temperature heat treatment.
【０００９】さらに、特開平８−２０８２７４号公報記
載のものは、ＴＶ管パネルなど陰極線管用パネル表面に
適用されるものであり、ガラス本体の透過率の低下を抑
えつつ画面のコントラスト比を向上させることを狙いと
するものであり、ガラス基板に成膜後に自動車用窓ガラ
スなどのような曲げ強化行った後、付加価値を付けるた
めに後処理としてアンテナ性能を高めるためのメッキ処
理、反成膜面への撥水処理を行う場合、膜起因よる不具
合が発生する可能性があるという危惧がある。Furthermore, the one described in JP-A-8-208274 is applied to the surface of a panel for a cathode ray tube such as a TV tube panel, and improves the contrast ratio of a screen while suppressing a decrease in transmittance of a glass body. After the film is formed on a glass substrate, it is subjected to bending strengthening like a window glass for automobiles, and then as a post-processing to add added value, a plating process to enhance the antenna performance and an anti-film formation When performing a water-repellent treatment on a surface, there is a concern that a defect due to a film may occur.
【００１０】さらに、特開平１０−２９７９３８号公報
記載のものは、塗膜を約２００〜４００℃の高温で加熱
することにより強固で耐久性に優れた膜を形成するもの
であるため、熱効率および装置を耐熱仕様にする必要が
ある。[0010] Furthermore, the method disclosed in Japanese Patent Application Laid-Open No. 10-297938 is to form a strong and durable film by heating a coating film at a high temperature of about 200 to 400 ° C. The equipment must be heat resistant.
【００１１】[0011]
【課題を解決するための手段】本発明は、前記従来の問
題点を解消したものであって、約１５０〜２００℃とい
う低温度で塗膜を加熱するだけで耐擦傷性、耐摩耗性、
および耐薬品性に優れた硬化膜を形成出来るとともに、
該膜付きガラスは、無彩色のグレー色調を有し、プライ
バシー性に優れ、また光反射性を抑えてグレアー感がな
く、目に対する刺激も小さく、周辺環境との調和しやす
いプライバシーガラスを提供するものである。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and it is possible to obtain a coating composition having a scratch resistance, abrasion resistance,
And a cured film with excellent chemical resistance can be formed,
The glass with a film has an achromatic gray color tone, is excellent in privacy, provides a privacy glass that suppresses light reflection, has no glare, is less irritating to the eyes, and is easily harmonized with the surrounding environment. Things.
【００１２】すなわち、本発明のプライバシーガラス
は、透明ガラス板の表面に、マトリックスとしてのシリ
カ中にＣｕＯ−Ｆｅ2Ｏ3−Ｍｎ2Ｏ3系からなる黒色系顔
料が分散された着色膜が被覆されたプライバシーガラス
であって、該シリカは、アルコキシシランの加水分解物
もしくは部分加水分解物並びにコロイダルシリカより構
成され、そのアルコキシシランの加水分解物もしくは部
分加水分解物の固形分に対するコロイダルシリカの重量
比が６０：４０〜４０：６０であり、且つ該黒色系顔料
は、シリカ固形分との合計重量の５〜１０重量％含有さ
れてなることを特徴とする。That is, in the privacy glass of the present invention, the surface of a transparent glass plate is coated with a colored film in which a black pigment composed of CuO—Fe 2 O 3 —Mn 2 O 3 is dispersed in silica as a matrix. Wherein the silica is composed of a hydrolyzate or partial hydrolyzate of alkoxysilane and colloidal silica, and the weight of the colloidal silica relative to the solid content of the hydrolyzate or partial hydrolyzate of the alkoxysilane The ratio is 60:40 to 40:60, and the black pigment is contained in an amount of 5 to 10% by weight based on the total weight of the solid pigment and the silica.
【００１３】また、本発明のプライバシーガラスは、着
色膜が濃色グレー色を有し、膜厚が３μｍ以上６μｍ以
下であり、しかも可視光線透過率が２０〜３０％、ヘー
ズ値が１．０％以下であることが好ましい。The privacy glass of the present invention has a colored film having a dark gray color, a film thickness of 3 μm to 6 μm, a visible light transmittance of 20 to 30%, and a haze value of 1.0. % Is preferable.
【００１４】またさらに、本発明のプライバシーガラス
は、ＪＩＳ Ｒ ３２１２に規定する耐摩耗試験法に基
づいたテーバー摩耗試験（荷重：５００ｇｆ×２，１０
０回転）の試験前と試験後のヘイズ値の変化量（試験後
のヘイズ値／試験前のヘイズ値）が、５．０以下である
ことが好ましい。Further, the privacy glass of the present invention can be subjected to a Taber abrasion test (load: 500 gf × 2,10) based on the abrasion resistance test method specified in JIS R3212.
The amount of change in the haze value before and after the test (0 rotations) (haze value after the test / haze value before the test) is preferably 5.0 or less.
【００１５】さらに、本発明のプライバシーガラスの製
法は、プライバシーガラスを製造するにあたり、（ａ）
透明ガラス板を用意する工程と、（ｂ）黒色系顔料をマ
トリックスとしてのシリカ固形分との合計重量の５〜１
０重量％となるように調合した黒色顔料およびシリカ系
混合ゾルを、分散剤、硬化触媒および溶媒とを含む液に
添加し、分散混合して塗布液を調製する工程と、（ｃ）
前記塗布液を、前記ガラス板表面上に塗布する工程、
（ｄ）塗布したガラス板を熱処理する工程と、によって
ガラス板表面上に着色膜を形成することを特徴とする。Further, the method for producing a privacy glass of the present invention comprises the steps of (a)
5 to 1 of the total weight of the step of preparing a transparent glass plate and (b) silica solids as a matrix with a black pigment.
(C) adding a black pigment and silica-based mixed sol prepared so as to be 0% by weight to a liquid containing a dispersant, a curing catalyst and a solvent, and dispersing and mixing to prepare a coating liquid;
A step of applying the coating liquid on the surface of the glass plate,
(D) a step of heat-treating the applied glass plate to form a colored film on the surface of the glass plate.
【００１６】また、本発明で用いるシリカ系のゾルは、
成分が一般式Ｒ２Ｓｉ（Ｏ−Ｒ１）3（式中、Ｒ１は炭
素数１または２のアルキル基、Ｒ２はエポキシ基を含有
する有機基を示す。）で表わされるオルガノトリアルコ
キシシランの加水分解物もしくは部分加水分解物並びに
コロイダルシリカの混合ゾルであることが好ましい。The silica sol used in the present invention is:
A hydrolyzate of an organotrialkoxysilane whose component is represented by the general formula R2Si (O-R1) 3 (wherein, R1 represents an alkyl group having 1 or 2 carbon atoms, and R2 represents an organic group containing an epoxy group). Alternatively, a mixed sol of a partially hydrolyzed product and colloidal silica is preferable.
【００１７】さらに、本発明で用いる硬化触媒は、シリ
カ固形分との合計重量の４〜６重量％添加することが好
適であり、その硬化触媒としては、Ａｌ・ＸmＹ3−
m（式中、ＸはＯＲ１（Ｒ１は炭素数１〜４のアルキル
基）、Ｙは一般式Ｒ２ＣＯＣＨ2 ＣＯＯＲ３（Ｒ２、Ｒ
３はいずれも炭素数１〜４のアルキル基）で示される化
合物に由来する配位子から選ばれる１つであり、ｍは
０，１または２である）で示されるアルミニウムキレー
ト化合物であることがより好ましい。さらにまた、熱処
理温度は１５０〜２００℃の温度であることが好まし
い。Further, the curing catalyst used in the present invention is a silicone.
It is preferable to add 4 to 6% by weight of the total weight with the solid content.
Al.X is suitable as the curing catalyst.mYThree−
m(Wherein X is OR1 (R1 is alkyl having 1 to 4 carbon atoms)
Group), Y is a general formula R2COCHTwo COOR3 (R2, R
3 is an alkyl group having 1 to 4 carbon atoms)
Is one selected from ligands derived from compounds, and m is
0, 1 or 2)
More preferably, it is a compound. Furthermore, heat treatment
Preferably, the temperature is between 150 and 200 ° C.
No.
【００１８】[0018]
【発明の実施の形態】本発明において、透明ガラス基板
としては、アルカリ（ソーダ）石灰系ガラス、アルミノ
珪酸系ガラス、ほう珪酸ガラス等各種のガラスが採用で
き、それらの製板法はフロート法、フルコール法、ペン
バーノン法、ロールアウト法、ロールアウト−表面研磨
法等いずれでもよいが、ソーダ石灰系ガラスをフロート
法により製板したものが最も一般的である。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, various glasses such as alkali (soda) lime glass, aluminosilicate glass, borosilicate glass and the like can be used as a transparent glass substrate. Any of the full coal method, the Pembernon method, the rollout method, the rollout-surface polishing method, etc. may be used, but the most common one is a soda-lime glass made by a float method.
【００１９】前記透明ガラス基板は、透明であれば着
色、無着色を問わない。勿論金属線入りガラス等の介在
物を有するガラスや、強化板ガラス、曲げ板ガラス等の
加工されたガラスも対象となる。The transparent glass substrate may be colored or uncolored as long as it is transparent. Of course, a glass having inclusions such as a glass containing a metal wire, and a processed glass such as a reinforced plate glass and a bent plate glass are also applicable.
【００２０】本発明の製法において、濃色グレー系着色
膜を形成するうえで、マトリックスとしてのシリカ系の
混合ゾルの成分として、例えばオルガノアルコキシシラ
ンを出発原料として、一般式Ｒ２Ｓｉ（Ｏ−Ｒ１）
3（式中、Ｒ１は炭素数１または２のアルキル基、Ｒ２
はエポキシ基を含有する有機基を示す。）で表わされる
オルガノトリアルコキシシランを採用し、その加水分解
物や、部分加水分解物を含むものを前駆体とすることが
できる。In the production method of the present invention, when forming a dark gray colored film, a silica-based mixed sol as a matrix, for example, an organoalkoxysilane as a starting material, and a general formula R2Si (O-R1)
3 (wherein R1 is an alkyl group having 1 or 2 carbon atoms, R2
Represents an organic group containing an epoxy group. The organotrialkoxysilane represented by the formula (1) can be used, and a precursor containing a hydrolyzate or a partial hydrolyzate thereof can be used.
【００２１】また、コロイダルシリカとしては、各種溶
媒で分散されている市販品があるが、例えば、低級アル
コール（例えば、メタノール、エタノール、イソプロパ
ノール）を分散溶媒と使用しているものが適する。As the colloidal silica, there are commercially available products dispersed in various solvents. For example, those using a lower alcohol (eg, methanol, ethanol, isopropanol) as a dispersion solvent are suitable.
【００２２】なお、マトリックスとしてのシリカは、ガ
ラス形成酸化物であり、着色顔料とのバインディング性
に優れ、耐摩耗性、耐薬品性、耐候性等各種物性にバラ
ンスよく優れさせるため、シリカ分中のアルコキシシラ
ン加水分解物の固形分：コロイダルシリカの重量比が６
０：４０〜４０：６０であることが望ましい。Silica as a matrix is a glass-forming oxide, has excellent binding properties with a coloring pigment, and has a good balance of various physical properties such as abrasion resistance, chemical resistance, and weather resistance. Weight ratio of solid content of the alkoxysilane hydrolyzate to colloidal silica is 6
It is desirable that the ratio be 0:40 to 40:60.
【００２３】コロイダルシリカの添加比率が６０を越え
る場合には、膜に濁りが生じヘーズ値が高くなり、４０
未満の場合には、耐摩耗性が悪化し規格をクリアー出来
ない。When the addition ratio of colloidal silica exceeds 60, the film becomes turbid and the haze value becomes high,
If it is less than the above, the abrasion resistance is deteriorated and the specification cannot be cleared.
【００２４】黒色顔料としては、ＣｕＯ−Ｆｅ2Ｏ3−Ｍ
ｎ2Ｏ3系からなる黒色系顔料を使用することにより、良
好な無彩色濃色グレー系の着色膜を形成することがで
き、耐薬品性、耐候性等においても優れた膜を形成でき
る。なお、該顔料は、市販品を用いても差し支えない。
前記黒色系顔料の平均粒径は２５〜５０ｎｍ程度である
ことが好ましい。２５ｎｍ未満では液中での分散安定性
に乏しく、５０ｎｍ超過では、成膜品に曇りが生じ易い
という不具合がある。Examples of the black pigment include CuO—Fe 2 O 3 —M
By using the n 2 O 3 -based black pigment, it is possible to form a good achromatic dark gray colored film, and to form a film excellent in chemical resistance, weather resistance and the like. In addition, a commercially available pigment may be used.
The average particle size of the black pigment is preferably about 25 to 50 nm. If it is less than 25 nm, the dispersion stability in the liquid is poor, and if it exceeds 50 nm, there is a problem that the film is likely to be fogged.
【００２５】黒色系顔料は、シリカ固形分（アルコキシ
シランの加水分解物もしくは部分加水分解物の固形分と
コロイダルシリカとの合計重量）の５〜１０重量％含有
され、該顔料の含有量が１０重量％を越えると所望の透
過率を得るためには膜厚を薄くする必要があり、薄くな
った場合、耐摩耗性、耐薬品性が劣る傾向にある。ま
た、５重量％未満であると所望の透過率を得るためには
膜厚を厚くする必要があり、厚くした場合、クラックが
発生し易くなる傾向にある。プライバシー性を得るうえ
で更に重要なファクターは可視光線透過率であり、その
範囲は２０〜３０％とすることが好ましい。可視光線透
過率が３０％を越えると、透過性が増大し、プライバシ
ー性を維持するのが困難である。また可視光線透過率が
２０％未満であると、逆に透視性が阻害され、窓材とし
ての役割をなし難い。The black pigment contains 5 to 10% by weight of silica solid content (total weight of solid content of hydrolyzate or partial hydrolyzate of alkoxysilane and colloidal silica), and the content of the pigment is 10%. If the amount exceeds 10% by weight, it is necessary to reduce the film thickness in order to obtain a desired transmittance. When the film thickness is reduced, abrasion resistance and chemical resistance tend to be inferior. On the other hand, if the content is less than 5% by weight, it is necessary to increase the film thickness in order to obtain a desired transmittance, and when the thickness is increased, cracks tend to occur easily. An even more important factor in obtaining privacy is the visible light transmittance, and the range is preferably 20 to 30%. When the visible light transmittance exceeds 30%, the transmittance increases, and it is difficult to maintain privacy. On the other hand, if the visible light transmittance is less than 20%, on the contrary, transparency is impaired, and it is difficult to function as a window material.
【００２６】また、光反射によるグレアー感を抑え、目
を刺激せず、周辺環境、特に自然環境と融和、調和させ
るためには、可視光線反射率が１０％未満、更に好まし
くは５％以下とするのがよい。なお、可視光線反射率
は、特にことわりがない限り膜面側の反射率をいう。In order to suppress glare caused by light reflection, not to irritate the eyes, and to integrate and harmonize with the surrounding environment, particularly the natural environment, the visible light reflectance is less than 10%, more preferably 5% or less. Good to do. Note that the visible light reflectance refers to the reflectance on the film surface side unless otherwise specified.
【００２７】硬化触媒としては、Ａｌ・ＸmＹ3−m（式
中、ＸはＯＲ１（Ｒ１は炭素数１〜４のアルキル基）、
Ｙは一般式Ｒ２ＣＯＣＨ2ＣＯＯＲ３（Ｒ２、Ｒ３はい
ずれも炭素数１〜４のアルキル基）で示される化合物に
由来する配位子から選ばれる１つであり、ｍは０，１ま
たは２である）で示されるアルミニウムキレート化合物
が好ましく、その添加量としてはシリカ固形分（アルコ
キシシランの加水分解物もしくは部分加水分解物の固形
分とコロイダルシリカとの合計重量）の４〜６重量％が
好ましく、４重量％未満であると硬化被膜の耐擦傷性が
不十分であり、６重量％を越えると硬化被膜にクラック
が生じやすくなり、更に硬化被膜の透明性が低下する危
険性がある。上記シリカ系のゾル形成用原料、黒色系顔
料、硬化触媒は、アルコール系、エステル系等の有機溶
媒に添加し、更に分散剤としての界面活性剤や、分散助
剤、粘度調整剤としての樹脂を添加する。界面活性剤と
しては、アニオン系やノニオン系の界面活性剤がよく、
樹脂としてはセルロース系、ポリビニルアルコール系等
の樹脂が好適に採用できる。[0027] As the curing catalyst, Al · X m Y 3 - m ( wherein, X is OR1 (R1 is an alkyl group having 1 to 4 carbon atoms),
Y is the formula R2COCH 2 COOR3 (R2, R3 are all alkyl group having 1 to 4 carbon atoms) is one selected from a ligand derived from a compound represented by, m is 0, 1 or 2 The aluminum chelate compound represented by the formula (1) is preferable, and its addition amount is preferably 4 to 6% by weight of solid content of silica (total weight of solid content of hydrolyzate or partial hydrolyzate of alkoxysilane and colloidal silica). If the amount is less than 4% by weight, the abrasion resistance of the cured film is insufficient. If the amount is more than 6% by weight, cracks are liable to occur in the cured film, and there is a risk that the transparency of the cured film is further reduced. The silica-based sol-forming raw material, the black pigment, and the curing catalyst are added to an organic solvent such as an alcohol-based or ester-based solvent, and further, a surfactant as a dispersant, a dispersion aid, and a resin as a viscosity modifier. Is added. As the surfactant, an anionic or nonionic surfactant is often used.
As the resin, a cellulose-based resin or a polyvinyl alcohol-based resin can be suitably employed.
【００２８】これらをボールミル、アトライタ、サンド
ミル、ジェットミル、ダイノーミル、ホモジナイザー等
の分散装置を使用することにより黒色顔料を微粉砕し、
均一混合する。These are finely pulverized into black pigments by using a dispersing device such as a ball mill, an attritor, a sand mill, a jet mill, a Dyno mill, a homogenizer, etc.
Mix evenly.
【００２９】次いでこれらを塗布液として、ガラス基板
上へ塗布する。塗布手段としてはディップコート、フロ
ーコート、スピンコート、ロールコート、スプレーコー
ト、スクリーン印刷、フレキソ印刷等の公知手段が採用
でき、適宣マスキングすることにより、例えば自動車の
シェードバンドにおけるような部分的な膜形成は勿論、
任意の形状、図柄に塗膜形成することもできる。Next, these are applied as a coating liquid on a glass substrate. As a coating means, known means such as dip coating, flow coating, spin coating, roll coating, spray coating, screen printing, flexographic printing and the like can be adopted. Not only film formation,
A coating film can be formed in any shape and pattern.
【００３０】膜厚は、熱処理後において３〜６μｍ程度
にするのが望ましく、３μｍ未満であると、濃色グレー
系の色調が得難く、可視光線透過率も高すぎてプライバ
シー性に劣るとともに膜強度も弱くなる。他方６μｍを
越えると熱処理において、膜の亀裂や剥離が生じ易い。The film thickness is desirably about 3 to 6 μm after the heat treatment, and if it is less than 3 μm, it is difficult to obtain a dark gray color tone, the visible light transmittance is too high, and the privacy is poor. The strength also decreases. On the other hand, if it exceeds 6 μm, cracks and peeling of the film are likely to occur during the heat treatment.
【００３１】塗布後、１５０℃〜２００℃の比較的低温
で、約３０分〜６０分加熱することにより、溶媒や有機
物の殆どが飛散するのと同時にシリカがバインダ作用を
発揮する。比較的低温度で加熱するだけで、耐久性の良
好な膜が形成されるのは、膜中にシリカの一部としての
コロイダルシリカを用いていること、或いは硬化触媒と
して前記に示したアルミニウムキレート化合物を用いて
いること等による。By heating at a relatively low temperature of 150 ° C. to 200 ° C. for about 30 to 60 minutes after coating, most of the solvent and organic substances are scattered, and at the same time, silica exerts a binder action. A film having good durability can be formed only by heating at a relatively low temperature because colloidal silica is used as a part of silica in the film, or the aluminum chelate described above as a curing catalyst is used. This is because the compound is used.
【００３２】[0032]
【実施例】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は
ない。なお、本発明および比較例で得られた、硬化被膜
を有するプライバシーガラスは、以下に示す測定法によ
り諸物性を測定した。The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment. The physical properties of the privacy glass having a cured film obtained in the present invention and the comparative example were measured by the following measurement methods.
【００３３】〔光学特性〕：（可視光線透過率、可視光
線反射率） ＪＩＳ Ｒ ３１０６に規定する透過率測定方法、反射
率測定方法に基づき、分光光度計（Ｕ ４０００型、日
立製作所製スペクトロフォトメーター）で波長３４０〜
１８００ｎｍの間の透過率を測定し、平均可視光線透過
率Ｔｖ（％）（３８０〜７８０ｎｍ）と平均可視光線反
射率Ｔｒ（％）（３８０〜７８０ｎｍ）を求めた。これ
と合わせ、目視により色調観察し、無彩色の濃色グレー
色調を合格とした。[Optical properties]: (Visible light transmittance, visible light reflectance) Based on the transmittance measurement method and the reflectance measurement method specified in JIS R 3106, a spectrophotometer (U4000 type, Spectrophoto manufactured by Hitachi, Ltd.) Meter)
The transmittance between 1800 nm was measured, and the average visible light transmittance Tv (%) (380 to 780 nm) and the average visible light reflectance Tr (%) (380 to 780 nm) were obtained. In conjunction with this, the color tone was visually observed, and an achromatic dark gray color tone was judged to be acceptable.
【００３４】〔光学特性〕：（曇価） 分光光度計（ＮＤＨ−２０Ｄ型、日本電色工業（株）製
ヘーズメーター）でヘイズ値を測定して、１．０以下の
ものを合格とした。[Optical properties]: (Haze value) The haze value was measured with a spectrophotometer (NDH-20D, a haze meter manufactured by Nippon Denshoku Industries Co., Ltd.). .
【００３５】〔耐摩耗性〕：ＪＩＳ Ｒ ３２１２ に
規定する耐摩耗性試験方法に基づき、テーバー摩耗試験
機（摩耗輪ＣＳ−１０Ｆ、荷重５００ｇｆ×２、１００
回転）により摩耗試験し、試験後のヘイズ値（Ｈ％）を
測定し、試験前のヘイズ値（Ｈｏ％）に対する変化量
（△Ｈ％）を求めて、５．０以下のものを合格とした。[Abrasion resistance]: Based on the abrasion resistance test method specified in JIS R 3212, a Taber abrasion tester (wear wheel CS-10F, load 500 gf × 2, 100
Rotation), a haze value (H%) after the test was measured, and a change (ΔH%) with respect to the haze value (Ho%) before the test was determined. did.
【００３６】〔耐薬品性〕：耐酸性；３ｗｔ％硫酸（Ｈ
2ＳＯ4）水溶液を着色膜面に滴下し、常温で約４時間放
置後、外観の変化を目視で評価した。滴下部と、周辺部
分の透過・反射色調に変化が認められず、異常ないもの
を合格とした。[Chemical resistance]: Acid resistance; 3 wt% sulfuric acid (H
An aqueous solution of 2 SO 4 ) was dropped on the surface of the colored film, allowed to stand at room temperature for about 4 hours, and the change in appearance was visually evaluated. No change was observed in the transmission / reflection color tone of the dripping portion and the peripheral portion, and those having no abnormality were judged as acceptable.
【００３７】〔耐候性〕：部分マスキングしたうえで、
サンシャインウエザーメーター（約８３℃、降雨無し）
により、約６００時間経過後の外観変化（色調の変化、
曇りの発生、膜のひび割れ等）を目視で評価した。マス
キング部との間に違和感なく異常ないものを合格とし
た。[Weather resistance]: After partial masking,
Sunshine weather meter (about 83 ℃, no rainfall)
Changes in appearance after about 600 hours (color change,
Occurrence of fogging, cracking of the film, etc.) were visually evaluated. Those that did not feel uncomfortable with the masking section were accepted.
【００３８】〔耐煮沸性〕：部分マスキングしたうえ
で、ＪＩＳ Ｒ ３２１２の耐熱試験方法に基づき、煮
沸水に約２時間浸漬した後、外観を目視で評価した。マ
スキング部との間に違和感なく異常ないものを合格とし
た。[Boiling resistance]: After partial masking, immersion in boiling water for about 2 hours based on the heat resistance test method of JIS R 3212, the appearance was visually evaluated. Those that did not feel uncomfortable with the masking section were accepted.
【００３９】〔耐湿性〕：部分マスキングしたうえで、
５０℃、９５ＲＨ％以上の環境室内に２４時間保持した
後、外観を目視で評価した。マスキング部との間に違和
感なく異常ないものを合格とした。[Moisture resistance]: After partial masking,
After being kept in an environment room at 50 ° C. and 95 RH% or more for 24 hours, the appearance was visually evaluated. Those that did not feel uncomfortable with the masking section were accepted.
【００４０】実施例１ （オルガノアルコキシシランの加水分解物の調製）水温
を１０℃に調整した冷却器内に攪拌機を備えたガラス製
の容器を設置し、γ−グリキドキシプロピルトリメトキ
シシラン（ＧＰＴＭＳ）１００ｇを加え、攪拌しなが
ら、０．０１Ｎ−ＨＣｌ２３ｇを３０分間かけ滴下して
加水分解物を得た。更に、２４時間攪拌することによ
り、シリカ固形分として４３ｗｔ％のシリカ系ゾルを調
整した。 Example 1 (Preparation of a hydrolyzate of an organoalkoxysilane) A glass vessel equipped with a stirrer was placed in a cooler whose water temperature was adjusted to 10 ° C, and γ-glycidoxypropyltrimethoxysilane ( (GPTMS) of 100 g, and with stirring, 23 g of 0.01 N HCl was added dropwise over 30 minutes to obtain a hydrolyzate. Further, by stirring for 24 hours, a silica-based sol having a silica solid content of 43 wt% was prepared.
【００４１】（顔料分散）顔料が酸化物換算でシリカ
（固形分）に対して７．５ｗｔ％となり、オルガノアル
コキシシラン加水分解物の固形分：コロイダルシリカの
重量比が５０：５０、Ａｌキレートをシリカ系ゾルの固
形分物に対して５ｗｔ％になるように、シリカ加水分解
物２０．７ｇに加えて、（Ｃｕ，Ｆｅ，Ｍｎ）Ｏ・（Ｆ
ｅ，Ｍｎ）2Ｏ3 で示される黒色顔料〔ダイピロキサイド
＃３５５０：大日精化工業（株）製、平均１次粒径約５
０ｎｍ〕１．３ｇと、メタノール分散コロイダルシリカ
（日産化学工業（株）製、メタノールゾル）４４．４ｇ
及びＡｌキレート０．９ｇ、ｉ−プロパノール溶液３
２．７ｇをミルポットの中に添加し、直径０．６５ｍｍ
のジルコニアビーズとともにボールミルで約２４時間粉
砕、分散、混合処理することにより黒色顔料を含む固形
分濃度が約２０ｗｔ％の分散溶液を得た。(Pigment dispersion) The pigment is converted to silica in terms of oxide.
(Solid content) to 7.5 wt%,
Solid content of Coxysilane hydrolyzate: Colloidal silica
The weight ratio is 50:50, and the Al chelate is mixed with silica-based sol.
Hydrolysis of silica to 5 wt% with respect to the form fraction
(Cu, Fe, Mn) O. (F
e, Mn)TwoOThree Black pigment represented by
# 3550: manufactured by Dainichi Seika Kogyo Co., Ltd., having an average primary particle size of about 5
0 nm] 1.3 g and methanol-dispersed colloidal silica
(Nissan Chemical Industries, Ltd., methanol sol) 44.4 g
And 0.9 g of Al chelate, i-propanol solution 3
2.7 g was added into a mill pot, and the diameter was 0.65 mm.
About 24 hours in a ball mill with zirconia beads
Solid containing black pigment by crushing, dispersing and mixing
A dispersion solution having a concentration of about 20 wt% was obtained.
【００４２】（硬化被膜の形成）この分散液を塗布液と
した浸漬槽内に、片面をマスキングしたガラス基板を浸
漬し引き上げるディッピング法により塗布し、該被塗布
ガラス基板を約２００℃で約１時間程度加熱乾燥するこ
とにより、膜厚約４．５μｍの着色膜付着ガラスを得
た。上記方法で得られた硬化被膜を有するガラスは、表
１に示すように、耐摩耗性，外観，耐薬品性が良好で、
さらに耐煮沸性にも優れたガラスであることが確認され
た。(Formation of Cured Film) A glass substrate having one side masked is dipped in a dipping tank using this dispersion as a coating solution, and the glass substrate to be coated is dipped at about 200 ° C. for about 1 hour. By heating and drying for about an hour, a glass with a colored film having a thickness of about 4.5 μm was obtained. As shown in Table 1, the glass having a cured film obtained by the above method has good abrasion resistance, appearance, and chemical resistance.
Further, it was confirmed that the glass had excellent boiling resistance.
【００４３】[0043]
【表１】 [Table 1]
【００４４】実施例２ オルガノアルコキシシラン加水分解物の固形分：コロイ
ダルシリカ＝６０：４０重量比とした以外は、実施例１
と同様の操作で膜厚が約４μｍの着色膜付着ガラスを得
た。評価結果は、実施例１同様優れた物性を有するもの
であった。 Example 2 Example 1 was repeated except that the solid content of the organoalkoxysilane hydrolyzate: colloidal silica was set at a weight ratio of 60:40.
By the same operation as described above, a colored film-adhered glass having a film thickness of about 4 μm was obtained. The evaluation results were as excellent as in Example 1.
【００４５】実施例３ オルガノアルコキシシラン加水分解物の固形分：コロイ
ダルシリカ＝４０：６０重量比とした以外は、実施例１
と同様の操作で膜厚が約４．５μｍの着色膜付着ガラス
を得た。評価結果は、実施例１同様優れた物性を有する
ものであった。 Example 3 Example 1 was repeated except that the solid content of the organoalkoxysilane hydrolyzate: colloidal silica was 40:60 by weight.
By the same operation as described above, a glass with a colored film having a thickness of about 4.5 μm was obtained. The evaluation results were as excellent as in Example 1.
【００４６】実施例４ 顔料が酸化物換算でシリカ（固形分）に対して１０ｗｔ
％とした以外は、実施例１と同様の操作で膜厚が約３．
５μｍの着色膜付着ガラスを得た。評価結果は、実施例
１同様優れた物性を有するものであった。 Example 4 The pigment was 10 wt.% Based on silica (solid content) in terms of oxide.
% Except that the film thickness was about 3%.
A 5 μm colored film-adhered glass was obtained. The evaluation results were as excellent as in Example 1.
【００４７】実施例５ 顔料が酸化物換算でシリカ（固形分）に対して５ｗｔ％
とした以外は、実施例１と同様の操作で膜厚が約５．５
μｍの着色膜付着ガラスを得た。評価結果は、実施例１
同様優れた物性を有するものであった。 Example 5 5% by weight of pigment based on silica (solid content) in terms of oxide
Except that the film thickness was about 5.5 by the same operation as in Example 1.
A glass with a colored film having a thickness of μm was obtained. The evaluation results are shown in Example 1.
Similarly, it had excellent physical properties.
【００４８】実施例６ Ａｌキレートをシリカ系ゾルの固形分物に対して４ｗｔ
％になるようにした以外は、実施例１と同様の操作で膜
厚が約４．５μｍの着色膜付着ガラスを得た。評価結果
は、実施例１同様優れた物性を有するものであった。 Example 6 Al chelate was added at 4 wt% to the solid content of silica sol.
%, Except that the glass was attached to a colored film having a thickness of about 4.5 μm by the same operation as in Example 1. The evaluation results were as excellent as in Example 1.
【００４９】実施例７ Ａｌキレートをシリカ系ゾルの固形分物に対して６ｗｔ
％になるようにした以外は、実施例１と同様の操作で膜
厚が約４．５μｍの着色膜付着ガラスを得た。評価結果
は、実施例１同様優れた物性を有するものであった。 Example 7 Al chelate was added in an amount of 6 wt.
%, Except that the glass was attached to a colored film having a thickness of about 4.5 μm by the same operation as in Example 1. The evaluation results were as excellent as in Example 1.
【００５０】比較例１ オルガノアルコキシシラン加水分解物の固形分：コロイ
ダルシリカ＝７０：３０重量比とした以外は、実施例１
と同様の操作で膜厚が約４．５μｍの着色膜付着ガラス
を得た。評価結果は、表２に示すように耐摩耗性におい
て規格値より劣っていた。 Comparative Example 1 Example 1 was repeated except that the weight ratio of the solid content of the organoalkoxysilane hydrolyzate: colloidal silica was 70:30.
By the same operation as described above, a glass with a colored film having a thickness of about 4.5 μm was obtained. As shown in Table 2, the evaluation result was inferior to the standard value in the abrasion resistance.
【００５１】[0051]
【表２】 [Table 2]
【００５２】比較例２ オルガノアルコキシシラン加水分解物の固形分：コロイ
ダルシリカ＝３０：７０重量比とした以外は、実施例１
と同様の操作で膜厚が約４μｍの着色膜付着ガラスを得
た。評価結果は、表２に示すように光学特性の曇価にお
いて濁りがみらるとともに耐煮沸性において膜がガラス
基板より剥離した。 Comparative Example 2 Example 1 was repeated except that the weight ratio of the solid content of the organoalkoxysilane hydrolyzate: colloidal silica was 30:70.
By the same operation as described above, a colored film-adhered glass having a film thickness of about 4 μm was obtained. As a result of evaluation, as shown in Table 2, turbidity was observed in the haze value of the optical characteristics, and the film was peeled from the glass substrate in boiling resistance.
【００５３】比較例３ 顔料が酸化物換算でシリカ（固形分）に対して１２ｗｔ
％とした以外は、実施例１と同様の操作で膜厚が約２．
５μｍの着色膜付着ガラスを得た。評価結果は、２表に
示すように耐摩耗性において膜剥離が確認された。 Comparative Example 3 The pigment was 12 wt.% Based on silica (solid content) in terms of oxide.
%, Except that the film thickness was about 2.%.
A 5 μm colored film-adhered glass was obtained. As a result of the evaluation, as shown in Table 2, film peeling was confirmed in abrasion resistance.
【００５４】比較例４ 顔料が酸化物換算でシリカ（固形分）に対して３ｗｔ％
とした以外は、実施例１と同様の操作で膜厚が約６．５
μｍの着色膜付着ガラスを得た。評価結果は、表２に示
すように膜厚が厚いために外観観察においてクラックが
確認された。 Comparative Example 4 The pigment was 3 wt% in terms of oxide based on silica (solid content).
Except that the film thickness was about 6.5 by the same operation as in Example 1.
A glass with a colored film having a thickness of μm was obtained. In the evaluation results, as shown in Table 2, since the film thickness was large, cracks were observed in appearance observation.
【００５５】比較例５ Ａｌキレートをシリカ系ゾルの固形分に対して３ｗｔ％
になるようにした以外は、実施例１と同様の操作で膜厚
が約４．５μｍの着色膜付着ガラスを得た。評価結果
は、表２に示すように耐摩耗性において規格値より劣っ
ていた。 Comparative Example 5 3 wt% of Al chelate based on the solid content of silica-based sol
A colored film-adhered glass having a film thickness of about 4.5 μm was obtained in the same manner as in Example 1, except that the film thickness was changed as follows. As shown in Table 2, the evaluation result was inferior to the standard value in the abrasion resistance.
【００５６】比較例６ Ａｌキレートをシリカ系ゾルの固形分に対して７ｗｔ％
になるようにした以外は、実施例１と同様の操作で膜厚
が約４．５μｍの着色膜付着ガラスを得た。評価結果
は、表２に示すように外観観察においてクラック、濁り
が確認されるとともに、耐煮沸性において膜がガラス基
板より剥離した。 Comparative Example 6 Al chelate was 7 wt% based on the solid content of silica sol.
A colored film-adhered glass having a film thickness of about 4.5 μm was obtained in the same manner as in Example 1, except that the film thickness was changed as follows. As shown in the evaluation results, as shown in Table 2, cracks and turbidity were confirmed in appearance observation, and the film was peeled off from the glass substrate in boiling resistance.
【００５７】比較例７ オルガノアルコキシシラン加水分解物の固形分：コロイ
ダルシリカ＝７０：３０重量比とし、顔料が酸化物換算
でシリカ（固形分）に対して１２ｗｔ％とし、Ａｌキレ
ートをシリカ系ゾルの固形分物に対して７ｗｔ％になる
ようにした以外は、実施例１と同様の操作で膜厚が約
２．５μｍの着色膜付着ガラスを得た。評価結果は、表
２に示すように外観観察において濁りが確認され、耐摩
耗性で膜剥離が確認されるとともに、耐煮沸性において
膜がガラス基板より剥離した。 Comparative Example 7 Solid content of organoalkoxysilane hydrolyzate: colloidal silica = 70: 30 weight ratio, pigment was 12 wt% based on silica (solid content) in terms of oxide, and Al chelate was silica-based sol. A colored film-adhered glass having a thickness of about 2.5 μm was obtained in the same manner as in Example 1 except that the content was adjusted to 7 wt% based on the solid content of. As shown in Table 2, as shown in Table 2, turbidity was observed in the appearance observation, film peeling was confirmed by abrasion resistance, and film was peeled from the glass substrate in boiling resistance.
【００５８】比較例８ オルガノアルコキシシラン加水分解物の固形分：コロイ
ダルシリカ＝３０：７０重量比とし、顔料が酸化物換算
でシリカ（固形分）に対して３ｗｔ％とし、Ａｌキレー
トをシリカ系ゾルの固形分物に対して２ｗｔ％になるよ
うにした以外は、実施例１と同様の操作で膜厚が約６．
５μｍの着色膜付着ガラスを得た。評価結果は、表２に
示すように外観観察において濁りが確認され、耐摩耗性
が規格値より劣っており、耐煮沸性において膜がガラス
基板より剥離した。 Comparative Example 8 Solid content of organoalkoxysilane hydrolyzate: colloidal silica = 30: 70 weight ratio, pigment was 3 wt% based on silica (solid content) in terms of oxide, and Al chelate was silica-based sol. Except that the content was 2 wt% with respect to the solid content of Example 1.
A 5 μm colored film-adhered glass was obtained. As shown in Table 2, as shown in Table 2, turbidity was observed in the appearance observation, the abrasion resistance was inferior to the standard value, and the film peeled from the glass substrate in boiling resistance.
【００５９】比較例９ シリカ分としてコロイダルシリカを添加せずオルガノア
ルコキシシラン加水分解物のみを使用して顔料が酸化物
換算でシリカ（固形分）に対して１２ｗｔ％となり、Ａ
ｌキレートをシリカ系ゾルの固形分物に対して２ｗｔ％
になるように、した以外は、実施例１と同様の操作で膜
厚が約２．５μｍの着色膜付着ガラスを得た。評価結果
は、表２に示すように、耐摩耗性で膜剥離が確認され
た。 Comparative Example 9 Using only organoalkoxysilane hydrolyzate without adding colloidal silica as the silica component, the pigment became 12 wt% based on silica (solid content) in terms of oxide.
1 chelate in 2 wt% based on silica-based sol solids
A colored film-adhered glass having a film thickness of about 2.5 μm was obtained in the same manner as in Example 1, except that In the evaluation results, as shown in Table 2, film peeling was confirmed due to abrasion resistance.
【００６０】比較例１０ シリカ分としてコロイダルシリカを添加せずオルガノア
ルコキシシラン加水分解物のみを使用して顔料が酸化物
換算でシリカ（固形分）に対して３ｗｔ％となり、Ａｌ
キレートをシリカ系ゾルの固形分に対して２ｗｔ％にな
るように、した以外は、実施例１と同様の操作で膜厚が
約６．５μｍの着色膜付着ガラスを得た。評価結果は、
表２に示すように、耐摩耗性で膜剥離が確認された。[0060]Comparative Example 10 No organoid without adding colloidal silica as silica
Pigment is oxide using only alkoxysilane hydrolyzate
In terms of silica (solid content), it is 3 wt%,
The chelate is reduced to 2% by weight based on the solid content of the silica-based sol.
As described above, except that the film thickness was changed by the same operation as in Example 1.
A glass having a colored film having a thickness of about 6.5 μm was obtained. The evaluation result is
As shown in Table 2, peeling of the film was confirmed due to abrasion resistance.
【００６１】比較例１１ （オルガノアルコキシシランの加水分解物の調製）水温
を１０℃に調整した冷却器内に攪拌機を備えたガラス製
の容器を設置し、メチルトリエトキシシラン１００ｇを
加え、攪拌しながら、０．０１Ｎ−ＨＣｌ３０ｇを３０
分間かけ滴下して加水分解物を得た。更に、２４時間攪
拌することにより、シリカ固形分として２９％のシリカ
系ゾルを調製した。 Comparative Example 11 (Preparation of Hydrolyzate of Organoalkoxysilane) A glass container equipped with a stirrer was placed in a cooler whose water temperature was adjusted to 10 ° C., and 100 g of methyltriethoxysilane was added and stirred. While adding 30 g of 0.01 N HCl for 30 minutes.
The mixture was dropped over a period of minutes to obtain a hydrolyzate. Further, by stirring for 24 hours, a silica-based sol having a silica solid content of 29% was prepared.
【００６２】（顔料分散）顔料が酸化物換算でシリカ
（固形分）に対して１２ｗｔ％となり、Ａｌキレートを
シリカ系ゾルの固形分物に対して５ｗｔ％になるよう
に、シリカ加水分解物６４．２ｇに加えて、（Ｃｕ，Ｆ
ｅ，Ｍｎ）Ｏ・（Ｆｅ，Ｍｎ）2Ｏ3で示される黒色顔料
〔ダイピロキサイド＃３５５０：大日精化工業（株）
製、平均１次粒径約５０ｎｍ〕２．２ｇと、Ａｌキレー
ト０．９ｇ、ｉ−プロパノール溶液３２．７ｇをミルポ
ットの中に添加し、直径０．６５ｍｍのジルコニアビー
ズとともにボールミルで約２４時間粉砕、分散、混合処
理することにより黒色顔料を含む固形分濃度が約２０ｗ
ｔ％の分散溶液を得た。(Pigment Dispersion) The silica hydrolyzate 64 is prepared such that the pigment becomes 12 wt% in terms of oxides based on silica (solid content) and the Al chelate becomes 5 wt% based on the solid content of the silica sol. .2 g, (Cu, F
e, Mn) O • (Fe, Mn) 2 O 3 [Dipiroxide # 3550: Dainichi Seika Kogyo Co., Ltd.
2.2 g, 0.9 g of Al chelate and 32.7 g of i-propanol solution were added into a mill pot, and ground with a ball mill for 0.6 hours together with zirconia beads having a diameter of 0.65 mm. , Dispersion and mixing process, the solid content concentration including black pigment is about 20w
A t% dispersion was obtained.
【００６３】（硬化被膜の形成）この分散液を塗布液と
した浸漬槽内に、片面をマスキングしたガラス基板を浸
漬し引き上げるディッピング法により塗布し、該被塗布
ガラス基板を約２００℃で約１時間程度加熱乾燥するこ
とにより、膜厚約２．５μｍの着色膜付着ガラスを得
た。上記方法で得られた硬化被膜を有するガラスは、第
２表に示すように、耐摩耗性で膜剥離が確認され、耐煮
沸性試験において膜がガラス基板より剥離した。(Formation of Cured Coating) A glass substrate having one side masked is dipped in a dipping tank using this dispersion as a coating solution, and the glass substrate to be coated is dipped at about 200 ° C. for about 1 hour. By heating and drying for about an hour, a colored film-adhered glass having a film thickness of about 2.5 μm was obtained. As shown in Table 2, the glass having a cured film obtained by the above method was confirmed to have abrasion resistance, and film peeling was observed. In the boiling resistance test, the film was peeled from the glass substrate.
【００６４】[0064]
【発明の効果】以上詳述したように、本発明によれば、
比較的低温でプライバシーガラスを製造できるため、曲
げ加工、整形まで完了した自動車用ガラスに、グレー色
系ないし黒色系の着色膜を全面もしくは部分的に成膜す
ることが可能となる。As described in detail above, according to the present invention,
Since privacy glass can be manufactured at a relatively low temperature, a gray or black colored film can be entirely or partially formed on an automotive glass that has been subjected to bending and shaping.
Claims (8)
てのシリカ中にＣｕＯ−Ｆｅ2Ｏ3−Ｍｎ2Ｏ3系からなる
黒色系顔料が分散された着色膜が被覆された濃色着色遮
光ガラスであって、該シリカは、アルコキシシランの加
水分解物もしくは部分加水分解物並びにコロイダルシリ
カより構成され、そのアルコキシシランの加水分解物も
しくは部分加水分解物の固形分に対するコロイダルシリ
カの重量比が６０：４０〜４０：６０であり、且つ該黒
色系顔料は、シリカ固形分との合計重量の５〜１０重量
％含有されてなることを特徴とする濃色着色遮光ガラ
ス。On the surface of the 1. A transparent glass plate, dark colored light shielding glass colored film black pigment is dispersed which in the silica as a matrix consisting of CuO-Fe 2 O 3 -Mn 2 O 3 system is covered Wherein the silica is composed of a hydrolyzate or partial hydrolyzate of alkoxysilane and colloidal silica, and the weight ratio of colloidal silica to the solid content of the hydrolyzate or partial hydrolyzate of alkoxysilane is 60: Dark colored light-shielding glass, characterized in that the ratio is 40 to 40:60 and the black pigment is contained in an amount of 5 to 10% by weight based on the total weight of the solid content of silica.
が３μｍ以上６μｍ以下であり、しかも可視光線透過率
が２０〜３０％、ヘーズ値が１．０％以下であることを
特徴とする請求項１記載の濃色着色遮光ガラス。2. The colored film has a dark gray color, a thickness of 3 μm or more and 6 μm or less, a visible light transmittance of 20 to 30%, and a haze value of 1.0% or less. The dark-colored light-shielding glass according to claim 1, wherein:
験法に基づいたテーバー摩耗試験（荷重：５００ｇｆ×
２，１００回転）の試験前と試験後のヘイズ値の変化量
（試験後のヘイズ値／試験前のヘイズ値）が、５．０以
下であることを特徴とする請求項１または２記載の濃色
着色遮光ガラス。3. A Taber abrasion test (load: 500 gf ×) based on a wear resistance test method specified in JIS R 3212.
The haze value change before and after the test (2,100 rotations) (haze value after the test / haze value before the test) is 5.0 or less. Dark colored shading glass.
するにあたり、（ａ）透明ガラス板を用意する工程と、
（ｂ）黒色系顔料をマトリックスとしてのシリカ固形分
との合計重量の５〜１０重量％となるように調合した黒
色顔料およびシリカ系混合ゾルを、分散剤、硬化触媒お
よび溶媒とを含む液に添加し、分散混合して塗布液を調
製する工程と、（ｃ）前記塗布液を、前記ガラス板表面
上に塗布する工程、（ｄ）塗布したガラス板を熱処理す
る工程と、によってガラス板表面上に着色膜を形成する
ことを特徴とする濃色着色遮光ガラスの製法。4. A process for producing a dark colored light-shielding glass according to claim 1, wherein (a) a step of preparing a transparent glass plate;
(B) A black pigment and a silica-based mixed sol prepared so that the total weight of the black pigment and the silica solid content as a matrix is 5 to 10% by weight are converted into a liquid containing a dispersant, a curing catalyst, and a solvent. Adding and dispersing and mixing to prepare a coating solution; (c) applying the coating solution on the glass plate surface; and (d) heat treating the coated glass plate. A method for producing a dark-colored light-shielding glass, comprising forming a colored film thereon.
（Ｏ−Ｒ１）3（式中、Ｒ１は炭素数１または２のアル
キル基、Ｒ２はエポキシ基を含有する有機基を示す。）
で表わされるオルガノトリアルコキシシランの加水分解
物もしくは部分加水分解物並びにコロイダルシリカの混
合ゾルであることを特徴とする請求項４記載の濃色着色
遮光ガラスの製法。5. A silica-based sol having a general formula R2Si
(O-R1) 3 (wherein, R1 represents an alkyl group having 1 or 2 carbon atoms, and R2 represents an organic group containing an epoxy group.)
5. The method for producing a dark-colored light-shielding glass according to claim 4, which is a mixed sol of a hydrolyzate or a partial hydrolyzate of an organotrialkoxysilane represented by the formula (1) and colloidal silica.
４〜６重量％添加することを特徴とする請求項４記載の
濃色着色遮光ガラスの製法。6. The method for producing a dark-colored light-shielding glass according to claim 4, wherein the curing catalyst is added in an amount of 4 to 6% by weight based on the total weight of the solid content and the silica solid content.
はＯＲ１（Ｒ１は炭素数１〜４のアルキル基）、Ｙは一
般式Ｒ２ＣＯＣＨ2ＣＯＯＲ３（Ｒ２、Ｒ３はいずれも
炭素数１〜４のアルキル基）で示される化合物に由来す
る配位子から選ばれる１つであり、ｍは０，１または２
である）で示されるアルミニウムキレート化合物である
ことを特徴とする請求項６記載の濃色着色遮光ガラスの
製法。7. curing catalyst, Al · X m Y 3 - m ( wherein, X
Is OR1 selected from ligands derived from compounds represented by (R1 is an alkyl group having 1 to 4 carbon atoms), Y is formula R2COCH 2 COOR3 (R2, R3 are both alkyl groups having 1 to 4 carbon atoms) M is 0, 1 or 2
7. The method for producing a dark-colored light-shielding glass according to claim 6, which is an aluminum chelate compound represented by the following formula:
を特徴とする請求項４記載の濃色着色遮光ガラスの製
法。8. The method for producing a dark-colored light-shielding glass according to claim 4, wherein the heat treatment temperature is 150 to 200 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11163505A JP2000351651A (en) | 1999-06-10 | 1999-06-10 | Deep colored shading glass and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11163505A JP2000351651A (en) | 1999-06-10 | 1999-06-10 | Deep colored shading glass and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000351651A true JP2000351651A (en) | 2000-12-19 |
Family
ID=15775149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11163505A Pending JP2000351651A (en) | 1999-06-10 | 1999-06-10 | Deep colored shading glass and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000351651A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008536791A (en) * | 2005-04-19 | 2008-09-11 | ショット アクチエンゲゼルシャフト | Glass with decorative coating, or glass-ceramic product |
| US7553519B2 (en) * | 2004-03-26 | 2009-06-30 | Eurokera | Glass-ceramic and glass plates, heating plates, and preparation |
-
1999
- 1999-06-10 JP JP11163505A patent/JP2000351651A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7553519B2 (en) * | 2004-03-26 | 2009-06-30 | Eurokera | Glass-ceramic and glass plates, heating plates, and preparation |
| JP2008536791A (en) * | 2005-04-19 | 2008-09-11 | ショット アクチエンゲゼルシャフト | Glass with decorative coating, or glass-ceramic product |
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