JPH10152349A - Colored glass absorbing ultraviolet light - Google Patents

Colored glass absorbing ultraviolet light

Info

Publication number
JPH10152349A
JPH10152349A JP30963896A JP30963896A JPH10152349A JP H10152349 A JPH10152349 A JP H10152349A JP 30963896 A JP30963896 A JP 30963896A JP 30963896 A JP30963896 A JP 30963896A JP H10152349 A JPH10152349 A JP H10152349A
Authority
JP
Japan
Prior art keywords
ultraviolet
film
silicone
chelate compound
absorbing
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
Application number
JP30963896A
Other languages
Japanese (ja)
Inventor
Masahiro Hirugawa
雅浩 晝河
Noboru Murata
昇 村田
Haruki Kuramasu
春喜 倉増
Toshikazu Nagashima
敏和 長嶋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central Glass Co Ltd
Original Assignee
Central Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to JP30963896A priority Critical patent/JPH10152349A/en
Publication of JPH10152349A publication Critical patent/JPH10152349A/en
Pending legal-status Critical Current

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
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions

Abstract

PROBLEM TO BE SOLVED: To obtain a ultraviolet absorbing colored glass plate improved in weather resistance in a state enlarged in a long wavelength ultraviolet light- absorbing force by coating the surface of a transparent glass substrate with a silicon primer coating solution containing a fluorescent brightening agent, a ultraviolet light absorbent and a metal chelate compound and subsequently curing the coated solution to form a ultraviolet absorbing colored film. SOLUTION: The fluorescent brightening agent absorb light in a ultraviolet light region, generates fluorescent light in a visible light region, can be dissolved in a silicon primer coating solution, is thermally not denaturated on the thermal curing of a coating film, is good in thermal stability, and has absorbing wavelengths at a place (400nm) near to the boundary between the ultraviolet light region and the visible light region. The coexisting ultraviolet absorbent includes a benzophenone ultraviolet absorbent and a benzotriazole ultraviolet adsorbent. The metal chelate compound is preferably a transtion metal chelate also useful for quenching the fluorescent brightening agent, and the stable chelate compound of Ni, Fe or Mn in the fourth period. The ligand of the chelate compound is preferably acetyl acetone, cyclohexyl butyrate, etc.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、紫外線吸収性の優
れた着色コーティング膜を有するガラスおよびこの膜を
耐摩耗性や耐薬品性など耐久性に優れた保護コーティン
グ膜で積層被覆した、より耐候性に優れた紫外線吸収着
色ガラスに関する。BACKGROUND OF THE INVENTION The present invention relates to a glass having a colored coating film excellent in ultraviolet absorption, and a film formed by laminating this film with a protective coating film having excellent durability such as abrasion resistance and chemical resistance. It relates to an ultraviolet absorbing colored glass having excellent properties.

【０００２】本発明は、意匠性のある紫外線遮蔽フィル
タ−的部材として各種窓材、例えばビルや住宅や自動車
等車両、あるいは船舶や航空機、または種々のディスプ
レイ機器などの窓材として有用な紫外線吸収着色ガラス
を提供する。[0002] The present invention relates to a UV-absorbing filter member having a design property, which is useful as a window material for various windows, for example, a building, a house, a vehicle such as an automobile, a ship, an aircraft, or various display devices. Provide colored glass.

【０００３】[0003]

【従来の技術】従来からガラス基板等に紫外線吸収性を
付与する処理方法としては、例えばソ−ダライムシリカ
ガラス中に酸化鉄や酸化セリウムや酸化チタンなどの金
属酸化物を溶解添加したもの（例えば、特開平4-224133
号公報、特開平6-321577号公報）、あるいはガラス基板
にCVD 法やスパッタ法などの気相成膜法で酸化亜鉛や酸
化チタンや窒化ケイ素などの膜を形成したもの（例え
ば、特開平5-152213号公報、特公平4-44721 号公報）、
あるいはゾルゲル法などの液相成膜で酸化チタンや酸化
セリウムや酸化亜鉛などの膜を形成したもの（例えば、
特開平4-97103 号公報、特開平5-345638号公報）または
ゾルゲル法などの液相成膜で酸化チタンや酸化セリウム
や酸化亜鉛などの超微粒子を樹脂マトリックスに分散し
て膜形成したもの（例えば、特開平2-265976号公報、特
開平5-222338号公報）等がある。2. Description of the Related Art Conventionally, as a treatment method for imparting ultraviolet absorption to a glass substrate or the like, for example, a soda lime silica glass in which a metal oxide such as iron oxide, cerium oxide or titanium oxide is dissolved and added ( For example, JP-A-4-224133
JP-A-6-321577) or a glass substrate on which a film of zinc oxide, titanium oxide, silicon nitride, or the like is formed by a vapor-phase film forming method such as a CVD method or a sputtering method (for example, JP-A-5-321577). -152213, Japanese Patent Publication No. 4-44721),
Alternatively, a film formed of titanium oxide, cerium oxide, zinc oxide, or the like by liquid phase film formation such as a sol-gel method (for example,
JP-A-4-97103, JP-A-5-345638) or a film formed by dispersing ultrafine particles such as titanium oxide, cerium oxide and zinc oxide in a resin matrix by liquid phase film forming such as sol-gel method ( For example, there are JP-A-2-265976 and JP-A-5-222338.

【０００４】これらはいずれも、無機系の紫外線吸収剤
を用いているため、長波長紫外線（UVA ）吸収力が不充
分であり、バルクガラスや気相成膜品には多品種少量生
産に対応しにくいという弱点があり、気相成膜品や液相
成膜品には屈折率、膜厚差に起因する干渉着色を厳密に
制御しなければならないという弱点がある。また、ゾル
ゲル法のように高温焼成を必要とする方法では、曲げ板
への直接成膜は難しい。また、酸化亜鉛を用いる場合に
は耐湿性や耐薬品性に弱いので保護対策が必要となる。[0004] Since all of these use an inorganic ultraviolet absorber, they have insufficient long-wavelength ultraviolet (UVA) absorption power, and can be used for bulk glass and vapor-phase film-formed products in a wide variety of small-lot production. There is a weak point that it is difficult to perform interference coloring, and in a vapor-phase film-formed product and a liquid-phase film-formed product, it is necessary to strictly control interference coloring caused by a difference in refractive index and film thickness. Further, it is difficult to form a film directly on a bent plate by a method requiring high-temperature baking such as a sol-gel method. In addition, when zinc oxide is used, it is weak in moisture resistance and chemical resistance, so that protection measures are required.

【０００５】これに対し、有機系の紫外線吸収剤を樹脂
マトリックスに溶解して膜を形成したものには、例えば
前記した特開平2-265976号公報などがあって、長波長紫
外線吸収力があり、耐熱性の関係から必然的に低温硬化
ができるので曲げ板や強化板への対応も容易であり、多
品種少量生産にも対応し易いものであるが、耐久性、耐
候性に信頼性がない。On the other hand, a film formed by dissolving an organic ultraviolet absorbent in a resin matrix is disclosed in, for example, the above-mentioned Japanese Patent Application Laid-Open No. 2-265976, which has a long wavelength ultraviolet absorbing power. Because of its heat resistance, it can inevitably be cured at low temperatures, so it is easy to handle bent plates and reinforced plates, and it is easy to cope with high-mix low-volume production. Absent.

【０００６】前述したように、少量多品種生産に向か
ず、長波長紫外線吸収力も不充分なものであったり、耐
薬品性、耐湿性、耐擦傷性、耐久性あるいは耐候性に不
安があって劣るものであったりする従来技術を改善し、
有機系の紫外線吸収剤と蛍光増白剤を組み合わせること
で長波長紫外線吸収力をよりアップし、シリコ−ン系樹
脂を用いることで耐久性あるいは耐候性をよりアップせ
しめたガラスを本出願人は既に出願（例えば、特開平6-
145837号公報、特願平6-318625号）してきた。[0006] As described above, it is not suitable for small-quantity multi-product production, and has insufficient long-wavelength ultraviolet ray absorbing power, or has concerns about chemical resistance, moisture resistance, scratch resistance, durability or weather resistance. Improve the inferior or conventional technology,
By combining an organic UV absorber and a fluorescent whitening agent, the applicant has obtained glass that has improved long-wavelength UV absorptivity and improved durability or weather resistance by using a silicone resin. Application has already been filed (for example,
145837, Japanese Patent Application No. 6-318625).

【０００７】[0007]

【発明が解決しようとする課題】最近、長波長紫外線吸
収力をよりアップした状態で、さらに過酷な環境のなか
で優れた耐候性を必要とするようなより厳しい用途にも
耐久性があって充分使用でき、少量多品種生産タイプで
ある紫外線吸収着色ガラスを安価で簡便に効率よく提供
することが望まれている。Recently, with increased long-wavelength ultraviolet absorption, it is durable even in harsher environments that require superior weather resistance in harsh environments. It is desired to provide an inexpensive, simple, and efficient UV-absorbing colored glass that can be used sufficiently and that can be produced in small quantities and in various types.

【０００８】[0008]

【課題を解決するための手段】本発明は、従来のかかる
問題点に鑑みてなしたものであって、長波長紫外線吸収
力をよりアップした状態で維持しつつ、金属キレ−ト化
合物を併用すれば、淡い着色は伴うものの、微量の該金
属キレ−ト化合物で耐候性をより効果的に向上すること
ができる有用な紫外線吸収着色ガラスを安価で簡便に効
率よく提供するものである。DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made in combination with a metal chelate compound while maintaining a longer-wavelength ultraviolet ray absorbing power in a more improved state. In this case, a useful ultraviolet absorbing colored glass capable of improving weather resistance more effectively with a trace amount of the metal chelate compound, although accompanied by pale coloring, is provided at low cost, simply and efficiently.

【０００９】すなわち、本発明は、透明ガラス基板の表
面に、蛍光増白剤および紫外線吸収剤および金属キレ−
ト化合物を溶解添加してなるシリコ−ン系プライマ−コ
−ティング溶液を塗布して加熱硬化した紫外線吸収着色
膜およびさらに該紫外線吸収着色膜上にシリコーン系ハ
ードコーティング溶液を塗布して被覆成膜した保護膜と
を積層成膜したことを特徴とする紫外線吸収着色ガラ
ス、ならびに、前記シリコ−ン系プライマ−が、オルガ
ノポリシロキサン系の溶液であることを特徴とする上述
した紫外線吸収着色ガラス、また、前記金属キレ−ト化
合物が、少なくとも１種類以上の遷移金属キレ−ト化合
物であることを特徴とする上述した紫外線吸収着色ガラ
ス、さらに、前記シリコーン系ハードコーティング溶液
が、オルガノポリシロキサン系を主体とする溶液である
ことを特徴とする上述した紫外線吸収着色ガラスを提供
するものである。That is, according to the present invention, an optical brightener, an ultraviolet absorber and a metal cleaner are provided on the surface of a transparent glass substrate.
A silicone-based primer coating solution obtained by dissolving and adding a silicon compound, and applying heat to cure an ultraviolet-absorbing colored film, and further applying a silicone-based hard coating solution on the ultraviolet-absorbing colored film to form a coating. An ultraviolet-absorbing colored glass, wherein the protective film is laminated and formed, and the above-mentioned ultraviolet-absorbing colored glass, wherein the silicone-based primer is an organopolysiloxane-based solution, Further, the above-mentioned ultraviolet absorbing colored glass, wherein the metal chelate compound is at least one kind of transition metal chelate compound, and the silicone-based hard coating solution comprises an organopolysiloxane-based solution. An object of the present invention is to provide the ultraviolet absorbing colored glass described above, which is a solution mainly used.

【００１０】[0010]

【発明の実施の形態】ここで、前述したように、前記蛍
光増白剤としては、紫外領域で吸収し、可視領域で蛍光
を発し、シリコーン系プライマーコーティング溶液に溶
解添加が可能であって、かつ塗膜の加熱硬化時に熱変性
しなければどのようなものでもよいものであり、しかも
適度の耐熱性があり、吸収波長が紫外／可視領域境界
（400nm付近）にある例えば、UvitexーOB（チバガイギ
ー社製、2, 5ビス(5' ーターシャリブチルベンゾオキサ
ゾリル) チオフェン）、あるいはEBー501(三井東圧染料
社製）、さらにNikkafluor SB 、KB、EFS 、OB（日本化
学工業所製）などが挙げられる。Here, as described above, the fluorescent whitening agent absorbs in the ultraviolet region, emits fluorescence in the visible region, and can be dissolved and added to a silicone-based primer coating solution, Any material may be used as long as it does not undergo thermal denaturation at the time of heat curing of the coating film. In addition, it has appropriate heat resistance, and has an absorption wavelength at the boundary between the ultraviolet and visible regions (around 400 nm). For example, Uvitex-OB ( 2,5 bis (5'-tert-butylbenzoxazolyl) thiophene manufactured by Ciba Geigy, or EB-501 (manufactured by Mitsui Toatsu Dyestuffs), and Nikkafluor SB, KB, EFS, OB (Nippon Chemical Industry Co., Ltd.) Manufactured).

【００１１】また、共存せしめる前記紫外線吸収剤とし
ては、例えばベンゾフェノン系、ベンゾトリアゾール
系、シアノアクリレート系あるいはサリシレート系ある
いはインドール系などが挙げられる。Examples of the ultraviolet absorber to be coexistent include benzophenone type, benzotriazole type, cyanoacrylate type, salicylate type and indole type.

【００１２】また、金属キレ−ト化合物としては、例え
ばシリコ−ン系プライマ−コ−ティング溶液に溶解添加
が可能であれば何でもよいが、蛍光増白剤の消光にも役
立つ遷移金属キレ−トが好ましい。液の安定性も良好で
あって特に好ましいものとしては、第４周期のNi、Fe、
Mn、Co、Crなどキレ−ト化合物が挙げられる。The metal chelate compound is not particularly limited as long as it can be dissolved and added to a silicone-based primer coating solution, but it is a transition metal chelate which is also useful for quenching the fluorescent brightener. Is preferred. The stability of the liquid is also good, and particularly preferable are Ni, Fe,
Chelate compounds such as Mn, Co, and Cr are exemplified.

【００１３】キレ−ト配位子としては、アセチルアセト
ン、テノイルトリフルオロアセトンなどのβ−ジケトン
類、シクロヘキシル酪酸などの脂肪族カルボン酸、オキ
シン類、ジチゾン類、クペロン類、α−ジオキシム類な
どが挙げられ、入手が容易でシリコ−ン系プライマ−コ
−ティング溶液への溶解性のよいアセチルアセトン、シ
クロヘキシル酪酸などが最も好ましい。Examples of the chelate ligand include β-diketones such as acetylacetone and thenoyltrifluoroacetone, aliphatic carboxylic acids such as cyclohexylbutyric acid, oxines, dithizones, cuperones, and α-dioximes. Most preferred are acetylacetone, cyclohexylbutyric acid and the like, which are easily available and have good solubility in silicone-based primer coating solutions.

【００１４】金属キレ−トの作用については、定かでな
いが、紫外線吸収剤とより安定なキレ−トを作り、新規
紫外線吸収剤としてその劣化を防止するのではないかと
推測される。Although the action of the metal chelate is not clear, it is speculated that a more stable chelate may be formed with the ultraviolet absorber to prevent its deterioration as a new ultraviolet absorber.

【００１５】また、該蛍光増白剤と該紫外線吸収剤の使
用割合としては、重量比率で１：0.5 から１：10程度で
あり、より安定確実にするための好ましい範囲としては
１：３〜１：６程度であり、蛍光増白剤が多くなると蛍
光で透視性が悪化し、少な過ぎると所望のUVA 吸収力が
得られない。これらは総計としてプライマーコーティン
グ液の0.1 〜10重量％が好ましく、溶解性に余裕があっ
ても必要以上に添加するのは不経済となる。The weight ratio of the fluorescent whitening agent to the ultraviolet absorber is about 1: 0.5 to 1:10, and a preferable range for ensuring more stable is 1: 3 to 1: 1. The ratio is about 1: 6, and when the amount of the fluorescent whitening agent is increased, the transparency deteriorates due to the fluorescence. When the amount is too small, the desired UVA absorbing power cannot be obtained. These are preferably used in a total amount of 0.1 to 10% by weight of the primer coating solution, and it is uneconomical to add more than necessary even if there is a margin in solubility.

【００１６】次いで、金属キレ−トであるが溶解度と着
色許容度の限界を考慮すると、蛍光増白剤と紫外線吸収
剤添加済みのプライマ−コ−ティング液に100 重量部に
対して0.1 〜５重量部程度であり、好ましくは0.5 〜３
重量部程度であって耐候性を改善し着色も黄色系、緑色
系、褐色系の淡い色調程度であり、少なすぎると耐候性
の改善に効果がなく、多くなると着色がはげしくなり、
液の安定性も悪くなる。Next, considering the limits of solubility and coloring tolerance of the metal chelate, 0.1 to 5 parts by weight per 100 parts by weight of the primer coating solution to which the fluorescent brightener and the ultraviolet absorber are added. Parts by weight, preferably 0.5 to 3 parts by weight.
It is about part by weight and improves weather resistance and coloring is also yellowish, greenish, brownish pale tone, if too small, there is no effect on weatherability improvement, and if it is too large, coloring becomes severe,
The stability of the liquid also deteriorates.

【００１７】さらにここで、シリコーン系プライマーに
ついては、上記した蛍光増白剤と紫外線吸収剤と金属キ
レ−トを充分溶解する必要があるため、溶解力があるシ
クロヘキサノンなどのケトン系溶剤やキシレンなどの芳
香族系溶剤とセロソルブなどのエ−テルアルコ−ル系溶
剤やブタノ−ルなどのアルコ−ル系溶剤が混合している
溶剤を使用するのが好ましい。Further, as for the silicone primer, since it is necessary to sufficiently dissolve the above-mentioned fluorescent whitening agent, ultraviolet absorber and metal chelate, a ketone-based solvent such as cyclohexanone or xylene, which has solubility, is used. It is preferable to use a solvent in which an aromatic solvent such as the above is mixed with an ether alcohol-based solvent such as cellosolve or an alcohol-based solvent such as butanol.

【００１８】さらにまた、前記シリコーン系プライマ−
の樹脂成分としては例えば、オルガノシロキサンポリマ
ーのみからなるものや、アクリル系樹脂、ウレタン系樹
脂、フッ素系樹脂、ポリエステル系樹脂等との共重合体
が挙げられ、必要に応じて耐熱性や耐摩耗性や密着性や
透明性の向上のため、例えば市販の塗料用シリコーンワ
ニスまたはシリコーン変性ワニス〔例えば東芝シリコー
ン（株）製あるいは信越化学工業（株）製〕やベルクリ
ーン〔日本油脂（株）製〕やOS-800〔大八化学（株）
製〕などを利用して濃度、粘度あるいは膜厚の関係によ
って調製すればよく、さらにシリカやアルミナなどの酸
化物超微粒子を添加するとよい。固形分濃度としては５
〜50wt％程度、、粘度としては２〜100cP 程度、プライ
マーによる紫外線吸収着色膜の膜厚としては0.5 〜10μ
程度が好ましく、また先に述べるがトップ膜層である保
護膜の膜厚としては１〜５μ程度が好ましいため、全膜
厚としては1.5 〜15μ程度が好ましいものとなる。Further, the silicone-based primer
Examples of the resin component include those composed of only an organosiloxane polymer and copolymers with an acrylic resin, a urethane resin, a fluorine resin, a polyester resin, and the like. In order to improve the properties, adhesion and transparency, for example, commercially available silicone varnishes for coatings or silicone-modified varnishes (eg, manufactured by Toshiba Silicone Co., Ltd. or Shin-Etsu Chemical Co., Ltd.) or Bellclean [manufactured by NOF CORPORATION] ] And OS-800 [Daichi Chemical Co., Ltd.]
And the thickness, viscosity or thickness of the film may be adjusted, and ultrafine oxide particles such as silica and alumina may be added. 5 as solids concentration
About 50 wt%, viscosity about 2-100 cP, thickness of UV-absorbing colored film with primer of 0.5-10 μm
The thickness is preferably about 1 to 5 μm, and the total thickness is preferably about 1.5 to 15 μm.

【００１９】特に、例えばベルクリーン（シリコーン変
性アクリルポリマー）についての好ましい濃度（対シリ
コーン系プライマー溶液）は約10〜30wt％程度であり、
10wt％程度未満では塗膜が白化し易くなり、30wt％程度
を超えて多過ぎると密着性の悪化やクラックの発生が見
られるようになる。また例えば OS800（シリコーン系ポ
リマー）についての好ましい濃度は約５〜30wt％程度で
あり、５wt％程度未満と次第に少なくなると耐熱水性や
主に被覆するシリコーン系ハードコート膜に対しての密
着性に影響し、少な過ぎると密着の効果がなくなり、30
wt％程度を超えて多過ぎると白化し易くなる。Particularly, for example, a preferable concentration (for a silicone-based primer solution) of Bellclean (silicone-modified acrylic polymer) is about 10 to 30% by weight,
If it is less than about 10% by weight, the coating film tends to be whitened, and if it is more than about 30% by weight, the adhesion is deteriorated and cracks appear. For example, the preferable concentration of OS800 (silicone-based polymer) is about 5 to 30% by weight, and when the concentration is gradually reduced to less than about 5% by weight, it affects the hot water resistance and the adhesion to the silicone-based hard coat film mainly coated. If too little, the effect of adhesion will be lost and 30
If the amount exceeds about wt%, whitening is apt to occur.

【００２０】さらに例えばコロイダルシリカXBA （キシ
レン、n-ブタノール分散型シリカ超微粒子オルガノゾ
ル）についての好ましい濃度は約20〜50wt％程度であ
り、20wt％程度未満と次第に少なくなるとクラックの発
生が見られるようになり、50wt％程度を超えて多過ぎる
と白化し易くなるようになる。さらにまた例えば密着性
をより向上せしめるためのシランカップリング剤である
S510（エポキシシラン）についての添加量としては約0.
5 〜20wt％程度を添加することが好ましく、0.5 重量％
程度未満と次第に少なくなると主にガラスに対しての密
着性に影響し少な過ぎると密着効果がなくなり、20重量
％程度を超えて多過ぎると不経済となる。Further, for example, the preferred concentration of colloidal silica XBA (xylene, n-butanol-dispersed silica ultrafine particle organosol) is about 20 to 50 wt%, and when the concentration is gradually reduced to less than about 20 wt%, generation of cracks may be observed. If the content exceeds about 50% by weight, whitening tends to occur. Furthermore, for example, it is a silane coupling agent for further improving adhesion.
The addition amount of S510 (epoxysilane) is about 0.
It is preferable to add about 5 to 20 wt%, and 0.5 wt%
When the amount is less than the degree, the adhesiveness to glass is mainly affected. When the amount is too small, the adhesion effect is lost. When the amount exceeds about 20% by weight, the amount is uneconomical.

【００２１】さらにまた、上述したように調製された前
記紫外線吸収性シリコーンプライマーは、均一膜厚とな
るように、例えばディッピング法、スプレー法、フロー
コート法、スピンコート法、ロールコート法あるいはス
クリ−ンやフレキソやグラビアやオフセット等の印刷法
などで塗布し被膜とし、例えば約80℃程度以上で約１時
間程度加熱乾燥するものであり、加熱不足であれば、シ
リコーン系ハードコート保護膜塗布時にプライマー成分
が溶出して例えばくもりあるいはクラック等を発現し易
く、耐熱水性も悪化し、また加熱が過多になると、焦げ
による着色や紫外線吸収性能の減少に至る。Further, the above-mentioned ultraviolet-absorbing silicone primer prepared as described above may have a uniform film thickness, for example, by dipping, spraying, flow coating, spin coating, roll coating, or screen coating. It is applied by a printing method such as printing, flexo, gravure, offset, etc. to form a film. For example, it is heated and dried at about 80 ° C. or more for about 1 hour. The primer component is eluted to easily develop, for example, cloudiness or cracks, and the hot water resistance deteriorates. Excessive heating leads to coloring due to burning and a decrease in ultraviolet absorption performance.

【００２２】さらに、塗布環境としては、例えば温度約
15〜25℃程度、湿度約40〜50RH％程度、さらにクリーン
度10,000以下程度が塗膜欠陥の防止の点で好ましい。塗
布性能を改善するため、フロー改良剤あるいはレオロジ
ーコントロール剤などを適宜添加してもよいことは言う
までもない。Further, as an application environment, for example, a temperature of about
A temperature of about 15 to 25 ° C., a humidity of about 40 to 50 RH%, and a cleanness of about 10,000 or less are preferred from the viewpoint of preventing coating film defects. It goes without saying that a flow improver or a rheology control agent may be appropriately added in order to improve the coating performance.

【００２３】さらに、前記シリコーン系プライマ−コ−
ティング溶液により形成した着色膜の保護膜として最も
適する前記シリコーン系ハードコーティング溶液として
は、テトラエトキシシラン加水分解物やコロイダルシリ
カなど高架橋密度のシロキサン結合が期待できるオルガ
ノポリシロキサン系であり、基本的にはメチルトリエト
キシシランなどの３官能性のオルガノアルコキシシラン
を加水分解して得られるシロキサンプレポリマーのアル
コール溶液をベースにしたものが好ましく、例えば本出
願人が既に出願した特開昭62-220531 号公報に記載の被
覆用組成物となるコロイダルシリカを含むものが好まし
く、さらにエポキシシラン成分を多く含んでいると接着
性や耐クラック性向上に役立つ。市販品では例えばトス
ガード510 〔東芝シリコーン（株）製〕あるいはSiコー
ト２〔大八化学（株）製〕などが挙げられる。Further, the silicone-based primer
The silicone-based hard coating solution that is most suitable as a protective film for a colored film formed by a coloring solution is an organopolysiloxane-based material that can be expected to have a high crosslink density siloxane bond such as tetraethoxysilane hydrolyzate or colloidal silica. Is preferably based on an alcohol solution of a siloxane prepolymer obtained by hydrolyzing a trifunctional organoalkoxysilane such as methyltriethoxysilane. For example, Japanese Patent Application Laid-Open No. 622-220531 has already been filed by the present applicant. The one containing colloidal silica as a coating composition described in the gazette is preferable, and further containing a large amount of an epoxysilane component is useful for improving adhesiveness and crack resistance. Commercially available products include, for example, Tosgard 510 (manufactured by Toshiba Silicone Co., Ltd.) and Si Coat 2 (manufactured by Daihachi Chemical Co., Ltd.).

【００２４】また、該シリコーン系ハードコーティング
溶液の被覆成膜については、均一膜厚となるような、例
えばディッピング法、スプレー法、フローコート法、ス
ピンコート法、ロールコート法あるいはスクリ−ンやフ
レキソやグラビアやオフセット等の印刷法などが利用で
き、膜厚としては約1.0 〜5.0 μ程度が好ましく、薄い
と表面保護強化の効果が少なくなり、厚いと加熱乾燥硬
化時にクラックを発現し易く、かつ経済的でなくなるも
のである。さらに加熱乾燥硬化には第１層に有機系の紫
外線吸収剤、蛍光増白剤および樹脂を含むため約100 ℃
程度以上約250℃程度以下の温度で処理する必要があ
り、好ましくは透明基板がガラス板状体等の場合は約13
0 〜230 ℃程度であり、約10〜60分間程度、好ましくは
約30分間前後程度の処理が表面硬度を高める上で好まし
い。The silicone hard coating solution may be formed into a film having a uniform thickness by, for example, dipping, spraying, flow coating, spin coating, roll coating, screen or flexo. Printing method such as gravure or offset can be used, and the film thickness is preferably about 1.0 to 5.0 μm.The thinner film reduces the effect of strengthening the surface protection, and the thicker film is more likely to develop cracks during heat drying and curing. It is not economic. Further, for heat drying and curing, the first layer contains an organic UV absorber, a fluorescent whitening agent and a resin, so that the temperature is about 100 ° C.
It is necessary to process at a temperature of about 250 ° C. or less, preferably about 13 ° C. when the transparent substrate is a glass plate or the like.
The treatment is performed at about 0 to 230 ° C. for about 10 to 60 minutes, preferably about 30 minutes, in order to increase the surface hardness.

【００２５】なお、塗布する際の環境としては、シリコ
ーン系プライマーと同様に例えば温度が約25℃程度の常
温で相対湿度が約20〜50％RH程度、好ましくは約40％RH
前後程度の空調された環境で行うことが好ましい。塗布
機能を改善するため、フロー改良剤あるいはレオロジー
コントロール剤などを適宜添加してもよいことは言うま
でもない。The environment for the application is the same as that of the silicone primer, for example, at a normal temperature of about 25 ° C. and a relative humidity of about 20 to 50% RH, preferably about 40% RH.
It is preferable to carry out in an air-conditioned environment of about front and rear. Needless to say, a flow improver or a rheology control agent may be appropriately added to improve the coating function.

【００２６】さらにまた、前記透明ガラス基板として
は、好ましくは無機質のガラス例えばフロートガラスで
あり、ことに形状等に特に限定されるものではなく各種
形状に、また大きさあるいは構成のもの、例えば曲げ板
ガラスとしてはもちろん、各種強化ガラスや強度アップ
ガラス、平板や単板で使用できるとともに、複層ガラス
あるいは合せガラスとしても適用できることは言うまで
もない。Further, the transparent glass substrate is preferably an inorganic glass such as a float glass, and is not particularly limited to a shape or the like, but may be formed into various shapes or having a size or configuration such as a bent glass. It goes without saying that it can be used not only as a sheet glass, but also as various strengthened glass, strengthened glass, a flat plate or a single plate, and also as a double-layer glass or a laminated glass.

【００２７】前述したとおり、本発明によれば、蛍光増
白剤と紫外線吸収剤と金属キレ−ト化合物とを共存せし
めるシリコーンプライマー溶液とする特異な構成よりな
る紫外線遮蔽性に優れる淡い着色コーティング膜の表面
に、表面硬度に優れたシリコーン系ハードコート膜を保
護膜として形成した積層膜であるので、蛍光増白剤の蛍
光も目立たない被膜として比較的低温で成膜でき、紫外
線吸収性に優れ、可視領域まで吸収の影響が多少及ぶも
のの、UVA を含む紫外線を格段に遮蔽することができ、
しかもクラック等欠陥の発現もなく鉛筆硬度が9Hないし
はそれ以上と硬くなり、密着性、耐薬品性、耐擦傷性あ
るいは耐久性に優れ、膜強度や平滑性も向上し、長期的
な耐候性をも格段に向上せしめ、淡い着色を伴うものの
視野確保が充分にでき、居住性を格段に高め、ビルや住
宅、車両あるいは各種の窓材等単板や外装用としての使
用はもちろん可能であり、ことに自動車用窓ガラスのフ
ロントガラス、リアガラスおよび昇降するサイドドアガ
ラス、サンルーフガラス、船舶や航空機の窓材などのよ
り過酷な使用条件と環境のなかでも長期的な使用が可能
となる等、さらには可視光の反射によるギラツキ感や電
波の反射による電波シールド性もない有用な紫外線遮蔽
ウィンドウ等になし得た透明な紫外線吸収着色ガラス
を、簡単なコーティング処理によって容易に効率よくか
つ安価に得ることができ、提供するものである。As described above, according to the present invention, a light-colored coating film excellent in ultraviolet-ray shielding properties and having a unique constitution is a silicone primer solution in which a fluorescent whitening agent, an ultraviolet absorber, and a metal chelate compound coexist. This is a laminated film in which a silicone hard coat film with excellent surface hardness is formed as a protective film on the surface of the film, so it can be formed at a relatively low temperature as a film in which the fluorescence of the fluorescent whitening agent is also inconspicuous, and has excellent UV absorption , Although the effect of absorption slightly extends to the visible region, it can significantly block ultraviolet rays including UVA,
Moreover, the pencil hardness becomes 9H or more without occurrence of defects such as cracks, excellent in adhesion, chemical resistance, scratch resistance or durability, film strength and smoothness are improved, and long-term weather resistance is improved. It is also significantly improved, and it is possible to sufficiently secure the field of view even though it is accompanied by pale coloration, dramatically enhance the livability, and it is of course possible to use it for buildings, houses, vehicles or various window materials such as veneers and exteriors, In particular, long-term use is possible under harsher operating conditions and environments such as windshields for automobiles, rear glass and side door glass that goes up and down, sunroof glass, window materials for ships and aircraft, and more. Is a transparent coat of transparent UV-absorbing colored glass that can be used as a useful UV-shielding window without glare due to visible light reflection or radio wave shielding due to radio wave reflection. Easily can be obtained efficiently and inexpensively by grayed process, there is provided.

【００２８】[0028]

【実施例】以下、実施例により本発明を具体的に説明す
る。ただし本発明は係る実施例に限定されるものではな
い。The present invention will be described below in detail with reference to examples. However, the present invention is not limited to such an embodiment.

【００２９】（紫外線吸収シリコーン系プライマーの調
製）ヘキサノン10.1ｇに常温で攪拌しながらシランカッ
プリング剤として S510 （チッソ社製）を10.0ｇ添加
し、その後オルガノコロイダルシリカXBA （日産化学社
製）を37.3ｇならびに蛍光増白剤としてUVITEX−OB（チ
バガイギー製）を0.7ｇ、紫外線吸収剤としてTINUVIN90
0（チバガイギー製）を2.8 ｇ、さらにベルクリーンNo1
000（日本油脂社製）を15.8ｇ添加し、さらにOS-800
〔大八化学（株）製〕を23.3ｇ添加することにより紫外
線吸収シリコーン系プライマーを得た。さらに、該紫外
線吸収シリコーン系プライマー100 重量部に対して各種
キレ−トを表１に示す割合で添加することにより着色し
た紫外線吸収シリコーン系プライマーを得た。(Preparation of UV-absorbing silicone primer) 10.0 g of S510 (manufactured by Chisso) was added as a silane coupling agent to 10.1 g of hexanone while stirring at room temperature, and then organocolloidal silica XBA (manufactured by Nissan Chemical) was added. 37.3 g, 0.7 g of UVITEX-OB (manufactured by Ciba Geigy) as a fluorescent whitening agent, and TINUVIN90 as an ultraviolet absorber
2.8 g of 0 (made by Ciba-Geigy), plus Bellclean No1
15.8g of 000 (manufactured by NOF CORPORATION) and OS-800
By adding 23.3 g of [Daihachi Chemical Co., Ltd.], an ultraviolet absorbing silicone primer was obtained. Further, a colored ultraviolet absorbing silicone primer was obtained by adding various chelate in the ratio shown in Table 1 to 100 parts by weight of the ultraviolet absorbing silicone primer.

【００３０】（シリコーン系ハードコーティング溶液の
調製）攪拌機付きの500ml 丸底フラスコにメチルトリエ
トキシシラン 100ｇとテトラエトキシシラン43ｇ、3-グ
リシドキシプロピルトリメトキシシラン18ｇをはり込
み、無水フタル酸0.45ｇ添加、湯浴で約40℃程度に加温
し溶解させ、その後オルガノコロイダルシリカ溶液であ
るIPA-ST〔日産化学（株）製、平均粒径約15μm程度、S
iO2含有量約20％程度〕143 ｇを添加し、水98ｇを少し
ずつ添加し約40℃程度で約２日間程度反応を行い、GPC
〔トーソー（株）製、ULC802A ）による数平均分子量約
1000程度で固形分を約28wt％程度の組成物を得た。(Preparation of Silicone Hard Coating Solution) A 500 ml round bottom flask equipped with a stirrer was charged with 100 g of methyltriethoxysilane, 43 g of tetraethoxysilane, and 18 g of 3-glycidoxypropyltrimethoxysilane, and 0.45 g of phthalic anhydride. After addition, the mixture was heated to about 40 ° C. in a hot water bath and dissolved, and then an organocolloidal silica solution IPA-ST [manufactured by Nissan Chemical Co., Ltd., average particle size of about 15 μm, S
iO 2 content about 20%] 143 g, water 98 g is added little by little, and the reaction is carried out at about 40 ° C for about 2 days.
[Number average molecular weight by Tosoh Corporation, ULC802A)
A composition having about 1000 and a solid content of about 28 wt% was obtained.

【００３１】これに163 ｇのイソプロピルアルコールを
添加し、固形分約20wt％程度の組成物を得た。該組成物
に硬化触媒としてジシアンジアミドを約 0.1部程度添加
してシリコーン系ハードコーティング溶液を得た。To this, 163 g of isopropyl alcohol was added to obtain a composition having a solid content of about 20% by weight. About 0.1 part of dicyandiamide was added as a curing catalyst to the composition to obtain a silicone-based hard coating solution.

【００３２】 （性能評価法） 紫外線吸収性：分光光度計で吸収スペクトルパターンを測定。（例えば日立ー Ｕ4000型） 蛍光性： 屋外の自然太陽光下で目視観察。（気になる発光、くもりがな い。） 耐摩耗性： JIS R 3221に準拠、摩耗輪CSー10F 、荷重 500ｇ、1000回転後 の△Ｈ（ヘーズ）値（％）。(Performance Evaluation Method) Ultraviolet Absorption: Absorption spectrum pattern is measured with a spectrophotometer. (Eg Hitachi-U4000) Fluorescence: Visual observation under natural sunlight outdoors. (No worrisome light emission and no cloudiness.) Abrasion resistance: Conforms to JIS R 3221, wear wheel CS-10F, load 500 g, ΔH (haze) value after 1000 rotations (%).

【００３３】 表面硬度： 鉛筆硬度。 密着性： JIS K5400 に準拠、碁盤目（１mm口）テープ剥離残数を／100 で表示。Surface hardness: Pencil hardness. Adhesion: Based on JIS K5400, the number of tape peeling (1 mm square) tape peeling remaining is indicated by / 100.

【００３４】 耐熱水性： 沸騰水（100 ℃）約２時間後の外観および密着性。 耐薬品性： 耐酸性---------1N HCl 浸漬テストで24hr。 耐アルカリ性---1N NaOH 浸漬テストで 4hr。Hot water resistance: Appearance and adhesion after boiling water (100 ° C.) for about 2 hours. Chemical resistance: Acid resistance -------- 24 hours in -1N HCl immersion test. Alkali resistance --- 4 hours in 1N NaOH immersion test.

【００３５】 耐溶剤性-------100％エタノール 浸漬テストで24hr。 耐候性： JIS D0205 に準拠、サンシャインカーボンウェザーメーターで 目視異常（膜クラック、剥離、顕著な黄変）がみられるまでの 時間。（但し、ガラス面照射） 紫外線吸収性能（ISO9050 準拠）Tuv （％）、可視光線透過率 Tv（％）、日射透過率Ts（％）の変化についても調査。Solvent resistance ----- 100% ethanol 24 hours in immersion test. Weather resistance: Based on JIS D0205, time until visual abnormalities (film cracks, peeling, noticeable yellowing) are observed with a sunshine carbon weather meter. (However, irradiation on the glass surface) Ultraviolet absorption performance (based on ISO9050) Investigation was also made on changes in Tuv (%), visible light transmittance Tv (%), and solar transmittance Ts (%).

【００３６】実施例１ 大きさ約300mm ｘ300mm 、厚さ約3.5mm のクリア・フロ
ートガラス基板を中性洗剤、水すすぎ、アルコールで順
次洗浄し、乾燥した後、アセトンで払拭し被膜用ガラス
基板とした。 Example 1 A clear float glass substrate having a size of about 300 mm × 300 mm and a thickness of about 3.5 mm was washed sequentially with a neutral detergent, water rinse, and alcohol, dried, and then wiped with acetone to form a glass substrate for coating. did.

【００３７】約25℃、約40％RHの空調されたクリーンル
ーム内で、該被覆用ガラス基板の片面をフイルムマスキ
ングし、表１に示すように、金属キレ−トとしてNi- ア
セチルアセトネ−トを１重量部添加した前記調製済の着
色した紫外線吸収シリコーン系プライマー溶液に浸漬
し、約1cm ／sec 程度のスピードで引き上げ、約175 ℃
程度で約１時間程度乾燥硬化し、膜厚約６μ程度の紫外
線吸収着色膜を形成した。In a clean room air-conditioned at about 25 ° C. and about 40% RH, one surface of the coating glass substrate was subjected to film masking, and as shown in Table 1, Ni-acetylacetonate was used as a metal chelate. Immersed in the above-prepared colored ultraviolet-absorbing silicone-based primer solution to which 1 part by weight was added, and pulled up at a speed of about 1 cm / sec.
After drying and curing for about 1 hour, an ultraviolet absorbing colored film having a thickness of about 6 μm was formed.

【００３８】次いで、該紫外線吸収着色膜付ガラス基板
のガラス面をフイルムマスキングして上記した調製済の
シリコーン系ハードコート溶液に浸漬し、前記膜面のみ
に塗布後、約10分間程度風乾し、続いて約175 ℃の熱風
循環乾燥器に約１時間程度入れ硬化し、約３μのシリカ
系保護膜を得た。該膜は有色透明のクラックのない良好
なものであった。なお遠赤外線炉での乾燥処理の際には
約200 ℃程度で約15分間程度で硬化できた。Next, the glass surface of the glass substrate with the ultraviolet absorbing colored film is film-masked, immersed in the prepared silicone hard coat solution described above, applied only to the film surface, and air-dried for about 10 minutes. Subsequently, the mixture was placed in a hot air circulating drier at about 175 ° C. for about 1 hour and cured to obtain a silica-based protective film of about 3 μm. The film was colored and transparent and had no cracks. In the case of drying treatment in a far-infrared furnace, curing was possible at about 200 ° C. for about 15 minutes.

【００３９】得られた紫外線吸収着色ガラスを上記した
性能評価法に従って評価した。その結果、分光光度曲線
で透過率（％）を図１に、また外観と光学特性を表１に
示すように、可視光線透過率が85.8％と透明で淡い黄色
な色調とやや着色しているものの、UVA をほぼ100 ％遮
蔽するもので紫外線透過率Tuv も0.8 ％と１％以下であ
り、表面硬度も9H以上の鉛筆硬度であって硬く、テーバ
ーテスト後のヘーズ値（△Ｈ）が4.2 と耐擦傷性も充分
に優れ、耐候性試験（SWM:1000Hr）を表２に示すよう
に、耐候性も1000時間以上で目視異常がなく、紫外線吸
収性能の低下も0.8 ％から1.3 ％と僅かであって過酷な
環境のなかで長期的な耐候性も充分にあり、密着性、耐
熱水性、耐薬品性も異常なく、屋外使用に耐える優れた
耐久性を有する紫外線吸収着色ガラスを得た。The obtained ultraviolet absorbing colored glass was evaluated according to the performance evaluation method described above. As a result, as shown in FIG. 1 showing the transmittance (%) in the spectrophotometric curve and the appearance and the optical characteristics in Table 1, the visible light transmittance was 85.8%, which was slightly colored with a transparent pale yellow color tone. However, it shields almost 100% of UVA, has an ultraviolet transmittance Tuv of 0.8% or less at 1% or less, has a pencil hardness of 9H or more and is hard, and has a haze value (△ H) of 4.2 after Taber test. As shown in Table 2, the weather resistance (SWM: 1000Hr) was sufficiently excellent, and the weather resistance was 1000 hours or more, there was no visual abnormality, and the decrease in ultraviolet absorption performance was only 0.8% to 1.3%. Thus, an ultraviolet-absorbing colored glass having sufficient long-term weather resistance in a harsh environment, excellent adhesion, hot water resistance and chemical resistance, and excellent durability for outdoor use was obtained.

【００４０】実施例２〜５ 実施例１と同様なガラス基板に、表１に示すような各種
金属キレ−トと添加量でなる前記調製済の着色した紫外
線吸収シリコーン系プライマー溶液を用い、かつ実施例
１と同様な成膜で、膜厚約６〜７μ程度の紫外線吸収着
色膜を形成した。 Examples 2 to 5 On the same glass substrate as in Example 1, the prepared colored ultraviolet-absorbing silicone-based primer solution containing various metal chelates and the added amounts shown in Table 1 was used, and By the same film formation as in Example 1, an ultraviolet absorbing colored film having a thickness of about 6 to 7 μm was formed.

【００４１】次いで、該紫外線吸収着色膜付ガラス基板
のガラス面をフイルムマスキングして上記した調製済の
シリコーン系ハードコート溶液に浸漬し、前記膜面のみ
に塗布し、約10分間程度風乾し、約175 ℃の熱風循環乾
燥器に約１時間程度入れて硬化し、約３μ程度のシリカ
系保護膜を得た。Next, the glass surface of the glass substrate with the ultraviolet absorbing colored film is film-masked, immersed in the prepared silicone hard coat solution described above, applied only to the film surface, and air-dried for about 10 minutes. It was placed in a hot air circulating drier at about 175 ° C. for about 1 hour to cure, and a silica-based protective film of about 3 μm was obtained.

【００４２】得られた紫外線吸収着色ガラスを実施例１
と同様に評価した。その結果、表１および２（実施例２
のみ図１）に示すように、着色の色調はそれぞれ異なる
が、例えばテーバーテスト後のヘーズ値（△Ｈ）が実施
例２は4.6、実施例３は4.5 、実施例４は4.3 、実施例
５は4.2 と耐擦傷性は充分に優れ、耐候性試験（SWM:10
00Hr）を表２に示すように、耐候性も1000時間以上で目
視異常がなく、紫外線吸収性能の低下も実施例２が0.7
％から3.2 ％、実施例３が1.1 ％から3.6 ％、実施例４
が2.0 ％から8.5 ％、実施例５が1.4 ％から8.9 ％と10
％以下にとどまって過酷な環境のなかで長期的な耐候性
もあり、他の評価も実施例１と同様な結果となり、実施
例１と同様に所期の優れた紫外線吸収着色ガラスであっ
た。The obtained ultraviolet absorbing colored glass was used in Example 1.
Was evaluated in the same way as As a result, Tables 1 and 2 (Example 2)
As shown in FIG. 1), the hue value (ΔH) after Taber test is 4.6 in Example 2, 4.5 in Example 3, 4.5 in Example 4, 4.3, and Example 5 after the Taber test. Is 4.2 and the abrasion resistance is sufficiently excellent, and the weather resistance test (SWM: 10
00Hr), as shown in Table 2, the weather resistance was 1000 hours or more, there was no visual abnormality, and the ultraviolet absorption performance was reduced by 0.7 in Example 2.
% To 3.2%, Example 3 is 1.1% to 3.6%, Example 4
Was 2.0% to 8.5%, and Example 5 was 1.4% to 8.9%.
% Or less, and there was long-term weather resistance in a harsh environment, and other evaluations resulted in the same results as in Example 1. As in Example 1, the expected ultraviolet absorbing colored glass was excellent. .

【００４３】比較例１ 表１に示すように、金属キレ−トを添加しないで調製し
た紫外線吸収シリコーン系プライマーを用いた以外は実
施例１と同様にして紫外線吸収ガラス基板を得た。 Comparative Example 1 As shown in Table 1, an ultraviolet absorbing glass substrate was obtained in the same manner as in Example 1 except that an ultraviolet absorbing silicone primer prepared without adding a metal chelate was used.

【００４４】得られた該紫外線吸収ガラス基板について
は、図１および表１に示すように、外観上は透明である
が、紫外に近い可視領域を遮断するものの、表２に示す
ように、耐候性試験では約1000時間程度でTuv が約13％
程度も増加する変化をし、長期の屋外使用には適しない
ものであり、到底所期の紫外線吸収着色ガラスとは言い
難いものであった。The obtained ultraviolet-absorbing glass substrate was transparent in appearance as shown in FIG. 1 and Table 1, but blocked the visible region near ultraviolet, but as shown in Table 2, Tuv is about 13% in about 1000 hours in sex test
The degree of change also increased, and it was not suitable for long-term outdoor use, and it was hard to say that it was the expected ultraviolet absorbing colored glass.

【００４５】[0045]

【表１】 [Table 1]

【００４６】[0046]

【表２】 [Table 2]

【００４７】[0047]

【発明の効果】以上前述したように、本発明によれば、
光学特性を損なうことなく、透明でしかも紫外線を遮
蔽、ことにUVA をほぼ完全に遮蔽することができ、耐候
性を格段に向上し、淡い着色を有するものの居住性を格
段に向上し、密着性、耐薬品性、耐擦傷性あるいは耐久
性に優れるものをさらに高め、ビルあるいは住宅、車両
等の窓材など単板や外装用としても使用可能なことはも
ちろん、特に自動車窓ガラス等の過酷な使用条件や環境
においても、長期的に使用できることとなる等、種々の
分野に広く採用できる有用な紫外線吸収着色ガラスを簡
便にかつ安価に提供することができる。As described above, according to the present invention,
Without impairing the optical properties, it is transparent and shields ultraviolet rays, especially UVA can be almost completely shielded, drastically improves weather resistance, dramatically improves the habitability of lightly colored items, and improves adhesion In addition, it can be used as a single panel or exterior for window materials of buildings, houses, vehicles, etc., as well as those with excellent chemical resistance, scratch resistance or durability. It is possible to easily and inexpensively provide useful ultraviolet-absorbing colored glass that can be widely used in various fields, such as being able to be used for a long period of time under use conditions and environments.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明の実施例１および２の紫外線吸収着色ガ
ラス（曲線１、２）、比較例１の紫外線吸収ガラス（曲
線３）ならびに通常のガラス基板（フロートガラス３mm
厚、曲線４）の透過率（％）を示す。FIG. 1 shows UV-absorbing colored glasses of Examples 1 and 2 of the present invention (curves 1 and 2), UV-absorbing glass of Comparative Example 1 (curve 3) and a conventional glass substrate (float glass 3 mm).
Thickness, curve 4) shows transmittance (%).

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｅ０６Ｂ 9/24 Ｅ０６Ｂ 9/24 Ｚ (72)発明者 長嶋 敏和 三重県松阪市大口町1510 セントラル硝子 株式会社硝子研究所内────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification code FI E06B 9/24 E06B 9/24 Z (72) Inventor Toshikazu Nagashima 1510 Oguchicho, Matsusaka-shi, Mie Central Glass Inside Glass Research Laboratory Co., Ltd.

Claims (5)

【特許請求の範囲】[Claims] 【請求項１】 透明ガラス基板の表面に、蛍光増白剤お
よび紫外線吸収剤および金属キレ−ト化合物を溶解添加
してなるシリコ−ン系プライマ−コ−ティング溶液を塗
布して加熱硬化した紫外線吸収着色膜を有することを特
徴とする紫外線吸収着色ガラス。An ultraviolet ray cured by applying a silicone-based primer coating solution obtained by dissolving and adding a fluorescent whitening agent, an ultraviolet absorber and a metal chelate compound onto the surface of a transparent glass substrate. An ultraviolet absorbing colored glass having an absorbing colored film. 【請求項２】 透明ガラス基板の表面に、蛍光増白剤お
よび紫外線吸収剤および金属キレ−ト化合物を溶解添加
してなるシリコ−ン系プライマ−コ−ティング溶液を塗
布して加熱硬化した紫外線吸収着色膜と、該紫外線吸収
着色膜上にシリコーン系ハードコーティング溶液を塗布
して被覆成膜した保護膜とを積層成膜したことを特徴と
する請求項１記載の紫外線吸収着色ガラス。2. An ultraviolet ray cured by heating by applying a silicone-based primer coating solution obtained by dissolving and adding a fluorescent whitening agent, an ultraviolet absorber and a metal chelate compound onto the surface of a transparent glass substrate. 2. The ultraviolet absorbing colored glass according to claim 1, wherein an absorbing colored film and a protective film formed by applying a silicone hard coating solution on the ultraviolet absorbing colored film to form a coating are laminated. 【請求項３】 前記シリコ−ン系プライマ−が、オルガ
ノポリシロキサン系の溶液であることを特徴とする請求
項１乃至２記載の紫外線吸収着色ガラス。3. The ultraviolet absorbing colored glass according to claim 1, wherein the silicone-based primer is an organopolysiloxane-based solution. 【請求項４】 前記金属キレ−ト化合物が、少なくとも
１種類以上の遷移金属キレ−ト化合物であることを特徴
とする請求項１乃至３記載の紫外線吸収着色ガラス。4. The ultraviolet absorbing colored glass according to claim 1, wherein said metal chelate compound is at least one kind of transition metal chelate compound. 【請求項５】 前記シリコーン系ハードコーティング溶
液が、オルガノポリシロキサン系を主体とする溶液であ
ることを特徴とする請求項１乃至４記載の紫外線吸収着
色ガラス。5. The ultraviolet absorbing colored glass according to claim 1, wherein the silicone-based hard coating solution is a solution mainly composed of an organopolysiloxane.
JP30963896A 1996-11-20 1996-11-20 Colored glass absorbing ultraviolet light Pending JPH10152349A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP30963896A JPH10152349A (en) 1996-11-20 1996-11-20 Colored glass absorbing ultraviolet light

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP30963896A JPH10152349A (en) 1996-11-20 1996-11-20 Colored glass absorbing ultraviolet light

Publications (1)

Publication Number Publication Date
JPH10152349A true JPH10152349A (en) 1998-06-09

Family

ID=17995456

Family Applications (1)

Application Number Title Priority Date Filing Date
JP30963896A Pending JPH10152349A (en) 1996-11-20 1996-11-20 Colored glass absorbing ultraviolet light

Country Status (1)

Country Link
JP (1) JPH10152349A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1393311A2 (en) * 2001-06-06 2004-03-03 Spectra Systems Corporation Marking and authenticating articles
JP2007126068A (en) * 2005-11-07 2007-05-24 Honda Motor Co Ltd Automobile
JP2007247279A (en) * 2006-03-16 2007-09-27 Dyflex Corp Repair method for existing external facing tile wall surface
JP2008208379A (en) * 1997-04-17 2008-09-11 Sdc Coatings Inc Composition for applying wear resistance coating on substrate
JP2010030792A (en) * 2008-07-25 2010-02-12 Asahi Glass Co Ltd Glass plate with ultraviolet shielding film and method for producing the same
DE102009055303A1 (en) 2008-12-25 2010-07-01 Ngk Insulators, Ltd., Nagoya Composite substrate and method of forming a metal pattern
WO2012124395A1 (en) * 2011-03-11 2012-09-20 住友精化株式会社 Composition for ultraviolet absorbing material and ultraviolet absorbing material using same

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008208379A (en) * 1997-04-17 2008-09-11 Sdc Coatings Inc Composition for applying wear resistance coating on substrate
EP1393311A2 (en) * 2001-06-06 2004-03-03 Spectra Systems Corporation Marking and authenticating articles
EP1393311A4 (en) * 2001-06-06 2008-03-12 Spectra Systems Corp Marking and authenticating articles
JP2007126068A (en) * 2005-11-07 2007-05-24 Honda Motor Co Ltd Automobile
JP2007247279A (en) * 2006-03-16 2007-09-27 Dyflex Corp Repair method for existing external facing tile wall surface
JP2010030792A (en) * 2008-07-25 2010-02-12 Asahi Glass Co Ltd Glass plate with ultraviolet shielding film and method for producing the same
DE102009055303A1 (en) 2008-12-25 2010-07-01 Ngk Insulators, Ltd., Nagoya Composite substrate and method of forming a metal pattern
JP2010171392A (en) * 2008-12-25 2010-08-05 Ngk Insulators Ltd Composite substrate and method for forming metal pattern
DE102009055303B4 (en) * 2008-12-25 2015-05-13 Ngk Insulators, Ltd. Composite substrate and method of forming a metal pattern
WO2012124395A1 (en) * 2011-03-11 2012-09-20 住友精化株式会社 Composition for ultraviolet absorbing material and ultraviolet absorbing material using same

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