JPH02256001A - Glass or plastic product having antireflection coating, its production and coating composition - Google Patents
Glass or plastic product having antireflection coating, its production and coating compositionInfo
- Publication number
- JPH02256001A JPH02256001A JP1281938A JP28193889A JPH02256001A JP H02256001 A JPH02256001 A JP H02256001A JP 1281938 A JP1281938 A JP 1281938A JP 28193889 A JP28193889 A JP 28193889A JP H02256001 A JPH02256001 A JP H02256001A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- coating composition
- glass
- antireflection coating
- 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
- 239000008199 coating composition Substances 0.000 title claims abstract description 17
- 239000011521 glass Substances 0.000 title claims description 29
- 238000000576 coating method Methods 0.000 title claims description 25
- 239000011248 coating agent Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims abstract description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 22
- 239000006117 anti-reflective coating Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000010419 fine particle Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- 238000009125 cardiac resynchronization therapy Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- -1 is small Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Landscapes
- Surface Treatment Of Optical Elements (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、反射防止膜を有するガラスまたはプラスチッ
ク製品、その製法および反射防止コーティング組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a glass or plastic product having an antireflection coating, a method for producing the same, and an antireflection coating composition.
本発明の反射防止コーティング用組成物はテレビのブラ
ウン管、絵の前面ガラス、ショーケース・ガラス板、メ
ガネレンズ等に塗布され、生成する塗膜はこれらのガラ
ス製品およびプラスチック製品からの可視光の反射を防
止し、ひいては反射による虚像の出現を防止するのに有
効である。The antireflection coating composition of the present invention is applied to television cathode ray tubes, picture front glasses, showcase glass plates, eyeglass lenses, etc., and the resulting coating film reflects visible light from these glass products and plastic products. This is effective in preventing the appearance of virtual images due to reflection.
〔従来の技術および発明が解決しようとする課題〕透明
な無機ガラスまたはプラスチックからなる固体物品の表
面反射は種々の障害を与えている。[Prior Art and Problems to be Solved by the Invention] Surface reflection of solid articles made of transparent inorganic glass or plastic presents various problems.
例えば、テレビのブラウン管に映る蛍光灯や窓外の景色
はテレビ映像を見にくくする。絵の前面ガラスやショー
ケースのガラス板は表面の反射光により絵や商品を不鮮
明にする。また、メガネレンズ表面の反射はメガネレン
ズの透光量を低減する。For example, fluorescent lights reflected on a TV's cathode ray tube and the scenery outside the window make it difficult to see the TV image. The front glass of a picture or the glass plate of a showcase makes the picture or product unclear due to the reflected light from the surface. Further, reflection on the surface of the eyeglass lens reduces the amount of light transmitted through the eyeglass lens.
従来、反射防止用コートとして、ＭｇＦ２膜を蒸着によ
り形成し、さらに焼付ける方法、および、チタン含有有
機金属化合物と珪素含有有機化合物とを加水分解してＴ
ｉ０ｚ膜とＳｉＯ□膜とからなる多層コートを形成する
方法が知られている。Conventionally, as an antireflection coating, there have been two methods: forming a MgF2 film by vapor deposition and then baking it, and forming a T film by hydrolyzing a titanium-containing organometallic compound and a silicon-containing organic compound.
A method of forming a multilayer coating consisting of an i0z film and a SiO□ film is known.
しかしながら、Ｍｌ？Ｆ２蒸着膜の場合は、蒸着設備の
制約を受けるため大きな物品へのコートができない、
ＭｇＦｚ膜は付着力が小さく、且つ硬度および耐擦傷性
が低いという難点があるためガラス製品では焼付けなけ
ればならず、また、プラスチック製品では焼付けできな
いため実用性のある塗膜とはならなかった。加えて、蒸
着で均一なコーｈ厚を得るには非常に高度な技術が要求
され、しがも、被蒸着物品の寸法、形状が変わるとその
都度蒸着条件および装置の調整を行って最良の設定を見
出さなければならないという難点がある。また、有機金
属化合物の加水分解による膜は１４ｇＦ２と比較して反
射防止効果に劣っている。However, Ml? In the case of F2 vapor deposition film, it is not possible to coat large items due to restrictions on vapor deposition equipment.
MgFz films have the drawbacks of low adhesion, low hardness, and low scratch resistance, so they must be baked on glass products, and cannot be baked on plastic products, so they have not been practical coatings. In addition, extremely advanced technology is required to obtain a uniform coating thickness through vapor deposition, and if the dimensions and shape of the object to be vaporized change, the vapor deposition conditions and equipment must be adjusted each time to find the best coating. The problem is that you have to find the settings. Furthermore, a film formed by hydrolyzing an organometallic compound is inferior in antireflection effect compared to 14gF2.
本発明の目的は、コーテイング膜の反射防止効果に優れ
、しかも膜を工業的有利に形成することができる反射防
止コーティング用組成物を提供するにある。An object of the present invention is to provide an antireflection coating composition that has an excellent antireflection effect for coating films and can be formed into industrially advantageous films.
本発明の他の目的は、そのような組成物を用いてガラス
製品およびプラスチック製品に反射防止膜を形成する方
法を提供するにある。Another object of the present invention is to provide a method of forming antireflective coatings on glass and plastic products using such compositions.
本発明は、平均粒径５００λ以下の８ｇＦ２、ならびに
、該ＭＢＦ２１重量部に基づき、０．５〜１．５重量部
のテトラアルコキシシラン、０，１〜１．０重量部の水
および３０〜５０重量部のエタノールからなり、且っｐ
Ｈ値が１〜４に調整されていることを特徴とする反射防
止コーティング用組成物を提供する。The present invention is based on 8g F2 with an average particle size of 500λ or less and 21 parts by weight of the MBF, 0.5 to 1.5 parts by weight of tetraalkoxysilane, 0.1 to 1.0 parts by weight of water, and 30 to 50 parts by weight of tetraalkoxysilane. Consisting of parts by weight of ethanol, and p
Provided is an antireflection coating composition characterized in that the H value is adjusted to 1 to 4.
本発明は、さらに、上記の反射防止コーティング組成物
をガラス製品またはプラスチック製品に塗布する方法、
およびそのようにして得られるガラス製品またはプラス
チック製品を提供°する。The present invention further provides a method of applying the above-described antireflective coating composition to a glass or plastic product;
and provide the glass or plastic products thus obtained.
本発明の反射防止コーテイング用組成物の第１の要点は
平均粒径５００Å以下のＭｇＦ２微粒子とテトラアルコ
キシシランが含有される点にある。−最に、本願発明で
用いるものより平均粒径の大きい８ｇＦ２では、ＭｇＦ
２微粒子の含有量が少ない（換言すれば、テトラアルコ
キシシランの含有量が多い）と膜強度が一定であり、Ｍ
ｇＦ Ｚｖ＆粒子の含有量が多いと膜強度は低下する。The first important point of the antireflection coating composition of the present invention is that it contains MgF2 fine particles with an average particle size of 500 Å or less and tetraalkoxysilane. -Finally, with 8gF2, which has a larger average particle size than that used in the present invention, MgF2
2. When the content of fine particles is low (in other words, when the content of tetraalkoxysilane is high), the film strength is constant, and M
When the content of gF Zv & particles is large, the film strength decreases.
しがしながら、意外なことに、本願発明で用いる平均粒
径５００Å以下のＭｇＦ、微粒子ではＭｇＦ２微粒子の
含有量が多い（テトラアルコキシシランの含有量が少な
い）と膜強度が高い、高い水準の膜強度を得るにはＭｇ
Ｆ２微粒子とテトラアルコキシシランとの配合比は前者
１重置部に対し、後者０．５〜１．５重量部、好ましく
は後者０．７〜１．０重量部である。また、高い水準の
膜強度を得るにはＭｇＦ２微粒子の平均粒径は、好まし
くは４００〜１０人、より好ましくは２００〜５０人で
あることが好ましい。However, surprisingly, in the MgF fine particles with an average particle size of 500 Å or less used in the present invention, when the content of MgF2 fine particles is high (the content of tetraalkoxysilane is low), the film strength is high and a high level is obtained. Mg to obtain film strength
The blending ratio of F2 fine particles and tetraalkoxysilane is 0.5 to 1.5 parts by weight, preferably 0.7 to 1.0 parts by weight, per one part by weight of the former. Further, in order to obtain a high level of film strength, the average particle size of the MgF2 fine particles is preferably 400 to 10 particles, more preferably 200 to 50 particles.
本発明で用いる上記のように微細なＭｇＦ２粒子は、例
えば、プラズマ蒸散させ空気中で析出させる方法によっ
て得ることができる。The above-mentioned fine MgF2 particles used in the present invention can be obtained, for example, by plasma evaporation and precipitation in air.
テトラアルコキシシランとしては、テトラメトキシシラ
ン、テトラエトキシシラン、テトラプロポキシシランお
よびテトラブトキシシランのような炭素数１〜４のアル
コキシ基をもつものが好ましい。As the tetraalkoxysilane, those having an alkoxy group having 1 to 4 carbon atoms are preferred, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane.
上記テトラアルコキシシランの他に、さらに、ＭｇＦ２
１重量部に基づき、 ０．０５〜０．５重量部のアルキ
ルトリアルコキシシランおよびジアルキルジアルコキシ
シランの中から選ばれた少なくとも一種の化合物を配合
すると膜強度はさらに向上する。In addition to the above tetraalkoxysilane, MgF2
When 0.05 to 0.5 parts by weight of at least one compound selected from alkyltrialkoxysilanes and dialkyldialkoxysilanes is added based on 1 part by weight, the film strength is further improved.
これらの化合物中のアルキル基およびアルコキシ基はい
ずれも炭素数１〜４のものが好ましい。The alkyl group and alkoxy group in these compounds preferably each have 1 to 4 carbon atoms.
本発明の反射防止コーティング用組成物は、溶剤成分と
して、ＭｇＦｚ １重量部に対し、水を０．１〜１．０
重量部、好ましくは０．２５〜０．５０重量部および炭
素数１〜４の１価アルコールを３０〜５０重量部含有す
る。１価アルコールの中ではエタノールが好ましい、ま
た、コーティング用組成物のｐＨ値は塩酸のような、Ｈ
調節剤を加えて１〜４とす′る。The antireflection coating composition of the present invention contains 0.1 to 1.0 parts of water as a solvent component to 1 part by weight of MgFz.
It contains 0.25 to 0.50 parts by weight, preferably 0.25 to 0.50 parts by weight, and 30 to 50 parts by weight of a monohydric alcohol having 1 to 4 carbon atoms. Among the monohydric alcohols, ethanol is preferred, and the pH value of the coating composition can be adjusted using H2O such as hydrochloric acid.
Adjustments are made to 1 to 4 by adding a regulator.
これら水およびエタノールの配合量およびｐａｔ値は重
要である。水の量が過大であると膜が白化したり、液状
組成物の貯蔵性が悪くなる。水の量が過少であると膜の
密着性および擦傷性が低下する。The amounts and pat values of these water and ethanol are important. If the amount of water is too large, the film may turn white or the storage stability of the liquid composition may deteriorate. If the amount of water is too small, the adhesion and scratch resistance of the film will be reduced.
１価アルコールの量が過少であると液の貯蔵性が悪くな
り、不均一な膜が形成され易い。１価アルコールの量が
過大であると塗布所要回数を増やさねばならず、その都
度乾燥を完全にしないと膜が剥離し易くなる。ｐＨ値が
大き過ぎると液の貯蔵性が低下し、不均一な膜が形成さ
れ易く、また、基材への密着性も悪い。If the amount of monohydric alcohol is too small, the storage property of the liquid will be poor and a non-uniform film will be likely to be formed. If the amount of monohydric alcohol is too large, the number of times the coating must be applied must be increased, and if drying is not completed each time, the film will easily peel off. If the pH value is too high, the storage property of the liquid decreases, a non-uniform film is likely to be formed, and the adhesion to the substrate is also poor.
反射防止コーティング用組成物の調製は多くの樹脂塗料
と同様な方法に従って行うことができ、まな、コーティ
ング用組成物の対象物品への塗布も薄い膜厚を形成でき
る方法であれば格別限定されることはなく通常の塗布方
法を使用できる。特に、膜厚が薄く且つ表面が平滑でヘ
イズの小さい塗膜が得られる点で、ディッピング、スピ
ンコード、グラビア印刷が好適である。The antireflective coating composition can be prepared in the same manner as many resin coatings, and the coating composition can be applied to the target article by any method that can form a thin film. Normal application methods can be used. In particular, dipping, spin cord printing, and gravure printing are suitable because they yield a coating film that is thin, has a smooth surface, and has low haze.
塗膜は、必要に応じて、用いた有機樹脂バインダーの種
類に応じて適当な条件下に常法により硬化処理を行う。If necessary, the coating film is cured by a conventional method under appropriate conditions depending on the type of organic resin binder used.
本発明の反射防止膜が形成されるガラス製品およびプラ
スチック製品としては、例えば、自動車、船舶、航空機
等の窓ガラス、フロントガラス；ＣＲＴ、テレビ等のブ
ラウン管および前面ガラスまたはプラスチック板；液晶
表示装置、計器類のガラス板；ショーウィンドウ、博物
館および美術館の展示品保護ガラス、時計のガラス板お
よびプラスチック板；眼鏡レンズおよびカメラレンズ；
および太陽電池用ガラス板およびプラスチック板が挙げ
られる。Glass products and plastic products on which the antireflection film of the present invention is formed include, for example, window glasses and windshields of automobiles, ships, aircraft, etc.; cathode ray tubes and front glasses or plastic plates of CRTs, televisions, etc.; liquid crystal display devices, Instrument glass plates; show windows, museum and art gallery exhibit protection glass, watch glass plates and plastic plates; eyeglass lenses and camera lenses;
and glass plates and plastic plates for solar cells.
本発明の反射防止コーティング用組成物から形成される
表面塗膜は、反射防止効果に優れ、しかも、表面が平滑
でヘイズが小さい。また、硬度および強度が高く、耐擦
傷性に優れている。プラスチック基村上に形成した従来
のＭｇＦ２蒸着膜の鉛筆硬度は約３Ｈ１高くても４Ｈで
あるが、本発明の組成物から得られる塗膜の鉛筆硬度は
４Ｈより高い
本発明のコーティング用組成物は概して樹脂バインダー
であるテトラアルコキシシランの量が少なく、且つＭｇ
Ｆ ２ 微粒子の平均粒径が小さいという特徴を有し、
このような特徴に基づいて、上記のように硬度、強度そ
の他多くの特性に優るという効果を奏するのは次のよう
な理由によると推定される。すなわち、テトラアルコキ
シシランの量が多いと、硬いが脆い膜となり、特に被塗
布基材が軟らかいと弾性係数の高いシランの膜は支持材
の変形に追随できず破損し易い、対照的に、本発明の組
成物のようにテトラアルコキシシランの配合量が少ない
と、接着層はＭｇＦ２微粒子の粒子間を単に継ぎ合わせ
た微細な点接合の集合になるので可撓性が向上するとと
もに、ＭｇＦ２粒子間が非常に接近するのでＭｇＦ２粒
子間のファンデルワールス力による接着力が増大する。The surface coating film formed from the antireflection coating composition of the present invention has an excellent antireflection effect, has a smooth surface, and has a small haze. It also has high hardness and strength, and excellent scratch resistance. The pencil hardness of a conventional MgF2 vapor deposited film formed on a plastic substrate is about 3H1 or 4H at most, but the coating composition of the present invention has a pencil hardness of more than 4H. In general, the amount of tetraalkoxysilane, which is a resin binder, is small, and Mg
It has the characteristic that the average particle size of F 2 fine particles is small,
Based on these characteristics, it is presumed that the reason for the superiority in hardness, strength, and many other properties as described above is due to the following reasons. In other words, if the amount of tetraalkoxysilane is large, the film will be hard but brittle, and especially if the substrate to be coated is soft, a silane film with a high elastic modulus will not be able to follow the deformation of the support material and will be easily damaged. When the amount of tetraalkoxysilane blended is small as in the composition of the invention, the adhesive layer becomes a collection of fine point bonds simply joining the particles of MgF2 fine particles, so flexibility is improved and the bonding between the MgF2 particles is improved. Since the MgF2 particles are very close to each other, the adhesion force between the MgF2 particles due to the van der Waals force increases.
以下、実施例について本発明を具体的に説明する。 The present invention will be specifically described below with reference to Examples.
各実施例において、表面反射率は分光光度計で測定した
。また、表面硬度（鉛筆硬度）はＪＩＳ Ｋ−５４００
および５４０１に準拠した。In each example, surface reflectance was measured with a spectrophotometer. In addition, the surface hardness (pencil hardness) is JIS K-5400.
and 5401 compliant.
実施例１
平均粒径１５０人（大部分は５０〜２５０人に分布）の
ＭｇＦ２３ｇ 、テトラエトキシシラン５ｇ、濃塩酸０
．１ｇ、水３ｇおよびエタノール８８ｇをボールミル中
で混合撹拌し、ｐｉ値２の反射防止コーティング用組成
物を得た。この組成物をハードコートしたジエチレング
リコールビスアリルカーボネート（ＣＲ３９）板上にス
ピンコード法で塗布し、１２０℃で５分間加熱して厚さ
０．１μｍの塗膜を得た。Example 1 23 g of MgF with an average particle size of 150 (mostly distributed between 50 and 250), 5 g of tetraethoxysilane, and 0 concentrated hydrochloric acid.
．． 1 g of water, 3 g of water, and 88 g of ethanol were mixed and stirred in a ball mill to obtain an antireflective coating composition with a pi value of 2. This composition was applied onto a hard-coated diethylene glycol bisallyl carbonate (CR39) plate by a spin cord method, and heated at 120° C. for 5 minutes to obtain a coating film with a thickness of 0.1 μm.
得られた塗膜の鉛筆硬度は７Ｈ１可視光の反射率は１．
８％であった。反射防止コートをしていないＣＲ３９の
鉛筆硬度は４Ｈ１可視光反射率は９．２％であった。The resulting paint film has a pencil hardness of 7H1 and a visible light reflectance of 1.
It was 8%. The pencil hardness of CR39 without antireflection coating was 4H1 visible light reflectance of 9.2%.
比較例ｌ
ＭｇＦ２を常法に従って真空蒸着法によりＣＲ−３９基
板上にコーティングし、０．１μｍ厚の膜をつくった。Comparative Example 1 MgF2 was coated on a CR-39 substrate by vacuum evaporation according to a conventional method to form a 0.1 μm thick film.
表面反射率は２．５％であったが、密着性に乏しく、容
易に剥離した。Although the surface reflectance was 2.5%, the adhesiveness was poor and it was easily peeled off.
実施例２
平均粒径１５０人（大部分は１００〜２００人に分布）
のＨｇＦ２１重量部、テトラエトキシシラン０．９重量
部、メチルトリメトキシシラン０．１重量部、ジメチル
ジメトキシシラン０．１５重量部、塩酸０．０３重量部
、水１重量部、エタノール２９重量部を混合し、実施例
１と同様に、ｐＨＨ２Ｏ２射防止膜用塗料を造った。こ
れをディッピング法によりメタクリル樹脂板に塗り、１
００℃で５分間加熱し、０．１μｍの厚さの膜を得た。Example 2 Average particle size: 150 people (mostly distributed between 100 and 200 people)
21 parts by weight of HgF, 0.9 parts by weight of tetraethoxysilane, 0.1 parts by weight of methyltrimethoxysilane, 0.15 parts by weight of dimethyldimethoxysilane, 0.03 parts by weight of hydrochloric acid, 1 part by weight of water, and 29 parts by weight of ethanol. These were mixed to prepare a coating material for a pHH2O2 radiation prevention film in the same manner as in Example 1. Apply this to a methacrylic resin board using the dipping method, and
The mixture was heated at 00° C. for 5 minutes to obtain a film with a thickness of 0.1 μm.
反射率は２゜０％、鉛筆硬度は６Ｈであった。The reflectance was 2.0% and the pencil hardness was 6H.
実施例３
平均粒径１５０人（大部分は５０〜２５０人に分布）の
ＭｇＦ２３ ｇ 、テトラエトキシシラン５ｇ、濃塩酸
０．１ｇ、水３ｇ、エタノール８８ｇを混合し、実施例
１と同様に、ｐＨＨＩ３５の反射防止用塗料を造り、洗
浄したソーダガラス板上にディッピング法により塗り、
１６０℃で５分間加熱して厚さ０．１μｍの塗膜を得た
。Example 3 23 g of MgF with an average particle size of 150 (mostly distributed between 50 and 250), 5 g of tetraethoxysilane, 0.1 g of concentrated hydrochloric acid, 3 g of water, and 88 g of ethanol were mixed, and in the same manner as in Example 1, An anti-reflective paint with a pH of 35 was made and applied onto a washed soda glass plate using the dipping method.
It was heated at 160° C. for 5 minutes to obtain a coating film with a thickness of 0.1 μm.
鉛筆硬度は９Ｈ１可視光の反射率は１．８％であった。The pencil hardness was 9H1 and the visible light reflectance was 1.8%.
反射防止コートをしていない生地のソーダガラスの表面
硬度は９Ｈ１可視光反射率は８．０であった。The surface hardness of the soda glass fabric without antireflection coating was 9H1, and the visible light reflectance was 8.0.
実施例４
エチルシリケート２３重量部と水８重量部と濃塩酸０．
１重量部とエタノール６９重量部を混合し、４０℃にて
６０分間加熱して、エチルシリケート部分加水分解を行
ない、その生成物に住友セメント社製の５０ヘ−１００
人の粒径のＭｇＦ２を６．６重量部とエタノール３５０
重量部を加え、混合し、ｐ！１２の反射防止塗料を造っ
た。Example 4 23 parts by weight of ethyl silicate, 8 parts by weight of water, and 0.0 parts by weight of concentrated hydrochloric acid.
1 part by weight and 69 parts by weight of ethanol were mixed and heated at 40°C for 60 minutes to partially hydrolyze ethyl silicate.
6.6 parts by weight of MgF2 of human particle size and 350 parts of ethanol
Add parts by weight, mix, p! 12 anti-reflective paints were created.
この塗料をショーケース用のガラス板（反射率８％）、
絵画用額の前面ガラス板（反射率８％）、掛時計用の前
面ガラス板（反射率７％）のそれぞれに対して表裏両面
にデイツプ法にて塗布し、’ ２５０℃１時間加熱し成
膜し、それぞれ厚さ１１０ｎｍ 、 １０５ｎａ＋ 、
９８ｎｍの膜を形成した。それぞれの反射率は４．０
％、４．２％、３．８％低く、ガラス面がらの反射によ
るギラつきが低下した。また、同じ塗料をテレビのブラ
ウン管の前面（反射率４．０％）にデイツプ法で塗布し
、１６０℃２０分間、加熱した。膜厚は１１５ｎｍで、
反射率は２％となり、この塗布面での蛍光灯等の映り込
みが弱くなっていることが目視でもはっきり感じられた
。This paint was applied to a glass plate (8% reflectance) for a showcase.
It was applied to both the front and back sides of the front glass plate of a picture frame (8% reflectance) and the front glass plate of a wall clock (7% reflectance) using the dip method, and heated at 250°C for 1 hour to form a film. The thickness is 110nm, 105na+, and
A 98 nm film was formed. Each reflectance is 4.0
%, 4.2%, and 3.8% lower, and the glare caused by reflection from the glass surface was reduced. Further, the same paint was applied to the front surface of a cathode ray tube of a television (reflectance: 4.0%) by the dip method, and heated at 160° C. for 20 minutes. The film thickness is 115 nm,
The reflectance was 2%, and it was clearly visible to the naked eye that the reflection of fluorescent lights, etc. on the coated surface was weakened.
実施例５
平均粒径１５０人（大部分は５０〜２００人に分布）の
ＭｇＦ２３０ｇ 、テトラエトキシシラン１０４ｇ、濃
塩酸０．２５ｇ、メチルトリメトキシシラン６．１ｇ、
エタノール８６０ｇを混合し、サンドグラインダーミル
で１時間分散処理し、Ｉ）Ｒ２の反射防止コーティング
用組成物を得た。この組成物に無機ガラス板を浸漬し、
２３℃、Ｒ）１５０％の雰囲気中で１０ｃｍ／ｓｉｎの
一定速度で引き上げ、８０℃で乾燥後、３００℃で１時
間焼き付けた。Example 5 230 g of MgF with an average particle size of 150 (mostly distributed between 50 and 200), 104 g of tetraethoxysilane, 0.25 g of concentrated hydrochloric acid, 6.1 g of methyltrimethoxysilane,
860 g of ethanol was mixed and dispersed in a sand grinder mill for 1 hour to obtain an antireflective coating composition of I) R2. An inorganic glass plate is immersed in this composition,
It was pulled up at a constant speed of 10 cm/sin in an atmosphere of 23° C. and R) 150%, dried at 80° C., and then baked at 300° C. for 1 hour.
得られた塗膜の厚みは０．１μｍで、透過率は９６．５
％であった。また、塗膜の鉛筆硬度は７Ｈであった。反
射防止コートをしていないガラス板の透過率は９２％で
あった。The thickness of the resulting coating film was 0.1 μm, and the transmittance was 96.5.
%Met. Further, the pencil hardness of the coating film was 7H. The transmittance of the glass plate without antireflection coating was 92%.
Claims (1)
ＭｇＦ＿２１重量部に基づき、０．５〜１．５重量部の
テトラアルコキシシラン、０．１〜１．０重量部の水お
よび３０〜５０重量部の炭素数１〜４の１価アルコール
からなり、且つｐＨ値が１〜４に調整されていることを
特徴とする反射防止コーティング用組成物。 ２、テトラアルコキシシランがテトラメトキシシラン、
テトラエトキシシラン、テトラプロポキシシランおよび
テトラブトキシシランの中から選ばれる請求項１記載の
反射防止コーティング用組成物。 ３、さらに、ＭｇＦ＿２１重量部に基づき、０．０５〜
０．５重量部のアルキルトリアルコキシシランおよびジ
アルキルジアルコキシシランの中から選ばれた少なくと
も一種の化合物を含有する請求項（１）または（２）記
載の反射防止コーティング用組成物。 ４、アルキルトリアルコキシシランおよびジアルキルジ
アルコキシシランのアルキル基が炭素数１〜４であり、
アルコキシ基が炭素数１〜４である請求項（３）記載の
反射防止コーティング用組成物。 ５、ＭｇＦ＿２の平均粒径が４００〜１０Åである請求
項（１）から（４）までのいずれかに記載の反射防止コ
ーティング用組成物。 ６、ＭｇＦ＿２の平均粒径が２００〜５０Åである請求
項（１）から（４）までのいずれかに記載の反射防止コ
ーティング用組成物。 ７、テトラアルコキシシランの量がＭｇＦ＿２１重量部
に基づき０．７〜１．０重量部である請求項（１）から
（６）までのいずれかに記載の反射防止コーティング用
組成物。 ８、水の量がＭｇＦ＿２１重量部に基づき０．２５〜０
．５０重量部である請求項（１）から（７）までのいず
れかに記載の反射防止コーティング用組成物。 ９、請求項（１）から請求項（８）までのいずれかに記
載の反射防止コーティング用組成物をガラスまたはプラ
スチック製品の表面に塗布することを特徴とする反射防
止膜を有するガラスまたはプラスチック製品の製造方法
。 １０、請求項（９）に記載される製造方法によって製造
される、反射防止膜を有するガラスまたはプラスチック
製品。[Claims] 1. MgF_2 with an average particle size of 500 Å or less, and based on 1 part by weight of MgF_2, 0.5 to 1.5 parts by weight of tetraalkoxysilane and 0.1 to 1.0 parts by weight of water. and 30 to 50 parts by weight of a monohydric alcohol having 1 to 4 carbon atoms, and having a pH value adjusted to 1 to 4. 2. Tetraalkoxysilane is tetramethoxysilane,
The antireflective coating composition according to claim 1, which is selected from tetraethoxysilane, tetrapropoxysilane and tetrabutoxysilane. 3. Furthermore, based on MgF_21 parts by weight, 0.05~
The antireflection coating composition according to claim 1 or 2, containing 0.5 parts by weight of at least one compound selected from alkyltrialkoxysilanes and dialkyldialkoxysilanes. 4. The alkyl group of the alkyltrialkoxysilane and dialkyldialkoxysilane has 1 to 4 carbon atoms,
4. The antireflection coating composition according to claim 3, wherein the alkoxy group has 1 to 4 carbon atoms. 5. The composition for antireflection coating according to any one of claims (1) to (4), wherein the average particle size of MgF_2 is 400 to 10 Å. 6. The composition for antireflection coating according to any one of claims (1) to (4), wherein the average particle size of MgF_2 is 200 to 50 Å. 7. The composition for antireflection coating according to any one of claims (1) to (6), wherein the amount of tetraalkoxysilane is 0.7 to 1.0 parts by weight based on 1 part by weight of MgF_2. 8. The amount of water is 0.25 to 0 based on MgF_21 parts by weight
．． The antireflection coating composition according to any one of claims (1) to (7), wherein the amount is 50 parts by weight. 9. A glass or plastic product having an antireflection film, characterized in that the antireflection coating composition according to any one of claims (1) to (8) is applied to the surface of the glass or plastic product. manufacturing method. 10. A glass or plastic product having an antireflection film manufactured by the manufacturing method according to claim (9).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1281938A JPH02256001A (en) | 1988-10-31 | 1989-10-31 | Glass or plastic product having antireflection coating, its production and coating composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63-275093 | 1988-10-31 | ||
| JP27509388 | 1988-10-31 | ||
| JP1281938A JPH02256001A (en) | 1988-10-31 | 1989-10-31 | Glass or plastic product having antireflection coating, its production and coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02256001A true JPH02256001A (en) | 1990-10-16 |
Family
ID=26551313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1281938A Pending JPH02256001A (en) | 1988-10-31 | 1989-10-31 | Glass or plastic product having antireflection coating, its production and coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02256001A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7133218B2 (en) * | 2001-09-20 | 2006-11-07 | Shinmaywa Industries, Ltd. | Optical system |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2601123A (en) * | 1947-04-05 | 1952-06-17 | American Optical Corp | Composition for reducing the reflection of light |
| JPS58126502A (en) * | 1982-01-25 | 1983-07-28 | Nippon Sheet Glass Co Ltd | Antireflection plastic optical parts |
| JPS6088901A (en) * | 1983-10-20 | 1985-05-18 | Seiko Epson Corp | Plastic lens |
| JPS6217044A (en) * | 1985-07-12 | 1987-01-26 | Hoya Corp | Formation of antireflection film resistant to laser damage and having high wear resistance on optical element surface |
| JPS63124332A (en) * | 1986-11-14 | 1988-05-27 | Hitachi Ltd | Manufacture of reflection preventing film |
| JPS63193101A (en) * | 1987-02-06 | 1988-08-10 | Hitachi Ltd | Antireflection film |
| JPS6476001A (en) * | 1987-09-18 | 1989-03-22 | Hitachi Ltd | Antireflection film |
-
1989
- 1989-10-31 JP JP1281938A patent/JPH02256001A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2601123A (en) * | 1947-04-05 | 1952-06-17 | American Optical Corp | Composition for reducing the reflection of light |
| JPS58126502A (en) * | 1982-01-25 | 1983-07-28 | Nippon Sheet Glass Co Ltd | Antireflection plastic optical parts |
| JPS6088901A (en) * | 1983-10-20 | 1985-05-18 | Seiko Epson Corp | Plastic lens |
| JPS6217044A (en) * | 1985-07-12 | 1987-01-26 | Hoya Corp | Formation of antireflection film resistant to laser damage and having high wear resistance on optical element surface |
| JPS63124332A (en) * | 1986-11-14 | 1988-05-27 | Hitachi Ltd | Manufacture of reflection preventing film |
| JPS63193101A (en) * | 1987-02-06 | 1988-08-10 | Hitachi Ltd | Antireflection film |
| JPS6476001A (en) * | 1987-09-18 | 1989-03-22 | Hitachi Ltd | Antireflection film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7133218B2 (en) * | 2001-09-20 | 2006-11-07 | Shinmaywa Industries, Ltd. | Optical system |
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