JPS59115840A - Low reflectivity coating - Google Patents
Low reflectivity coatingInfo
- Publication number
- JPS59115840A JPS59115840A JP57225787A JP22578782A JPS59115840A JP S59115840 A JPS59115840 A JP S59115840A JP 57225787 A JP57225787 A JP 57225787A JP 22578782 A JP22578782 A JP 22578782A JP S59115840 A JPS59115840 A JP S59115840A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- reflectance
- compound
- thin film
- glass
- 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.)
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Links
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- Surface Treatment Of Optical Elements (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
本発明はガラス又は透明プラスチックなどの透明基体の
表面に処理して、該基体の表面反射を低下させるような
用途に用いる多層構造からなる低反射率塗膜に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a low reflectance coating film having a multilayer structure that is applied to the surface of a transparent substrate such as glass or transparent plastic to reduce the surface reflection of the substrate. be.
建築物、車輌などの窓、ドアーあるいはショーウィンド
、ショーケース、光学レンズなどはガラス又は透明プラ
スチックなどの透明材料が好適に用いられる。しかしな
がら、かかる材料の表面は太陽光、照明光の反射による
ギラツキや眩しさを生ずるといつ欠点があり、さらに周
囲の景観が映ることによシ、材料に特有な透明性や透視
性が損なわれ易い。Transparent materials such as glass or transparent plastic are preferably used for windows, doors, show windows, showcases, optical lenses, etc. of buildings, vehicles, etc. However, the surface of such materials has the disadvantage that it causes glare and dazzle due to reflection of sunlight and illumination light, and furthermore, the transparency and see-through characteristic of the material are impaired due to reflection of the surrounding scenery. easy.
又、近年、省エネルギー政策から太陽光の利用が進めら
れ、太陽光集光器が開発されているが、集熱効率を向上
させるには集光部に用いるガラス又は透明プラスチック
などの透光材料の表面からの反射損失を除去あるいは低
減せしめ、大量のエネルギーを通過させることが盛装と
なつ、ている。In addition, in recent years, the use of sunlight has been promoted due to energy conservation policies, and solar collectors have been developed, but in order to improve heat collection efficiency, it is necessary to The goal is to eliminate or reduce reflection loss from the source and allow a large amount of energy to pass through.
従来から、ガラス又は透明プラスチックなどの透明基体
の表面の反射防止法は光学部品全中心に開発が進められ
ていて、し1」えばガラス表面に金属酸化物、金属フッ
化物、金属窒化物などの薄膜を形成せしめる真空蒸着法
あるいはスパッタリング法が光学レンズ、メガネレンズ
、フイルターなどに実用化されている。又、ガラスある
いは透明プラスチックなどの透明基体の表面に、高分子
物質からなる低反射処理剤を塗布、吹付け、あるいは処
理剤中に浸漬することにより、低反射性の塗膜を形成す
るための処理方法あるいは低反射処理剤が提案されてい
る。Conventionally, anti-reflection methods for the surface of transparent substrates such as glass or transparent plastic have been developed for all optical components. Vacuum deposition or sputtering methods for forming thin films have been put to practical use in optical lenses, eyeglass lenses, filters, and the like. In addition, it is possible to form a low-reflectivity coating film by coating, spraying, or immersing a low-reflection treatment agent made of a polymeric substance on the surface of a transparent substrate such as glass or transparent plastic. Treatment methods or low-reflection treatment agents have been proposed.
しかしながら、前記方法において、真空蒸着法あるいは
スパッタリング法は装置のm88上及びコスト面から適
応物品は小型精密光学部品に限足され、更に連続的生産
には適していない。However, in the above methods, the vacuum evaporation method or the sputtering method is limited to small precision optical parts due to the size of the equipment and the cost, and is not suitable for continuous production.
低反射処理剤の塗膜を塗布、吹付け、あるいは浸漬など
の方法によシ形成する方法では、形成された低反射性塗
膜は、汚染などに対する洗浄作業によって損傷を受け、
・剥離するなど硬度や耐久性に欠点がある。When a coating film of a low-reflection treatment agent is formed by coating, spraying, or dipping, the formed low-reflection coating film may be damaged by cleaning operations to prevent contamination, etc.
- It has shortcomings in hardness and durability, such as peeling.
本発明者は上記の如き問題点の認識に基づいて、ガラス
又は透明プラスチックなどの透明基体の透明性、透視性
を損なうことなく、該基体の表面上に塗布、吹付け、あ
るいは浸漬などの既知の方法あるいは新規な方法によっ
て該基体の表面を低反射性とし、且つ、その性能が長期
にわたって持続する耐久性の良好な低反射率塗膜を提供
すべく種々研究、検討を行なった。Based on the recognition of the above-mentioned problems, the inventors of the present invention have proposed a method of coating, spraying, dipping, etc. on the surface of a transparent substrate such as glass or transparent plastic without impairing the transparency and see-through of the substrate. Various studies and studies have been carried out in order to provide a low-reflectance coating film that makes the surface of the substrate low-reflectivity using the above method or a new method, and has good durability and maintains its performance over a long period of time.
その結果、ポリフルオロ化基含有化合物はフッ素原子の
分極率が小さく、従って屈折率も低く、例えば08F、
8の屈折率(25℃、以下同じ〕fil、271、(C
4F、)3N id 1,290、(CF2=CF2/
cF’30CF=CF、)の重合体は1.330であシ
、ガラス又は透明プラスチックなどの透明基体の表面に
塗膜を形成することにより低反射率化が可能となること
、又、ポリフルオロ化基含有化合物は基体への凝集力は
強いが、塗膜の硬度は膜厚に依存し、ある程度の膜厚全
必要とするが、低反射性能からは薄膜であるのが好まし
いこと、更にポリフルオロ化基含有化合物の薄膜の硬度
を向上せしめるには、透明基体の表面上に接着力及び硬
度の高い他の材料からなる透明塗膜を形成し、該塗膜上
にポリフルオロ化基含有化合物からなる薄膜を形成する
ことによシ、低反射性能及び膜硬度の優れた塗膜が得ら
れるという知見が得られた。As a result, polyfluorinated group-containing compounds have a low polarizability of fluorine atoms and therefore a low refractive index, such as 08F,
Refractive index of 8 (25°C, same below) fil, 271, (C
4F, )3N id 1,290, (CF2=CF2/
The polymer of cF'30CF=CF,) is 1.330, and it is possible to reduce the reflectance by forming a coating film on the surface of a transparent substrate such as glass or transparent plastic. The chemical group-containing compound has a strong cohesive force to the substrate, but the hardness of the coating film depends on the film thickness, and a certain amount of total film thickness is required, but a thin film is preferable from the viewpoint of low reflection performance. In order to improve the hardness of a thin film of a fluorinated group-containing compound, a transparent coating film made of another material with high adhesive strength and hardness is formed on the surface of a transparent substrate, and a polyfluorinated group-containing compound is applied on the coating film. It has been found that by forming a thin film consisting of the following, a coating film with excellent low reflection performance and film hardness can be obtained.
本発明者はかかる知見から、ガラス又は透明プラスチッ
クなどの透明基体の表面に形成する塗膜(以下、下層塗
膜という)は、透明基体に強固に接着し、硬度が高く、
透明性を有するものであって、該塗膜上に形成するポリ
フルオロ化基含有化合物との良好な接着性を有し、且つ
屈折率が透明基体と同程度か、それより大きいシラン化
合物又は透明性樹脂であるのが好ましく、更に該塗膜上
に形成する薄膜(以下、上層薄膜という)はポリフルオ
ロ化基含有化合物からなっていて、重合体の薄膜を形成
するものが好葦しく、このような多層構造の塗膜とする
ことにより、薄膜であっても硬度が大きく、しかも低反
射性能の優れた塗膜となるという事実を見出し、本発明
を完成したものである。Based on this knowledge, the present inventors have found that a coating film formed on the surface of a transparent substrate such as glass or transparent plastic (hereinafter referred to as the "lower coating film") firmly adheres to the transparent substrate, has high hardness,
A silane compound or a transparent compound that is transparent, has good adhesion to the polyfluorinated group-containing compound formed on the coating film, and has a refractive index comparable to or higher than that of the transparent substrate. The thin film formed on the coating film (hereinafter referred to as the upper layer thin film) is preferably made of a compound containing a polyfluorinated group and forms a thin film of a polymer. The present invention was completed based on the discovery that by creating a coating film with such a multilayer structure, a coating film with high hardness and excellent low reflection performance can be obtained even if it is a thin film.
即ち、本発明はガラス又は透明プラスチックなどの透明
基体の表面に処理する低反射率塗膜において、透明基体
と同程度以上の屈折率を有するシラン化合物、又は透明
性樹脂の塗膜と、該塗膜上にポリフルオロ化基含有化合
物からなる厚さ0.2μ以下の薄膜を形成してなること
を特徴とする多層構造の低反射率塗膜を提供するもので
ある。That is, the present invention provides a low reflectance coating film to be applied to the surface of a transparent substrate such as glass or transparent plastic, which comprises a coating film of a silane compound or transparent resin having a refractive index comparable to or higher than that of the transparent substrate, and the coating film. The present invention provides a low reflectance coating film with a multilayer structure, which is characterized by forming a thin film of a polyfluorinated group-containing compound with a thickness of 0.2 μm or less on the film.
本発明における下層塗膜において透明基体と同程度以上
の屈折率を有するシラン化合物は、一般式 (x(A)
c)aSi(Z)bY4−a−bで表わされるシランカ
ップリング剤が好筐しい。前記一般式%式%
NGO−1人はアルキレン基、2は炭素数1〜4の低級
アルキル基、Yはノーロゲン、アルコキシ基が遠足され
、aは1〜3の整数、bはO又は1〜2の整数、CはO
又は1の整数である。かかるシランカップリング剤とし
て(は、例えばC:H2−CHCH,,0(CH2,)
3Si(OCH3)3 、 N馬(CH,方NH(鵠%
5i(OCH3)3゜\ど
W馬(CH,)、、5i(OCR,、)、、C%二〇H
81(0(1’H3)3. C4=CH8iC13゜
CH3
0I(2=CC00(CH2)3S1(OCH3)3.
H8(CII2)3S1(OcH9〕3゜NC0(CH
2)3Si(QC:2H5)3. C1(CH2)3
Si(OCI(3)3゜0H2=C4CH2NH(CH
2)2NH(C:H2)3Si(OCH3) 。In the present invention, the silane compound having a refractive index comparable to or higher than that of the transparent substrate in the lower coating film has the general formula (x(A)
c) A silane coupling agent represented by aSi(Z)bY4-ab is preferred. The general formula % Formula % NGO-1 is an alkylene group, 2 is a lower alkyl group having 1 to 4 carbon atoms, Y is a norogen, an alkoxy group is excursion, a is an integer of 1 to 3, and b is O or 1 to 3. 2 integer, C is O
or an integer of 1. As such a silane coupling agent (for example, C:H2-CHCH,,0(CH2,)
3Si(OCH3)3, Numa(CH, NH(鵠%)
5i (OCH3) 3゜\doW horse (CH,), 5i (OCR,, ), C%20H
81(0(1'H3)3. C4=CH8iC13°CH3 0I(2=CC00(CH2)3S1(OCH3)3.
H8(CII2)3S1(OcH9)3゜NC0(CH
2) 3Si (QC:2H5)3. C1(CH2)3
Si(OCI(3)3゜0H2=C4CH2NH(CH
2) 2NH(C:H2)3Si(OCH3).
0て)ca、c4sBocH,)3
が挙げられる。かかるシランカップリング剤縮合物の屈
折率は1.47〜1.60であり、ガラス又はポリカー
ボネートなどの透明プラスチックと同程度かそれより太
きい。シラ/化合物は2種以上の組合せ物であっても好
ましい結果が得られる。0te)ca, c4sBocH,)3. The refractive index of such a silane coupling agent condensate is 1.47 to 1.60, which is comparable to or thicker than that of transparent plastics such as glass or polycarbonate. Preferable results can be obtained even when two or more types of sila/compounds are used in combination.
透明基体と同程度以上の屈折率を有する透明性樹脂は、
例えばエポキシ樹脂系、メラミン樹脂系、ウレタン樹脂
系などが挙げられる。A transparent resin having a refractive index comparable to or higher than that of the transparent substrate is
Examples include epoxy resin, melamine resin, and urethane resin.
下層塗膜は透明基体の屈折率に応じて適宜選択されるが
、透明基体よシ屈折率が0.1以上低いものを選択した
場曾は、性能の優れた低反射率塗膜は得られない。The lower coating film is appropriately selected depending on the refractive index of the transparent substrate, but if a coating with a refractive index lower than that of the transparent substrate by 0.1 or more is selected, a low reflectance coating film with excellent performance cannot be obtained. do not have.
上層薄膜のポリフルオロ化基含有化合物は、例えば
”f(CH2)2Sic131 Rf(CH2)z=(
CH3)C12,(RfcH,、CH2)2sic12
゜Rf(CH2)zsl(QCl(s)3+ RfCO
NH(CH2)3Si(QC2H,)31RfCONH
CCH2)2 NH(CHz)s 51(OCzHs
)s +RfBO2N(CH3) (CH,)2 C0
NHりCH,)3s1(oc2a5)s 。The polyfluorinated group-containing compound of the upper thin film is, for example, “f(CH2)2Sic131 Rf(CH2)z=(
CH3)C12, (RfcH,,CH2)2sic12
゜Rf(CH2)zsl(QCl(s)3+ RfCO
NH(CH2)3Si(QC2H,)31RfCONH
CCH2)2NH(CHz)s 51(OCzHs
)s +RfBO2N(CH3) (CH,)2 C0
NHriCH,)3s1(oc2a5)s.
Rf(CHz)z 0Co(”’z)2sCcH2)3
S’(QCl3)3 +Rf(CH2)20CON
H(CHl)3 si、(oc2a、 )s 。Rf(CHz)z 0Co(”'z)2sCcH2)3
S'(QCl3)3 +Rf(CH2)20CON
H(CHl)3si, (oc2a, )s.
RfCCH2)2NH(CH2)281(OCH3)3
+RfCCH2)2NH(CH2)2si(OCR
2cH20CH3)3゜(但し、Rfは炭素数4〜16
のポリフルオロアルキル基、mは1以上の整数)
などのポリフルオロアルキル基含有シラン化合物、ポリ
フルオロアルキル基がエーテル結合を有するシラン化合
物、かかるシラン化合物と他のシラ/化合物との混合物
、
c13Si(CH2)2 (C:F2)n(CH2)2
SiC13゜CH3C0)351(CJ(2)2 (”
2 )n(CH2)2 Sl(QCl9)1h但し、n
は4〜16の整数、以下同じ〕などのポリフルオロアル
キレン基含有シラン化金物、及び
などのポリフルオロアルキレン基含有ジェポキシ化合物
が挙げられる。RfCCH2)2NH(CH2)281(OCH3)3
+RfCCH2)2NH(CH2)2si(OCR
2cH20CH3)3゜(However, Rf has 4 to 16 carbon atoms.
polyfluoroalkyl group, m is an integer of 1 or more); silane compounds in which the polyfluoroalkyl group has an ether bond; mixtures of such silane compounds and other sila/compounds; c13Si( CH2)2 (C:F2)n(CH2)2
SiC13゜CH3C0)351(CJ(2)2 (”
2)n(CH2)2Sl(QCl9)1hHowever, n
is an integer of 4 to 16, the same applies hereinafter] and polyfluoroalkylene group-containing silanized metal compounds, and polyfluoroalkylene group-containing jepoxy compounds such as.
又、ポリフルオロアルキル基含有メタクリレートとメタ
クリル酸誘導体との共重合体、例えば
ポリフルオロアルキル基含有アルコールとメラミン誘導
体との反応物、例えば
などが挙げられる。Also included are copolymers of polyfluoroalkyl group-containing methacrylates and methacrylic acid derivatives, for example, reaction products of polyfluoroalkyl group-containing alcohols and melamine derivatives.
更に、C8F、7CH:CH,CF3CEC−CF3.
C3FL87iどのプラ2ぐマ重合性化合物を用いる
ことができる。Furthermore, C8F, 7CH:CH, CF3CEC-CF3.
Any plastic polymerizable compound such as C3FL87i can be used.
本発明の低反射率塗膜は透明基体の表面上に下層塗膜を
形成し、該塗膜上に上層薄膜を形成した多層構造からな
るが、下層塗膜の厚さは少なくとも0.1μ、特に0.
5〜5μであるのが好ましい。塗膜の厚さ0.1μ以下
では塗膜材料の分子の絡み合いが不十分となり、塗膜強
度が保持されず、該塗膜上に形成する上層薄膜の硬度の
向上は得られない。下層塗膜の厚さは厚いほど該塗膜上
に形成する上層薄膜の硬度は向上するが、光透過性への
影響、塗布の作業性及び経済性の点から必要以上に厚く
することは好ましくなく、上限は10μまでである。The low reflectance coating film of the present invention has a multilayer structure in which a lower layer coating film is formed on the surface of a transparent substrate, and an upper layer thin film is formed on the coating film, and the thickness of the lower layer coating film is at least 0.1μ, Especially 0.
It is preferable that it is 5-5μ. If the thickness of the coating film is less than 0.1 μm, the entanglement of the molecules of the coating material becomes insufficient, the strength of the coating film cannot be maintained, and the hardness of the upper thin film formed on the coating film cannot be improved. The thicker the lower coating film is, the higher the hardness of the upper thin film formed on the coating film, but it is preferable to make it thicker than necessary from the viewpoint of the influence on light transmittance, workability of coating, and economic efficiency. The upper limit is 10μ.
下層塗膜の透明基体表面上への形成方法は特に限定され
ない。シラン化合物を用いる場合は、例えばシラン化合
物をアセトン、テトラヒドロフラン、低級アルコールな
どの有機溶剤に溶解し、5〜50重量俤、好ましくは1
5〜40重i%溶液として塗布、吹付け、浸漬など既知
の方法により行なわれる。塗布後は室温、あるいは必要
に応じて100℃程度の温度で30分〜1時間乾燥して
シラン化合物の架橋が部分的に進行した状態の塗膜とし
、その上に上層薄膜材料を塗布し薄膜を形成する。シラ
ン化合物ば2種以上組合せてもよく、かかる場合は2独
以上のシラン化合物を混合攪拌して反応させた後、有機
溶剤を加えて粘塵を調整し、前記と同様に塗布及び処理
して塗膜全形成する。透明性樹脂?用いる場合は、例え
ばエポキシ樹脂として“エピコー) −1001,”
(商品名二油化シェル化学社製品)、メラミン樹脂とし
て゛′サイメルー325”(商品名:三井東圧化学社製
品〕、ウレタン樹脂として”オレスターM75−50F
i #(闇品名:三井東圧化学社製品)が好適に用いら
れる。エポキシ樹脂及びメラミン樹脂は架橋剤あるいは
重合開始剤を加えて透明基体の表面に塗布して部分架橋
を進めた後、上層薄膜材料を塗布して薄膜を形成する。The method of forming the lower coating film on the surface of the transparent substrate is not particularly limited. When using a silane compound, for example, dissolve the silane compound in an organic solvent such as acetone, tetrahydrofuran, or lower alcohol, and add 5 to 50% by weight, preferably 1% by weight.
It can be applied as a 5 to 40 weight percent solution by known methods such as coating, spraying, and dipping. After coating, dry at room temperature or, if necessary, at a temperature of about 100°C for 30 minutes to 1 hour to form a coating film in which crosslinking of the silane compound has partially progressed, and then apply the upper layer thin film material on top of it to form a thin film. form. Two or more types of silane compounds may be combined. In such a case, two or more silane compounds are mixed and stirred to react, and then an organic solvent is added to adjust the viscous dust, and then applied and treated in the same manner as above. Complete coating is formed. Transparent resin? When used, for example, as an epoxy resin "Epicor) -1001,"
(Product name: Dioilka Shell Chemical Co., Ltd. product), melamine resin "Cymeru 325" (Product name: Mitsui Toatsu Chemical Co. product), urethane resin "Orestar M75-50F"
i# (black market name: Mitsui Toatsu Chemical Co., Ltd. product) is preferably used. After adding a crosslinking agent or a polymerization initiator to the epoxy resin and melamine resin and applying them to the surface of the transparent substrate to proceed with partial crosslinking, an upper layer thin film material is applied to form a thin film.
ウレタン樹脂は透明基体の表面に塗布後、空気中の水分
によって部分的に重合硬化せしめた後、上層薄膜材料を
塗布して薄膜を形成する。かかる下N塗膜材料に帯電防
止剤あるいは高屈折率?付与する他の成分を含有せしめ
ることもできる。After the urethane resin is applied to the surface of the transparent substrate, it is partially polymerized and cured by moisture in the air, and then an upper layer thin film material is applied to form a thin film. Is there an antistatic agent or high refractive index in the bottom N coating material? Other components may also be included.
下層塗膜上に形成するポリフルオロ化基化合物からなる
上層薄膜の形成方法は、既知の塗布方法によって行なう
ことができるが、該化合物の塗布に好適な調製法は用い
る化合物によって異なる。The method for forming the upper layer thin film made of the polyfluorinated group compound on the lower layer coating film can be carried out by any known coating method, but the preparation method suitable for coating the compound differs depending on the compound used.
即チ、前記ポリフルオロアルキル基含有シラン化合物、
ポリフルオロアルキル基がエーテル結合を有するシラン
化合物及びかかるシラン化合物と他のシラン化合物との
混゛合物あるいはポリフルオロアルキレン基含有シラン
化合物の場合は、該化合物又は混合物をアセトン、テト
ラヒドロフラン、塩素系あるいはフッ素系などの有機溶
剤の1種又は2種以上の混合溶剤に希釈して1〜15重
量係溶剤溶液、好ましくは3〜10重量係溶剤溶液とし
7て、下層塗膜上に塗布、吹付け、浸漬など既知の方法
により塗布する。i.e., the polyfluoroalkyl group-containing silane compound;
In the case of a silane compound in which the polyfluoroalkyl group has an ether bond, a mixture of such a silane compound and another silane compound, or a silane compound containing a polyfluoroalkylene group, the compound or mixture may be mixed with acetone, tetrahydrofuran, chlorine-based or Dilute with one or more mixed organic solvents such as fluorine-based solvents to form a 1 to 15 weight solvent solution, preferably a 3 to 10 weight solvent solution, and apply and spray onto the lower coating film. , by dipping or other known methods.
塗布後は100℃以上の温度で20分以上キユアリング
することによって薄膜を形成することができる。After coating, a thin film can be formed by curing at a temperature of 100° C. or higher for 20 minutes or more.
ポリフルオロアルキレン基含有ジェポキシ化合物の場合
は、該化合物に、ポリフルオロアルキレン基含有アミン
化合物、他のアミン類、アミン類のBF3塩、カルボン
酸無水物から選ばれる1種の硬化剤を硬化反応が進行す
るに十分なに’に加え、室温〜150℃にて5分〜3時
間反応させて部分重合物とするO硬化剤は硬化剤自身が
低屈折率物であるものを用いるのが好ましく、この場合
使用量全増加しても低反射性能に影響を与えることはな
い。例えば、
”2N(CH2)2 (”2)6 (CH2)2NH2
は10〜50重量加えることができる。In the case of a polyfluoroalkylene group-containing jepoxy compound, one type of curing agent selected from polyfluoroalkylene group-containing amine compounds, other amines, BF3 salts of amines, and carboxylic acid anhydrides is added to the compound in a curing reaction. It is preferable to use a curing agent that has a low refractive index and is reacted at room temperature to 150°C for 5 minutes to 3 hours to form a partially polymerized product. In this case, even if the total amount used increases, the low reflection performance will not be affected. For example, “2N(CH2)2 (”2)6 (CH2)2NH2
can be added by 10 to 50 weight.
ポリフルオロアルキル基含有メタクリレートとメタクリ
ル酸誘導体との共重合は該化合物の混曾物に重合開始剤
を加えて加熱して共重合物とする。ポリフルオロアルキ
ル基含有アルコールとメラミン誘導体との反応物は固形
成分に対して1重量係のP−)ルエンスルホン酸を触媒
成分として加え、加熱して反応生成物を得る。For copolymerization of a polyfluoroalkyl group-containing methacrylate and a methacrylic acid derivative, a polymerization initiator is added to a mixture of the compounds and heated to form a copolymer. To the reaction product of the polyfluoroalkyl group-containing alcohol and the melamine derivative, 1 part by weight of P-)luenesulfonic acid is added as a catalyst component based on the solid component, and the mixture is heated to obtain a reaction product.
かかる共重合体あるいは反応生成物は前記の化合物と同
様に溶剤に希釈して、下層塗膜上に塗布した後、キユア
リングすることによって薄膜を形成することができる。Such a copolymer or reaction product can be diluted in a solvent in the same manner as the above-mentioned compounds, applied onto the lower coating film, and then cured to form a thin film.
プラズマ重合性化合物は下層塗膜上に、プラズマ重合装
置を使用して装置内で重合を行なうことによって薄膜を
形成することができる。A thin film of the plasma polymerizable compound can be formed on the lower coating film by polymerizing it in a plasma polymerization device.
かかる方法によって形成される上層薄膜の厚さは0.2
μ以下、特に008〜0.2μであるのが好ましい。0
.2μより厚い場合は低反射率塗膜としての性能は著る
しく劣ったものとなるC薄膜の厚さは塗布条件によって
変化し、例えば浸漬法ではポリフルオロ化基含有化合物
の有機溶剤との希訳濃度と引上速度の関係で決定される
0
ポリフルオロ化基含有化合物からなる上層薄膜材料には
無機物フィラー、例えばシリカゲル。The thickness of the upper thin film formed by this method is 0.2
It is preferably less than μ, particularly 0.08 to 0.2 μ. 0
.. If it is thicker than 2 μm, the performance as a low reflectance coating will be significantly inferior. The thickness of the C thin film varies depending on the coating conditions. The upper layer thin film material made of a polyfluorinated group-containing compound contains an inorganic filler, such as silica gel.
Li□SiF6. MgF2. Na2SiF6.
MgSi’F、などを添加して薄膜の硬度を更に向
上せしめることができる。又、上層薄膜材料の使用形態
は常法に従って、溶剤溶液、溶媒分散液、乳濁液。Li□SiF6. MgF2. Na2SiF6.
The hardness of the thin film can be further improved by adding MgSi'F, etc. In addition, the upper layer thin film material can be used in the usual manner, such as a solvent solution, a solvent dispersion, or an emulsion.
エアゾールなど任意の形態に調製すること、あるいは帯
電防止剤、架橋剤など適宜添加剤を添加することができ
る。It can be prepared in any form such as an aerosol, or additives such as an antistatic agent and a crosslinking agent can be added as appropriate.
本発明の低反射率塗膜を形成した透明基体の可視光にお
ける反射率は0.6〜1.4係であり、通常のソーダ石
灰ガラスの反射率42チ、メタアクリル樹脂の反射率3
.9%、ポリカーボネートの反射率4.8%に対し優れ
た効果が認められる。更に塗膜の硬度は鉛筆硬度B〜〉
5Hであり、ポリフルオロ化基含有化合物のみの塗膜の
鉛筆硬度>2Bに対し顕著な向上が認められる。The visible light reflectance of the transparent substrate on which the low reflectance coating film of the present invention is formed is 0.6 to 1.4, the reflectance of ordinary soda lime glass is 42, and the reflectance of methacrylic resin is 3.
.. 9%, and an excellent effect compared to that of polycarbonate, which has a reflectance of 4.8%. Furthermore, the hardness of the coating film is pencil hardness B~〉
5H, which is a significant improvement over the pencil hardness >2B of the coating film containing only the polyfluorinated group-containing compound.
又、透明性あるいは透視性を損なうことはない。Further, transparency or visibility is not impaired.
本発明の低反射、率塗膜の用途は特に限定され−ること
なく、例えば建築物の窓!車輌の窓、ドアー、ショーウ
ィンド、ショーケース、光学機器類、メガネ類、太陽光
集光部材などのガラス又は透明プラスチック材料に用い
ることができる。The application of the low-reflection, low-reflection coating film of the present invention is not particularly limited, and includes, for example, windows of buildings! It can be used for glass or transparent plastic materials such as vehicle windows, doors, show windows, showcases, optical instruments, eyeglasses, and sunlight condensing members.
本発明の低反射率塗膜の評価方法は次の通りである。即
ち、自記分光光度計反射光測足付域、。The evaluation method for the low reflectance coating film of the present invention is as follows. That is, a self-recording spectrophotometer reflection light measurement area.
装置(323型:日立製作新製)を使用して波長540
mμの入射角5°における反射率を測定することにより
行ない、塗膜の厚さは透明基体上に形成された膜厚(下
層塗膜と上層薄膜の合計)全1′タリステツプ” (R
ank Taylor Hobson社製)を使用して
針圧を測定することにより行ない、更に塗膜の硬度は鉛
傘引かき試験機(JXB −K 5401 )を使用し
て鉛藻硬度を測定することにより行なった。Wavelength 540 using a device (type 323: newly manufactured by Hitachi)
This is done by measuring the reflectance of mμ at an incident angle of 5°.
The hardness of the coating film was determined by measuring the stylus pressure using an ank (manufactured by Taylor Hobson), and the hardness of the paint film was measured by measuring the hardness of lead algae using a lead umbrella scratch tester (JXB-K 5401). Ta.
以下に、本発明を実施例により具体的に説明するが、本
発明はこれら実施例のみに限定されるものではない。EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.
合成例I
RfCH= CH2(但し、Rf : Cn’2n4−
t 、 n: 6.8.10゜12の混合物で平均値
9.0 ) 49.6 F (0,1モル)、H81C
1315,9j (0,12モル)、H2PtCl6・
6H20050%イソプロパツール溶液01M’を内容
積100vtlのガラス製耐圧アンプルに入れ、振盪し
ながら85℃で200時間反応せた。反応終了後、減圧
蒸留をすることにより反応生成物を得た。Synthesis Example I RfCH=CH2 (However, Rf: Cn'2n4-
t, n: 6.8.10゜12 mixture with average value 9.0) 49.6 F (0.1 mol), H81C
1315,9j (0.12 mol), H2PtCl6.
A 50% isopropanol solution 01M' of 6H200 was placed in a pressure-resistant glass ampoule with an internal volume of 100 vtl, and reacted at 85° C. for 200 hours with shaking. After the reaction was completed, a reaction product was obtained by distillation under reduced pressure.
反応生成物はガスクロマトグラフィーで分析するとRf
(C)I2)2SiC:13(b、P、 85℃〜1o
o℃/3〜5wnHy)であり、それへの転化率Fi9
5%であった。When the reaction product is analyzed by gas chromatography, Rf
(C)I2)2SiC:13(b,P, 85℃~1o
o℃/3~5wnHy), and the conversion rate Fi9 to that is
It was 5%.
合成列2
合成I+01の反応生成物Rf(CH2)2EiiC1
350,3t(008モル〕、メタノール15fを混合
し、乾燥窒素をバグリングして生成するHCl1除去し
ながら反応させた。この反応の終点は生成したHCl−
<定量して確認した。反応終了後、過剰のメタノールを
留去して反応生成物を得た。反応生成物はガスクロマト
グラフィーで分析するとRf(CH2)2Si(OCH
3)3 であシ、それへの転化率は100饅であった。Synthesis row 2 Reaction product Rf(CH2)2EiiC1 of synthesis I+01
350.3t (008 mol) and 15f of methanol were mixed, and the mixture was reacted with dry nitrogen to remove the generated HCl1.The end point of this reaction was to remove the generated HCl-
<Confirmed by quantitative determination. After the reaction was completed, excess methanol was distilled off to obtain a reaction product. When the reaction product was analyzed by gas chromatography, it was found to be Rf(CH2)2Si(OCH
3) The conversion rate to 3-dashi was 100 yen.
合成例3
RfCOOCH(CH3)2 (但し、Rf : Cn
l’2n4−t、 n : 6゜8、IQ、12の混
合物で平均値9.0 ) 111.2f (0,2モル
)、H2N(CH2)3Si(QC,H5)344.2
? (0,2モル)、乾燥テトラヒドロフラン150
9を温度計、攪拌機、冷却管を装着した内容積300m
1の四つロフラスコに入れ、乾燥窒素気流下にゅっくシ
攪拌しながら還流温度〔約80℃〕で5時間反応させた
。テトラヒドロフランを留去し反応生成物を得た。反応
生成物はガスクロマトグラフィーで分析するとRfCO
NH(CH2)3汎(OC2H5)3であシ、ツレへの
転化率は100%であった。Synthesis Example 3 RfCOOCH(CH3)2 (However, Rf: Cn
l'2n4-t, n: 6°8, IQ, average value 9.0 in a mixture of 12) 111.2f (0.2 mol), H2N(CH2)3Si(QC, H5) 344.2
? (0.2 mol), dry tetrahydrofuran 150
9 is equipped with a thermometer, stirrer, and cooling pipe with an internal volume of 300 m.
The mixture was placed in a four-bottle flask and reacted for 5 hours at reflux temperature [approximately 80° C.] while stirring under a stream of dry nitrogen. Tetrahydrofuran was distilled off to obtain a reaction product. The reaction product was analyzed by gas chromatography and was found to be RfCO
The conversion rate to NH(CH2)3(OC2H5)3 was 100%.
合成νす4
ビa、 CF3
CF3CF2CF2O+CFCF20 % CFCOO
C2H569,017’(0,1モル〕、H2N(cI
■2)3Bi、(OC2H5)322.1F(0,1モ
/l、) 、乾燥テトラヒドロフラン150f’i合
成例3と同様の方法で反応させた。反応生成物はガスク
は100%であった。Synthesis νS4 Via, CF3 CF3CF2CF2O+CFCF20% CFCOO
C2H569,017' (0.1 mol), H2N (cI
(2) 3Bi, (OC2H5)322.1F (0.1 mo/l), 150 f'i of dry tetrahydrofuran was reacted in the same manner as in Synthesis Example 3. The gas content of the reaction product was 100%.
合成例5
CH2: CHC,F1□CH−CH222,6F (
0,06モル)、H81C1325,9(0,19モル
)、H2Pj、C16・6H20の50%イソプロパツ
ール溶液0.22を内容積100−のガラス製耐圧アン
プルに入れ振盪しながら85℃で200時間反応せた。Synthesis example 5 CH2: CHC,F1□CH-CH222,6F (
0.22 of a 50% isopropanol solution of H81C1325,9 (0.19 mol), H2Pj, C16.6H20 was placed in a glass pressure-resistant ampoule with an internal volume of 100 - 200 °C at 85 °C with shaking. Time reacted.
反応終了後、フロン(R−113:旭硝子社製品)30
2を加え、沢過し、f液から低沸点物を留去して反応生
成物を得た。反応生成物はガスクロマトグラフィーで分
析すると(:13Si(C晒C6ち(1商5iC13で
あり、それへの転化率は97%であった。After the reaction, add 30 fluorocarbons (R-113: Asahi Glass Co., Ltd. product)
2 was added, filtered, and low boiling point substances were distilled off from liquid f to obtain a reaction product. When the reaction product was analyzed by gas chromatography, it was found to be 13Si(C-bleached C6) (1 quotient 5iC13), and the conversion rate to it was 97%.
合成例6
合成列5の反応生成物C13S1(CH2)2C6F1
□(CH2)2SIC1335? (o、 o 56モ
ル)、メタノール157を混合し、合成例2と同様の方
法で反応させ、反応生成物を得7’Co反応生成物はガ
スクロマトグラフィーで分析すると(HaCO)aSi
(CH2)2CaF+2(CH2)2Si(OCH3)
3であシ、それへの転化率は100饅であった。Synthesis Example 6 Reaction product C13S1(CH2)2C6F1 of synthesis sequence 5
□(CH2)2SIC1335? (o, o 56 mol) and methanol 157 were mixed and reacted in the same manner as in Synthesis Example 2 to obtain a reaction product. When analyzed by gas chromatography, the 7'Co reaction product was (HaCO)aSi
(CH2)2CaF+2(CH2)2Si(OCH3)
3, and the conversion rate to it was 100.
合成例7
エC6F12工 22.、2 f (0,4モル)、
CH2= CHCH20H92,8r(1,6モル)を
温度計、攪拌機、冷却管を装置した内容積500mJの
四つロフラスコに入れ、乾燥窒素気流下、攪拌しなから
内温ヲ80℃に昇温した。これにα、α′−アゾビスイ
ソブチロニトリルを30分〜1時間毎に合計10.5
f添加し、反応温度80℃〜95℃で12時間反応させ
た。反応生成物はガスクロマトグラフィーで分析すると
HOCH2CM工CH2C6F’、6CH2CH工CH
20Hであり、それへの転化率は90チであった。次に
この反応生成物61 f (0,1モル〕、25%Na
OH水溶液35 f (0,22モル) f 4iJ記
ト同様なフラスコに入れ、50℃〜60℃で300時間
反応せ、反応混合物をエーテルにて抽出し、エーテルを
留去後、減圧蒸留することにょシ、/3〜5順H7)を
得た。Synthesis Example 7 EC6F12 Engineering 22. , 2 f (0.4 mol),
CH2 = CHCH20H92,8r (1.6 mol) was placed in a four-lobe flask with an internal volume of 500 mJ equipped with a thermometer, a stirrer, and a cooling tube, and the internal temperature was raised to 80°C while stirring under a stream of dry nitrogen. . To this, add α,α'-azobisisobutyronitrile for a total of 10.5 liters every 30 minutes to 1 hour.
f was added, and the reaction was carried out at a reaction temperature of 80°C to 95°C for 12 hours. When analyzed by gas chromatography, the reaction products were HOCH2CM-CH2C6F', 6CH2CH-CH
20H, and the conversion rate thereto was 90H. Next, this reaction product 61 f (0.1 mol), 25% Na
OH aqueous solution 35 f (0.22 mol) f Place in a flask similar to that described in 4iJ, react at 50°C to 60°C for 300 hours, extract the reaction mixture with ether, and after distilling off the ether, distill under reduced pressure. The results were as follows: H7).
合成例8
τH3
CH2= C−Coo C2H4Rf(但し、Rf :
cn’2n41 +n : 6.8.10.12の混
合物で平均値9.0)10F、スイソブチロニトリルo
37、フoン(R−113:旭硝子社製品)501i”
iloomJのガラス製耐圧アンプルに入れ65℃で1
5時間反応して共重合体を得た。Synthesis Example 8 τH3 CH2= C-Coo C2H4Rf (However, Rf:
cn'2n41 +n: 6.8.10.12 mixture with average value 9.0) 10F, Swissobutyronitrile o
37, Fon (R-113: Asahi Glass Company product) 501i”
Place in iloomJ glass pressure-resistant ampoule and heat at 65°C.
A copolymer was obtained by reacting for 5 hours.
合成例9
CH3
CH2=C−Coo(CH2)2Rf(但し、Rf :
cn’2n−1−t +n : 6.8.10.12
の混合物で平均値9.0)10r、ロニトリル0.37
、フロン(R−113,旭硝子社製品)30f、テトラ
ヒドロフラン20S’1100m/のガラス製耐圧アン
プルに入れ65℃で15時間反応して共重合体を得た。Synthesis Example 9 CH3 CH2=C-Coo(CH2)2Rf (However, Rf:
cn'2n-1-t +n: 6.8.10.12
Average value for a mixture of 9.0) 10r, ronitrile 0.37
, Freon (R-113, product of Asahi Glass Co., Ltd.) 30f, and tetrahydrofuran 20S'1100m/glass pressure-resistant ampoule were charged and reacted at 65° C. for 15 hours to obtain a copolymer.
合成例10
CH30CH20H20CH3
\/
「
RfC,、H40H(但しs Rf: cnFZn+1
、 n : 6.8.10゜12の混合物で平均
値9.0 ) 34.3 f (0,67モル)’11
00mllの三つロフラスコに入れ、12゜℃に加熱し
、生成するメタノールを留去しなから22時間反応させ
て、RfC2H40Hとの反応物及びメラミンが部分的
に縮合した混合物を得た。Synthesis example 10 CH30CH20H20CH3 \/ " RfC,, H40H (s Rf: cnFZn+1
, n: 6.8.10°12 mixture with average value 9.0) 34.3 f (0.67 mol)'11
The mixture was placed in a 00ml three-necked flask, heated to 12°C, and reacted for 22 hours after distilling off the methanol produced, to obtain a mixture in which the reaction product with RfC2H40H and melamine were partially condensed.
合成例11
CH,、pHcH20(CH2)3Si(QC2H5)
383.4 f、H2N(CH2)2NH(CH2)3
Si(OCH3)366.6 r S:温度計、攪拌機
、冷却管を装着した内容積500 mlの四っロフラス
コに入れ、80℃で2時n」J反応させた後、室温に冷
却し、テトラヒドロフラン1701を加えて、粘度6.
7cpのシラン化合物溶液を調製した。Synthesis Example 11 CH,, pHcH20(CH2)3Si(QC2H5)
383.4 f, H2N(CH2)2NH(CH2)3
Si(OCH3) 366.6 rS: Pour into a 500 ml four-bottle flask equipped with a thermometer, stirrer, and cooling tube, react at 80°C for 2 hours, cool to room temperature, and add tetrahydrofuran. 1701 was added and the viscosity was 6.
A 7 cp silane compound solution was prepared.
合成例12
CH2−C1(CH20(CH2)3Si(QC2H5
八 139 F 、 0.lN−HClゝ。′
27ft攪拌機を装着した内容積5o o meの四つ
ロフラスコに入れ、室温で48時間反応させた後、シリ
カゾルのメタノール30%溶W 1501、メタノール
51gを加えて、粘度3.5cpのシラン化合物溶液を
調製した。Synthesis Example 12 CH2-C1(CH20(CH2)3Si(QC2H5
8 139 F, 0. 1N-HCl. ' Place the mixture in a four-bottle flask with an internal volume of 5 o'me equipped with a 27 ft stirrer and react at room temperature for 48 hours, then add a 30% methanol solution of silica sol W 1501 and 51 g of methanol to prepare a silane compound solution with a viscosity of 3.5 cp. was prepared.
実施例
合成例2の反応生成物Rf(OH2)2Si(OCH3
)325 ?會フロン(R−113:旭硝子社製品):
アセトン=3:1重針比の混会溶媒で希釈して5007
としたポリフルオロ化基含南”化上゛物の溶液を調製し
た。別に洗剤で洗浄し、2係フツ酸溶液に浸漬して水洗
吸、乾燥したカラス板−(ソーダ石灰ガラス5 X 5
cm)¥用意し、合成例11のシラン化合物溶液に浸
漬し、引上速度9、Ocnt 7分で引上げた後、室温
で30分乾燥した。次に、先きに調製したポリフルオロ
化基含有化物溶液に浸漬し、引上速度4.5crn/分
で引上げた後、160℃でキユアリングした。処理後の
ガラス表面に形成された塗膜の厚さは2.1μ、塗膜の
鉛筆硬度はB1反射率は06%であった。Examples Reaction product of Synthesis Example 2 Rf(OH2)2Si(OCH3
)325? Freon (R-113: Asahi Glass Company product):
Acetone = 5007 diluted with a mixed solvent with a heavy needle ratio of 3:1
A solution of a polyfluorinated group-containing material was prepared. Separately, a glass plate (soda lime glass 5 x 5
cm) was prepared, immersed in the silane compound solution of Synthesis Example 11, pulled up at a pulling rate of 9 and Oct. 7 minutes, and then dried at room temperature for 30 minutes. Next, it was immersed in the polyfluorinated group-containing compound solution prepared earlier, pulled up at a pulling rate of 4.5 crn/min, and then cured at 160°C. The thickness of the coating film formed on the glass surface after treatment was 2.1μ, the pencil hardness of the coating film was B1, and the reflectance was 06%.
実施例2〜4
笑施ヒ111のポリフルオロ化基含有化合物を合成例1
の反応生成物Rf(CH2)2S i C13、合成例
3CONH(CH2)3Si(QC2H5)3に変えた
他は実施例1と同様の方法でガラス板に処理し、塗膜の
厚さ、鉛筆硬度及び反射率を測定した。Examples 2 to 4 Synthesis Example 1 of the polyfluorinated group-containing compound of Shoshihi 111
A glass plate was treated in the same manner as in Example 1, except that the reaction product Rf(CH2)2S i C13 was changed to Synthesis Example 3CONH(CH2)3Si(QC2H5)3, and the coating film thickness and pencil hardness were and reflectance was measured.
測定結果を第1表に示した。The measurement results are shown in Table 1.
実施例5
合成例6の反応生成物(HaCO)3si(CH2)z
CsF、2(CH2)2Si(○CHs)s 21.2
y、アセト7150f、フロン(R−113:旭硝子
社製品)128f、1%酢酸水溶液0.6 r ′t−
室温で12時間攪拌してポリフルオロ化基含有化合物溶
液を調製した。別に実施例1と同様の方法でシラン化合
物を処理したガラス板を用意し、あらかじめ調製した前
記溶液に浸漬し、実施例1と同様の方法でガラス板に処
理した。処理後のガラス表面に形成された塗膜の厚さは
1.6μ、鉛筆硬度は5111反射率は1.3%であっ
た。Example 5 Reaction product of Synthesis Example 6 (HaCO)3si(CH2)z
CsF, 2(CH2)2Si(○CHs)s 21.2
y, Aceto 7150f, Freon (R-113: Asahi Glass Co., Ltd. product) 128f, 1% acetic acid aqueous solution 0.6 r't-
A polyfluorinated group-containing compound solution was prepared by stirring at room temperature for 12 hours. Separately, a glass plate treated with a silane compound in the same manner as in Example 1 was prepared, immersed in the solution prepared in advance, and treated in the same manner as in Example 1. The coating film formed on the glass surface after treatment had a thickness of 1.6 μm, a pencil hardness of 5111, and a reflectance of 1.3%.
実施例6
合成例5の反応生成物C13Si(CH,汲C6F’、
□(Q(2)2Si C13を用いた他は実施例5と同
様の方法で処理した後、塗膜の厚さ、鉛筆硬度及び反射
率を測定した。Example 6 Reaction product of Synthesis Example 5 C13Si(CH, 汲C6F',
□(Q(2) After processing in the same manner as in Example 5 except that 2Si C13 was used, the thickness, pencil hardness, and reflectance of the coating film were measured.
測定結果を第2表に示した。The measurement results are shown in Table 2.
実施例7
合成し1]6の反応生成物(H3co)s 51(CH
2)2に−p、F)2 (CH2)2Si(,0CH3
)317. Of? 、 Rf(CH,)2S、t(O
CH3)3a、 4 ? (但し、RfはCnF2n+
1、n (rf:、 6.8.10.12 +7) 混
合ell テ平均値9.0)、アセト7150 f、7
0ン(R−113:旭硝子社製品)129f、1%酢酸
水溶液0、67 f室温で12時間攪拌してポリフルオ
ロ化基含有化合物溶iを調製した。この溶液を実施レリ
5と同様の方法で処理した後、塗膜の厚さ、鉛筆硬度及
び反射率を測定した。Example 7 Synthesis 1] Reaction product of 6 (H3co)s 51(CH
2) 2-p, F)2 (CH2)2Si(,0CH3
)317. Of? , Rf(CH,)2S,t(O
CH3) 3a, 4? (However, Rf is CnF2n+
1, n (RF:, 6.8.10.12 +7) Mixed ell Te average value 9.0), Aceto 7150 f, 7
A polyfluorinated group-containing compound solution i was prepared by stirring at room temperature for 12 hours. After treating this solution in the same manner as in Example 5, the thickness, pencil hardness, and reflectance of the coating film were measured.
測定結果を第2表に示した。The measurement results are shown in Table 2.
実施例8
合成例6の反応生成物O13”)(sl(”2)2O2
% (”z)2si(OcHa)al 9、 l ?、
Cm2CH−CH20(CH2)、5i(QC2H5)
32.5 F、アセ\1
トン150F、フロン(Fj−113:旭硝子社製品〕
12.8r、1%酢酸水溶液0.75 fを実施例7と
同様の方法で攪拌してポリフルオロ化基含有化合物を調
製した。この溶液を実施例5と同様の方法で処理した後
、塗膜の厚さ、鉛筆硬度及び反射率を測定した。Example 8 Reaction product O13'')(sl(''2)2O2 of Synthesis Example 6
% (”z)2si(OcHa)al 9, l?,
Cm2CH-CH20(CH2), 5i(QC2H5)
32.5 F, Ace\1 ton 150F, Freon (Fj-113: Asahi Glass product)
12.8r and 0.75f of a 1% acetic acid aqueous solution were stirred in the same manner as in Example 7 to prepare a polyfluorinated group-containing compound. After treating this solution in the same manner as in Example 5, the thickness, pencil hardness, and reflectance of the coating film were measured.
測定結果を第2表に示した。The measurement results are shown in Table 2.
実施例9
1’1L06r、H2N(CH2)2C4Il′1ll
(CH2)2NH242fを120℃で3時間反応後、
アセトン:フロン(R−113:旭硝子社製品)、=2
06f: 103rの混合溶媒で希釈しポリフルオロ化
基含有化合物の溶液を調製した。別に実施例1と同様の
方法でシラン化合物を処理したガラス板を用意し、あら
かじめ調製した前記溶液に浸漬し、引上速度8.8ff
i/分で引上後、160℃でキユアリングした。処理後
のガラス表面に形成された塗膜の厚さは21μ、塗膜の
鉛筆硬度は3H1反射率は1.4%であった。Example 9 1'1L06r, H2N(CH2)2C4Il'1ll
After reacting (CH2)2NH242f at 120°C for 3 hours,
Acetone: Freon (R-113: Asahi Glass Company product), =2
06f: A solution of a polyfluorinated group-containing compound was prepared by diluting with a mixed solvent of 103r. Separately, a glass plate treated with a silane compound in the same manner as in Example 1 was prepared, immersed in the solution prepared in advance, and pulled up at a pulling rate of 8.8ff.
After pulling up at a rate of i/min, curing was performed at 160°C. The thickness of the coating film formed on the glass surface after treatment was 21 μm, and the pencil hardness and 3H1 reflectance of the coating film was 1.4%.
実施例10〜12
合成例8□9の共重合体及び合成例10の混合物それぞ
れに対し、1%のP−)ルエンスルホン酸を加え、それ
ぞれ全フロン(R−113:旭硝子社製品):アセトン
=3:1重量比の混合溶媒で希釈して5飴溶液を調製し
た。別に実施し111と同様の方法でシラン化合物を処
理したガラス板を用意し、あらかじめ調製した前記溶液
に浸漬実施例13〜15
実施例1と同様の方法でシラン化合物を処理したガラス
板を用意し、CF3−CミC−CF3、C8F、7CI
l=CH。Examples 10 to 12 To each of the copolymer of Synthesis Example 8□9 and the mixture of Synthesis Example 10, 1% P-)luenesulfonic acid was added, and total fluorocarbon (R-113: product of Asahi Glass Co., Ltd.): acetone was added, respectively. A 5-candy solution was prepared by diluting with a mixed solvent at a weight ratio of 3:1. A glass plate treated with a silane compound in the same manner as in Example 111 was prepared separately and immersed in the solution prepared in advance.Examples 13-15 A glass plate treated with a silane compound in the same manner as in Example 1 was prepared. , CF3-CmiC-CF3, C8F, 7CI
l=CH.
C5F1s ”rそれぞれアルゴンで希釈した気体にょ
シ表面にプラズマ重合薄膜を作成し、塗膜の厚さ、鉛傘
硬度及び反射率を測定した。A plasma-polymerized thin film was created on the surface of each C5F1s''r using a gas diluted with argon, and the thickness, hardness and reflectance of the coating were measured.
測定結果を第4表に示した。The measurement results are shown in Table 4.
第4表
実施例16〜25
実施例1〜6、及び9〜12におけるガラス板に処理し
たシラン化合物を合成例12のシラン化合物に変え、浸
漬、引上後100℃で1゜分間乾燥した他は実施例1〜
6及び9〜12と同様の方法で処理した後、塗膜の厚さ
、鉛筆硬度及び反射率を測定した。Table 4 Examples 16 to 25 The silane compound treated on the glass plates in Examples 1 to 6 and 9 to 12 was changed to the silane compound of Synthesis Example 12, and after being immersed and pulled up, it was dried at 100°C for 1°. is Example 1~
After processing in the same manner as in Examples 6 and 9 to 12, the thickness, pencil hardness, and reflectance of the coating film were measured.
測定結果を第5表に示した。The measurement results are shown in Table 5.
実施例26〜30
に希釈して5002とした溶液を用いた他は実施例5と
同様の方法で処理した後、塗膜の厚さ、鉛鎖硬度、及び
反射率を測定した。Examples 26-30 After processing in the same manner as in Example 5 except that a solution diluted to 5002 was used, the thickness, lead chain hardness, and reflectance of the coating film were measured.
測定結果を第6表に示しfCO
第6表
実施例31〜32
実施例1におけるガラス板に処理したシラン化合物をエ
ポ干シ樹脂”エピコー) −1001”(商品名−油化
シエル社製品)ニトリエチレンテトラミン−90:10
(重量比〕、メラミン楠脂”サイメルー325”(商品
名二三井東圧化学社製品): “キャタリス) 600
0’″(商品名:三井東圧化学製品)=99:l(重量
比)tlo。Measurement results are shown in Table 6. Ethylenetetramine-90:10
(Weight ratio) Melamine camphor resin “Cymeru 325” (product name: Nimitsui Toatsu Chemical Co., Ltd. product): “Catalys” 600
0''' (Product name: Mitsui Toatsu Chemical Products) = 99:l (weight ratio) tlo.
℃にて10分間加熱した部分重合体75ffテトラヒド
ロフランに希釈して5001とした溶液に変えた他は実
施例5と同様の方法で処理した後、塗膜の厚さ、鉛疵硬
度及び反射率を測定した。The partial polymer heated at ℃ for 10 minutes was treated in the same manner as in Example 5, except that the solution was changed to 5001 by diluting it with 75ff tetrahydrofuran. It was measured.
測定結果を第7表に示した。The measurement results are shown in Table 7.
実施例33
実施レリ5におけるガラス板に処理したシラン化合物を
ウレタン樹脂″オレスターM75−50Fi”(商品名
:三井東圧化学製品)75fiデトラヒドロフランに希
釈して5002とした溶液に変えた他は実施レリ5と同
様の方法で処理した後、塗膜の厚さ、鉛鍬硬度及び反射
率を測定した。Example 33 The silane compound treated on the glass plate in Example 5 was diluted with urethane resin "Olestar M75-50Fi" (trade name: Mitsui Toatsu Chemicals) 75fi detrahydrofuran to create a solution of 5002. After processing in the same manner as in Example 5, the thickness of the coating film, lead hoe hardness, and reflectance were measured.
測定結果全第7表に示した。All measurement results are shown in Table 7.
第7表
実施例34〜46
実施例における透明基体のガラス板をポリカーボネート
板(旭硝子社製品〕に変え、キユアリング温度を100
℃とした他は実施例1〜6.9〜10.13.21.2
6.27及び31 と同様の方法で処理した後、塗膜の
厚さ、鉛筆硬度及び反射率を測定した。Table 7 Examples 34 to 46 The glass plate of the transparent substrate in the example was replaced with a polycarbonate plate (product of Asahi Glass Co., Ltd.), and the curing temperature was set to 100.
Examples 1 to 6.9 to 10.13.21.2 except that the temperature was ℃
After processing in the same manner as in 6.27 and 31, the coating film thickness, pencil hardness and reflectance were measured.
測定結果を第8表に示した。The measurement results are shown in Table 8.
実施例47〜60
実施例における透明基体のガラス板をポリメチルメタク
リレート板(三菱レイヨン社製品)又はポリスチレン板
(ダウケミカル社製ペレッ)Y板に成形)に、キユアリ
ング温度を100℃に変えた他は実施例1、5.9.1
0.13.21及び31と同様の方法で処理した後、塗
膜の厚さ、鉛銀硬度及び反射率を測定した。Examples 47 to 60 The glass plate of the transparent substrate in the example was changed to a polymethyl methacrylate plate (manufactured by Mitsubishi Rayon Co., Ltd.) or a polystyrene plate (Pellet Y plate made by Dow Chemical Company), and the curing temperature was changed to 100 ° C. is Example 1, 5.9.1
After processing in the same manner as 0.13.21 and 31, the coating film thickness, lead-silver hardness and reflectance were measured.
測定結果を第9表に示した。The measurement results are shown in Table 9.
比較例1−12
実施例に使用したと同様のガラス板、ポリカーボネート
板、ポリメチルメタクリレート板、ポリスチレン板の反
射率の測定結果を第1O表に示した。Comparative Examples 1-12 Table 1O shows the measurement results of the reflectance of the same glass plates, polycarbonate plates, polymethyl methacrylate plates, and polystyrene plates used in the examples.
実施例1.10.13及び34において、ンラン化合物
の処理を行なわない他は同様の方法で処理した後(ポリ
フルオロ化基化合物の薄膜のみ〕の、塗膜の厚さ、鉛筆
硬度及び反射率の測定結果を第10表に示した。Example 1. Thickness, pencil hardness, and reflectance of the coating film after treatment in the same manner as in 10.13 and 34 (only a thin film of the polyfluorinated group compound), except that the treatment with the Nran compound was not performed. The measurement results are shown in Table 10.
実施例1.16.26及び31において、ポリフルオロ
化基化合物の薄膜形成処理を行なわない他は同様の方法
で処理した後(下層塗膜のみ〕の塗膜の厚さ、鉛筆硬度
及び反射率の測定結果を第10表に示した。Example 1. Thickness, pencil hardness, and reflectance of the coating film after processing in the same manner as in 26 and 31 except that the thin film formation treatment of the polyfluorinated group compound was not performed (lower coating film only) The measurement results are shown in Table 10.
比較例13〜16
実施例1において、ガラス板にシラン化合物を刷毛で塗
膜厚さが10μ以上になるように塗布し、塗膜を形成し
、該塗膜上にポリフルオロ化基含有化合物の調製液を流
延して、160℃でキユアリングした後、形成された塗
膜の厚さ、塗膜の鉛筆硬度及び反射率を測定した。Comparative Examples 13 to 16 In Example 1, a silane compound was applied to a glass plate with a brush to a coating thickness of 10μ or more to form a coating film, and a polyfluorinated group-containing compound was applied on the coating film. After the prepared solution was cast and cured at 160° C., the thickness, pencil hardness and reflectance of the formed coating film were measured.
又、実施例1.5及び34において、ガラス板又はポリ
カーボネート板にシラン化合物の処理を行なわず、直接
ポリフルオロ化基化合物の調製液を厚さ05以上になる
ように流延して、ガラス板は160℃、ポリカーボネー
ト板は100℃でキユアリングした後、形成された塗膜
の厚さ、塗膜の鉛筆硬度及び反射率を測定した。In addition, in Examples 1.5 and 34, the glass plate or polycarbonate plate was not treated with the silane compound, but the prepared solution of the polyfluorinated group compound was directly cast to a thickness of 0.5 mm or more, and the glass plate was After curing the polycarbonate plate at 160° C. and 100° C., the thickness of the formed coating film, the pencil hardness and reflectance of the coating film were measured.
測定結果全第11表に示した。All measurement results are shown in Table 11.
手続補正書(岐)
昭和58年7月)3日
特許庁長官 若杉和夫殿
■、小事件表示
昭和574「′侍許願第225787号2、発明の名称
低反!)1率塗膜
3、補正をする者
事1件との関係 特許出願人
住所 東京都千代田区丸の内二丁目1s2号氏名 (
004)旭硝子株式会社
4、代理人
5、hIi正の対象
明細書の発明の詳細な説明の欄
6、補正の内容
(1)明細書第7頁第2行目
「CH2= CH+OH2NB(OH2)z NH(O
H2)3Si(O0)la )、Jを[CH2−CH+
CH2NH(CH2)zNH(CH2)3si(OCH
3)3.」に訂正する。Procedural Amendment (Ki) July 3, 1981 Mr. Kazuo Wakasugi, Commissioner of the Patent Office■, Minor Case Indication 1987 ``'Samurai Permit Application No. 225787 2, Name of Invention Low Resistance!) 1 Rate Coating 3, Amendment Relationship with one case Patent applicant address 2-1s2 Marunouchi, Chiyoda-ku, Tokyo Name (
004) Asahi Glass Co., Ltd. 4, Agent 5, Detailed explanation of the invention column 6 in the subject specification of hIi, Contents of amendment (1) Page 7, line 2 of the specification “CH2= CH+OH2NB(OH2)z NH(O
H2)3Si(O0)la ), J is [CH2-CH+
CH2NH(CH2)zNH(CH2)3si(OCH
3)3. ” is corrected.
(2)明細書第7頁第3行目
「0リ−0H2(:!H2S1(OCH2)3Jを「0
XD−aH2aH2s1(OCH3)3jに訂正する。(2) Page 7, line 3 of the specification “0 Lee-0H2(:!H2S1(OCH2)3J)”
Corrected to XD-aH2aH2s1(OCH3)3j.
(3)明細書第8頁最下行
r (H300)35i(OH2)2(OFz)n(C
H2)25i(OCH3) 、 jをr (Ha C0
)35i(OH2)2(OFz)n(OHz)zsi(
00)(3)3 + jに訂正する。(3) Bottom line r (H300)35i(OH2)2(OFz)n(C
H2) 25i (OCH3), j to r (Ha C0
)35i(OH2)2(OFz)n(OHz)zsi(
Correct it to 00) (3) 3 + j.
(4)明細書第10頁第1行目
1− Rf (CI()20Hと」を「Rf(OH,、
)20Hと」に訂正する。(4) Specification page 10, line 1 1 - Rf(CI()20H and) is replaced with Rf(OH,
) 20H”.
(5)明細書第12頁第12行目 「ポリフルオロ化基
化合」 を「ポリフルオロ化基含有化合」に訂正する。(5) On page 12, line 12 of the specification, "polyfluorinated group compound" is corrected to "polyfluorinated group-containing compound."
(6)明細書第20頁第7行目「装置した」を 「装着
した」に訂正する。(6) In the 7th line of page 20 of the specification, “equipped” is corrected to “equipped”.
Claims (2)
、透明基体と同程度以上の屈折率を有するシラン化合物
又は透明性樹脂の塗膜と、該塗膜上にポリフルオロ化基
含有化合物からなる薄膜を形成してなることを特徴とす
る多層構造の低反射率塗膜。(1) In a low reflectance coating film treated on the surface of a transparent substrate, a coating film of a silane compound or transparent resin having a refractive index comparable to or higher than that of the transparent substrate, and a polyfluorinated group-containing compound on the coating film. A multilayer structure low reflectance coating film characterized by forming a thin film consisting of.
下の厚さである特許請求の範囲第1項記載の低反射率塗
膜。(2) The low reflectance coating film according to claim 1, wherein the thin film of the polyfluorinated group-containing compound has a thickness of 0.2 μm or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57225787A JPS59115840A (en) | 1982-12-24 | 1982-12-24 | Low reflectivity coating |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57225787A JPS59115840A (en) | 1982-12-24 | 1982-12-24 | Low reflectivity coating |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59115840A true JPS59115840A (en) | 1984-07-04 |
JPH0330492B2 JPH0330492B2 (en) | 1991-04-30 |
Family
ID=16834767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57225787A Granted JPS59115840A (en) | 1982-12-24 | 1982-12-24 | Low reflectivity coating |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59115840A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63135435A (en) * | 1986-11-28 | 1988-06-07 | Asahi Glass Co Ltd | Water-repellent and oil-repellent plastic molding and its production |
JPS63228101A (en) * | 1987-03-17 | 1988-09-22 | Nippon Sheet Glass Co Ltd | Antistatic non-reflection plate having stain resistance |
JPH02248480A (en) * | 1989-03-22 | 1990-10-04 | Asahi Glass Co Ltd | Transparent substrate material with water-repellent and antistaining properties, and structure equipped therewith |
JPH04224137A (en) * | 1990-04-03 | 1992-08-13 | Ppg Ind Inc | Glass article having nonreactive surface and method of its manufacture |
JPH05238781A (en) * | 1991-11-29 | 1993-09-17 | Ppg Ind Inc | Glass article having durable water repellent surface |
US5851674A (en) * | 1997-07-30 | 1998-12-22 | Minnesota Mining And Manufacturing Company | Antisoiling coatings for antireflective surfaces and methods of preparation |
US6277485B1 (en) | 1998-01-27 | 2001-08-21 | 3M Innovative Properties Company | Antisoiling coatings for antireflective surfaces and methods of preparation |
JPWO2006093156A1 (en) * | 2005-03-02 | 2008-08-07 | 松下電工株式会社 | Coating material composition and painted product |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4531622B2 (en) * | 2005-05-09 | 2010-08-25 | 四国化工機株式会社 | Rotating filling valve device with cutter |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5698166A (en) * | 1979-12-29 | 1981-08-07 | Nitto Electric Ind Co | Complex of polytetrafluoroethylene and glass |
-
1982
- 1982-12-24 JP JP57225787A patent/JPS59115840A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5698166A (en) * | 1979-12-29 | 1981-08-07 | Nitto Electric Ind Co | Complex of polytetrafluoroethylene and glass |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63135435A (en) * | 1986-11-28 | 1988-06-07 | Asahi Glass Co Ltd | Water-repellent and oil-repellent plastic molding and its production |
JPS63228101A (en) * | 1987-03-17 | 1988-09-22 | Nippon Sheet Glass Co Ltd | Antistatic non-reflection plate having stain resistance |
JPH02248480A (en) * | 1989-03-22 | 1990-10-04 | Asahi Glass Co Ltd | Transparent substrate material with water-repellent and antistaining properties, and structure equipped therewith |
JPH04224137A (en) * | 1990-04-03 | 1992-08-13 | Ppg Ind Inc | Glass article having nonreactive surface and method of its manufacture |
JP2525516B2 (en) * | 1990-04-03 | 1996-08-21 | ピーピージー インダストリーズ, インコーポレーテツド | Glass article having non-reactive surface and method for producing the same |
JPH05238781A (en) * | 1991-11-29 | 1993-09-17 | Ppg Ind Inc | Glass article having durable water repellent surface |
US5851674A (en) * | 1997-07-30 | 1998-12-22 | Minnesota Mining And Manufacturing Company | Antisoiling coatings for antireflective surfaces and methods of preparation |
US6277485B1 (en) | 1998-01-27 | 2001-08-21 | 3M Innovative Properties Company | Antisoiling coatings for antireflective surfaces and methods of preparation |
JPWO2006093156A1 (en) * | 2005-03-02 | 2008-08-07 | 松下電工株式会社 | Coating material composition and painted product |
US8273811B2 (en) | 2005-03-02 | 2012-09-25 | Panasonic Corporation | Coating material composite and coated article |
Also Published As
Publication number | Publication date |
---|---|
JPH0330492B2 (en) | 1991-04-30 |
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