JPH0629332B2 - Antifouling / low-reflective plastic - Google Patents
Antifouling / low-reflective plasticInfo
- Publication number
- JPH0629332B2 JPH0629332B2 JP8877685A JP8877685A JPH0629332B2 JP H0629332 B2 JPH0629332 B2 JP H0629332B2 JP 8877685 A JP8877685 A JP 8877685A JP 8877685 A JP8877685 A JP 8877685A JP H0629332 B2 JPH0629332 B2 JP H0629332B2
- Authority
- JP
- Japan
- Prior art keywords
- plastic
- low
- coating film
- weight
- antireflection
- 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.)
- Expired - Lifetime
Links
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は表面に反射防止塗膜が形成されたプラスチツク
に関し、特に、防汚性と低反射性に優れ、しかも耐擦傷
性をも有する低反射性プラスチツクに関するものであ
る。TECHNICAL FIELD The present invention relates to a plastic having an antireflection coating film formed on the surface thereof, and in particular, it is excellent in antifouling property and low reflection property, and also has low scratch resistance. It concerns reflective plastics.
一般に、プラスチツク材料、特に透明プラスチツク材料
は透明性に加えて、自身の有する軽量、耐衝撃性及び易
加工性などの利点を活かして、建築物の窓・ドアー・間
仕切り、シヨーウインド・シヨーケース、車輛の窓・照
明灯レンズ、２輪車の風防、ＯＡ機器のハウジング、光
学レンズ、メガネレンズなどの広い分野に利用されてい
る。In general, plastic materials, especially transparent plastic materials, take advantage of their own lightness, impact resistance, and easy workability in addition to transparency, and take advantage of their own advantages such as windows / doors / partitions for buildings, shoe windows / yoyo cases, and vehicles. It is used in a wide range of fields such as window / illumination lenses, windshields for two-wheeled vehicles, housings for office automation equipment, optical lenses, and eyeglass lenses.
しかしながら、それらプラスチツク材料からなる成形品
は太陽光、照明光の反射によるギラツキや眩しさ、ある
いは周囲の景観が映り、透視性や透明性に支障を与えた
り、光の反射により光線透過率が低下して、プラスチツ
クを通して見ると明るさが損なわれるという問題があ
る。However, molded products made of these plastic materials show glare and glare due to reflection of sunlight and illumination light, or the surrounding landscape is reflected, impairing transparency and transparency, and light transmittance decreases due to light reflection. Then, there is a problem that the brightness is impaired when viewed through the plastic.
従来から、ガラス、プラスチツクなどの透明物品表面の
低反射化は光学部品を中心に開発が進められてきてい
て、通常、プラスチツク成形体の表面に反射防止膜を形
成することによつて行なわれている。反射防止膜は例え
ば、MgF2、LiF、ThF4、氷晶石などの無機フツ化物、Si
O、SiO2、ZrO2、CeO2、Al2O3、などの金属酸化物を真空
蒸着やスパツタリングなどの方法によつて単層あるいは
複層の塗膜として形成されている。一方、高分子物質か
らなる低反射性処理剤を直接塗布あるいは処理剤中に浸
漬することによる反射防止塗膜の形成方法ならびに処理
剤が提案されている。しかしながら、かかる処理剤はガ
ラス、プラスチツクなどの表面への接着性に劣るため、
多くの場合、プレコート層が形成され、その層上に処理
されて、反射防止塗膜として形成される。これらの改良
された反射防止塗膜の形成方法として、例えば、透明材
料、特にプラスチツク基材上に金属酸化物含有組成物を
水を含む条件下で処理してプレコート層を設け、該プレ
コート層上に有機ケイ素化合物を含有する組成物からな
る反射防止塗膜を形成させる方法（特開昭５９−４９９
６０号公報が開示されている。また、本発明者も硬度と
低反射性に優れた反射防止塗膜としてシラン化合物とポ
リフルオロ化基含有化合物からなる多層構造の低反射率
塗膜（特開昭５９−１１５８４０号公報）を提案してい
る。Conventionally, the development of low reflection on the surface of transparent articles such as glass and plastics has been developed mainly for optical parts, and it is usually carried out by forming an antireflection film on the surface of the plastic molded body. There is. The antireflection film is made of, for example, MgF 2 , LiF, ThF 4 , inorganic fluoride such as cryolite, Si
A metal oxide such as O, SiO 2 , ZrO 2 , CeO 2 , and Al 2 O 3 is formed as a single-layer or multi-layer coating film by a method such as vacuum deposition or sputtering. On the other hand, there has been proposed a method for forming an antireflection coating film by directly coating or dipping a low-reflective treatment agent composed of a polymer substance, and a treatment agent. However, since such a treatment agent has poor adhesion to the surface of glass, plastic, etc.,
Often, a precoat layer is formed and processed on to form an antireflective coating. As a method for forming these improved antireflection coatings, for example, a transparent material, particularly a plastic substrate is treated with a metal oxide-containing composition under conditions containing water to form a precoat layer, and the precoat layer is formed on the precoat layer. To form an antireflection coating film comprising a composition containing an organosilicon compound (JP-A-59-499)
Japanese Patent Publication No. 60 is disclosed. The present inventor also proposed a low reflectance coating film having a multilayer structure composed of a silane compound and a polyfluorinated group-containing compound (Japanese Patent Laid-Open No. 59-115840) as an antireflection coating film excellent in hardness and low reflectance. is doing.
前記の反射防止膜の形成方法において、真空蒸着あるい
はスパツタリング法は装置の機構上及びコスト面から適
応物品は小型精密光学部品などに限定されるという制約
があり、更に連続的製造には適していない。In the method of forming the antireflection film, the vacuum deposition or the sputtering method has a limitation that the applicable articles are limited to small precision optical parts and the like from the viewpoint of the mechanism of the apparatus and the cost, and it is not suitable for continuous production. .
一方前記のごとき公知の低反射処理剤はプラスチツク表
面への接着性は充分でなく、プレコート層の形成を必要
とし、低反射処理工程を煩雑なものとして、コスト的に
不利である。しかも形成されら反射防止塗膜は大気中に
浮遊する塵埃、水滴、油滴などが付着して汚染されると
塗膜の構造特性から通常の洗浄作業によつては容易に除
去されず、例えば強く払拭すると塗膜に傷を生じ、つい
には剥離してしまい、耐擦傷性に劣るという問題があ
る。On the other hand, the above-mentioned known low-reflection treatment agents are not sufficient in adhesiveness to the plastic surface and require the formation of a precoat layer, which makes the low-reflection treatment step complicated and is disadvantageous in terms of cost. Moreover, if formed, the antireflection coating is not easily removed by ordinary washing work due to the structural characteristics of the coating when dust, water droplets, oil droplets, etc. floating in the air are contaminated. If it is wiped off strongly, the coating film will be scratched and eventually peeled off, resulting in poor scratch resistance.
したがつて、低反射処理工程が簡単であり、しかも形成
された反射防止塗膜は耐擦傷性と防汚性とに優れている
低反射性プラスチツクの開発が望まれている。Therefore, there is a demand for the development of a low-reflective plastic which has a simple low-reflective treatment step and has excellent anti-scratch property and anti-fouling property in the formed anti-reflective coating film.
本発明者は、前記問題点に鑑み、プラスチツク表面に対
して接着性に優れ、しかも形成された反射防止塗膜は耐
擦傷性と防汚性とを満足する低反射処理剤について種々
研究、検討を行なつた。その結果、特定の含フツ素シリ
コーン化合物の２種とシリコーン化合物との三成分から
なる組成物は反射防止塗膜としてプラスチツク表面に形
成されると、前記問題点を解決するに足る塗膜となり得
るという事実を見い出し本発明を完成するに至つたもの
である。In view of the above problems, the present inventor has various studies and studies on a low-reflection treatment agent having excellent adhesiveness to a plastic surface, and the antireflection coating film formed has satisfactory scratch resistance and stain resistance. Was done. As a result, when a composition composed of two components of a specific fluorine-containing silicone compound and a silicone compound is formed on the plastic surface as an antireflection coating, it may be a coating sufficient to solve the above problems. That is, the present invention has been completed and the present invention has been completed.
而して、上記組成物において、三成分のいずれが欠けて
も特性は満足されないが、三成分が含まれることによつ
て各種プラスチツクに応用が可能であつて、プラスチツ
クの有する透明性、透視性を損なうことなく、塗布、吹
付け、浸漬など既知の簡便な方法によつてプラスチツク
表面上に塗膜として形成されることによつて、可視光全
域を平均に低反射化し、しかも耐擦傷性、防汚性にも優
れた低反射性プラスチツクが得られるものである。Thus, in the above composition, the characteristics are not satisfied even if any of the three components is lacking, but it is possible to apply to various plastics due to the inclusion of the three components, and the transparency and transparency of the plastics are possessed. Without being damaged, coating, spraying, by being formed as a coating film on the plastic surface by a known simple method such as dipping, the visible light region has a low average reflectance, and scratch resistance, It is possible to obtain a low-reflection plastic excellent in antifouling property.
即ち、本発明は、表面に反射防止膜が形成された低反射
性プラスチツクにおいて、下記一般式で表わされる化合
物を含有する反射防止膜組成物からなる塗膜が形成され
てなることを特徴とする防汚性・低反射性プラスチツク
を提供するものである。That is, the present invention is characterized in that, in a low-reflection plastic having an antireflection film formed on its surface, a coating film made of an antireflection film composition containing a compound represented by the following general formula is formed. It provides an antifouling and low-reflective plastic.
一般式 Rf 1-A-SiX3 ５〜80重量％ X3Si-A-Rf 2-A-SiX3 ５〜94重量％ SiX4 １〜90重量％ （但し、式中Ａは二価の有機基、Ｘはハロゲン、 OR、Ｒは低級アルキル基、Rf 1はポリフルオロアルキル
基、Rf 2はフツ素を含有する炭素数２以上の二価の有機
基を示す。） 本発明におけるプラスチツクとしては、表面の反射を低
下させる目的から透明プラスチツクであるのが好適であ
る。かかる透明プラスチツクとしては、例えば、ポリ
（ジエチレングリコールビスアリルカーボネート）、ポ
リカーボネート、ポリメタアクリレート、ポリスチレ
ン、ポリエステル、ポリウレタン、ポリ塩化ビニル、ジ
アリルフタレート樹脂、メラミン樹脂などが挙げられ
る。而して、かかる透明プラスチツクのみに限定される
ものではない。General formula R f 1 -A-SiX 3 5 to 80% by weight X 3 Si-AR f 2 -A-SiX 3 5 to 94% by weight SiX 4 1 to 90% by weight (where A is a divalent organic compound) Group, X is halogen, OR and R are lower alkyl groups, R f 1 is a polyfluoroalkyl group, and R f 2 is a fluorine-containing divalent organic group having 2 or more carbon atoms. The plastic in the present invention is preferably a transparent plastic for the purpose of reducing the reflection on the surface. Examples of such transparent plastics include poly (diethylene glycol bisallyl carbonate), polycarbonate, polymethacrylate, polystyrene, polyester, polyurethane, polyvinyl chloride, diallyl phthalate resin, and melamine resin. Thus, the transparent plastic is not the only one.
本発明の反射防止膜組成物は一般式Rf 1-A-SiX3、X3Si-A
-Rf 2-A-SiX3、SiX4で表わされる各化合物の三成分より
なるが、Rf 1-A-SiX3で表わされる化合物は塗膜の低屈折
率化及び防汚性付与、X3Si-A-Rf 2-A-SiX3で表わされる
化合物は低屈折率化及び耐擦傷性向上、そしてSiX4は耐
擦傷性向上に有用であつて、これら三成分が最適な割合
で組合せられることによつて低反射性、防汚性及び耐擦
傷が発現されるものである。The antireflection coating composition of the present invention has the general formula R f 1 -A-SiX 3 , X 3 Si-A
-R f 2 -A-SiX 3 , consisting of three components of each compound represented by SiX 4 , the compound represented by R f 1 -A-SiX 3 imparts a low refractive index and antifouling property to the coating film, The compound represented by X 3 Si-AR f 2 -A-SiX 3 is useful for lowering the refractive index and improving the scratch resistance, and SiX 4 is useful for improving the scratch resistance, and these three components are combined in an optimum ratio. As a result, low reflectivity, antifouling property and scratch resistance are exhibited.
ここで、一般式Rf 1-A-SiX3 で表わされる化合物は、Rf 1は防汚性の付与と、その向
上という点でポリフルオロアルキル基であるのが好まし
く、エーテル結合が含まれていてもよい。Ａは二価の有
機基、Ｘはハロゲン、 ORであつてＲは低級アルキル基である。かかる化合物を
例示すると、 Rf(CH2)2SiCl3，Rf(CH2)2Si(OCH3)3， RfCONH(CH2)3Si(OC2H5)3， RfCONH(CH2)3NH(CH2)3Si(OC2H5)3， RfSO2N(CH3)(CH2)2CONH(CH2)3Si(OC2H5)3， Rf(CH2)2OCO(CH2)2S(CH2)3Si(OCH3)3， Rf(CH2)2OCONH(CH2)3Si(OC2H5)3， Rf(CH2)2NH(CH2)2Si(OCH3)3， Rf(CH2)2NH(CH2)2Si(OCH2CH2OCH3)3， （但し、Rfは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
物が挙げられる。Here, in the compound represented by the general formula R f 1 -A-SiX 3 , R f 1 is preferably a polyfluoroalkyl group from the viewpoint of imparting antifouling property and improving it, and contains an ether bond. May be. A is a divalent organic group, X is a halogen, In OR, R is a lower alkyl group. Examples of such compounds include R f (CH 2 ) 2 SiCl 3 , R f (CH 2 ) 2 Si (OCH 3 ) 3 , R f CONH (CH 2 ) 3 Si (OC 2 H 5 ) 3 , R f CONH (CH 2) 3 NH (CH 2) 3 Si (OC 2 H 5) 3, R f SO 2 N (CH 3) (CH 2) 2 CONH (CH 2) 3 Si (OC 2 H 5) 3, R f (CH 2 ) 2 OCO (CH 2 ) 2 S (CH 2 ) 3 Si (OCH 3 ) 3 , R f (CH 2 ) 2 OCONH (CH 2 ) 3 Si (OC 2 H 5 ) 3 , R f (CH 2 ) 2 NH (CH 2 ) 2 Si (OCH 3 ) 3 , R f (CH 2 ) 2 NH (CH 2 ) 2 Si (OCH 2 CH 2 OCH 3 ) 3 , (However, R f is a polyfluoroalkyl group, m is an integer of 1 or more), and the like, and silane compounds having a polyfluoroalkyl group and silane compounds having a polyfluoroalkyl group having an ether bond.
上記一般式Rf 1-A-SiXで表わされる化合物は反射防止膜
組成物中５〜８０重量％含まれるのが好ましい。５重量
％以下では防汚性が、また８０重量％以上であると耐擦
傷性が低下する。The compound represented by the above general formula R f 1 -A-SiX is preferably contained in the antireflection coating composition in an amount of 5 to 80% by weight. If it is 5% by weight or less, the antifouling property is lowered, and if it is 80% by weight or more, the scratch resistance is lowered.
次に一般式X3Si-A-Rf 2-A-SiX3で表わされる化合物は、R
f 2がフツ素を含有する炭素数２以上の二価の有機基であ
つてＡ、Ｘは前記と同一である。かかる化合物としては
例えば、 Cl3SiC2H4(CF2)nC2H4SiCl3， (CH3O)3SiC2H4(CF2)nC2H4Si(OCH3)3， （但し、ｎは２〜１４の整数） などが挙げられる。Next, the compound represented by the general formula X 3 Si-AR f 2 -A-SiX 3 is R
f 2 is a fluorine-containing divalent organic group having 2 or more carbon atoms, and A and X are the same as defined above. Examples of such a compound include Cl 3 SiC 2 H 4 (CF 2 ) nC 2 H 4 SiCl 3 , (CH 3 O) 3 SiC 2 H 4 (CF 2 ) n C 2 H 4 Si (OCH 3 ) 3 , (However, n is an integer of 2 to 14) and the like.
上記、一般式X3Si-A-Rf 2-A-SiX3で表わされる化合物は
反射防止膜組成物中５〜９４重量％含まれるのが好まし
く、５重量％以下であると耐擦傷性が、９４重量％以上
であると防汚性が低下する。The compound represented by the general formula X 3 Si-AR f 2 -A-SiX 3 is preferably contained in the antireflection film composition in an amount of 5 to 94% by weight, and when the amount is 5% by weight or less, scratch resistance is If it is 94% by weight or more, the antifouling property deteriorates.
更に一般式SiX4で表わされる化合物はＸは前記と同一で
ある。この化合物としては SiCl4，Si(OCH3)4，Si(OCH2H5)4， などを例示することができる。この一般式SiX4で表わさ
れる化合物は反射防止膜組成物中１〜９０重量％含まれ
るのが好ましく、１重量％以下では耐擦傷性が、９０重
量％以上では低反射性、防汚性が低下する。Further, in the compound represented by the general formula SiX 4 , X is the same as above. The compounds are SiCl 4 , Si (OCH 3 ) 4 , Si (OCH 2 H 5 ) 4 , And the like. The compound represented by the general formula SiX 4 is preferably contained in the antireflection coating composition in an amount of 1 to 90% by weight, and a scratch resistance of 1% by weight or less, a low reflection property and an antifouling property of 90% by weight or more. descend.
上記、三成分を構成する化合物において、それぞれの化
合物内で数種が組合わされてもよい。In the above-mentioned compounds constituting the three components, several kinds may be combined in each compound.
反射防止膜組成物は上記、三成分を構成する化合物の他
に反射防止膜の特性を向上させる目的で、シリカゾルな
どの無機質フイラーや、例えば NH2(CH2)2NH(CH2)3Si(OCH3)3， NH2(CH2)3Si(OCH3)3，CH2=CHSi(OCH3)3，CH2=CHSiCl3， HS(CH2)3Si(OCH3)3，HCO(CH2)3Si(OC2H5)3，Cl(CH2)3Si
(OCH3)3， などのシランカップリング剤、あるいは架橋剤、帯電防
止剤、その他の特性改良用の添加剤などが配合、含有さ
れてもよい。The antireflection film composition is an inorganic filler such as silica sol or the like for the purpose of improving the properties of the antireflection film in addition to the above-mentioned three-component compound. NH 2 (CH 2) 2 NH (CH 2) 3 Si (OCH 3) 3, NH 2 (CH 2) 3 Si (OCH 3) 3, CH 2 = CHSi (OCH 3) 3, CH 2 = CHSiCl 3, HS (CH 2) 3 Si ( OCH 3) 3, HCO (CH 2) 3 Si (OC 2 H 5) 3, Cl (CH 2) 3 Si
(OCH 3 ) 3 , A silane coupling agent such as the above, or a cross-linking agent, an antistatic agent, and other additives for improving properties may be blended and contained.
反射防止膜組成物は塗膜形成用の処理液として次のよう
に調製される。即ち、前記三成分を構成するそれぞれの
化合物を所定の割合に従つて混合して、溶媒中触媒の存
在下に加水分解反応せしめて、部分縮合体となし、溶媒
に溶解された処理液として調製される。かかる加水分解
反応における溶媒はアルコール類、例えば、ブタノー
ル、好ましくはtert−ブタノールが用いられ、触媒とし
ては塩酸、酢酸あるいは他の有機酸が使用され、反応は
室温にて撹拌することによつて行なわれる。溶媒の量は
調製された処理液のプラスチツク表面への塗布性あるい
は形成される塗膜の膜厚が考慮され、部分縮合体が１〜
２０重量％、好ましくは２〜５重量％となるように調整
される。The antireflection film composition is prepared as follows as a treatment liquid for forming a coating film. That is, the respective compounds constituting the above three components are mixed according to a predetermined ratio and subjected to a hydrolysis reaction in a solvent in the presence of a catalyst to form a partial condensate, which is prepared as a treatment liquid dissolved in a solvent. To be done. Alcohols such as butanol, preferably tert-butanol are used as a solvent in such a hydrolysis reaction, hydrochloric acid, acetic acid or other organic acid is used as a catalyst, and the reaction is carried out by stirring at room temperature. Be done. The amount of the solvent is determined in consideration of the coating property of the prepared treatment liquid on the plastic surface or the film thickness of the formed coating film, and the partial condensate is
It is adjusted to 20% by weight, preferably 2 to 5% by weight.
かくして調製された塗膜形成用の処理液のプラスチツク
表面への塗布方法は、はけ塗り、ロール塗り、スピニン
グ、吹付け、あるいは浸漬など既知の方法によつて行な
われる。The method of coating the coating solution thus prepared on the plastic surface is carried out by a known method such as brush coating, roll coating, spinning, spraying or dipping.
塗布後は５０〜１５０℃の温度で２０分以上硬化するこ
とによつて塗膜が形成される。硬化処理における温度の
設定はプラスチツクの軟化温度との関係において適当に
選定される。形成される塗膜の膜厚は0.2μ以下、好ま
しくは0.05〜0.1μであつて、かかる膜厚の調整は塗布
方法の条件によつてなし得るものであり、例えば浸漬法
においては組成物濃度と引上げ速度とによつて決定され
る。After coating, the coating film is formed by curing at a temperature of 50 to 150 ° C. for 20 minutes or more. The setting of the temperature in the curing treatment is appropriately selected in relation to the softening temperature of the plastic. The film thickness of the coating film formed is 0.2 μ or less, preferably 0.05 to 0.1 μ, and the adjustment of the film thickness can be made according to the conditions of the coating method. And the pulling speed.
プラスチツク表面に形成される塗膜の密着性は上記の方
法によれば実用上は充分であるが、プラスチツク表面を
予め、アルカリ処理、グロー放電処理、プラズマ処理な
どの活性処理を施こすことによつて、更に向上せしめる
ことができる。Although the adhesion of the coating film formed on the plastic surface is sufficient in practice according to the above method, it is possible to subject the plastic surface to an activation treatment such as an alkali treatment, a glow discharge treatment or a plasma treatment in advance. Therefore, it can be further improved.
次に、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。尚、実
施例において防汚性・低反射性プラスチツクとしての評
価試験方法は次の通りである。Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the examples, the evaluation test method as an antifouling / low-reflective plastic is as follows.
反射率測定：自記分光光度計正反射光測定付属装置（日
立製作所製：３２３型）を使用し、波長４００nm〜７０
０nmの入射角５°における平均反射率を測定。Reflectance measurement: Autograph spectrophotometer specular reflection measurement accessory device (Hitachi: 323 type) is used, wavelength 400nm-70
Measure the average reflectance at an incident angle of 5 ° at 0 nm.
膜厚測定：“タリステツプ”（Rank Taylor Hobson社
製）を使用し針圧測定より求める。Film thickness measurement: It is determined by measuring the stylus pressure using "Taliste step" (manufactured by Rank Taylor Hobson).
耐擦傷性：綿布を５００ｇ荷重下、１０００回摩擦し傷
の発生の有無を確認 防汚性：油性フエルトペンにて汚染し、１時間放置後、
綿布で払拭し、インクの除去性を確認。Scratch resistance: A cotton cloth is rubbed 1000 times under a load of 500 g to check for scratches. Antifouling property: Contaminate with an oil-based felt-tip pen and leave for 1 hour.
Wipe with a cotton cloth to check the ink removability.
実施例１ 下記〔Ａ〕〜〔Ｃ〕の化合物とtert−ブタノール２５０
０ｇとを混合し、それに１％塩酸水溶液16.2ｇを加え室
温２４時間撹拌しながら反応させて、反射防止塗膜形成
用の処理液を調製した。Example 1 Compounds [A] to [C] below and tert-butanol 250
0 g was mixed, 16.2 g of a 1% hydrochloric acid aqueous solution was added thereto, and the mixture was reacted with stirring at room temperature for 24 hours to prepare a treatment liquid for forming an antireflection coating film.
〔Ａ〕RfC2H4Si(OCH3)3 50g （ここで、RfはCnF2n+1でｎは６〜16で平均値９） 〔Ｂ〕(CH3O)3SiC2H4C6F12C2H4Si(OCH3)3 40g 〔Ｃ〕Si(OCH3)4 10g 別にポリ（ジエチレングリコールビスアリルカーボネー
ト）製の平板（５０mm×５０mm×３０mm）を１０％苛性
ソーダ水溶液に浸漬後、水洗、乾燥して用意し、これを
上記処理液に浸漬し7.5cm/minの速度で引上げ、室温に
て１０分間乾燥後、続いて１２０℃で６０分間加熱して
硬化させ、反射防止塗膜を形成した。形成された塗膜の
厚膜は0.09μ、波長４００nmから７００nmにおける平均
反射率は片面当り1.7％であつた。また、塗膜の耐擦傷
性試験において傷の発生は全く認められず、防汚性試験
においてはインクは、はじかれ、払拭することによつて
完全に除去することができた。[A] R f C 2 H 4 Si (OCH 3 ) 3 50 g (where R f is C n F 2n + 1 and n is 6 to 16 and the average value is 9) [B] (CH 3 O) 3 SiC 2 H 4 C 6 F 12 C 2 H 4 Si (OCH 3 ) 3 40g [C] Si (OCH 3 ) 4 10g Separately, a plate made of poly (diethylene glycol bisallyl carbonate) (50 mm × 50 mm × 30 mm) is 10% caustic soda. After dipping in an aqueous solution, rinsing with water and drying, the sample is dipped in the above treatment solution, pulled up at a rate of 7.5 cm / min, dried at room temperature for 10 minutes, and subsequently heated at 120 ° C. for 60 minutes to cure. Then, an antireflection coating film was formed. The thick film thus formed was 0.09μ, and the average reflectance in the wavelength range of 400 nm to 700 nm was 1.7% per surface. In addition, no scratch was observed in the scratch resistance test of the coating film, and the ink was repelled in the antifouling test and could be completely removed by wiping.
実施例２〜６、比較例１〜４ 実施例１における〔Ａ〕〜〔Ｃ〕の化合物の量を第１表
に示す量に変えた他は、実施例１と同様の方法により、
反射防止塗膜形成用の処理液を調製した。次いで、実施
例１と同様に平板に処理して反射防止塗膜の形成された
平板を得て、その評価試験を行なつた。試験結果を第１
表に示した。Examples 2 to 6 and Comparative Examples 1 to 4 By the same method as in Example 1, except that the amounts of the compounds [A] to [C] in Example 1 were changed to the amounts shown in Table 1.
A treatment liquid for forming an antireflection coating film was prepared. Then, a flat plate was treated in the same manner as in Example 1 to obtain a flat plate on which an antireflection coating was formed, and the evaluation test was conducted. First test result
Shown in the table.
実施例７〜８ 実施例１における〔Ａ〕の化合物を第２表に示す量に変
えた他は実施例１と同様の方法により、反射防止塗膜形
成用の処理液を調製した。続いて平板に処理して反射防
止膜の形成された平板を得た。その評価試験を行ない結
果を第２表に示す。 Examples 7 to 8 A treating liquid for forming an antireflection coating film was prepared in the same manner as in Example 1 except that the amount of the compound [A] in Example 1 was changed to the amounts shown in Table 2. Then, it processed into a flat plate and obtained the flat plate in which the antireflection film was formed. The results of the evaluation test are shown in Table 2.
実施例９ 実施例１における〔Ｂ〕の化合物を に変えた他は実施例１と同様の方法により、反射防止塗
膜形成用の処理液を調製した。続いて平板に処理して反
射防止膜の形成された平板を得た。形成された塗膜の膜
厚は0.09μ、平均反射率は片面当り1.6％であつた。ま
た塗膜の耐擦傷性試験において傷の発生は全く認められ
ず、防汚性試験においてはインクは、はじかれ、払拭す
ることによつて完全に除去することができた。 Example 9 The compound of [B] in Example 1 A treatment liquid for forming an antireflection coating film was prepared in the same manner as in Example 1 except that Then, it processed into a flat plate and obtained the flat plate in which the antireflection film was formed. The thickness of the coating film formed was 0.09μ, and the average reflectance was 1.6% on each side. No scratch was observed in the scratch resistance test of the coating film, and the ink was repelled in the antifouling test and could be completely removed by wiping.
実施例１０〜１１ 実施例１における平板をポリメタクリル製及びポリウレ
タン製の平板とした他は実施例１と同様に処理して、反
射防止塗膜の形成された平板を得た。その評価試験を行
ない、結果を第３表に示した。Examples 10 to 11 A flat plate having an antireflection coating film was obtained by the same treatment as in Example 1 except that the flat plate made in Example 1 was made of polymethacryl and polyurethane. The evaluation test was conducted and the results are shown in Table 3.
〔発明の効果〕 本発明の防汚性・低反射性プラスチツクは、従来、得ら
れなかつた防汚性と低反射性という両特性を同時に満足
させ、しかも耐擦傷性にも優れているという効果が認め
られるものである。 [Effects of the Invention] The antifouling / low-reflective plastic of the present invention has the effect of simultaneously satisfying both of the previously unobtainable antifouling and low-reflective properties, and is also excellent in scratch resistance. Is recognized.
特にプラスチツク表面に形成される反射防止塗膜は塗膜
の形成工程が簡略化され、コスト的にも有利であるとい
う効果をも有するものである。In particular, the antireflection coating film formed on the plastic surface has the effect of simplifying the coating film forming process and being advantageous in terms of cost.
Claims (3)
ラスチツクにおいて、下記一般式で表わされる化合物を
含有する反射防止膜組成物からなる塗膜が形成されてな
ることを特徴とする防汚性・低反射性プラスチツク。 一般式 Rf 1-A-SiX3 ５〜80重量％ X3Si-A-Rf 2-A-SiX3 ５〜94重量％ SiX4 １〜90重量％ （但し、式中Ａは二価の有機基、Ｘはハロゲン、 OR、Ｒは低級アルキル基、Rf 1はポリフルオロアルキル
基、Rf 2はフツ素を含有する炭素数２以上の二価の有機
基を示す。）1. A low-reflection plastic having an antireflection film formed on the surface thereof, wherein a coating film made of an antireflection film composition containing a compound represented by the following general formula is formed. Dirty and low reflective plastic. General formula R f 1 -A-SiX 3 5 to 80% by weight X 3 Si-AR f 2 -A-SiX 3 5 to 94% by weight SiX 4 1 to 90% by weight (where A is a divalent organic compound) Group, X is halogen, OR and R are lower alkyl groups, R f 1 is a polyfluoroalkyl group, and R f 2 is a fluorine-containing divalent organic group having 2 or more carbon atoms. )
許請求の範囲第１項記載の低反射性プラスチツク。2. The low reflective plastic according to claim 1, wherein the plastic is a transparent plastic.
特許請求の範囲第１項記載の低反射性プラスチツク。3. The low reflective plastic according to claim 1, wherein the surface of the plastic is subjected to activation treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8877685A JPH0629332B2 (en) | 1985-04-26 | 1985-04-26 | Antifouling / low-reflective plastic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8877685A JPH0629332B2 (en) | 1985-04-26 | 1985-04-26 | Antifouling / low-reflective plastic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61247743A JPS61247743A (en) | 1986-11-05 |
| JPH0629332B2 true JPH0629332B2 (en) | 1994-04-20 |
Family
ID=13952253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8877685A Expired - Lifetime JPH0629332B2 (en) | 1985-04-26 | 1985-04-26 | Antifouling / low-reflective plastic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629332B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0749021A3 (en) * | 1995-06-15 | 1997-11-26 | Sumitomo Chemical Company, Limited | Antireflection filter |
| US7226982B2 (en) | 2003-04-18 | 2007-06-05 | Shin-Etsu Chemical Co., Ltd. | Protective coat-forming coating composition, coated article, and multilayer laminate |
| EP1970196A2 (en) | 2007-03-13 | 2008-09-17 | FUJIFILM Corporation | Hydrophilic member and process for producing the same |
| EP1975194A2 (en) | 2007-03-28 | 2008-10-01 | FUJIFILM Corporation | Hydrophilic member and undercoating composition |
| WO2009035105A1 (en) | 2007-09-12 | 2009-03-19 | Fujifilm Corporation | Hydrophilic composition |
| WO2009041511A1 (en) | 2007-09-26 | 2009-04-02 | Fujifilm Corporation | Composition for formation of hydrophilic film, and hydrophilic member |
| WO2009096531A1 (en) | 2008-02-01 | 2009-08-06 | Fujifilm Corporation | Hydrophilic members |
| US7763678B2 (en) | 2006-04-14 | 2010-07-27 | Shin-Etsu Chemical Co., Ltd. | Anti-smudge agent, smudge proof coating composition, smudge proof film, and article coated with smudge proof film |
| WO2011059430A1 (en) | 2009-11-11 | 2011-05-19 | Essilor International | Surface treatment composition, process for producing the same, and surface-treated article |
| US8012591B2 (en) | 2006-09-21 | 2011-09-06 | Fujifilm Corporation | Hydrophilic composition and hydrophilic member |
| US9013795B2 (en) | 2011-11-30 | 2015-04-21 | Corning Incorporated | Optical coating method, apparatus and product |
| US9523004B2 (en) | 2009-11-11 | 2016-12-20 | Essilor International | Surface treatment composition, process for producing the same, and surface-treated article |
| US9957609B2 (en) | 2011-11-30 | 2018-05-01 | Corning Incorporated | Process for making of glass articles with optical and easy-to-clean coatings |
| US11180410B2 (en) | 2011-11-30 | 2021-11-23 | Corning Incorporated | Optical coating method, apparatus and product |
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|---|---|---|---|---|
| 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 |
| TW557368B (en) | 2001-06-29 | 2003-10-11 | Jsr Corp | Anti-reflection film laminated body and method of manufacturing the laminated body |
| JP2005338549A (en) * | 2004-05-28 | 2005-12-08 | Konica Minolta Opto Inc | Antireflection film, polarizing plate, and image display device |
| CN103551075B (en) | 2005-04-01 | 2016-07-06 | 大金工业株式会社 | Surface modifier |
| EP1869103B1 (en) | 2005-04-01 | 2017-05-03 | Daikin Industries, Ltd. | Surface modifier, article with a coated surface and method of coating |
| FR2907915B1 (en) * | 2006-10-31 | 2009-01-23 | Essilor Int | OPTICAL ARTICLE COMPRISING ANTI-SOIL COATING |
-
1985
- 1985-04-26 JP JP8877685A patent/JPH0629332B2/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0749021A3 (en) * | 1995-06-15 | 1997-11-26 | Sumitomo Chemical Company, Limited | Antireflection filter |
| US7226982B2 (en) | 2003-04-18 | 2007-06-05 | Shin-Etsu Chemical Co., Ltd. | Protective coat-forming coating composition, coated article, and multilayer laminate |
| US7763678B2 (en) | 2006-04-14 | 2010-07-27 | Shin-Etsu Chemical Co., Ltd. | Anti-smudge agent, smudge proof coating composition, smudge proof film, and article coated with smudge proof film |
| US8012591B2 (en) | 2006-09-21 | 2011-09-06 | Fujifilm Corporation | Hydrophilic composition and hydrophilic member |
| EP1970196A2 (en) | 2007-03-13 | 2008-09-17 | FUJIFILM Corporation | Hydrophilic member and process for producing the same |
| EP1975194A2 (en) | 2007-03-28 | 2008-10-01 | FUJIFILM Corporation | Hydrophilic member and undercoating composition |
| WO2009035105A1 (en) | 2007-09-12 | 2009-03-19 | Fujifilm Corporation | Hydrophilic composition |
| WO2009041511A1 (en) | 2007-09-26 | 2009-04-02 | Fujifilm Corporation | Composition for formation of hydrophilic film, and hydrophilic member |
| WO2009096531A1 (en) | 2008-02-01 | 2009-08-06 | Fujifilm Corporation | Hydrophilic members |
| WO2011060047A1 (en) | 2009-11-11 | 2011-05-19 | Essilor International (Compagnie General D'optique) | Surface treatment composition, process for producing the same, and surface-treated article |
| WO2011059430A1 (en) | 2009-11-11 | 2011-05-19 | Essilor International | Surface treatment composition, process for producing the same, and surface-treated article |
| US9523004B2 (en) | 2009-11-11 | 2016-12-20 | Essilor International | Surface treatment composition, process for producing the same, and surface-treated article |
| US9013795B2 (en) | 2011-11-30 | 2015-04-21 | Corning Incorporated | Optical coating method, apparatus and product |
| US9957609B2 (en) | 2011-11-30 | 2018-05-01 | Corning Incorporated | Process for making of glass articles with optical and easy-to-clean coatings |
| US11180410B2 (en) | 2011-11-30 | 2021-11-23 | Corning Incorporated | Optical coating method, apparatus and product |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61247743A (en) | 1986-11-05 |
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