JPS6118932B2 - - Google Patents
Info
- Publication number
- JPS6118932B2 JPS6118932B2 JP56082135A JP8213581A JPS6118932B2 JP S6118932 B2 JPS6118932 B2 JP S6118932B2 JP 56082135 A JP56082135 A JP 56082135A JP 8213581 A JP8213581 A JP 8213581A JP S6118932 B2 JPS6118932 B2 JP S6118932B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- group
- hard
- hard coating
- organic
- 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
Links
- 239000011248 coating agent Substances 0.000 claims description 15
- 125000000962 organic group Chemical group 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- DVQHRBFGRZHMSR-UHFFFAOYSA-N sodium methyl 2,2-dimethyl-4,6-dioxo-5-(N-prop-2-enoxy-C-propylcarbonimidoyl)cyclohexane-1-carboxylate Chemical compound [Na+].C=CCON=C(CCC)[C-]1C(=O)CC(C)(C)C(C(=O)OC)C1=O DVQHRBFGRZHMSR-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920002574 CR-39 Polymers 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011491 glass wool Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 1
- PWYOLUNMUKEIMH-UHFFFAOYSA-N tetramethyl silicate;trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)OC.CO[Si](OC)(OC)CCCOCC1CO1 PWYOLUNMUKEIMH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 γ-glycidoxypropyl group Chemical group 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
本発明は有機金属の分解被膜から得られるハー
ドコート剤に関するものである。
従来からプラスチツクの表面のスクラツチ防止
耐薬品、耐油性、耐摩耗性等の向上のため有機金
属の分解被膜を用いたハードコート剤が知られて
いる。これらのハードコート剤は、本来の前記特
性の他に、基板プラスチツクの耐熱性の問題か
ら、少なくとも150℃以下、望ましくは100℃以下
で分解して硬質被膜となること、基板との密着性
に優れていること、光学的に用いる場合（例えば
プラスチツク眼鏡レンズ等）には無色透明である
こと等の特性を有していなくてはならない。従来
かむ知られているハードコート剤は一般式RSi
（OR′）3とSi（OR′）4と酸又はアミン等の重合開始
剤から成るものが多かつた。（ここにＲ：エポキ
シ基を含む有機基、R1：C1〜C8のアルキル基を
示す）これらのハードコート剤は、液寿命が非常
に短かい、基板との密着性が不十分、硬さもエン
ピツ硬度で５〜6H程度で十分でなかつた。１方
前記有機ラン化合物にTi（OR′）4等の重合開始剤
を用いる方法もあるが、TiO2被膜は黄変しやす
く特に耐湿下においてそれが進行するという欠点
を有していた。
本発明者はかかる欠点にかんがみ、重合開始剤
となり、しかも前記欠点を有しない、更に硬い被
膜を得る有機金属化合物を検討した結果、５族金
属、特にTa，Nbの有機金属であるアルコラート
が優れていることを発見し本発明に至つた。
本発明に用いられるハードコート剤は一般式
RSi（OR′）3，Si（OR′）4，Me（OR′）5の混合物か
ら成り、場合によつてはアルコール、エステル等
の有機溶媒を含有しても良い。ここにＲはグリシ
ジル基を含む有機基であり、その代表例として
は、
The present invention relates to a hard coating agent obtained from a decomposed film of an organic metal. BACKGROUND ART Hard coating agents using organic metal decomposition films have been known for the purpose of preventing scratches and improving chemical resistance, oil resistance, abrasion resistance, etc. on the surface of plastics. In addition to the above-mentioned original properties, these hard coating agents decompose into a hard film at temperatures below 150°C, preferably below 100°C, due to the heat resistance of the plastic substrate, and have poor adhesion to the substrate. When used optically (for example, in plastic eyeglass lenses), it must have properties such as being colorless and transparent. The conventionally known hard coating agent is the general formula RSi
Many of them consisted of (OR') 3 , Si(OR') 4 , and a polymerization initiator such as an acid or amine. (Here, R: An organic group containing an epoxy group, R1 : An alkyl group of C1 to C8 .) These hard coating agents have a very short liquid life, insufficient adhesion to the substrate, The hardness was about 5 to 6H on a pencil scale, which was not sufficient. On the other hand, there is a method in which a polymerization initiator such as Ti(OR') 4 is used in the organic orchid compound, but this method has the drawback that the TiO 2 film is prone to yellowing, and this yellowing progresses particularly under moisture-resistant conditions. In view of these drawbacks, the present inventors investigated organometallic compounds that can act as polymerization initiators, do not have the above-mentioned drawbacks, and provide even harder films. This discovery led to the present invention. The hard coating agent used in the present invention has the general formula
It consists of a mixture of RSi(OR') 3 , Si(OR') 4 and Me(OR') 5 and may contain an organic solvent such as alcohol or ester depending on the case. Here, R is an organic group containing a glycidyl group, and representative examples thereof include:
【式】で表わされる
γ−グリシドオキシプロピル基で表わされるγ−
モルフオリルプロピル基、γ- represented by γ-glycidoxypropyl group represented by [Formula]
morpholylpropyl group,
【式】で表
わされるエポキシクロヘキシル基等である。
R′はアルキル基でありC1〜C8の直鎖又は側鎖の
ものが用いられる。Meは５族金属でありTa，Nb
が良い。これら三種の有機金属の混合割合は、目
的によつて任意に選ばれるが通常RSi
（OR′）320wt％〜90wt％：Si（OR′）42wt％〜50wt
％，Me（OR′）51wt％〜20wt％である。後者二つ
の割合が増加すると被膜は硬くなるが非常にもろ
くなる。これらをあらかじめ混合し適当な有機溶
媒に10wt％〜90wt％程度溶解し、場合によつて
は30℃〜80℃で還流下重合をある程度進行させ用
いても良い。これらのコート剤をアクリル、ポリ
カーポネート、CR−39、ポリエステル、セルロ
ース類等の基板に塗布し常温〜120℃で重合しハ
ード被膜を得る。重合時間は１時間〜数日であ
り、低温で長時間反応させた方が均一な硬い被膜
が得られやすい。又最初低温で重合し後に80℃〜
120℃の高温で重合するやり方が密着性の良い、
均一な硬い被膜を得るのに適している。この場合
特に低温80℃以下で行なわれる初期重合において
は低湿度程望ましく、RH，50％以下が望まし
い。続いて行なわれる高温重合はかなり高湿度下
で（RH70〜90％）で行なつてもよい。基板への
塗布法としてはスピンナー法、浸漬等速引上げ
法、スプレー法、ロールコーター法、印刷法等が
用いられる。被膜の厚みは、5000Å以上が望まし
く、さらに望ましくは１μ〜50μである。薄いと
ハードコートの効果がうすれ、又厚すぎると密着
性、均一性が低下する。
以下実施例に従い本発明を詳細に説明する。
実施例 １
γ−グリシドオキシプロピルトリメトキシシラ
ン ７部
テトラメトキシシラン
Si（OCH3）4（日本曹達製アトロンTMS） ２部
ペンタエトキシタンタル
Ta（OC2H5）5（日本曹達製アトロンNTA−
10） １部
を混合し、イソプロピルアルコール10部を加え
40℃で還流下３時間予備重合させた。次に基板と
してアクリル板、眼鏡用CR−39を常温下浸漬
し、15cm／minで等速引上げを行ない塗布した。
次に30℃でRH，20％に保つた恒温恒湿槽中で３
時間重合させ、次に80℃で２時間本重合させた。
被膜の厚みは10μであつた。硬さはエンピツ程度
で7H、グラスウールの引つかき試験では300回後
も何のキズも入らなかつた。耐湿下80℃90％で
400Hγ、サンシヤインウエザーメーターで200H
γ後も何の変色、特性の劣化もみられなかつた。
又−20℃←→80℃の温度シヨツク試験でも密着性の
低下はみられなかつた。
実施例 ２
エポキシシクロヘキシルエチルトリメトオシシ
ラン
テトラエトキシシラン
Si（OC2H5）4（日本曹達製アトロンTES） 40部
ペンタエトキシニオブ
Nb（OC2H5）5（日本曹達製アトロンNNB−
10）
10部
を混合しメタノール50部中に溶解し、ポリエス
ルフイルム浸漬等速引上げ法でコートした。常温
で24Hγ重合後、120℃で3Hγ重合させた。硬度
はエンピツ硬度７〜8Hであつた。被膜の厚みは
15μであつた。その他の特性は実施例１と同等で
あつた。又これらの被膜は、耐温水、耐油、耐溶
剤性共に非常に優れていた。
これらのハードコート剤を施したプラスチツク
基板は、プラスチツク眼鏡レンズ、プラスチツク
フオトマスク、プラスチツク液晶パネル基板等に
用いられる。It is an epoxychlorohexyl group represented by [Formula].
R' is an alkyl group, and a C 1 to C 8 straight chain or side chain is used. Me is a group 5 metal, Ta, Nb
is good. The mixing ratio of these three types of organic metals can be arbitrarily selected depending on the purpose, but usually RSi
(OR') 3 20wt% ~ 90wt%: Si (OR') 4 2wt% ~ 50wt
%, Me(OR′) 5 1wt% to 20wt%. As the ratio of the latter two increases, the coating becomes harder but also very brittle. These may be mixed in advance and dissolved in a suitable organic solvent at about 10 wt % to 90 wt %, and as the case may be, polymerization may proceed to some extent under reflux at 30° C. to 80° C. before use. These coating agents are applied to a substrate made of acrylic, polycarbonate, CR-39, polyester, cellulose, etc. and polymerized at room temperature to 120°C to obtain a hard film. The polymerization time is from 1 hour to several days, and it is easier to obtain a uniform hard film if the reaction is carried out at a low temperature for a long time. In addition, after polymerizing at low temperature first, 80℃~
Polymerization at a high temperature of 120℃ provides good adhesion.
Suitable for obtaining uniform hard coatings. In this case, especially in the initial polymerization carried out at a low temperature of 80° C. or lower, lower humidity is more desirable, and RH is preferably 50% or less. The subsequent high temperature polymerization may be carried out at fairly high humidity (70-90% RH). As a method for coating the substrate, a spinner method, a dipping constant velocity pulling method, a spray method, a roll coater method, a printing method, etc. are used. The thickness of the coating is preferably 5000 Å or more, more preferably 1 μ to 50 μ. If it is too thin, the effect of the hard coat will be diminished, and if it is too thick, adhesion and uniformity will decrease. The present invention will be described in detail below with reference to Examples. Example 1 7 parts of γ-glycidoxypropyltrimethoxysilane Tetramethoxysilane Si (OCH 3 ) 4 (Atron TMS manufactured by Nippon Soda) 2 parts Pentaethoxytantalum Ta (OC 2 H 5 ) 5 (Atron NTA− manufactured by Nippon Soda)
10) Mix 1 part and add 10 parts of isopropyl alcohol.
Prepolymerization was carried out at 40°C under reflux for 3 hours. Next, as a substrate, an acrylic plate, CR-39 for eyeglasses, was immersed at room temperature and then pulled up at a constant speed of 15 cm/min for coating.
Next, 3.
Polymerization was carried out for an hour, and then main polymerization was carried out at 80°C for 2 hours.
The thickness of the coating was 10μ. The hardness is 7H, about the same as that of a pencil, and there were no scratches even after 300 times in the glass wool scratch test. Humidity resistant at 80℃90%
400Hγ, 200H with sunshine weather meter
No discoloration or deterioration of properties was observed even after γ.
Also, no decrease in adhesion was observed in a temperature shock test of -20°C←→80°C. Example 2 Epoxycyclohexylethyltrimethoxysilane Tetraethoxysilane Si (OC 2 H 5 ) 4 (Atron TES manufactured by Nippon Soda) 40 parts Pentaethoxyniobium Nb (OC 2 H 5 ) 5 (Atron NNB− manufactured by Nippon Soda)
10) 10 parts were mixed, dissolved in 50 parts of methanol, and coated using a polyester film dipping constant velocity pulling method. After 24Hγ polymerization at room temperature, 3Hγ polymerization was performed at 120°C. The hardness was 7 to 8H on a pencil hardness scale. The thickness of the coating is
It was 15μ. Other properties were the same as in Example 1. Furthermore, these coatings had excellent resistance to hot water, oil, and solvents. Plastic substrates coated with these hard coating agents are used for plastic eyeglass lenses, plastic photomasks, plastic liquid crystal panel substrates, and the like.
Claims (1)
（OR′）5の混合分解被膜から成ることを特徴とす
るハードコート剤 Ｒ ：エポキシ基を含む有機基 R′：C1〜C8のアルキル基 Me：Ta，Nbを示す。[Claims] 1 General formula RSi(OR') 3 , Si(OR') 4 , Me
(OR') A hard coating agent characterized by being composed of a mixed decomposition film of 5. R: Organic group containing an epoxy group R': C1 to C8 alkyl group Me: Ta, Nb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56082135A JPS57195735A (en) | 1981-05-29 | 1981-05-29 | Hard coating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56082135A JPS57195735A (en) | 1981-05-29 | 1981-05-29 | Hard coating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57195735A JPS57195735A (en) | 1982-12-01 |
| JPS6118932B2 true JPS6118932B2 (en) | 1986-05-15 |
Family
ID=13765969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56082135A Granted JPS57195735A (en) | 1981-05-29 | 1981-05-29 | Hard coating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57195735A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL84025A0 (en) * | 1986-10-03 | 1988-02-29 | Ppg Industries Inc | Organosiloxane/metal oxide coating compositions and their production |
| US6444008B1 (en) * | 1998-03-19 | 2002-09-03 | Cabot Corporation | Paint and coating compositions containing tantalum and/or niobium powders |
-
1981
- 1981-05-29 JP JP56082135A patent/JPS57195735A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57195735A (en) | 1982-12-01 |
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